Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, pp. 1668 1669. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001,
pp. 1738 1739.
Original Russian Text Copyright
2001 by Mamatkulov, Abdushukurov, Khidirov, Rakhmonova.
SHORT
COMMUNICATIONS
Synthesis and Rearrangement of p-Tolyl Chloroacetate
N. N. Mamatkulov, A. K. Abdushukurov, Sh. Khidirov, and S. Rakhmonova
Mirzo Ulugbek Uzbekistan National University, Vuzgorodok, Tashkent, 700174 Uzbekistan
e-mail: avkooo@tashsu.silk.org
Received March 14, 2001
Rearrangements of phenol esters into hydroxy
p-Tolyl chloroacetate. A mixture of 10.8 g
(0.1 mol) of p-cresol, 11.3 g (0.1 mol) of chloroacetyl
chloride, and 50 ml of dry benzene was refluxed for
17 h (until hydrogen chloride no longer evolved). The
mixture was washed with a dilute solution of NaOH,
and the aqueous phase was extracted with benzene.
ketones in the presence of AlCl have been well
3
documented (see, e.g., [1 4]). However, there are
no published data on rearrangements of esters derived
from cresol in the presence of small amounts of metal
salts. The present communication describes the syn-
thesis and rearrangement of p-tolyl chloroacetate in
The benzene extract was dried over CaCl , the solvent
2
the presence of FeCl , FeCl 6H O, Fe (SO ) ,
3
3
2
2
4 3
was distilled off, and p-tolyl chloroacetate was dis-
tilled under reduced pressure. Yield 16.6 g (90%),
bp 145 150 C (20 mm).
ZnCl , and iron acetylacetonate. The reactions fol-
2
lowed the scheme given below:
Rearrangement of p-tolyl chloroacetate.
a. A mixture of 3.69 g (0.02 mol) of p-tolyl chloro-
acetate and 0.025 g (1.5 10 4 mol) of anhydrous
FeCl was heated for 3 h at 180 200 C and was then
3
distilled under reduced pressure. We isolated 3.39 g
(92%) of a product with bp 140 145 C (20 mm)
which contained (according to the GLC data) 97.9%
of p-tolyl chloroacetate and 2.1% of 2-hydroxy-5-
methylphenacyl chloride.
b. A mixture of 3.69 g (0.02 mol) of p-tolyl
chloroacetate and 0.05 g (3 10 4 mol) of FeCl was
3
heated for 3 h at 200 230 C. Vacuum distillation
gave 3.3 g (89%) of a liquid with bp 140 145 C
Optimal conditions for the formation of p-tolyl
chloroacetate were found. The rearrangement of
p-tolyl chloroacetate was carried out in the tempera-
ture ranges from 180 to 200 C and from 200 to 230 C
at various ester-to-catalyst ratios. The results are
summarized in table. The yields of the rearrangement
product in the presence of FeCl , FeCl 6H O, and
(
20 mm) which contained (GLC) 2% of p-tolyl
chloroacetate and 98% of 2-hydroxy-5-methylphen-
acyl chloride.
Thin-layer chromatography was performed on
Silufol UV-254 plates using carbon tetrachloride
chloroform (1:1) as eluent; chromatograms were
developed with iodine vapor. p-Tolyl chloroacetate,
Rf 0.7; 2-hydroxy-5-methylphenacyl chloride, Rf 0.09.
The products were separated by column chromatog-
raphy on Silicagel L (100/160 m) or Al O , and their
3
3
2
Fe (SO ) at 180 200 C were low; in the presence
2
4 3
of ZnCl and Fe(acac) at the same temperature the
2
3
yields of 2-hydroxy-5-methylphenacyl chloride were
3
2
6 and 60%, respectively. Raising the temperature to
30 C strongly increases the yield of the final product
2
3
melting points were determined. p-Tolyl chloroacetate,
mp 29 30 C (published data [2]: mp 30 32 C);
2-hydroxy-5-methylphenacyl chloride: bp 140 145 C
(20 mm), mp 63 65 C (published data [2]: mp 65 C).
in the rearrangements catalyzed by FeCl , FeCl3
3
6
H O, ZnCl , and Fe(acac) . The best results were
2 2 3
obtained with FeCl as catalyst (yield 98%).
3
1
070-4280/01/3711-1668$25.00 2001 MAIK Nauka/Interperiodica