REACTIVITY OF CARBOXAMIDES TOWARD BENZOYL CHLORIDE
1123
1
The apparent rate constants k (s ) were calculated as
in [3].
5. Litvinenko, L.M., Titskii, G.D., and Tarasov, V.A.,
Reakts. Sposobn. Org. Soed., 1968, vol. 5, no. 2
(16), pp. 325 340; Titskii, G.D. and Litvinen-
ko, L.M., Zh. Obshch. Khim. 1970, vol. 40, no. 12,
pp. 2680 2688; Litvinenko, L.M., Titskii, G.D.,
Stepko, O.P., and Kirpenko, N.F., Zh. Org. Khim.,
1973, vol. 43, no. 8, pp. 1794 1799; Titskii, G.D.,
Litvinenko, L.M., and Stepko, O.P., Zh. Obshch.
Khim. 1974, vol. 44, no. 8, pp. 1688 1694.
6. Savelova, V.A., Popov, A.F., Solomoichenko, T.N.,
Sadovskii, Yu.S., Piskunova, Zh.P., and Lobano-
va, O.V., Zh. Org. Khim., 2000, vol. 36, no. 10,
pp. 1502 1510.
7. Tablitsy konstant skorosti i ravnovesiya geteroliti-
cheskikh organicheskikh reaktsii (Tables of Rate and
Equilibrium Constants of Organic Reactions),
Palm, V.A., Ed., Moscow: VINITI, 1979, vol. 5.
8. Palm, V.A., Osnovy kolichestvennoi teorii organiche-
skikh reaktsii (Principles of Quantitative Theory of
Organic Reactions), Leningrad: Khimiya, 1977.
9. Stewart, W.E. and Siddall, T.H., Chem. Rev., 1970,
vol. 70, no. 5, pp. 517 551.
10. Savelova, V.A. and Oleinik, N.M. Mekhanizmy
deistviya organicheskikh katalizatorov: Bifunktsional,-
nyi i vnutrimolekulyarnyi kataliz (Mechanism of
Action of Organic Catalists: Bifunctional and Inter-
molecular Catalysis), Kiev: Naukova Dumka, 1990.
11. Sadovskii, Yu.S., Shvets, A.A., Solomoichenko, T.N.,
Savelova, V.A., Safaryan, G.P., Tsvetkov, E.N., and
Bondarenko, N.A., Zh. Org. Khim., 1996, vol. 32,
no. 4, pp. 567 571.
Benzoyl chloride was subjected to vacuum distill-
ation, acetonitrile was purified as described in [15].
2-Methylpropionamide and N-methylbenzamide were
recrystallized from benzene, trichloro and -chloro-
acetamides, N-methyl-4-chlorobenzamide, N-methyl-
trichloroacetamide, and trichloroacetanilide from
ethanol, 2-methylpropionanilide from 2-propanol,
N,N-dimethylbenzamide, N-methyl-2-methylpropion-
amide, and N,N-dimethyltrichloroacetamide were
distilled in a vacuum. The other amides were purified
as described elsewhere [3].
The hydrolysis product of benzoyl chloride was
isolated for the cases of catalysis with acetamide and
formamide. To 604 mg of benzoyl chloride at stirring
was added a solution of 1.181 g of acetamide in a
mixture of 5 ml of acetonitrile and 3.6 ml of water.
The reaction mixture was left standing at room
temperature for 24 h. The benzoic acid formed was
precipitated by adding a little cold water, filtered off,
and dried at room temperature, yield 0.504 g
(quantitative), mp 122 C (mp 122.5 C [16]). Similar-
ly was demonstrated that at catalysis with formamide
benzoyl chloride was hydrolyzed also to benzoic acid
(quantitative yield).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001