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SMITHSONIAN MISCELLANEOUS COLLECTIONS
- 970 -

BIBLIOGRAPHY

OF

ACETO ACETIC ESTER

AND ITS DERIVATIVES

BY

PAUL H. SEYMOUR, M. S.

If

instructor in Chemistry, Lake Forest University

CITY OF WASHINGTON
PUBLISHED BY THE SMITHSONIAN INSTITUTION

1894

<ftD30.fr

BIOLOGY

UBRARY

G

PRINTED FOR THE SMITHSONIAN INSTITUTION
BY W. F. ROBERTS, WASHINGTON
,894

BIOLOGY LIBRARY

LETTER OF TRANSMITTAL.

NEW YORK, August 22, 1892.

The Committee of the American Association for the Advance-
ment of Science having charge of Indexing Chemical Literature
has voted to recommend to the Smithsonian Institution for publi-
cation the following Index :—

Bibliography of Aceto Acetic Ester and its Derivatives, by P. H.
Seymour, M. S., Assistant in General Chemistry, University of
Michigan,

This work was compiled under the direction of Prof. Albert B.
Prescott, Ph. D., a member of this Committee.

H. CARRINGTON BOLTON,

Chairman.

To THE SECRETARY OF THK

vSMlTHSONIAN INSTITUTION.

880865

PREFACE.

It is the purpose of this brief contribution to point out the existing
literature upon acetoacetic ester, rather than to make an addition to
this literature. The outlines of memoirs are given, not to enable the
reader to do without the originals, but to help him to find just the
ones he may require. To this end it has been undertaken to furnish a
description, without the detail of a condensation, of so much literary
material as has been cited. The subject is one so far interwoven with
research upon organic oxygen derivatives in general that its boundaries
have been often drawn at a venture. In questions upon the subject-
matter Mr. Seymour has had the benefit of consultation with Professor
Paul C. Freer, of this University, who has carried on investigations of
acetoacetic ester for some years. For the plan of the bibliography,
whatever defects the plan may have, the undersigned acknowledges
himself responsible. In the execution of the task Mr. Seymour has
devoted studious care, with clear critical inquiry on his own part, from
first to last. And his work is offered with confidence by the under-
signed, to the Committee on Indexing Chemical Literature, for issue
under the beneficent provisions of THE SMITHSONIAN INSTITUTION,
to whose time-saving publications chemists are so greatly indebted.

ALBERT B. PRESCOTT.

UNIVERSITY OF MICHIGAN,
August, 1892.

TABLE OF CONTENTS.

Introduction, ..... ix,

List of Periodicals consulted, . . x.

Abstracts of Articles, . . . i to 136.

Author-Index, . . . . 137 to 139.

Subject- Index, .... 141-148.

SMITHSONIAN INSTITUTION.

WASHINGTON CITY, November, 1894..

This work (No. 970), " BIBLIOGRAPHY OF ACETO ACETIC ESTER,"
by Paul H. Seymour, forms part of Volume 38, Smithsonian Miscella-
neous Collections. Other parts of the volume are in preparation.

LIBRARY CATALOGUE SLIPS.

Smithsonian Institution,

Bibliography of Aceto Acetic Ester. By
Paul H. Seymour, M. S. City of Washing-
ton, published by the Smithsonian Institution,
November, 1894. 8°, x, 148 pp.

From : Smithsonian Miscellaneous Collections,
vol. 38. (Number 970.)

Seymour, (Paul H.)

Bibliography of Aceto Acetic Ester. By
Paul H. Seymour, M. S. City of Washing-
ton, published by the Smithsonian Institution,
November, 1894." 8°, x, 148 pp.

From : Smithsonian Miscellaneous Collections,
vol. 38. (Number 970.)

Bibliography of Aceto Acetic Ester. By
Paul H. Seymour, M. S. City of Washing-
ton, published by the Smithsonian Institution,
November, 1894. 8°, x, 148 pp.

from : Smithsonian Miscellaneous Collections,
vol. 38. (Number 970.)

INTRODUCTION.

In the following work the articles were abstracted with reference
to the subject of the bibliography, consequently some articles were
abstracted only in part ; that is, omitting what had no relation to
acetoacetic ester. The word "ester " has been used to mean an acid
in which the carboxylic hydrogen has been replaced by an alkyl radi-
cal, and where the alkyl radical is not specified, ethyl is understood.

The bibliography is arranged in chronological order, with author
and subject indices appended.

All references given were verified, except where otherwise stated.

The reference given first in each case is the original publication, the
others are reprints or abstracts.

The literature on the subject begins in 1840.

I wish to express my gratitude to Professors Prescott and Freer for
direction and aid in the work.

PAUL H. SEYMOUR.

UNIVERSITY OF MICHIGAN,
June 1 1, 1892.

IX

LIST OF PERIODICALS CONSULTED.

The following periodicals were examined carefully for articles upon
the subject of the bibliography from the first volume in each case to
the end of 1891 :

Annalen der Chemie nnd Pharmadc (Vol. /., 1832).
Bcrichte der deutschen Chemischen Gesellschaft ( Vol. I. , 1868).
*Jahresbericht 'iiber die Fortschritte der Chemie ( Vol. I. , 184.7').
Journal of the Chemical Society ( J W. I., 184.9).
Bulletin de la Societe chimique de Paris ( Vol. /., 1864).

\
The following were consulted upon references :

Comptes rendus de V Academie des Sciences.

Annalen der Physik und Chemie, Poggendorff.

Journal of the American Chemical Society.

Journal fur praktische Chemie.

Archiv der Pharmacie.

[ahresbericht uber die Fortschritte der Chemie, Berzelius.

Chemical Neivs.

American Chemical Journal.

Ann ales de Chimie et de Physique.

* Of this 1887 was the last volume published.

BIBLIOGRAPHY

OF

ACETO ACETIC ESTER.

LOWIG, CARL AND SAL. WEIDEMANN, 1840.

Ann. der Phys. Pogg. 50, 95-125 ; Ann. Chem. 36, 297-304; Berzelius'

Jsb. 21, 425.

Action of Potassium and Sodium on Some Ethers.

Potassium attacks acetic ester at once and is dissolved. No gas is
given off ; the mass solidifies and is found to be composed of potassium
ethoxid and a compound of acetyl and oxygen, having less oxygen
than acetic ester ; in other words the potassium abstracts oxygen from
acetic ester. The product obtained, treated with sulfuric acid, gives
acetic acid. The author decides that it is probably " Hypoacetous
acid " (unteracetylig-saure) C4 H6

GEUTHER, A., 1863.

Arch, der Pharm. 116, 97-110; Jsb. Chem. 1863, 323.
Researches Upon Monobasic Acids.

Acetic ester was boiled with sodium and a stream of hydrogen passed
through. Sodium acetate and a compound *CI2 H9 Na Oe were formed.
This compound was named dimethylen-carbonethylen ether sodium, as

) OH
the author supposed it to be formed thus : — 2 *C2 H2, C2 O2 j OH,C4

* C2 H2 C2 02 I Na O

H4 + 2 Na= C2 H2, C2 O2 j H O, C4 H4 + C4 H5 Na O2 + H2. By
treating this compound with ethyl iodid he formed dimethylen-carbon-
ethylen ether * de HI4 Oe, boiling at 198° with a specific gravity of .998
at 12° By using methyl iodid dimethylen-carbonmethylen ether
*CI4 HI2 O6 boiling at 186.8° was produced. By the action of ammonia
on the former, two bodies were formed ; — * de HI5 NO4i insoluble in
water, melting at 59.5°, and CI2 Hn * NO4, soluble in water, melting
at 90° and subliming at 100° By passing carbon dioxid through * CI2
H9 Na Oe, CI2 HIO Oe was produced. It colors ferric chlorid, a dark
violet.
*C = 6; 0 = 8.

t OF

VVANKLYN^ jAx; l8<&4.
J. Chem. Soc. 17* 371-377 ; Chem. News. 10, 195 ; Jsb. Chem.

1864, 461.
Some Actions of Sodium and Sodethoxid.

The difference is shown between treating sodethoxid with an alkyl
iodid and an alkyl acetate.

In the first case sodium iodid is produced thus :

Na ) 0 , I I __ Na j C2 H5

C2 H5 j C h C2 H5 j - I } +C2 H5
In the second case the sodium replaces the acetyl group and not the
ethyl. This could not be shown in acetic ester, therefore valeric ester
was worked with. It was treated with metallic sodium, reaction took
place and no gas was given off.

The reaction was 2 C^H9 ° 1 0 + 2 Na= 2 ^a w 1 O+ S5 29 n f
L2 H5 j C2 H5 ) L5 H9 (J }

GEUTHER, A., 1866.

Arch, der Pharm. 125, 29-50, and 201,223; J- Prakt. Chem. 99 113-
125 ; Jsb. Chem. 1865. 302 ; Bull. Soc. chim. 6, 222.

Acetic Acid.

Acetic ester was treated with sodium and Ce H9 Na O3 was produced.
By boiling with water it was decomposed into acetone, alcohol, carbon
dioxid and sodium carbonate. C& HIO O3 was produced from its sodium
compound by treating with hydrochloric acid, carbon dioxid or acetic
acid, when it was called by the author ethyl-diacetic acid ; it has a
specific gravity of 1.03 at 5°, boils at 180.8° and reddens litmus only
when water is added. In obtaining it some dehydracetic acid was
always formed. It has the composition Cg H8 O4 and melts at 108.5°
and boils at 269.6°. The barium and copper compounds of ethyl-
diacetic acid and the barium, sodium and calcium salts of dehydracetic
acid were described. Ethyl-diacetic ethyl C8 HI4 O3 produced by ethyl
iodid boils at 198° and colors ferric chlorid blue. Btttyl-diacetic methyl
C7 HI2O3 boils at 186.8° has a specific gravity of 1.009 at 6° and colors
ferric chlorid a deep blue.

FRANKLAND, E., AND B. F. DUPPA, 1866.

J. Chem. Soc. 19. 395~434 I Ann. Chem. 138, 204-225 and 328-360 ;
Phil. Trans. Lond. 156, 37 ; Jsb. Chem. 1865, 304.

Synthetical Researches on Esters. Part I.

Acetic ester was made from sodium acetate, alcohol and sulfuric
acid. It was treated with sodium when an action took place and hydro-
gen was given off. The product was treated with ethyl iodid and the

ACETO ACETIC ESTER. 3

result was a small amount of Ce H9 (C2 H5 )O3 and a larger amount of
Ce H8 ( C2 H5 )2 O3. The latter is colorless, insoluble in water, miscible
with alcohol and ether, boils at i37.5°-i39° and has a specific gravity
of .8171 at 22°

Ethylic ethacetone carbonate Ce H9 ( C2 H5 ) O3 is colorless, almost
insoluble in water, miscible with alcohol and ether, boils at 195° and
distils unchanged, it has a specific gravity of .9834 at 16°. When
saponified with a water solution of potassium hydroxid, ethyl acetone,
CH3CO C (C2H5) H2, is produced which boils at 101° and has a
specific gravity of .8046 at 22°. Both of these acetones have the smell
and the taste of camphor. The di-methylderivative of acetoacetic ester
(as it is now known) was prepared, the reactions given were 2 CH3 CO2
C2 Hs + 2 Na= CH3 CO C Na2 CO2 C2 H5 + C2 H5 OH + H2 and CH3
CO CNa2 C02 C2 H5 +2CH3 I = CH3 CO C ( CH3 )2 CO2 C2 H5 + 2 Na
I. Some of the mono methyl derivative was also formed but was decom-
posed by a water solution of potassium hydroxid. Methyl acetone. CH3
CO C H2 ( CH3 ) , boils at 81° and has a specific gravity of .8125 at 13°.
Dimethyl acetone, CH3 CO C H ( CH3 )2) boils at 93° and has a specific
gravity of .8099 at 13°

Ethylic dimethyl acetone carbonate, CH3 CO C ( CH3 )2 CO2 C2 H5,
boils at 184° and has a specific gravity of .9913 at 16°.

BRANDES, R., 1866.

Arch, der Pharm. [2] 129, 193-212 ; Jsb. Chem. 1866, 305; Bull. Soc.

chim. 7» 501.
Acetic Acid.

Methylen-dimethylen carboxylic acid, C5 H8 O3 (acetoacetic methyl
ester), is produced from acetic methyl ester and sodium, sodmethoxid
and hydrogen being formed in the reaction. It is supposed to be an acid,
and to be acetic acid in which two hydrogen atoms of the methyl group
are replaced, one by methyl and the other by acetyl. It is colorless,
boils at 169° 170°, and has a specific gravity of 1.037 a^ 9°. Blue lit-
mus is scarcely changed by it until water is added. Alkalis and acids
decompose it into acetone, carbon dioxid and methyl alcohol. The
copper salt was made and described. Methylen-dimethylen carboxylic
acid ethylen (ethyl-acetoacetic methyl ester), prepared from the former
by treating with sodium and then with ethyl iodid, is colorless, boils at
189.7° and has a specific gravity of .995 at 14° It is isomeric with
Geuther's ethyl-dimethylen carboxylic acid methylen (methyl acet6
acetic ester). By using methyl iodid methylen-dimethylen carboxylic
acid methylen (methyl acetoacetic methyl ester), was produced, it boils

4 BIBLIOGRAPHY OF

at 177.4° and has a specific gravity of 1.020 at 9° Methylen-di-
metrylen carboxylic acid ethylen treated with ammonia gives two com-
pounds ; C7 HI3NO2) which is insoluble in water, andC5 H9 NO2, which
is soluble in water. When the above esters are distilled some dehydra-
cetic acid Cg Hg O4 is formed as a solid in the flask.

Geuther appends a note to this article in which he gives his opinion
as to the constitution of dehydracetic acid. He supposes it to be acetic
acid in which two hydrogen atoms have been replaced by acryl, C3 H3
O, thus : C H (C3 H3 O)2 CO2 H.

FRANKLAND, E., AND B. F. DUPPA, 1867.

J. Chem. Soc. 20, 102-116; Ann. Chem. 145. 78-93 ; Jsb. Chem. 1867,

394-
Synthetical Researches on Esters. Part II.

By the action of sodium and then isopropyl iodid on acetic ester,
monoisopropyl acetoacetic ester was produced, it is insoluble in water,
miscible with ether and alcohol, has a specific gravity of .9804, boils at
201° with 758.4 m. m. pressure and distils unchanged. When saponified
isopropyl acetone, CH3 CO CH2 CH ( CH3 )2, is produced, it is sparingly
soluble in water, miscible with alcohol and ether, boils at 114° with
758.4 m. m. pressure and has a specific gravity of .8189 at o°.

The difference is shown between it and two isomers, methyl valeral
and ethyl butyral.

GEUTHER, A., 1869.

Ztschr. *Chem. 5, 27 ; Bull. Soc. chim. 12, 377.
Changing Acetoacetic Ester into Ethylacetic Ester.

Acetoacetic ester heated to 1 20° with sodethoxid and acetic ester is
changed into ethyl acetic acid, CH2 C2 H5 CO2 H.
^Original article not consulted.

WANKLYN, A., 1869.

Ann. Chem. 149, 43-49 ; Jsb. Chem. 1868, 509.
Research upon Esters.

The action of sodium in sealed tubes upon a number of esters was
investigated and in no case was hydrogen evolved. The esters thus
worked with were acetic ester ; acetic allyl ester ; butyric ester ; valeric
ester and benzoic ester. The equation for sodium and acetic ester was
given as follows :

ACETO ACETIC ESTER. 5

3 C2 H3 02 C2 H5 + 4 Na = 3 Na OC2 H5 + Na ( C2 H3 O )3. The
author looks upon sod acetoacetic ester as a triacetyl derivative of sodium
and upon acetoacetic ester as a triacetyl derivative of hydrogen ; mak-
ing sodium and hydrogen trivalent.

WISLICENUS, J., 1869

Ann. Chem. 149, 205-215.

/2-Oxy butyric Acid.

The source of obtaining /9-oxybutyric acid is acetoacetic ester which
is treated with sodium amalgam and must be kept cool during the re-
action for other- wise enough heat is generated by the reaction to decom-
pose the substances into carbonates, acetone and alcohol.

WANKLYN, A., 1869.

Ber. 2, 64-65 ; Ann. Chem. 150, 206-208.
Action of Sodium on Alcohol.

By the action of sodium on alcohol, sodethoxid was formed, from
which the author concludes that sodium is trivalent [Na'"( C2 H4 )"]'
OH. This gives rise to a new set of compounds by replacing the hydro-
xyl hydrogen by radicals.

WANKLYN, A., 1869.

Ber. 2, 425-427.

Product of the action of Sodium and then Ethyl lodid on
Acetoacetic Ester.

No hydrogen is evolved in the first part of this reaction, the chief
products of which are sodethoxid and sodacetoacetic ester. Then sod-
ethoxid reacts with acetic ester to form ethyl acetate of sodium, CH2
( C2 H5 ) CO2 Na. This reacts with ethyl iodid thus : 2 CH2 ( C2 H5 )
C02 Na + 2 C2 H5 1 = 2 Na I + C2 H5 OH + C6 H8 ( C2 H5 )2 O3 and
finally C6 H8 ( C2 Hs )2 O3 reacts with sodethoxid to form CH2 ( C2 H5 )
CO2 Na and butyric ester, C6 HI2 O2.

LADENBURG, A., 1870.

Ber. 3, 305-306.
Action of Sodium on Acetic Ester.

By experimenting on this reaction the author concludes that no hydro-
gen is given off, and that with perfectly dry acetic ester no action will
take place below 100°

6 BIBLIOGRAPHY OF

GEUTHER, A., 1871.

Ztschr. *Chem. 7, 237 ; Bull. Soc. chim. 16, 107.
Acetoacetic Ester and Some of its Derivatives.

When acetoacetic ester is treated with phosphorus pentachlorid, two
metameric acids of the formula C4 H^ O2 are formed, quartenylic and
tetracrylic. Chlortetracrylic acid C4 H5 Cl O2, and its salts are described.
Tetrolic acid, C4 H4 O2v is formed from Chlortetracrylic ester by an excess
of alcoholic potash. Ammonia in the cold acts on acetoacetic ester to
form a soluble amid, Ce H:I NO2, and an insoluble amid, Cg HI5 NO2.
^Original article not consulted.

MIXTER, WM. Q., 1874.

Ber. 7, 499-504 ; Bull. Soc. chim. 22, 279.
Knowledge of Derivatives of Sodacetic Esters.

Sodacetoacetic ester was treated with isobutyl iodid and Ce Hg (C4
H9 )2 O3 was obtained together with some of the mono-butyl derivative,
Ce H9 (C4 H9 )O3. The dibutyl derivative is colorless, insoluble in
water, miscible with alcohol and ether and boils at 250° to 253° Ce H9
( C4 H9 ) O3 treated with barium hydroxid is saponified to iso-butyl
acetone, CH3 CO CH2 ( C4 H9 ).

WISLICENUS, J., 1874.

Ber. 7, 683-692 ; J. Chem. Soc. 27, 883 ; Bull. Soc. chim. 22, 457.
Researches on Derivatives of Acetoacetic Ester.

In regard to the disputed action of sodium on acetic ester the author
agrees with Geuther that as final products only sodethoxid and sodaceto-
acetic ester are produced. By the action of sodium on acetoacetic ester
only one hydrogen atom can be replaced, but by replacing that sodium
atom by an alkyl group the other hydrogen of the methylene group is
rendered replaceable by sodium and then by an alkyl group. The ethyl
and diethyl substituted esters were produced and described.

WISLICENUS, J., RUEGHEIMER, CONRAD, EHRLICH AND
ZEIDLER, 1874.

Ber. 7» 892-893 ; J. Chem. Soc. 29, 367 ; Bull. Soc. chim. 23, 72.
Derivatives of Acetoacetic Ester.

Sodacetoacetic ester treated with iodin forms diacetosuccinic ester
which melts with decomposition at 77° Sodacetoacetic ester treated with

ACETO ACETIC ESTER. 7

nionochloracetic ester forms acetosuccinic ester which boils at 260° to
263° with partial decomposition, its specific gravity is 1.079 at 2I°

Sodacetoacetic ester treated with chlorcarbonic ester, Cl CO2 C2 H5i
forms aceto-malonic ester which boils at 238° to 240° and has a specific
gravity of 1.080 at 23°

Sodacetoacetic ester treated with allyl iodid forms allylacetoacetic
ester an oil with a specific gravity of .982 at 20°

WISLICENUS, J., ZEIDLER, EHRLICH, ROHRBECK, WALD-
SCHM1DT, SAUR AND CONRAD, 1875.

Ber. 8, 1034-1040 ; J. Chem. Soc. 29, 368 ; Bull. Soc. chim. 25, 299.
Derivatives of Acetoacetic Ester.

Allylacetoacetic ester is saponified to allylacetone, CH3 CO CH2 CH2
CH CH2, which boils at 130° Allylacetoacetic ester when treated
with sodethoxicl gives allylacetic ester, CH2 ( C3 H5 ) CO2 C2 H5 boiling
at 142° to 144° from which comes allylacetic acid boiling at 182° Ben-
zylacetoacetic ester CH3.CO CH ( CH2 C6 H5 ) CO2 C2 H5 and the
dibenzyl derivative are prepared. Methylacetoacetic ester is converted
into tt-methyl /2-oxybutyric acid and ^-methyl crotonic acid, a-ethyl
/9-oxy butyric acid and «-ethyl crotonic acid are obtained similarly.
Ethyl-methyl acetoacetic ester boiling at 198° is prepared and from it
ethyl-methyl acetic ester boiling at 132° and its acid (valeric) boiling at

137-

Dichlor-acetoacetic ester boiling at 205° -207° is prepared and from it
dichloracetone. Ethyl acetoacetic ester will form but a mono chlor
derivative therefore it is CH3 CO C Cl ( C2 H5 ) CO2 R not CH2 Cl CO
CH ( C2 H5 ) C02 R.

WISLICENUS, J., F. CLOWES AND C. HUGQENBERQ, 1875.

Ber. 8, 1206-1209 ; J. Chem. Soc. 29, 565 ; Bull. Soc. chim. 25, 460.

Ethyl-aceto Succinic Esters.

/9-Ethyl-acetosuccinic ester was obtained from sodaceto acetic ester
and a-brombutyric ester. Its formula is CH3 CH3

CO' CH2

CH- -CH

CO2 C2 H5 CO2 C2 H5, it is

a colorless oil, boils at 262 and dissolves sodium at ordinary tempera-
tures, giving off hydrogen. a-ethyl-acetosuccinic ester was obtained

8 BIBLIOGRAPHY OF

by treating aceto succinic ester with sodium, and the product with ethyl
iodid. Its formula is CH3

CO

C (C2 H5 )-CH2

CO2 C2 H5 CO2 C2 H5, it boils at 263° to 265°,

and does not dissolve sodium at ordinary temperatures nor when
gently heated.

OPPENHEIM, A., AND H. PRECHT, 1876.

Ber. 9, 318-323; J. Chem. Soc. 30, 69; Jsb. Chem. 1876, 604; Bull.

Soc. chim. 26, 355.

Formation of Acetoacetic Ester and Oxyuvitic Acid.

After studying the action of sodium on acetic ester the authors con-
clude that no hydrogen is given off, and that the reaction is as follows:
3 CH3 C02 C2 H5 + 4 Na=CH3 CO CH Na CO2 C2 H5 +3 C2 H5 ONa.

In reference to oxyuvitic acid, they conclude that it cannot be formed
directly from sodacetoacetic ester and chloroform but that the presence
of sodium ethoxid is necessary.

OPPENHEIM, A., AND H. PRECHT, 1876.

Ber. 9*323-325; J. Chem. Soc. 30, 69; Jsb. Chem. 1876, 572.
Production and Properties of Dehydracetic Acid.

Dehydracetic acid was made by passing the vapor of aceto acetic
ester through an iron tube heated to dull redness. It is a crystalline
substance of the formula Cg H8 04 which melts at 108 and boils at 269°
Acids do not affect it but alkalis decompose it into acetone and acetic
acid.

DEMARCAY, E., 1876.

Compt. rend. 82, 1337-1339 ; J. Chem. Soc. 30, 403 ; Ber. 9» 962;
Jsb. Chem. 1876, 551 ; Bull. Soc. chim. 27, 120.

Oxypyrotartaric Acid — A Derivative of Acetoacetic Ester.

Acetoacetic ester treated with hydrocyanic acid forms an addition
product, CH3 COH (CN) CH2 CO2 C2 H5) which is decomposed by water,
forming oxypyrotartaric acid, CH3 C OH (CO2 H) CH2 CO2 H, ammo-
nia, and alcohol.

DEMARCAY, E., 1876.

Compt. rend 83, 449-451 ; J. Chem. Soc. 30, 506 ; Jsb. Chem.

1876, 569.
Research upon the Derivatives of Acetovaleric Ester.

Sodacetoacetic ester and isopropyl iodid, CH I (C H3 )2, react to form
isopropyl acetoacetic ester, CH3 CO CH (C3 H7 ) CO2 C2 H5, which is

ACETO ACETIC ESTER 9

acetovaleric ester. It boils at 200 to 202.°, colors ferric chlorid rose
violet, when treated with bromin and then alcoholic potash and then
hydrochloric acid, two acids are formed according to the amount of
bromin used. The acids resemble angelic and oxy-angelic acids.

EMMERLING, O. AND A. OPPENHEIM, 1876.

Ber. 9, 1096-1097 ; Bull. Soc. chim. 27, 298.
A New Ester of Acetoacetic Acid.

Isobutyl-acetoacetic ester was formed which boils at 202° to 206° with
some decomposition ; its specific gravity is . 979 at o° The ester dis-
solves sodium, and oxyuvitic acid can be made from it.

OPPENHEIM, A. AND H. PRECHT, 1876.

Ber. 9, 1098 ; Bull. Soc. chim. 27, 299.
Action of Anilin on Acetoacetic Ester.

Acetoacetic ester was treated with anilin in hopes of producing an

f "M"pr r* TJ
anilid but diphenyl carbamid CO -j ^JTT n6 -rr5 melting at 235°, was

produced instead.

EMMERLING, O. AND A. OPPENHEIM, 1876.

Ber. 9, 1098 ; Bull. Soc. chim. 27, 299.
Oxidization of Acetoacetic Ester.

When acetoacetic ester is oxidized by potassium permanganate,
potassium acetate, potassium oxalate, alcohol and water are formed.

OPPENHEIM, A. AND H. PRECHT, 1876.

Ber. 9, 1099-1102 ; Bull. Soc. chim. 27, 299.
Dehydracetic Acid.

Dehydracetic acid boiled with phosphorus trichlorid gives no reaction
but when treated with phosphorus oxychlorid and phosphorus penta-

10 BIBLIOGRAPHY OF

chlorid a compound, Cg He C12 O2) melting at 101° is formed, which
proves the presence of the hydroxyl and carboxyl groups, and also that
the fourth oxygen atom is united to carbon. Dehydracetic ester, Cg
H7 (C2 H5 ) O4, melts at 91.6°, dehydracetanilid, C8 H7 (N HC6 H5 ) O3,
fuses at 115 , and chlor-dehydracetic acid, Cs H7 Cl O4, fuses at 93°,
brom-dehydracetic acid, Cg H7 Br O4, was also described. The formula
assigned to dehydracetic acid is CH3 OH CO2 H

CO C = C

CH2-C = CH

WISLICENUS, J., 1877.

Ann. Chem. 186, 161-228 ; J. Chem. Soc. 32, 432.
Acetoacetic Ester.

A short review is given -of the work done by different chemists on
the reaction between sodium and acetoacetic ester. The methylene
hydrogen atoms of acetoacetic ester can be replaced by alkyl groups
only by passing through the mono-sodium, mono-alkyl, and sodium-
alkyl compounds, in that order. Diethyl acetoacetic ester boils at 218°
and is not attacked by sodium even at 100° In the reaction between
sodium and acetic ester, sodium acetoacetic ester and sodethoxid are
formed, and if ethyl iodid be added now, ethyl- acetoacetic ester is
formed, upon some of which sodethoxid will instantly act and form
sodethylacetoacetic ester, which, in contact with ethyl iodid now gives
diethylacetoacetic ester. Frankland and Duppa wrongly attribute the
last named body to the first action of sodium on acetic ester. These
complications are due to not removing sodethoxid before adding ethyl
iodid. The saponification of acetoacetic ester derivatives yields either
substituted ketones and a carbonate, or substituted acetates and alcohol.

CONRAD, M., 1877.
Ann. Chem. 186, 228-232 ; J. Chem. Soc. 32, 435 ; Jsb. Chem.

1877, 689.
Acetoacetic Amyl Ester

Amyl acetate treated with sodium produces acetoacetic amyl ester,
CH3 CO CH2 CO2 C5 HZI, with no evolution of hydrogen if cold,, and

ACETO ACETIC ESTER I I

only slight evolution in a warm reaction. Amyl alcohol is also pro-
duced. Acetoacetic amyl ester is colorless, boils at 223°, has a specific
gravity of .954 at 10°, and colors ferric chlorid red. Ethylacetoacetic
amyl ester, CH3 CO CH ( C2 H5 ) CO2 C5 HIX, was also produced, it
boils at 233° to 236°, has a specific gravity of .937 at 26° and gives no
color with ferric chlorid.

CONRAD, M., 1877.
Ann. Chem. 186, 232-244 ; J. Chem. Soc. 32, 435 ; Jsb. Chem.

1877, 690.
Halogen Substitution Products of Acetoacetic Ester.

When acetoacetic ester is treated with bromin it takes it up and hydro-
bromic acid is given off, forming the compound Ce Hg Br4 O3. Its
specific gravity is 2.32 at 21° and it is decomposed upon distillation.
Chlorin passed through acetoacetic ester is absorbed, hydrochloric acid
is given off, and Ce H8 C12 O3 is formed, This boils at 205° to 207° and
its specific gravity is 1.293 at 16! To prove the constitution of the last
compound it was treated with hydrochloric acid at 180°, when dichlor-
acetone, CH3 CO CH C12, was formed, and with caustic potash when
dichloracetic ester, CH C12 CO2 C2 H5i was separated. Kthylacetoacetic
ester was treated with chlorin and CH3 CO C Cl (C2 H5 ) CO2 C2 H5
was obtained. The author decides that the dichloracetoacetic ester is
CH3 CO C C12 CO2 C2 H5. Amyl ester of acetoacetic acid and the amyl
ester of ethylacetoacetic acid were treated with chlorin, and dichlor-
acetoacetic amyl ester and ethyl-monochloracetoacetic amyl ester were
produced.

BONNE, JULIUS, 1877.

Ann. Chem. 187, i-u ; J. Chem. Soc. 32, 437
Benzoylacetoacetic Ester.

When benzoyl chlorid acts upon sodacetoacetic ester the two sub-
stances combine and sodium chlorid is formed. The compound, ben-
zoylacetoacetic ester, CH3 CO CH ( CO C6 H5 ) CO2 C2 H5, decomposes,
upon being distilled, into carbon monoxid, carbon dioxid, benzoic ester
and benzoic acid. When treated with caustic potash methyl phenyl
ketone, CH3 CO Ce H5, and a little benzoic acid are produced.

12 BIBLIOGRAPHY OF

EHRLICH, FRANZ LOUIS, 1877.
Ann. Chem. 187, 11-30; J. Chem. Soc. 32, 438 ; Jsb. Chem.

1877, 689.
Benzylacetoacetic Ester.

Benzylacetoacetic ester was made by treating sodacetoacetic ester
with benzyl chlorid, it is CH3 CO OH (CH2 C6 H5) CO2 C2 H5, it has
a specific gravity of 1.083 at 18.4° and cannot be distilled. When
saponified methyl-phenylethyl ketone, CH3 CO CH2 (CH2 C6 H5), is
obtained, it boils at 235°-236° and has a specific gravity of .989 at 23.5:
When this ketone is oxidized acetic and benzoic acids, carbon dioxid
and water are produced. Dibenzylacetoacetic ester was also pro-
duced. The action of nascent hydrogen on benzylacetoacetic ester was
found to be analogous to that on acetoacetic ester, that is, a-benzyj
/9-oxybutyric ester was produced.

ZEIDLER, FRANZ, 1877.

Ann. Chem. 187, 30-47 ; J. Chem. Soc. 32, 437.
Allyl-acetoacetic Ester.

Allyl-acetoacetic ester boils at 206° and gives a carmine color with
ferric chlorid, its specific gravity is .982 at 20? When saponified it
yields ally 1- acetone, CH3 CO CH2 C3 H5, which boils at 128° to 130°
and has a specific gravity of .834 at 27!" It is isomeric with mesityl
oxid, boiling point I3i°-i32°; with dumasin boiling point I2o°-i25°, and
with metacetone boiling point &40-86° Allyl acetic acid, CH2 (C3 H5)
CO2 H, also obtained from the saponification, when oxidized becomes
succinic acid. Nascent hydrogen converts allyl acetoacetic ester into
<7-allyl /9-oxybutyric acid.

CONRAD, M., 1877.

Ann. Chem. 188, 217-226; J. Chem. Soc. 34, 137.
Acetsuccinic Esters and Derivatives.

Acetsuccinic ester CH3
CO

CH- -CH2

CO2 C2 H5 CO2 C2 H5 was obtained from sod-
acetoacetic ester and monochlor-acetic ester, it is insoluble in water,

ACETO ACETIC ESTER I 3

soluble in alcohol, ether and benzene, and boils at 254° to 256? When
saponified with alcoholic potash, acetic and succinic acids are pro-
duced. Barium hydroxid produces /?-aceto-propionic acid CH3 CO
CH2 CH2 CO2 H, a crystalline substance which melts at 31? This is
probably the same as the levolinic acid of Grote and Tollens (Ann.
Chem. I75> 181) The ethyl ester was also produced.

CONRAD, M, 1877.

Ann. Chem. 188, 226-228 ; J. Chem. Soc. 34, 137.
Synthesis of Pyrotartaric Acid from Acetoacetic Ester.

When sodacetoacetic ester is treated with a-brom-propionic ester,
^-methyl-aceto-succinic ester is formed, thus: — CH3 CO C H Na CO2
C2 H5 + CH3 C H Br CO2 C2 H5 = CH3

CO CH3

CH- — CH
C02 C2 H5 CO2 C2 H5

,2- Methyl aceto-succinic ester is acted upon by barium hydroxid and
the barium salt of pyrotartaric acid is formed.

ROHRBECK, HERMANN, 1877.

Ann. Chem. 188, 229-239 ; J. Chem. Soc. 34» 136.

tt-Methyl ^9-Oxybutyric Acid and «=Methyl Crotonic Acid.

a- Methyl /9-oxy butyric acid was obtained from methyl-acetoacetic
ester by the action of sodium amalgam and when heated this a-methyl
/9-oxy butyric acid was changed into a-methyl crotonic acid, CH3 CH : C
CH3 CO2 H. The properties and salts of each acid were described.

WALDSCHMIDT, ERNST, 1877.

Ann. Chem. 188, 240-248 ; J. Chem. Soc. 34. 136.

Reactions of Acetoacetic Ester.

tt-Ethyl /9-oxybutyric acid and a-ethyl-crotonic acid were produced
from acetoacetic ester, the reactions being similar to those of Rohrbeck*
which proves that they are general. The salts of these two acids were
studied and described.
*See pages 7 and 13.

14 BIBLIOGRAPHY OF

SAUR, RICHARD, 1877.
Ann. Chem. 188, 257-269.

Methyl=ethyl=acetoacetic Ester, Methyl=ethyl=acetic Acid and
«=Methyl=ethyI=/?=oxybutyric Acid.

Methyl-ethyl-acetoacetic ester, CH3 CO C(CH3)(C2 H5)CO2 C2 H5,
is colorless, boils at 198° and its specific gravity is .974 at 22.° It pro-
duces a violet color with ferric chlorid. When treated with sodium
ethoxid it gives methyl-ethyl acetic ester, CH (CH3)(C2 H5) CO2 C2 H5,
while sodium amalgam acting on it produces a-methyl-ethyl-/9-oxybu-
tyric ester.

CONRAD, M., 1877.

Ann. Chem. 188, 269-274.
Metal Acetoacetic Esters.

The copper, nickel, cobalt, magnesium, and aluminum salts of aceto-
acetic ester were produced and described. In each case but one hy-
drogen atom of the methylene group in acetoacetic ester can be re-
placed. This can be replaced by either a metal or a non-metal because
its position between two carbonyl groups weakens its positive character.

NORTON, TH. AND A. OPPENHEIM, 1877.

Ber. 10, 701-704 ; Jsb. Chem. 1877, 685.
Action of Carbon Bisulfid on Acetoacetic Ester.

By this action a monobasic acid of the forrnula CH3

CO
r f C: S2 H

{ C: S O C2 H5
C02 C2H5

was formed which was named by the authors thiorufic acid. A metallic
oxid and carbon bisulfid acting on acetoacetic ester produce a compound
CH3 CO C (:C: S) CO2 C2 H5 which the authors consider as the acetyl
derivative of CH (:C: S) CO2 H, which they name thio-carbacetic acid.

