Chloromethyl chloroformate chloride

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. 

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... 

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... 

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

A soln. of m-(hydroxymethyl) phenoxyacetic acid in thionyl chloride refluxed 3 hrs., evaporated in vacuo, the residue dissolved in ethylene dichloride, and again evaporated in vacuo —crude m-(chloromethyl) phenoxyacetyl chloride (Y 96%) dissolved in methylene chloride, a soln. of 2 moles of m-nitraniline in the same solvent added with stirring during ca. 15 min., stirring continued for 10 min., treated with anhydrous HCl until the yellow color of free m-nitraniline has disappeared, filtered, crude 2-[(m-chloromethyl)phenoxy]-3 -nitro-acetanilide isolated from the filtrate, dissolved in chloroform containing diethanolamine, and refluxed 6 hrs. 2-(m-[bis-(2-hydroxyethyl) aminomethyl]-... 

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 ... 

Chloroethanol, see Ethylene chlorhydrin Chloroelhylene, see Vinyl chloride Chloroform (trichloromethane) bis-Chloromethyl ether... 

Chloroethanol, see Ethylene chlorohydrin Chloroethylene, see Vinyl chloride Chloroform"1 1 bis(Chloromethyl)ether Chloromethyl methyl ether"1 ... 

Diethylene Glyccl Monomethyl Ether Ethylene Glycol Momomethyl Ether Methyl Chloride Methyl Chloroformate Trichloroethane Methyl Chloroformate Chloromethyl Methyl Ether Acetonitrile... 

Chloromethylation.1 Chloromethyl methyl ether has been generally used for electrophilic aromatic chloromethylation, but it is highly toxic and now considered a carcinogen. Chloromethylation can be effected by use of a trimethylsilyl ether (1) of a chlorohydrin prepared as shown from trioxane and chlorotrimethylsilane in the presence of stannic chloride in chloroform. This reagent, generated in situ, is effective for chloromethylation of styrene in the presence of SnCl4 any excess is easily decomposed by hydrolysis. Bromomethylation is possible by replacement of ClSi(CH3)3 by BrSi(CH3)3. 

In the reaction using cadmium promoter, the selectivity for tris(chloro-silyl)methane 8b was the highest among the four tris(chlorosilyl)methanes 7b-10b and about 73% in the distribution of their four compounds. These are consistent with the results observed for the direct reactions of silicon with (chloromethyl)silanes,20,21 allyl chloride,27 methylene chloride,22 and chloroform.23... 

The direct reaction of (trichloromethyl)chlorosilanes was applied under the same reaction condition described in the direct reaction of elemental silicon with (dichloromethyl)chlorosilanes above. In this reaction, an admixed gases of hydrogen chloride and 40 wt% (trichloromethyl)chlorosilanes in toluene injected using a syringe pump in pre-heater zone was fed into a reactor charged with elemental silicon (90%) and copper catalyst (10%) (Fig. 1). This reaction afforded no tetrakis (chlorosilyl)methane instead, tris(silyl)methanes and bis(silyl)methanes were obtained, which were the same products derived from the reactions of (dichloromethyl)chlorosilanes or chloroform, and (chloromethyl)chlor-osilanes or methylene chloride, respectively. This result may be rationalized by decomposition of (trichloromethyl)chlorosilanes to (dichloromethyl)-chlorosilanes and (chloromethyl)chlorosilanes on silicon-copper contact mass during the reaction, followed by reaction with elemental silicon to afford the products or the decomposition tetrakis(silyl)methane products.16... 

Amino-5-chloromethyl-3-cyanopyrazine 1-oxide with triphenylphosphine in dimethylformamide at 80-90° gave 2-amino-3-cyano-5-(triphenylphosphonio)-methylpyrazine 1-oxide chloride (97) (520) and the 5-bromomethyl analogue reacted similarly with triphenylphosphine in propan-2-ol (542). Compound (97) on hydrolysis with 30% aqueous ethanol containing a small amount of triethylamine gave 2-amino-3-cyano-5-methylpyrazine 1-oxide and thus enabled removal of the chloro substituent from the chloromethylpyrazine (529) compound (97) with triethylamine and acetaldehyde (and other aldehydes) in chloroform at room temperature gave 2-amino-3-cyano-5-(prop-l -enyl)pyrazine 1-oxide (and other alkenyl analogues) (529). 

Both benzyltriethylammonium chloride (1) and benzyltriethylammonium hydroxide (2) partition between the aqueous and organic phases. In the aqueous phase, the quaternary ammonium chloride (1) reacts with concentrated hydroxide to give the quaternary ammonium hydroxide (2). In the chloroform phase, 2 reacts with chloroform to give the tri-chloromethyl anion (3), which eliminates chloride ion to give dichlorocarbene, iCClj, (4), and 1. The carbene (4) reacts with the olefin to give product (5). 

Friedel-Craets reaction Aluminum chloride. Benzenesulfonic anhydride. Boron trifluoride. 7-Butyrolactone. Catechol dichloromethylene ether. Chloroform (solvent). Chloromethyl methyl ether. 1,1-Didilorodimethyl ether. 2,4-Dinitrobenzenesulfenyl chloride. Hydrogen fluoride. Iodine. Folyphosphoric add. Sodium aluminum chloride. Stannic chloride. Sulfur. Sulfur monochloride. Titanium tetrachloride. Trichloramine. Zirconium tetrachloride. Friedel-Craets type reactions Dimethylacetamide. lodosobenzene. 

Monochlormethyl chloride—Metkene chloride—Dichloromethane— Methylene chloride Chloromethyl—OH,Cl,Cl—85—is obtained by the action of Cl upon CH,C1 or by shaking on alcoholic solution of chloroform with powdered zinc and a little ammonium hydrate. In either case the product must be purified. 

The OH group in 3-hydroxymethyl-3,4-dihydro-l,2,3-benzotriazin-4-one is replaced by chlorine under treatment with thionyl chloride in chloroform <1956USP2758115> and by bromine under treatment with phosphorus tribromide in acetonitrile <1955DEP927270>. 3-Chloromethyl-3,4-dihydro-l,2,3-benzotriazin -one is used for the manufacture of Azinphos methyl by exchange of the chlorine with O,0 -diethyl-dithiophosphate in the presence of sodium bicarbonate in acetone <1955DEP927270>. 

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