Bis(benzotriazol-1-yl) methylimine as a novel cyanating agent for labile β-diketonates

Properties and Synthetic Utility ofN-Substituted Benzotriazoles

“…Benzotriazole reacts readily with cyanamide and p -toluenesulfonic acid to afford benzotriazole-1-carboxamidinium tosylate ( 204 ) in 77% yield (Scheme ) . Reaction of an excess of benzotriazole with cyanogen bromide under basic conditions as a result of both bromine substitution by the benzotriazole moiety and addition to C⋮N bond gives dibenzotriazol-1-ylmethylimine ( 205 ) in 80% yield or diarylnitrile imines affords oximes 206 and 207 and arylhydrazones 208 and 209 , respectively.…”

“…Dibenzotriazol-1-ylmethylimine ( 205 ) undergoes debenzotriazolation in the presence of labile β-diketonates 1114 (M = Cu(II), Ni(II), etc.) to generate in situ 1-cyanobenzotriazole 1115 . This reaction is possibly induced by labile metal−oxygen bond in chelates 1114 (Scheme ), because it does not occur with inert or less labile β-diketonates.…”

“…160 Reaction of an excess of benzotriazole with cyanogen bromide under basic conditions as a result of both bromine substitution by the benzotriazole moiety and addition to CtN bond gives dibenzotriazol-1-ylmethylimine (205) in 80% yield. 161 Addition of benzotriazole to the CtN of benzonitrile oxide 162 or diarylnitrile imines 163…”

Benzotriazole-Mediated Synthesis of Nitrogen-Containing Heterocycles

“…The thermal [3+2] cycloaddition of benzyl azide with N-propioloylbenzotriazole 211 gave the benzotriazolylcarbonyl-substituted 1,2,3-triazole 212, which can be further reacted with amines to provide the corresponding Ccarbamoyl 1,2,3-triazoles 213 (Scheme 76) [162]. Benzotriazole-1-carboximidamides 214 [163,164] can be easily converted into acyl derivatives 215, which served as precursors in the synthesis of triazoles. Thus, cyclization of acyl derivatives 215 with hydrazines led to 3-amino-1,2,4-triazoles 216 as single regioisomers, when unsubstituted or methyl-substituted hydrazine is used.…”

1,2,3-Triazoles

“…A reaction of benzotriazole with cyanogen bromide carried out in ethanol in the presence of NaOH provides dibenzotriazolylmethanimine 904 as a mixture of benzotriazol-1-yl and 2-yl isomers 1996POL4011 , 2000JOC8080 . To simplify the picture, only the benzotriazol-1-yl isomer is shown in Scheme 149 .…”