ACETO ACETIC ESTER 15

DEMARCAY, E., 1877.
Ber. 10, 1177-1178.
Acetoacetic Ester.

The author has worked on the chlorcrotonic acids. The methyl,—
ethyl, — and propyl-acetoacetic esters were converted into the correspond-
ing chlorcrotonic acids and described.

ROHN, WILHELM, 1877.

Ann. Chem. 190, 305-322 ; Ber. n, 252; Jsb. Chem. 1877, 688.
Isobutyl-acetoacetic Ester and Isobutyl-acetic Acid.

Acetoacetic ester treated with isobutyl iodid gives isobutyl aceto-
acetic ester CH3

CO

CH CH2 CH (CH3)2

CO2 C2 H5 which boils at 2i7°-2i8° and has a

specific gravity of .951 at 17.5.° When saponified it yields isobutyl
acetone, CH3 CO CH2 [CH2 CH (CH3)J, which boils at 142° to 144°
and has a specific gravity of .817 at 17° and isobutyl acetic acid,
CH2 [CH2 CH (CH3)J C02 H.

MIEHLE, GUSTAV., 1877.
Ann. Chem. 190, 322-327 ; J. Chem. Soc. 34» 490 ; Jsb. Chem.

1877, 688.
Synthesis of Tricarballylic Acid.

Acetosuccinic ester, made from sodacetoacetic ester and monochlor-
acetic ester, was treated with sodium and then with monochlor-acetic
ester and aceto-tricarballylic ester CH2 CO2 C2 H5

CH3 CO-C CO2 C2 H5

CH2 CO2 C2 H5 was produced.

It boils, with decomposition at 280° to 300.° When treated with hot
potassium hydroxid it gives potassium tricarballylate from which can
be obtained tricarballylic acid C3 H5 (CO2 H)3.

1 6 BIBLIOGRAPHY OF

DEMARCAY, E., 1877.

Compt. rend. 84, 554-556 and 1087-1089 ; J. Chem, Soc. 32» 590 ;
Ber. 10, 732 ; Jsb. Chem. 1877, 690.

Simple Method of Preparing Certain Mono, Di, and Trichlor Acids.

Phosphoric pentachlorid, acting on a compound of the formula CH3
CO CH X CO2 C2 H5, forms a substituted monochlor crotonic ester of the
formula CH2 : C Cl CH X CO2 C2 H5. In this manner the methyl,
ethyl, propyl, isopropyl and allyl crotonic monochlor esters were pre-
pared. Also some di-radical monochlor crotonic esters of the formula
CH2 : C Cl C X Y CO2 C2 H5 both where X and Y were alkyl radicals
and where they were acid radicals. The ethyl-monochlor crotonic ester
and its isomer dimethyl -monochlor crotonic ester were prepared and
the differences between them noted.

DEMARCAY, E., 1877.

Compt. rend. 84, 1032-1033 ; J. Chem. Soc. 32, 594.
Some Derivatives of Acetoacetic Ester.

By treating ethyl- and methyl-acetoacetic esters each with a quan-
tity of bromin representing one molecule and saponifying the products,
two compounds of the composition 3 C5 H6 O2 + 'H2 O and 3 C4 H4 O2
-f- H2 O were obtained, which were named pentic and tetric acids re-
spectively. Just double the amount of bromin being used, two acids
were formed each containing one atom of oxygen more. These were
named pentenic and tetrenic. Mono- and di-brom-isopropyl acetoacetic
esters also gave rise to two acids, hexic, 3 C& H8 O2 -f H2 O, and hexenic,
3 C6, H8 03 + H2 O.

SCHNAPP, HEINR., 1877.
Ber. 10, 1953-1954 and 2227 ; Ann. Chem. 201, 62-73; Jsb. Chem.

1877, 7i8.
Di-ethyl-/9-oxybutyric Acid.

Di-ethyl-acetoacetic ester when treated with sodium amalgam gives
diethyl-/?-oxybutyric acid CH3 CH (OH) C (C2 H5)2 CO2 H. By heat-
ing instead of forming the crotonic acid by splitting off water, it forms
acetic aldehyde and di-ethyl-acetic acid. The latter boils at 195° to
197° and has a specific gravity of .945.

ACETO ACETIC ESTER I 7

RUCKER, AUG., 1877.
Ber. 10, 1954 ; Ann. Chem. 201, 54 ; J. Chem. Soc. 34» 292 ; Jsb. Chem.

1880, 810.
Methyl Crotonic Acid.

Methyl-acetoacetic ester. CH3 CO CH (CH3) CO2 C2 H5, treated with
phosphorus pentachlorid gives only one compound a-methyl /9-chlor
crotonic acid CH2

C-C1

CH (CH3)

CO2 H which melts at 69.5° The barium, sodium and
silver salts and the ethyl ester were described.

WOLFF, CARL, 1877.

Ber. 10, 1956-1958; Ann. Chem. 201, 45; Jsb. Chem. 1877, 687.
Diallyl-acetoacetic Ester and its Derivatives.

Diallylacetoacetic Ester, CH3 CO C (C3 H5)2 CO2 C2 H5, boils at 239°
to 241° and has a specific gravity of .948 at 25° It is decomposed by
alkalis in two ways forming (i) diallylacetone which boils at 174°- 175°
and (2) into diallyl acetic acid which boils at 221 "-22 2° and has a
specific gravity of .949 at 25.° To obtain the first product the alkali
is added cold and the substance is shaken out with ether. To obtain
the second add sulfuric acid to the dry mixture and the acid separates
as an oil. The barium, calcium and silver salts are described.
Possibly this diallylacetic acid C H (C3 H5)2 CO2 H when oxidized
will give tricarballylic acid C3 H5 (CO2 H)3 since allylacetic acid
gives succinic acid.

MEYER, VICTOR, 1877.

Ber. 10, 2075-2078; Jsb. Chem. 1877, 518 and 770.
Azophenylacetoacetic Acid.

When azobenzene nitrate C& H5 N2 NO3 is treated with potassium
acetoacetic ester, azophenylacetoacetic acid CH3 CO CH (Na C6 H5)

I 8 BIBLIOGRAPHY OF

CO2 H is formed, it melts at 154° 155.° A new acid, Ce H9 NO4, was
produced by treating acetoacetic ester with nitrous acid, it is so un-
stable that it cannot be distilled. Its constitution is either

CH3 or CH3

CO CO

C=N— OH CH— N = 0
C02 C2 H5 C02 C2 Hs

WISLICENUS, J., 1877.

Ber. 10, 2226-2227.
The Saponification of Acetoacetic Esters.

The author calls attention to the double saponification of acetoacetic
esters. Substituted acetic esters or acids are obtained as well as sub-
stituted ketones.

WISLICENUS, J., 1878.

Ann. Chem. 190, 257-281 ; J. Chem. Soc. 34» 402 ; Ber. n, 251.
Decomposition of Acetoacetic Ester by Alkalis.

A large number of experiments have been performed and tables are
given showing the proportions of the different products of saponification
under different conditions. It was found that the more concentrated
the alkali and the more it was in excess the larger was the proportion
of acetic acid and substituted acetic acids and the smaller was the pro-
portion of carbonate and ketones.

CONRAD, M., 1878.

Ber. ii, 58-60; J. Chem. Soc. 34. 4°3 ; Jsb. Chem. 1878, 687.
Action of Sodium on Ethoxy acetic Ester.

By the action of sodium and then acetic acid on ethoxyacetic ester,
CH2 (O C2 H5) CO2 C2 H5, a compound CIO Hl8 O5 is formed which
boils at 245° and is believed to be ethoxyacetyl-ethoxyacetic ester,
CH2 (OC2 H5) CO CH (O C2 H5) CO2 C2 H5. It colors ferric chlorid
violet, dissolves sodium and forms a barium compound. Heated with
an alkali it gives ethoxyacetic ester.

ACETO ACHTIC HSTHR IQ

MEYER, VICTOR AND J. ZUBLIN, 1878.
Ber. ii, 320-324 ; J. Chein. Soc. 34. 487 ; Jsb. Chem. 1878, 426.

Nitroso Compounds of Fatty Series. Part I.
By the action of nitrous acid on acetoacetic ester a compound Ce H9
NO4 was produced. It was liquid even at 25° below zero but after
standing some months some of it crystallized. Acetyl chlorid has no
action on it which is one proof of the formula CH3

CO'

CH N=O
C02 C2 H5

Methyl acetoacetic ester treated with nitrous acid gives nitroso-methyl
acetone, CH3 CO CH (CH3) NO, which forms white crystals soluble in
alcohol, ether and chloroform ; it melts at 74°, and boils at 185° 186°
undecomposed. It is the first nitroso compound whose vapor density
has been determined. Kthyl-acetoacetic ester treated with nitrous acid
gives nitroso-ethyl-acetone, CH3 CO CH (C2 H5) NO, crystals which
are soluble in alcohol, ether and chloroform and slightly soluble in
water, it melts at 53°-55°

ALLIHN, F., 1878.

Ber. ii, 567-570; J. Chem. Soc. 34. 566 ; Jsb. Chem. 1878, 707.
Action of Sulfuryl Chlorid on Acetoacetic Ester.

This action produces two compounds according to the proportions of
the chlorid used. If an excess of sulfuryl chlorid act upon acetoacetic
ester, CH3 CO C C12 CO2 C2 H5, is formed. If molecular quantities of
the two substances are taken, CH3 CO C HC1 CO2.C2 H5, is formed
which is a colorless liquid boiling at 193° to 195.° Its specific gravity is
1.19 at 14.° When saponified mono-chlor-acetic ester is produced.

MEYER, VICTOR AND J. ZUBLIN, 1878.
Ber. ii, 692-697 ; J. Chem. Soc. 34» 659 ; Jsb. Chem. 1878, 726.

Nitroso Compounds of the Fatty Series. Part II.
By different manipulations of nitrous acid and methyl-acetoacetic
ester three bodies were obtained : —

2O BIBLIOGRAPHY OF

1) Nitroso-methyl acetone CH3 CO CH (CH3) (NO),

2) Nitroso-propionic ester CH3 CH (NO) CO2 C2 H5.

3) Nitroso-propionic acid CH3 CH (NO) CO2 H.

Each one was described, as was nitroso acetone, CH3 CO CH2 (NO),
also.

CONRAD, M., 1878.

Ber. ii, 1055-1058; J. Chem. Soc. 34» 732 ; Jsb. Chem. 1878, 743.
Synthesis of Phenylated Fatty Acids.

Benzylacetoacetic ester, CH3 CO CH (C7 H7) CO2 C2 H5, made from
acetoacetic ester, sodium ethoxid and benzyl chlorid is a colorless liquid
with boiling point 276° and specific gravity 1.036 at 15.5.° When this
is treated with sodium and then with methyl iodid CH3 CO C (CH3)
(C7 H7) CO2 C2 H5 is produced. It is colorless, its boiling point is 287°
and its specific gravity 1.046 at 23°; when saponified it yields methyl
benzyl acetic acid, CH (CH3) (C7 H7) CO2 H. Methyl benzyl acetic
benzyl ester or methyl-hydrocinnamein, ethyl benzyl acetoacetic ester,
CH3 CO C (C2 H5) (C7 H7), CO2 C2 H5; and benzyl acetosuccinic
ester CH3

CO

C(C7H7)--CH2

CO2 C2 H5 CO2 C2 H5 were prepared and described.

WISL1CENUS, J. AND L. LIMPACH, 1878.

Ann. Chem. 192, 128-135 J J- Chem. Soc. 34» 783 ; Ber. u, 1245 J

Jsb. Chem. 1878, 720.
Synthesis of Glutaric (Pyrotartaric) and a-Methyl Qlutaric Acids.

When sodacetoacetic ester is treated with /9-iodio-propionic ester,
CH2 i CH2 CO2 C2 Hs, aceto-glutaric ester, CH3

CO

CH— CH2 CH2 CO2 C2 H5,
CO2 C2 Hs is produced.

ACETO ACETIC ESTER 21

It is a colorless oil boiling at 271 "-272°, it has a specific gravity of
1.0505 at 14.1.° Treating this with alcoholic potash and then sulfuric
acid, glutaric acid, CH2 CO2 H

CH2

CH2 CO2 H, is produced. Methyl-aceto-glutaric
ester, formed similarly from sodmethylacetoacetic ester boils at 280°-
281° and has a specific gravity of 1.043 at 2O° When this is saponified
potassium methyl-glutarate CH (CH3) CO2 K

CH2

CH2 CO2 K is produced which is a crystal-
line substance melting at 76° The zinc and silver salts were described.

KRESSNER, G., 1878.

Ann. Chem. 192, 135-141 ; J. Chem. Soc, 24, 783; Ber. H, 1245;

Chem. 1878, 721.

Synthesis of Pyrotartaric Acid from a-Methyl-aceto-succinic

Ester.

a-Methyl-aceto-succinic ester saponified yields pyrotartaric acid
identical with that produced by Conrad, (Ann. Chem. 188, 226,) from
/9-methyl-aceto-succinic ester. The two equations are ( i ) a
CH3
CO

C (CH3)- -CH2
C02 C2 H5, C02 C2 H5 + 3 KOH=CH3 CO2 K+

CH (CH3)— CH2-f2 C2 H5 OH
CO2 K C02 K

CO CH3

CH— — CH

C02 C2 H5 C02 C2H5+3 KOH=CH3 CO2 K+

CH2 -- CH (CH3) + 2 C2 H5OH

COa K CO2 K

22 BIBLIOGRAPHY OF

HARDTMUTH, F, 1878.

Ann. Chem. 192, 142-146; J. Chem. Soc. 34» 782; Ber. n, 1245;

Jsb. Chem. 1878, 726.

a-/9-DimethyI-acetosuccinic Ester and Symmetrical Dimethyl-

succinic Acid.

' ^-Methyl-acetosuccinic ester CH3

CO CH3

CH CH

CO2 R CO2 R is treated with sodium

and then with methyl iodid and thus «-/9-dimethyl-acetosuccinic ester
CH3

CO CH3

C (CH3)— CH

CO2 R CO2 R was produced. It boils at 270° to 272° and its specific
gravity is i 057 at 27! When saponified it gives symmetrical dimethyl

succinic acid. CH3 CH3

CH- CH

CO2 H CO2 H.

HUQQENBERQ, CARL, 1878.

Ann* Chem. 192, 146-152; J. Chem. Soc. 34* 782; Ber. n. 1246;

Jsb. Chem. 1878, 725.
«-Ethyl-aceto-succinic Ester and Ethyl-succinic Acid.

When sodacetosuccinic ester is treated with ethyl iodid «-ethyl-
acetosucciriic ester CH3

CO

C (C2 H5)— CH2

CO2 R CO2 R results. It boils at 263° to 265°

and sodium will not act upon it. When this is saponified ethyl-
succinic acid is produced which melts at 98.° The barium, calcium and
silver salts and ethvl ester of this acid were described.

ACETO ACETIC ESTER 23

CONRAD, M. AND LEONARD LIMPACH, 1878.
Ann. Chetn. 192, 153-160; Ber. n, 1246; J. Chem. Soc. 34» 781;

Jsb. Chem. 1878, 706.

Improved Method of Production of Mono- and Di-organic
Substituted Acetoacetic Esters.

Add the ester to a solution of sodium ethoxid made by dissolving
sodium in absolute alcohol and then add the alkyl iodid. The products
are obtained very free from the byproducts which are formed in the
usual methods.

PRECHT, H., 1878.

Ber. n, 1193-1195; J. Chem. Soc. 34, 970; Jsb. Chem. 1878, 706.
Action of Ammonia on Acetoacetic Ester.

By this action the compound C6 HXI NO2 is formed. It is insoluble
in water, soluble in alcohol and ether, and is decomposed by heating.
It is probably an amid and is isomeric, not identical with the substance
which Geuther obtained and called ammonium ethylene-dimethylene
carbonate.*

*See pages i and 6.

HARROW, GEO. H. U., 1878.

J. Chem. Soc. 33» 425-438 ; Ann. Chem. 201, 141 ; Jsb. Chem. 1878, 731.
Pyrotritartaric and Carbopyrotritartaric Acids.

Diacetosuccinic ester CH3 CH3

CO CO

CH- -CH

CO2 C2 H5 CO2 C2 H5 made from sodacetoacetic

ester and iodin, is crystalline and melts at 78°-79° This treated with
dilute sulfuric acid yields the two acids, pyrotritartaric or uvic C7 H8 O3
melting at 135°- 136° and Carbopyrotritartaric, C8 H8 O5 which melts at
3ir Carbopyrotritartaric acid heated gives pyrotritartaric acid

24 BIBLIOGRAPHY OF

and carbon dioxid. Carbopyrotritartaric acid fused with potassium
hydroxid gives succinic and acetic acids. The formula assigned to
Carbopyrotritartaric acid is CH3 CO CH CO2 H

CH-C=C=H2

CO— O, and the one, assigned to
pyrotritartaric acid is CH3
CO

CH-CH = C=CH2
C02 H

ZUBLIN, J., 1878.

Ber. n, 1417-1420; J. Chem. Soc. 34» 879; Jsb. Chem. 1878, 811.
Azobenzene=acetoacetic Acid.

This name is proposed for what V. Meyer calls Azo-phenylacetoacetic
acid* (Ber. 10, 2075.) CH3

CO

CH-N=N-C6 H5

CO2 H. The potassium, barium, lead, silver and

copper salts and ethyl ester are described and also paraazotoluol-aceto-
acetic acid, CH3 CO CH (N2 C6 H4 CH3) CO2 H, and its ethyl ester.

*See page 17.

BANDROWSKI, E., 1879.

Ber. 12, 344-346 ; J. Chem. Soc. 36, 523 ; Jsb. Chem. 1879, 628.
Behavior of Dibromsuccinic Acid with Water.

At high temperatures water decomposes dibromsuccinic acid by
abstracting hydrobromic acid. Two acids are left, one with a boiling
point between 129° and 130° which is bromomaleic acid, the other one
boils at 172!

HILQER, A., 1879.
Ann. Chem. I95» 314-317 ; Ber. 12, 664 ; J. Chem. Soc. 36, 560 ; Jsb.

Chem. 1879, 1081.
Detection of Acetoacetic Ester in Urine.

Acetoacetic ester was found in the urine of diabetic patients to the
amount of .0399 to .1909 in 100 parts.

ACETO ACETIC ESTER 25

KONIG, HEINR., 1879.

Ber. 12, 768-770 ; J. Chem. Soc. 36. 706 ; Jsb. Chem. 1879, 662.

Action of Hydrocyanic and Hydrochloric Acids on Methyl-aceto-

acetic Ester.

Just as these acids act on acetoacetic ester to produce oxypyrotartaric
acid so they act on methyl-acetoacetic ester and produce the next high-
er homologue, oxyadipic acid thus : CH3 CO CH (CH3) CO2 C2 H5 +
HCN=CH3 COH (CN) CH (CH3) CO2 C2 H5 and then CH3 C OH
(CN) CH (CH3) C02 C2 H5 + 2 HC1 + 2 H2 O=CH3 COH (CO2H) CH
(CH3) C02 H + N H4 C1 + C2 H5 Cl.

LADENBURG, A. AND L. RUGHEIMER, 1879.

Ber. 12, 953-954; J. Chem. Soc. 3<>» 715 ; Jsb. Chem. 1879, 435.
Acetoacetic Ester Derivatives of Ortho-tolylendiamin.

Ortho-tolylendiamin C6 H3 CH3 (NH2)2 reacts with acetoacetic ester
to formC6 H3 CH3<*J**> C <^3CO2 C2 H5, a solid, melting at 82.°
It is insoluble in water, soluble in alcohol and such solvents; when heated
it decomposes into ethenyl-tolylendiamin C6 H3
a solid which melts at 198°- 199.°

ALLIHN, F., 1879.

Ber. 12, 1298-1300; J. Chem. Soc. 36, 915 ; Jsb. Chem. 1879, 627.
Chlorinated Metal Derivatives of Acetoacetic Ester.

The chlorinated metal derivatives, corresponding to the formula
(CH3 CO CC1 CO2 C2 H5)x M, may be produced by shaking the
monochlor-acetoacetic ester with an ammoniacal solution of the salt.
The copper, magnesium, nickel, and cobalt salts were described. The
dichlor-acetoacetic ester will give no metal derivatives.

26 BIBLIOGRAPHY OF

JOURDAN, FRIEDRICH, 1879.

Ann. Chem. 200, 101-119; J. Chem. Soc. 38, 313; Jsb. Chem. 1879, 668.
Mono= and Di-heptyl-acetoacetic Esters.

Acetoacetic ester treated with heptyl iodid, C7 HI5 i, and sodium
ethoxid forms heptyl-acetoacetic ester, CH3 CO CH C7 HI5 CO2 C2 H5,
a colorless oil which boils at 271° to 273° and has a specific gravity of
.9324 at 17. i.° This was saponified and heptyl acetone, CH3 CO CH2
C7 HI5, boiling at 2i4°-2i5°, with a specific gravity of .829 at 17.7°,
and heptyl-acetic acid, identical with nonyl acid, were produced. Di-
heptyl-acetoacetic ester was made in the similar way, and from this
methyl diheptyl carbin ketone (diheptyl acetone), CH3 CO CH (C7
HI5)2, and diheptyl acetic acid, CH (C7 HI5)2 CO2 H, were produced.

VENABLE, F. P., 1880.

Ber. 13, 1649-1652 ; Jsb. Chem. 1880, 438.

Derivatives of Heptanes.

Heptyl-acetoacetic ester was produced by the Conrad and Limpach
method, it boils at 250° to 260.° When saponified it yielded methyl
octyl ketone, CH3 CO CH2 CH CH3

C5 Hn, which boils at 196° to 198°

This formula was assigned to it because the heptyl bromide, C5 HIX CH
Br CH3, was used to start with.

MORRIS, QEO. H., 1880.

J. Chem. Soc. 37, 6-14 ; Ber. 13, 427 ; Jsb. Chem. 1880, 813.
tt-Methyl-hydroxy-succinic Acid.

Acetoacetic ester treated with hydrocyanic acid and then with hydro-
chloric acid gives, CH3 C (OH) CH2 CO2 H,

CO2 H a crystalline substance, soluble in water,

alcohol and ether which melts at io8f It is the same acid as Demarc-
ay's oxy-pyrotartaric described in Compt. rend. 82, 1337. The barium,
calcium, potassium, silver, lead and copper salts were described. The
three isomeric acids of this formula were shortly discussed.

ACETO ACETIC ESTER 27

DEMARCAY, E., 1880.

Bull. Soc. chim. 33, 516-525 and 575-580 and 34, 31-37; J- Chem.

Soc. 38, 625.

Tetric and Oxytetric Acids and their Homologues.

Methyl-acetoacetic ester when treated with bromin forms two com-
pounds, CH3 CO C (CH3) Br CO2 C2 H5 and CH2 Br CO C (CH3)
Br CO2 C2 H5. If these are allowed to stand they form CH3 CO C
(CH3) Br H and CH2 Br CO C (CH3) Br H, but if treated with
alcoholic potash they form tetric, 3 C4 H4 O2 + H2 O, and pxytetric acids,
3 C4 H4 O3+H2 O. Three sets of salts of tetric acid are formed, (i)
Cu O, C4 H4 O2 ; (2) Ba O, 2 C4 H4 O2 ; (3) 2 M2 O, 5 C4 H4 O2.
Phosphoric pentachlorid with tetric acid forms C4 H4 OC12 which when
treated with chlorin gives C4 H4 C14 O.

In the above manner, from the alkyl substituted acetoacetic esters,
the following acids and many of their salts were produced ; pentic, 3
C5 H6 O2-h H2 O ; hexic, 3 C6 H8 O2 + H2 O ; heptic, 3 C7 HIO O2 + H2
O; oxypentic, 3 C5 H6 O3 + H2 O ; oxyhexic, 3 C6 H8 O3 + H2 O ;
oxyheptic, 3 C7 HIO O3-f-H2 O, and isohexic and isoxyhexic. The
constitution of these was worked out to be ;

CH2— CH2 CH2— CH (CH3)
CO — CO and CO —CO etc.

HOFMANN, OTTO, 1880.

Ann. Chem. 201, 73-89; Ber. 13. 431.

Action of Zinc and Allyl lodid on Acetoacetic and Diethyl-aceto-

acetic Esters.

The action is the same as with sodium and an alkyl halogen, that is,
with acetoacetic ester the mono- and the di-alkyl acetoacetic esters are
produced ; C6 H9 (C3 H5) O3 and C6 H8 (C3 H5)2 O3. when allyl iodid
is used. When the diallyl acetoacetic ester is treated with zinc and
allyl iodid, diallyl acetic ester, CH (C3 H5)2 CO2 C2 H5 is produced.

28 BIBLIOGRAPHY OF

GUTHZEIT, MAX, 1880.

Ann. Chem. 204, 1-14; Ber. 13, 1983; J. Chem. Soc. 38, 871 ; Jsb.

Chem. 1880, 827.

Octylic-acetoacetic Ester and its Derivatives.

Sodacetoacetic ester treated with octylic iodid, Cs HI7 i, gives octy-
licacetoacetic ester, CH3 CO CH (C8 HI7) CO2 C2 H5, which boils at
280° to 282° and has a specific gravity of .9354 at 18.5.° It yields the
two usual saponification products, methyl nonyl ketone CH3 CO C H2
(Cg HI7), which boils at 224° to 226°, and octylacetic acid CH2 (C8 HI7)
CO2 H which is capric acid which boils at 265° to 267° The barium
and calcium salts and ethyl ester of this acid were described.
Di-octyl-acetoacetic ester is formed by further treatment of the
monoctyl derivative with sodium and octyl iodid, it boils at 340° to 342°
This upon saponification gives dioctylacetone, boiling at 325° to 330°
and dioctylacetic or isostearic acid which melts at 37°- 38° and boils at
270° to 275° under 100 m. m. pressure. The barium and silver salts
and ethyl ester were described.

BOOKING, EDUARD, 1880.

Ann. Chem. 204, 14-26; Ber. 13, 1983; J. Chem. Soc. 38, 872. Jsb.

Chem. 1880, 812.

Two New Syntheses of Ethyl=methyl=oxy=acetic Acid.

(1) From ethyl-methyl ketone, C2 H5 CO CH3, by treating it with
hydrocyanic acid and then with hydrochloric acid, C (C2 H5) (CH,)
(OH) C02 H, is produced.

(2) From ethyl-methyl-acetic acid (active valeric) which was
obtained from ethyl-methyl-acetoacetic ester by saponification. CH
(CH3) (C2 H5) CO2 H boils at 170° to 175°, when treated with bromin,
a brom-ethyl-methyl-acetic acid is produced and this with water gives
ethyl-methyl-oxy-acetic acid, C (C2 H5) (CH3) (OH) CO2 H.

ACETO ACETIC ESTER 29

WISLICENUS, J., 1880.

Ann. Chem. 206, 308-313 ; J. Chem. Soc. 40, 409 ; Ber. 14, 843 ; Jsb.
Chem. 1 88 1, 502 ; Bull. Soc. chim. 36, 657.

Decomposition of Polybasic Acetoacetic Esters by Alkalis.

By a great number of experiments it was found that the proportion
of ketone or ketonic acid and carbonate increased with the dilution of
the alkali and the proportion of acetates or substituted acetates increased
with the concentration of the alkali ; also that isomers do not give the
same proportions of like products.

BISCHOFF, CARL, 1880.

Ann. Chem. 206, 313-337 ; J. Chem. Soc. 40* 412 ; Jsb. Chem. 1881,

744 ; Ber. 14, 844.

Two Homologues of Aceto-propionic Acid.

/9-Aceto-isobutyric or a-methyl-aceto-propionic acid, CH3 CO CH2
CH (CH3) CO2 H, and /3-aceto-butyric acid, CH3 CH (COCH3) CH2
CO2 H, were described together with their production and their salts.

CLA1SEN, L., 1881.

Ber. 14* 345-349 ; J- Chem. Soc. 4<>» 405; Jsb. Chem. 1881, 580 ; Bull.

Soc. chim. 36, 357.

Condensation of Aldehyde with Acetoacetic Ester.

The condensation is effected by passing hydrochloric acid gas through
a mixture of the substances. With acetaldehyde, acetethylidenacetic
ester, CH3 CO C (CH CH3) CO2 C2 H5, is produced. It boils at 210°
to 212° and will take up two molecules of bromin. Acetobenzyliden-
acetic ester, CH3 CO C (CH C6 Hs) CO2 C2 H5, produced similarly from
benzaldehyde boils at 295° to 297.° This also will take up two molecules
of bromin.

30 BIBLIOGRAPHY OF

GABRIEL, S., 1881.

Ber. 14. 919-927; J. Chetn. Soc. 40, 733; Jsb. Chem. 1881, 798;

Bull. Soc. chim. 36, 598.
Condensation Products of Phthalic Anhydrid.

Acetoacetic ester, phthalic anhydrid, Ce H4 (CO)2 O, and sodium
acetate react together to form ortho-tri-benzoyl-benzene, C27 HI2 O3,
and a compound, CI2 H8 O2, the composition of which is unknown
which boils at 209 to 211 Ortho-tribenzoyl-benzene has the constitu-
tion : —

C6H4-

co —

/ \ 1
- C C— C6 H4

• C C— CO

\ / 1

r> o TJ

HANTZSCH, A., 1881.

Ber. 14, 1637-1638; J. Chem. Soc. 40, 1028 ; Jsb. Chem. 1881, 586;

Bull. Soc. chim. 36, 569.

Condensation Product of Aldehyde=ammonia and Acetoacetic

Ester.

Acetoacetic ester treated with aldehyde-ammonia in presence of zinc
chlorid gives CI4 H2i NO4 which melts at 131° and boils at 310° Boiled
with hydrochloric acid it is entirely decomposed, treated with . dry hy-
drochloric acid gas it gives two bases, CIt HI7 NO2, and Cg HI3 N. It
combines with bromin to form CI4 HI9 Br4 NO4, and this treated with
nitric acid gives d4 HI5 Br4 NO4, which melts at 102°. CI4 H2I NO4 can
be oxidized to the base, d4 HI9 NO4, which is the ester of collidine-
dicarboxylic acid and has the formula C5 N (C H3)3 (CO2 C2 H5)2.

DEICHMULLER, A., 1881.

Ann. Chem. 209, 22-30 ; J. Chem. Soc. 4°» 1162 ; Jsb. Chem. 1881, 1054.

Diabetic Urine.

The author decides that the substance in diabetic urine which
produces a red color with ferric chlorid is acetoacetic acid, not the ester
of that acid because by acidification and distillation acetone but no
alcohol is obtained.

ACETO ACETIC ESTER 3 1

TOLLENS, B., 1881.

Ann. Chem. 209,30-38 ; J. Chem. Soc. 40, 1162 ; Jsb. Chem. 1881, 1054.

Diabetic Urine.

The author decides that the substance in urine of diabetic
patients which gives a red color with ferric chlorid is not acetoacetic
ester as is claimed, but the free acid of that ester.

THORNE, L. T., 1881.

J. Chem. Soc. 39» 336-344 ; Ber. 14, 2238, Jsb. Chem. 1881, 759.
Products of the Action of Alkalis on ^9-Ethylaceto-succinic Ester.

Acetoacetic ester treated with a-brom-butyric ester gives /5-ethyl-
aceto-succinic ester, CH3 C2 H5

CO*

CH- — CH

CO2 C2 H5 CO2 C2 H5, which boils at 263° and has
a specific gravity of 1,064 at l& When this is treated with an alkali
ethyl-succiuic acid is formed which is identical with that produced from
«-ethyl-aceto-succinic ester, CH3

CO

C C2 H5- -CH2

CO2 C2 H5 CO2 C2 H5, by Huggenberg

(Ann. Chem. I92> 146.) and also «-ethyl-/9-aceto-propionic acid, ( CH3
CO) CH2 CH (C2 H5) CO2 H.

BURTON, BEVERLY 5., 1881.

Am. Chem. J, 3» 385-395 ; J. Chem. Soc. 42, 599 ; Ber. 15. 949 ; Jsb.

Chem. 1882, 653.

On the Propyl Derivatives and Decomposition Products
of Acetoacetic Ester.

Propyl-acetoacetic ester is a liquid which boils at 208° to 209°
and has a specific gravity of .981 at o.°

Di-propyl-acetoacetic ester boils at 235° to 236° and has a specific
gravity of .958 at o.° Quantitive experiments were made in the saponi-
fication of these esters and results were obtained, similar to those of

32 BIBLIOGRAPHY OF

Wislicenus,* which are given in a table. Di-propyl-acetic acid boils
at 219.5° and has a specific gravity of .9215 at o° Di-propyl-acetone
boils at 173° to 174? Sodium amalgam acting upon di-propyl-aceto-
acetic ester failed to produce di-propyl-/3-oxy-butyric acid as was
expected but decomposition resulted.

*Ann. Chem. 186, 161. See pages ro and 29.

WISLICENUS, J., 1882.

Ann. Chem. 212, 239-250; J. Chem. Soc. 42> 934;
Jsb. Chem. 1882, 370.

Comparisons of the Combining Energies of the Halogens and
Sodium with Different Organic Residues.

Many experiments were performed with acetoacetic esters and
the following results formulated :

1) Towards similar organic residues the combining energy of chlorin
is greatest and of iodin is the least.

2) Among compounds of the same halogen with isomeric radicals,
the primary show the least and the tertiary the greatest combining
energy.

3) The combining energy of iodin for alcohol radicals of the same
category (primary or secondary) increases with the molecular weight
(addition of CH2) this increase being the reciprocal of the increase of
the molecular weight.

4) The combining energy of the halogen is considerably less when
the residue is an unsaturated primary alcohol radical (allyl for example)
but is considerably increased when the halogen is united to a primary
but unsaturated carbon atom (vinyl iodid for example.)

5) A diminution of combining energy is produced by linking of CH2
group united with the halogen to carboxyL The author also shows
that the combining energy of the sodium in the sodium-acetoacetic
esters is greater than that of the sodium in the sodium-alkyl-acetoacetic
esters.

ACETO ACETIC ESTER 33

WLEUGEL, S., 1882.

Ber. 15, 1050-1056 ; J. Chem. Soc. 42» 949 ; Jsb. Chem. 1882, 839 ;
Bull. Soc. chim. 38, 389.

Upon the Knowledge of Nitroso-acetoacetic Esters.

Since of the three compounds formed by the treatment of acetoacetic
ester with nitrous acid, namely : (i) the nitroso-acetoacetic ester ; (2)
nitroso-propionic acid and (3) nitroso-acetone, only the second can be
reduced to an amid, while the third forms a ketine, the author in-
vestigates the action of nascent hydrogen on the first, nitroso-aceto-
acetic ester, and obtained a dibasic acid which he calls ketindicarboxylic
acid, Cg H8 N2 O4 . The barium, silver, potassium, ammonium and
lead salts were described. The author advances the structural for-
mula

N

/ ^
CH3 C C C02 H

CH3C C C02H

\ //

N

PROPPER, MAX, 1882.
Ber. 15, 1154 ; J. Chem. Soc. 42, 1193.

Action of Fuming Nitric Acid on Acetoacetic and on Mono-chlor-

acetoacetic Esters.

A preliminary notice stating that the author has obtained nitroso-
acetic and mono-chlor nitrosoacetic esters by these reactions.

34 BIBLIOGRAPHY OF

HANTZSCH, A., 1882.

Ann. Chem, 215, 1-82 ; J. Chem. Soc. 44> 82 ; Ber. 15. 2912 ; Jsb.

Chem. 1882, 491.

Synthesis of Pyridin Derivatives from Acetoacetic Ester and
Aldehyde=Ammonia.

The condensation product of acetoacetic ester and aldehyde-ammonia
is dihydrocollidin-dicarboxylic ester,

OH,

c

C02C2H5C — H C — C02C2H5

CH3C— H C — CH3

\ /

N

The author describes this and many of its derivatives.

CERESOLE, M., 1882.

Ber. 15, 1326-1328 ; J. Chem. Soc. 42, 1052 ; Jsb. Chem. 1882, 758 ;
Bull. Soc. chim. 38, 390.

Nitrosoacetone and Acetoacetic Acid.

By allowing a mixture of acetoacetic ester and potassium hydroxid
'to stand a day and then treating it with an acid, acetoacetic acid is
produced. This is the first production of it. It is a colorless liquid,
mixes with water and is strongly acid. It is very unstable, decompos-
ing at less than ioo.°

DUISBERG, C., 1882.

Ber. 15, 1378-1388; Ann. Chem. 213, 133-181 ; J. Chem. Soc. 42,
1192 ; Jsb. Chem. 1882, 841 ; Bull. Soc. chim. 38, 391.

Contribution to the Knowledge of Acetoacetic Ester.

