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598 MELDRUM : -4 @-T,ACTONIC ACID FROM

LIV. -A @-lactonic Acid ,fi*om A ccto”r~c?rmcl Malom’c

Acid.
By ANDREW NORMAN MELDRUM (Carnegie Research Fellow).
Published on 01 January 1908 on http://pubs.rsc.org | doi:10.1039/CT9089300598

THE condensation between acetone and malonic acid might well be

expected to yield isopropylenemalonic acid, Me,C:C(CO, H),, and from
this, by the loss of carbon dioxide, dimethylacrylic acid,
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Me,C:CH*CO,H,
might result. Actually the condensation, as i t proceeds in presence of
acetic anhydride* (Massot, Rev., 1894, 27, 1225) or ammonium
mnlonate (Knoevonngel, D.R.-P. 162281) does result in dimethyl-
acrylic acid.
Ethyl isopropylenemalonate, Me,C:C(CO,Et),, is produced by heating
together ethyl malonate, acetone, acetic anhydride, and zinc chloride.
On hydrolysis of the ester, isopropylenemalonic acid is obtained
(Meyenberg, Be?*.,1895, 28, 785).
Wishing to study the reaction between acetone and malonic acid, the
author, on Professor Japp’s suggestion, employed as condensing agent
acetic anhydride with the addition of a little sulphuric acid, Under
these conditions, the reaction, which proceeds smoothly and without
the application of heat, yields in the course of twenty-four hours R
crystalline acid melting a t 9 7 O , which is a new condensation product
of acetone and malonic acid, since it is neither dimethylacrylic acid
(m. p. 70”) nor isopropylenemalonic acid (m. p. 170-171’).
Analysis and molecular weight determination lead to the formula
C,H,O, for the substance, which is evidently formed according t o the
equation :
C,H60 + C,H,O, = H20+ C,H80,.
Titration with alkali showed t h a t the acid is monobasic, so t h a t it is
probably n lactonic acid. Treatment with excess of alkali, with the
object of obtaining direct evidence of the presence of the lactonic group,
was found to cause disruption into acetone and malonic acid. Neverthe-
less, there can hardly be a doubt that the substance, considering the
Me,F--QA*CO,H
method of its formation, has the constitution
0-co 1

that is, it is the /3-lactone of /3-h?/drox~isopl.op?lZmaZonic acid. The

formation of the lactone may therefore be represented as follows :
Me,CO + CH2(C0,H), = Me,C(OH)*C.H(C0,H)2=
H,O + Me,y-?H*CO,H
0-CO
* Komnenos (Annalen, 1883, H8, 147, 168), using ncctic acid as condensing
agent, obtained crotonic acid, MeCH:CH*CO,H, from malonic acid and paraldehyde,
but found that there was no reaction between nislonic acid and acetone.
 ACETONE A N D MALONIC ACID. 599
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Closely related to this /I-lactone is one which has been described by
Baeyer and Villiger (Ber., 1897, 30,1954, see also Fichter and Hirsch,
Ber., 1900, 33,3270). The parent Substance of Baeyer and Villiger's
lactone is as-dimethylmalic acid, Me,C( C0,H) =CH(OH) *CO,H (in which
the relative positions of the *OH and *CO,H groups are precisely the
Published on 01 January 1908 on http://pubs.rsc.org | doi:10.1039/CT9089300598

reverse of what they are in the isomeric p-hydroxyisopropylmalonic

R;Ie2~--QH*C0,H
acid), and the lactone itself is
coo0
It is remarkable t h a t the only two /I-lactones known in the fatty
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series should be isomerides, and should both contain the grouping

..
Me,*C*CH*CO,H. It would appear that the grouping, Me,C*CH, is
..
specially adapted to the formation of p-lactones, although it is difficult
t o find an explanation of this interesting point. The fullowing com-
parison shows t h a t the two lactones, closely related as they are, differ
considerably in properties :
~

Me,C-CH'C0,H Me,C'CH*CO,H
I I I I
CO'O O'CO
(Baeyer and Villiger). (Meldrum).

Melting point ...........

I 45-47'. I
97".
With water ............... Gives C,HsO,,H,O. Gives no compound.
Hydrolysis by dilute Gives as-dimethylmalic acid. Gives malonic acid and acet-
acid. one.
Action of heat ............ Gives the anhydride of as- Gives carbon dioxide and
dimethylmalic acid, with- resinous products.
out elimination of carbon
dioxide.

