Journal of Chemical & Engineering Data, Vol. 54, No. 3, 2009 1137
Table 3. Parameters of Equation 2 for Solubility of 3- and 4-Chlorophthalic Anhydride in Organic Solvents and 3- and 4-Chlorophthalic Acid
in Water
3
3
solvent
A
B
C
10 rmsd
A
B
C
10 rmsd
3
-Chlorophthalic Anhydride
4-Chlorophthalic Anhydride
ethyl acetate
acetone
-450.47
-147.32
334.20
18436
5107.19
-16737.20
67.86
22.58
-49.02
2.15
2.18
3.68
-305.90
-77.11
-181.26
11926
1487.49
5243.13
46.41
12.44
28.39
3.13
6.97
2.57
1
,4-dioxane
3
-Chlorophthalic Acid
4-Chlorophthalic Acid
464.96 10.63
water
-42.03
-3.84
6.35
0.04
-64.18
1.85
When the chloro is in the para-position of the phenyl ring (4-
chlorophthalic anhydride), the chloro behaves to some extent of
steric effect and conjugate effect in the molecule, which makes
the electron in 4-chlorophthalic anhydride more disperse than in
in water increases greatly with an increase in temperature;
however, the solubility of 3-chlorophthalic acid in water
increases slightly. Besides, the solubility of 4-chlorophthalic acid
in water is higher than that of 3-chlorophthalic acid. The
calculated solubility shows good agreement with the experi-
mental values. These experimental data were able to be regressed
by eq 2 for each solvent. The experimental solubility and
correlation equation in this work can be used as essential data
and models in the purification process of 3-chlorophthalic
anhydride and 4-chlorophthalic anhydride.
4-chlorophthalic anhydride. As a result, the solubility of 3-chlo-
rophthalic anhydride is higher in 1,4-dioxane than in the other
solvents, and the solubility of 4-chlorophatalic anhydride is higher
in ethyl acetate and acetone than in 1,4-dioxane.
As shown in Figures 1, 2, and 3, the mole fraction solutility
(x) of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride
or its corresponding acid was correlated as a function of
temperature. The temperature dependence of solubility in
solvents is described by the modified Apelblat equation,
which is a semiempirical equation
Literature Cited
1
8,19
(1) Chodnekar, M. S.; Pfiffner, A.; Rigassi, N.; Schwieter, U.; Suchy, M.
Phenyl DeriVatiVes. U. S. Patent 3,879,429, April 22, 1975.
2) Khouri, F. F.; Stella, A. S. Method of Making Bisimides. U. S. Patent
(
B
T ⁄ K
2,008,119,660, May 22, 2008.
ln x ) A +
+ C ln(T ⁄ K)
(2)
(3) Zhang, Q. Y.; Li, W. M.; Wang, J. H.; Zhang, S. B. Synthesis of
Isomeric Bis(amine anhydride)s for Novel Poly(amine imide)s by Pd-
Catalyzed Amination of 4-Chlorophthalic Anhydride. Polymer 2008,
where x is the mole fraction solubility of solute; T is the absolute
temperature; and A, B, and C are the empirical parameters in
eq 2. The values of these parameters are given in Table 3. The
solubility values of 3/4-chlorophthalic anhydride and 3/4-
chlorophthalic acid can be calculated according to these
empirical parameters. The experimental solubility in the studied
solvents was compared with calculated solubility (x
relative deviations (RD) between the experimental and calculated
values of solubilities are also calculated by eq 3 and are given
in Tables 1 and 2.
4
9, 1191–1198.
4) Wu, J. Y.; Zhao, Y. F.; Chen, Y. S.; Guo, C. L. Preparing Method of
,4,3′,4′-Biphenyltetracarbosylic Dianhydride. CN Patent 101,016,284,
(
3
August 15, 2007.
(
(
(
5) Liu, S. H. Process for Synthesizing Bibenzene Tetracarboxylic
Dianhydride. CN Patent 1,944,419, April 11, 2007.
6) Arnold, Z.; Martin, E. 3-Chlorophthalic Anhydride through Chlorina-
tion of Phthalic Anhydride. J. Org. Chem. 1978, 43, 3690–3692.