By treating acetoacetic ester with bromin the author cannot get L,ipp-
mann's dibrom addition product or Conrad's dibrom addition dibrom

ACETO ACETIC ESTER 35

substitution product but gets the five successive substitution products
and describes each one. The monobrom product treated with ammonia
gives Ce Hg O3, the ethyl ester of an acid which the author names oxy-
tetrolic. This ester is also produced if sodium act in place of ammonia,
and the acid can be obtained by treating the ester with sodium hydroxid.
Oxytetrolic acid has just half the molecular formula of Herrmann's suc-
cinosuccinic ester (Ann. Chem. 211, 306). Passing ammonia through
acetoacetic ester gives a substance which melts at 20° to 21° which the
author calls paramidoacetoacetic ester. Passing hydrochloric acid gas
through acetoacetic ester gives a substance Cg HIO O3, which boils at
290° to 295° and the author calls it carbacetoacetic ester.

GOTTSTEIN, L., 1882.

Ann. Chem. 216, 29-38 ; J. Chem. Soc. 44, 454 ; Ber. 16, 403 ; Jsb.

Chem. 1882, 869.

Two New Caprolactones.

When acetoacetic ester is treated with a brom propionic ester, ft
acetoisobutyric acid can be obtained, and when sodium amalgam acts

OTT
upon this, a methyl valero-lactone, CH3CH<pic2>CHCH3 is formed.

OT-TOTT ^^2

ft Methyl valero-lactone, CH2<^Q 3>CHCH3, can be formed in an

impure state by the action of sodium amalgam on ft acetobutyric acid,
CH3CH(C2H3O)CH2CO2H, which is formed from acetosuccinic ester.

JAKSCH, R. v., 1882.

Ber. 15, 1496; J. Chem. Soc. 42, 1120; Jsb. Chem. 1882, 1219.
Occurrence of Acetoacetic Acid in Urine.

The substance occurring in diseased urine, which gives a red color
with ferric chlorid, is proven to be acetoacetic acid.

}6 BIBLIOGRAPHY OF

HALLER, A. AND A. HELD, 1882.

Compt. rend. 95» 235 237; J. Chem. Soc. 42, 1280; Jsb. Chem. 1882, 845.
Cyanacetoacetic Ester and its Derivatives.

Cyanacetoacetic ester, CH3 CO CH (CN) CO2 C2 H5, was produced
by passing cyanogen chlorid into sodacetoacetic ester. It is a solid,
melts at 26° and remains in a superfused condition even at — 15° ; the
liquid has a specific gravity of 1.102 at 19° Potassium hydroxid de-
composes it. The sodium and calcium derivatives were described.

SCHMID, WILHELM, 1882.

J. prakt. Chem. 133, 81-83.

New Method of Producing Resocyanin.

Acetoacetic ester and resorcin react in the presence of zinc chlorid to
form resocyanin, which is : C6H3(OH)2C(CH3) : CHCO2H [C : OH :
OH= 1:2:4].

WITTENBERG, MAX, 1882.

J. prakt. Chem. 134, 66-78 ; J. Chem. Soc. 42, 1289; Ber. 15, 2908 ;
Jsb. Chem. 1882, 716 ; Bull. Soc. chim. 39, 72.

Resocyanin and the Action of Acetoacetic Ester on Phenols in
Presence of Dehydrating Agents.

Pyrogallol, C6H3(OH)3, and acetoacetic ester react in the presence of
sulfuric acid to form allylene-digallein, CI5HI2O6, which melts at 235°

(OH

and has the constitution : C6H3 ] O— CH2

C6H3 1 O- CH2

OH If orcinol, C6H3(CH3) (OH)2,

ACETO ACETIC ESTER 37

be used, a substance is produced which answers either to the formula

( CH2-CH2
CI7HI6O5, which would be C6H3 ] OH |

(OH ' Q

roH ,

C6H3 ] OH

( CH = CH, or to the formula C3IH30
( CH2- CH - CH2 )

O9, which is C6H3 \ OH OH \ C6H3

(.OH I OH )

(OH V OH -)

C6HJOH OH

( CH2- CH - CH2

CERESOLE, M., 1882.

Ber. 15, 1871-1878 ; J. Chem. Soc. 44» 41 ; Jsb. Chem. 1882, 860 ; Bull.

Soc. chim. 39, 35-

Acetoacetic Acids.

Acetoacetic acid, methyl-, dimethyl- and benzyl-acetoacetic acids
were prepared by treating their esters with an alkali in the col'd, proving
this to be an intermediate action in the ordinary saponification of these
esters. The ease with which these compounds decompose, as they do
below 100°, is attributed to the position of the carbonyl and carboxyl
groups separated by only one methylene or alkyl substituted methylene
group.

CONRAD, M., 1882.

Ber. 15. 2133-2134 ; J. Chem. Soc. 44, 177 ; Jsb. Chem. 1882, 845.
Halogen Substituted Acetoacetic Esters.

The author admits that his formerly described dibrom-acetoacetic
dibromid* is probably only Duisberg's tetrabrom-acetoacetic ester, f

* See page n.
t See page 34.

38 BIBLIOGRAPHY OF

LIPPMANN, E., 1882.

Ber. 15, 2142 — 2144. Jsb. Chem. 1882, 845.

The Position of Bromin in Acetoacetic Ester.

The author insists upon the correctness of his former statement,
which Duisberg denies, that a dibrom-addition dibrom-substitution
product of acetoacetic ester, Ce Hg Br2 O3 Br2, exists.

MATTHEWS, A. E. AND W. R. HODKINSON, 1882.

Ber. 15, 2679 ; J. Chem. Soc. 44, 311 ; Jsb. Chem. 1882, 839.

Production of Acetoacetic Ester.

Monochlor acetone, CH3 CO CH2 Cl, was treated with potassium
cyanid and the cyanid of acetone, CH3 COCH2 (CN), was obtained.
This, when treated with hydrochloric acid, gave acetoacetic ester.

YOUNG, SIDNEY, 1882.

Ann. Chem. 216, 45-52 ; J. Chem. Soc. 44, 456 ; Ber. 16, 405 ; Jsb.

Chem. 1882, 883.

Peculiar Decomposition of Substituted Acetoacetic Esters.

91*3 C2 Hs

CO i

When /3-ethyl-aceto-succinic ester, • C H , is heated

V-.XJ. I

C02C2H5 CO*C2H5
it breaks down into ketolactonic ester which can be changed into keto-

CH3 O CH2 O

I \\ \\ \\

., C — O— C C— O— C

lactonic acid, tt , or , ,

C CHC2 H5 CH CHC2 H5

CO2 H CO2 H

ACETO ACETIC ESTER 39

JANNY, ALOIS, 1882.

Ber. 15, 2778-2783.

Acetoxim.

Near the close of this article the author records having treated
acetoacetic ester with hydroxylamin and obtaining a very stable, nitro-
genous acid body.

JAPP, FRANCIS R. AND F. W. STREATFEILD, 1883.

J. Chem. Soc. 43» 27-34.
Condensation Product of Phenanthraquinone with Acetoacetic Ester.

These substances will condense in presence of either ammonia or
an alkali, preterably the latter, to form phenanthroxylene-acetoacetic
ester which is : —

OO OTT
C6 H4-C : C<C02 ^ ^ It decomposes at I84 5 _I85 5

C6H4-CO

It was reduced by hydriodic acid by which the acetyl oxygen was
removed giving phenanthroxylene-isocrotonic ester. This was dis-
solved in an alkali and by adding an acid another substance was pro-

duced which was : — 0 TT /^TJ_/^ ^CH : CH2
U H4-Ci -<^C02 H

C6H4-COOH
The investigation is being continued.

PROPPER, MAX, 1883.
Ber. 16, 67 ; Ann. Chem. 222, 46 ; J. Chem. Soc. 44, 573 ; Ber. 17, 14 (c).

Action of Fuming Nitric Acid on Acetoacetic and on
Mono-chlor-acetoacetic Esters.

The author has decided after further study that the two compounds,
C4 H7 O3 N and C4 H6 Cl O3 N, obtained by these reactions are oximido

CH : N • OH C Cl : N • OH

bodies, I , and I , not nitroso bodies, as he

C02 C2 H5 CO2 C2 H5

thought at first. His principal reason for this belief is that no cor-

40 BIBLIOGRAPHY OF

responding body can be formed from the dichlor-acetoacetic ester as
should be the case if it were the monad nitroso group which was intro-
duced.

CLAISEN, L. AND F. E. MATTHEWS, 1883.

Ann. Chem. 218, 170-185 ; J. Chem. Soc. 46. 443 ; Jsb. Chem. 1883,
963 ; Bull. Soc. chim. 40, 473.

Condensation of Acetoacetic Ester with Aldehydes.

By treating acetoacetic ester with aldehydes, the following two com-
pounds are formed, the first one much more easily than the second,
CH3 CO C : (: CHR) CO2 C2 H5 and CH : (: CHR) COCH2 CO2 C2 H5.
Acet-ethylidenacetic ester, CH3 COC : (: CHCH3) CO2 C2 H5, made by
passing hydrochloric acid gas through a mixture of acetoacetic ester
and aldehyde is a colorless liquid which boils at 210.° to 212° Its
specific gravity is 1.022 at 15? It easily changes back into aldehyde
and acetoacetic ester. The following were prepared and described.
Acetisobutylidenacetic ester, Ce H8 (C4 H8) O3 ; acetisamylidenacetic
ester, C6 H8 (C5 HIO)O3 ; acet-trichlor-ethyliden acetic ester, C6 H8 (C2
HC13) O3, which is a aceto-trichlor-crotonic ester; aceto-furfural acetic
ester, C6 H8 (C5 H4 O) O3, which is a acet-furfuracrylic ester ; aceto
benzal acetic ester Ce H8 (CHCe H5) O3 , which is a acet-cinnamic
ester ; benzal- ace toethylacetic ester, C6 H5 CH : CHCOCH (C2 H5)
CO2 C2 H5 ; and benzalacetodiethylacetic ester, C6 H5 CH : CHCOC
(C2H5)2C02C2H5.

DUISBERG, C., 1883.
Ber. 16, 133-139; Jsb. Chem. 1883, 1112.

Converting Acetoacetic Ester into Succinosuccinic Ester which
is Convertable into Hydroquinone.

Succinic ester, made from acetoacetic ester, was treated with sodium
and sodium succinosuccinic ester, CI2HI4O6Na2, prepared. As in dry
acetic ester, the sodium caused no reaction even at 100° until some
sodium ethoxid was added. Sodium succinosuccinic ester which has

ACETO ACETIC ESTER 41

CH2 — COCHC02C2H5

the formula I melts at 127° and was found to

CH2— COCHC02C2H5

be identical with the substance produced from brom-acetoacetic ester
and sodium. This can be changed into hydroquinone, C6H4 (OH)2,
so that these reactions show a case of changing an acid of the fatty
series (acetic) into a benzene ring. .

PERKIN, Jr., W. H., 1883.

Ber. 16, 208-210; Jsb. Chem. 1883, IOI5 '> Bull. Soc. chim. 40, 46.
Action of Trimethylene Bromid on Sod-acetoacetic Ester.

This reaction gives acetotetramethylene carboxylic ester,

CH3

CO

I

^ -"* 2

C02 C2 H5

which boils at 223° to 225.° From this the acid and the silver salt
of the acid can be obtained.

DUISBERG, C., 1883.

Ber. 16, 295-297 ; J. Chem. Soc. 44, 656.

Addition of Bromin to Acetoacetic Ester.

This article is a reply to Lippmann and Conrad on this subject. The
author declares that acetoacetic ester is saturated and cannot form an
addition product.

CHANCEL, G., 1883.

Compt. rend. 96, 1466-1470 ; J. Chem. Soc. 44, 914 ; Jsb. Chem.. 1883,

1078 ; Ber. 16, 1495.

New Method of Synthesis of Alkylnitrous Acids.

Acetoacetic ester and its alkyl derivatives are treated with nitric acid
and then with alcoholic potash when the nitrites are formed. Treated

42 BIBLIOGRAPHY OF

in this manner acetomethyl- acetic ester yields potassium ethyl nitrite,
CH3 C(NO2)2 K. Ethyl-acetoacetic ester gives potassium propyl nitrite,
CH3CH2C(NO2)2K. Propyl-acetoacetic ester boils at 212° at
750 m-m- pressure and has a specific gravity of .979 at o.° When treated
with nitric acid it gives potassium butyl nitrite, CH3 CH2 CH2 C(NO2)2
K. By acidifying the latter butyl nitrous acid is obtained, which boils
with some decomposition at 197° and has a specific gravity of 1.205
at 15.°

HANTZSCH, A., 1883.

Ber. 16, 740-742 ; J. Chem. Soc. 44, 1083.

Condensation Products of Acetoacetic Esters.

Strong sulfuric acid acting on acetoacetic ester produces (i) mesityl-

C TT
2 ~2 ^5

2 \^2 -tig

HS' and

CO C TT
oxid-di-carboxylic ester, C6H8O<rA<~2 ~2 ^5 (2) mesityl-oxid-anhydro-

dicarboxylic ester,

CO
<C02C2H5

(3) a crystalline body, polymeric with dehydracetic acid which is a
dibasic acid, the formula for which is probably Ci4 HI4 O7 ; the name
metadehydracetic acid is proposed for it. Ammonia acts on mesityl-

OO P TT

oxid-anhydrodicarboxylic ester to form a salt C6 H8 O NH3 < ~X2 XT 55

l^vJ2 -N -H-4

CO C TT

which with hydrochloric acid gives Ce H8O<pQ2 ^ 5 which in turn

OO TT
can be saponified to C6 H8 O < ^2 j

CERESOLE, M., 1883.

Ber. 16, 830-832.
Diethyl-acetoacetic Acid.

Diethyl-acetoacetic ester is allowed to stand several weeks with a
% solution of potassium hydroxid, the salt produced is treated with

ACETO ACETIC ESTER 43

hydrochloric acid and diethyl-acetoacetic acid, CH3CO C(C2 H5)2
CO2 H, is thus produced. It is very unstable, decomposing at 60 into
diethyl-acetone, CH3 CO CH (C2 H5)2, which boils at 135° to 137.°
Diethyl-acetoacetate of sodium was produced.

ELION, H., 1883.

Rec.* trav. chim. 2, 33-34 and 202-204 ; Ber. 16, 1368 and 2762.
Diacetyl-acetic Ester.

By treating ethyl- acetoacetic ester with water-free, sodium hydroxid
and the product with acetyl chlorid, ethyl-diacetyl-acetic ester was
produced, it boils at 235.° Acetoacetic ester treated thus gives diacetyl-
acetic ester which boils at 210° to 213° with some decomposition, its
specific gravity is i.i at 15° It is decomposed by boiling with water.

Original article not consulted.

MATTHEWS, F. E., 1883.
J. Chetn. Soc. 43, 200-207 ; Ber. 16, 1372.

Condensation Products of Aldehydes with Acetoacetic Ester and
some Substituted Acetoacetic Esters.

This article is almost the same as the one by Claisen and Matthews
in fAnn. Chem. 218, 170. The author concludes that all aldehyde
condensations with acetoacetic ester take place with the methylene
group and are easily accomplished because of the position of the
methylene group between the carbonyl and carboxyl groups, but that
such condensations with mono-or di-substitution acetoacetic ester take
place in the methyl group and consequently are more difficult to ac-
complish.

f vSee page 40.

44 BIBLIOGRAPHY OF

PERKIN, Jr., W. H.. 1883.
Ber. 16, 1787-1789; J. Chem. Soc. 44» 1083; Jsb. Chem. 1883, 1015.

Action of Trimethylene Bromid on Acetoacetic, Benzoylacetic
and Malonic Esters.

By the action of trimethylene bromid on acetoacetic ester, aceto-tetra-

CH3

CO

I r^TT

methylene carboxylic ester, C <r;;;2>CH2, is formed which isisomeric

I <-H2

C02 C2 H5

but not identical with allyl-acetoacetic ester. From this is obtained
aceto-tetramethylene, CH3COCH (CH2)3, which boils at 109°- no?

C6H5

CO

I OTT

Benzoyl-tetra-methylene carboxylic ester, C <r; 2>CH2, was formed

I (~tt-2

C02C2H5

from tri-methylene-bromid and benzoyl-acetic ester and from it the acid,
the silver salt and benzoyl-tetra-methylene, C6H5COCH (CH2)3, were
obtained.

WEDEL, WILHELM, 1883.

Ann. Chem. 219* 71-119 ; J- Chem. Soc. 46. 834; Jsb. Chem. 1883,
1060; Bull. Soc. chim. 41* 181 ; Ber. 16, 2288.

Derivatives of Acetoacetic Ester.

By treating dibrom- acetoacetic ester with sodium, an ester, C6H7
O3, is produced and from this its acid, C4H3O3. These resemble in
properties Duisberg's oxytetrolic acid and ester, but the author decides
that the ester is identical with Herrmann's quinon-hydrodicarboxylic
ester of the formula CI2 HI4 Oe- By the action of acetyl chlorid on this
ester, a diacetyl compound is formed which the author takes as proof

ACETO ACETIC ESTER 45

of the existance of the hydroxyl group in both quinon-hydrodicar-

CH2 CH2

I I

boxylic ester and acetoacetic ester thus : — COH COH and

II II
C — C

C02 C2 H5 C02 C2 H5

CH3 CH2

COH or COH

II i

CH CH2

I i

CO2 C2 H5 CO2 C2 H5. By the action of bromin on acetoacetic ester

the mono-, di-, and tri-derivatives only could be formed, therefore it
was decided that all compounds seeming to have more than three atoms
of bromin are mixtures containing some per-brom- acetoacetic ester,
C6 BrIO O3, which was formed and which melts at 79°-8o.° By heating
mono-brom-ethyl-acetoacetic ester ethyl-succino-succinic acid is pro-
duced, CH2 CH2

I I

which is CO CO , according to the common formula for

C(C2H5)-C(C2H5)
CO2 H CO2 H

CH- -CH

acetoacetic ester or COC2 H5 COC2 H5, according to the author's

CH- -CH

C02 H C02 H

formula. Acetoacetic ester is decomposed by being heated to 140° with
acetic acid. Acetyl chlorid decomposes acetoacetic ester and some
carbacetoacetic ester is formed, which shows the presence of hydroxyl
in acetoacetic ester with which the acetyl chlorid formed hydrochloric
acid which produced the carbacetoacetic ester. Glycolic, oxalic and
succinic acids decompose acetoacetic ester into carbon dioxid and
acetone.

46 BIBLIOGRAPHY OF

HANTZSCH, A., 1883.
Ber. 16, 1946-1948 ; J. Chem. Soc. 44» 1082 ; Jsb. Chem. 1883, 1068.

Condensation of Acetoacetic Methyl Ester with
Aldehyde=am monia.

This condensation is entirely similar to that with the ethyl ester, a
dihydro-collidin-dicarboxylic methyl ester, C5 N H2 (CH3)3(CO2CH3)2,
being formed. From this were formed dihydro-collidin-monocarboxylic
methyl ester, C5 NH2 (CH3)3 H (CO2 CH3), and collidin-dicarboxylic
methyl ester, C5 N (CH3)3 (CO2 CH3)2.

HANTZSCH, A., 1883.

Ber. 16, 1948-1952 ; J. Chem. Soc. 44» mi ; Jsb. Chem. 1883, 1069 ;
Bull. Soc. chim. 42, 182.

Condensation of Acetoacetic Ester and Ortho=amidophenol.

These substances condense as follows :

r* TT /• OH I /^v p\ ,^-Cri3 _ p TT ^^ ^r* .^3

-r- ~

H5-f-H20.

The product, very unstable, being easily decomposed into its com-
ponents, melts at io7°-io8.° A potassium salt, C24H29KO6N2, was
formed ; one hydrogen atom of the amid group of every two molecules
apparently being replaceable.

PECHMANN, H. v. AND C. DUISBERG, 1883.

Ber. 16,2119-2128; J. Chem. Soc. 46, 66; Jsb. Chem. 1883, 1065;
Bull. Soc. chim. 42, 587.

Compounds of Phenols and Acetoacetic Ester.

In the presence of a dehydrating agent phenols and acetoacetic ester
react to form substituted coumarins.

ACETO ACETIC ESTER 47

If resorcin, Ce H4 (OH)2, is used /9methyl-umbelliferone,

C* TT OH^^ (CH3): CH,

<- _

QQ

is formed which when treated with potassium hydroxid gives resaceto-
phenon, C6H3 (OH)2 CO CH3. The methyl ester and the carboxylic acid
of /3methyl-umbelliferone were formed. «-/?-Di-methyl-umbelliferone,

C6 H3 (OH) <

was formed from resorcin and dimethyl- acetoactic ester. Metatoluene-/9-

r\ /• f^TT \ • QTT

methyl-coumarin, C6H3CH3<Q^_ _' CO
cresol, Ce H4 OH CH3, and acetoacetic ester.

r\ /• f^TT \ • QTT

methyl-coumarin, C6H3CH3<Q^_ _' CO was ^orme<^ from para-

PERKIN, Jr., W. H., 1883.

Ber. 16, 2136-2140 ; J. Chem. Soc. 46, 64.

Action of Ethylene Bromid on Acetoacetic and Benzoyl-acetic Esters.

From acetoacetic ester, ethylene bromid and sodium, aceto-tri-

CH3

CO

I CH2

methylene carboxylic ester, C < I , is formed, which boils at 193° to

I CH2
C02 C2 H5

195.° The acid and the silver salt were obtained. Benzoyl-trimethy-
lene carboxylic ester and acid and benzoyl-trimethylene were also
produced.

GEUTHER, A., 1883.

Ann. Chem. 219, 119-128 ; J. Chem. Soc. 46, 836 ; Ber. 16, 2290 ;
Jsb. Chem. 1883, 1065.

Constitution of Acetoacetic Esters and of Benzene.

The formation of tri-brom- acetoacetic ester by Wedel and the forma-
tion of acetoacetic ester from acetic ester are cited as proof of the
formula CH3 COH : C H CO2 C2 H5 and against CH2 : COH CH2 CO2

48 BIBLIOGRAPHY OF

C2 H5. Attention is called to the colors produced by acetoacetic com-
pounds and phenol compounds with ferric chlorid as indicating by
their similarity that these bodies are similarly constituted. Comment
is made upon changing the fatty acid into the benzene ring as pointed
out by Wedel, that is, acetic ester into acetoacetic ester and this into
quinonehydrodicarboxylic ester and this finally into hydroquinone.

JAKSCH, R. v., 1883.

*Ztschr. physiol. Chem. 7, 487-490, Ber. 16, 2314.
Acetoacetic Acid in Urine.

The author states that he published a paper in 1880 identifying
acetoacetic acid in urine, he therefore claims priority to Tollens f (Ber.
14, 2594).

* Original article not consulted,
f See page 31.

KNORR, L., 1883.

Ber. 16, 2593-2596 ; J. Chem. Soc. 46, 334 ; Bull. Soc. chim. 42, 654.
New Synthesis of Quinolin Derivatives.

By varied conditions a reaction between acetoacetic ester and anilin
is obtained which forms the compound CH3 C (NC6 H5) CH2 CO2 C2 H5,
which is very unstable. If the reaction be interrupted by adding sul-
furic acid, f oxy-a-methyl quinolin is obtained, which comes from the
compound cited above by its losing alcohol thus : CH3 C (NC& H5) CH2

N= CCH,

CO2C2H5=C6H4< | +C2H5OH. It melts at 222 The

C(OH) :CH

intermediate anilin-acetoacetic acid, CH3 C (NC6 H5) CH2 CO2 H, was
also obtained.

ACETO ACETIC ESTER 49

KNORR, L., 1883.

Ber. 16, 2597-2599; J. Chem. Soc. 4<*» 3°2 ; Jsb. Chera. 1883, 795;
Bull. Soc. chim. 42, 655.

Action of Acetoacetic Ester on Phenylhydrazin.

When these substances react there is formed CH3 C (HN2 C6 H5)
CH2 CO2 C2 H5. If this be heated on the water bath alcohol is given
off and a body CIO HIO N2 O, is left which melts at 127°; it resembles car-
bostyril ; its constitution is unknown. When it is heated with an
excess of phenylhydrazin its anhydrid C20 Hl8 N4 O is produced,
which from its reactions is shown to contain a hydroxyl group.

WISLICENUS, J., 1883.

Ann. Chem. 219, 307-321 ; J. Chem. Soc. 44» 966 ; Jsb. Chem. 1883,

980.

Methyls-butyl Ketone and its Derivatives.

Ethyl-methyl-acetoacetic ester is saponified and methyl-/9-butyl
ketone, CH3 COCH (CH3) (C2 H5), obtained, it boils at 118° and has a
specific gravity of .818 at 14. 5? By treating it with sodium and water
two products were obtained, methyl-/9-butyl carbinol,

CH3 CHOHCH—
CH3 CH3

- (CH3)(C2H5), and methyl-/9-butyl pinacone, COH - COH

CHCH3 CHCH3
C2 H5 C2 H5

Methyl-/9-butyl carbinol is changed into the iodid and then
by substituting hydrogen for this iodin methyl-di-ethyl-methane,

H
C2 H5 — C — CH3, is formed.

C2H,

5O BIBLIOGRAPHY OF

HECKMANN, JACOB, 1883.

Ann. Chem. 220, 128-146 ; Ber. 16, 2675 ; J. Chem. Soc. 46. i?8 ;
Jsb. Chem. 1883, 1147 ; Bull. Soc. chim. 42» 54-

Dinitro=phenyl=acetoacetic Ester.

By treating sodacetoacetic ester with dinitro-brom-benzene, dinitro-
phenyl-acetoacetic ester, CH3 CO C H [C6 H3 (NO2) J CO2 C2 H5,
is produced, it is crystalline and melts at 94° From this is produced,
by potassium hydroxid, ortho-para-dinitrophenyl acetic acid, CH2 Ce
H3 (NO2)2CO2 H, which melts at 160° and some di-nitro-toluol, Ce
H3 CH3 (NO2)2. By means of boiling alkalis several complicated
decomposition products are obtained C24 Hl8 N6 OI5, melting at 105.5°
and from this, C24 Hl6 K2 N6 OJ5, C4g H32 N6 OI9 and a silver salt
C48 H29 Ag3 N6 0I9.

PAAL, C., 1883.

Ber. 16, 2865-2869; J. Chem. Soc. 46, 598; Jsb. Chem. 1883, 1220;
Bull. Soc. chim. 42, 541.

Action of Brom=acetophenon on Sodacetoacetic Ester.

These substances react with separation of sodium bromid to form
CH3COCH(CH2COC6H5)C02C2H5, which easily decomposes into
the acid and then into acetophenonacetone, (C6H5COCH2)CH2COCH3 .
When acetophenonacetoacetic ester is boiled with potassium hydroxid
an acid CI2 HIO O3 , is formed by the separation of alcohol and water.

ROSER, W., 1883.

Ann. Chem. 220, 271-278 ; J. Chem. Soc. 46, 423.
Isopropyl-succinic or Pimelic Acid.

Isopropyl-succinic acid was made from acetoacetic ester, mono-
chloracetic ester and isopropyl iodid, the acetyl being removed and the
ester obtained being changed to the acid. This was proven to be

identical with pimelic acid CH (CH,)2— CH <^2 ^ obtained

Url2 CU2 fl,

from camphoric acid.

ACETO ACETIC ESTER 51

WESTENBERGER, BERNHARD, 1883.

Ber. 16, 2991-2998 ; J. Chem. Soc. 46, 581 ; Jsb. Chem. 1883, 978 ;
Bull. Soc. chim. 42, 444.

Isonitroso Bodies.

The action of hydroxylamin on acetoacetic ester is given on page
2996 of this article. From this reaction /?-isonitroso-butyric ester,
CH3C(NOH)CH2CO2C2H5, results which is very unstable. The
acid is formed from it. Isonitroso-methyl-acetoacetic ester, CH3 C
(NOH) CH (CH3) CO2 C2 H5 , and the corresponding ethyl- and di-
ethyl- products were produced from the corresponding substituted
acetoacetic esters, proving the reaction to be a general one.

HANTZSCH, A., 1883.

Ann. Chem. 222, 1-46 ; Ber. 17, 12 (C) ; Jsb. Chem. 1883, 1070 ; Bull.

Soc. chim. 42, 502.

Condensation Products of Acetoacetic Ester.

Acetoacetic ester treated with sulfuric acid gives a condensation
product Ci8 H22 O9 , which is formed from four molecules of acetoacetic
ester by the separation of three molecules of alcohol. Its formula is

( OH C02 C2 H5 )

C6 H7 ] CO2H CO2 H [ C6 H7 . When treated with potassium
(CO — O \

O
hydroxid and an acid it yields two products, i) Ce H7 •{ CO , called

C02H

mesiten-lactone-carboxylic acid, and 2) its ethyl ester. The radical
(Ce H9)' being designated as mesiten. The mesiten-lactone-carboxylic

CO2H

I
acidorisodehydraceticacidhastheformulaCH3 — C : C • C (CH3) : CH,

O CO

52 BIBLIOGRAPHY OF

and with potassium hydroxid it yields mesityl oxid. It is a monobasic
acid and many of its metallic salts were described. A few complicated
salts were investigated which appeared to come from the acid,

OH 0

-, 4 CO2 H. Mesiten-lactone, C6 H8 <rv^> , was produced and
(C02H

OO TT

described and also oxymesitencarboxylic acid, CeHg <QTT > an<^ its

barium and calcium salts. Mesiten-lactone-carboxylic ester,

(0 C02C2H5

C6 H7 ] CO> , or CH, — C : C • C (CH3) : CH , is unstable, tends

6 ___ CO

C02C2H5

to take up water, its boiling point is not constant, it boils between 270°

(O fONH4

and 310.° C6H6Br 1 CO> , and also C6H7 -! CO2 NH4 , were

(C02C2H5 (C02C2H5

prepared and described. The latter easily loses ammonia, and when
heated with water and hydrochloric acid it gives oxymesitendicarboxylic

f OH

acid ester, Ce H7 •] CO2 H , which melts at 76° and easily loses
( C02 C2 H5

(OH

water to form the lactone. It forms salts of the formula C6H7 •< CO2 M ,

( C02C2H5

of which the copper and lead salts were described. The lactone
treated with potassium hydroxid produces homo-mesaconic acid,

CO2H

I

H2 C - C (CH3) : CH -CO2 H , melting at 147.° It forms acid and nor-
mal salts, the barium, calcium, copper, silver, acid potassium and acid
ammonium salts were described. The author concludes that Duisberg's
carbacetoacetic ester, Cg HIO O3 , is identical with his mesiten-lactone-
carboxylic ester and also that the hydroxyl group does not exist in
acetoacetic ester but that an intermolecular change occurs during con-
densation, the two acetoacetic ester molecules first lose water and are
connected, then an intermolecular change forms a hydroxyl group
which gives up its hydrogen to form the lactone. The author thinks
the general case to be true that where such a group as X2 C : C (OH) X
occurs it will change into X2 CH - COX but can change back to the
hydroxyl form again during a reaction such as the forming of a lactone.

ACETO ACETIC ESTER 53

BEHREND, ROBERT, 1883.
Ber. 16, 3027-3028 ; J. Chem. Soc. 46, 583.
Action of Car bam id on Acetoacetic Ester.

These substances unite thus :

C6 HIO 03 + (NH2)2 CO = C7 HI2 N2 O3 + H2O .

The product formed is crystalline and melts at 147.° Acids decom-
pose it into acetoacetic ester and carbamid again. From it can be
obtained the sodium salt of the acid C5H8N2 O3 , which is C5H7NaN2O3 .
The author is investigating the structure of the compound.

JAMES, J. WM., 1884.

Ann. Chem. 226, 202-222 ; J. Chem. Soc. 47, i-n ; Ber. 17. 604 (C).
Jsb. Chem. 1884, 1120.

Acetoacetic Ester.

According to Wedel, ethyl-acetoacetic ester is CH3COC2H5: CHCO2R
and sodiumethylacetoacetic ester would be CH3 CO Na : C (C2H5) CO2R,
so that if it were treated with acetic acid an isomeric ethylacetoacetic
ester should be obtained, but the author proves that an identical ethyl-
acetoacetic ester is recovered. Experiments were made to determine if
the order of introduction of alkyl radicals in the di-substitution pro-
ducts affects the products. No difference could be detected between
allyl-methyl-acetoacetic ester and methyl-allyl-acetoacetic ester or
between ethyl-methyl- and methyl-ethyl-acetoacetic esters. Acetyl-
acetoacetic ester was produced from acetoacetic ester and acetyl chlorid,
it boils at 2oo°-2O5° with slight decomposition. It is decomposed by
water at ordinary temperatures into acetoacetic ester. The copper
and nickel compounds were described. An attempt was made to
substitute the hydrogen by sodium but it failed as decomposition took
place. The acetyl-methyl-acetoacetic ester was prepared from methyl-
acetoacetic ester and acetyl chlorid. Benzoyl-acetoacetic ester, CH3
COCH (COC6 H5) CO2 C2 H5 , and its copper compound were prepared
and described.

54 BIBLIOGRAPHY OF

JONES, E. J., 1884.

Ann. Chem. 226, 287-294; J. Chem. Soc. 48, 376; Jsb. Chem. 1884,

1188.

Decomposition of a-Methyl-propyl^oxybutyric Acid by Heat.

This substance, CH3 CHOHC (CH3)(C3H7) CO2 H, is obtained by
the action of sodium amalgam on methyl-propyl-acetoacetic ester.
Heated to 170° it decomposes into acetaldehyde and methyl-propyl-
acetic acid. When methyl-propyl-acetoacetic ester is saponified it
yields methyl- a-secondary pentyl ketone, CH3 COCH (CH3) (C3 H7),
which boils at 142° to 147° and methyl-propyl-acetic acid which boils
at 193.°

COLLIE, J. NORMAN, 1884.

Ann. Chem. 226, 294-322 ; J. Chem. Soc. 48, 373 ; Ber. 18, 25 (C) ;
Jsb. Chem. 1884, 1116.

Action of Ammonia on Acetoacetic Ester.

Paramido-acetoacetic ester, C6HXINO2, is formed which may be
either CH3 C (NH2) : CHCO2 C2 H5 or CH3 C (: NH) CH2 CO2 C2 H5. It
is easily decomposed into the substances started with. Sodium amal-
gam changes it into /9-oxy butyric acid. It reacts with acetic acid
anhydrid to produce /9-acetamido-«-crotonic ester, CH3 C (NHCOCH3):
CHCO2 C2 H5 . When heated it condenses to CIO HI3 NO3 from which
the acid Cg H9 NO3 , can be produced, which is hydroxylutidin-mono-
carboxylic acid,

CH3

|

C

/ \

HC C — CO2

H

HOC CCH3

\ X

N

ACETO ACETIC ESTER 55

When treated with paraldehyde and sulfuric acid it gives dihydrocollidin
dicarboxylic ester,

CH3

c

/ \
CH3 CH CC02 C2 H5 .

CH3 CH CC02 C2 H5
\ /

N

CANZONERI, F. and G. SPICA, 1884.

Gazz.* chim. 14, 448-453 ; Ber. 18, 107 (C) ; J. Chem. Soc. 48, 75.
Action of Am ids on Acetoacetic Ester.

Formamid reacts with acetoacetic ester to form lutidin-mono- and di-
carboxylic esters and a compound CI2 HJ5 NO2 , to which is attributed
the formula

NH2 NH

CH C — CH — C — O — C2H5 CH— C CH2— COC2H5

I II or II II H

C C = C C — H C C=C — -C— H

O — C2H5 O— C2H5

The results of the reaction when acetamid is used will be given later.

Original article not consulted.

CHANLAROFF, MOEHSIN BEG, 1884.

Ann. Chem. 226, 325-343 ; Ber. 18, 26 (C) ; J. Chem. Soc. 48, 374.

Butyrolactone.

This is quite a long article on butyrolactone which is produced from
acetoacetic ester as follows :

CH3COCHNaCO2C2H5 + CH2C1CH2OH=CH3COCHCO2C2H5 .

CH2CH2OH

56 BIBLIOGRAPHY OF

This substance treated with barium hydroxid and then an acid gives
CH2 CO2 HCH2 CH2 OH , which upon heating gives the butyrolactone,
CH2 CH2

CH2 CO > ° *

ELION, H., 1884.

Rec.* trav. chim. 3» 231-270 ; Ber. 17, 568 (C).
Ethyl-sodacetoacetic Ester and Sodacetoacetic Ester.

Kthyl-sodacetoacetic ester hydrate, Cg HI3 NaO3 + H2O , and sodace-
toacetic ester hydrate, C6H9 NaO3-f- H2O , were prepared. Sodium
bisulfite forms a compound with acetoacetic ester but will form none
with diacetyl- , ethylacetyl- and ethyldiacetyl- acetic esters. Kthyl-
diacetyl-acetic ester, CH3COC (C2 H5) (C2 H3 O) CO2 C2 H5 , could not
be prepared from sodium diacetyl-acetic ester but could be from ethyl-
acetoacetic ester and acetyl chlorid.

^Original article not consulted.

HELD, A., 1884.

