An Improved and Easy Method for the Preparation of 2,2-Disubstituted 1-Nitroalkenes
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- 作者：Wen-Wei Lin ; Yeong-Jiunn Jang ; Yeh Wang ; Ju-Tsung Liu ; Shin-Ru Hu ; Lian-Yong Wang ; and Ching-Fa Yao
- 刊名：Journal of Organic Chemistry
- 出版年：2001
- 出版时间：March 23, 2001
- 年：2001
- 卷：66
- 期：6
- 页码：1984 - 1991
- 全文大小：101K
- 年卷期：v.66,no.6(March 23, 2001)
- ISSN：1520-6904
文摘
Reactions of ketones 1, nitromethane 2, and catalytic amount of piperidine 3 in the presence ofmercaptan 6 generate 
-nitroalkyl sulfides 7-9. At 0 
C and by the use of dichloromethane assolvent, -nitroalkyl sulfides 7-9 can be oxidized by m-chloroperoxybenzoic acid (m-CPBA) 10 togenerate -nitroalkyl sulfoxides 11-13 and undergo elimination in carbon tetrachloride solutionto produce medium to high yield of 2,2-disubstituted 1-nitroalkenes 5. The irreversibility of thesynthetic mechanism not only can overcome the reversibility of the Henry reaction in the synthesisof 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 of5-substituted-2-nitromethyl-2-phenylthioadamantane 17 also can be prepared from the reactionof 5-substituted-2-adamantanones 15, nitromethane 2, piperidine 3, thiophenol 6a. The intermediate17 can be oxidized by m-CPBA 10 in dichloromethane solution and then undergo elimination atroom temperature or can be dissolved in solvent, coated on silica gel, and then heated at 90-100C to generate 5-substituted-2-nitromethyleneadamantane 16.
-nitroalkyl sulfides 7-9. At 0 C and by the use of dichloromethane assolvent, -nitroalkyl sulfides 7-9 can be oxidized by m-chloroperoxybenzoic acid (m-CPBA) 10 togenerate -nitroalkyl sulfoxides 11-13 and undergo elimination in carbon tetrachloride solutionto produce medium to high yield of 2,2-disubstituted 1-nitroalkenes 5. The irreversibility of thesynthetic mechanism not only can overcome the reversibility of the Henry reaction in the synthesisof 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 of5-substituted-2-nitromethyl-2-phenylthioadamantane 17 also can be prepared from the reactionof 5-substituted-2-adamantanones 15, nitromethane 2, piperidine 3, thiophenol 6a. The intermediate17 can be oxidized by m-CPBA 10 in dichloromethane solution and then undergo elimination atroom temperature or can be dissolved in solvent, coated on silica gel, and then heated at 90-100C to generate 5-substituted-2-nitromethyleneadamantane 16.