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合成了两个N-(ω-三甲基硅烷基醚)马来酰亚胺衍生物(2a,2b),并以2a,2b为光反应底物在HCN,MeOH,30%H_2O-HCN,丙酮等溶剂中进行了光反应.结果显示,化合物2a在强的亲硅性溶剂MeOH,30%H_2O-MeOH,30%H_2O-HCN中经单电子转移反应以很高的产率和区域选择性生成环胺醇产物3,在HCN、丙酮等弱的亲硅性溶剂中发生[2+2]环加成副反应生成双分子偶合产物5;2b无论是在强的亲硅性溶剂,还是在弱的亲硅性溶剂HCN、丙酮中,部发生分子内单电子转移反应,生成分子内双离子自由基中间体8.一部分8发生脱三甲基硅烷基反应生成环化物4的前体分子内双自由基9,多数8发生特殊的分子间偶合反应得到不对称双分子偶合产物6.所有新化合物均经NMR和质谱验证.
Two (N- (ω-trimethylsilyl ether) maleimide derivatives (2a, 2b) were synthesized and the photoconductive substrates 2a and 2b were used in the reaction of HCN, MeOH, 30% H 2 O-HCN, Acetone and other solvents.The results showed that the compound 2a in a strong hydrophilicity solvent MeOH, 30% H_2O-MeOH, 30% H_2O-HCN by single-electron transfer reaction with a high yield and regioselectivity Generate cyclic amine alcohol product 3, [2 + 2] cycloaddition side reactions occur in weak hydrophilic solvent such as HCN, acetone and the like to generate bimolecular coupling product 5; 2b, whether in a strong hydrophilic solvent or in Weak hydrophilic silicon solvent HCN, acetone, intramolecular single electron transfer reaction, the generation of intramolecular ion free radical intermediates 8. Part of the de-trimethylsilyl reaction occurred cyclization 4 precursor molecules Double free radical 9, the majority of 8 special intermolecular coupling reaction to obtain asymmetric bimolecular coupling products 6. All new compounds were confirmed by NMR and mass spectrometry.