EXPERIMENTAL.
Me,q*yH*CO,H
p-Lactone of p-HydroxyisopropyhaZonic Acid, o*co
When malonic acid (104 grams), acetone (116 grams), and acetic
anhydride (204 grams) are mixed there is little change, but on
addition of sulphuric acid (5 c.c.) a rise in temperature occurs and the
malonic acid soon dissolves. After twenty-four hours the liquid gives
a crystalline deposit, which can be increased by leaving in a freezing
mixture for a short time. The yield of the crude substance is 65-70
grams, and is apparently not increased by varying the proportions of
material or the other conditions of the experiment. The mother
VOL. XCIII. R R
 600 MELDRUM: A &LACTONIC ACID FROM
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liquor, on evaporation at the ordinary temperature, yields only impure
malonic acid (30 grams). The solid is collected, washed with cold
water, and crystallised from acetone, from which it separates in
colourless, transparent four-sided plates or prisms obliquely terminated,
and melting at 9 7 O .
Published on 01 January 1908 on http://pubs.rsc.org | doi:10.1039/CT9089300598

When the temperature is raised above 97" the liquid turns yellow
and finally brown, while carbon dioxide is evolved, the decomposition
from 130" upwards being rapid. In hot water, ether, alcohol, or
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chloroform, the substance is much more soluble than in t h e cold

solvent :
0.2934 gave 0.53'78 CO, and 0.1465 H,O. C = 49.98 ; H = 5.55.
C,H,O, requires C = 50.00 ; H = 5.55 per cent.
The lactone is decomposed by hydrobromic acid in the cold, with
separation of malonic acid; when digested with baryta water, a
precipitate of barium malonate is produced. Heated with aniline, it
yields acetone, carbon dioxide, and acetanilido.
A determination of the molecular weight in acetone solution by the
boiling-point method (in the Lumsden-Walker apparatus), which
Mr. W. E. S. Turner, M.Sc., kindly undertook, gave the following
numbers :

Weight of
substance, in grams. Elevation. Volume, in C.C. Mol. wt.
1.51 1 *03" 27 -I 123
0.93 29.4 125
0.84 324 126
0.74 36'3 127 -5

(The boilirg point elevations have been corrected for the change in
boiling point due to the increase of liquid and therefore of pressure in
the boiling tube.) As the solution becomes more dilute, the molecular
weight seems to increase, a phenomenon often observed in acetone
solution. On plotting the molecular weight against the elevation, the
molecular weight at zero elevation, that is, a t infinite dilution, is found
to be 139. C,E,O, requires mol. w t . =144.
The equivalent of the acid was determined by titration with
standard alkali (of which 4293 C.C. neutralise the equivalent in grams
of any acid):
x 4293 - 142,2,
0.4405 required 13.3 C.C. Equivalent= 0.4405 ___~____ -
13.3
The potassium and sodium salts, which are very soluble in water,
are obtained by evaporating the respective solutions in a vacuum
desiccator. The potassium salt consists of prisms or striated plates.
Two different specimens were analysed :
 ACETONE A N D MALONIC ACID. 601
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0-3722 gave 0,1576 K,SO,. K = 19.03.
0.3211 ,, 0.1396 ,, K = 19.54.
C,H70,K,H20requires 19.56 per cent.
The sodium salt consists of six-sided plates :
Published on 01 January 1908 on http://pubs.rsc.org | doi:10.1039/CT9089300598

0,4747 gave 0.2003 Na,,SO,. Na = 13.67.

C,H70,Na requires 13-85 per cent.
The sodium and potassium salts are white, but they turn yellow in
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the course of two or three months.

The silver salt is obtained as a white, microcrystalline precipitate on
adding silver nitrate to a solution of the sodium salt. It darkens when
kept for some time:
0.1948 gave 0.0838 Ag. Ag = 43.01.
C,H70,Ag requires 43.02 per cent.
The buriurn salt is very soluble in water and was not analysed. On
boiling its solution, a white substance separated which was found to
consist of barium malonate :
0.2’33 gave 0.2708 BaSO,. Ba = 54-41.
C,H,O,Ba,H,O requires Ba = 53.4 per cent.
The readiness with which the P-lactone of P-hydroxyisopropyl-
malonic acid decomposes, either into malonic acid and acetone, or i n
other directions, has proved a great hindrance to its investigation
The author has commenced the study of its behaviour with various
reagents, in particular with phosphorus pentachloride and with
ammonia.

The author, who first prepared this substance nearly four years ago
in the Chemical Department of Aberdeen University, but had to
discontinue the investigation for some time, feels grateful to Professor
J a p p and to Professor Perkin for the interest they have shown in it.
The expenses of the investigation have been defrayed by the Executive
Committee of the Carnegie Trust for the Universities of Scotland.
CHEMICALDEPARTMENT,
THE UNIVERSITY,
b1ANCHESTEIL

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