Ethyl chlorosulphonate

Methyl ethyl sulphate can be prepared by adding ethyl chlorosulphonate... 

In the war of 1914-18 methyl chlorosulphonate and ethyl chlorosulphonate were employed as war gases. Owing to the presence of halogen in their molecules, these substances have a powerful lachr5miatory action, but their toxicity is less than that of the sulphates. 

Also halogenated derivatives of ethyl chlorosulphonate Chloroethyl Chlorosulphonate... 

Sulphuryl chloride was chiefly prepared during the war for the manufacture of methyl and ethyl chlorosulphonates, but was occasionally employed also in admixture with cyanogen chloride, phosgene or chloropicrin (Prentiss). 

Physical and Chemical Properties Ethyl chlorosulphonate is a colourless, oily liquid fuming in damp air and having a pungent odour. It boils at ordinary pressure at 152° to 153° C. and at 100 mm. pressure at 93° to 95° C. Its specific gravity at 0° C. is 1379, and its vapour density is five times that of air. It has a low vapour pressure. 

Ethyl chlorosulphonate does not attack iron or steel, but attacks copper slightly and lead and tin vigorously. 

Ethyl chlorosulphonate, Sulvanite. Colourless liquid, bp 135°C, fumes in air. Pungent smell, more lachrymatory and toxic than the methyl compound but less volatile. Intolerable at 50 mg/m3 and toxic at lg/m3. 

Sulvinite, ethyl chlorosulphonate, colourless oily liquid, bp 152°C, pungent odour, irritant at > 2 mg/m3. Used by the French with bromoace-tone in WWI. 

Sulphuryl chloride, SOgClg (acide chlorosulfurique) was discovered by Regnault by the action of dry chlorine on a mixture of sulphur dioxide and ethylene, or on sulphur dioxide alone. He determined its vapour density (4 652, air = i) and by the action of ammonia on it discovered sulphamide, S02(NH2)2 Disulphuryl chloride, SgOgClg, discovered by Rose, was prepared by Armstrong by the action of sulphur trioxide on carbon tetrachloride CCI4 +2803 = 8205012 + 00012. Ethyl chlorosulphonate, discovered by Kuhlmann, was more carefully examined by Williamson, who formulated it... 

Ethyl chlorosulphonate ChloromUphonie acid ethyl eater)... 

Baumgarten 80, 1204 showed the pyridine-sulphur trioxide complex to be converted rapidly by alkali into the yellow compound (144). This could be hydrolysed to glutacondialdehyde, and as a source of this compound the reaction has found synthetic use os, xhe quaternary salt from pyridine and ethyl chlorosulphonate is similarly split by alkali, to glutacondialdehyde and sulphamic acid oe. 

The majority of plasticiser consumption is in CR and NBR. Plasticisers are also technically important in chlorosulphonated polyethylene, hydrogenated nitrile, ethyl acrylate copolymer, epichlorohydrin copolymer and ethylene-acrylic terpolymer. At around 10 kt/annum (Europe), total consumption of plasticisers is on a much smaller scale than the process oils used in hydrocarbon rubbers. Typical addition levels are below 20 phr. 

The simple acidic nature of chlorosulphonic acid is also manifested in the existence of corresponding ethereal salts, the ethyl ester C1.S02. OCaII8 being obtainable indirectly by the action of phosphorus penta-chloride on ethyl hydrogen sulphate (ethylsulphuric acid), C2H50. S03.0H, or by the interaction of sulphuryl chloride and ethyl alcohol 1... 

In order to resolve phenolic acids better, Scott [168] developed sulphonyl-TMS derivatives. Several milligrams of a free acid were dissolved in 2 ml of ethyl acetate and 0.3 ml of chlorosulphonic acid was added. The mixture was heated at 60°C for 5 min, cooled and 2 ml of water were slowly added. The mixture was then extracted with three 3-ml portions of ethyl acetate and the extracts were combined and re-extracted with two... 

Tin ethyl propyl dichloride. — This compound is obtained from tin ethyl propyl dibenzyl by the action of concentrated sulphuric and chlorosulphonic acid. The aqueous solution of the sulphonatiori product is treated with ammonium hydroxide, the precipitate filtered off, dissolved in hydrochloric acid, and the acid solution extracted with ether. Removal of the solvent yields the dichloride in needles, M.pt. 57 to 58° C., which have an unpleasant odour, and are readily soluble in alcohol, water, or ether, sparingly in light petroleum. 

N-(5 chloro-2-methoxybenzoyl)-2-phenylethylamine-2-14C (107) was prepared by reacting non-labelled 104 with CDI in DMF and treating directly the reaction mixture with 106. Subsequent chlorosulphonation and sulphonamide formation gave (5-chloro-2-methoxybenzamido)ethyl-l-14C benzenesulphonamide (103-14C), which after condensation with cyclohexyl isocyanate yielded the carbon-14 labelled, radiochemically pure glyburide (102-14C). 

The kinetics of the formation of chlorosulphonic acid from sulphuric acid have been followed in a hetero neous system the activation ener is 23.8 kcal mol. The hydrolysis of sulphite esters in carboxylate buffer has been examined as a model for the corresponding pepsin-catalysed process. The carboxylate anion acts as a nucleophile, attacking the sulphur, with the formation of a mixed anhydride. The rate of the alkaline hydrolysis of para-substituted ethyl benzenesulphinates has been studied. This reaction, which occurs with S—O bond fission, occurs by nucleophilic attack on sulphur to form a tetrahedral intermediate. The value of A5 v — 30 cal mol and p = + 1.60. It is concluded that ki>k-u and the reaction is... 

New syntheses of enamino-ketones by the ring-opening of isoxazoles with samarium di-iodide and with pentacarbonyliron, by the reaction of 2-alkyl-thiomethyl-3-alkylthioacrylophenones with amines, and by the intramolecular photoarylation of A -[2-(haloaryl)ethyl]-(3-enaminones, of enamino-diketones by the reaction of (3-chlorosulphonic acid chlorides with amines and by amino-methylenation of cyclic (3-dicarbonyl compounds, and of enamino-esters by aminomethylenation of esters and lactones and by the reaction of nitriles with magnesium enolates have been reported. 

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