Conversion of bis(trichloromethyl) carbonate to phosgene and reactivity of triphosgene, diphosgene, and phosgene with methanol(1)

• Published in: Journal of organic chemistry Vol. 65; no. 24; pp. 8224 - 8228
• Main Authors: Pasquato, L, Modena, G, Cotarca, L, Delogu, P, Mantovani, S
• Format: Journal Article
• Language: English
• Published: United States 01-12-2000
• ISSN: 1520-6904
• DOI: 10.1021/jo000820u

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.