Compt. rend. gS, 522-525 ; Bull. Soc. chim. 41, 330 ; J. Chem. Soc. 46,
727; Jsb. Chem. 1884, II21 ; Ber !7» 2O4 (C).

Ethyl- and Methyl-cyanacetoacetic Esters.

The esters could not be prepared from the cyan-acetoacetic esters but
were successfully prepared by treating ethyl-acetoacetic ester and
methyl-acetoacetic ester with cyanogen gas. Bthylcyanacetoacetic
ester boils at io5°-iio° under 15 to 2 m.m. pressure, its specific gravity
is .976 at 20° Methylcyanacetoacetic ester boils at 9O°-95° under 15
to 20 m.m. pressure, and has a specific gravity of .996 at 20.° The
decomposition products with potassium hydroxid show that the for-
mulae must be CH3 COC (CN)(C2 H5) CO2 C2 H5 and CH3 COC (CN)
(CH3)C02C2H5. -

ACETO ACETIC ESTER 57

WELTNER, A., 1884.

Ber. 17, 66-73 ; J. Chem. Soc. 4<*» 746; Jsb. Chem. 1885, 1415 ; Bull.

Soc. chim. 43» 336.

Action of Chlor- and Brom -acetone, Aceto-phenon Bromid and
Phenyl-brom-acetic Acid on Acetoacetic Ester.

Chlor- and Brom-acetone act on acetoacetic ester but no definite
results were obtained. Aceto-phenon bromid, Ce H5 COCH2 Br, acting
on acetoacetic ester produces aceto-phenon-acetoacetic ester, which,
when treated with sodium amalgam becomes a hydroxylactone,

CH3CHOHCH<£Q2> CHC6H5. Phenyl-brom-acetic ester and
acetoacetic ester produce phenyl-aceto-succinic ester,

CH3 CH3

CO C6 H5 ; from this the ketone acid, CO C6 H5 ,

II II

CH CH CH2 CH

C02C2H5 C02C2H5 C02H

is formed, and from this by the action of sodium amalgam the lactone,

°- is formed-

CANZONERI, F. and G. SPICA, 1884.

Gazz.* chim. 14* 491-492 ; Ber. 18, 141 (C) ; J. Chem. Soc. 48, 750.
Acetyl-^-imidobutyric Ester.

By heating acetoacetic ester with acetamid and aluminum chlorid
under reduced pressure there is produced acetyl-/9-imidobutyric ester
which melts at 64° to 65? Its formula is

CH3 CO — N = C (CH3) CH2 CO2 C2 H5 .

^Original article not consulted.

58 BIBLIOGRAPHY OF

PERKIN, W. H., 1884.
J. Chem. Soc. 45» 493 and 540.

Magnetic Rotary Polarization of Compounds in Relation to
Chemical Structure.

Tables of very many substances are given, among them are: —
Acetoacetic ester at 16.25° specific rotation =0.9278 and molecular
rotation = 6.501. Allylacetoacetic ester at 13.9° specific rotation
= 1.09022 ; molecular rotation = 10.382.

KNORR, L., 1884.

Ber. 17, 546-552; J. Chem. Soc. 46, 1153; Jsb. Chem., 1884, 874;
Bull. Soc. chim. 43, 406.

Action of Acetoacetic Ester on Phenylhydrazin.
Quinizin Derivatives.*

The compound CIO HIO N2 O , before described, is now supposed to
have the formula

CH — NH
/ \ N |
HC C/ \ CCH3,

I I i

HC C CH2

\ / \ /

C C

H O

and is named oxymethylquinizin. The reaction between phenylhy-
drazin and acetoacetic esters is general and consists of two parts : —
(i) C6 H5 NHNH2 + CH3 COCH2 CO2 R = CH3 CCH2 CO2 R

A
HN-N-C6H5

and (2) this loses alcohol and leaves CH3 CCH2 CO

A

HN-N-C6 H4 .

This substance was studied and a number of its derivatives described,
among them were orthotoluoxymethylquinizin, paratoluoxymethyl-
quinizin and /3-napthodiinethyloxyquinizin.

*See page 49.

ACETO ACETIC ESTER 59

PAAL, C., 1884.

Ber. 17, 913-918 ; J. Chem. Soc. 46, 1177 ; Bull. Soc. chim. 43, 626.
Derivatives of Acetophenon-acetoacetic Ester.

CH3COCHCO2 C2 H5 ,

Acetophenon-acetoacetic ester, I when saponi-

CH2 COC6 H5

fied yields acetophenonacetone, CH3 COCH2 (CH2 COC6 H5), from
which were produced two isomeric compounds CiiHIOO, one of
which melts at 4i°-42°, boils at 235° to 240° and yields, on oxidation,
benzoic acid. The acid CI2HIOO3, previously described, gives by
oxidation benzoic, acetic and carbonic acids. An oil CI2 H9 O3 C2 H5 ,
was produced from this acid. The work is being continued.

LIEBERMANN, C. and S. KLEEMANN, 1884.

Ber. 17, 918-921; J. Chem. Soc. 4<*» 1120; Jsb. Chem. 1884, 1158;
Bull. Soc. chim. 43. 628.

Methyl-propyl-acetic Acid.

This acid, produced from methyl-propyl-acetoacetic ester which was
made from methyl-acetoacetic ester and normal propyl iodid is proven
to be identical with the acid of the same name produced from saccha-
rose.

PERKIN, Jr., W. H., 1884.

Ber. 17, 1440-1444 ; J. Chem. Soc. 46, 1154 ; Jsb. Chem. 1884, 1081 ;
Bull. Soc. chim. 44. 538.

Trimethylene Derivatives.

Aceto-methyl-tri-methylene-carboxylic ester,

CH3

CO

CHCH3 ,

| CH2
C02C2H5

60 BIBLIOGRAPHY OF

formed from acetoacetic ester and propylene bromid, boils at 210° tcf
215° From it were produced the free acid and aceto-methyl-trimethy-
lene.

PERKIN, Jr., W. H. and C. BERNHART, 1884.

Ber. 17* 1522-1527; J. Chem. Soc. 46, 1121.

Dehydracetic Acid.

Dehydracetic acid and hydroxylamin form dehydracetoxim, C7 H8 O3
CNOH ; dehydracetic acid and phenylhydrazin form dehydraceto
phenylhydrazin, Cs H8 O3 NNH Ce H5. Monobromdehydracetic acid
melting at 136°- 137° was obtained and if this be allowed to stand with
alcoholic potash it forms hydroxyl dehydracetic acid, CsH7O4OH,
which melts with decomposition at 250° to 255.° The silver salt, CsH6
O5 Ag2, was formed showing the acid to be dibasic. By careful treat-
ment of dehydracetic acid with cold potash an oil was obtained which
was thought to be acetoacetic acid.

RICHTER, V. v. AND H. MUNZER, 1884.

Ber. 17, 1926-1930; J. Chem. Soc. 46, 1342; Jsb. Chem. 1884, 1051 ;
Bull. Soc. chim. 44> 242.

Benzene-azo Ketone.

Benzene-azo-acetoacetic ester, CH3 COCH (N2 C6 H5) CO2 C2 H5,
formed from acetoacetic ester and diazobenzene chlorid melts at 75.°
When saponified no substituted acetic acid could be obtained, only the
benzene-azo acetone, CH3 CO CH2 N2 Ce H5, which melts at 148°- 149.°
In the same manner para-toluene-azo- acetoacetic ester and para-toluene-
azo-acetone were produced.

ACETO ACETIC ESTER 6 1

KNORR, L., 1884.

Ber. 17, 2032-2049 ; J. Chem. Soc. 46* 1377 ; Jsb. Chem. 1884, 877.
Constitution of Quinizin Derivatives.

Experiments were made which tend to prove the constitution of these
bodies. They probably come from the hypothetical base quinizin,
which is : —

CH — NH
/ \ N |
HC C / \ CH

I I I

HC C CH2

\ / \ /
C C
H H2

Many of the derivatives were described, among them antipyrin, which
is dimethyloxyquinizin,

CH — NCH3
/ \ N |
f HC C / \ CCH3 ,

I I I

HC C CO

\ / \ /

C C

H H2

and some of its derivatives.

KNORR, L. and A. BLANK, 1884.

Ber. 17* 2049-2052 ; J. Chem. Soc. 46, 1380.
Action of Substituted Acetoacetic Esters on Phenylhydrazin.

Methyl-acetoacetic ester and phenylhydrazin form 2' : 3' dimethyl-
oxyquinizin,

H

C -NH

/ \ N |
HC C/ x CCH3,

I I I

HC C CHCH3

\ / \ /
C C
H O

62 BIBLIOGRAPHY OF

which melts at 127° to 132° It is isomeric with antipyrin. Ethyl-
acetoacetic ester and phenylhydrazin form 2' : 3' methyl- ethyl-
oxyquinizin which melts at 108.°

PINNER, A., 1884.

Ber. 17, 2519-2520; J. Chem. Soc. 48, 158; Jsb. Chem. 1884, 596.
Action of Acetoacetic Ester on A mid ins. Part I.

When an amidin of the formula R — C ~ ^ , acts on acetoacetic

ester a compound of the formula

R
C

/ ^

N N

II I
CH3 C CO ,

\ /
C
H2

is formed and this compound is changed by phosphorus pentachlorid
into the nucleus

HC

/^

N N

II I
HC CH

\ //
C
H

Benzamidin gives a compound, CITHION2O, which melts at 215.5°-
216° and gives a platinic chlorid salt. Treated with phosphorus
pentachlorid it gives Cu H9 N2 Cl , which is probably

C6H5-C

/ \\

N N

II I
CH3 C CC1

\ //
C
H

Acetamidin gives C6 H8 N2 O , which the author is studying.

ACETO ACETIC ESTER 6}

PAAL, C., 1884.
Ber. 17, 2756-2767 ; J. Chem. Soc. 48, 248.

Derivatives of Acetophenonacetoacetic Ester and Acetonylaceto-

acetic Ester.

One of the two isomeric compounds CIT Hi0O, obtained by dehydrat-
ing acetophenon-acetone is named dehydraceto-phenon-acetone
and given one of the three formulae : C6 H5C i C CH2 CO CH3 ;
C6 H5 COCH2 C ; CCH3 ; C6 H5 COCH2 CH2 C \ CH ; and the other

CH : C ( CH3)

compound is named phenyl-methyl-furfurane ,l > O .

CH:C(C6H5)

Acetophenon-acetoacetic ester yields analogous dehydrated derivatives.

CH3 COCHC02 C2 H5 ,

Acetonyl-acetoacetic ester, when treated with

CH2 COCH3

hydrochloric acid becomes pyrotritartaric ester,

HC — CC02 C2 H5

II II
CH3 C CCH3

\ /
O

A number of other derivatives of the above compounds are described,
and their constitution indicated.

BEHREND, ROBERT, 1884.

Ber. 17, 2846-2847 ; J. Chem. Soc. 48, 246.

Derivatives of Carbamid.

The author is investigating the products of the action of carbamid
on acetoacetic ester. From the first compound formed C5 Hg N2 O3, are
obtained C5 H6 N2 O2 ; C5 H3 N3 O6 ; C4 H3 N3 O4 and C5 H6 N4 O3.

64 BIBLIOGRAPHY OF

PERKIN, Jr., W. H., 1885.

Ber. 18, 218-220; J. Chem. Soc. 48, 515.

Dehydracetic Acid.

The subject of the constitution of dehydracetic acid is reviewed and
the formula CO2 HC<£° ^H)Q >CCH3, is advanced. The methyl

ester melts at 90.5°, is soluble in water and the solution is decidedly
acid. From the methyl ester and sodethoxid the compound Cg H6 Na
CH3 O4 is formed.

JUST, FEODOR, 1885.
Ber. 18, 319-320 ; J. Chem. Soc. 48, 513 ; Ber. 19, 45 (C).

New Method of Introducing Nitrogenous Radicals in Malonic and

Acetoacetic Esters.

This is by the action of imido-chlorids, — benzanilidimido-chlorid, C&
H5 C1=N — CsHj, for instance. The chlorin is eliminated and the
remaining monad radical is substituted. The author is working in this
line.

ALLEN, WM.-AND ALFRED KOLLIKER, 1885.

Ann. Chem. 227, 107-118; J. Chem. Soc. 48, 655 ; Ber. 18, 154 (C) ;
Jsb. Chem. 1885, 768.

Some derivatives of Triphenyl=carbinyl-bromid.

When sodacetoacetic ester is treated with triphenyl-carbinyl-bromid,
C Br (C6H5)3, there is produced triphenyl-carbinyl-acetoacetic ester,
CH3 CO C[C(C6 H5)3]2 CO2 C2 H5, a substance which melts at 159.5° to

ACETO ACETIC ESTER 65

160.5.° When saponified, this yields triphenyl-carbinyl ethel ether,
C2H5OC(C6H5)3, melting at 83°, which, treated with acetyl chlorid,
gives CH3CO2 C(C6H5)3. Triphenyl-carbinyl-acetoacetic ester when
distilled yields triphenyl methane, CH (Ce H5)3, which melts at 92° and
boils at 358° to 360.°

GEUTHER, A,, 1885.

Ann. Chem. 227, 383-384.

Upon the History of Acetyl-acetoacetic Esters.

After noticing the claims made by James and by Hlion to the first
production of these esters, the author calls attention to the fact that
Lippmann produced mono- and di- acetyl-acetoacetic esters in 1869
(Ztschr. Chem. 1869, 28).

HAITINGER, L., 1885.

Ber. 18, 452-453; J. Chem. Soc. 48, 761.

Dehydracetic Acid.

Dehydracetic acid when treated with aqueous ammonia gives
Cs H9 NO3 and C7 H9 NO. The former is an acid which, when heated,
gives the latter, which is a weak base. When C7 H9 NO is distilled
with zinc dust lutidin, C7 H9 N , boiling at 147° to 151° is obtained.
Some analogous reactions of dehydracetic acid and chelidonic acid are

given. Chelidonic is ; C (CO2 H) < ° ~_^ ^°2 H) > CH and dehy-

dracetic acid is ; C (CH3) < — > CC°2>H •

66 BIBLIOGRAPHY OF

BEHREND, ROBERT, 1885.

Ann. Chem. 229, 5-31 ; Ber. 18, 543 (C) ; Jsb. Chem. 1885, 654.
Bull. Soc. chim. 46, 360.

Action of Urea on Acetoacetic Ester.

NH — C — CH,
I ii

By this action /9 Uramidocrotonic ester, CO CH , is formed.

NH2 CO2 C2 H5

NH — C — CH3

! il

From this was formed methyluracyl, CO CH , which decom-

I I

NH — CO

poses at 270°— 280° without melting. From this, trimethyluracyl,
C7HION2O2, melting point 103°; and nitrouracyl carboxylic acid,
C5H3N3O6 , were formed, and from the latter, nitrouracyl, C4H3N3O4 ;
amidouracyl, C4 H5 N3 O2 ; and oxyuracyl, C4 H4 N2 O3 . Amidouracyl
salts give with potassium cyanate, hydroxyxanthin, C5 H6 N4 O3 +
^H2 O, which may be oxidized to alloxan and this reduced to allox-
antin.

KUCKERT, OTTO, 1885.

Ber. 18, 618-620 ; J. Chem. Soc. 48, 751 ; Jsb. 1885, 1351 ; Bull Soc.

chim. 46, 8.

Action of Alkylamins on Acetoacetic Esters.

Acetoacetic ester when treated with methylamin • forms two com-
pounds according to the temperature. If kept at o° an addition pro-
duct is formed which melts at 42°-43° and easily changes into an oil,
the same as the product which is formed if the temperature is not kept

CH3 CH3

low. This is either C = N — CH3 or C— NHCH3. Diethylamin

I il

CH2 CH

C02 C2 H5 C02 C2 H5

ACETO ACETIC ESTER 67

CH3

produces the compound of the formula C — N (C2 H5)2 . The methyl-

CH
C02C2H5

amin product when treated with paraldehyde and sulfuric acid forms
a condensation product CI5 H23 NO4 , resembling dihydro-collidin
dicarboxylic ester.

HALLER, S., 1885.

Ber. 18, 706-709 ; J. Chem. Soc. 48, 818 ; Jsb. Chem. 1885, 1082.
Trimethyl-quinizin Derivatives.

The following derivatives of acetoacetic ester were described : —
pseudo-cumylizinacetoacetic ester, Ci5H22O2N2, which melts at 77°-
78° and has the constitution :—

CH3

C N— NH

/x / \ I

HC C CCH3 ;

I I I

CH3C CH CH2

\ / \ /
C C02 C2 H5

CH3

tetramethyl-oxyquinizin, C9 NH3 (CH3)4 ONH, [(CH3)4 = 1:3:4:2'];*
pentamethyl-oxyquinizin (pseudo-cumylantipyrine) C9NH3 (CH3) 4
ONCH3 , [(CH3)3 : NCH3 : CH3 : O = i : 3 : 4 : i' : 2' : 4' *] and isoni-
trosotetramethyl oxyquinizin, Cr2 HI5 O2 N3 .

i i'

*A A ,

__ r\/ O O

*The carbon atoms were numbered thus : —

3C C C3

\ / \ /

C C

4 4'

68 BIBLIOGRAPHY OF

PINNER, A., 1885.

Ber. 18, 759-763; J. Chem. Soc. 48» 751; Jsb. Chem. 1885, 838;
Bull. Soc. chim. 45. 778.

Action of Acetoacetic Ester on Amidins. Part II. — Pyrimidins.

The formula

R — C

/ \\

N N

CH3-C C-OH ,

\ //
C
H

is substituted for that previously assigned to these bodies and the
nucleus C4 H4 N2 is termed pyrimidin. Phenyl-methyl-hydroxy-pyri-
midin is further described.

GRIESS, PETER, 1885.
Ber. 18, 960-966 ; J. Chem. Soc. 48, 788.
New Researches upon Diazo Compounds.

In this article (p. 962) azo-acetoacetic-benzoic acid,

CH3

p w . C02 H CO
<-6±i4 <* N=N-CH '

C02H

is described. It is produced by treating acetoacetic ester with sulfuric

CO "H"

acid and meta diazo-benzoic acid sulphate, C6 H4 < iTT_-£r or>. TT

-W — JN — oO,« ri .

ACETO ACETIC ESTER 69

SCHILLER-WECHSLER, MAX, 1885.

Ber. 18, 1037-1052 ; J. Chem. Soc. 48, 900.

Anilido-pyrotartaric Acid.

In this article mention is made of cyanhydrin of acetoacetic ester or
^-cyan-^-oxybutyric ester, CH3 C (CN)(OH)-CH2 CO2C2 H5 , which
was produced by treating acetoacetic ester with hydrocyanic acid. It
is very unstable, from it was prepared /?-cyan-/3-anilido-butyric ester,
CH3 C (CN) — (NHC6 H5) CH2 CO2 C2 H5 , by the action of anilin.

HANTZSCH, A., 1885.

Ber. 18, 1744-1749; J. Chem. Soc. 48, 1078; Jsb. Chem. 1885, 815;
Bull. Soc. chim. 46, 166.

Constitution of Synthetical Pyridin Derivatives

After discussing the reactions of these bodies the author decides
that the tri-methyl-pyridin-dicarboxylic acid obtained from ammonia,
aldehyde and acetoacetic ester has the formula :

CH3
C

/ \\

C02HC C — C02H

CH3— C C — CH3

\ //

N

MICHAEL, R., 1885.
Ber. 18, 2020-2029; J. Chem. Soc. 48, 1244; Jsb. Chem. 1885, 826.

Synthesis of Pyridin Derivatives from Acetoacetic Ester,
Aldehyde and Ammonia.

By using an excess of aldehyde a product different from the usual
one is formed which is a — 7--lutidin-/9-carboxylic ester, C5 NH2 (CH3)2

70 BIBLIOGRAPHY OF

CO2 C2 H5 . It is an oil which boils at 246° to 247° and from it, its
acid can be formed, the calcium salt of which, when distilled from lime,
yields 2:4, lutidin. The free acid C5 NH2 (CH3)2 CO2 H , can be
oxidized to carbocinchomeronic acid, C5 NH2 (CO2 H)3 [2 : 3 : 4] ,
which yields cinchomeronic acid, C5 NH3 (CO2 H)2 [2:3].

BUCHKA, K., 1885.

Ber. 18, 2090-2093; J. Chem. Soc. 48, 1200; Jsb. Chem. 1885, 1351.
Action of Sulfur Chlorid on Sodacetoacetic Ester.

The sulfid of acetoacetic ester (CH3 COCHCO2 C2 H5)2 S , is produced
by this action. It melts at 80° to 81° The reduction or condensation
of this was impossible because of its unstability. Carbonyl chlorid
acts on sodacetoacetic ester to form chloracetoacetic ester.

FITTIG, R., 1885.

Ber. 18, 2526-2527 ; J. Chem. Soc. 50, 47.
Condensation of Acetoacetic Ester with Dibasic Acids.

Acetoacetic ester condenses with succinic acid to form a compound
CIQ HI2 O5 , which melts at 75° -76° and which is a mono-ethyl salt of
a dibasic acid, Cg H8 O5 . This acid melts at 199° to 200.° With
sodium pyrotartrate, acetoacetic ester gives the mono-ethyl ester of the
acid C9 HIO O5 . Further investigations are being made in this line.

HANTZSCH, A., 1885.

Ber. 18, 2579-2586 ; J. Chem. Soc. 50, 77 ; Jsb. Chem. 1885, 830.
Constitution of the Synthetical Hydro-pyridin Derivatives.

The hydrogen in these compounds has been assumed to be in con-
nection with carbon but as Kukart has obtained a substituted hydro-
pyridin derivative by the action of paraldehyde and sulfuric acid on the

ACETO ACETIC ESTER 71

product of reaction between methyl-amin and acetoacetic ester, it
follows that nitrogen must be present as an imido group which gives
for the nucleus formula :

H
C

/ \
C C
I I
C C

\ /

N
H

Benzylidin-diacetoacetic ester, C6H5 CH (C6H9O3)2 , melting at 152°-
153° and dehydrobenzylidin diacetoacetic ester,

C • CH3 : C • CO2 C2 H5

o 3 2

^ CCH3 : C • CO2 C2 H5

melting at 87°-88° were formed from acetoacetic ester and benzal-
dehyde but the presence of some primary amin is necessary.

JAKSCH, R. v., 1885.

Ber. 19, 781 (C).
Acetonurea and Diaceturea.

The author states that acetoacetic acid is not found in normal urine
and as an explanation of its origin in diseased urine he supposes that
it came from acetone by the taking up of oxygen, uniting with formic
acid and then splitting off water.

PERKIN, Jr., W. H., 1885.

J. Chem. Soc. 47. 801-855.

Synthetical Formation of Closed Carbon Chains.

On pages 834-835 of this long article, the author shows the many
differences in behavior between acetyl tri-methylene carboxylic ester,

72 BIBLIOGRAPHY OF

CH3 CO c

- -

and di-methyl-acetoacetic ester,

3 .

CH3CO c CH

C02C2H5^ <CH3

although they only differ in composition by two hydrogen atoms.

PINNER, A., 1885.

Ber. 18, 2845-2852 ; J. Chem. Soc. 50, 45 ; Jsb. Chem. 1885, 840;
Bull. Soc. chim. 45, 852.

Action of Acetoacetic Ester on Amidins. Part III, — Pyrimidins.

With the exception of formamidin all the amidins experimented with
form pyrimidins ; formamidin yields cyanacetoacetic ester. Aceta-
midin yields di-methyl-hydroxy-pyrimidin, propionamidin yields ethyl-
methyl-hydroxy-pyrimidin, .

C2H5C

/ ^

N N

CH3 C COH

\ /
C
H

Phenyl-methyl-hydroxy-pyrimidin, CnH^NsO ; phenyl-methyl-pyri-
midin, CnHION2 ; phenyl-methyl-ethoxy-pyrimidin, CnH9(OC2H5)N2 ;
and phenyl-methyl-pyrimidin anilid, CuH9N2NHC6H5 were described.

ACETO ACETIC ESTER 73

EPSTEIN, W., 1885.

Ann. Chem. 231, 1-36 ; J. Chem. Soc 5<>» 257 ; Ber. 19, 18 (C) ;
Bull. Soc. chim. 46, 435.

Condensation of Cinnamaldehyde with Ammonia and Acetoacetic

Ester.

These substances condense to form benzylidenedihydrocollidin-dicar-
boxylic ester which melts at 148° to 149° and which can be oxidized
to benzylidene-collidin-dicarboxylic acid,

CH : CHC6 H5

C,
/\
C02 HC CC02 H + 2H2 O ,

CH3 C CCH3

\ /

N

which melts at 218° to 219° When anhydrous it melts at 241.° The
potassium salt may be oxidized by potassium permanganate to lutidin-
tricarboxylic acid which is different from the one described by Hantzsch
in Ber. 15, 2915 and 17, 2908. By reduction it gives lutidin which is
#-a'-dimethylpyridine, an isomer of Hantzsch' s lutidin.

ENGELMANN, FRANZ, 1885,

Ann. Chem. 231, 37-71 ; Ber. 19. 16 (C) ; J. Chem. Soc. 50, 258 ; Jsb.
Chem. 1885, J357 1 Bull. Soc. chim. 46, 437.

Action of Homologues of Acetaldehyde on Ammonia and
Acetoacetic Ester.

Hydroparvolin-dicarboxylic ester, C5NH2(CH3)2 C2H5 (CO2C2H5)2 ,
is formed from acetoacetic ester, propaldehyde and alcoholic ammonia,
it melts at 110° By oxidation it loses its two hydrogen atoms and
then by saponification parvolin-dicarboxylic acid, C5 N (CH3)2C2 H5
(CO2H)2, is formed which melts at 289° to 290.° Parvolin, C5 NH2
(CH3)2C2H5, boils at 186° and has a specific gravity of .916
at 14 Hydroisopropyl-lutidindicarboxylic ester, C5 NH2 (CH3 )2 C3 H7
(CO2 C2 H5)2 , obtained by using isobutylaldehyde melts at 97 From

74 BIBLIOGRAPHY OF

it were obtained lutidin-dicarboxylic ester and acid. Hydroisobutyl-
lutidindicarboxylic ester, C5 N (CH3)2 C4 H9 H2 (CO2 C2 H5)2 , obtained
by using valeraldehyde melts at ioo.° The mono-ethyl salt and free
acid of isobutyl-lutidin dicarboxylic were obtained and also isobutyl-
lutidin, C5 N (CH3)2 H2 C4 H9 , a liquid boiling at 210° to 213.°

FITTIQ, R., 1885.

Ber. 18, 3410-3413 ; J. Chem. Soc. 50, 225.
Constitution of Carbopyrotritartaric Acid.

The product of the action of acetoacetic ester and succinic acid,
Cg Hg O5 , which is isomeric with Carbopyrotritartaric acid is called
methronic acid and the two acids are given the following formulse :
Carbopyrotritartaric acid :

CH3 — C — C— HC02H

II I

H— C CHC02 H
\ /
C

Methronic acid :

CH3 — C— C— HC02H

II I

CO2H — C CH2
\ /
C

When heated they both give carbon dioxid and pyrotritartaric acid

CH3 — C— CHCO2H,

II I

H — C CH2
\ /
C
II

o

ACETO ACETIC ESTER 75

BAEYER, ADOLF, 1885.

Ber. 18, 3454-3460 ; J. Chem. Soc. 50, 223 ; Jsb. Chetn. 1885, 1346 ;
Bull. Soc. chim. 46, 440.

Synthesis of Acetoacetic Ester and Phloroglucin.

The author discusses the constitution of sodacetoacetic ester, siding
with Frankland and Duppa and Wislicenus against Geuther, showing
the inconsistancies of the formula CH3 CO Na : CH CO2 C2 H5 and
inclining to Frankland and Duppa' s view that sodacetic ester is
formed as an intermediate product in the action of sodium on
acetic ester. Phloroglucin is prepared by treating the product of the
action of sodium on malonic ester with caustic potash, and the formula

CO < > CH2 is suggested for it.

CONRAD, M. AND M. GUTHZEIT, 1886.

Ber. 19, 19-26 ; J. Chem. Soc. 50, 333 ; Jsb. Chem. 1886, 1331.

Action of Carbonyl Chlorid on Cupracetoacetic Ester.

Dehydro-diacetyl-acetone-dicarboxylic ester is thus produced. It is
a crystalline substance melting at 79°-8o°, and it has the following
structural formula :

O

/ \
CH3 C C CH3

II II

C02C2H5C CC02C2H5

\ /

C

O

Acted upon by ammonia this compound gives lutidone-dicarboxylic
ester melting at 221°; by simply substituting NH for the oxygen of
the ring. Trimethyl-pyridone-dicarboxylic ester melting at 193° and
phenyl-dimethyl-pyridone-dicarboxylic ester melting at 170°-! 71°
were prepared from the dehydro-compound.

76 BIBLIOGRAPHY OF

JAMES, J. WM., 1886.

J. Chem. Soc. 49> 50-58 ; Ann. Chem. 231, 235-244.
Action of Phosphorus Pentachlorid on Diethyl=acetoacetic Ester.

By this action diethyl-monochlor-acetoacetic ester, CH2 Cl — COC
(C2 H5)2 CO2 C2 H5 , and the corresponding dichlor derivative were
formed. Diethyl-monochlor-acetoacetic ester treated with sodium
methoxid gave methoxy-diethyl-acetoacetic ester, CH2 (CH3 O) COC
(C2 H5)2 CO2 C2 H5 , and methoxy-methyl-ethyl acetone, CH2 (CH3 O)
COCH (CH3) (C2 H5). Di-methoxy-diethyl-acetoacetic ester, CH
(CH3O)2COC(C2H5)2CO2C2H5, and di-methoxy-diethyl acetone,
CH (CH3 O)2 COCH (C2 H5)2 , were also prepared.

JAMES, J. WM., 1886.

Ann. Chem. 231, 245-248 ; J. Chem. Soc. 50, 333 ; Ber. 19, 101 (C) ;
Bull. Soc. chim. 46, 758.

Synthesis of Acetoacetic Ester from Cyanacetone.

The author has repeated the experiment of Matthew * and Hodgkin-
son's and failed to produce any trace of a'cetoacetic ester from
cyanacetone with hydrochloric acid or an alkali.

SOC. FOR CHEM. INDUSTRY IN BASEL, 1886.
D. P.f 39,564 of May 4th, 1886, Kl. 22 ; Ber. 20, 443 (C).

Production of Quinizins by the Action of Hydrazobenzenes on

Acetoacetic Esters.

Acetoacetic ester treated with hydrazobenzene gives phenyl-methyl-
oxyquinizin which melts at 122?

*See page 38.

f Original article not consulted.

ACETO ACETIC ESTER 77

SCHIFF, ROBERT, 1886.

Ber. I9» 561.
Some Molecular Volumes. — Acetoacetic Ester.

B. P. = 180-1803. 60=754.5 mm. Dj = specific gravity at t°
compared to water at 4° — = molecular volume.

D° =1.0465

D48 =1.0375
Df'8 =0.9880

DJ»- 2 = 0.9644

D'35-5 _ 0.9029

Vt = i.-h .ooi093oit -f .000001 38951* -f .0000000 i465t3, from which
Df = 0.8458, ^=153.34.

PERKIN, Jr., W. H., 1886.

Ber. 19* 1244-1247 ; J. Chem. Soc. 5°» 689 ; Jsb. Chem. 1886, 1332 ;
Bull. Soc. chim. 46, 834.

Action of Trimethylen-bromid on Sodacetoacetic Ester.

An oil C9 HI4O3 , boiling at 223° is obtained which cannot be an
aceto-tetramethylen carboxylic ester because its properties when com-
pared to the acetotrimethylen carboxylic ester and to the tetramethylen
dicarboxylic ester are too irregular and because it will not react with
phenylhydrazin. The author gives it the formula —

CH3

C— O— CH2

II

C — CH2-CH2

C02 C2 H5

78 BIBLIOGRAPHY OF

BEHREND, ROBERT, R. LIST AND A. KOHLER, 1886.

Ann. Chem. 233, 1-15 ; Ber. 19* 219-221 ; Ber. 19. 395 (C) ; J. Chem.
Soc. 50, 443 ; Jsb. Chem. 1886, 549 ; Bull. Soc. chim. 46, 544.

Condensation of Carbarn ids with Acetoacetic Ester.

Acetoacetic ester treated with phenylcarbamid gives a compound

Ci3 Hl6 N2 O3 , which when treated with an alkali yields acetone,

alcohol, carbon dioxid and analin and when treated with an acid it

yields in addition to these products ethyl phenylcarbamate, C9 HU NO2.

Thiocarbamid and acetoacetic ester unite to form an unstable

compound which, when saponified, yields C5 H6 N2 SO which is

pq" NH —

^

Guanidin, CN3 H5 , and acetoacetic ester form a compound C5 H7
N3 O, which has both acid and basic properties. Its formula probably is

NH_C<NH-C(CH3)VCH

~ u < NH — CO ^---

ISBERT, A., 1886.

Ann. Chem. 234, 160-196 ; J. Chem. Soc. 50, 1009 ; Ber. 19, 684 (C) ;
Jsb. Chem. 1886, 1328 ; Bull. Soc. chim. 47, 585.

Acetoacetic Ester and Its Derivatives.

When acetoacetic ester is decomposed by sodium alkyl oxids in the
presence of an alcohol, the acetate derived from the free alcohol is the
chief product, while the acetate derived from the alkyl oxid is formed
in smaller proportions. Resacetic acid, ds H22 O5 , is formed during
the same operation. Acetoacetic ester is not decomposed by ethyl or
propyl alcohol at 180°, but is completely decomposed upon adding a
little sodium alkyl oxid to such a mixture. The amid, C6 H0 NO2 ,
obtained by treating acetoacetic ester with ammonia, melts at 90° and
is soluble in water. From its reactions the formula CH3 • CO C2 H5 :.
CH • CO NH2 , is assigned to it. Phosphoric chlorid acting on ethyl
acetoacetic ester gives ethyl-monochlorcrotonic acid and the ethyl
esters of mono- and di-chlor-ethylacetoacetic acids, arid acting on
methylacetoacetic ester it forms the corresponding compounds.
Ethoxy-ethyl-acetoacetic ester, (C2 H5 O)CH2 COC2 H5 : CH CO2C2 H5 ,
and ethoxy-methyl-acetoacetic ester are formed by the action of an

ACETO ACETIC ESTER 79

alcoholic solution of sodium ethoxid on monochlor-ethyl and mono-
chlor methyl-acetoacetic esters and are decomposed by alcoholic soda
into ethoxy-ethyl acetone, (C2 H5 O) CH2 CO CH2 (C2 H5), and ethoxy-
methyl acetone, (C2 H5 O) CH2 CO CH2 (C H3), which boil at 112° to
115° and 100° to 105° respectively.

SOC. FOR CHEM. INDUSTRY IN BASEL, 1886.

D. P.* 39,149 of June 5th, 1886, Kl. 12 ; Ber. 20, 351 (C).

The Production of the Ester of a New Acid.

If acetoacetic ester be treated with a water solution of ethylenedi-
amin, C2 H4 (NH2)2 , they unite to form the compound,
CH3 CH3

C : N- CH2- CH2- N : C
I I

CH2 CH2

C02 C2 H5 C02 C2 H5

which melts at 126°, is insoluble in water but soluble in alcohols,
ether, chloroform, benzene and dilute acids.

CANZONERI, F. AND G. SPICA, 1886.

Gazz.* chim. 16, 449-453 ; Ber. 20, 219 (C) ; J. Chem. Soc. 52, 499.
Synthesis of Ethoxy-lutidin.

By treating acetoacetic ester in a sealed tube with an excess of
ammoniacal zinc chlorid, ethoxy-lutidin,

N

/ \
CH3C COC2H5 ,

HC CH

\ /

C

CH3

^Original article not consulted.

80 BIBLIOGRAPHY OF

is formed, a pale yellow liquid boiling at 245° to 247° By repeating
former experiments with acetoacetic ester and formamid, a liquid boil-
ing at 250° to 255° was obtained which was mono-lutidin-carboxylic
ester and which apparently is isomeric with Michael's body of the same
name which he obtained from aldehyde, aldehyde ammonia and
acetoacetic ester.

MULLER, ALBERT, 1886.

Ber. 19, 1771-1772 ; J. Chem. Soc. 50, 899; Jsb. Chem. 1886, 1035.
Action of Acetoacetic Ester on Hydrazo-benzene.

When acetoacetic ester is treated with hydrazo-benzene, C& H5
NH — NHC6 H5 , a compound Cl6 HI4 N2 O. which melts at 120° and
is weakly basic and acid is formed. It is probably a phenylated
quinizin,

H

C N-NC6H5

• / \ / \ I

HC C CCH3 ,

I I I

HC C CH

\ / \ /
C C
H OH

ESCALES, R. AND E. BAUMANN, 1886.
Ber. 19, 1787-1796; J. Chem. Soc. 50, 878.

Compounds of Phenyl Mercaptan with Ketonic Acids.
Phenyl Mercaptan and Acetoacetic Ester.

