Phosgene chloroformylation with

Some polysulfides contain in the polymer backbone other groups besides -S-. A common type of group is oxycarbonyloxy, such as in the polymer resulting from the reaction of phosgene (chloroformyl chloride or carbonic acid dichloride) with 4,4 -thiobisphenol. This reaction can be considered a polycondensation and can be written as follows ... 

Looking at Scheme 4.1, one can see that in chloroformylation, carhonylation, and chlorination reactions, phosgene reacts with nucleophilic groups Y-Z of monovalent type Z is always H, and Y is represented by the classical nucleophilic elements the reactivity (nucleophilicity) of the nucleophiles increases according to thiols <... 

Phosgene reacts with oximes to form 0-(ch oroformyl) oximes 124, which, on addition of antimony pentachloride, undergo smooth Beckmann rearrangement with loss of carbon dioxide to give the nitrilium salts 125 almost quantitatively [66]. With oxygen or nitrogen nucleophiles, O-(chloroformyl) oximes 124 form symmetrical and unsymmetrical oxalyl derivatives. 

A solution in dry benzene of 82 grams of bis(p-chloroethyl)amine freshly liberated from its hydrochloride is added gradually to a solution of 36 grams of carbonyl chloride (phosgene) in benzene at a temperature below 10°C. The mixture is mechanically stirred for 3 hours, the precipitate of bis(p-chloroethyl)amine hydrochloride is removed by filtration and the benzene is distilled off on a water bath. The residue is distilled in vacuo and the N-chloroformyl-bis(p-chloroethyl)amine is obtained as a pale yellow oil with a BP of 114° to 116°C at 1 mm Hg. 

Condensation of phosgene with a carbohydrate by any one of the first three methods yields derivatives containing intramolecular cyclic-carbonate groups, chloroformyl groups, or intermolecular carbonate groups. The type of derivative obtained depends largely upon the stereochemistry of the carbohydrate used and also upon the reaction conditions. Initial reaction produces a chloroformyl derivative, which may then be involved... 

Haworth, Porter, and Waine examined the reaction of D-galactose and of D-xylose with phosgene in acetone, and isolated, respectively, 6-0-(chloroformyl)-l,2 3,4-di-0-isopropylidene-D-galactopyranose (XIV) and 1,2-0-isopropylidene-D-xylofuranose 3,5-carbonate (X). The reactive chloroformyl compound could be converted to the 6-0-(phenylaminocar-bonyl) derivative XXXVI by treatment with aniline, or to the 6-0-(meth-oxycarbonyl) derivative with methanol, and its possible use in the optical... 

Carbohydrates, allyloxycarbonates, 123 carbonates of, 151 chloroformyl esters of, 102 conformational analysis of, 12 reaction of, with carbon dioxide, 129 with carbon disulfide, 135 with carbonic acid, 129 with phosgene in acetone, 105 thermochemical properties of, 21 thiocarbonates of, 157 Carbonic acid, esters, 91,92,151 bis(methyl 3,4-0-isopropylidene-/3-D-arabinopyranoside), 2,2 -, 96 bis(1,2,3,4 - tetra - O - acetyl -/J - D - glucose), 6,6 -, 104 cyclic, 103... 

Phosgene (CG, Carbonyl or chloroformyl chloride, Carbon oxychloride). COCI2, mw 98.92 colorl, highly toxic gas suffocating odor when much diluted with air there is an odor reminiscent of moldy hay fr pt —127.76°, bp 8.2°, d 1.392g/cc at 19/4°. SI sol in w and slowly hydrolyzed by it freely sol in benz, toluene, gl acet acid, and most liq hydrocarbons. Can be prepd by passing a mixt of carbon monoxide and chlorine over activated carbon, or by other methods described in Refs 1 8... 

The reaction proceeds via the formation of an isolable tetrasubstituted urea derivative, the carbonyl group of which reacts with phosgene to give an intermediate chloroformyl group, which then undergoes decarboxylation. Other derivatives (R = R = Et, Pr, Me CH, or Me(CH2)3 R = Me, R = Ph) were found to behave in a similar way [433]. 

At higher temperatures, in an inert solvent such as chlorobenzene,, lV -disubstituted ureas react with COCl to give guanidine derivatives, RNHC(=NR)NHR (R = various alkyl or aryl substituents) [724a], formed from the further reaction of the Vilsmeier salt with an excess of urea. With an excess of phosgene present, -chloroformyl derivatives may be obtained [724a] ... 

The reactions of IV-SiMe 3-substituted derivatives of imidazole, 3(5)-methylpyrazole, 3,5-dimethylpyrazole, benzotriazole and benzimidazole (see below, X = SiMej) with an excess of phosgene have been examined recently [1855], and are found to give high yields of the Af-chloroformyl derivatives illustrated below ... 

Reactions of phosgene with trialkyl(trimethylsilyl) ureas in toluene, at low temperatures, give trialkyl(chloroformyl) ureas [1406] ... 

The treatment of IV-silyl-substituted carbamate esters with phosgene at room temperature results in the formation of a thermally stable W-chloroformyl derivative [1406] ... 

Oxalyl chloride (ethanedioyl dichioride) can be an effective, alternative, chloroformylating agent to phosgene. The reaction of oxalyl chloride with diphenyl ketene, for example, proceeds under milder conditions than with phosgene to give the identical organic product [1938] ... 

The preparation of berbines (Scheme 38) through treatment of 1-benzyl-1,2,3,4-tetrahydro-iso-quinolines with phosgene gas to yield the iV-chloroformyl derivatives (208) is another example of the use of intramolecular Friedel-Crafts reactions in the construction of quinolizidine systems. These intermediates gave berbin-8-ones (209) by intramolecular ring closure in the presence of several Lewis acid catalysts (Scheme 38) <85T169>. 

Azlocillin [37091-66-0], antibiotic, 10. Phosgenation of 2-imidazolidinone 6 with phosgene in THF gives 1-chloroformyl-imidazolidinone 7, a key intermediate that forms the corresponding urea 9 upon reaction with d-(—)-a-phenylglycine 8 [7-9]. 

Estramustine phosphate [4891-15-0], antineoplastic, 99. N-Chloroformyl-bis(2-chlo-roethyl)amine 98, prepared with phosgene from the corresponding amine 97, is used to form the carbamate of estradiol 99 [77-79]. 

Mezlocillin [51481-65-3], antibiotic, 156. Chloroformylation of 1-methanesulfonyl-2-imidazolidinone 153 with phosgene results in the key intermediate, 3-chloro-formyl-l-methanesulfonyl-2-imidazolidinone 154 [121-125]. 

A colloidal suspension of L-proline in dioxane added slowly together with a soln. of phosgene in dioxane to the same solvent, stirred 1 hr. at 45° until a clear soln. results, traces of reactant removed by filtration, degassed in vacuo at 35° for ca. 45 min., the amount of N-chloroformyl-L-proline formed estimated by titration of 1 ml. of the soln. with 0.1 A Ag-nitrate, an equivalent amount of triethylamine added, and stirred 30 min. at room temp. N-carboxy-L-proline anhydride. Y 88%. A. A. Randall, Soc. 1962, 374. 

N-Hydroxyphthalimide alkali or trialkylammonium salt allowed to react at -5 to 0° with excess phosgene in methylene chloride or GGI4 o-chloroformyl-hydroxylamine derivative. Y 92%. F. e. and reactions, e.g. use in peptide synthesis, s. H. Gross and L. Bilk, Ang. Ch. 79, 532 (1967). 

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