Sulfur reaction with, phosgene

Here, a key factor in selecting the appropriate method is the environmental impact of the by-products. Both reactions release hydrogen chloride, which can easily be removed by a scrubber filled with aqueous sodium hydroxide. The scrubber also decomposes traces of phosgene. In contrast to the reaction with phosgene, which liberates harmless carbon dioxide as a second by-product, thionyl chloride releases gaseous sulfur dioxide, which significantly burdens the environment, and cannot be removed by simple methods. 

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. 

Catalysis. Catalytic properties of the activated carbon surface are useful in both inorganic and organic synthesis. For example, the fumigant sulfuryl fluoride is made by reaction of sulfur dioxide with hydrogen fluoride and fluorine over activated carbon (114). Activated carbon also catalyzes the addition of halogens across a carbon—carbon double bond in the production of a variety of organic haUdes (85) and is used in the production of phosgene... 

Other chlorinated solvents such as tetrachloroethylene or chloroform may be used in place of carbon tetrachloride. Caution The reaction of sulfur trioxide with chlorinated solvents has been reported to give phosgene and other toxic products. Adequate venting of all by-product gases is essential. 

A series of reactions with gases have been selected for the rapid quantification of many of the major products from the oxidation of polyolefins. Infrared spectroscopy is used to measure absorptions after gas treatments. The gases used and the groups quantified include phosgene to convert alcohols and hydroperoxides to chloroformates, diazomethane to convert acids and peracids to their respective methyl esters, sulfur tetrafluoride to convert acids to acid fluorides and nitric oxide to convert alcohols and hydroperoxides to nitrites and nitrates respectively. 

When thionophosphonic esters are used for conversion to the phosphonothiochloridates, observation of the stereospecificities of the reactions is possible. Alternative results may be attained through judicious choice of the reagent system. For example, the optically active O-isopropyl methylphosphonothioate, as shown in Equation 4.10, reacts with phosgene at sulfur only to form the O-isopropyl methylphosphonochloridate with inversion of configuration at phosphorus.20... 

The diazepine 85 (tetramethyleneurea) has been prepared by a variety of routes. Among these are the treatment of tetramethylene diisocyanate with water,70-72 the rearrangement of the oxime (86) in polyphosphoric acid,73,74 and the reaction of 1,4-diaminobutane with sulfur, methanol, and carbon monoxide at high pressure.75 A novel preparation of 85 involves the reaction of 1,4-diaminobutane with 87 to give the silylated diamine (88). Reaction of 88 with phosgene and triethylamine yielded the bistrimethylsilyldiazepine (89) which was then hydrolyzed in aqueous ethanol to give 85.76... 

Violent reaction with benzoyl chloride combined with KOH, Bt2, barium carbonate, CS2, Cr(OCl)2, Cu, Pb, HNO3, BaCOs, H2SO4, hot water, (CH3)2S04, dibromomalononitrile, sulfuric acid. Incompatible with acids, ammonium chloride + trichloroacetonitrile, phosgene, cyanuric chloride, 2,5-dinitro-3-methylbenzoic acid + oleum, trifiuroroacryloyl chloride. Reacts with heavy metals (e.g., brass, copper, lead) to form dangerously explosive heavy metal azides, a particular problem in laboratory equipment and drain traps. When heated to decomposition it emits very toxic fumes of NOx and Na20. See also AZIDES. 

N-Methyl-N-methoxycarbamoyl chloride made by phos-genation of methoxy methyl amine hydrochloride is a very useful intermediate for the synthesis of N-methoxy ureas herbicides. However, we found the method to be unsatisfactory for the production on a large scale, because of rather low yields and also of technical difficulties. To overcome these problems, we developed a new procedure based on the reaction of phosgene with methoxy methyl amine sulfate as depicted in scheme 124. Sulfuric acid formed is easily removed by decantation (Ref. 177). 

Reaction of phosgene with EtO(EtS)P(0)Me results in the elimination of carbon dioxide, Equation (10.47), whereas reaction with the isomeric thionate, (EtO) jP(S)Me, is accompanied by the loss of sulfur. Equation (10.48) [317] ... 

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] ... 

Reaction of PhSOjH with phosgene, in the presence of dmf and sulfuric acid, gave PhSOjCl in a yield of 98.5% [204]. Similarly, treatment of the bisbenzenesulfonic acid... 

Sulfur tetrafluoride is a hazardous and highly toxic gas [4], in some aspects comparable with phosgene [12]. For reactions with SF4 with or without HF autoclaves made from Hastelloy C with Monel 400 piping and valves are recommended [13]. When handling SF4 sufficient ventilation must be provided and protective goggles and gloves should be worn. On autoclave depressurization, excess SF4 and HF should be scrubbed with potassium hydroxide solution. 

---