By treating a mixture of two molecules phenyl mercaptan and one
molecule acetoacetic ester with hydrochloric acid, /3 dithiophenylbutyric
ester, CH3 C (SC6 H5)2 CH2 CO2 C2 H5, is obtained; it melts at 57°-58°,

ACETO ACETIC ESTER 8 1

is insoluble in water, soluble in ether, benzene and chloroform and
gives a red color with concentrated sulfuric acid. When heated with
an alkali it is decomposed into phenyl mercaptan and /9-thio-phenyl-
crotonic acid, CH3(SC6H5) : CHCO2H, which melts at i76°-i77°,
is insoluble in water, soluble in benzene and hot alcohol. When
heated this decomposes, giving thio-phenyl-propylene, C3 H5 SCe H5 ,
which boils at 2o6°-2io° and gives a blue color with sulfuric acid,
which turns violet upon being heated.

LIST, R., 1886.

Ann. Chem. 236, 1-32 ; J. Chem. Soc. 52, 127 ; Ber. 19, 825 (C) ;
Jsb. Chem. 1886, 564 ; Bull. Soc. chim. 47» 587.

Action of Thiocarbamid on Acetoacetic Ester.

Thiomethyl-uracyl is formed, thus : CH3COCH2 CO2 C2 H5 + NH2
CSNH2 = CH3 C (OH) CH2 CO2 C2 H5

NH — C = S — NH2 and then water and alcohol
breaking off it leaves CH3 C : CHC : O

I *s

NH— C=S— N— H.

The silver, copper, mercury, potassium, and sodium salts and the
methyl and ethyl esters were produced and described. The sulfur can
be removed from the thiomethyl-uracyl by bromin or by silver or
mercuric oxid. Thiomethyl-uracyl acetic acid, C7 H8 N2 SO3 , and its
ethyl ester were made by using monochlor-acetic ester.

In the formation of the esters an intermolecular change is supposed

to take place and the formulae are written CH3 — C : CH • C : O

I I

N : C - N • H

S— R.

82 BIBLIOGRAPHY OF

KNORR, L., 1886.

Ann. Chem. 236, 69-115 ; J. Chem. Soc. 52, 159; Ber. 19, 827 (C) ;
Jsb. Chem. 1886, 1336 ; Bull. Soc. chim. 47, 633.

Synthetical Experiments with Acetoacetic Ester. — Part I.

Acetoacetic ester and anilin react at ordinary temperatures to form
/?-phenylamido-tt-crotonic ester, but at iio°-i5o° the anilid of aceto-
acetic acid is formed, which melts at 85° and gives, when distilled,

diphenyl-carbamid, CO<NHCH' which melts at 235°~236°
anilid, when heated with chloroform and bromin, yields the anilid of
monobrom-acetoacetic acid, CH3 CO CH Br CO NHC6 H5 , which melts
with decomposition at 138.° Isonitroso-acetoacetic anilid, CH3 CO C :
(NOH) CONHCeH5 , is a crystalline substance melting at 99°-ioo.°
Reducing agents change acetoacetic acid anilid into hydroxylepidin,
C9 NH5 CH3 OH, [4' : 2'] which can be changed into ^-lepidin and
chlorolepidin. Methoxy-lepidin formed from chlorolepidin boils at
275°— 276.° Bthoxy-lepidin melts at 51 Methyl-lepidone,

P TT ^ CCH3 : CH^
^4 <• NCH3CO ^'

may be formed from methyl anilin and acetoacetic ester. It melts at
130°, sublimes and is a strong base.

DEQEN, JOS., 1886.

Ann. Chem. 236, 151-164; Ber. 19, 829 (C).
Indol from Methyl-phenylhydrazin.

In this article an account is given of making methyl-phenylhydrazin
acetoacetic ester, CH3 C : (N2 CH3 C6 H5) CH2CO2C2H5 , from methyl-
phenylhydrazin and acetoacetic ester. The product, a yellowish red
oil could not be distilled, but seemed quite stable towards water
solutions of the alkalis. With alcoholic potash it was decomposed
into methyl-phenylhydrazin acetoacetic acid.

ACETO ACETIC ESTER 8}

BULOW, CARL, 1886.

Ann. Chem. 236, 184-194 ; J. Chem. Soc. 52, 144 ; Jsb. Chem.
1886, 1515 ; Bull. Soc. chim. 47, 600.

Phthalyl-acetoacetic Ester.

This is obtained from phthalyl chlorid and acetoacetic ester and is
represented thus :

CH3

CO

C=C— C6H4

I I I

o— c = o

C02 C2 H5

It is decomposed by sulfuric acid yielding phthalyl acetic acid.
Ammonia converts it into phthalyldiamid or phthalyl-imid according to
the temperature. Several complicated derivatives were described,
among them those formed by phenylhydrazin.

KNORR, L., 1886.

Ann Chem. 236, 290-332 ; J. Chem. Soc. 52» 275 ; Ber. 20, 55 (C) ;
Jsb. Chem. 1886, 1338 ; Bull. Soc. chim. 47» 811.

Synthetical Experiments with Acetoacetic Ester. — Part II.

The first part of this article (pp. 290-317) is devoted to diaceto
succinic esters, the remainder to forming pyrrol derivatives from aceto-
acetic ester. This treated with sodium nitrite forms nitrosoacetoacetic
ester which mixed with acetoacetic ester and reduced, gives dimethyl-
pyrrol-di-carboxylic ester, C4 NH (C H3)2 (CO2 C2 H5)2 [2:4:3:5]. This
melts at 134°-! 35° and can be distinguished from its symmetrical
isomer by its absence of basic properties. By eliminating one of the
ethyl groups two isomeric mono-ethyl esters of dimethyl-pyrrol-dicar-
boxylic acid can be produced and from these (i) by eliminating
ethyl, dimethyl-pyrrol-dicarboxylic acid (2) by eliminating carbon
dioxid, dimethyl-pyrrol-mono-carboxylic ester. Dimethyl-pyrrol-
mono-carboxylic acid and dimethyl-pyrrol, C4N(CH3)2H3, were also
produced. By using the anilid of acetoacetic ester corresponding
compounds were made and their properties described.

84 BIBLIOGRAPHY OF

PERKIN, Jr., W. H. AND M. OBREMBSKY, 1886.

Ber. 19, 2045-2055 ; J. Chem. Soc. 5°» 936 ; Jsb. Chem. 1886, 1397.
Upon ^-oLj-Diacetyl-adipic Acid.

From the high-boiling residue from the action of ethylene bromid on
sodacetoacetic ester the authors have isolated di-acetyl-adipic ester,

CH2 — CH(CH3 CO)CO2 C2 H5

which is I .It will unite with phenyl-

CH2 — CH(CH3 CO)CO2 C2 H5

hydrazin, one molecule of (C6H5N2H)" displacing each atom of oxygen
of the carbonyl groups. Ethylene-di-methyl-oxyquinizin is also
formed. The actions of diacetyl-adipic ester with alcoholic ammonia,
sulfuric acid and alcoholic potash are given.

POLONOWSKA, NATALIE, 1886.

Ber. 19, 2402-2406; J. Chem. Soc. 5°» ion ; Jsb. Chem. 1886, 1386.
So-called Carbacetoacetic Ester.

The action of hydrochloric acid on acetoacetic ester is the same as
that of sulfuric producing an anhydrid, dg H22 O9 , which breaks down
into isodehydracetic acid and its ethyl ester (as shown by Hantzsch)
so that Duisberg's so-called carbacetoacetic ester, Cg HIO O3 » must be
isodehydracetic ester, CIO HI2 O4 .

PERKIN, JR., W. H., 1886.

Ber. 19. 2557-2561 ; J. Chem. Soc. 52, 32 ; Jsb. Chem. 1886, 1332.
Action of Trimethylenbromid on Acetoacetic Ester.

The ester,

CH3

C — O CH2

C — CH2 — CH2 '
C02C2H5

ACETO ACETIC ESTER 85

and its acid are further studied. The acid heated with water gives
aceto-butyl alcohol and by distillation of this, acetobutyl alcohol
anhydrid is obtained. The ester dissolves in hydrobromic acid to form
brom-butyl methylketone, CH3CO(CH2)4 Br. Analogous compounds
of some aromatic derivatives are cited.

PERKIN, JR., W. H. AND P. C. FREER, 1886.

Ber. 19. 2561-2569 ; J. Chem. Soc. 52, 33.

Upon Aceto-trimethylenecarboxylic Ester.

This substance was proven by its physical properties to have a
trimethylene formula and thus to be :

CH3 CH3

CO CO

I CH2 I

C< L and not CH— CH=CH2

I ^Aia and not

C02C2H5 CO2C2H5 C02C2H5

It was united with hydrobromic acid to form omega-brom-ethyl-aceto-
acetic ester, CH3 COCH(CH2 CH2Br)CO2 C2 H5 , which is an oil
which cannot be distilled. Saponifying this oil, aceto-propyl alcohol is
obtained, (CH3 CO)CH2 CH2 CH2 OH, and sodium amalgam reduces
this to gamma-pentylene glycol, CH3 CHOHCH2 CH2 CH2 OH.

WITT, OTTO N., 1886.

Ber. 19. 2977-2978 and 3299 ; J. Chem. Soc. 52, 247 ; Jsb. Chem.
1886, 783 ; Bull Soc. chim. 47, 434.

Action of Acetoacetic Ester on Aromatic Diamins.

Acetoacetic ester heated with ortho-toluylene-diamin Ce H3 CH3
(NH2)2 , gives ethenyl-toluylene-diamin, C6H3CH3 <^^C — CH3 ,

which melts at 2oi°-2O2.°

In the second communication the author acknowledges the priority
of L,adenburg and Riigheimer in the preparation of this compound.

86 BIBLIOGRAPHY OF

KNORR, L., 1886.

Ann. Chem. 238, 137-219; J. Chem. Soc. 52, 601 ; Ber. 20, 259 (C).

Synthetical Experiments with Acetoacetic Ester. — Part III.

The compounds obtained from the action of phenylhydrazin on
acetoacetic ester, heretofore described by the author as quinizin deriva-
tives are now considered pyrazolone derivatives, pyrazolone being

CH2- CO

I > NH. Thus antipyrin is phenyl-dimethyl pyrazolone

C — H = N

[1:2:3] and not di-methyl oxyquinizin Phenylmethyl pyrazolone is
described. Phenyltrimethyl pyrazolone [1:3:4:4] obtained from di-
methyl-acetoacetic ester melts at 55°-56° boils at 300° to 303° and is
isomeric with methyl antipyrin. Disphenyl-methyl pyrazolone, [1:3:5]

CO — CH — CH — CO
C6H5N< I I >NC6H5, and a number of its

I I

CH3 CH3

derivatives are produced and described, among which is pyrazol blue,
obtained from the above by abstracting the two hydrogen atoms from
the CH groups. Some of the aromatic and nitrogen compounds of
the pyrazolones are described and also some halogen compounds of
antipyrin.

CONRAD, M. and M. GUTHZEIT, 1887.

Ber. 20, 151-154; J. Chem. Soc. 52, 502; Jsb. Chem, 1887, 1818 ;
Bull. Soc. chim. 48, 154.

Dimethyl-pyrondicarboxylic Ester

This substance, obtained from cupracetoacetic ester and carbonyl
chlorid, formerly called dehydro-carbonyl-diacetoacetic ester is now
considered to be a derivative of pyron,

O

/ \
HC CH,

II II

HC CH

\ /

C

II

O

ACETO ACETIC ESTER 87

in which the methyl groups occupy the 2 and 6 places and the carboxyl
groups have the 3 and 5 places. It melts at 80 Alkalis decompose
it into carbon dioxid and acetoacetic ester which is further decomposed
to its usual decomposition products.

JAflES, J. WM., 1887,

J. Chem. Soc. 51, 287-290; Ann. Chem. 240, 61-66.
Formation of Cyan-acetoacetic Ester.

By trefting monochloracetoacetic ester with potassium cyanid,
potassium cyanacetoacetic ester was formed to which was given
the formula CH2 (CN)COCHKCO2 C2 H5 . Treating this with an
acid, produced cyanacetoacetic ester, a liquid which cannot be dis-
tilled under ordinary pressure. By treating dichloracetoacetic ester,
called by the author CHC12 COCH2 CO2 C2 H5 , with potassium cyanid
no corresponding compound was formed but potassium dichloracetate,
CHC12 CO2 K, was the chief product.

niCHAEL, A., 1887.

Am. Chem. J. 9. 112-124; J- prakt. Chem. 143. 349~357 ; J. Chem.
Soc. 52, 672 ; Ber. 20, 258 (C) and 504 (C) ; Jsb. Chem.

1887, 1542 ; Bull. Soc. chim. 48, 520.

Addition of Sodacetoacetic Ester and Sodomalonic Ester to the
Esters of Unsatu rated Acids.

When sodacetoacetic ester is treated with cinnamic ester they unite
directly and then split off sodium ethoxid forming a compound

CH3

CO C6H5

i i

CH-CH
i i

CO-CH

C02C2H5

which is very unstable decomposing at 100 It acts as a mono-basic
acid. Acetoacetic ester and citraconic ester, C5 H4 (C2 H5)2 O4, combine
directly to form Ci5H24O7an unstable oil boiling at 173°-! 74° at
26m. m. pressure. The author makes the point that these substances
are addition products.

BIBLIOGRAPHY OF

MICHAEL, A., 1887.

J. prakt. Chem. i43» 449-459; Am. Chem. J. 9, 124-129; J. Chem.
Soc. 52, 716 ; Ber. 20, 320 (C) ; Jsb. Chem. 1887, 1536 ;

Bull. Soc. chim 48, 521.
Some New Reactions with Sodacetoacetic Ester.

By the action of benzole aldehyde on sodacetoacetic ester a com-
pound C22H2oNa2O7 is formed which melts at 126°-! 27° and is solu-
ble in alkalis. Mustard oils react with sodacetoacetic ester to form
mono-thio-amids. Phenyl isocyanate forms two compounds with
sodacetoacetic ester. Anhydrids of dibasic organic acids unite directly
with sodacetoacetic ester : phthalic anhydrid forming

COCH

The action of phenols is to form coumarins. Ureas react to form the
ureids and sulfo-ureas form the corresponding sulfo derivatives.
Aldehyde ammonia forms condensation products, with sodacetoacetic
ester it forms Cg HI2 NaNO2 . Sodacetoaeetic ester was also found to
react with lactones, amidins, primary bases, guanidin, cyanamid,
cyanic acid and benzoquinone.

PERKIN, Jr., W. H., 1887.

J. Chem. Soc. 5'» 484-500 ; Jsb. Chem. 1887, 1815.

Dehydracetic Acid.

After reviewing the work done by other chemists on this acid the
author deduces the formula

CO2H— C — CO — CH

CH3C — O -CCH3

for it. The proof that it contains carbonyl is that it unites with
phenylhydrazin to form Cg HgC^ (N2 HCe H5). It will form no
acetyl derivative, therefore (two oxygen atoms being in the form of
carboxyl) the fourth one must be between two carbon atoms. When
carefully treated with potassium hydroxid, dehydracetic acid gives
acetoacetic acid therefore it must contain two methyl groups. When
treated with anilin, dehydracetic methyl ester forms lutidone deriva-
tives, phenyl-lutidone-carboxylic methyl ester being first produced
which is decomposed into phenyl lutidone, C5 NH(OH) (CH3)2 C6 H5 .
The bromid acetate, oxim and phenylhydrazin derivatives of dehy-
dracetic acid were prepared and described.

ACETO ACETIC ESTER 89

FREER, P. C. AND W. H. PERKIN, Jr., 1887.
J. Chem. Soc. 5'» 820-849 ; Am. Chem. J. 10, 446-457.

Action of Ethylene Bromid on Sodium Derivatives of Acetoacetic
Ester

Experiments with acetoacetic ester and ethylene bromid being
repeated, it was found that two substances were produced, one as before
described in Ber. 19. 2561 and the other having the formula

CH3

CO - CH2

II I

C - CH2

I

C02 C2 H5

and being termed methyl-dehydropentone-carboxylic ester. The former
is produced in much the larger quantities. Acetyltrimethylenecar-
boxylic ester,

CH3

CO

' CH2
C<|

I CH2
C02C2H5

(which is the one formerly described) when boiled with water gives
acetopropyl alcohol, (CH3 CO) CH2 CH2 CH2 OH, but upon being
heated it becomes acetopropyl anhydrid, CH3 C : CHCH2, and acetyl-

O CH2

trimethylene,

CH2
CH3 CO - CH < I

CH2

HAULER, A. AND A. HELD, 1887.

Compt. rend. 104, 1627-1629 ; J. Chem. Soc. 52, 799.

Cyanacetoacetic Ester.

This substance obtained by James (J. Chem. Soc. 51, 287) is the
same as that obtained by the authors in 1882 (Compt. rend. 95, 235) by
the action of cyanogen chlorid on sodacetoacetic ester. The authors
give it the composition CH3 COCH (CN) CO2 C2 H5 , not as James gave
it CH2 (CN) COCH2 CO2 C2 H5 .

90 BIBLIOGRAPHY OF

WALLACH, O., 1887.

Ann. Chem. 241, 288-315 ; J. Chem. Soc. 54» 37 ; Jsb. Chem. 1887, 763;
Bull. Soc. chim. 50, 297.

Nitrosates, Nitrosites and their Derivatives.

Amylene and nitrogen peroxid unite directly and form, not a dinitrite
but a nitroso nitrate. This compound C5 HIO N2 O4, unites with aceto-
acetic ester to form the crystalline compound CH3 COCH (NOC5 HIO)
C02C2H5.

CLAISEN, Lo AND O. LOWMAN, 1887.

Ber. 20, 651-654 ; J. Chem. Soc. 52» 583 ; Jsb. Chem. 1887, 2050;

Bull. Soc. chim. 48, 394.
Preparation of Benzolacetic Ester.

Acetoacetic ester is formed in this operation which consists of mixing
sodium ethoxid and benzoic ester and treating the product with acetic
acid. The theory is advanced that here as well as in the ordinary
production of acetoacetic ester an intermediate, addition product is

formed. In the case of acetoacetic ester it would be CH C

which is acted upon by acetic ester thus :— CH3

H2 CHCO2 C2 H5=CH3 C (ONa) : CHCO2 C2 H5+ 2C2 H5 OH.

CONRAD, M. AND L. LIMPACH, 1887.

Ber. 20, 944-948 ; J. Chem. Soc. 52» 679 ; Jsb. Chem. 1887, 1046 ;
Bull. Soc. chim. 48, 320.

Synthesis of Quinolin Derivatives from Acetoacetic Ester.

By heating anilacetoacetic ester, CH3 C (NHC6H5) : CHCO2 C2H5,
it is decomposed and besides alcohol, acetone and carbanilid,
CO: (NHC6 H5)2, it forms r-hydroxy-quinaldin, C6 H4 C3 HOHCH3 N,
[OH:CH3=2':4'], which melts at 23o°-23i° and distills at 360° with
some decomposition. It is very bitter and gives an intensely reddish
yellow color with ferric chlorid. A number of its salts and derivatives
were described, phenylamidoquinaldin, methoxyquinaldin and some
derivatives containing chlorin, bromin and nitrogen.

ACETO ACETIC ESTER 91

HANTZSCH, A. AND H. ZURCHER, 1887.

Ber. 20, 1328-1332 ; Jsb. Chem. 1887, 1461 ; Bull. Soc. chim. 48,747.

Polycoumarins.

By treating polyhydric phenols with an excess of acetoacetic ester
and sulfuric acid, polycoumarins are formed. Di-methyl di-coumarin,

( OOH * OTT ^
C6H2 < Q ^ ^Q > 2, formed from acetoacetic ester and resorcin,

Ce H4 (OH) 2, is a white powder almost insoluble in ordinary solvents,
soluble in alkalis from which solution acids precipitate di-methyl dicou-

f OOTT OTTOO TT ^
marie acid, C6H2< ^~« j 2. Acetoacetic ester treated

C OOTT OTT ^

with phloroglucin gives trimethyl tricoumarin, C&< X r?r? >

1<J— LO J3,

which is also a powder difficultly soluble except in alkalis from which
solution the corresponding acid is obtained. These acids easily give
up water and are changed back into the lactones.

DELISLE, A., 1887.

Ber. 20, 2008 ; J. Chem. Soc. 52, 915 ; Jsb. Chem. 1887, I7I9 J
Bull. Soc. chim. 48, 659.

Action of Sulfur Dichlorid on Acetoacetic Ester.
Preliminary Notice.

By treating acetoacetic ester with sulfur dichlorid, hydrochloric acid
was given off and the mixture solidified. The new substance,
CjoH^OeS, forms beautiful colorless crystals which are insoluble in
water but soluble in barium hydroxid, forming a barium salt. The
substance softens at 75° and melts at 90° to 91.°

BENDER, Q., 1887.

Ber. 20, 2747-2752 ; J. Chem. Soc. 54. 53.
Action of Phenylhydrazin on Chloracetoacetic Ester.

By this action a compound C12 HI4 N2 O2 was formed, it is probable
that CH3C(N2HC6H5)CHC1C02R is first formed which changes
first into CH3 CH (N2C6H5) CHC1CO2 R and then into CH3C
(N2 Ce H5) : CHCO2 R which is /?-phenylazocrotonic ester, melting at
50. 5.° This can be reduced to phenylmethyl-pyrazolone.

a-Naphthylamin and chloracetoacetic ester unite to form a compound
CI6HI6NO2C1, which melts at 75?

92 BIBLIOGRAPHY OF

JAPP, FRANCIS AND FELIX KLINQEMANN, 1887

Ber. 20, 2942-2944.
Benzene=azo= and Benzenehydrazo=fatty Acids.

When sodium-methyl-acetoacetic ester is treated with diazobenzene-
chlorid, Ce H5 N2 Cl, the diazo group takes the place of the acetyl group
and benzene-a-azo-propionic ester, C& H5 N2 CH (CH3) CO2 C2 H5, is
produced. It is a yellow crystalline substance which melts at 117?
The free acid and a number of its aromatic derivatives were produced
from it.

SCHIFF, HUGO, 1887.

Ann. Chem. 244, 19-28 ; J. Chem. Soc. 54, 572.
Compounds of Sugars with Aldehydes and Acetone.

Among other compounds described in this article is the one obtained
from sugar and acetoacetic ester, corresponding to the formula
Ce HIO O3 Ce HI2 O6j which is quite stable.

CONRAD, M. AND W. EPSTEIN, 1887.
Ber. 20, 3052-3058 ; J. Chem. Soc. 54» 253 ; Jsb. Chem. 1887, 1719 ;

Bull. Soc. chim. 49, 639.
Action of Ammonia on Acetoacetic Esters.

Amido- acetoacetic methyl ester, CH3C- (NH2) : CHCO2 CH3 , pre-
pared from acetoacetic methyl ester and ammonia gas is a colorless
crystalline substance, which melts at 85° and sublimes unchanged.
Amido-ethylacetoacetic methyl ester, CH3C- (NH2) C (C2 H5) CO2 CH3,
formed from ethylacetoacetic methyl ester, melts at 36°-37° Referring
to Brandes' obtaining two compounds from this reaction the author
thinks it probable that he had some acetoacetic ester with his ethyl-
acetoacetic ester and so obtained the two corresponding compounds,
Amido-acetoacetic esters acted upon by sodium form sodium compounds
which with an alkyl iodid form amidoalkylacetoacetic esters. Amido-
ethyl-acetoacetic ethyl ester formed similarly melts at 6o.° Di-ethyl-
acetoacetic ester will give no amid which proves that these compounds

ACETO ACETIC ESTER 9}

are amido-crotonic-esters and not imido-butyric esters. An interesting
fact is noted in regard to the melting points of these compounds. In-
troducing a methyl into the methyl ester lowers the melting point 26°
and introducing an ethyl lowers it 8°, while in the ethyl ester the intro-
duction of a methyl raises the melting point 15° and the introduction of
an ethyl raises it 23.°

JAPP, FRANCIS AND FELIX KLINQEMANN, 1887.
Ber. 20, 3284-3286 and 3398-3401.

Benzene-azo- and Benzenehydrazopropionic Acids.

Discussion is taken up in regard to the constitution of the benzene-
a-azopropionic acid, before described, and the formula is changed to
CH3 C (: NH = N — C6 H5) CO2 H, as it is found to be identical with
phenylhydrazin pyroracemic acid.

PETERS, T., 1887.

Ber. 20, 3318-3324 ; J. Chem. Soc. 54» 253 ; Jsb. Chem. 1887, 3318 ;
Bull. Soc. chim. 49» 696.

Action of Aqueous Ammonia on Alkylated Acetoacetic Esters and

of Alcohols on the Carboxylic Alkyl Group in

Acetoacetic Esters.

Repeating Brandes1 experiment with aqueous ammonia, the author
obtained with ethyl-acetoacetic ester besides amido-ethyl-acetoacetic
ester, an ethyl-acetoacetamid, CH3 COCH (C2 H5) CONH2 melting at
96° which is undoubtedly Brandes' second body. Methyl-, isobutyl-
and isoamyl-acetoacetamids were obtained from the corresponding
esters ; they melt respectively at 73°, 85° and 1 27° The author finds that
the isobutyl and isoamyl esters may be readily prepared by the action
of the respective alcohol on the ethyl ester, especially in the presence
of a small quantity of sodium.

94 BIBLIOGRAPHY OF

OTTO, ROBERT, 1888.
Ber. 21, 89-99 ; J. Chem. Soc. 54, 360.

Analogy between the Ketonic Acids and the Alkyl Sulfones of

the Fatty Acids.

Some alkyl sulfones of the fatty acids of the formulae RSO2 CO2 H ;
RSO2 CH2 CO2 H and RSO2 CH2 CH2 CO2 H were described and the
points of resemblance between them and the corresponding ketonic
acids pointed out.

BERQREEN, HENRY, 1888.

Ber. 21, 337-352 ; J. Chem. Soc. 54» 444 ; Bull. Soc. chim. 50, 556.
Thiocarbonyl Chlorid.

The action of thiocarbonyl chlorid on sodium and copper acetoacetic
esters is given in this article (Ber. pps. 347-348) by which is produced
thiocarbonylacetoacetic ester, a solid which softens at 15 2° and melts at
156° to 162.° The formula [CH3 COC (CS) CO2 C2 H5]x is ascribed to it,
as the author thinks it is not a simple molecule. It will not react with
phenylhydrazin or hydroxyl-amin. Thiocarbonyl chlorid acting on
sodium methyl-acetoacetic ester produces an oil free from chlorin, which
contains sulfur. It cannot be distilled and no crystalline product can
be obtained from it.

BONGARTZ, J., 1888.
Ber. 21, 478-487 ; J. Chem. Soc. 54. 478.

Compounds of Aldehydes, Ketones and Ketonic Acids with
Thioglycollic Acid.

The action of hydrochloric acid gas on a mixture of thioglycollic
acid and acetoacetic ester is given in this article (Ber. p. 485) by which
a white crystalline powder is formed which melts at 95° to 96° It is
acetoacetic ester dithioglycollic acid and has the formula

H2CO2H)2
C02 C2 H5

ACETO ACETIC ESTER 95

HALLER, A. AND A. HELD, 1888.

Compt. rend. 105, 115-117 ; J. Chem. Soc. 52» 1029.

Cyan-acetoacetic Ester.

A new method of producing this compound is given. Cyanacetic
ester dissolved in alcohol is mixed with sodium dissolved in alcohol and
acetyl chlorid in ether. The equation given is 2 CH(CN)NaCO2C2H5
+ CH3 COCl=NaCl+CH2(CN)C02C2H5+ CH3COC(CN)NaCO2C2H5.
This shows conclusively that the composition of the compound is that
here assigned to it.

HALLER, A. AND A. HELD, 1888.

Compt. rend. 106, 210-213 ; Bull. Soc. chim. 49» 243 ; J. Chem. Soc.

54, 579; Ber- ai, 187 (C).
Cyan-acetoacetic Methyl Ester.

This body, CH3 COCH (CN) CO2 CH3, was prepared from cyanogen
chlorid and a mixture of acetoacetic methyl ester and sodium methoxid.
It melts at 46.5° It was also prepared by treating sodcyanacetic methyl
ester with acetyl chlorid. The sodium and calcium compounds were
prepared.

GENVRESSE, P., 1888.

Compt. rend. 107, 687-689; J. Chem. Soc. 56. 122 ;-Ber. ai, 831 (C).
Chlorin Derivatives of Acetoacetic Ester.

Dichlor-acetoacetic ester can be decomposed by hydrochloric acid
into unsymmetrical dichloracetone, wherefore, (?) the formula CHC12
COCH2 CO2 C2 H5 is assigned to it. For similar reasons the trichlor-
derivative is supposed to be CC13 COCH2 CO2 C2 H5, tetrachlor deriva-
tive CC13 COCHC1CO2 C2 H5, and the penta-chlor derivative CC13
COCC12 CO2 C2 H5. Two compounds containing, one, seven and the
other nine atoms of chlorin were also produced, described and given
the formulae CC13 COCC12 CO2 C2 H3 C12 and CC13 COCC12 CO2 CHC14.
Acetoacetic methyl ester yields similar derivatives.

96 BIBLIOGRAPHY OF

QEUTHER, A., 1888.
Ann. Chem. 244, 190-221 ; J. Chem. Soc. 54* 579; Ber. 21, 295 (C).

Constitution of Acetoacetic, Succinosuccinic and
Quinone-hydro-dicarboxylic Acids.

The author contends for the constitution of acetoacetic ester as
CH3 COH : CHCO2 C2 H5, giving as a proof of the hydroxyl group the
similarity of reactions between acetoacetic ester and phenol and salicylic-
ester, (i) towards potassium hydroxid and then carbon dioxid when,
he states, the original substances are regained, (2) towards potassium
cyanid, when potassium compounds are produced, although the potas-
sium compounds of salicylic and succinosuccinic esters are decomposed
into alcohol and the potassium salts and the acetoacetic ester compound
is decomposed into alcohol and the potassium salt, which latter is then
further decomposed into potassium carbonate and acetone, (3) towards
ferric chlorid, as to the colors produced. He cites the easy decompo-
sition of acetyl-acetoacetic ester as a proof that it has the formula
CH3 CO (COCH3) : CHCO2 C2 H5. In the formation of sod-acetoacetic
ester he supposes the intermediate bivalent group CH3 CONa : is formed
which unites with acetic ester liberating two atoms of hydrogen.

MEISTER, JOHANNES, 1888.

Ann. Chem. 244, 233-253 ; J. Chem. Soc. 54» 675 ; Ber. 21, 427 (C).
Condensation Product of Urethane and Acetoacetic Ester.

Acetoacetic ester and urethane condense thus : CH3 COCH2 CO2 R+

. The product is the

same as that produced from chlor-carbonic ester and paramido-aceto-
acetic ester and so is given the above formula. Alcoholic potash saponi-
fies it giving an oil CI2 H23 NOe , considered as

CH3 C (OH) CH2 C02 C2 H5.

>NH
CH3 C (OH) CH2 C02 C2 H5.

A tribrom-derivative of the condensation product was formed but a
trichlor-derivative could not be formed.

ACETO ACETIC ESTER 97

Alcoholic ammonia acts on it to form a body C7 HI5 N3 O3 , which

/ NHCONH2
may be represented thus : — CH3 C / NH2 and which is

^CHC-OH

\OC2H5

;?-uramidocrotonic amid together with one molecule of alcohol.
Boiling this with water decomposes it into urea, acetone, alcohol, car-
bon dioxid and ammonia.

MEWES, W., 1888.

Ann. Chem. 245, 58-84 ; J. Chem. Soc. 54» .817 ; Ber. 21, 473 (C).

Halogen Substitution Products of Acetoacetic Ester

and their Behavior with Sodethoxid.

Passing chlorin through acetoacetic ester produces the mono-, di-,
tri- and tetra-chlor-acetoacetic esters which boil at 194°, 2O5°-2O7°, 223°-
225°, and 245°-25o° respectively. Some difficulty was found in entirely
separating them from one another. The bromo-chlor- acetoacetic esters
were formed by treating the chlor-acetoacetic esters with bromin and
also by treating the bromo-acetoacetic esters with chlorin. Sodethoxid
decomposes all of the halogen derivatives forming the mono- or di-
halogen acetic esters. Bromoacetoacetic ester with Sodethoxid yields
succinosuccinic ester. When the chlorobrom-substitution products are
treated with sodethoxid, sodium bromid is always formed.

KNORR, L., 1888.

Ann. Chem. 245, 357-382 ; J. Chem Soc. 54. mi ; Ber. 21, 628 (C).
Synthetical Researches on Acetoacetic Ester. Part IV.

Methyl-acetoaceticanilid, CH3COCH (CH3) CONHC6H5 , which was
prepared from methyl-acetoacetic ester and anilin, melts at 138° to 140.°
Sulfuric acid changes it into dimethyl-carbostyril [3' 14'], a weak acid
from which the dimethyl product C9 H4 OH (CH3)2 N was obtained.
Chlor-dimethyl-quinolin [Cl : (CH3)2=2':3':4'], ortho- [4': i], meta-and
para- [4' : 3] dimethyl-quinolin were described together with some phenyl;
nitrogenous derivatives.

98 BIBLIOGRAPHY OF

JAPP, FRANCIS AND FELIX KLINQMANN, 1888.

Ber. 21, 549-551.
Formation of Mono- and Di-hydrazin Derivatives of «-Di-ketones.

Methyl-acetoacetic acid and diazobenzene chlorid, Ce H5 N2 Cl, react
and form the monophenylhydrazin derivative of diacetyl,

CH3 COCCH3

N-NHC6 H5

which melts at 133? If treated with phenylhydrazin the di-phenyl-
hydrazin derivative is formed. Ethyl-acetoacetic acid reacts similarly
and gives rise to the corresponding compounds.

CLAISEN, L. AND N. STYLOS, 1888.

Ber. 21, 1144-1149; J. Chem. Soc. 54» 671.

Acetoacetic-aldehyde.

The sodium compound of acetoacetic-aldehyde, CH3 COCHNaCHO,
was prepared from acetone, formic ester and sodium ethoxid. The free
aldehyde could not be isolated on account of its tendancy to break down
into symmetrical triacetyl benzene, which was made and described.
The anilid, toluidid and napthalid of the aldehyde were prepared.
Treated with phenylhydrazin, methyl-phenyl-pyrazole,

CH =C(CH3KXTO „

3V^NC6 H5, was obtained.

„ 3

CH=N-

PECHMANN, H. v., 1888.

Ber. 21, 1411-1422; J. Chem. Soc. 54. 811.
a-Diketones.

The diketones described in this article are prepared from monoalkyl
acetoacetic esters, by saponifying with dilute alkali, treating the pro-
duct with sodium nitrite and sulfuric acid and after removing the alco-
hol by distillation, adding twenty times the volume of dilute sulfuric
acid and distilling with steam. Methyl-acetoacetic ester treated in this
manner gives diacetyl, CH3 COCOCH3, and ethyl-acetoacetic ester gives
acetyl-propionyl, CH3 COCOCH2 CH3.

ACETO ACETIC ESTER 99

BEYER, C. AND L. CLAISEN, 1888.

Ber. 21, 1697-1705.
Mixed Azo Compounds.

In this article some azo compounds are described which are formed
from acetoacetic esters.

GRIESS, P. AND Q. HARROW, 1888.

Ber. 21, 2740-2743 ; J. Chem. Soc. 54» ^313-
Action of Acetoacetic Ester on Hexamethylenetetramin.

When acetoacetic ester acts on hexamethylenetetramin, (CH2)6N4,
in presence of zinc chlorid, lutidin-di-carboxylic ester and hydro-
lutidin-di-carboxylic ester are formed. The latter, C5NHH2(CH3)2
(CO2C2H5)2, melts at 170°, is neutral and is considerably decomposed
upon being distilled. Treated with hydrochloric acid it gives two pro-
ducts, the mono- and di-ethyl esters of lutidin-dicarboxylic acid.

MICHAEL, A., 1888.

J. prakt. Chem. 145.473-530; Am Chem. J. 10, 158-160; J. Chem.
Soc. 54, 1054 ; Ber. 21, 530 (C) ; Bull. Soc. chim. 5°. 690.

Constitution of Sodacetoacetic Ester.

By the action of chlor:carbonic ester on sod acetoacetic ester, carb-
ethoxacetoacetic ester was produced which boils unchanged at 127° at
i7m.m. pressure. No sodium derivative of this could be prepared, con-
sequently it was considered to be an isomer of aceto-malonic ester,
which does easily form a sodium derivative, and its formation was
supposed to be thus :— CH3 CONa:CHCO2C2H5+ClCO2C2H5=CH3CO
(CO2 C2 H5 ) : CHCO2 C2 H5 + NaCl. In the author's opinion acetoacetic
ester itself is a ketone. He gives as a formula for benzalacetoacetic
ester CH3 C : C ' CO2C2H5 , which explains its loss of ketone properties

O— CHC6H5

and to explain the reactions between bodies analogous to acetoacetic
ester such as levolinic acid, CH3 COCH2 CH2 CO2 H, and acetyl chlorid,

he supposes an addition product thus : —

^O— COCH3
CH3CO--- etc.+CH3COCl=CH3— C etc.

