Tetrahedron Letters No.4, pp. 321-322, 1971. Pergamon Press. Printed in Great Britain.

SYNTHESIS OF AMIDES BY ADINOLYSIS OF ESTERS USING

SODIUD SYDBIDE IN DIMBTEYL SULFoxIDg

Baldev Singh

Sterling-Winthrop Research Institute, Rensselaer, N.Y. 12144

(Received in USA 16 November 1970; received in LK for publication 21 December 1970)

N-Substituted amides have been prepared by aminolysiB of esters using the

magnesium halide,' eodiumae3 and lithium3 salts of primary amines. Sodium

methoxide4 and bifunctional catalysts (such as 2-pyridone)5 have aleo been

employed in the aminolyeis of esters by primary amine8 but yield8 are not

uniformly high and no general method seems available for such aminolysis.

This communication describes the use of sodium hydride in dimethyl-

sulfoxide, hexamethylphoephoramide, N-methyl-2-pyrrolidone or N,N-diaethyl-

acetamide for the preparation of amides from primary amine8 and esters. The

representative amides in the table were obtained in 68 to 94% yields using the

folloving general procedure.

An equimolar mixture (0.10 mole) of eater, amine and sodium hydride (oil

dispersion) in 50 ml of dimethylsulfoxide (or alternate solvent above) was

stirred overnight at room temperature and then poured into ice-water with

stirring. The crystalline solid was filtered, washed with water, air-dried

and washed with pentane to remove oil (from sodium hydride).

522 No.4

Bthyl

Ethyl

Ethyl

Bthyl

Ethyl

Ethyl

a:

Table

Bster Anllne

panisate Aniline

E-diethglaminobenzoate Aniline

acetate Aniline

nicotinate Cyclohexylamine

E-anisate Cyclohexylamine

cyclopropane carboxylate Cyclohexylamine

Amide Yield,!@

92

94

85

85

82

68

Yields are based on reaction run in dimethylsulfoxide solvent.

-c mP9

172-36

123-4'

113-148

140-19

161-31°

139-14011

The author expresses his thanks to his colleagues, Drs. Phillips, Bailey

and Lesher, for their valuable suggestions regarding this work.

References

1. H. L. Bassett and C. B. Thomas, 1. e. &., 1188 (1954).

2. B. S. Stern, a. E. (London), 277 (1956).

3. Kim-Kenn Yong, J. G. Cannon and J. G. Rose, E. Let., 1791 (1970).

4. B. J. DeFeo and P. 1). Strickler, J-. org. e., 28, 2915 (1963). -

5. H. T. Openshar and 1. Whittaker, z. . s., 89 (1969).

6. D. B. Denney, 2. &. Chem. e., 78, 590 (1956). -

7. J. Heisenheimer, R. Von Budkewioz and G. Kananow, &., s, 75 (1921).

8. 1. Gasopoulos, s., 59, 2187 (1926). -

9. C. 0. Badgett et. al., 2. Am. Chem. &., 67, 1135 (1945). -- =

10. F. Bffenberger and R. Gleiter, E., 97, 472 (1964). -

11. W. F. Rrown,U.S.B 2,692,282, October 19, 1954.