Oxygenates reaction with phosgene

Phosgene reacts with a multitude of nitrogen, oxygen, sulfur, and carbon centers. Reaction with primary alkyl and aryl amines yield carbamoyl chlorides which are readily dehydrohalogenated to isocyanates. Secondary amines also form carbamoyl chlorides. 

Hexanitroethylcarbonate, [(03N)3C.CH20]2C0 mw 388.13, N 21.65% crysts, mp 115°, d 1 88, sensitivity approx that of Pentolite. It is prepd by reaction of phosgene with Trinitioethanol in the presence of AlClg. This expl has a higjh oxygen content (62%), high aystal density and excellent stabiliry Ref D V. Sickman W.F. Sager, NAVORD Report 486(1954)... 

Azine approach. DCC dehydration of the 3-oxoquinazoline-4-hydroxamic acid (602) gives an isocyanate (603) via a Lossen rearrangement addition of the AT-oxide oxygen to the isocyanate group effects the cyclization. The same product is formed by the phosgene reaction with 4-amino-2-methylquinazoline 3-oxide (76TL3615). 

Hazard Explosive reaction with carbon, forms phosgene on reaction with oxygen. 

The reaction of oxygen atoms with CCl, results in the formation of phosgene, in addition to dichlorine, CO and COj [2088a]. The primary reactions in this system are... 

In a recent fascinating publication, pentacarbonyl(methoxyphenylcarbene)tungsten(0), [W(CO)5 C(OMe)Ph ], was treated with phosgene in octane in a sealed tube at 70 C this reaction produced a mixture of methyi benzoate, PhC(0)0Me, and tetrachloroethene [1143]. The proposed mechanism, aithough tentative, is of some interest, as it involves initial coordination of the phosgene, and then oxygen loss to form a dichlorocarbene ligand [1143] ... 

The reaction of phosgene with iV,iV-dimethylbenzamide at room temperature results in the substitution of two atoms of chlorine for the oxygen atom [870b] ... 

Surprisingly little work has been published on the reactions of phosgene and ketones. Unlike phosphorus(V) chloride, phosgene is reported not to react with ketones to replace the carbonyl oxygen with chlorine, even at elevated temperatures [1704]. 

Salts of the thiolate anions represented in Equation (10.49) combine with phosgene with the loss of the sulfur, rather than the loss of the oxygen atom [317]. Reaction between COClj and the anion of the corresponding dithionic acid, however, gives the readily isolated product of Equation (10.50) [317]. 

Owing to the greater nucleophilic character of sulfur relative to oxygen, reaction of 1,3-disubstituted thioureas with phosgene usually occurs at the sulfur atom, to give high yields of chloroformamidinium chlorides [2083a, 2087] ... 

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