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- Title
Pyrazinyl- and pyrimidinylketenes, bisketenes, and ylides: direct observation and nucleophilic reactivity.
- Authors
Allen, Annette D.; Fedorov, Andrei V.; Fu, Nanyan; Kobayashi, Shinjiro; Tidwell, Thomas T.; Vukovic, Sinisa; Badal, Md. Mizanur Rahman; Mishima, Masaaki
- Abstract
Pyrazinylketene ( 9) and 4-pyrimidinylketene ( 11), identified by their IR absorption at 2128 and 2130 cm−1, respectively, are formed in CH3CN as transient intermediates by photolysis of the corresponding diazoketones. The corresponding ylides 10 and 12 are formed concurrently as longer-lived intermediates identified by their distinctive IR and UV absorption. Reactions of 2-pyridylketene and of 9 and 11 with diethylamine form initial amide enol intermediates leading to dihydroheteroarene intermediates and then to amides, whereas amide enols are not observed in reactions with n-butylamine. Reactions with water give observable dihydroheteroarenes. 2,5-Bis(ketenyl)pyrazine ( 33) is formed by photolysis of 2,5-bis(diazoacetyl)pyrazine ( 32) together with the corresponding bis(ylide) 35. The latter is calculated to have two geometrically isomeric structures (bond-stretch isomers) with similar energies, one with a central six-membered aromatic ring and another with a 10-pi electron aromatic system.
- Subjects
NUCLEOPHILIC reactions; KETENES; ULTRAVIOLET photolysis; PHOTOLYSIS (Chemistry); DIAZOKETONES
- Publication
Canadian Journal of Chemistry, 2014, Vol 92, Issue 12, p1119
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2014-0208