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VOLUME63
[CONTRIBUTION FROM
THE
NUMBER
8
CHEMICAL LABORATORY
O F HARVARD
UNIVERSITY ]
+ AH
(1)
Acid (s or 1) 4-AH
(2)
Experimental Procedure
The calorimeter used in these measurements has been described in a previous paper of this series. I t was used in
(1) Conn, Kistiakowsky and Roberts, THISJOURNAL, 62, 1895
(1940).
1747
174s
1. B.
CONN,
G. B.
KISTIAKOWSKY,
Vol. 64
Aug., 1942
HEATSOF HYDROLYSIS
OF ACIDANHYDRIDES
1749
J. B.CONN,G . B. KISTIAKOWSKY,
R. M. ROBERTSAND E. A. SMITH
1750
Vol. 64
It was finally recrystallized from a mixture of anhydrous where A H 2 is now the heat of neutralization of one
ether and ligroin.
mole of the dicarboxylic acid by two moles of soTetramethylsuccinic Acid and Anhydride.-As starting
dium hydroxide.
material, commercial phorone was used. Neither repeated
Table I consists of the heats of hydrolysis and
fractionation through our tall columns nor partial freezing
sufficed t o obtain a flat boiling fraction.z1 The best sample neutralization of the anhydrides. The letters A,
(1065 g. from 1 gallon) boiled at 103.0-104.2"(35 mm.), B and C in the column headed "Solution" refer
began t o freeze at 23.4",and had ?z*OD 1.4912. Following to the compositions of the solutions in which
the steps were: (1')
the synthesis of Francis and 'CVill~on,~*
the reactions were carried out ; these composiphorone to phorone tetrabromide, yield, 50%; (2)phororic
tetrabromide t o dibromophorone, yield, 67%; (3) di- tions are given in Table I11 along with the heats
bromophorone t o 2,2,3,3-tetramethyl-4-bromo-5-hydroxy-of dilution. Table I1 contains heats of neutraliA'-cyclopentenone-1, yield of crude product, nearly quari- zation of the acids. Heats of neutralization are
titative; (4)oxidation to or-ketotetramethylglutaric acitl, given for some acids for which the heats of hyyield, 86%; (5) keto-acid to tetramethylsucciriic acid, drolysis and neutralization of the corresponding
quantitative. The crude acid was dissolved ixi excess
acetyl chloride and distilled. 'The anhydride, b. p. 218- anhydrides could not be obtained, due to side
220",formed a white powder which quickly became sticky reactions. These cases were discussed in the secand reverted to a waxy mass. T h a t this is not due to tion on preparation of materials. In Tables I and
hydration has been shown by Auwers and Meyer,23
I1 the mean temperatures listed refer to the temSuccessive calorimetric runs on this material showed a
perature of the thermostat bath during the reacsteadily diminishing heat of hydrolysis. Since this seemed
tion. This temperature was measured with a
to be due to alteration in crystal form, a portion of the
five-junction
thermel, one end of which was imanhydride was left for two weeks in contact with a saturated ether solution of the material, theether being allowed mersed in ice. This thermel was previously calit o evaporate slowly. Large waxy crystals were deposited
brated against a platinum resistance thermomewhich underwent no change on standing. This presunter. The temperature of the calorimeter during
ably stable form of the solid was used in the calorimeter.
A portion of the best anhydride was dissolved in sodiiim reaction in no case differed by more than one dehydroxide solution, and the acid recovered by acidification. gree from that of the bath.
It melted a t 200--201 with decomposition (bath preheated
"rABLE 1
to 190").
FfeATs OF HYDROLYSIS
AND NEUTKALIZATION,
- AH,
Mean
I Anhydride (1)
H20 (dioxane-water)
2XaOH (d -- w! = 2NaA (d - w ) -i-2H?O (d .- w'i .f
AH1 ( 3 )
1HA (s or li
1n'aOH id
w) = lNaA (d - \vi IlHzO (d - w) AH? i4-i
lHzO (1) == 1HzO (d - wj i- AI13
(5)
+ 111.20 (1)
= 2HA (s or 1) -C
AH: - 2 A H :
+ AH3
(ti)
Acetic
Propionic
1
1
Isobutyric
Trirnethylacetic
Maleic
Xfethylrnaleic
State
i s or 1)
AH3
SI2
(811
Succinic
Methylsuccinic
a,a-Dimethylsuccinic
tunns-a,p-Dimeth ylsuccinic
Tetramethylsuccinic
1
5
Sola.
temp.,
'C.
