Abstact
Thermal transformations of 2H-benzimidazole 1,3-dioxides represented by spiro[2H-benz-imidazole-2,1′-cyclohexane] 1,3-dioxide and its 5-nitro derivative were studied. Their heating resulted in reversible isomerization to spiro[3H-[2,1,4]benzoxadiazine-3,1′-cyclohexane] 4-oxides. More prolonged heating of 2H-benzimidazole 1,3-dioxides caused sequential elimination of the first and then (at higher temperature) the second N-oxide oxygen atom to form 2H-benzimidazole derivatives, which upon further heating were transformed to 7,8,9,10-tetrahydro-6H-azepino[1,2-a]benzimidazoles. A scheme of the process was suggested, which described the experimental data obtained. Spiro[3H-[2,1,4]benzoxadiazine-3,1′-cyclohexane] 4-oxides on exposure to the sunlight were quantitatively transformed to 2H-benzimidazole 1,3-dioxides.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
H. Suschitzky, Croat. Chem. Acta, 1986, 59, 57.
I. Brian, Bull. Soc. Chim. Belg., 1990, 99, 673.
D. W. S. Latham, O. Meth-Cohn, H. Suschitzky, J. A. L. Herbert, J. Chem. Soc., Perkin Trans. 1, 1977, 470.
M. Boiani, L. Boiani, A. Denicola, S. Torres de Ortiz, E. Serna, N. V. Bilbao, L. Sanabria, G. Yaluff, H. Nakayama, A. R. Arias, C. Vega, M. Rolan, A. Gomez-Barrio, H. Cerecetto, M. Gonzalez, J. Med. Chem., 2006, 49, 3215.
M. Boiani, L. Boiani, A. Merlino, P. Hernandez, A. Chidichimo, J. J. Cazzulo, H. Cerecetto, M. Gonzalez, Eur. J. Med. Chem., 2009, 44, 4426.
A. Merlino, D. Benitez, S. Chavez, J. Da Cunha, P. Hernandez, L. W. Tinoco, N. E. Campillo, J. A. Paez, H. Cerecetto, M. Gonzalez, Med. Chem. Commun., 2010, 1, 216.
J. A. L. Herbert, B. Iddon, A. G. Robinson, H. Suschitzky, J. Chem. Soc., Perkin Trans. 1, 1988, 991.
K. H. Saunders, J. Chem. Soc., 1955, 3275.
V. A. Samsonov, L. B. Volodarskii, O. V. Shamirzaeva, Khim. Geterotsikl. Soedin., 1994, 524 [Chem. Heterocycl. Compd. (Engl. Transl.), 1994, 30, 460].
F. H. Allen, Acta Crystallogr., 2002, B58, 380.
I. J. Bruno, J. C. Cole, P. R. Edgington, M. Kessler, C. F. Macrae, P. McCabe, J. Pearson, R. Taylor, Acta Crystallogr., 2002, B58, 389.
J. C. Barnes, A. Hetherington, Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem., 1978, 34, 2146.
M. Kaftory, V. Shteiman, M. Botoshansky, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 2002, 58, o183.
J. C. Hazelton, B. Iddon, A. D. Redhouse, H. Suschitzky, Tetrahedron, 1995, 51, 5597.
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc., Perkin Trans 2, 1987, S1.
A. Albini, S. Pietra, Heterocyclic N-Oxides, CRC Press, Boca Raton-Ann Arbor-Boston, 1991, 312.
Yu. A. Gubarev, N. Sh. Lebedeva, V. P. Andreev, Ya. P. Nizhnik, A. I. V’yugin, Zh. Obshch. Khim., 2007, 77, 1006 [Russ. J. Gen. Chem. (Engl. Transl.), 2007, 77, 1093].
J. Hamer, A. Macaluso, Chem. Rev., 1964, 64, 473.
W. Rundel, in Houben-Weyl, Thieme Verlag, Stuttgart, 1968, Band X/4, Teil 4, 315.
A. C. Cope, A. C. Haven, Jr, J. Am. Chem. Soc., 1950, 72, 4896.
A. H. Blatt, J. Org. Chem., 1950, 15, 869.
E. J. Grubbs, J. D. McCullough, Jr, B. H. Weber, J. R. Maley, J. Org. Chem., 1966, 31, 1098.
D. F. Ioffe, L. S. Efros, Usp. Khim., 1961, 30, 1325 [Russ. Chem. Rev. (Engl. Transl.), 1961, 30].
G. M. Sheldrick, SHELXL-97, SHELXS-97, Programs for Crystal Structure Determination and Refinement, Göttingen University, Göttingen (Germany), 1997.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1697–1702, August, 2011.
Rights and permissions
About this article
Cite this article
Samsonov, V.A., Bagryanskaya, I.Y., Gatilov, Y.V. et al. Thermal transformations of 2H-benzimidazole 1,3-dioxides. Russ Chem Bull 60, 1723–1728 (2011). https://doi.org/10.1007/s11172-011-0257-x
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-011-0257-x