• Bulletin of the Korean Chemical Society
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• v.34 no.5
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• pp.1361-1365
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• 2013

The smallest ketenimine and hydrogen cyanide N-methylide ($CH_2CNH$ and $CH_2NCH$) are provided from the argon/acetonitrile matrix samples exposed to radiation from laser ablation of transition-metals. New infrared bands are observed in addition to better determination of the vibrational characteristics for the previously reported bands, and the $^{13}C$ substituted isotopomers ($^{13}{CH_2}^{13}CNH$ and $^{13}CH_2N^{13}CH$) are also generated. Density functional frequency calculations and the D and $^{13}C$ isotopic shifts substantiate the vibrational assignments. $CH_2CNH$ is probably produced through single-step conversion of $CH_3CN$, whereas $CH_2NCH$ through two-step conversion via 2H-azirine. Inter-conversions between these two products evidently do not occur during photolysis and annealing.

• Journal of Photoscience
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• v.7 no.3
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• pp.109-110
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• 2000

No Abstract. See Full-text

• Bulletin of the Korean Chemical Society
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• v.17 no.5
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• pp.437-442
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• 1996

Electrocyclic ring-closure of 6-vinylcyclohepta-1,3,5-isocyanate has been carried out in the presence of triphenylphosphine to examine a catalyzing effect of the triphenylphosphine. The preparation of 10-(1-carboalkoxyalkyl)-2,7-methanoaza[10]annulenes by the electrocyclic ring-closure of ketenimine intermediates, which are formed by the reaction of triphenylalkylidenephosphorane and 6-vinylcyclo-hepta-1,3,5-isocyanate, is described. 10-Alkyl-2,7-methanoaza[10]annulenes were prepared by basic hydrolysis of the carboalkoxyaza[10]annulenes and decarboxylation of the acid intermediates. In the same manner, 10-(N-alkyl(or aryl))-2,7-methanoaza[10]annulenes were prepared from the reaction of the isocyanate and N-alkyl(or aryl)iminotriphenylphosphorane via electrocylic ring-closure of carbodiimide intermediate.