100 BIBLIOGRAPHY OF

and a subsequent separation of hydrochloric acid forming a lactone.

In the formation of sodacetoacetic ester an aldol polymerization is

supposed to take place first, the product of which is acted upon by

/ OC2 H5
sodium thus:— 2 CH3 CO2 C2 H5=CH3 C- -CH2 CO2 C2 H5, then

-OH
^OC2H5

sodium forms CH3 C CH2 CO2 C2 H5 , which is again acted upon by

\ONa

sodium to form CH3 CONaCHCO2 C2 H5 , NaOC2 H5 and H. If sodium
be made to act on acetoacetic ester, CH3 COCHNaCO2 C2 H5 is formed
but the sodium is immediately attracted to the carbonyl group and it
changes to form CH3 CONa:CHCO2 C2 H5. When this last compound
is treated with an alkyl iodid, C2 H5 i for example, there is an addition
product formed and as the group — CONa=is more positive than the
group=CH — , the iodin add to the former and the ethyl adds to the

/ONa

= CH— group forming CH3 C CH (C2 H5) CO2 C2 H5 from which

\ i.

sodium iodid separates leaving CH3 COCH (C2 H5) CO2 C2 H5.

POLONOWSKY, M., 1888.

Ann. Chem. 246, 1-32 ; J. Chem. Soc. 54» 1067 ; Ber. 21, 636 (C).
Condensation of Glyoxal with Acetoacetic Esters.

By treating a mixture of glyoxal, CHOCHO, and acetoacetic ester
with zinc chlorid two products are formed, (i) a part soluble in alkalis
which contains methyl-furfuran carboxyacetic or sylvanecarboxyacetic

acid, 0<£^\9S2/oA:(^>, wnich melts at 2°7- The normal
^ (<~"-3; • ^ (<-U2 -tl;

and acid, methyl and ethyl esters were produced and described ; (2) a
part insoluble in alkalis which consists of a heavy oil and a crystalline
substance, both having the composition CI4 Hl8 Oe- The oil is di-ethyl-
sylvane-carboxy-acetoacetic ester which is : —
CH3

CO CH (CH3) C

i I >O

CH C: (C02 C2 H5) C

C02 C2 Hs

ACETO ACETIC ESTE^ \ '-'.

ViJ 101

JAECKLE, A.,

Ann. Chem. 246, 32-52 ; J. Chem. Soc. 54, 1103 ; Ber. 21, 638 (C).
Higher Homologues of the Synthetical Pyridins and Piperidins.

The normal propyl-lutidin hydrodicarboxylic ester, C5 NH2 (CH3)2
C3 H7 (CO2 C2H5)2 , obtained from normal butaldehyde and ammonia
acting on acetoacetic ester and alcohol, is a crystalline substance melt-
ing at 1 1 8° From this the normal propyl-lutidin-dicarboxylic ester,
the free acid and the normal propyl-lutidin were prepared. Hexyl-
lutidin hydrodicarboxylic ester was prepared from ammonia, acetoacetic
ester and oenanthol, C& HI3 CHO, and from it normal hexyl-lutidin,
C5NH2 (CH3)2C6HI3. A number of piperidins were obtained from
the corresponding pyridins and described.

WISLICENUS, WILHELM, 1888.

Ann. Chem. 246, 306-309.
Synthesis of Ketone Acid Esters.

As a portion of this article the author briefly reviews the controversy
as to the formation of acetoacetic ester from sodium and acetic ester.
He thinks that sodium acts on alcohol to form sodethoxid and liberate
hydrogen, that the sodethoxid reacts with acetic ester to produce
sodacetoacetic ester and alcohol and that thus alcohol is continually
produced and used up again. Some of the hydrogen is used up in
secondary reactions and some is given off. He doubts the formation of
a sodacetic ester as an intermediate product.

JAPP, FRANCIS R. AND FELIX KLINGEMANN, 1888.

Ann. Chem. 247, 190-225 ; J. Chem. Soc. 53. 519-544.
Constitution of the So-called Mixed Azo Compounds.

The compounds treated of in this article were prepared from aceto-
acetic esters.

102 .- BIBLIOGRAPHY OF

v :[>^CKMANN, H. v., 1888.

Ber. 21, 3005-3006 ; J. Chem. Soc. 56, 42.
Condensation Product of Quinone and Acetoacetic Ester,

When quinone, C& H4 O2 , is brought in contact with acetoacetic ester
in the presence of zinc chlorid they react to form a substance Ci6 Hl6 Oe ,
which melts at 184! This substance will not react with phenylhydrazin,
benzoic chlorid, sodium ethoxid or alkyl iodids. Treated with potas-
sium hydroxid and then an acid a crystalline dibasic acid Ci4 HI2 O&
is formed which is insoluble in ordinary solvents and sublimes without
melting. The salt CI4 HIO K2 Oe + 2H2O was prepared.

CLAISEN, L. AND W. ZEDEL, 1888.
Ber. 21, 3397-3398 ; J. Chem. Soc. 54, 377-

Action of Chlorcarbonic Ester on the Sodium Derivatives of
Acetylacetone, Acetoacetic Ester and Malonic Ester.

The product obtained by treating acetoacetic ester with chlorcarbonic
ester was thought to be the dicarboxylic ester of acetoacetic ester and
to 'have the formula CH3 COC (CO2 C2 H5)2 CO2 C2 H5.*

CLAISEN, L., 1888.
Ber. 21, 3567.
A Correction.

By further experiments the author has decided that the compound
formed from acetoacetic ester and chlorcarbonic ester is the mono- not
the di-carboxylic derivative of acetoacetic ester, that it is CH3 COCH
(CO2 C2 H5) C02 C2 H5 and not CH3 COC (CO2 C2 H5)2 CO2 C2 H5 as
stated by him in Ber. 21, 3397^

*See following article.
fSee preceding article.

ACETO ACETIC ESTER 10}

KNORR, L., 1889.

Ber. 22, 146-152 ; J. Chem. Soc. 5<*» 384.
Constitution of Carbopyrotritartaric Acid.

Fittig gives this acid the unsymmetrical formula

CH3-C CHC02H,

||

HC CHC02 H
\ /

C

o

while the author gives it a symmetrical one : —

CO2HC-CC02H

II II
CH3 C CCH3

\ /
O

and says that this formula is proven by the fact that only one pyrotri-
tartaric acid and only one hydrogen-ethyl ester can be formed from it.

RAYMANN, B. AND K. CHODOUNSKY, 1889.

Ber. 22, 304-305 ; J. Chem. Soc. 56. 485.

Rhamnodiazin.

Rhamnodiazin, ds H32 N2 Og, is formed from rhamnose, CH3
(CHOH)4 CHO, and ammonia and acetoacetic ester in methyl alcohol
solution. It melts at 186.° Other glucoses seem to yield similar com-
pounds when treated with acetoacetic ester and ammonia.

104 BIBLIOGRAPHY OF

DELISLE, A., 1889.

Ber. 22, 306-309 ; J. Chem. Soc. 56, 488.
Ketosulfids and Ketosulfid Acids.

The compound described in Ber. 20, 2008, obtained from acetoacetic
ester and sulfur dichlorid is found to be CI2Hl8O6S intead of CIOHI4O6S
and the formula

CH3C:CHC02C2H5
I

O
\

s

/
O

I

CH3C:CHCO2C2H5
is ascribed to it.

HELD, A., 1889.

Ann. chim. phys. [6] 18, 468-531 ; Ber. 23, 287 (C).
Derivatives of Cyanacetoacetic Esters.

The first part of this article is the same as that in Bull. Soc. chim.
[3]!> 306^. By treating Cyanacetoacetic ester with ammonia, amido-
cyanacetoacetic ester, CH3 C (NH2) :C (CN) CO2 R, is obtained which
melts at 188.° It is neutral wherefore the above formula is given to it.
When it is treated with an alkali, sodcyanacetoacetic ester is obtained.
If sulfuric acid be added to the mother liquor left after the formation of
the above, a monobasic acid C7 He N2 O2 is obtained. The sodium,
barium, ammonium, silver, copper and lead salts and ethyl ester were
described. When heated with hydrochloric acid, carbon dioxid is given
off and another acid Ce H7 NO2 is formed. The author is at work on
the constitution of these acids. Ethylamin acts on Cyanacetoacetic
ester to produce the compound CH3 C (NHC2 H5):C(CN) CO2 R and
the acid C9 HIO N2 O3. Cyanacetoacetic ester boiled with water gives
Cs H8 N2 O which sublimes at 200° and is a condensation product of
cyanacetone,

CHCOCH2(CN)

CH3CCH2(CN).

*See page 105.

ACETO ACETIC ESTER 1 05

HALLER, A. AND A. HELD, 1889.

Compt. rend. 108, 516-518 ; J. Chem. Soc. 56, 588 : Ber. 22, 255 (C).
Monochlor-acetoacetic Esters.

Two monochlor derivatives of acetoacetic ester were formed, the a,
and the f. The latter by passing chlorin into acetoacetic ester at low
temperatures. It boils at 1 88°- 189° It can be distinguished from the
a product by the fact that the latter readily forms an insoluble cyanid
with potassium cyanid.

HELD, A., 1889.

.' Bull. Soc. chim. [3] i, 306-311 ; Ber. 22, 407 (C) ; J. Chem.

Soc. 5<>, 1141.
Derivatives of Cyanacetoacetic Ester.

Bromin reacts with cyanacetoacetic ester to form a dibrom derivative,
CH2 BrCOCBr (CN) CO2 C2 H5 , a yellowish red liquid which decom-
poses upon being distilled even under reduced pressure. Chlorin forms
with cyanacetoacetic ester Ce H7 (CN) C12 O3 , which boils at 90° to 105°
with 20 to 25 m. m. pressure and decomposes spontaneously. Ethyl-
cyan acetoacetic ester CH3 COC (C2 H5) (CN) CO2 C2 H5 , prepared from
ethyl-sodacetoacetic ester and cyanogen chlorid, boils at 103° to 105° at
25 m. m. pressure. Potassium hydroxid decomposes it into acetic and
butyric acids. Methyl-cyan acetoacetic ester prepared similarly boils at
90° to 92° at 20 m. m. pressure. Potassium hydroxid decomposes it into
acetic and propionic acids. Unsuccessful attempts were made to pre-
pare cyanacetoacetic acid.

CURTIUS, TH. AND R. JAY, 1889.

J. prakt. Chem. [2] 39. 27-58 ; Ber. 22, 134 (C); J. Chem. Soc. 5<*» 393-

Hydrazin.

On pages 51 and 52 of this article the reaction between acetoacetic
ester and hydrazin hydrate, N2 H4, H2 O, is treated of. Methyl pyra-

H2C— CO
zolone, >NH, is formed which is a crystalline substance

CH3C=N
melting at 215°, which will dissolve in both acids and alkalis.

106 BIBLIOGRAPHY OF

BIGINELLI, P., 1889.

Gazz.* chim. 19, 212-214 ; Ber. 22, 688 (C) ; J. Chem. Soc. 58. 768.
Action of Acetoacetic Ester on Cinnamaldehyde.

When acetoacetic ester, cinnamaldehyde and ethylen-diamin are
mixed and heated, a reaction takes place and a crystalline substance,
C2i H26 Oe is formed which melts at i6o°-i6i.° It will give a bromin
derivative and is decomposed by caustic potash. Methylamin or anilin
may be used in place of ethylendiamin without changing the result.
If benzaldehyde be used in place of cinnamaldehyde a compound free
from nitrogen is obtained but if propaldehyde is used a compound con-
taining nitrogen is produced.

BIGINELLI, P., 1889.

Gazz.* chim. 19, 215-217 ; Ber. 22, 689 (C) ; J. Chem. Soc. 58, 732.

Action of Acetoacetic Ester on Dextrose in
Alcoholic Ammonia.

In this reaction two compounds are formed, C^H^OsN a neutral
substance which melts at 189°- 190° and CIOHl6O5N, which melts at
I3°°-I3I° The latter was formed in sealed tubes at 100° to no.0 The
author is continuing the investigation of these reactions.

KIPPING, F. STANLEY AND W. H. PERKIN, Jr., 1889.

J. Chem. Soc. 55. 33O-351 ; Ber. 22, 571 (C).
a-w-diacetyl-pentane and a-w-dibenzoyl-pentane.

In the researches upon these compounds the first one was made from
acetoacetic ester. Sodacetoacetic ester was treated with trimethylene
bromid and after the reaction more sodium dissolved in alcohol was

^Original article not consulted.

ACETO ACETIC ESTER IOy

added. This process gave a much better yield than any other method
tried. The product obtained is methyl-dehydrohexone carboxylic ester,

CH3

C — O -CH2
ii I

C— CH2 — CH2,

C02 C2 H5

This is changed by hydrobromic acid into aceto-butyl-bromid, CH3 CO
(CH2)4 Br, and this by sodacetoacetic ester into a-w-diacetylcaproate.

CH3

CO

CH— (CH2)4COCH3,

C02 C2 H5

Treating this with potassium hydroxid the free acid is produced and by
heating this carbon dioxid is given off and a-w-diacetyl-pentane,
CH3 CO (CH2)5 COCH3 , is obtained. Several derivatives of this are
described.

FITTIG, R., FRITZ VON EYNERN AND ADOLF DIETZEL, 1889,

Ann. Chem. 250, 166-211 ; J. Chem. Soc. 56, 592 ;
Ber. 22, 200 (C).

Condensation of /3-Ketonic Esters with Dibasic Acids.

After a discussion of the constitution of the products of condensation
of succinic and pyruvic acids with acetoacetic ester, it is decided that
they are all derived from, either

CH:CH /CH:CH

Pyrotritartaric acid is now called uvitic acid and carbpyrotritartaric
acid is now called carbuvitic acid. When acetoacetic ester, acetic
anhydrid and sodium succinate are heated together they give hydrogen

108 BIBLIOGRAPHY OF

methronic ester, Cg H7 (C2 H5) O5, a crystalline substance which melts
at 75°-76.° The calcium, barium and silver salts were described. From
it was prepared methronic acid,

CH3 C - CHCO2 H

II I
C02 HC CH2

\ /
C
O

which decomposes at high temperatures to form uvic acid. Methronic
diethyl ester, Cs H6 (C2H5)2O5, and a phenylhydrazin derivative were
also described. By heating acetoacetic ester and pyruvic acid,
CH3 COCO2 H, with acetic anhydrid, hydrogen methyl methronic ester
is formed and from this the methyl-methronic acid which is

CH3 C — CHC02 H CH, C —

II I I 2'

CO2HC CHCH3 or CO2 HC CH2

\ / \ /

C C

O O

No acid salts of this are known but the normal calcium, barium and
silver salts were described. Methyl-methronic diethyl ester was also
described. From methyl-methronic acid were obtained methyl-uvic acid,

CH3 C - CHC02 H CH3 C - C

II I II I

HC CHCH3 or HC CH2

\ / \ /

C C

O O

and dimethyl-keto-pentene,

CH3 C - CH2 CH3 C - CHCH3 ,

II I or || |

HC CHCH3 HC CH2

\ / \ /

C C

O O

ACETO ACETIC ESTER IO9

ZURCHER, H., 1889.
Ann. Chem. 250, 281-294 ; J. Chem. Soc. 56. 725 ; Ber. 22, 258 (C).

Action of Thiocyanates and Thiocarbarnids on
Chlorinated Acetoacetic Esters.

Methyl-oxythiazole-carboxylic ester,

C02C2H5C — S,

II I
CH3 C COH

\ ^

N

is formed from monochlor-acetoacetic ester and a metallic thiocyanate.
Some of its reactions and derivatives are described. Thiocarbamid
acting on monochlor-acetoacetic ester gives amidomethyl-thiazole-
carboxylic ester,

C02C2H5— C— S

II I
CH3 — C CNH2

\ S

N

from which the free acid and some of its salts were obtained. Dichlor-
acetoacetic ester reacts with barium thiocyanate to form a compound
d4 H^Oy N2S2 . With thiocarbamid dtchlor-acetoacetic ester does
not react.

FEIST, FRANZ, 1889.

Ber. 22, 1570-1571 ; J. Chem. Soc. 56, 957; Bull. Soc. chim.

Dehydracetic Acid.

Dehydracetic acid when treated with hydriodic acid gives dimethyl-
\

pyrone, co< > °' which melts at X2°' boils at

110 BIBLIOGRAPHY OF

at 719 m. m. pressure. An aqueous solution of this gives with barium
hydroxid C7 H8 O3 Ba a (xantho) barium salt,

O-Ba-O

I I
CH3 C CCH3 ,

II II
CH CH

\ /
CO

which, when treated with hydrochloric acid gives a tri-ketone
CH3 COCH2 COCH2 COCH3 , which melts at 49° and at higher
temperatures gives off water and forms dimethyl-pyrone again.
When the triketone is heated with ammonia, lutidone is formed.

KRAFFT, F. AND J. MAI, 1889.
Ber. 22, 1757-1759 ; J. Chem. Soc. 56, 1017.
Myristic Aldehyde.

When myristic aldehyde, CI3 H27 CHO, ammonia and acetoacetic ester
are mixed a reaction takes place and hydrotridecyl-lutidin-dicarboxylic
ester,

Ci3 H27

C

/ ^
CO2 C2 H5 CH CCO2 C2 H5 ,

CH3CH C — CH3

\ ^

N

is formed, which melts at 6o.° From this were formed the corres-
ponding compounds ; — tridecyl-lutidin-di-carboxylic ester, tridecyl-
lutidin-di-carboxylic acid and tridecyl-lutidin.

ACETO ACETIC ESTER III

SCHONBRODT, R., 1889.

Ann. Chem. 253, 168-205 ; J. Chem. Soc. 58, 27 ; Ber. 22, 680 (C).
Derivatives of Acetoacetic Ester.

By passing chlorin through cupracetoacetic ester in chloroform the
mono- and di-chlor derivatives were formed and the corresponding
bromin derivatives were similarly formed. lodacetoacetic ester pro-
duced from cupracetoacetic ester and iodin is an unstable oil which
decomposes at 25° in a vacuum, its specific gravity is 1.705 at 14°, in
alcoholic solution it gives a blood red color with ferric chlorid. Silver
chlorid converts it into mono-chlor-acetoacetic ester. When treated
with silver nitrite an oil is produced which gives a blood red color with
ferric chlorid and suifuric acid and which is probably nitroacetoacetic
ester. Treated with phenylhydrazin it gives phenyl-methyl-nitroso-
pyrazolone [ i 13:4:5]. Sodacetoacetic ester and iodacetoacetic ester
give diacetosuccinic ester. lodacetoacetic ester and metallic silver give

CH3 COCCO2 R
diacetofumaric ester, COCCO R' Cupracetoacetic ester boiled in

benzene with sulfur gives thioacetoacetic ester. In presence of alcohol,
phosphorus acts on cupracetoacetic ester to form acetoacetic ester and
tri-ethyl phosphite, P (OC2 H5)3. Cupracetoacetic ester and arsenic
trichlorid form cuprous chlorid, arsenic and mono-chlor-acetoacetic
ester. Unsuccessful attempts were made to replace hydrogen by copper
in methyl-acetoacetic ester.

GABRIEL, S. AND J. HAUSMANN, 1889.

Ber. 22, 2017-2019 ; J. Chem. Soc. 56, 1172.

Action of Orthocyanobenzylchlorid on Sodacetoacetic Ester.

In this reaction two products are formed, a small amount of di-ortho-
cyanobenzylacetoacetic ester, CH3 COC (CNC6 H4 CH2)2 CO2 C2 H5 ,
and a much larger amount of orthocyanobenzylacetic ester, or ortho-
cyanohydro-cinnamic ester, (CNC6 H4 CH2) CH2 CO2 C2 H5. The latter
is a colorless, crystalline substance melting at 98°-99° which is decom-
posed when warmed with hydrochloric acid into a-hydrindone, carbon

CO
dioxid, alcohol and ammonia. a-Hydrindone. Ce H4 <OTT > CH2,

crystallizes and melts at 40° and boils at 243°-245? Diortho-cyano-
benzylacetoacetic ester is a colorless crystalline substance which melts
at 1 20.°

112 BIBLIOGRAPHY OF

TIEMANN, F., 1889.

Ber. 22, 2412-2417 ; J. Chem. Soc. 58, 44.

Action of Acetaldehyde and Acetoacetic Ester on BenzenyF-

amidoxim.

Acetoacetic ester and benzenyl-amidoxim, Ce H5 C ^ ^jj
react to form benzenylaceto-ethenylazoxim,

C6 H5 C ^ I £icCH2 COCH3 .
Alkalis decompose it, forming benzenyl-ethenyl-azoxim,

^6 ±15
and acetic acid. The oxim,

C6 H5 C^ N~ ^CCH2 C : (NOH) CH3 ,
and the hydrazone,

C6 H5 cf ^ 2=CCH2 C : (N2 H C6 H5) CH3
were also described.

BUCHKA, K. AND C. SPRAGUE, 1889.

Ber. 22, 2541-2556 ; J. Chem. Soc. 58, 28.
Thioacetoacetic Ester.

This substance, CI2Hl8O6S, melts at 76° and forms a sodium
derivative CI2 Hl6Na2 O6S. Schonbrodt has proven that the sulfur is
joined to the a-carbon atom and not to oxygen. Phenylhydrazin
reacts with it to form phenylmethyl-pyrazoloneketo-phenylhydrazone
or phenylmethyl-pyrazolonazobenzene,

NHNC6 H5
II

C — CO ,
\
NC6H5

CH3C = N

and a yellow substance which appears to be CIOH8N2SO. The
compound which Schonbrodt describes as phenylmethyl-nitrosopyra-
zolone is identical with phenylmethyl-pyrazolonazobenzene. Thio-
acetoacetic ester unites with paratolylhydrazin and «-naphthylhydrazin
yielding a series of complicated compounds in each case.

ACETO ACETIC ESTER II)

MICHAELIS, A. AND OSCAR BURCHARD, 1889.

Ann. Chem. 254, 115-128.

Syntheses by Means of Sodium-phenylhydrazin. Ethylenphenyl-

hydrazin.

In the last paragraph of this article mention is made that ethylen-
phenylhydrazin easily condenses with acetoacetic ester to form a
beautiful crystalline substance which melts at 54.° It is being
investigated by the authors.

RAYMAN, B. AND O. POHL, 1889.

Ber. 22, 3247-3249 ; J. Chem. Soc. 58, 355.
Rhamnodiazin.

Rhamnodiazin, Cis H32 Os N2 , is further studied but no very definite
results are obtained. Its constitution is probably CH3 (CHOH)4CH

PTT

(N:C < ^-rj3 n^. ^ TT N When rhamnose, acetoacetic ester and an
v^ri2 i~U2 L-2 ti5)2 •

amin are mixed they form rhamnosamin.

KIPPING, F. STANLEY AND W. H. PERKIN, Jr., 1890.

J. Chem. Soc. 57. 29-38 ; Ber. 23, 249 (C).
a-fo-Diacetyl-a-w-diethylpentane.

This substance whose properties and reactions are described is
obtained by treating sodacetoacetic ester with tri-methylene bromid.
These substances combine to form a-w-diacetyl-a-w-diethyl-pimelic
ester which is

CH3 CH3

CO CO

C(C2H5)-(CH2)3-C(C2H5)

C02 C2 H5 CO2 C2 H5

and when this is boiled with alcoholic potash there is formed «- w-diacetyl-
a-oi-diethyl-pentane, CH3 COCH (C2 H5) (CH2)3 CH (C2 H5) COCH3,
as well as some w-acetyl-a-w-diethyl-caproic acid.

I 14 BIBLIOGRAPHY OF

PERKIN, Jr., W. H., 1890.

J. Chem. Soc. 57> 204-241.
a— a'-Diacetyladipic Ester.

Sodacetoacetic ester and ethyleue bromid react to form two products,

CH CO CH2

(i) acetyl-trimethylene-carboxylic ester, QQSR >C<! , and (2)

a— a'-diacetyladipic ester, QQ3R> CHCH2 CH2 CH <QoR3 The

latter compound is a thick colorless oil, rather difficultly separable
from impurities, which decomposes some when distilled yielding a
mixture of several compounds. It will give a diphenylhydrazin
derivative,

L^O2 -K. ^ OTTOTT OT-T OTT --" ^-^2 -K-

CH3 C (N2 HC6 N5) ** ^ C(N2 HC6 H5)CH3,

which melts at 145° and when heated higher gives bis-phenyl-methyl
methylene-pyrazolone,

C6 H5 N NC6 H5

/ \ / \

N CO OC N

II I I II

CH3 C-CHCH2 CH2 CH-CCH3

Many other reactions and derivatives of «— a'-diacetyladipic ester were
given.

FEIST, FRANZ, 1890.

Ann. Chem. 257, 253-297 ; Ber. 23, 463 (C).
Dehydracetic Acid.

In this long article account is given of a study of dehydracetic acid
made in order to determine its constitutional formula and its relation to
its isomers. A large number of reactions are described and a great
many of its derivatives are produced and their constitution determined.
A figure is given representing the most important reactions and a table

ACETO ACETIC ESTER 115

of comparisons of the three isomeric bodies Cg Hg O4 . They are
assigned the following formulae. For dehydracetic : —

CH3C— O- C=0

CH-CO— CHCOCH3
or the tautomeric forms of: —

CH3-C— O- C=O CH3— C— O — C:O

CHC (OH) : CCOCH3 or :- CHCO— CC (OH) CH3 .

For a — a-dimethyl-pyron-carboxylic acid :—

CH3C— O— CCH3
il II

CHCO— C— CO2H

and for isodehydracetic acid : —

CH3C O C:O

CHC(CH3):CC02H.

PETERS, THEODOR, 1890.

Ann. Chem. 257, 339-353 ; J. Chem. Soc. 58, 1097 ; Ber. 23, 468 (C).
Action of Alkyl Substituted Acetoacetic Esters with Ammonia.

By the action of ammonia on these esters two products are formed
(i) «-alkyl-/9-amido-crotonic acid, CH3 C (NH2) : CRCO2 R, and (2)
amids of alkylacetoacetic acid, CH3 COCHRCONH2 , but the former
only is produced when anhydrous ammonia is employed. Ethyl-
acetoacetic methyl ester yields ethyl-amido-crotonic methyl ester,
CH3 C (NH2) : C (C2 H5) CO2 CH3 , which melts at 35°-36°, and ethyl-
acetoacetamid, CH3 COCH (C2 H5) CONH2 , melting at 96.° Methyl-
acetoacetic ester yields methyl-acetoacetamid, CH3COCH(CH3)CONH2,
melting at 73.° a-Methyl-/3-amido-crotonic ester melts at 53° Isobutyl
acetoacetamid melts at 88°, a-isobutyl-/9-amido-crotonic ester melts
at 41° -42°, isoamyl-acetoacetamid, CH3 COCH (C5 HXI) CONH2 , melts
at 129° and a-isoamyl-/3-amido-crotonic ester, CH3C (NH2) : C (C5 HIt)
CO2 C2 H5 , melts at 50? Diethyl-acetoacetic ester is not attacked by
either anhydrous or aqueous ammonia.

Jl6 BIBLIOGRAPHY OF

PETERS, THEODOR, 1890.

Ann. Chem. 257, 353-358 ; J. Chem. Soc. 58, 1096 ; Ber. 23, 468 (C).
Action of Alcohols on Acetoacetic Ester.

When a little sodium is dissolved in the alcohol, methyl, isopropyl
and isoamyl alcohols will convert acetoacetic ester into the methyl,
isopropyl and isoamyl esters respectively, slowly at ordinary tempera-
tures but quickly if heated. Kven in the absence of sodium, isopropyl
and isoamyl alcohols will thus convert acetoacetic ester if the mixtures
be boiled together, while methyl alcohol has no action in the absence
of sodium. Ethyl-acetoacetic ester reacts similarly with these alcohols.
Acetoacetic isobutyl ester, CH3 COCH2 CO2 C4 H9 , boils at i98°-2O2°
and its ethyl derivative, CH3COCH(C2H5)CO2C4H9, boils at 2ii°-2i5.°
Acetoacetic isoamyl ester, CH3 COCH2 CO2 C5 HTI , boils at 2ij°-2ig°
and its ethyl derivative, CH3COCH (C2 H5) CO2 C5 HIX , boils at

226°-230.°

MICHAELIS, A. AND B. PHILIPS, 1890.

Ber. 23, 559-561 ; J. Chem. Soc. 58, 582.
Thio=acetoacetic Ester.

This substance was prepared by treating acetoacetic ester with
thionyl chlorid, SOC12; it melts at ioo°-ioi.° When treated with an
excess of phenylhydrazin it gives phenylmethylpyrazolonazobenzene
which melts at 156°, but when twice the molecular proportion of
phenylhydrazin is added in cold, acetic acid a compound of the com-
position C20 H22 N4 O4S is produced. This is probably thioacetoacetic
phenylhydrazid which is

CH3 COCHCON2 H2 C6 H5
>S

CH3 COCHCON2 H2 C6 H5

it decomposes at 185.° When this is heated with an excess of phenyl-
hydrazin it forms phenylmethyl pyrazolonazobenzene,

N— C6H5
/ \

N C:O
II I
CH,C — C = NNHC6HS.

ACETO ACETIC ESTER 117

BUCKA, K. AND CH. SPRAGUE, 1890.

Ber. 23, 847-855 ; J. Chem. Soc 58, 796.
Action of Phenylhydrazin on Thioacetoacetic Ester.

When these substances react in cold, glacial acetic acid in the pro-
portion of one molecule of thioacetoacetic ester to two molecules of
phenylhydrazin they form thiophenylmethylpyrazolone,

C20HI8N4S02= | |

N

Ce H5 Ce H5

|

N

/ \ / \

N CO OC N

II I I II

CH3 C — CH - S - HC — C • CH3

and not C20 H22 N4 SO4 as Michaelis and Philips state in their article
(*which see). It decomposes at 183° without melting, is soluble in
alkalis and forms stable salts with strong acids. When heated with
an excess of phenylhydrazin it goes over into phenylmethylpyrazolone-
ketophenylhydrazone which is the same as Michaelis' phenyl-methyl-
pyrazolonazobenzene,

C6H5

N

/ \
N CO

II I
CH3C - C = N — N — H — C6H5

CLOEZ, C., 1890.

Compt. rend, no, 583-586 ; J. Chem. Soc. 58, 739 ; Ber. 23, 284 (C).

Hydroxytetric Acid.

By treating methyl-acetoacetic ester with bromin dibrom-methyl-
acetoacetic ester, C6 H7 Br2 (CH3) O3 , is formed, and when this is
treated with alcoholic potash, hydroxytetric acid, C5 H6 O4 , is obtained,

See page 116.

I 1 8 BIBLIOGRAPHY OF

which melts at 201. "-202? By the action of water on dibrom-methyl-
acetoacetic ester in presence of barium chlorid hydroxytetric ester,
C5 H5 (C2H5) O4 , is obtained, it melts at 67°-68° and has an acid re-
action. By treating an alcoholic solution of hydroxytetric acid with
gaseous hydrochloric acid a body boiling at 224°-226° and having the
composition of hydroxytetric diethyl ester is obtained.

CLOEZ, C., 1890.

Bull. Soc. chim. [3] 3» 602-605 ; Ber. 23, 435 (C).
Identity of Hydroxytetric and Mesaconic Acids.

The author proves the identity of these acids by their melting points,
solubility in water, volatilization, brown color given with ferric chlorid
and the same reactions towards bromin and acetyl chlorid.

HALLER, A. AND A. HELD, 1890.

Compt. rend. HI, 647-650 ; J. Chem. Soc. 60, 171.
f-Cyanacetoacetic Esters and their Chlor-imido Derivatives.

f-Cyanacetoacetic ester boils at 135° to 138°, at 40 to 45 m.m. pres-
sure, with some decomposition. Treated with hydrochloric acid in
alcoholic solution the hydrochlorid of the imido ester of acetone-dicar-
boxylic ester, QH2 (CO2C2H5) COCH2C(OC2H5) (NH),HC1, is formed
which is very unstable being decomposed by water. f-Cyanacetoacetic
methyl ester boils at 217° to 218° and when treated with hydrochloric
acid in methyl alcohol it yields the hydrochlorid of the imido ester of
acetondicarboxylic methyl ester + one molecule of HC1 which is either
CH2(CO2CH3)CH(OH)CHC1C(OCH3)(NH),HC1 or CHC1(CO2CH3)
CH(OH)CH2C(OCH3)(NH),HC1.

ACETO ACETIC ESTER 119

NEF, J. U., 1890.

Ann. Chem. 258, 261-318, Am. Chem. J. 12, 379-425 ; J. Chem.

Soc. 58, 983.

Tautomeric Compounds.

In this article acetoacetic ester is considered and the author decides
that it is a tautomeric compound ; that the sodium derivative has the
sodium combined to oxygen, thus : CH3 CONa : CHCO2 C2 H5 , but
that the ester itself and its alkyl derivatives have the ketonic oxygen,
thus: CH3 COCHRCO2 R. By treating sodacetoacetic ester with
benzoyl chlorid two compounds were produced, the principal one was
monobenzoyl-acetoacetic ester and the minor one was dibenzoyl-aceto-
acetic ester, CH3COC (COC6 H5)2CO2 C2 H5 , which has never been
prepared before. It is very unstable and cannot be distilled even in
vacuum.

BEHREND, R. AND PAUL ERNERT, 1890.

Ann. Chem. 258, 360-362; J. Chem. Soc. 58, 1240; Ber. 23, 643(C).
Condensation of Carbarn id with Acetoacetic Ester.

Carbamid condenses with sodacetoacetic ester to form a compound
CI3 H22 N2 O7 Na 2 which is probably represented by the formula

CH3 CH3

CONa-HN-CO- NH— CONa
CH2 CH2

CO2C2H5 CO2C2H5.

It melts at 165° and is decomposed by water. It is also decomposed,
by passing carbon dioxid into its alcohol solution, into carbamid,
acetoacetic ester and sodium ethyl carbonate, NaC2 H5 CO3.

I2O BIBLIOGRAPHY OF

HANTZSCH, A., 1890.

Ber 23, 2339-2342; J. Chem. Soc. 58* 1238.

Halogen Derivatives of Acetoacetic Ester.

The action of thiocarbamid and thioacetamid on the halogen
derivatives of acetoacetic ester are used to distinguish between the «
and Y positions for the halogen thus :

CH2Br HS CH-S

II II I

CO + C-(NH2orCH3)= C C-(NH2orCH3)

I S I \ //

CO2 RCH2 HN CO2 R- CH2 N

which is amido- or methyl- thiazylacetic ester and

CO2R-CHBr HS CO2RC-S

II II I

CH3CO + C-(NH2orCH3)= CH3C C-(NH2 or CH3).

^ \ //

HN N

Bromin acting on acetoacetic ester gives the y product but when
cupracetoacetic ester is treated with bromin the a product is obtained.
Chlorin acting on acetoacetic ester gives the a product. Methyl-ethyl-
thiazole,

CH-S

II I

Cv C-CH3,

l\ ^
C2H5 N

was produced from methyl-brotn-acetoacetic ester showing it to be the
7 product and trimethyl-thiazole,

CH3-C— S

II I
CH3C CCH3,

\/l

N

was produced from methyl-chlor-acetoacetic ester showing it to be the
a derivative.

ACETO ACETIC ESTER 121

DITTRICH, E., 1890.

Ber. 23, 2720-2725 ; J. Chetn. Soc. 58, 1418.
Action of Picric Chlorid on Sodacetoacetic Ester.

By the action of picric chlorid, Ce H2 (NO2)3 Cl, on sodacetoacetic
ester the mono- or di- trinitrophenyl-acetoacetic ester is formed,
according to the proportion of picric chlorid used. Trinitrophenyl-
acetoacetic ester, CH3 COCH [C6 H2 (NO2)3] CO2 C2 H5 , melts at 98°,
dissolves in alkalis from which solution weak acids precipitate it.
Di- (trinitrophenyl) acetoacetic ester, CH3COC[C6H2(NO2)3]2CO2C2H5,
melts at 205° with decomposition ; alcoholic potash dissolves it and
acids precipitate not the same but trinitrophenyl-acetoacetic ester.
When trinitrophenyl-acetoacetic ester is boiled with sulfuric acid trini-
trophenyl acetone, CH3 COCH2 [C6 H2 (NO2)3], is formed which melts
at 89° This condenses with phenylhydrazin to Ci5 HI3 N5 O& , which
melts with decomposition at 125°

ANSCHUTZ, R., P. BENDIX AND W. KERP, 1890.

Ann. Chem. 259, 148-186; J. Chem. Soc. 60, 172 ; Ber 23, 734 (C).

