Chemical Reviews Volume
70,
Number
August
4
439
1970
CYCLIC CARBOXYLIC MONOIMIDES . K. HARGREAVES, J. G. PRITCHARD, West Ham College
of Technology,
and
H. R. DAVE*
London, England
Received February 2, 1968 (Revised Manuscript Received December 19, 1969)
Contents I. II.
Introduction Synthesis of Imides A. General Methods Special Methods Chemical Properties A. Ring-Opening Reactions B. Reaction at the N-Hydrogen C. Substitutions on Carbon in Imides D. Reactions of Imides with Unsaturated Compounds E. Special Reactions of Maleimide and Its Derivatives F. Reduction of Imides G. Metal-Organic Complexes of Imides H. Photolysis, Pyrolysis, and Miscellaneous Reactions Physical Properties A. Some Thermodynamic Properties B. Crystal Structures and Dimensions of the Imide Ring C. Dipole Moments D Magnetic Resonance E. Infrared Spectra F. Mass Spectra G. Ultraviolet Spectra H. Optical Rotatory Dispersion and
B.
III.
IV.
V.
VI.
VIII.
Circular Dichroism I. Fluorescence Spectra of Imides Detection of Imides Uses of Imides A. Qualitative Analysis B Industrial Uses C. Biological Uses of Imides D. Pharmacological Uses of Imides Isoimides
439 440 440 442 443 443 447 449
450 451
452 453
N—R 454 454 454 455 456 457 458 460 461
462 463 464 464 464 465 466 467 468
I. Introduction The chemistry of aliphatic imides has been briefly reviewed up to the year 1936 by Amagat.* 1 Up to that time imides were regarded as derivatives of acids and were not looked upon as a separate class of compounds with broad industrial or pharmacological applications of their own, as is now the case. As
*
Present address: Vithalbhai Patel Mahavidyalaya (Science College),
Vallabh Vidyanagar, W. Rly., District Kaina, India. (1) P. Amagat, “Traite de Chemie Organique," Vol. XIII, V. Grignard, Ed., Masson, Paris, 1941, pp 502-521.
so many other classes of compounds, reliable measurements of their physical properties have only been available within the last 10 years. In general imides are the diacyl derivatives of ammonia or of a primary amine. This review has been confined essentially to monocyclic dicarboxylic monoimides of general formula I, where A is an aliphatic, alicyclic, or aromatic divalent group. These restrictions were imposed so as to exclude compounds like uric acid, alloxan, barbiturates, and others on which there is also an extensive literature. The N-halo derivatives of imides have also been largely excluded, because separate reviews of the reactions of these are available.2-4 To a minor extent this review does include isoimides of the formula II.
with
>20
II. Synthesis of Imides A. GENERAL METHODS number of related methods of general applicabe used for the preparation of most simple aliphatic imides, and these are discussed below in this section. Section II.B lists, under the name of the imide concerned, methods of less general applicability, and this section particularly applies to aromatic and alicyclic imides in which the nature of the ring system sometimes allows special methods to be used. There
are a
bility which may
1.
Reaction
of the Corresponding
Acid with Ammonia CO
/COOH '^COOH
