Chloromethyl chloroformate

Phosgene can be replaced by a 0.5 molar equivalent of tri-chloromethyl chloroformate. This reagent may be purchased from... 

Also reported as a mixture with Chloromethyl chloroformate (C13-A010). 

C-Stoff Chloromethyl Chloroformate (70-90%) and Dichloromethyl Chloroformate (30-10%) Mixture Cl 3-A... 

Palite Chloromethyl Chloroformate and Stannic Chloride Mixture ... 

Ferric chloride and anhydrous aluminium chloride decompose chloromethyl chloroformate even in the cold, while on heating to about 70° C. the reaction is more rapid, phosgene being formed. 

The method proposed by Delepine for carrying out this determination depends on the differences between the behaviour of the chloromethyl chloroformates when treated with alkaline solutions. As already described, monochloromethyl chloroformate on treatment with alkali gives formaldehyde, carbon dioxide and hydrochloric acid according to the equation ... 

It has been found that while the aliphatic arsines and phenyl carbylamine chloride produce a similar turbidity at high concentration (4%), other substances such as mono-, di- and tri-chloromethyl chloroformates, chloropicrin, benzyl bromide, acrolein, the aromatic arsines, thiodiglycol, etc., do not react. 

On a laboratory scale, one of the favored catalyst is the benzyl tri-n-butyl ammonium chloride (BTBAC). The most important reagent, a-chloroethyl chloroformate ( ACE-CI ), typically is isolated in 96% yield by stirring acetaldehyde with phosgene (1.1 eq.) neat for an hour in the presence of 3 mol. % BTBAC. Even chloromethyl chloroformate can be prepared using this process, but it is essential to introduce the monomeric gaseous formaldehyde into the... 

Chloromethyl chloroformate reacts also selectively with tertiary alkyl amines to afford 0-chtoromethyl N,N-dialkyl carbamates in yields ranging from 83 to 99 % (Ref. 193). 

For example, N-methylpiperidine was refluxed with 1.5 eq. of chloromethyl chloroformate in 1,2-dichlorome-thane (DCE) for 30 min.. After vacuum evaporation of the volatiles, the distilled 0-chloromethyl carbamate was isolated in 97 % yield. 

Blasser, J. Synthesis and uses of pure chloromethyl chloroformate and an economical new route to trichloro-acryloyl chloride Ph. D. Thesis, The Pennsylvania State University, 1993... 

The properties of chloromethyl chloroformate which has been made also by phosgenation of monomeric formaldehyde (Ref. 29), are discussed further in section 3-2-2. 

This method useful for chloromethyl chloroformate synthesis gives poor yields and bad quality in the case of... 

An investigation of the mechanism of the charcoal catalysed reaction (10.17) reveals that the reaction proceeds via a strongly absorbed intermediate, identified as chloromethyl chloroformate, CHjC10C(0)Cl [1765]. This compound is found to form rapidly above 100 C in co-adsorption/desorption experiments, and decomposes rapidly above 170 C without significant desorption [1765], to give the final products, CH Clj and COj. The... 

Authentic chloromethyl chloroformate has been synthesised by the passage of gaseous methanal (diluted in a stream of dinitrogen) into a solution of phosgene in dichloromethane containing a small quantity of pyridine and held at -5 C [1765], Equation (10.19). 

Methyl sulfuryl chloride Chloromethyl chloroformate Ethyl sulfuryl chloride Dimethyl sulfate Perchloromethylmercaptan Phosgene... 

K-Stoff was introduced by the Germans in June 1915 as a more lethal replacement for chlorine. A low-boiling liquid (boiling point 1°C), it was loaded into artillery shells, hence was more convenient to use in combat, and could be delivered independent of the prevailing wind direction. It was manufactured as a mixture of chloromethyl chloroformate and dichloromethyl chloroformate, variously reported to be 70/30 and 90/10, respectively. It is about twice as toxic as chlorine. K-Stoff was itself soon replaced by the more lethal phosgene and diphosgene. The latter are of comparable toxicities, about six times more toxic than chlorine, and soon became the most heavily used nonpersistent lethal agents of the war ... 

Carbonochloridic acid, chloromethyl ester Chloromethyl chloroformate EINECS 244-793-3 UN2746. A military poison gas. 

The process of chlorination takes place in a stepwise manner, methyl chloro-formate being formed first and then, successively, the monochloro-, dichloro-, and trichloromethyl chloroformates. Methyl formate reacts readily with chlorine in the dark, giving methyl chloroformate. Further chlorination in the dark without the aid of a catalyst gives some chloromethyl chloroformate, but the reaction is slow and the yield is poor. Complete conversion can only be achieved by photochlorination at near the boiling point of the liquid [51, 70]. 

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