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Photolysis of alkylchlorodiazirines (1) in the presence of olefins gives a cyclopropane (3) by addition of the generated carbene to the olefin and a vinyl chloride derivative (2) resulting from a 1,2-H shift rearrangement. This rearrangement may occur either in the carbene or in some excited state, ...
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The thermal decomposition of phenylehlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H] diazirine (3) has been studied in solution in the presence Of C-60. The C-60 probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazir...
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Photolysis of 3-chloro-3-benzyldiazirine in tetramethylethylene gives E- and Z-beta-chlorostyrenes and cyclopropane. Relative rate studies show that the styrenes to cyclopropane ratio increases with increasing diazirine concentration. This permits the determination of the ratio k(D)/k(i) = 8 where k...
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By employing C-60 as a chemical probe, the photolysis of benzylchlorodiazirine has been proposed to form carbene and the rearranged products via the excited state. (c) 2006 Elsevier Ltd. All rights reserved.
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Laser flash photolysis of para-substituted 3-chloro-3-benzyldiazirines in isooctane produces the corresponding carbenes, which react with pyridine to form ylides or undergo 1,2-H migration to form the (Z)- and (E)-beta-chlorostyrenes. The rate for the 1,2-H migration is determined by plotting the ps...
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Laser flash photolysis of 3-chloro-3-(p-nitrophenyl)diazirine (1) generates the corresponding ground-state singlet carbene (lambda-max = 310 nm), which reacts with ethyl acetate to form a carbonyl ylide of the ester (lambda-max = 490 nm). The absolute rate constant for ylide formation in CH2Cl2 is k...
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Laser Flash Photolysis of arylchlorodiazirines in isooctane/CH2Cl2 in the presence of substituted vinylpyridines yields substituted vinylpyridinium ylide (lambda = 540 nm). As the ylide decays a concomitant growth causes an absorption at 330 nm, attributed to the formation of substituted indolizine....
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The article presents a research which discusses the preparation and characterization of the nanorods of the endohedral metallofullerene derivative lanthanum (La)@carbon(C)82(Ad). The nanorods of La@C82(Ad) were prepared by a liquid-liquid interfacial precipitation method. The s...
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Photolysis of 3-benzyl-3-chlorodiazirine and its deuterated homologues 3-chloro-3-(phenyldideuteriomethyl)diazirine and 3-chloro-3-((pentadeuteriophenyl)methyl)diazirine has been investigated by means of IR and UV-vis spectroscopy in argon and xenon matrices. Parent benzylchlorocarbene was produced ...
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The first determination of a 1,2-phenyl shift in alpha,alpha-dimethylbenzylchlorocarbene was achieved by nanosecond laser flash photolysis, tau = 50 ns.
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