Abstract
Reactions of alanto-, isoalanto-, and alloalantolactones, which are unsaturated eudesmane-type lactones, with diazocyclopropane generated in situ from N-cyclopropyl-N-nitrosourea under the action of sodium methoxide proceed alike, are highly regio- and stereoselective, and always give spiro-fused pyrazolines via cycloaddition to the exocyclic double bond of the methylidene group of the lactone ring. Their thermolysis at 195–210 °C results in elimination of molecular nitrogen, mainly yielding spiropentane-containing lactones. Minor thermolysis products (10–12%) are isomeric 13-cyclopropyl lactones.
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A. D. Kagarlitskii, S. M. Adekenov, A. N. Kupriyanov, Seskviterpenovye laktony rastenii Tsentral’nogo Kazakhstana [Sesquiterpene Lactones Found in the Plants of Central Kazakhstan], Izd. Akad. Nauk Kazakhskoi SSR, Alma-Ata, 1987, 240 pp. (in Russian).
S. M. Adekenov, Khim. Prir. Soedin., 1995, 29 [Chem. Nat. Compd. (Engl. Transl.), 1995].
Y. Ohta, N. H. Andersen, C.-B. Liu, Tetrahedron, 1977, 33, 617.
T. Konishi, Y. Shimada, T. Nagao, H. Okabe, T. Konoshima, Biol. Pharm. Bull., 2002, 25, 1370.
N. J. Lawrence, A. T. McGown, J. Nduka, J. A. Hadfield, R. G. Pritchard, Bioorg. Med. Chem. Lett., 2001, 429.
S. M. Adekenov, Ross. Bioter. Zh. [Russian Biotherapeutic Journal], 2002, 1, 5 (in Russian).
J. A. Marshall, N. Cohen, J. Org. Chem., 1964, 29, 3727.
S. G. Klochkov, S. V. Afanas’eva, A. N. Pushin, Khim. Prir. Soedin., 2006, 325 [Chem. Nat. Compd. (Engl. Transl.), 2006].
P. S. Kalsi, B. Kaur, K. K. Talwar, Indian J. Chem., 1985, 24B, 835.
Yu. V. Tomilov, I. V. Kostyuchenko, E. V. Shulishov, O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim., 1997, 532 [Russ. Chem. Bull. (Engl. Transl.), 1997, 46, 511].
Yu. V. Tomilov, E. V. Shulishov, O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., 1991, 1057 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1991, 40, 939].
Yu. V. Tomilov, I. V. Kostyuchenko, O. M. Nefedov, Usp. Khim., 2000, 69, 507 [Russ. Chem. Rev. (Engl. Transl.), 2000, 69, 461].
R. R. Rafikov, R. A. Novikov, E. V. Shulishov, L. D. Konyushkin, V. V. Semenov, Yu. V. Tomilov, Izv. Akad. Nauk, Ser. Khim., 2009, 1866 [Russ. Chem. Bull., Int. Ed., 2009, 58, 1927].
Yu. V. Tomilov, E. V. Shulishov, S. A. Yarygin, O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim., 1995, 2203 [Russ. Chem. Bull. (Engl. Transl.), 1995, 44, 2109].
P. Bladon, D. R. Rae, A. D. Tait, J. Chem. Soc., Perkin Trans. 1, 1974, 1468.
P. A. Belyakov, V. P. Ananikov, Izv. Akad. Nauk, Ser. Khim., 2011, 765 [Russ. Chem. Bull., Int. Ed., 2011, 60, 783].
A. V. Belovodskii, E. E. Shul’ts, M. M. Shakirov, I. Yu. Bagryanskaya, Yu. V. Gatilov, G. A. Tolstikov, Zh. Org. Khim., 2010, 46, 1710 [Russ. J. Org. Chem. (Engl. Transl.), 2010, 46].
W. Kirmse, H. Schütte, Chem. Ber., 1968, 101, 1674.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 280–286, February, 2012.
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Tomilov, Y.V., Revunov, E.V., Shulishov, E.V. et al. 1,3-Dipolar addition of diazocyclopropane to eudesmane-type methylidene lactones and thermolysis of the resulting spiro-fused pyrazolines. Russ Chem Bull 61, 280–286 (2012). https://doi.org/10.1007/s11172-012-0039-0
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DOI: https://doi.org/10.1007/s11172-012-0039-0