Preparation of the Maleic Anhydride Nucleus from Dichloro γ-Lactams: Focus on the Role of the N-Substituent in the Functional Rearrangement and in the Hydrolytic Steps

Abstract

The preparation of the 3,4-dialkyl-substituted maleic anhydride nucleus, through the functional rearrangement of dichloro γ-lactams, allowed the comparison of various N-substituents in the functional rearrangement step. The 2-pyridyl group proved to be the most appropriate N-substituent for the hydrolysis of the 5-methoxy-1,5-dihydro-2H-pyrrol-2-one intermediate into the 5-hydroxy adduct, and for the hydrolysis of the maleimide nucleus into the maleic anhydride. The oxidation of the 5-hydroxy-1,5-dihydro-2H-pyrrol-2-one into the corresponding maleimide was achieved with manganese(IV) oxide.

Key words

rearrangement - radical reactions - substituent effects - halo compounds - γ-lactams

References

• 1 Chen X. Zheng Y. Shen Y. Chem. Rev.  2007,  107:  1777 
• 2 Haval KP. Argade NP. Tetrahedron  2006,  62:  3557 
• 3 Baumann ME. Bosshard H. Breitenstein W. Rihs G. Winkler T. Helv. Chim. Acta  1986,  69:  396 
• 4 Bellesia F. Danieli C. De Buyck L. Galeazzi R. Ghelfi F. Mucci A. Orena M. Pagnoni UM. Parsons AF. Roncaglia F. Tetrahedron  2006,  62:  746 
• 5 Schulze K. Richter F. Weisheit R. Krause R. Mühlstädt M. Mühlstädt M. J. Prakt. Chem.  1980,  322:  629 
• 6 Baumann ME. Bosshard H. Breitenstein W. Rihs G. Winkler T. Helv. Chim. Acta  1984,  67:  1897 
• 7 Mangaleswaran S. Argade NP. Synthesis  2002,  865 
• 8 Jaime-Figueroa S. Liu T. Muchowski JM. Putman DG. Tetrahedron Lett.  1998,  39:  1313 
• 9 Clark AJ. Chem. Soc. Rev.  2002,  31:  1 
• 10 The term isohypsic (‘equal level’ from the Greek word hypsis: level) describes a reaction that occurs with no change in the oxidation state: Hendrickson JB. J. Am. Chem. Soc.  1971,  93:  6847 
• 11 Ghelfi F. Stevens C. Laureyn I. Van Meenen E. Rogge TM. De Buyck L. Nikitin KV. Grandi R. Libertini MC. Pagnoni UM. Schenetti L. Tetrahedron  2003,  59:  1147 
• 13 Berdinskii IS. Glushkov VA. Zh. Org. Khim.  1984,  20:  2149 
• 14 Heilmann D. Sicker D. Chem.-Ztg.  1991,  115:  219 
• 15 Hino K. Nagai Y. Uno H. Chem. Pharm. Bull.  1988,  36:  2386 
• 16 Carey FA. Sundberg RJ. Advanced Organic Chemistry. Part A: Structure and Mechanisms   Kluwer Academic/Plenum Press; New York: 2000.  p.300-302  
• 17 Motoyama Y. Hanada S. Shimamoto K. Nagashima H. Tetrahedron  2006,  62:  2779 
• 18 Von Rohrscheidt C. Fritz H. Justus Liebigs Ann. Chem.  1978,  680 
• 19 Pal M. Swamy NK. Hameed PS. Padakanti S. Yeleswarapu KR. Tetrahedron  2004,  60:  3987 
• 20 Anselmi C. Camparini A. Scotton M. J. Heterocycl. Chem.  1983,  20:  687 
• 21 Renaud P. Seebach D. Synthesis  1986,  424 
• 22 Nikaido M. Aslanian R. Scavo F. Helquist P. Åkermark B. Bäckvall JE. J. Org. Chem.  1984,  49:  4740 
• 23 Padwa A. Jacqueez MN. Schmidt A. J. Org. Chem.  2004,  69:  33 
• 24 De Mayo P. Reid ST. Chem. Ind. (London)  1962,  35:  1576 
• 25 Megges R. Weiland J. Schon R. Repke H. Repke KRH. Collect. Czech. Chem. Commun.  2002,  67:  336 
• 26 Taylor RJK. Reid M. Foot J. Raw SA. Acc. Chem. Res.  2005,  38:  851 
• 27 Boehner B, and Baumann M. inventors; CH  633678.  Chem. Abstr. 1983, 98, 121386
• 28 Ince J. Ross TM. Shipman M. Slawin AMZ. Tetrahedron  1996,  52:  7037 
• 29 Whitehead CW. Traverso JJ. J. Am. Chem. Soc.  1958,  80:  2182