7) Lawrence, B. F.; Neil, J. O. R.; Kathleen, M. C. Optimization of
Reaction Variables in the Selective Hydrodechlorination of Chlorinated
Phthalic Anhydrides and Acids: Preparation of 3,6-Dichlorophthalic
Acid and 3-Chlorophthalic Acid. J. Org. Chem. 1993, 58, 261–263.
8) Lawrence, B. F.; Neil, J. O. R.; Henry, C. Preparation of Halogenated
Phthalic Anhydrides. U. S. Patent 5,059,697, October 22, 1991.
calc
i
). The
(
calc
x - x
RD )
(3)
(9) Karl, W. S.; John, R. Mo. Photochlorination of Phthalic Anhydride.
U. S. Patent 5,300,201, April 5, 1994.
x
(
(
(
10) Karl, G. B.; Erwin, B.; Eckhardt, B. Preparation of 3-Chlorophthalic
Anhydride. U. S. Patent 5,683.553, November 4, 1997.
11) Karl, W. S.; Jeffrey, S. S.; Gary, H. O. Synthesis of 4-Substituted
Phthalic Anhydrides. U. S. Patent 5,322,954, June 21, 1994.
12) John, W. V. J.; Louella, W. Remarkably Selective Chlorination of
Phthalic Anhydride and Its Monochlorinated Derivatives. J. Org.
Chem. 1983, 48, 2465–2468.
13) William, M. ImproVements in and Relating to the Production of
Phthalic Anhydride DeriVatiVes. GB Patent 357,165, September 14,
1931.
Further, the root-mean-square deviations (rmsd), calculated
by eq 4, are listed in Table 3.
N
1⁄2
calc 2
1,j
(
x - x
)
∑
1,j
j)1
rmsd )
[
]
(4)
(
N - 1
calc
where N is the number of experimental points; x1,j represents
the solubility calculated from eq 2; and x1,j represents the
experimental solubility values.
(
14) Newman, M. S.; Scheurer, P. G. The Behavior of 3-Chlorophthalic
Anhydride in Friedel-Crafts and Grignard Condensations. J. Am. Chem.
Soc. 1956, 78, 5005–5007.
(
(
15) Ding, M. X.; Zhang J.; Yang Z. H. Separation of Isomers of Chloro-
Benzoic Anhydride. CN Patent 1,186,063, July 1, 1998.
16) Stephen, H.; Stephen, T. Solubility of Inorganic and Organic Com-
pounds; Pergamon: Oxford, 1979.
Conclusions
The solubility of 3-chlorophthalic anhydride and 4-chlo-
rophthalic anhydride in ethyl acetate, acetone, and 1,4-dioxane
and the solubility of 3-chlorophthalic acid and 4-chlorophthalic
acid in water were determined using Schreinemaker’s wet
residue method at temperatures ranging from (283.15 to 333.15)
K. The solubility of 3-chlorophthalic anhydrides and 4-chlo-
rophthalic anhydrides increases with an increase in temperature
in the studied organic solvents. The solubility of 3-chlorophthalic
anhydride is higher in 1,4-dioxane than that in ethyl acetate
and acetone, while the solubility of 4-chlorophthalic anhydride
is lower in 1,4-dioxane. The solubility of 4-chlorophthalic acid
(17) Schott, H. A Mathematical Extrapolation for the Method of Wet
Residues. J. Chem. Eng. Data 1961, 6, 324–324.
(
18) Gao, J.; Wang, Z. W.; Xu, D. M.; Zhang, R. K. Solubilities of
Triphenylphosphine in Ethanol, 2-Propanol, Acetone, Benzene and
Toluene. J. Chem. Eng. Data 2007, 52, 189–191.
(
19) Kong, M. Z.; Shi, X. H.; Cao, Y. C.; Zhou, C. R. Solubility of
Imidacloprid in Different Solvents. J. Chem. Eng. Data 2008, 53, 615–
6
18.
Received for review November 16, 2008. Accepted January 15, 2009.
JE800869G