Monochloromethyl chloroformate

Cyanogen bromide. Monochloromethyl chloroformate Chloropicrin. Dichloroethyl sulphide Chloroacetophenone... 

In considering the influence of the number of halogen atoms present it is found that while one halogen atom confers predominantly lachrymatory properties on the molecule, an increase in the number of the halogen atoms diminishes the lachr5miatory but increases the asphyxiant action. A typical example of this observation is the series of halogenated esters of formic acid. In this the first member, monochloromethyl chloroformate, has a predominantly lachrymatory action, while the last, trichloro-methyl chloroformate, has an essentially asphyxiant action and practically no lachrymatory property. 

The mixture of monochloromethyl chloroformate with dichloromethyl chloroformate, used in 1915 by the Germans under the name of K-Stoff," and later also by the Allies, especially the French, by whom it was called " Palite."... 

Monochloromethyl chloroformate is hydrolysed by water at ordinary temperatures this decomposition takes place more rapidly and completely by the action of hot water or in the presence of alkali. Formaldehyde, hydrochloric acid and carbon dioxide are formed ... 

Monochloromethyl chloroformate, like phosgene, liberates iodine from sodium iodide, but the reaction is not quantitative, proceeding only to about 70% completion. ... 

Monochloromethyl chloroformate, unlike methyl chloroformate, reacts with difficulty with chlorosulphonic acid, forming monochloromethyl chlorosulphonate only after boiling on the water bath for 4 hours ... 

Monochloromethyl chloroformate also reacts with benzoic acid, forming monochloromethyl benzoate (Kraft) ... 

Identification of Monochloromethyl Chloroformate. Monochloro-methyl chloroformate when treated with water or aqueous sodium hydroxide is decomposed even in the cold according to the equation ... 

Determination of Monochloromethyl Chloroformate. The substance under examination is treated with sodium hydroxide and the amount of formaldehyde formed is then determined. 

Quantitative Determination of Monochloromethyl Formate in presence of Monochloromethyl Chloroformate. In controlling the manufacture by analysis it is frequently necessary to determine the quantity of chloroformate present in the chlorination product of methyl formate that is, to determine if the product obtained from the methyl formate still contains some hydrogen in the form of HCO— group which is not substituted by chlorine. 

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 ... 

However, as the formaldehyde formed by the hydrolysis of monochloromethyl chloroformate is also oxidised by potassium permanganate it must be first determined by titration with iodine solution. Then, by subtracting from the number of ml. permanganate solution decolorised, twice the number of ml. of iodine solution used (for formaldehyde needs twice as much oxygen as formic acid for its oxidation), the result is the number of ml. permanganate corresponding to the quantity of formic acid present and from this the chloromethyl formate in the sample may be calculated. 

It reacts with monochloromethyl chloroformate, forming monochloromethyl chlorosulphonate ... 

With monochloromethyl chloroformate it reacts to form methyl chlorosulphonate ... 

Phosgene (CG) was released from 4000 cylinders (88 tons) on December 19, 1915, at Nieltje in Flanders phosgene remained a significant chemical warfare agent through World War II. Monochloromethyl chloroformate was first used by the Germans at the Somme in the summer of 1916. 

Trichloromethyl chloroformate (DP, diphosgene) was first used in the summer of 1915. It eventually replaced monochloromethyl chloroformate in German gas shells and was used extensively through the end of the war. 

Methyl chloroforms te, C1C(0)0CH3, prepared from the action of phosgene on methanol, whilst not used alone, was used as a solvent for other toxic materials. Monochloromethyl chloroformate, ClC(0)OCHjCI, is more lachramatory than phosgene, and was compressed in grenades and bombs. The dichlorinated derivative, dichloromethyl... 

Colourless liquid, bp 110°C, irritant less so than the mono form but more toxic. Used as a war gas mixed with monochloromethyl chloroformate qv. 

Palite. Monochloromethyl chloroformate and dichloromethyl chloroformate. Also used, according to Beadnell (1943) and Sartori (1939), as an abbreviation for phenylcarbylamine chloride. 

---