Chloromethyl formate, hydrolysis

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. 

No information is available on the transport and partitioning of BCME in the environment. Due to the relatively short half-life in both air and water, it is unlikely that significant partitioning between media or transport occurs. Primary process for BCME degradation in air is believed to be reaction with photochemically generated hydroxyl radicals to yield chloromethyl formate CICHO, formaldehyde, and HCl. Atmospheric half-life due to reaction with hydroxyl radicals is estimated to be 1.36 h. Hydrolysis in the vapor phase is found to be slower with an estimated half-life of 25 h. 

During the next fifty years the interest in derivatives of divalent carbon was mainly confined to methylene (CHg) and substituted methylenes obtained by decomposition of the corresponding diazo compounds this phase has been fully reviewed by Huisgen. The first convincing evidence for the formation of dichlorocarbene from chloroform was presented by Hine in 1950. Kinetic studies of the basic hydrolysis of chloroform in aqueous dioxane led to the suggestion that the rate-determining step was loss of chloride ion from the tri-chloromethyl anion which is formed in a rapid pre-equilibrium with hydroxide ions ... 

Serine has been prepared by the Strecker method from glycol-aldehyde 1 and from ethoxyacetaldehyde,2 3 by the condensation of ethyl formate with ethyl hippurate followed by reduction and hydrolysis,4 5 from the reaction product of chloromethyl ether with ethyl sodium phthalimidomalonate,6 and by amination of a-bromo-/3-methoxypropionic acid with subsequent demethyla-tion.7... 

This procedure is illustrative of a general method for preparing a wide range of pure 3,5-disubstituted-4-isoxazole-carboxylic esters and (by hydrolysis) their acids,2 free from positional isomers. A wide range of both primary nitro compounds and of enamino esters can be used,2,3 and the esters thus obtained may then be used as reagents in the isoxazole annela-tion reaction.3,4 The only other general synthesis of these compounds involves chloromethylation and oxidation of a suitable 4-unsubstituted isoxazole.5 This procedure suffers from two difficulties low yields and the unavailability of starting isoxazole. Most methods of isoxazole formation yield a... 

Aminoalkylquinoxalines (17) have been derived from a-amino acids (10) as shown in Scheme 2, the amino group is protected by formation of a phthalimide derivative (11). The intermediate chloromethyl ketone (12) is converted via a pyridinium salt (13) to a nitrone (14) which on hydrolysis yields the a-dicarbonyl compound (15) required for diamine condensation. Finally the phthalimide residue is removed from the condensation product (16) by hydrazine treatment. ... 

The formation of ethers can also occur with cyclization and the synthesis of heterocyclic phosphorus compounds (Scheme 37). The reaction between the benzodioxaphosph(V)ole 241 and a Grignard reagent (R = alkyl or aryl) followed by a treatment of the product 242 with base affords the dihydrobenzodioxaphosph(V)orin 243 also available from catechol and bis(chloromethyl)phosphinic chloride. The hydrolysis of243 and cyclization of... 

Mechanism of Chlorination of ajS-Unsaturated Ketones in Methanol and in Trifluoroacetic Acid . Reactivity of Ethylenic Compounds. Bromination. XXXIII. Modification of Reaction Scheme in Trifluoroacetic Acid Solution [rate-determining step in CFj-COsH for bromination of RCHt CHtCHj is the disappearance (mechanism Ad%C, d) of a tight ion pair]. Solvent and Temperature Effects in the Neutral Hydrolysis of Methyl Trifluoroacetate and Chloromethyl Dichloroacetate in Dimethyl Sulphoxide-Water Mixtures . Electron Impact Studies. LiKXXVlII. Formation of an Adduct between the Trifluoroacetate Ion and Perfluoroacetic Anhydride by Ion Cyclotron Resonance . ... 

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