Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 79, Issue 3, Pages 1247-1253Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo402667y
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Funding
- Deutsche Forschungsgemeinschaft
- University of Queensland
- National Computing Infrastructure facility [NCMAS g01]
- Australian Government
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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 degrees 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 degrees C or 4,4-dimethyl-3-phenyl-isoxazolone (20) at 600 degrees 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 nitrite 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 degrees 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.
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