Mesitene Lactone and Isodehydracetic Acid,

Much of the work done by Hantzsch on the condensation products
of acetoacetic ester has been repeated by the authors. They corroborate
his formulae for mesitene lactone and isodehydracetic acid, (Cg H8O4),
but find that the first condensation product is a mixture of isodehydra-
cetic acid and its ethyl ester. Isodehydracetic methyl ester melts at
67° and boils at 167° under 14 m.m. pressure, it can be obtained by
treating the potassium salt with methyl iodid or by condensing aceto-
acetic methyl ester. Unsuccessful attempts were made to prepare
Hantzsch 's homomesaconic acid ; by treating isodehydracetic ester with
potash two acids were obtained ; (i) CIO HI2 O4 which melts with decom-
position at 221°. is almost insoluble in ether, benzene, chloroform and cold
water and but moderately soluble in boiling water. Its potassium,
barium and copper salts and methyl ester were described. The second

122 BIBLIOGRAPHY OF

acid Cg HIO O3 , melts at 149°, is soluble in alcohol, ether and chloroform
and decomposes at 160°; its barium and silver salts were described.
Isodehydracetic ester is converted by warm anhydrous ammonia into
the corresponding lactam, identical with the substance obtained by
Collie by the condensation of /9-amido-crotonic ester. The change is
represented thus :

CH3 CH3

C C

' ^ / ^

C02C2H5C CH C02C2H5C CH

I I I

CH3C CO CH3C CO

\ / \ /

O N

H
Isodehydracetic ester Caroxethylmesitenlactam.

Mesitene lactone

C

/ \
HC CH

I !

CH3 C CO

\ / ,
O

is changed by ammonia into mesitene lactam

CH,
C

/ \

HC CH

I I
CH3 C CO

\ /
N
H

An alcoholic ethereal solution of isodehydracetic ester treated in the

ACETO ACETIC ESTER 12}

cold with ammonia forms a compound CIO HX8 N2 O4, if moisture be
excluded. It is represented thus :—

CH,

NH2
ONH4

/ \
C02 RC CH

I I
CH3 C C <

\ /
O

Isodehydracetic ester can be prepared from sodacetoacetic ester and
/3-chlorcrotonic ester which proves its constitution thus : —

C02 C2 H5 CH3 CO2 C2 H5 CH

CH3 CO— C

C : CH— CH3 C : C C : CH.

C:O

AUTENRIETH, W., 1890.
Ann. Chem 259, 365-373 ; J. Chem. Soc. 60, 204.

Sulfur Derivatives of Acetoacetic, Methylacetoacetic and
Ethylacetoacetic Esters.

By treating /9-dithiophenylbutyric ester, CH3C(SC6H5)2CH2CO2C2H5,
with sulfuric acid and potassium permanganate, /?-diphenylsulfone-
butyric ester, CH3 C (SO2 C6 H5)2 CH2 CO2 C2 H5 , is obtained, it melts
at 97°, is soluble in hot alcohol, ether and benzene and insoluble in
water. «-Ethyl-/9-diethylsulfonebutyric ester, CH3 C (SO2 C2 H5)2 CH
(C2 H5) CO2 C2 H5 , formed in a similar manner from the condensation
product of ethyl mercaptan and ethyl-acetoacetic ester, melts at
87°-88° a-Methyl-/9-diethylsulfonebutyric ester melts at 79? a-Ethyl-
/9-dithiophenylbutyric ester, CH3 C (SC6 H5)2 CH (C2 H5) CO2 C2 H5 ,
is made by condensing ethyl-acetoacetic ester and phenyl mercaptan,
and melts at jo°-rji° From this by the above method was prepared
tt-ethyl-^-diphenylsulfonebutyric ester, CH3C(SO2C6H5)2CH(C2H5)
CO2C2H5, which melts at ui.°

124 BIBLIOGRAPHY OF

ELION, H., 1890.

Ber. 23, 3123-3124 ; J. Chem. Soc. 60, 171.

Preparation and Properties of Sodacetoacetic and
Sod=ethylacetoactic Esters.

Both these substances when anhydrous are soluble in ether but both
form hydrous compounds insoluble in ether. The anhydrous com-
pounds cannot be obtained by keeping the hydrous compounds over
sulfuric acid as has been stated and the author thinks that there is but
one form of anhydrous sodacetoacetic ester and not two, one of which
is insoluble in ether as stated by Michael.

PINNER, A., 1890.

Ber. 23, 3820-3826 ; J. Chem. Soc. 60, 468.
Imido Esters and their Derivatives.

Acetoacetic ester is treated with imidobenzoic ester and the chief
product is found to be phenylmethyl-hydroxypyrimidin,

C6H5C CH,

^N : C(OH)/

melting at 216.° The imidobenzoic ester is probably first converted
into benzoic ester and ammonia thus: C6H5 C (NH) OC2H5H-H2O=
C6H5 CO2 C2 H5-|-NH3 ; the ammonia acts on some imido-benzoic
ester forming alcohol and benzamidin which last product unites with
the acetoacetic ester.

JAPP, FRANCIS R. AND FELIX KLINGEMANN, 1891.

J. Chem. Soc. 59, 1-26.
Phenanth roxy lene-acetoacetic Ester.

This compound, prepared from acetoacetic ester and phenanthra-
quinone and given the formula,

C6H4-C
C6 H4— CO

ACETO ACETIC ESTER 12s)

has been further studied. When treated with formic or sulfuric acid
an isomer is formed, to which the formula,

/~V TT (~\

C6H4-C

C6H4— C(OH)— CH

is provisionally given, and which is called isophenanthroxylene-aceto-
acetic ester; it melts at 177.° It forms a mono-acetyl derivative, C20
HI5 (C2 H3 O) O4 , which melts between 165° and 170°, and a mouo-
hydrazone, C20 Hl6 O3 (N2 HC6 H5). No pyrazolone could be obtained
from this, and phenanthroxylene-acetoacetic ester does not react with
phenylhydrazin. With bromin the iso compound gave C20HI5BrO4.
When reduced the iso compound gave CaoH^Oj, which is also pro-
duced from the phenanthroxylene-acetoacetic ester by means of
hydriodic acid. This gave a phenylhydrazin derivative, C20 Hl6O2
(N2HC6H5). When treated with hydriodic acid the iso compound
gave CI7 HI2 O , which is the compound to which Japp and Streatfield *
gave the formula CH HIO O . It is probably a ketone containing the
carbonyl group in a penta-carbon ring. Treated with an alkali the iso
compound gave the iso-phenanthroxylene-acetoacetic acid, CjsH^
O4 , which is mono-basic. The action of acetic, propionic, sulfuric,
alcoholic hydrochloric acids and of alcoholic potash and ammonia on
phenanthroxylene-acetoacetic ester was determined and an account
given of the experiments. The subject requires more study before the
composition of these bodies can be definitely settled. The formula
proposed for the iso compound explains some reactions but leaves
others quite unexplained.

*See page 39.

CLAISEN, L. AND E. HORI, 1891.

Ber. 24, 139-140; J. Chem. Soc. 60, 416.
Action of Hydroxylamin on Acetoacetic Aldehyde.

By this action a compound Cs HI3 N3O3 , was produced which
crystallizes in white needles, melting at 174 ° It is sparingly soluble in
ether, benzene and chloroform. Other compounds which were expected
from this reaction were not obtained.

126 BIBLIOGRAPHY OF

EMERY, W. O., 1891.

Ber. 24, 282-286 ; J. Chem. Soc. 60, 547.
Action of /5-Bromopropion ic Ester on Acetoacetic Ester.

By the action of /9-bromopropionic ester on sodacetoacetic ester,

CH,

CO
«-acetylglutaric ester, CH — CH2— CH2 CO2 C2 H5 , was produced. It

C02 C2 H5

boils at 162° at n m. m. pressure and has a specific gravity of 1.071 at
20° It reacts with ammonia and with amins, yielding amido-derivatives
of a-ethylidineglutaric ester, which can be converted into lactams.

HANTZSCH, A., 1891.

Ber. 24, 495-506 ; J. Chem. Soc. 60, 739.
Action of Hydroxylamin on /3*=Ketonic Acids and /9-Diketones.

By the action of hydroxylamin on acetoacetic ester in alkaline solu-
tion and subsequent acidification the chief product is methyl-isoxazol-

^N — O

one, CH3C ' I , which melts at 169°- 170° and is a base towards
'-CH2 CO

strong acids. In alkaline solutions it is partially changed into oximido-
butyric acid, CH3 C : (NOH) CH2 CO2 H . By the action of hydroxyl-
amin on acetoacetic ester in neutral or acid solution, an oil is obtained
which, on being hydrolyzed, gives a crystalline substance, C20 H26 N4
O7 , which melts at 140° and can by hydrolysis be changed into methyl-
isoxazolone. By the action of hydroxylamin on acetoacetic ester in
ammoniacal solution an unstable product was obtained which may be

the hydroxamic acid of acetoacetic acid, CH3 CO CH, C

ACETO ACETIC ESTER 1 27

COLLIE, J. NORMAN, 1891.

J. Chem. Soc. 59» 172-179.
Action of Heat on ^-Amidocrotonic Ester.

When this substance is distilled a small amount of substance is
always left which has been found to be CIO HI3 NO3, the ethyl ester of
an acid, Cg H9 NO3, which is dimethyl-pyridone-monocarboxylic acid,

NH
/ \
CH3C C-CH3

II II
CO2 HC CH

\ /

c
o

The ester, CIO HI3 NO3, melts at 163°- 164° and boils with slight decom-
position at 240° to 250.° It does not form a compound with phenyl-
hydrazin or hydroxylamin. With bromin it forms Ci0HI2BrNO3;
with PC15 it gives Cio HI2 NO2 Cl, which can be changed into chloro-
lutidin boiling at 177° to 180.° The acid C8 H9 NO3, melts at 257°-258°
and is converted into a-a'-dimethyl-pyridone,

NH
/ \
CH3 C CCH3 .

I
HC CH

\ /
CO

This was also prepared from dehydracetic acid. Phosphorus penta-
chlorid acts on a-a'-dimethyl-pyridone to form chlorolutidin boiling at
1 78°- 1 79? a-a'-Dimethyl-pyridin or lutidin was obtained in four ways,
(i) by the action of nascent hydrogen on chloroludidin ; only a little
could be formed in this way ; (2) from vapors of chlorolutidin and zinc
dust in an atmosphere of hydrogen ; (3) from chlorolutidin made from
dehydracetic acid ; (4) from the potassium salt of lutidone-mono.
carboxylic acid heated with an excess of solid potassium hydroxid.
By oxidation of the lutidin, dipicolinic acid, C5 H3 N (CO2 H)2, was
obtained.

128

BIBLIOGRAPHY OF

COLLIE, J. NORMAN, 1891.

J. Chem. Soc. 59> 179-189.
Constitution of Dehydracetic Acid.

The author, having studied this acid and its reactions, determines
that Feist* did not present the correct formula for it and proposes the
formula

CH3COCH2C-0-C=0
II I

CHCO ' CH2
or the tautomeric form

CH3 C (OH) : CHC-O— — C=O

CHC (OH) : CH

By this formula he thinks that all of its reactions, the most important
ones of which he illustrates, can best be explained. He considers it as

CH - O - CO

built up on the nucleus of a-oxypyrone, II I . Its forma-

CH— CO-CH2

tion from acetic acid is illustrated thus : —

CH.CO

OH H

CH2CO

CH2CO

OH H

CH2 C O O H

and then CH, COCH2 C : CHCOCH2 CO

O H

OH

STEUDE, M., 1891.

Ann. Chem. 261, 22-47 ; J. Chem. Soc. 60, 742
Thiazole Derivatives from Bromacetoacetic Ester.

The thiazole derivatives obtained from bromacetoacetic ester and
thio-carbamid and thiacetamid are isomeric with those obtained if
chloracetoacetic ester be used, but those obtained both ways can be
converted into /*-amido-«-methyl-thiazole or «-/>dimethyl-thiazole as
the case may be. This proves that bromacetoacetic ester has the
formula CH2 Br COCH2 CO2 R . fJ.- Amido-thiazylacetic ester,

c oi~r ^-«

i ^'CCH2C02C2H5

C(NH2):N^

See page 114.

ACETO ACETIC ESTER 129

obtained from bromacetoacetic ester and thiocarbamid melts at 94 , the
free acid melts at 130.° Thiacetamidoacetic ester, CH2(SCNHCH3)
COCH2 CO2 C2 H5 , is formed besides //-methyl-thiazylacetic ester from
bromacetoacetic ester and thiacetamid in alcoholic solution. Methyl-
thiazylacetic ester,

S - CH

I > CCH2 CO2 R

C(CH3):N

boils at 238° to 240^ r-Thiacetoacetoacetic ester, CH2 (SCOCH3) CO
CH2 CO2 R , results when thiacetamidacetoacetic ester hydrobromid is
warmed with water. It boils at 155° at 15 m. m. pressure. A com-

_ ^s v
pound, probably of the formula CO2 RCH2 C CCH2 C°2 R '

was also described.

PECHMANN, H. v. AND M. DUNSCHMANN, 1891.

Ann. Chem. 261, 162-166 ; J. Chem. Soc. 60, 672.

Decomposition of Acetone-dicar boxy lie Ester.

When acetone-dicarboxylic ester, CO2 C2 H5 CH2 COCH2 CO2 C2 H5 ,
is changed to the potassium salt and then boiled with water, acetoacetic
ester is produced which is identified by being treated with phenylhy-
drazin and changed into methyl-phenylpyrazolone.

JAEGER, J., 1891.

Ann. Chem. 262, 365-372 ; J. Chem. Soc. 60, 1007.
Condensation of Guanidin with /3-Ketonic Esters.

Guanidin carbonate and acetoacetic ester condense to form imido-

methyl-uracyl, CH xCCCH )NH ^ C : NH ' which melts with decom-
position at 270? The hydrochlorid, nitrate and sulfate were described.

Dibromohydroxyimidomethyl-uracyl, NH < > CCH3 OH '

is formed together with bromimidomethyluracyl, C5H6BrN3O , when
imidomethyl-uracyl is heated with bromin ; it melts at 160" When

I3O BIBLIOGRAPHY OF

imidomethyluracyl is heated with an excess of methyl iodid a com-
pound, (C5 H6 N3O CH3)2 HI , is obtained, which melts at 212° and can
be converted into methyl-imidomethyl-uracyl, C5 H6 N3 OCH3 , which
melts at 312° Imidodimethyluracyl formed from guanidin carbonate
and methyl-acetoacetic ester melts at 320°, and imido-phenyl-uracyl
formed from guanidin carbonate and benzoylacetic ester melts at 294.°

BREDT, J., 1891.

Ber. 24, 603-605; J. Chem. Soc. 60, 712.
Action of Sodacetoacetic Ester on Benzalmalonic Ester.

By this reaction in alcoholic solution at o a crystalline sodium
compound is formed which when decomposed by an acid gives a
compound dg H20 O& , which is sparingly soluble in water and melts
with decomposition at 155

OTTO, R. AND A. ROSSING, 1891,

Ber. 24, 685-687; J. Chem. Soc. 60, 712.
Action of Sodium Phenylmercaptid on Chloracetoacetic Ester.

When equivalent quantities of these substances are made to react in
alcoholic solutions, an oil is obtained, which will not crystallize and
has but a feeble odor. It appears to be thiophenylacetoacetic ester,
CH3 COCH (SC6 H5 ) C02 C2 H5 .

BIQINELLI, P., 1891.

Ber. 24, 1317-1319; J. Chem. Soc. 60, 908.
Aldehydeuramids of Acetoacetic Ester. Part i.

Molecular proportions of acetoacetic ester, benzaldehyde and carb-
amid are allowed to react and a crystalline compound melting at 207 -
208 is obtained. It is either

CH3 CH3

C : N • CO— N : CHC6 H5 or C— NH • CO • N : CHC6 H5

I II

CH2 ' . CH

C02 C2 H5 C02 C2 H5

ACETO ACETIC ESTER

but probably is the latter. The same substance can be formed from
uramidocrotonic ester and benzaldehyde. It is very stable as it is not
affected by strong acids or alkalis in the cold. Heating it with
potassium hydroxid gives benzyl alcohol, benzaldehyde, ammonia and
potassium carbonate, besides an unknown solid substance. Salicylal-
dehyde, cinnamaldehyde, furfuraldehyde, cumaldehyde and others
react similarly.

BEYER, C., 1891.

Ber 24, 1662-1670; J. Chem. Soc. 60, 1090.
Hantzsch's Pyridin Synthesis,

The author believes that in these reactions acetoacetic ester and
aldehyde first react to form ethylidin-acetoacetic ester,

CH3
7/CH,
C02 RC
CH3CO

and that this then unites with acetoacetic ester to form ethylidin-
diacetoacetic ester,

CH,

CH

/ \
CO2 RC CHC02 R

H| I
CH3 COOCCH3

which unites with ammonia to form dihydrocollidin-dicarboxylic ester,

CH,

CH
/\
CO2R. C C-C02R.

II II
CH3C C-CH3

V

N

I
H

1)2 BIBLIOGRAPHY OF

Kthylidinacetoacetic ester and paramido-acetoacetic ester were mixed
in molecular proportions and united to form dihydrocollidin-dicarboxy-
lic ester. Several other experiments were performed and several
pyridin derivatives made and described. They all agreed with these
reactions.

FREER, P. C., 1891.

Am. Chem. J. 13, 308-322; J. Chem. Soc. 60, 1181.

Constitution of Aliphatic Ketones and the Action of Sodium on

Acetone.

The constitution of acetoacetic ester is discussed at length and
mention is made of the work done by different chemists upon it.
Acetic ester dried over calcium chlorid and by being boiled over
phosphorus pentoxid is found to react with sodium readily which
inclines the author to believe in the intermediate sodacetic ester. A
comparison of the properties and reactions of tetric acid and acetoacetic
ester seems to show that the former contains a hydroxyl group and the
latter does not. In the sodium derivative the author believes the sodium
is joined to the oxygen, therefore that its constitution is different from
that of acetoacetic ester itself. This is shown by the fact that sodaceto-
acetic ester will form addition products with unsaturated compounds
like cinnamic ester while the acetoacetic ester itself will not.

FREER, PAUL C. AND QEO. O. HIGLEY, 1891.

Am. Chem. J. 13, 322-326; J. Chem. Soc. 60, 1182.
Action of Chlorcarbonic Ester on Acetone Sodium.

By this action a colorless oil boiling at about 125° was obtained which
appears to be an isomer of acetoacetic ester. It is insoluble in water,
miscible with alcohol and ether and does not react with phenyl hydrazin
or ferric chlorid. On boiling with hydro chloric acid it is decomposed
into carbon dioxid, alcohol and acetone. The authors suggest for it

the formula 2C-O-CO2 C2 H

ACETO ACETIC ESTER I}}

WALDEN, P., 1891.

Ber. 24, 2025-2039; J. Chem. Soc. 60, 1187.
Tetric and Oxytetric Acids and their Homologues.

Experiments were performed attempting to determine whether tetric
acid and its homologues contain the carboxylic group but no definite
conclusions were reached. Oxytetric acid and its homologues were
shown to be alkyl substituted fumaric acids, thus oxytetric is mesaconic
or methyl fumaric, oxypentic is ethyl fumaric. etc. The acids described
by Demarcay as hydroxy tetric, etc., are identical with alkyl succinic
acids, hydroxytetric is methyl succinic and hydroxypentic is ethyl
succinic, etc. The acids are all obtained from the bromated alkyl ace to-
acetic esters.

SPRAQUE, CHARLES T., 1891.

J. Chem. Soc. 59* 329-343.
Thiacetoacetic Ester.

This substance was produced and after carefully determining the
melting point it was found to be between 75° and 78.° By the action of
phenylhydrazin four bodies were produced : — (i) thiophenyl-methyl-
pyrazolone ; (2) Knorr's phenylmethyl-pyrazolone-azobenzene ; (3) a
substance, CIO H9* N2 SO ; (4) Knorr's bisphenyl-methyl-pyrazolone.
The first one is

NC6 H5 NC6 H5

/\ / \

N CO OC N

II I I II
CH3 C— CH— S— HC CCH3

it is a weak base; dissolves in alkalis and weak acids reprecipitate it.
If it be heated with phenylhydrazin the other three above mentioned
compounds are produced. To the third product the author gave the
formula CIO H8* N2 SO, but states that Holtzcka has since proven it to
be bisulphid of phenylmethyl pyrazolone (CIO H9 N2 O)2 S2. A method
was given for preparing a good yield of each one of the four products.

* A disagreement, Cio Hs N2 SO is probably correct

134 BIBLIOGRAPHY OF

COLLIE, J. NORMAN, 1891.

J. Chem. Soc. 59, 617-621.
Some Reactions of Dehydracetic Acid.

In the preparation of dehydracetic acid by passing acetoacetic ester
through a red-hot iron tube, there were formed, besides the dehydra-
cetic acid, acetone, alcohol, carbon dioxid, ethylene and a residue.
Acetoacetic methyl ester similarly treated gave large quantities of
dehydracetic acid, but ethylacetoacetic ester gave none at all. De-
hydracetic acid is slightly decomposed by water into carbon dioxid and
dimethylpyrone. When boiled with hydrochloric acid it is totally
decomposed into carbon dioxid and a compound, C;!!!^^!, which
melts at 83 -85 and is acid in water solution. Barium and copper
salts of dehydracetic acid were prepared, the former corresponded most
nearly with (CsH9O5)2Ba and was considered to be the salt of
tetracetic acid, CH3 COCH2 COCH2COCH2 CO2H; and the latter
corresponded to C24 H25 O9 N3 Cu, being formed by ammonia and copper
acetate. Hydrocyanic acid has no action on dehydracetic acid.

BIGINELLI, P., 1891.

Ber. 24, 2962-2967; J. Chem. Soc. 62, 56.
Aldehydeuramids of Acetoacetic Ester. Part II.

In the continuation of the subject it is found that two isomers, cor-
responding to the two formulae given in the first article on this subject,*
are always produced. The compounds

CH3

C,4 HI6 N2 04 ;-C : N. CO. N. CH C6 H4 OH
I

CH2

C02 C2 H5
CH3
and C— NH— CO-N— CH— C6H4OH

II

CH

C02 C2 H5

formed from carbamid, salicylaldehyde and acetoacetic ester, and the
similar compounds, Ci7H22N2O3, formed from cumaldehyde, CeH4
(C3 H7) COH, carbamid and acetoacetic ester ; Cl6 Hl8 N2 O3 , obtained
by using cinnamaldehyde, and CI2 HI4 N2 O4 , obtained by using
furfural dehyde, are produced and described.

* See page 130.

ACETO ACETIC ESTER I}5

CONRAD, M. AND L. LIMPACH, 1891.

Ber. 24, 2990-2992, J. Chem. Soc. 62, 78.

Synthesis of Quinolin Derivatives by means of Alkyl Acetoacetic

Esters.

Methyl-acetoacetic methyl ester and anilin, when mixed and allowed
to stand, form phenyl-amido-methyl-crotonic methyl ester. By quickly
heating this, it is changed into dimethyl-hydroxyquinolin, C9 NH4
(CH3)2 OH , [(CH3)2 : OH = 2': 3': 4']. Methyl-ethyl-hydroxy-quin-
olin is produced similarly from phenyl-amido-ethyl-crotonic methyl
ester.

NEF, J. U., 1891.

Ann. Chem. 266, 52-138; J. Chem. Soc. 62, 140.
Acetoacetic Ester.

A large number of experiments are performed relative to determining
the constitution of acetoacetic ester and the position of the sodium in
the sodium derivative, and the conclusions drawn are that acetoacetic
ester is not a ketone but is represented by CH3 COH : CHCO2 C2 H5
and that in the sodium derivative the sodium is joined to oxygen. If
by heating the sodacetoacetic ester with an alkyl halogen the alkyl is
substituted for the sodium, the reaction should be more energetic if the
heavier metals, such as copper or lead, be in the acetoacetic ester in
place of sodium, but solutions of the copper or lead derivatives of aceto-
acetic ester do riot react with ethyl iodid at ordinary temperatures —
which proves that no direct substitution of the metal takes place. The
author supposes an intermediate addition product to be formed with
an alkyl iodid, for example, with benzylchlorid, CH3 CONaClCH
(CH2C6H5)CO2R is first formed and then HC1 splits off leaving
CH3CONa : C (CH2C6H5) CO2R and by continued action CH3CONaClC
(CH2 C6 H5)2 C02 R and then CH3 COC (CH2 C6 H5)2 CO2 R are formed.
As proof of the existence of hydroxyl in acetoacetic ester its acid
properties and its behavior towards phenyl hydrazin, ammonia and
the amids are mentioned, also the fact that acetoacetic ester and
its mono-alky 1 derivatives are not reduced by treatment with sodium
in ethereal solution while the diethyl derivative is converted into

I}6 ACETO ACETIC ESTER

diethyl-hydroxybutyric ester. The substitution of the «-hydrogen
atom affects the compound according to the character of the
substituted group, making it more alcoholic or more acidic as that
group is more or less positive than hydrogen. By the action of phenyl-
hydrazin on acetoacetic ester phenyl-/9-hydrazo-crotonic ester, CH3 C
(N2 H2 C6 H5) : CHCO2 R, melting at 50 is formed and by heating this
with mercuric oxid phenyl-/9-azocrotonic ester, CH3 C (N2C6H5):
CHCO2 R, melting at 5 r ° is obtained. The product obtained by the
action of bromin on acetoacetic is a mixture of the a and the f brom-
derivatives. a-Brom-methyl-acetoacetic ester, C7 HIT BrO3, boiling at
107° at 30 m.m. pressure, is obtained by treating sodmethyl-acetoacetic
ester or methyl-acetoacetic ester with bromin. When this is heated
in a sealed tube tetric acid is formed for which the author gives the
formula

CH2 : C (OH) CCH3<°£°> CCH3 C (OH) : CH2

«-Bromethylacetoacetic ester, Cg HI3 Br O3 , is prepared similarly and is
described. Dibenzoyl-acetoacetic ester, C20 Hjg O5 , and triacetylacetic
ester, CH3 CO C (CH3 CO)2 CO2 R, and acetylcarbintricarboxylic ester,
CH3COC (CO2R)2CO2R, are also described. A large number of
pyrazolone derivatives are prepared and studied, and the author decides
that their acid properties are due to the presence of an imido group.
The formula for phenylmethyl-pyrazolone he gives as

C (CH3)-NH

NC6H5
CH— CO

PECHMANN, H. v., 1891.

Ber. 24, 3600; J. Chem. Soc. 62, 296.
Preparation of Dehydracetic Acid.

By treating acetondicarboxylic acid with acetic anhydrid, a substance
either isomeric or identical with the carboxylic acid of dehydracetic
acid is produced. This may be easily changed into dehydracetic acid
by dissolving in soda, evaporating to dryness and precipitating the
aqueous solution with acetic acid.

AUTHOR INDEX.

Allen, Win. and Alfred Kolliker, 64.

Allihn, F., 19, 25.

Anschiitz, R., P. Bendix and W. Kerp,

121.

Autenrieth, W., 123.

Baeyer, Adolf, 75.
Bandrowski, E., 24.
Baumann, E. (See Escales), 80.
Behrend, Robert, 53, 63, 66.

and Paul Ernert, 119.

R. List and A. Kohler, 78.
Bender, G., 91.

Bendix, P. (See Anschiitz), 121.
Bergreen, Henry, 94.
Bernhart, C. (See Perkin), 60.
Beyer, C., 131.

and L. Claisen, 99.
Biginelli, P., 106, 130, 134.
Bischoff, Carl, 29.
Blank, A. (See Knorr), 61.
Booking, Eduard, 28.
Bongartz, J., 94.
Bonne, Julius, n.
Brandes, R., 3.
Bredt, J., 130.
Bucka, K., 70.

and Ch. Sprague, 112, 117.
Billow, Carl, 83. •

Burchard, Oscar (See Michaelis), 113.
Burton, Beverly S., 31.

Canzoneri, F. and G. Spica, 55, 57, 79.
Ceresole, M., 34, 37, 42.
Chancel, G., 41.
Chanlaroff, Moehsin Beg, 55.
Chodounsky, K. (See Raymann), 103.
Claisen. L., 29, 102.
See Beyer, 99.
and E. Hori, 125.

O. Lowmann, 90.

F. E. Matthews, 40.

N. Stylos, 98.

W. Zedel, 102.

Cloez, C., 117, 118.
Clowes, F. (See Wislicenus), 7.
Collie, J. Norman, 54, 127, 128, 134.
Conrad, M., 10, u, 12, 13, 14, 18, 20, 37.
and W. Epstein, 92.

M. Guthzeit, 75. 86.
L. lyimpach, 23, 90, 135.
See Wislicenus, 6, 7.
Curtius, Th. and R. Jay, 105.

Degen, Jos., 82.
Deichmiiller, A., 30.
Delisle, A., 91, 104.
Demarcay, E., 8, 15, 16, 27.
Dietzel, Adolf, (See Fittig), 107.
Dittrich, E., 121.
Duisberg, C., 34, 40, 41.

See Pechmann, 46

Diinschmann, M. (See Pechmann), 129.
Duppa, B. F., (See Frankland), 2, 4.

Ehrlich, Franz Louis, 12.

See Wislicenus, 6, 7.
Elion, H., 43, 56, 124.
Emery. W. O., 126.
Emmerliug, O. and A. Oppenheim, 9.
Engelmann, Franz, 73.
Epstein, W., 73.

See Conrad, 92.

Ernert, Paul (See Behrend), 119.
Escales, R. and E. Baumann, 80.
Eynern, Fritz v. (See Fittig), 107. ^

Feist, Franz, 109, 114.
Fittig, R., 70, 74.

Fritz von Eynern and Adolf Dietzel,

107.

Frankland, E. and B. F. Duppa, 2, 4.
Freer, P. C., 132.
and Geo. O. Higley, 132.
W. H. Perkin Jr., 89.
See Perkin, 85.

i38

AUTHOR INDEX

Gabriel, S., 30.

and J. Hausmann, in.
Genvresse, P., 95.
Geuther, A., i, 2, 4, 6, 47, 65, 96.
Gottstein, L., 35.
Griess, Peter, 68.

and G. Harrow, 99.
Guthzeit, Max, 28.

See Conrad, 75, 86.

Haitinger, L., 65.

Haller, A. and A. Held, 36, 89, 95, 105,

118.

Haller, S., 67.

Hantzsch, A., 30, 34, 42, 46, 51, 69, 70,
1 20, 126.

and H. Ziircher, 91.
Hardtmuth, F., 22.
Harrow, Geo. H. U., 23.

See Griess, 99.

Hausmann, J. (See Gabriel), in.
Heckmann, Jacob, 50.
Held, A., 56, 104, 105.

See Haller, 36, 89, 95, 105, 118.
Higley, Geo. O. (See Freer), 132.
Hilger, A., 24.

Hodkinson, W. R. (See Matthews), 38.
Hofmann, Otto, 27.
Hori, E. (See Claisen), 125.
Huggenberg, Carl, 22.

See Wislicenus, 7.

Isbert, A., 78.

Jaeckle, A., 101.

Jaeger, J., 129.

Jaksch, R. v., 35, 48, 71.

James, J. Wm., 53, 76, 87.

Janny, Alois, 39.

Japp, Francis R. and Felix Klingmann,

92, 93. 98, 101, 124.
F. W. Streatfeild, 39.
Jay, R. (See Curtius), 105.
Jones, E. J-, 54-.
Jourdan, Friedrich, 26.
Just, Feodor, 64.

Kerp, W. (See Anschiitz), 121.
Kipping, F. Stanley and W. H. Perkin,

Jr., 106, 113.

Kleemann, S. (See Liebermann), 59.
Klingmann, Felix, (See Japp), 92, 93,

98, 101, 124.
Knorr, L., 48, 49, 58, 61, 82, 83, 86, 97,

103.

and A. Blank, 61.
Kohler, A. (See Behrend), 78.
Kolliker, Alfred (See Allen), 64.
Konig, Heinr., 25.

Kraft, F. and J. Mai, no.
Kressner, G., 21.
Kuckert, Otto, 66.

Ladenburg, A., 5.

and L. Riigheimer, 25.
Liebermann, C. and S. Kleemann, 59.
L/impach, L,. (See Conrad), 23, 90, 135.

See Wislicenus, 20.
Lippmann, E., 38.
List, R., 81.

See Behrend, 78.

Lowig, Carl and Sal. Weidermann, i.
lyowmann, O. (See Claisen), 90.

Mai, J. (See Kraft), no.
Matthews, F. E., 43.

See Claisen, 40.

and W. R. Hodkinson, 38.
Meister, Johannes, 96.
Mewes, W., 97.
Meyer, Victor, 17.

and J. Ziiblin, 19.
Michael, A., 87, 88, 99.
Michael, R , 69.
Michaelis, A. and Oscar Burchard, 113.

B. Philips, 1 1 6.
Miehle, Gustav, 15.
Mixter, Wm. G., 6.
Morris, Geo. H., 26.
Miiller, Albert, 80.
Miinzer, H., (See Richter), 60.

Nef, J. U., 119, 135.

Norton, Th. and A. Oppenheim, 14.

Obrembsky, M. (See Perkin), 84.
Oppenheim, A. (See Emmerling), 9.

See Norton, 14.

and H. Precht, 8, 9.
Otto, Robert, 94.

and A. Rossing, 130.

Paal, C., 50, 59, 63.
Pechmann, H. v., 98, 102, 136.
Pechmann, H. v. and C. Duisberg, 46.

and M. Diinschmann, 129.
Perkin, Jr. W. H., 41, 44, 47, 59, 64, 71*
77, 84, 88, 114.

and C. Bernhart, 60.
P. C. Freer, 85.

See P. C. Freer, 89.
Kipping, 106, 113.

and M. Obrembsky, 84.
Perkin, Sr., W. H., 58.
Peters, T., 93, 115, 116.
Philips, B. (See Michaelis), 116.
Pinner, A., 62, 68, 72, 124.
Pohl, O., (See Raymann), 113.
Palonowska, Natalie, 84.

AUTHOR INDEX

139

Polonowsky, M., 100.
Precht, H., 23.

See Oppenheim, 8, 9.
Propper, Max, 33, 39.

Raymann, B. and K. Chodounsky, 103.

O. Pahl, 113.

Richter, V. v. and H. Miinzer, 60.
Rohn, Wilhelm, 15.
Rohrbeck, Hermann, 13.

See Wislicenus, 7.
Roser, W., 50.

Rossing, A. (See Otto), 130.
Riicker, Aug., 17.
Ruegheimer (See Wislicenus), 6.
Riigheimer, L,., (See Ladenburg), 25.

Saur, Richard, 14.

See Wislicenus, 7.
Schiff, Hugo, 92.
Schiff, Robert, 77.
Schiller- Wechslef, Max, 69.
Schmid, Wilhelm, 36.
Schnapp, Heinr., 16.
Schonbrodt, R., in.
Society for Chem. Industry in Basel, 76,

. 79-

Spica, G. (See Canzoneri), 55, 57, 79.
Sprague, Charles T., 133.

See Bucka, 112, 117.
Steude, M., 128.

Streatfeild, F. W. (See Japp), 39.
Stylos, N. (See Claisen), 98.

Thome, L. T., 31.
Tiemann, F., 112.
Tollens, B., 31.

Venable, F. P., 26.

Walden, P., 133.
Waldschmidt, Ernst, 13.

See Wislicenus, 7.
Wallach, O., 90.
Wanklyn, A., 2, 4, 5.
Wedel, Wilhelm, 44.
Weidermann, Sal. (See Lowig), i.
Weltner, A., 57.
Westenberger, Bernhard, 51.
Wislicenus, J., 5, 6, 10, 18, 29, 32, 49.

F. Clowes and C. Huggenberg, 7.

and L. Limpach, 20.

Ruegheimer, Conrad, Ehrlich and
Zeidler, 6.

Zeidler, Ehrlich, Rohrbeck, Wald-
schmidt, Saur and Conrad, 7.
Wislicenus, Wilhelm, 101.
Witt, Otto N., 85.
Wittenberg, Max, 36.
Wleiigel, S., 33-
Wolff, Carl, 17.

Young, Sidney, 38.

Zedel, W. (See Claisen), 102.
Zeidler, Franz, 12.

See Wislicenus, 6, 7.
Zublin, J., 24.

See Meyer, 19.
Ziircher, H., 109.

See Hantzsch, 91.

SUBJECT INDEX.

Acetaldehyde, 54.

Acetamid, 57.

Acetamidin, 62, 72.
/3-Acet-amido-a-crotonic ester, 54.
«-Acet-cinnamic ester, 40.

Acetethyliden-acetic ester, 29, 40.

Acet-isamyliden-acetic ester, 40.

Acet-isobutyliden-acetic ester, 40.

Acetoacetic acid, 30, 31, 34, 35, 37,
48, 60, 88.

Acetoacetic aldehyde, 98.

Acetoacetic amyl ester, 10, n.

Acetoacetic anilid, 82, 83.

Acetoacetic ester dithio-glycollic
acid, 94.

Acetoacetic iso-amyl ester, 116.

