TRANSFORMATION OF TRICHLOROMETHYL ARENES
487
2
00 C. Compound IIIa, 1.78 g (58.7%) was obtained,
is a mixture of compounds Ib, IIIb, and IVb. From
the chloroform solution of the solid part of reaction
mixture 0.48 g (41%) of the anhydride IV was ob-
2
0
bp 79 80 C (10 mm), n 1.5147.
D
c. A mixture of 5.05 g of compound Ia and 14 g of
compound VIII was heated for 27 h at 200 C to give
tained, mp 111 112 C,
16 ppm.
P
3
n
.0 g (86%) of compound IIIa, bp 80 81 C (10 mm),
Benzoyl chloride (VIa). A mixture of 5.45 g of
trichloromethylbenzene Ia and 3.46 g of compound II
was heated in a sealed ampule for 30 h at 180 C.
Distillation of reaction mixture gave 3.04 g (78%) of
2
0
1.5150, and 8.31 g (71.2%) of diethylphosphinic
D
acid anhydride, bp 113 C (0.05 mm),
Found, %: P 27.50. C H O P . Calculated, %: P
2
60 ppm.
P
8
20
3 2
compound VIa, bp 75 76 C (10 mm), n2 1.5521 [4].
0
7.39.
D
Crystallization of the solid part from chloroform gave
d. A mixture of 5.71 g of acid chloride VI and
.04 g of phosphonate III was heated for 16 h at
10 C to give 8.1 g (67.5%) of compound IIIa, bp
1.82 g (57%) of methylphosphonuc acid anhydride IV
5
2
1
mp 111 3112 C.
2
0
03 105 C (40 mm), n 1.5135, and 2.15 g (66%) of
IR spectra of compounds were recorded on an UR-
20 spectrometer in thin layer in the range of 400
D
anhydride IV, mp 111 113 C,
16 ppm.
P
1
1
4
600 cm . H NMR spectra were measured on a
Methyl 3-chlorobenzoate (IIIb). A mixture of
.28 g of 3-(trichloromethyl)chlorobenzene Ib and
.46 g of phosphonate II was heated for 53 h at
80 C to give 1.37 g (81%) of compound IIIb, bp
Tesla BS-567A spectrometer (100 MHz) against in-
2
2
1
1
31
ternal TMS. P NMR spectra were registered on a
RYa-2303 spectrometer (21.0 MHz) against external
85% phosphoric acid. Mass spectra were obtained on
a MX-1310 spectrometer at the ionizing voltage 70 V,
ion collector current 30 A, and the average tem-
perature of the ion source 120 C. Accurate measure-
ment of mass was carried out automatically by the
reference peaks of perfluorocerosene at the resolving
power R 15000.
2
0
1
40 142 C (12 mm), n 1.5490 [6]. H NMR spec-
D
trum (CDCl ), , ppm: 3.8 s (3H, COOCH ), 7.2
3
3
1
8
.2 m (4H, C H ). IR spectrum, , cm 1733 (C=O).
6 4
From the chloroform solution 0.98 g (42%) of an-
hydride IV were isolated, mp 112 113 C, 16 ppm.
P
Methyl 4-chlorobenzoate (IIIc). This compound
was obtained analogously from 2.35 g of compound
Ic and 2.54 g of phosphonate II. Yield 1.38 g (79%),
REFERENCES
1
bp 136 137 C (10 mm), mp 43 C [6]. H NMR spe-
ctrum (CDCl ), , ppm: 3.8 s (3H, COOCH ), 7.2
1. Pudovik, A.N., Muratova, A.A., Kopnova, T.I., Feoktis-
tovam T.N., and Levkoeva, A.B., Zh. Obshch. Khim.,
1960, vol. 30, no. 8, pp. 2624 2630.
3
3
1
8
.2 m (4H, C H ). IR spectrum, , cm : 1735 (C=O).
6 4
From the chloroform solution 1.05 g (44%) of the an-
hydride IV was isolated, mp 111 113 C, 16 ppm.
P
2. Rabinowitch, R., J. Org. Chem., 1963, vol. 28, no. 11,
pp. 2975 2978.
Reaction of 3-(trichloromethyl)chlorobenzene
(
Ib) with compound (II). A mixture of 2.32 g of
3. US patent 2787629, 1952, C.A., 1957, vol. 51,
compound Ib and 1.25 g of phosphonate II was
heated for 40 h at 180 C. Fractionation of the liquid
part of reaction mixture gave two fractions with bp
p. 10831.
4
5
. Rabinovich, V.A. and Khavin, Z.Ya., Kratkii spravo-
chnik khimika (Short Chemists Handbook), Leningrad:
Khimiya, 1977.
1
07 110 C (14 mm) and 110 130 C (14 mm).
1
According to IR and H NMR spectra the first frac-
. Dictionary of Organic Compounds, Heilbron, I. and
Bunbury, H.M., Eds., London, 1946, vol. 1.
tion consisted of a mixture of compounds IIIb and
1
VIb in 2:1 ratio. H NMR spectrum (CDCl ), , ppm:
3
3
.8 s (3H, COOCH ), 7.2 8.2 m (4H, C H ). IR spec-
6. Perel’man, V.I., Kratkii spravochnik khimika (Short
3
6
4
1
trum, , cm : 1733, 1766 (C=O). The second fraction
Chemists Handbook), Moscow: Khimiya, 1977.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001