80.40
30.44
B
30.44
A 30.44
A
30.44
A
80.45
A
30.45
-4
30.45
-1 30.45
A
30.45
X
30.63
A
30.45
.-I
30.45
.i\
30.44
'-4
30.44
A
21.04
-4
31.04
A
50.12
-4
50.12
C
50.13
C
50.24
-4
50. 12
A
30.12
.i
R
-AH,,
cal. per
mole
-AH,,
mean, cal.
per mole
40174
38703
38815
38904
38931
37048
36924
37104
30326
30333
30310
31483
31430
30183
30202
34035
33992
32442
32456
29105
29118
40174
38754
38918
37025
30323
31457
30192
34013
32449
29112
27737
27869
27803
It was hoped that the heat of reaction of equatinn 1 could be obtained by conversion of the
HEATS
OF HYDROLYSIS
OF ACIDANHYDRIDES
Aug., 1942
TABLE
I1
1751
17.52
j . R . CONN,G. E. KISTTAKOWSRY,
R.M. ROBERTSAND E. A. SMITH
Vol. A4
TABLE Iv
HEATSOF HYDROLYSIS,. A H
.. .
.
Anhydride
.4cetic
Propionic
Isobutyric
Trimethylacetic
Maleic
,Methylmaleic
Succinic
Methylsuccinic
a,a-Dimethylsuccinic"
trans-a,p-Dimethylsuccinic"
Tetrainethylsuccinic"
Present investigation----.
State
- AH
Anhydride
Acid
kral. per h
I
1
I
I
1
5
<
>
"
---------From
heats of combustion-----State
AH,
Anhydrjde
Acid
kcal. per mole
13 .96
13 52
14.59
15.12
8.33
8.13
11.20
13.11
1 3 .63
7 .l i j
8.43
12.5'
14.6'
12.1'
7.5h
3 . I'
-1
tatively, i t is more than probable that interactions are here involved similar to those which
show themselves in the heats of hydrogenation of
some five-memhered carbon ring compounds2Gand
which have been interpreted as "steric hindrance"
between hydrogen atoms on adjacent carbons.
In line with this conclusion is also the difference
in the heats of hydrolysis of maleic and of succinic
anhydrides, while the conventional view would
take maleic anhydride for the more strained of the
two five-membered rings, the data actually indicate the reverse, in line with the above-mentioned
data on the cpclopentene-cyclopentane relationship.27
Finally, the absence of methyl substitution
effects in straight-chain anhydrides, where complete freedom of orientation exists, points again
to "steric hindrance" as the main if not the sole
cause of the observed variations of the heats of
hydrolysis. It mdy be noted in passing that these
effects seem to bear no relation t o the heats of
ionization of the corresponding acids, for which
Table I1 gives a series of relative values.
Without knowledge of the entropy changes concerned, i t is rather futile to discuss in detail the
relation of the thermal data obtained to the thermodynamic stability of the anhydrides and acids.
I t may be noted, however, that the increased stability of cyclic, as against the straight-chain, acid
anhydrides, can be accounted for by their gen(26) Dolliver, Gresham, Kictiakowsky and Vaughnn, THISJ O I I R
58, 839 (1937)
(27) Some resonance interactions in maleic anhydride are not e\
cluded, although they are unlikely in view of previous results on the
heat$ of hydrogenation of the system -C=C-CO-O-,
cf Dollii e r , Gresham Kisthkowsky, Smith and Vaughan, rbid , 60, 448
NAL,
<lr)3S)
Summary
Heats of the hydrolytic reaction: Anhydride
(s or 1)
H20 (1) = Acid (s or 1) computed from
heats of reaction in solution are reported here for
a number of straight-chain and cyclic (five-membered ring) acid anhydrides.
Acetic, propionic, isobutyric and trimethylacetic anhydrides were found to have the same
heat of hydrolysis, showing no effect due to methyl
substitution.
Methyl substitution in the ring compounds
markedly alters the heat of hydrolysis. Unsymmetrical substitution of methyl groups in succinic anhydride increases the heat of hydrolysis,
while symmetrical substitution decreases it. The
presence of a double bond in the ring also decreases the heat of hydrolysis.
These effects are qualitatively discussed, and
similarities to the trend of heats of hydrogenation
of five-membered carbon ring compounds are
pointed out.
CAMBRIDGE,
MASS
-_ _( 2 8 ) Verkade, Rcc 1rao. chin.,
RECEIVED
MARCH10, 1912
40, 199 (1921).