3-Fluoro-2-Methylbenzaldehyde Cyclohexylimine置于盐酸体系中,化学反应生成3-氟-2-甲基苯甲醛
参考文献:Directed Metalation Of Aromatic Aldimines With Lithium 2,2,6,6-Tetramethylpiperidide
标题:Directed Metalation Of Aromatic Aldimines With Lithium 2,2,6,6-Tetramethylpiperidide
摘要:N-Cyclohexyl Aromatic Aldimines Are Ortho-Lithiated Or O-Methyl-Lithiated With 2 Equiv Of Lithium 2,2,6,6-Tetramethylpiperidide (Ltmp) In Thf Solution It-15-Degrees-C. The Lithiated Intermediates Generally Reacted With Alkyl Halides Or Co2 To Provide Ortho-Functionalized Aldimine Products Which Could Be Readily Converted To The Corresponding Aldehydes By Hydrolysis With Aqueous 4 M Hci. Aromatic Aldimines Derived From (+/-)-Trans-2-Methylcyclohexylamine Or 3-Amino-2,4-Dimethylpentane Are Resistant Toward C=n Addition With 1 Equiv Of N-Buli At 0-Degrees-C In Thf Solution; However,They Are Also Surprisingly Resistant Toward Directed Metalation Reactions With Either Ltmp Or N-Buli. Exceptions To The Ortho-Directing And O-Methyl-Directing Effects Of The Aldimine Group Were Observed In A Reaction Of 3-Methylthiophene-2-Carboxaldehyde Cyclohexylimine (7) With Ltmp,Followed By Ch3I,Which Gave A 9:1 Mixture Of 3,5-Dimethylthiophene-2-Carboxaldehyde Cyclohexylimine (22) And 5-Ethyl-3-Methylthiophene-2-Carboxaldehyde Cyclohexylimine (23),And A Reaction Of P-Tolualdehyde 2,4-Dimethylpent-3-Ylimine (11) With Either N-Buli Or Ltmp,Followed By Ch3I,Which Gave P-Ethylbenzaldehyde 2,4-Dimethylpent-3-Ylimine (25).
Doi:10.1021/jo00061A020