503-38-8Relevant articles and documents
Synthesis of Some Aromatic Diisocyanides with Trichloromethyl Chloroformate
Efraty, Avi,Feinstein, Irene,Wackerle, Lorenz,Goldman, Alexander
, p. 4059 - 4061 (1980)
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Process for preparing cyclopropylacetylene
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, (2008/06/13)
The invention relates to a process for the halogenation of cyclopropylmethyl ketone with at least one dihalo-triorganophosphorane of the general formula I R3PHal2??(I), in which the radicals R can be the same or different and denote a saturated or unsaturated aliphatic C1-C20hydrocarbon radical, a phenyl or (C1-C4alkyl)phenyl radical, which may be optionally substituted by one or two fluorine, chlorine and/or nitro groups, P stands for phosphorus and Hal denotes chlorine, bromine, or iodine, at a temperature of from 800° to 130° C., where the dihalo-triorganophosphane of the general formula (I) is synthesized in situ from triorganophosphane oxide or triorganophosphane sulfide of the general formula II R3PA ??(II), in which R is as defined above with respect to formula I and A denotes oxygen or sulfur, using a halogenating agent, wherein the triorganophosphane oxide or triorganophosphane sulfide is used in catalytic amounts, to the halogenation product of cyclopropylmethyl ketone obtained in said process, and to a process for the conversion of said halogenation product to cyclopropylacetytene.
Conversion of bis(trichloromethyl), carbonate to phosgene and reactivity of triphosgene, diphosgene, and phosgene with methanol
Pasquato,Modena,Cotarca,Delogu,Mantovani
, p. 8224 - 8228 (2007/10/03)
Triphosgene was decomposed quantitatively to phosgene by chloride ion. The reaction course was monitored by IR spectroscopy (React-IR), showing that diphosgene was an intermediate. The methanolysis of triphosgene in deuterated chloroform, monitored by proton NMR spectroscopy, gave methyl chloroformate and methyl 1,1,1-trichloromethyl carbonate in about a 1:1 ratio, as primary products. The reaction carried out in the presence of large excess of methanol (0.3 M, 30 equiv) was a pseudo-first-order process with a k(obs) of 1.0 x 10-4 s-1. Under the same conditions, values of k(obs) of 0.9 x 10-3 s-1 and 1.7 x 10-2 s-1 for the methanolysis of diphosgene and phosgene, respectively, were determined. The experimental data suggest that, under these conditions, the maximum concentration of phosgene during the methanolysis of triphosgene and diphosgene was lower than 1 x 10-5 M. Methyl 1,1,1-trichloromethyl carbonate was synthesized and characterized also by the APCI-MS technique.