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- W2087299052 abstract "Following our previous reports on the spectroscopy and photochemistry of methyl and ethyl ethers of simple acyclic and non-strained cyclic α-oxo oximes, we have now studied 4-(methoxyimino)-2,2,3,3-tetramethylcyclobutanone (1), of which the ring is severely strained, 3,5,5-trimethyl-4(5H)-isoxazolone (8), of which the (Z)-oxime function is constrained in a five-membered ring, and 6-(benzyloxyimino)-2,2,5,5-tetramethylcyclohexanone (10), which is a benzyl ether. Upon irradiation of (E)-1 with λ 254 nm, the main process is photodissociation, leading to the same type of products as obtained with the six-membered ring homologue 3, but in addition to 2,2,3,3-tetramethyl-4-oxobutanenitrile (13) and 2,2,3,3-tetramethylcyclopropanone O-methyloxime (21). The triplet-sensitized irradiation of (E)-l, in contrast to that of the higher homologues, leads, in addition to E-Z isomerization, to photodissociation, yielding the same photoproducts as obtained after direct irradiation with 254 nm.The 4-isoxazolone 8 is photostable against radiation of 350 and 300 nm. Irradiation of 8 with λ. 254 nm leads to population of the excited singlet ππ* state and subsequent photodecomposition as a result of inital N-O homolysis, the observed products being carbon monoxide, acetonitrile, acetone and small amounts of ethanol. The occurrence of the photodecomposition is in agreement with the theoretical prediction' that the excited singlet ππ* (Z)-α-oxo oxime ethers would give N-O homolysis, provided that the other route of deactivation via Z-E isomerization, which has a much lower energy barrier on the potential energy surface, cannot take place.The photochemistry of the benzyl ether (Z)-10, of which the intercarbonyl-iminyl dihedral angle is approx. 45° and the π systems of the phenyl and the C = N-O moieties are perpendicular to one another, with λ 350, 300 and 254 nm is different from that of the corresponding methyl ether 36 in two ways. Firstly, on using λ 350 and 300 nm decomposition was observed which is, however, slow relative to the Z-E isomerization and, secondly, the photodecomposition products are of a different nature, since the assigned primary and secondary product from 10 are benzaldehyde and 6-(benzoylamino)-2,2,5,5-tetramethylcyclohexanone (32), respectively.Mechanisms have been presented to explain the formation of the photoproducts obtained from 1, 8 and 10." @default.
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- W2087299052 date "2010-09-02" @default.
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- W2087299052 title "Photochemistry and spectroscopy of three α-oxo oxime ethers: 4-(methoxyimino)-2,2,3,3-tetramethylcyclobutanone, 3,3,5-trimethyl-4(5H)-isoxazolone and 6-(benzyloxyimino)-2,2,5,5-tetramethylcyclohexanone" @default.
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- W2087299052 doi "https://doi.org/10.1002/recl.19911100202" @default.
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