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Photogeneration and reactivity of acyl nitroso compounds

Evans, Anthony S ; Cohen, Andrew D ; Gurard-Levin, Zachary A ; Kebede, Naod ; Celius, Tevye C ; Miceli, Alexander P ; Toscano, John P

Canadian Journal of Chemistry (Revue canadienne de chimie), 2011, Vol.89(2), pp.130-138 [Periódico revisado por pares]

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  • Título:
    Photogeneration and reactivity of acyl nitroso compounds
  • Autor: Evans, Anthony S ; Cohen, Andrew D ; Gurard-Levin, Zachary A ; Kebede, Naod ; Celius, Tevye C ; Miceli, Alexander P ; Toscano, John P
  • Assuntos: Acyl Nitroso ; Nitrodiazo ; Nitronate Photochemistry ; 1,2,4-oxadiazole-4-oxides ; Time-resolved Ir Spectroscopy ; Acylnitroso ; Nitrodiazo ; Photochimie Du Nitronate ; 4-oxydes De 1,2,4-oxadiazoles ; Spectroscopie Infrarouge Rsolue En Fonction Du Temps (IR-RT)
  • É parte de: Canadian Journal of Chemistry (Revue canadienne de chimie), 2011, Vol.89(2), pp.130-138
  • Descrição: Acyl nitroso compounds have been generated by photolysis of several different classes of precursors including 9,10-dimethylanthracene adducts, nitrodiazo compounds, and 1,2,4-oxadiazole-4-oxides. Consideration of the nitronate-like resonance structure of nitrodiazo compounds led to an examination of the photochemistry of nitronates with -leaving groups. Photolysis of such nitronates has been shown to generate an acyl nitroso species along with a carbene intermediate. Nanosecond time-resolved infrared (TRIR) spectroscopy has been used to detect photogenerated acyl nitroso compounds directly and to examine their reaction kinetics with amines and thiols. The mechanism of acyl nitroso aminolysis by primary amines involves general base catalysis, while the mechanism of aminolysis by secondary amines is strictly bimolecular. Thiols do not seem to be reactive with acyl nitroso compounds on the microsecond time scale, but thiolates are quite reactive. The reaction between benzoyl nitroside and an organic-soluble thiolate, tetrabutylammonium dodecanethiolate, proceeds via a proposed tetrahedral intermediate, which is observable by TRIR spectroscopy.
    On a gnr des composs acylnitroso par photolyse des plusieurs classes diffrentes de prcurseurs, y compris des adduits du 9,10-dimthylanthracne, des composs nitrodiazo et des 4-oxydes de 1,2,4-oxadiazoles. Une considration de la structure des composs nitrodiazo qui est similaire la structure de rsonance des nitronates a conduit un examen de la photochimie des nitronates possdant un groupe partant en position . On a montr que la photolyse de tels nitronates conduit la formation despces acylnitroso aux cts dun intermdiaire carbne. On a fait appel la spectroscopie infrarouge rsolue en fonction du temps (IR-RT) pour dtecter directement les composs acylnitroso photognrs et pour dterminer la cintique de leurs ractions avec des amines et des thiols. Le mcanisme de laminolyse dun acylnitroso par les amines primaires implique une catalyse basique gnrale alors que le mcanisme de laminolyse dun acylnitroso par les amines secondaires est strictement bimolculaire. Les thiols ne semblent pas tre ractifs vis--vis des composs acylnitroso lchelle de temps de la microseconde, mais les thiolates sont trs ractifs. La raction entre le nitroside de benzoyle et le thiolate organique soluble, dcanethiolate de ttrabutylammonium, se fait par le biais dune intermdiaire ttradrique que lon peut observer par spectroscopie IR-RT.

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