Izvestiya of Saratov University.

Chemistry. Biology. Ecology

ISSN 1816-9775 (Print)
ISSN 2541-8971 (Online)

Full text:
(downloads: 134)
Article type: 

Interaction of Maleic Anhydride with 1,2-phenylenediamine under Different Conditions

Grinev Vyacheslav Sergeevich, Institute of Biochemistry and Physiology of Plants and Microorganisms of the Russian Academy of Sciences
Volkova Anna V., Saratov State University
Linkova Elena I., Saratov State Agrarian University named after V.I. Vavilov.
Yegorova Alevtina Yu., Saratov State University

The reaction of maleic anhydride with 1,2-phenylenediamine when heated in an aprotic solvent, regardless of temperature, proceeds with the initial formation of the primary addition product, namely, 4-[(2-aminophenyl)amino)-4-oxobut-2-enoic acid, which further undergoes heterocyclization within two ways, due to the presence of several electrophilic centers in the molecule, depending on the reaction conditions. Under mild conditions, the formation of 3-(2-hydroxy-2, 3-dihydro-1H-benzo[d]imidazol-2-yl)acrylic acid is observed, the formation of which is explained by the nucleophilic attack of free amino acid on the amide carbon atom, while in more severe conditions, with azeotropic removal of water, the Michael reaction takes place, with the participation of an electron-deficient carbon atom of an exocyclic multiple bond with the formation of isomeric 2-(3-oxo-1, 2, 3, 4-tetrahydroquinoxalin-2-yl)acetic acid. The structures of the compounds obtained were proved using a combination of data of IR, 1H, 13C NMR spectroscopy, as well as two-dimensional NMR experiments of heteronuclear correlation, HSQC and HMBC.


1. Watson W. H., Wu G., Richmond M. G. Sequential reaction of p-toluidine with 2,3-dichloromaleic anhydride: Synthesis and molecular structure of 2-chloro-3-p-toluidino- N-p-tolylmaleimide. J. Chem. Cryst., 2003, vol. 33, no. 12, pp. 983–988. DOI: https://doi.org/10.1023/A:1027498202694

2. Watson W. H., Wu G., Richmond M. G. Reaction of ophenylenediamine with 2,3-dichloromaleic anhydride: synthesis of N-substituted maleimide derivatives and 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one. X-ray structures of 2,3-dichloro-N-o-C6H4(NH2)maleimide and N,N’-o-C6H4-bis(2,3-dichloromaleimide). J. Chem. Cryst., 2004, vol. 34, no. 11, pp. 757–764. DOI: https://doi.org/10.1007/s10870-004-7651-2

3. Dawood K. M., Elwan N. M., Abdel-Wahab B. F. Recent advances on the synthesis of azoles, azines and azepines fused to benzimidazole. Arkivoc., 2011(i), pp. 111–195. DOI: https://doi.org/10.3998/ark.5550190.0012.102

4. Balasubramaniyan V., Balasubramaniyan P., Patil S. V. Reactions of Cyclic Anhydrides. Part 17. Synthesis of Pyrrolobenzimidazoles and Benzimidazolylacrylic Acids. Ind. J. Chem., Sect. B29, 1990, vol. 2, pp. 124–127. DOI: https://doi.org/10.1002/chin.199021168

5. Lozinskiy M. O., Demchenko A. M., Shivanyuk A. F. Sintez i svoystva proizvodnykh 1,4-benzotiazina [Synthesis and properties of derivatives of 1,4-benzothiazine]. Izbrannye metody sinteza i modifi katsii geterotsiklov [Selected methods for the synthesis and modifi cation of heterocycles]. Moscow, IBS PRESS Publ., 2003, vol. 2. 565 p. (in Russian).

6. Okafor C. O., Akpuaka M. U. New synthesis of pyrrolobenzothiazine and pyrrolobenzoxazine ring systems. J. Chem. Soc., Perkin Trans 1, 1993, pp. 159–161. DOI: https://doi.org/10.1039/P19930000159