title: An improved and easy method for the preparation of 2,2-disubstituted 1-nitroalkenes.
abstract: Reactions of ketones 1, nitromethane 2, and catalytic amount of piperidine 3 in the presence of mercaptan 6 generate beta-nitroalkyl sulfides 7-9. At 0 degrees C and by the use of dichloromethane as solvent, beta-nitroalkyl sulfides 7-9 can be oxidized by m-chloroperoxybenzoic acid (m-CPBA) 10 to generate beta-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 intermediate17 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 degrees C to generate 5-substituted-2-nitromethyleneadamantane 16.
authors: Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei, Taiwan 116 ROC.
authors: W W
authors: WW
authors: Lin
authors: Y J
authors: YJ
authors: Jang
authors: Y
authors: Y
authors: Wang
authors: J T
authors: JT
authors: Liu
authors: S R
authors: SR
authors: Hu
authors: L Y
authors: LY
authors: Wang
authors: C F
authors: CF
authors: Yao