Sulfonyl derivatives of benzotriazole: Part 1. A novel approach to the activation of carboxylic acids

doi:10.1016/S0040-4020(01)80459-2

Tetrahedron

Volume 48, Issue 37, 1992, Pages 7817-7822

In honor of the 65th anniversary of Charles Rees and in commemoration of 4 decades of friendship.

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Abstract

1-Acylbenzotriazoles (8, R = Me, Et, n-Bu and Ph) are prepared in good yields by fusion of benzotriazole and acid chlorides at 80 – 100°C. In cases when the corresponding acid chlorides are not available, 1-acylbenzotriazoles are conveniently available from 1-(1-methanesulfonyl)benzotriazole and the respective carboxylic acids as illustrated by the preparation of 2-, 3-, and 4-pyridoyl-, 2-pyrrolylcarbonyl- and 2-furoyl-benzotriazole in yields of 80 – 95%. Preparations of two sulfonyl derivatives of benzotriazole are also described.

1-Acylbenzotriazoles are easily prepared from 1-(1-methanesulfonyl)benzotriazole and carboxylic acids as illustrated by the preparation of 1-(2-pyridoyl)-, 1-(3-pyridoyl)-, 1-(4-pyridoyl)-, 1-(2-pyrrolylcarbonyl)- and 1-(2-furoyl)-benzotriazole in yields of 80 – 95%.

References (30)

N.G. Gaylord
J. Am. Chem. Soc.
(1954)
M.R. Grimmett
T. Keumi et al.
Bull. Chem. Soc. Jpn
(1980)
W. Walter et al.
Liebigs Ann. Chem.
(1979)
T. Keumi et al.
Bull. Chem. Soc. Jpn.
(1981)
H.A. Staab et al.
M. Ogata et al.
Heterocycles
(1980)
H.K. Reimschuessel et al.
Chem. Abstr.
(1968)
M. Reboud-Ravaux et al.
Eur. J. Biochem.
(1976)
G.A. Tolstikov et al.
Dokl. Akad. Nauk SSSR
(1982)
Chem. Abstr.
(1983)
K. Tsujimoto et al.
Bull. Chem. Soc. Jpn.
(1972)

A.J. Hubert et al.

Chem. Ber.

(1970)

J.D. Druliner

J. Am. Chem. Soc.

(1968)

M. Reboud-Ravaux

J. Am. Chem. Soc.

(1980)

G. Gopalakrishnan et al.

J. Org. Chem.

(1981)

J.P. Gasparani et al.

J. Organometallic Chem.

(1980)

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Sulfonyl derivatives of benzotriazole: Part 1. A novel approach to the activation of carboxylic acids

Abstract

J. Am. Chem. Soc.

Bull. Chem. Soc. Jpn

Liebigs Ann. Chem.

Bull. Chem. Soc. Jpn.

Heterocycles

Chem. Abstr.

Eur. J. Biochem.

Dokl. Akad. Nauk SSSR

Chem. Abstr.

Bull. Chem. Soc. Jpn.

Chem. Ber.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Org. Chem.

J. Organometallic Chem.