An improved and easy method for the preparation of 2,2-disubstituted 1-nitroalkenes

W. W. Lin, Y. J. Jang, Y. Wang, J. T. Liu, S. R. Hu, L. Y. Wang, C. F. Yao

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16 Citations (Scopus)

Abstract

Reactions of ketones 1, nitromethane 2, and catalytic amount of piperidine 3 in the presence of mercaptan 6 generate β-nitroalkyl sulfides 7-9. At 0 °C and by the use of dichloromethane as solvent, β-nitroalkyl sulfides 7-9 can be oxidized by m-chloroperoxybenzoic acid (m-CPBA) 10 to generate β-nitroalkyl sulfoxides 11-13 and undergo elimination in carbon tetrachloride solution to produce medium to high yield of 2,2-disubstituted 1-nitroalkenes 5. The irreversibility of the synthetic mechanism not only can overcome the reversibility of the Henry reaction in the synthesis of 2,2-disubstituted 1-nitroalkenes 5 but also can generate the major products "exo-nitro olefins" 5c-e when cyclic ketones 1c-e were used. Under similar conditions, medium to high yield of 5-substituted-2-nitromethyl-2-phenylthioadamantane 17 also can be prepared from the reaction of 5-substituted-2-adamantanones 15, nitromethane 2, piperidine 3, thiophenol 6a. The intermediate 17 can be oxidized by m-CPBA 10 in dichloromethane solution and then undergo elimination at room temperature or can be dissolved in solvent, coated on silica gel, and then heated at 90-100 °C to generate 5-substituted-2-nitromethyleneadamantane 16.

Original languageEnglish
Pages (from-to)1984-1991
Number of pages8
JournalJournal of Organic Chemistry
Volume66
Issue number6
DOIs
Publication statusPublished - 2001 Mar 23

ASJC Scopus subject areas

  • Organic Chemistry

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