Acetoacetic isobutyl ester, 116.

Acetoacetic isopropyl ester, 116.

Acetoacetic methyl ester, 3, 92, 95,
116, 121, 134.

Aceto-benzal-acetic ester, 40.

Aceto-benzyliden-acetic ester, 29.

Aceto-butyl alcohol, 84.

Aceto-butyl bromid, 107.
•I- Ace to-butyric acid, 29, 35.
a-Aceto-furfuracrylic ester, 40.

Aceto-furfural-acetic ester, 40.

Aceto-glutaric ester, 20.
,3-Aceto-isobutyric acid, 29, 35.

Aceto-malonic ester, 7.

Aceto-methyl-trimethylene, 59.

Aceto-methyl-trimethylene-carboxy-
lic ester, 59.

Acetone-dicarboxylic acid, 136.

Acetone-dicarboxylic ester, 129.

Acetone-dicarboxylic ester imido-hy-
drochlorid, 118.

Acetone-dicarboxylic methyl ester
imido-hydrochlorid, 118.

Acetone sodium, 132.

Acetonyl-acetoacetic ester, 63.

Aceto-phenon-acetoacetic ester, 50,

57, 59. 63-
Aceto-phenou-acetone, 50, 59, 63.

Aceto-phenon bromid, 57.
,^-Aceto-propionic acid, 13.

Aceto-propyl alcohol, 85, 89.

Aceto-propyl anhydrid, 89.

Aceto-succinic ester, 7, 12, 15.

Aceto-tetramethylene, 44.

Aceto-tetramethylene-carboxylic es-
ter, 41, 44.

Aceto-tricarballylic ester, 15.
«-Aceto-trichlor-crotonic ester, 40.

Aceto-trichlor-ethyliden-acetic ester,
40.

Aceto-trimethylene carboxylic ester,

47-

Aceto-valeric ester, 8.

Acetoxim, 39.

Acetyl-acetoacetic ester, 53, 65, 96.

Acetyl-carbin-tricarboxylic ester, 136.
w-Acetyl-a-w-diethyl-caproic acid, 113.
a-Acetyl-glutaric ester, 126.

Acetyl-/Mmidobutyric ester, 57.

Acetyl-methyl-acetoacetic ester, 53.

Acetyl-propionyl, 98.

Acetyl-thio-carb-acetic acid, 14.

Acetyl-trimethylene, 89.

Acetyl-trimethylene-carboxylic ester
71, 85, 89, 114.

Aldehydeuramids, 130, 134.

Aldol polymerization, 100.

Alkyl sulfones, 94.

Allyl-acetic acid, 7, 12.

Allyl-acetic ester, 7.

Allyl-acetoacetic ester, 6, 7, 12, 27,
58.

Allyl-acetone, 7, 12.

Allylene-digallein, 36.

Allyl-methyl-acetpacetic ester, 53.
«-Allyl-/3-oxy-butyric acid, 12.

Alloxan, 66.

Alloxantin, 66.

Amids, i, 4, 6, 23, 35, 55, 78, 126, 136.

Amidins, 62, 68, 72, 88.

Amido-acetoacetic methyl ester, 92.

Amido-alkyl-acetoacetic esters, 92.

142

SUBJECT INDEX

Amido-crotonic esters, 92, 122, 127.

Amido-cyan-acetoacetic ester, 104.

Amido-ethyl-acetoacetic ester, 92.
//-Amido-a-methyl-thiazole, 128.

Amido-methyl thiazole carboxylic

ester, 109.
o-Amido-phenol, 46.

Amido-thiazyl-acetic ester, 120.
//-Amido-thiazyl-acetic ester, 128.

Amido-uracyl salts, 66.

Angelic acid, 9.

Anil-acetoacetic ester, 90.

Anilin-acetoacetic acid, 48.

Anilin, 48, 69, 82, 97, 106, 135.

Antipyrin, 61, 86.

Azo-acetoacetic benzoic acid, 68.

Azo-benzene-acetoacetic acid, 24.

Azo-compounds, 99, 101.

Azo-phenyl-acetoacetic acid, 17.
/>-Azo-toluol-acetoacetic acid, 24.

Benzal-acetoacetic ester, 7, 12, 20, 99.

Benzal-aceto-diethyl-acetic ester, 40.

Benzal-aceto-ethyl-acetic ester, 40.

Benzaldehyde, 131.

Benzal-malonic ester, 130.

Benzamidin, 62.

Benzanilid-imido chlorid, 64.

Benzene-azo-acetoacetic ester, 60.

Benzene-azo-acetone, 60.

Benzene-a-azo-propionic acid, 93.

Benzene-a-azo-propionic ester, 92.

Benzene-hydrazo-propionic acid, 93.

Benzenyl-aceto-ethenyl-azoxim, 112.

Benzenyl-amidoxim, 112.

Benzenyl-ethenyl-azoxim, 112.

Benzo-quinone, 88.

Benzoyl-acetoacetic ester, u, 53, 119.

Benzoyl-tetramethylene, 44.

Benzoyl - tetramethylene - carboxylic
ester, 44.

Benzoyl-trimethylene, 47.

Benzoyl-trimethylene-carboxylic es-
ter, 47.

Benzyl -acetoacetic acid, 37.

Benzyl-aceto-succinic ester, 20.

Benzylidin-collidin-dicarboxylic es-
ter, 73.

Benzylidin-diacetoacetic ester, 71.

Benzylidin-dihydro - collidin - dicarb-

oxylic ester, 73.
«-Benzyl-/3-oxybutyric acid, 12.

Bis-phenyl-methyl-methylene pyra-
zolone, 114.

Bis-phenyl-methyl pyrazolone, 133.

Brom-acetoacetic anilid, 82.

Brom-acetoacetic ester, u, 27, 41, 44,
97, in, 120, 128, 133.

Brom-acetone, 57.

Brom-aceto-phenon, 50.

Brom-butyl-methyl ketone, 84.

Brom-chlor-acetoacetic esters, 97.

Brom-dehydracetic acid, 10, 60.

Brom-ethyl-acetoacetic ester, 45, 136.
w-Brom-ethyl-acetoacetic ester, 85.
a-Brom-ethyl- methyl-acetic acid, 28.
a-Brom-methyl-acetoacetic ester, 136.

Brom-imido-methyl-uracyl, 134.

Bromin addition product, u, 37, 38,
41.

Bromo-maleic acid, 24.
/3-Brom-propionic ester, 126.

Butaldehyde, 101.

Butyl-acetoacetic ester, 6.

Butyl nitrous acid, 42.

Butyrolactone, 55.

Capric acid, 28.

Carbacetoacetic ester, 35, 45, 52, 84^.
Carbamid, 53, 63, 119, 130, 134.
Carbanilid, 90.

Carbethoxacetoacetic ester, 09.
Carbo-cinchomeronic acid, 70.
Carbo-pyrotritartaric acid, 23, 74, 103,

107.'

Carbostyril, 49.
Carboxylic ester of acetoacetic ester,

102.

Carbuvitic acid, 107.
Caroxethyl-mesiten lactam, 122.
Chelidonic acid, 65.
Chlor-acetic ester, 19.
Chlor-acetoacetic ester, u, 19, 25, 50,

70, 87, 97, 105, 109, in, 120, 128,

130.

> -Chlor-acetoacetic ester, 105.
Chlor-acetone, 38, 57.
Chlor-carbonic ester, 7, 96, 99, 102,

132.

Chlor-crotonic esters, 15.
/3-Chlor-crotonic esters, 123.
Chlor-dehydracetic acid, 10.
Chlor-dimethyl-quinolin, 97.
Chlor-metal derivatives of acetoacetic

ester, 25.

Chlor-nitroso-acetic ester, 33.
Chloro-lepidin, 82.
Chloro-lutidin, 127.
Chlor-tetracrylic acid, 6.
Cinchomeronic acid, 70.
Cinnamaldehyde, 73, 106, 131, 134.
Cinnamic ester, 87.
Citraconic ester, 87.
Collidin-dicarboxylic ester, 30.
Collidin-dicarboxylic methyl ester,

46.
Combining energy of halogens with

organic residues, 32.

SUBJECT INDEX

143

Condensation of acetoacetic esters,
29, 30, 34, 40, 42, 43, 46, 51, 66,
69, 70, 73, 78, 96, loo, 102, 107,

I 19, 121, 123, 129.

Constitution of acetoacetic ester,
47, 90, 96, 100, 132, 135.

Coumarins, 46, 88.
/•-Cresol, 47.

Cumaldehyde, 131, 134.
Y'-Cumyl-antipyrin, 67.

Cyan-acetic ester, 95.

Cyan-acetic methyl ester, 95.

Cyan -acetoacetic acid, 105.

Cyan-acetoacetic ester, 36, 56, 72, 87,

89, 91, 95, 104, 105.
3 -Cyan-acetoacetic ester, 118.

Cyan-acetoacetic methyl ester,95.
} -Cyan-acetoacetic methyl ester, 118.

Cyan-acetone, 38, 76.

Cyan-amid, 88.
/i-Cyan-.V-anilido-butyric ester, 69.

Cyan-hydrin of acetoacetic ester, 69.

Cyanic acid, 88.

o-Cyanobenzyl-acetic ester, in.
o-Cyano-hydro-cinnamic ester, in.
,?-Cyan-/:?-oxybutyric ester, 69.

Decomposition of acetoacetic ester,

2, 18, 29, 45.
Decomposition of acetoacetic methyl

ester, 3.
Decomposition of dehydracetic acid,

8.

Dehydracet-anilid, 10.
Dehydracetic acid, 2, 4, 8, 9, 60, 64,

65, 88, 109, 114, 127, 134, 136.
Dehydracetic ester, 10.
Dehydracetic methyl ester, 64, 88.
Dehydraceto-phenon-acetone, 63.
Dehydraceto-phenylhydrazin, 60.
Dehydracetoxim, 60.
Dehydro-beuzylidin-di-acetoacetic

ester, 71.

Dehydro-carbonyl-diacetoacetic es-
ter, 86.
Dehydro - diacetyl - acetone - dicar-

boxylic ester, 75.
Dextrose, 106.
Diace to- fumaric ester, in.
Diaceto-succinic ester, 6, 23, in.
Diacetyl, 98.
Diacetyl-acetic ester, 43.
Diacetyl-acetoacetic ester, 65.
a-w-Diacetyl-adipic ester, 84, 1 14.
rt-fcKDiacetyl-a-w-diethyl-pentane, 113.
«-«-Diacetyl -a - G>- diethy 1 - pimelic ester,

. TI3-
«-w-Diacetyl-caproic ester, 107.

Diacetyl-ethyl-acetyl-acetic ester, 56.

a-w-Diacetyl-pentane, 106.
Di-allyl-acetic acid, 17.
Di-allyl-acetic ester, 27.
Di-allyl-acetoacetic ester, 17, 27.
Di-allyl-acetone, 17.
Diazo-compounds, 68.
Di-benzoyl-acetoacetic ester, 119,

136.

Dibenzyl acetoacetic ester, 7, 12.
Dibrom-acetoacetic dibromid, 11, 37,

38.

Dibrom-acetoacetic ester, 44, in.
Dibrom-cyan-acetoacetic ester, 105.
Dibrom-hydroxy-imido-methyl ura-

cyl, 129.
Dibrom - methyl - acetoacetic ester,

117. •

Dibrom-succinic acid, 24.
Dibutyl-acetoacetic ester, 6.
Dicarboxylic ester of acetoacetic es-
ter, 102.

Dichlor-acetic ester, n.
Dichlor-acetoacetic amyl ester, n.
Dichlor-acetoacetic ester, 7, n, 19,

. 25, 39, 87, 95, 97, 109, in.
Dichlor-acetone, 7, n, 95.
Di-o-cyano- benzyl-acetoacetic ester,

in.

Diethyl-acetic acid, 16.
Diethyl -acetoacetic acid, 42.
Diethyl-acetoacetic ester, 2, 6, 10, 16,

42, 76, 92, 115, 136.
Diethy 1-acetone, 2, 43.
Diethyl-amin, 66.
Diethyl-chlor-acetoacetic ester, 76.
Diethyl-dichlor-acetoacetic ester, 76.
Diethy 1-hydroxy butyric ester, 136.
Diethy l-/3-oxy butyric acid, 16.
Diethyl-sylvane-carboxy- acetoacetic

ester, 100.

Diheptyl-acetic acid, 26.
Diheptyl-acetoacetic ester, 26.
Diheptyl-acetone, 26.
Dihydro-collidin-dicarboxylic ester,

34, 55, 131-

Dihydro-collidin-dicarboxylic me-
thyl ester, 46.

Dihydro - collidin - mono - carboxylic

methyl ester, 46.
a-Diketones, 98.

Dimethoxy-diethyl-acetoacetic ester,
76.

Dimethoxy-diethyl-acetpne, 76.

Dimethyl-acetoacetic acid, 37.

Dimethyl-acetoacetic ester, 3, 47, 72,
86.

Dimethyl-acetone, 3.
rt-/*-Diniethyl-aceto-succinic ester, 22.

Dimethyl-carbostyril, 97.

Dimethyl-chlor-crotonic ester, 1 6.

144

SUBJECT INDEX

Dimethyl-dicoumaric acid, 91.
Dimethyl-dicoumarin, 91.
Dimethyl-hydroxy-pyridin, 72.
Dimethyl-hydroxy-quinolin, 135.
Dimethyl-keto-pentane, 108.
Dimethyl-oxyquinizin, 61.
2/-3/-Dimethyl-oxyquinizin, 61.
a-a'-Dimethyl-pyridin, 73, 127.
a-a'-Dimethyl-pyridone, 127.

Dimethyl-pyridone-mono-carboxy-

lic acid, 127.

Dimethyl-pyrone, no, 134.
o-tt-Dimethyl-pyrone-carboxylic acid,

US-

Dimethyl-pyrone-dicarboxylic es-
ter, 86.

Dimethyl-pyrrol, 83.
Dimethyl-pyrrol-dicarboxylicacid,

. 83-
Dimethyl-pyrrol-dicarboxylic

mono-ester, 83.
Dimethyl-pyrrol -monocarboxy lie

acid, 83.

Dimethyl-quinolins, 97.
Dimethyl-succinic acid, 22.
a-^-Dimethyl-thiazole, 128.
«-/3-Dimethyl-umbelliferone, 47.

Dinitro-brom-benzene, 50.
o-/-Dinitro-phenyl-acetic acid, 50.

Dinitro-phenyl-acetoacetic ester, 50
Dinitro-toluol, 50.
Dioctyl-acetic acid, 28.
Dioctyl-acetoacetic ester, 28.
Dioctyl-acetone, 28.
Diphenyl-carbamid, 9, 82.
Diphenylhydrazin derivatives of

diacetyl, 98.
Diphenylhydrazin derivatives of

diacetyl adipic ester, 114.
Diphenyl-methyl-pyrazolone, 86.
,3-Diphenyl-sulfone-butyric ester,

123.

Dipicolinic acid, 127.
Dipropyl-acetic acid, 32.
Dipropyl-acetoacetic ester, 31.
Dipropyl-acetone, 32.
/i-Dithio-phenyl-butyric ester, 80,

123.

Di (trinitrophenyl) acetoacetic es-
ter, 121.

Ethenyl-toluylene-diamin, 25, 85.
Ethoxy-acetic ester, 18.
Ethoxy-acetyl-ethoxy-acetic ester,

18.

Ethoxy-ethyl-acetoacetic ester, 78.
Ethoxy-ethyl-acetone, 79.
Ethoxy-lepidin, 82.
Ethoxy-lutidin, 79.
Ethoxy-methyl-acetoacetic ester,

78.

Ethoxy-methyl-acetone, 79.
Ethyl acetate of sodium, 5.
Ethyl-acetic acid, 4.
Ethyl-acetoacet-amid, 93, 115.
Ethyl-acetoacetic acid, 98.
Ethyl-acetoacetic amyl ester, 10, n.
Ethyl-acetoacetic ester, i, 2, 3, 6, 7,

43, 53, 56, 62, 78, 93, 98, 105, 116,

123- 134.
Ethyl-acetoacetic methyl ester, 3, 92,

US-

Ethyl-acetone, 3.

a-Ethyl-/3-aceto-propionic acid, 31.
a-Ethyl-aceto-succinic ester, 7, 22, 31.
/3-Ethyl-aceto-succinic ester, 7, 31, 38.
Ethyl-amido-crotonic methyl ester,

US-

Ethylamin, 104.

Ethyl-benzyl-acetoacetic ester, 20.
Ethyl-butyral, 4.

Ethyl-chlor-acetoacetic amyl ester, 1 1.
Ethyl-chlor-acetoacetic ester, u, 78.
Ethyl- chlor-crotonic acid, 78.
Ethyl-chlor-crotonic ester, 16.
o-Ethyl-crotonic acid, 7, 13.
Ethyl-cyan-acetoacetic ester, 56, 105.
Ethyl-diacetyl-acetic ester, 43, 56.
Ethyl-dichlor-acetoacetic ester, 78.
«-Ethyl-/3-diethyl-sulfone-butyric ester,

123.

«-Ethyl-/3-diphenyl-sulfone-butyric es-
ter, 123.

a-Ethyl-/3-dithiophenyl butyric ester,
123.

Ethylene bromid 47, 84, 89, 114.

Ethylene-diamin, 80, 106.

Ethylene-phenylhydrazin, 113.

Ethyl-fumaric acid, 133.

Ethylidin-acetoacetic ester, 131.

Ethylidin-diacetoacetic ester, 131.

Ethylidin-glutaric ester, 126.

Ethyl-ketolactonic acid, 38.

Ethyl-mercaptan, 123.

Ethyl-methyl-acetic ester, 7.

Ethyl-methyl-acetoacetic ester, 7, 28,
49. 53-

Ethyl-methyl-hydroxy-pyrimidin, 72.

Ethyl-tnethyl-ketone, 28.

Ethyl-methyl-oxyacetic acid, 28.
«-Ethyl-/3-oxybutyric acid, 7, 13.

Ethyl-phenyl-carbamate, 78.

Ethyl-sodacetoacetic ester hydrate,
56.

Ethyl -succinic acid, 22, 31, 133.

Ethyl-succino-succinic acid, 45.

Formamid, 55, 79.
Formamidin, 72.
Furfuraldehyde, 131, 134.

SUBJECT INDEX

Glutaric acid, 20,
Glycolic acid, 45.
Glyoxal, 100.
Guanidin, 78, 88, 129.

Heptic acid, 27.
Heptyl-acetic acid, 26.
Heptyl-acetoacetic ester, 26.
Heptyl-acetone, 26.
Hexa-methylenetetramin, 99.
Hexenic acid, 16.
Hexic acid, 16, 27.
Hexyl-lutidin, 101.

Hexyl-lutidin-hydro-dicarboxylic es-
ter, 101.

Homomesaconic acid, 52. 121.
Ilydrazin hydrate, 105.
Hydrazobenzene, 76, 80.
"-Hydrindone, in.
Hydrogen methronic ester, 107.
Hydrogen methyl methronic ester,

Hydro-isobuty 1 - lutidin-dicarboxylic

ester, 74.
Hydro-isopropyl-lutidin-dicarboxylic

ester, 73.

Hydro-lutidin-dicarboxylic ester, 99.
Hydro-parvolin-dicarboxylic ester, 73.
Hydro-pyridin derivatives, 70.
Hydroquinone, 40, 48.
Hydro-tridecyl- lutidin-dicarboxylic

ester, no.
Hydroxamic acid of acetoacetic acid,

126.

Hydroxylamin, 39, 51, 60, 94, 125, 126.
Hydroxyl-dehydracetic acid, 60.
Hydroxylepidin, 82.
Hydroxy - lutidin - monocarboxylic

acid, 54.

Hydroxy-pentic acid, 133.
y-Hydroxy-quinaldin, 90.
Hydroxy-tetric acid, 117, 118, 133.
Hydroxy-tetric diethyl ester, 118.
Hydroxy-tetric ester, 117.
Hydroxyxanthin, 66.
Hypo-acetous acid, i.

Imido-benzoic ester, 124.

Imido-dimethyl-uracyl, 1 29.

Iniido-methyl-uracyl, 129.

Imido-phiMiyl-uracyl, 130.

lodacetoacetic ester, in.

Isoamyl-acetoacet-amid, 93, 115.
rt-Isoamyl-/?-amido-crotonic ester, 115.

Isobutyl-acetic acid, 15.

Isobutyl-acetoacet-amid, 93, 115.

Isobutyl-acetoacetic ester, 9, 15.

Isobutyl-acetone, 0, 15.

Isohutyl -aldehyde, 73.
a-Isobutyl- V-amido-crotonic ester, 115.

Isobutyl-lutidin, 74.

Isodehydracetic acid, 51, 84, 115, 121.

Isodehydracetic lactam, 122.

Isodehydracetic methyl ester, 121.

Isohexic acid, 27.

Isonitroso-acetoacetic anilid, 82.

Isonitroso bodies, 5 1 .
/3-Isonitroso-butyric ester, 51.

Isonitroso-diethyl-acetoacetic ester,
5«.

Isonitroso-ethyl-acetoacetic ester, 51.

Isonitroso-methyl-acetoacetic ester,
Si-

Isonitroso-tetra-methyl-oxyquinizin,
67.

Isophenanthroxylene-acetoacetic es-
ter, 125.

Isopropyl-acetoacetic ester, 4, 8.

Isopropyl-acetone, 4.

Isopropyl-chlor-crotonic ester, 16.

Isopropyl-succinic acid, 50.

Isostearic acid, 28.

Isoxyhexic acid, 27.

Ketin-dicarboxylic acid, 33.
Keto-sulfids, 104.

Lactams, 126.

Lactones, 88.

Laevulinic acid, 99.
}-Ivepidin, 82.

Lutidin, 65, 70, 73, 109, 127.
«->-Lutidin-/i-carboxylic ester, 69.

Lutidin-dicarboxylic ester, 55, 74, 99.

Lutidin-mono-carboxylic ester, 55, 79.

Lutidin-tri-carboxylic acid, 73.

Lutidone-dicarboxylic ester, 75.

Magnetic rotary polarization, 58.

Malonic ester, 75.

Melting points of acetoacetic esters,
92.

Mesaconic acid, 118, 133.

Mesitene lactam, 122.

Mesiten-lactone, 52, 121.

Mesiten-lactone carboxylic acid, 51.

Mesityl oxid, 52.

Mesityl oxid-anhydro-dicarboxylic es-
ter, 42.

Mesityl oxid-dicarboxylic ester, 42.

Meta-dehydracetic acid, 42.

Metal acetoacetic esters, 14.

Method of production of substituted
acetoacetic esters, 23.

Methoxy-diethyl-acetoacetic ester, 76.

Methoxy-lepidin, 82.

Methoxy-methyl-ethyl acetone, 76.

Methoxy-quinaldin, 90.

Mi-thronic acid, 74, 108.

Mrthronic diethvl ester, 108.

146

SUBJECT INDEX

Methyl -aceto-acet-amid, 93, 115.
Methyl-aceto-acet-anilid, 97.
Methyl-acetoacetic acid, 37, 98.
Methyl-acetoacetic ester, I, 2, 4, 7, 13,

17, 25, 27, 53, 56, 61, 79, 97, 98> nr>

115, 117, 130. ;

Methyl-aceto-glutaric acid, 21.
Methyl-acetoacetic methyl ester, 4,

135-

Methyl-acetone, 3.
rt-Methyl-aceto-propionic acid, 29.
a-Methyl-aceto succinic ester, 21.
/3-Methyl-aceto-succinic ester, 13, 22.

Methyl-allyl-acetoacetic ester, 53.
«-Methyl-/3-amido-crotonic ester, 115.

Methyl-amin, 66, 70, 106.

Methyl-benzyl-acetic acid, 20.

Methyl-benzyl-acetic-benzyl ester, 20.

Methyl -ben zyl-acetoacetic ester, 20.

Methyl-brom-acetoacetic ester, 120.

Methyl-/3-butyl-carbinol, 49.

Methyl-/?-butyl-ketone, 49.

Methyl-/3-butyl-pinacone, 49.

Methyl-chlor-acetoacetic ester, 78,

120.
a-Methyl-3-chlor-crotonic acid, 17.

Methyl-chlor-crotonic ester, 16.
a-Methyl-crotonic acid, 7, 13.

Methyl-cyan-acetoacetic ester, 56,
105.

Methyl-dehydrohexone-carboxylic es-
ter, 107.

Methyl - dehydropentone - carboxylic
ester, 89.

Methyl-dichlor-acetoacetic ester, 78.

Methyl-diethyl-methane, 49.
o-Methyl-/^-diethyl - sulfone - butyric es-
ter, 123.

Methyl-diheptyl-carbin-ketone, 26.

Methyl-ethyl-acetic ester, 14.

Methyl-ethyl-acetoacetic ester, 14, 53.

Methyl-ethyl-hydroxyquinolin, 135.

Methyl-ethyl-/3-oxybutyric ester, 14.
2/-3/-Methyl-ethyl-oxyquinizin, 62.

Methyl-ethyl-thiazole, 120.

Methyl-fumaric acid, 133.

Methyl-furfuran - carboxy-acetic acid,
100.

Methyl-glutaric acid, 21.

Methyl-hydro-cinnamein, 20.
n-Methyl-hydroxy-succinic acid, 26.

Methyl-imido-methyl-uracyl, 130.

Methyl-isoxazolone, 126.

Methyl-lepidone, 82.

Methyl-methronic acid, 108.

Methyl-methronic diethyl ester, 108.

Methyl-nonyl-ketone, 28.

Methyl-octyl-ketone, 26.
o-Methyl-/3-oxybutric acid, 7, 13,

Methyl-oxythiazole-carboxylic ester,
109.

Methyl-phenyl-ethyl-ketone, 12.

Methyl-phenylhydrazin, 82.

Methyl -phenylhydrazin - acetoacetic
acid, 82.

Methyl-phenyl-ketone, n.

Methyl-phenyl-pyrazole, 98.

Methyl-phenyl-pyrazolone, 105, 129.

Methyl-propyl-acetic acid, 54, 59.

Methyl-propyl-acetoacetic ester, 54, 59.
«-Methyl-propyl-/:?-oxybutric acid, 54.

Methyl-a-secondary-pentyl-ketone, 54.

Methyl-succinic acid, 133.
jU-Methyl-thiazyl-acetic ester, 120, 129.
/3-Methyl-umbelliferone, 47.

Methyl-uracyl, 66.

Methyl uvic acid, 108.

Methyl-valeral, 4.
«-Methyl-valerolactone, 35.
/i-Methyl-valerolactone, 35.

Mustard oils, 88.

Myristic aldehyde, no.

/3-Naphtho-dimethyl-oxyquinizin, 58.
a-Naphthylamin, 91.
«-Naphthyl-hydrazin, 112.

Nitro-acetoacetic ester, in.

Nitrogenous radicals, 64.

Nitrosates, 90.

Nitroso-acetic ester, 33.

Nitroso-acetoacetic ester, 33, 83.

Nitroso-acetone, 20, 33.

Nitroso-compounds, 39.

Nitroso-ethyl-acetone, 19.

Nitroso-methyl-acetone, 20.

Nitroso-propionic acid, 20, 33.

Nitro-uracyl, 66.

Nitro-uracyl-carboxylic acid, 66.

Nitrous acid on acetoacetic ester, 18,

*9» 33-.

Nitrous acid on ethyl-acetoacetic es-
ter, 19.

Nitrous acid on methyl-acetoacetic
ester 19.

Nonyl acid, 26.

Octylic-acetic acid, 28.
Octylic-acetoacetic ester, 28.
Oenanthol, 101.
Orcinol, 36.
Oxalic acid, 45.

Oxidation of acetoacetic ester, 9.
Oximido-bodies, 39.
Oximido-butyric acid, 126.
Oxy-adipic acid, 25.
Oxy-angelic acid, 9.
/?-Oxy-butyric acid, 5, 54.
Oxy-heptic acid, 27.
Oxy-hexic acid, 27.
Oxy-mesiten-carboxylic acid, 52.
Oxy-mesiten-dicarboxylic acid, 52.
Oxy-methyl-quinizin, 58.

SUBJECT INDEX

"47

; -Oxy-rt-methyl-quinolin,48.

Oxy-pentic acid, 27, 133.
«-Oxy-pyrone, 128.

Oxy-pyro-tartaric acid, 8, 26.

Oxy-teteric acid, 27, 133.

Oxy-tetrolic acid, 35, 44.

Oxy-uvitic acid, 8, 9.

Paraldehyde, 55.
Paramido-acetoacetic ester, 35, 54, 96,

132.

Parvolin, 73.

Parvolin-dicarboxylic acid, 73.
Penta-chlor-acetoacetic ester, 35, 95.
Pentaniethyl-oxyquinizin, 67.
Pentenic acid, 16.
Pentic acid, 16, 27.
}-Pentylene-glycol, 85.
Perbrom-acetoacetic ester, 45.
Phenanthraquinone, 39, 124.
Phenanthroxylene - acetoacetic ester,

39. I24,
Phenanthroxylene - isocrotonic ester,

39-

Phenols, action of, 88.
Phenyl-aceto-succinic ester, 57.
-•'-Phenyl-amido-rt-crotonic ester, 82.
Phenyl-amido-ethyl - crotonic methyl

ester, 135.
Phenyl-amido-methyl-crotonic methyl

ester, 135.

Phenyl-amido-quinaldin, 90.
1-Phen'yl-azo-crotonic ester, 91, 136.
Phenyl-brom-acetic ester, 57.
Phenyl-carbamid, 78.
Phenyl-dimethyl-pyrazolone, 86.
Phenyl-dimethyl-pyridone-dicarbox-

ylic ester, 75.
Phenylhydrazin, 49, 58, 60, 61, 83, 84,

86, 88, 91, 94, 98, 108, in, 112,

116, 117, 121, 125, 129, 133, 136.
Phenylhydrazin derivative of diacetyl,

98.

Phenylhydrazin-pyroracemic acid, 93.
Phenyl-,V-hydrazo-crotonic ester, 136.
Phenyl-isocyanate, 88.
Phenyl-lutidone, 88.
Phenyl-lutidone-carboxylic methyl

ester, 88.

Phenyl-mercaptan, 80, 123.
Phenyl-mercaptid of sodium, 130.
Phenyl-methyl-ethoxy-pyrimidin, 72.
PlK-nyl-methyl-furfurane, 63.
Phenyl-methyl-hydroxy-pyrimidin,

68, 72, 124.
rhenyl-methyl-nitroso-pyrazolone,

in, 112.

Phenyl-methyl-oxyquinizin, 76.
Phenyl-methyl-pyrazolone, 86, 91, 136.
1 'hen yl-methyl-pyrazolone azoben-

zene, 112, 116, 117, 133.

Phenyl - methyl - pyrazolone bisulfid,
133-

Phenyl-methyl-pyrazolone-ketophen-
yl-hydrazone, 112, 116.

Phenyl-methyl-pyrimidin, 72.

Phenyl-methyl-pyrimidin-anilid, 72.

Pheny-trimethyl-pyrazolone, 86.

Phloroglucin, 75, 91.

Phthalic anhydrid, 88.

Phthalyl-acetic acid, 83.

Phthalyl-acetoacetic ester, 83.

Phthalyl-diamid, 83.

Phthalyl-imid, 83.

Picric chlorid, 121.

Pimelic acid, 50.

Piperidins, 101.

Polycoumarins, 91.

Potassium butyl nitrite, 42.

Potassium ethyl nitrite, 41.

Potassium on acetic ester, r.

Potassium propyl nitrite, 41.

Propaldehyde, 73.

Production of acetoacetic ester, i, 2.

Propionamidin, 72.

Propyl-acetoacetic ester, 31, 41.

Propyl-chlor-crotonic ester, 16.

Propyl-lutidin, 101.

Propyl-lutidin-dicarboxylic ester, 101.

Propyl-lutidin-hydro-dicarboxylic es-
ter, 101.

Pseudo - cumylizin - acetoacetic ester,

67.

Pyrazol blue, 86.
Pyrazolone derivatives, 136.
Pyridin derivatives, 69, 131.
Pyridins, 101.
Pyrimidins, 68, 72.
Pyrogallol, 36.
Pyron, 86.

Pyrotartaric acid, 13, 20, 21.
Pyrotritartaric acid, 23, 63, 74, 103,

107.

Pyrrol derivatives, 83.
Pyruvic acid, 107.

Quartenylic acid, 6.
Quinizin, 61.
Quinizin derivatives, 76.
Quinolin derivatives, 48, 90, 135.
Quinone, 102.

Quinon-hydro-dicarboxylic ester, 44.
48-

Resaceticacid, 78.
Resaceto-phenou, 47.
Resocyamn, 36.
Resorcin, 36, 47, 91.
Rhamnodiazin, 103, 113.
Rliamnosaniin, 113.
Rhamnose, 103, 113.

148

SUBJECT INDEX

Salicylaldehyde, 131, 134.
Sod-acetoacetic ester hydrate, 56, 124.
Sod-ethyl-acetoacetic ester, 1 24.
Sodium-diacetyl-acetic ester, 56.
Sodium on acetic ester, i, 4, 5, 6, 8,

10, 101, 132.
Sodium on alcohol, 5.
Sod-methyl-acetoacetic ester, 92, 94,

136.

Succinic acid, 45, 70, 74, 107.
Succinic ester, 40.
Succino-succinic ester, 40, 97.
Sugar, 92.

Sulfid of acetoacetic ester, 70.
Sulfo-ureas, 88.
Sulfur dichlorid, 91.
Sylvane-carboxyacetic acid, TOO.

Tautomeric compounds, 119.
Tetracetic acid, 134.
Tetra-chlor-acetoacetic ester, 37, 95,

97-

Tetracrylic acid, 6.
Tetra-methyl-oxyquinizin, 67.
Tetrenic acid, 16.
Tetric acid, 16, 27, 132, 133, 136.
Tetrolic acid, 6.
Thiacetamid, 120, 128.
Thiacet-amido-acetic ester, 128.
Thiacet-amido-acetoacetic ester hydro-

bromid, 128.

y-Thiaceto-acetoacetic ester, 128.
Thio-acetoacetic ester, in, 112, 116,

i*7, 133-

Thio-acetoacetic phenylhydrazid, 116.
Thio-amids, 88.
Thio-carbacetic acid, 14.
Thio-carbamid, 78, 81, 109, 120, 128.
Thio-carbonyl-acetoacetic ester, 94.
Thio-carbonyl chlorid, 94.
Thio-cyanates, 109.
Thio-glycollic acid, 94.
Thiom ethyl uracyl, 81.
Thio-methyl uracyl-acetic acid, 8r.
Thio-phenyl-acetoacetic ester, 130.
/3-Thio-phenyl-crotonic acid, 81.
Thio-phenyl-methyl-pyrazolone, 1 17,

133-

Thiophenyl-propylene, 81.
Thio.rufic acid, 14.
^-Toluene-acetoacetic ester, 60.

/>-Toluene-azo-acetoacetic ester, 60.
/>-Toluene-azo-acetone, 60.
?«-Toluene-/:?-methyl-coumarin, 47.
o-Toluoxy-methyl-quinizin, 58.
/-Toluoxy-methyl-quinizin, 58.
o-Toluylene-diamin, 25, 85.
^-Tolyl-hydrazin, 112.

Triacetyl-acetic ester, 136.

Triacetyl-benzene, 98.

Triacetyl-hydrogen, 5.

Triacetyl-sodium, 5.
o-Tribenzoyl-benzene, 30.

Tribrom-acetoacetic ester, 45.

Tricarballylic acid, 15, 17.

Trichlor-acetoacetic ester, 95, 97.

Tridecyl-lutidin, no.

Tridecyl - lutidin - dicarboxylic acid,
no.

Tri-ethyl-phosphite, in.

Trimethylen bromid, 4r, 44, 77, 84,
106, 113.

Trimethyl-pyridin-dicarboxylic acid,
69.

Trimethyl-pyridon-dicarboxylic ester,

75-

Trimethyl-quinizin derivatives, 67.
Trimethyl-thiazole, 120.
Trimethyl-tri-coumaric acid, 91.
Trimethyl-tricoumarin, 91.
Trimethyl-uracyl, 66.
Trinitro-phenyl-acetoacetic ester, 121.
Trinitro-phenyl-acetone, 121.
Triphenyl-carbinyl-acetoacetic ester,

64.

Triphenyl-carbinyl bromid, 64.
Triphenyl- carbinyl ethyl ester, 65.
Triphenyl-methane, 65.

Uramido-crotonic amid, 97.

Uramido-cro tonic ester, 66, 131.

Urea, 66.

Ureas, 88.

Ureids, 88.

Urethane, 96.

Urine, 24, 30, 31, 35, 48, 71.

Uvic acid, 23, 107.

Uvitic acid, 107.

Valeraldehyde, 74,
Valeric acid, 28.

Photomount

Pamphlet

Binder

Gaylord Bros., Inc

Makers

Stockton, Calif.
PAT. JAN. 21. 1908

880865

'

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