TY - JOUR
T1 - Nucleophilic attacks on carbon-nitrogen double bonds. Part 4. Substitution of n-arylbenzimidoyl cyanides by amines in acetonitrile and by alkoxides in alcohols
AU - Ta-Shma, Rachel
AU - Rappoport, Zvi
PY - 1977
Y1 - 1977
N2 - The substitution of the cyano-group of N-arylbenzimidoyl cyanides PhC(CN)=NC6H4Y by nucleophiles was studied. With amines in acetonitrile several reactions had showed first- (k′) and second-order (k″) terms in the amine. With EtO- in EtOH, both zero- (k0) and first-order (k′) terms in the nucieophile were found, while with Bu tO- in ButOH the reaction is of first order in the base. It is suggested that a common initial step in these reactions is nucleophilic attack of the amine, an alkoxide ion, or ethanol on the imidoyl cyanide. The subsequent expulsion of the leaving group may be uncatalysed or amine-catalysed in acetonitrile, and solvent-assisted in the alcohols. The reactions were compared with those of the corresponding N-arylbenzimidoyl chlorides.
AB - The substitution of the cyano-group of N-arylbenzimidoyl cyanides PhC(CN)=NC6H4Y by nucleophiles was studied. With amines in acetonitrile several reactions had showed first- (k′) and second-order (k″) terms in the amine. With EtO- in EtOH, both zero- (k0) and first-order (k′) terms in the nucieophile were found, while with Bu tO- in ButOH the reaction is of first order in the base. It is suggested that a common initial step in these reactions is nucleophilic attack of the amine, an alkoxide ion, or ethanol on the imidoyl cyanide. The subsequent expulsion of the leaving group may be uncatalysed or amine-catalysed in acetonitrile, and solvent-assisted in the alcohols. The reactions were compared with those of the corresponding N-arylbenzimidoyl chlorides.
UR - http://www.scopus.com/inward/record.url?scp=37049106697&partnerID=8YFLogxK
U2 - 10.1039/P29770000659
DO - 10.1039/P29770000659
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AN - SCOPUS:37049106697
SN - 1472-779X
SP - 659
EP - 667
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 5
ER -