Chloroformate chlorosulphonate

Reaction with chlorosulphonic acid ( chlorosulphonyl-ation ). Sulphonamides. Many aryl hahdes, either alone or in chloroform solution, when treated with excess of chlorosulphonic acid afford the corresponding sulphonyl chlorides in good yield (compare Section IV.106) the latter may be readily converted into the aryl sulphonamides by reaction with concentrated ammonia solution or with sohd ammonium carbonate. 

Procedure 1. Dissolve 1 g. of the compound in 5 ml. of chloroform in a test-tube and cool in ice. Add 5 ml. of chlorosulphonic acid CA UTION in handhng) dropwise and with shaking. When the initial evolution of hydrogen chloride subsides, remove the reaction mixture from the ice and, after 20 minutes, pour it into a 50 ml. beaker filled with crushed ice. Separate the chloroform layer, wash it well with water, and evaporate the solvent. Recrystallise the residual aryl sulphonyl chloride from light petroleum (b.p. 40-60°), chloroform or benzene this is not essential for conversion into the sulphonamide. 

Sulphonamides of aryl ethers. Aromatic ethers react smoothly in chloroform solution with chlorosulphonic acid at 0° to give suljihonyl chlorides, for example ... 

Charcoal screenings, wet Charcoal, wet Chlorine azide Chlorine dioxide Chloroacetaldehyde Chloroacetone (unstabilized) Chloroacetonitrile Chloroformates, n.o.s. Chloroprene, uninhibited Chlorosulphonic acid Coal briquettes, hot Coke, hot Copper acetylide... 

Dissolve l.Og of the compound in 5 ml of dry (CaCl2) chloroform in a dry test tube, cool it in a beaker of ice and add 3-5 ml of chlorosulphonic acid (CAUTION) dropwise. When the evolution of hydrogen chloride has subsided, remove the test tube from the ice bath and allow to stand at room temperature for 20-30 minutes then pour on to crushed ice (30 g). Separate the chloroform layer, wash it with water, dry (CaCl2), and evaporate the solvent. 

Chlorosulphonic acid also reacts with methyl chloroformate to give a good yield of methyl chlorosulphonate (see p. 266). 

Monochloromethyl chloroformate, unlike methyl chloroformate, reacts with difficulty with chlorosulphonic acid, forming monochloromethyl chlorosulphonate only after boiling on the water bath for 4 hours ... 

It reacts with monochloromethyl chloroformate, forming monochloromethyl chlorosulphonate ... 

With monochloromethyl chloroformate it reacts to form methyl chlorosulphonate ... 

The synthesis of anionics is complicated in the case of unsaturated cardanol (ref. 282) by polymerisation reactions although the use of chlorosulphonic acid in chloroform at ambient temperature affords an unstable surface active product which probably contains side chain products and the phenol sulphate as well as the sulphonic add. 

Pyridine (IL) was distilled from chlorosulphonic acid (10 ml) and kept under nitrogen. All acylations were performed under a blanketing nitrogen atmosphere. TLC analysis was performed on Merck Kieselgel 60 F 254 plates using chloroform-methanol 85 15 (v/v) as the solvent and UV and/or iodine vapor visualization. Mobilities of compounds were expressed relative to reference compounds. H-n.m.r. spectra (80 MHz) and I.R. spectra were recorded on a Bruker WP-80 and Beckman IR-33 apparatus, respectively. 

Roychoudhury et al. showed that the double peak of a blend of ENR-50 with chlorosulphonated polyethylene (CSM) at 1 1 weight ratio was changed to a single one (at 2.7 °C) when carboxylated nitrile rubber (XNBR) was added in the stock at 50 wt% (i.e. ENR-50/CSM/XNBR 25/25/50). Additionally, an exothermic peak was detected at 205 °C during a differential thermal analysis of a 33.3/33.3/33.3 mixture of this ternary blend. Taking into consideration that CSM, XNBR and ENR are soluble in chloroform whereas their blend is insoluble, the exothermic peak was attributed to self-crosslinking behaviour of this ternary compound (in the absence of curatives). 

Dissolve 1 g of the substance in 5 ml of chloroform previously dried with calcium chloride, cool the solution in an ice-bath, and when at 0°, add drops of chlorosulphonic add very carefully. When 3 ml of the add have been added in this way (keeping the mixture at 0°) and evolution of hydrogen chloride has ceased, allow the temperature to rise. Stir for about 30 minutes, and then pour, very slowly and with the greatest care, on to about 25 g of crushed ice. Protect the eyes during the last operation as spattering often occurs. Separate the chloroform layer, wash it wifli water, dry with anhydrous calcium chloride, and remove the solvent. If a solid, the crude arylsulphonyl chloride may be recrystallized from chloroform. It is then converted into the amide by heating 0 5 g of it with 5 ml of O 880 ammonia for 10 minutes. Cool and add 10 ml of water. Filter, wash the solid with water and recrystallize it from aqueous alcohol. 

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