Nitrile imines and nitrile ylides: Rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and

Begue, Didier, Dargelos, Alain, Berstermann, Hans M., Netsch, Klaus P., Bednarek, Pawel and Wentrup, Curt (2014) Nitrile imines and nitrile ylides: Rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and. Journal of Organic Chemistry, 79 3: 1247-1253. doi:10.1021/jo402667y


Author Begue, Didier
Dargelos, Alain
Berstermann, Hans M.
Netsch, Klaus P.
Bednarek, Pawel
Wentrup, Curt
Title Nitrile imines and nitrile ylides: Rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2014-02-07
Year available 2014
Sub-type Article (original research)
DOI 10.1021/jo402667y
Open Access Status Not Open Access
Volume 79
Issue 3
Start page 1247
End page 1253
Total pages 7
Place of publication Washington, DC United States
Publisher American Chemical Society
Language eng
Subject 1605 Policy and Administration
Abstract Flash vacuum thermolysis (FVT) of 1-methyl-5-phenyltetrazole (5b), 2-methyl-5-phenyltetrazole (1b), and 3-methyl-5-phenyl-1,3,4-oxadiazol-2(3H)-one (3b) affords the nitrile imine (2b), which rearranges in part to N-methyl-N′-phenylcarbodiimide (7b). Another part of 2b undergoes a 1,4-H shift to the diazabutadiene (13). 13 undergoes two chemically activated decompositions, to benzonitrile and CH2=NH and to styrene and N 2. FVT of 2,2-dimethyl-4-phenyl-oxazol-5(2H)-one (16) at 400 C yields 3-methyl-1-phenyl-2-azabutadiene (18) in high yield. In contrast, FVT of 3,3-dimethyl-2-phenyl-1-azirene (21) at 600 C or 4,4-dimethyl-3-phenyl- isoxazolone (20) at 600 C affords only a low yield of azabutadiene (18) due to chemically activated decomposition of 18 to styrene and acetonitrile. There are two reaction paths from azirene (21): one (path a) leading to nitrile ylide (17) and the major products styrene and acetonitrile and the other (path b) leading to the vinylnitrene (22) and ketenimine (23). The nitrile ylide PhC -=N+=C(CH3)2 (17) is implicated as the immediate precursor of azabutadiene (18). FVT of either 3-phenylisoxazol- 5(4H)one (25) or 2-phenylazirene (26) at 600 C affords N-phenylketenimine (28). The nitrile ylide PhC-=N+=CH2 (30) is postulated as a reversibly formed intermediate. N-Phenylketenimine (28) undergoes chemically activated free radical rearrangement to benzyl cyanide. The mechanistic interpretations are supported by calculations of the energies of key intermediates and transition states.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
 
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