- Photolysis of 1,1,1-Triarylalk-2-enes and 1,1,1-Triarylhept-2-ynes. A Novel Generation of Aryl(alk-1-enyl)carbenes ans Aryl(alk-1-ynyl)carbenes
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Upon UV irradiation in methanol, 1,1,1-triarylhept-2-ynes underwent an α,α-elimination of two aryl groups to give a biaryl and the corresponding carbene which reacted with methanol to give a 1-aryl-1-methoxyhept-2-yne. 1,1,1-Triphenylalk-2-enes underwent α,α-elimination of two phenyl groups and also elimination of an alkene and a phenyl group to give biphenyl and a 1-phenylalkene respectively.In both cases, the corresponding carbenes were formed and were isolated as methanol insertion products (a 1-methoxy-1-phenylalk-2-ene and diphenylmethyl methyl ether, respectively).A rearrangement product, a 1,1,2-triphenylcyclopropane, was also formed.
- Shi, Min,Shouki, Kouji,Okamoto, Yoshiki,Takamuku, Setsuo
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p. 2443 - 2450
(2007/10/02)
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- Photolysis of 1,1,1-Triphenyl-2-alkenes and Methyl Triphenylacetate
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Upon UV irradiation in methanol 1,1,1-triphenyl-2-alkene or methyl triphenylacetate underwent two kinds of α,α-elimination of two phenyl groups and phenyl-alkenyl groups or phenyl-methoxycarbonyl groups to give biphenyl, 1-phenylalkene or methyl benzoate, and two kinds of correspondending carbene intermediates, which inserted into the O-H bond of methanol to afford two kinds of methyl ethers, respectively.
- Shi, Min,Okamoto, Yoshiki,Takamuku, Setsuo
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p. 1079 - 1082
(2007/10/02)
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- Photochemistry of Arylbutadienes. Part 2. Preparation and Photochemistry of 1-(Substituted-aryl)butadienes. A Ground-state Substituent Effect on an Excited-state Reaction
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Yields and quantum yields are reported for the photoaddition of methanol to 1-phenylbutadiene and eight substituted 1-phenylbutadienes.For allyl and homoallyl products log Φ correlates more satisfactorily with ground-state substituent constants than with excited-state constants; for cyclopropylmethyl products, no correlation is observed with either set of constants.
- Baldry, Peter J.
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p. 805 - 808
(2007/10/02)
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- Photochemistry of Arylbutadienes. Part 3. Mechanisms of Photoaddition of Methanol to 1-Arylbutadienes
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The mechanism of formation of methyl ethers from irradiation of 1-arylbutadienes in methanol has been studied by deuterium labelling, fluorescence quenching, sensitisation, and kinetic studies.Cyclopropylmethyl ethers arise by a bicyclobutane mechanism; allyl and homoallyl ethers are formed by reaction of methanol with the 1Bu-like excited singlet diene to produce carbocation intermediates.
- Baldry, Peter
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p. 809 - 815
(2007/10/02)
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