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Laser flash photolysis of 3-chloro-3-benzyldiazirine and 3-chloro-3-(phenyldideuteriomethyl)diazirine in isooctane over the 60 to -80-degrees-C temperature range gives rise to curved Arrhenius plots for both 1,2-H and 1,2-D migration in benzylchlorcarbene. The k(H)/k(D) values increase smoothly from...
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Phenylchlorocarbene, generated by photolysis or thermolysis of the phenylchlorodiazirine, reacts with 2,2'-bipyridyl to give, in alkane solvents, the 6-phenyldipyrido[1,2-c:2',1'-e]i-midazolium chloride. We investigated the mechanism of the reaction by flash photolysis. Like the mechanism of formati...
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C-60 acts as a mechanistic probe for the formation of carbene, diazo compound, and for the rearranged product via the excited state in the photolysis of 3-chloro-3-isopropyldiazirine and 3-chloro-3-chloromethyldiazirine. The carbene adds to C-60 to form methanofullerene, whereas the diazo compound a...
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An ultraviolet photoelectron (PE) spectrometer apparatus that utilizes a tuneable 50 W CW CO2 laser as a directed heat source was used to study the vacuum pyrolysis of diazoacetophenone (la) and its p-methyl, p-methoxy, p-chloro, and p-nitro analogues Ib, Ic, Id, and le. Analysis of the pyrolysate w...
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C-60 acts as a mechanistic probe for the formation of carbene and for the rearranged product via the excited state in the photolysis of 3-t-butyl-3-chlorodiazirine. (C) 2004 Published by Elsevier Ltd.
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The rate constant for the reaction of benzylchlorocarbene with HCl is 4.7 x 10(9) dm3 mol-1 s-1.
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Irradiation of 2-adamantane-2,3'-[3H]-diazirine (1) in isooctane at room temperature gives two primary photoproducts, 2-diazoadamantane and 2-adamantylidene (Ad:), with quantum yields of about 0.5 each. The fluorescence quantum yield of 1 is small, phi(f) approximate to 10(-4). The reactivity of Ad:...
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Substituted pyrazoles and pyrrolo[1,2-c]pyrimidines were prepared from the reaction of arylchlorocarbenes with 1,2-diazabuta-1,3-dienes and 4-vinylpyrimidines, respectively.
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Benzylchlorocarbene (1, BCC) was generated photochemically from benzylchlorodiazirine (2) in isooctane, methylcyclohexane (MCH), and tetrachloroethane (TCE) at temperatures from similar to 30 to -75 degrees C. At -70 degrees C in isooctane, the identified products included Z/E-beta-chlorostyrenes 4 ...
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