Methyl chlorosulphonate

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

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. 

Chlorosulphonic acid also reacts with dimethyl sulphate to form methyl chlorosulphonate ... 

Dimethyl sulphate was used by the Germans mixed with methyl chlorosulphonate, this being the product obtained in the industrial manufacture from methanol and chlorosulphonic acid when the esterification is incomplete. Dimethyl sulphate mixed with chlorosulphonic acid was used by the French under the name of Rationite. ... 

Methyl chlorosulphonate was employed by the Germans both alone, and in admixture with dimethyl sulphate (75 parts dimethyl sulphate and 25 parts methyl chlorosulphonate) under the name of C-Stoff. ... 

Selective hydrolysis of the 3a-acetoxy-group of fully acetylated cholic acid derivatives has been achieved with methanolic HCl. The hydrolysis occurs more rapidly than the methylation of the side-chain carboxylic acid. The 3-monosulphates of cholic, chenodeoxycholic, and deoxycholic acids have been prepared using this selective hydrolysis on the fully acetylated methyl esters. The resultant 3a-hydroxy-compounds were then treated with chlorosulphonic acid and the... 

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

Carbon-13 n.m.r. spectroscopy has been used to study benzylisoquinoline and tetrahydroisoquinoline alkaloids and their JV-methyl quaternary salts.30 N-Benzylpapaverinium bromide has been shown to undergo aerial oxidation in alkaline solution to 2-benzyl-6,7-dimethoxyisoquinolone and to give bases of general structure (10) with methylamine, benzylamine, and pyrrolidine.31 Chlorosulphonation of papaverinol affords the sulphonic acid ester (11), mild hydrolysis of which yields the acid (12), which with diazomethane is esterified and dehydrated to (13).32 N-Methyl-l,2-dihydropapaverine has been shown by kinetic studies and orbital-symmetry requirements to rearrange to the salt (14) by the route previously postulated.33... 

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

By the action of chlorosulphonic acid on methyl alcohol at — 5° C., methyl sulphuric acid is formed (see p. 261),... 

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). 

In the laboratory it is prepared by the action of methanol on chlorosulphonic acid. According to Claesson, the chlorosulphonic acid is placed in a small flask, which is fitted with a tap-funnel and externally cooled with ice. Water-free methyl alcohol, previously distilled from lime, is slowly introduced in quantity stoichiometrically equivalent to the chlorosulphonic acid. As each drop of alcohol comes into contact with the chlorosulphonic acid, hydrochloric acid is evolved. At the end of addition of the alcohol the flask is heated gently while a current of dry air is passed through in order to remove the hydrochloric acid dissolved in the mixture. The product obtained contains about 90% methyl sulphuric acid. 

In the laboratory it is preferable to prepare dimethyl sulphate by Ullmann s method, that is, by the action of methyl alcohol on chlorosulphonic acid. 

TOO gm. chlorosulphonic acid are placed in a 200 ml. distillation flask which is closed with a rubber stopper containing two holes. Through one of the holes passes a thermometer and through the other a tap-funnel of the Bulk type containing 27 gm. water-free methyl alcohol. The exit tube of the distillation flask is connected with a wash-bottle containing a little sulphuric acid, and the exit from this leads to a second bottle partly filled with water which serves to absorb the hydrochloric acid formed in the reaction. 

Determination of Chlorosulphonic Acid. About i gm. of the sample is introduced into a small glass bulb which is then sealed in the flame and weighed accurately. This bulb is then placed in a tall glass cylinder of about 150 ml. capacity, containing about 100 ml. water. The cylinder is stoppered tightly and shaken violently so as to break the bulb, and then allowed to stand until the cloud which first forms in the cylinder completely disappears. The contents are then transferred to a 500 ml. flask and made up to volume. 200 ml. of the solution are then titrated with a decinormal sodium hydroxide solution, to the methyl-orange end-point, so as to obtain the total hydrochloric and sulphuric acid content. In another 200 ml. the hydrochloric acid is titrated with a decinormal solution of silver nitrate in presence of a few drops of potassium chromate solution, after addition of excess of pure calcium carbonate. 

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. 

Chlorosulphonation of the 3-methyl ether of oestradiol 17-acetate, and subsequent treatment with various amines, has given rise to a series of 2-sulph-amoyl oestratrienes, and a number of /V-substituted sulphamoyl derivatives of 17a-ethynyl-oestradiol have also been made. Methane- and butane-sulphonamido-oestra-l,3,5(10)-trienes prepared from the 3-amino-analogue of oestrone have shown poor biological activity. 

In class B are placed all simple esters, CHjF CO i , of fluoro-aoetic acid, where iZ = Me, Et, Pr , Pr , Ph, etc. When substitution takes place in the a-hydrogen atoms, e.g. in methyl a-fluoropropionate or a-fluoroisobutyrate, then the compound is devoid of toxicity. This indicates the importance of the unsubstituted fluoromethyl group. On pp. 125 et seq. it was shown that fluoroacetamide and a variety of substituted amides such as CHjF CO NH CHg CHjCl were, molecule for molecule, equally toxic with fluoroacetic acid and produced the same symptoms. The 2 chloroethyl group therefore contributed nothing appreciable to the toxicity of the molecule. The majority of the esters of fluoroethanol showed the toxicity of the parent alcohol, e.g. 2-fluoroethyl chlorosulphonate, CHgF CHg O SOjCl, di-(2-fluoroethyl) sulphate and 2-fluoroethylglycine hydrochloride. 

Chlorosulphonation of 4 -chloro-o-acetotoluidine yields the eorresponding sulphonyl chloride derivative whieh on amination forms the sulphonamide derivative. Oxidation of the methyl moiety gives the respeetive anthranilamide derivative whieh on hydrolysis eliminates the acetyl group to yield the substituted anthranilic acid. Fusion of this amino acid with propionamide first gives rise to an intermediate by the loss of a mole of water and ultimately helps in the closure of the ring to generate the quinazoline ring system. Catalytic reduction of this finally produces the official compound. 

The effect of the mode of annelation on the acidity of the fluorenic hydrogens is clearly noticeable. (456) is metalated by butyl-lithium only at the 4-position, whereas (457) gives upon metalation and carbonation a mixture consisting of 38% of the 8-acid, 14% of the 1-acid, and 48% of the 3-acid of (457). 26c Treatment of 3-thienylmandelic acid (460) with Aids in benzene gave the 4-acid of (456). A similar ring-closure to (461) was obtained upon treatment of methyl 3,3 -dithienylglycolIate with chlorosulphonic acid in methylene chloride. ... 

A copolymer of methyl methacrylate and vinyl chloride containing labelled chlorine ( "Cl) has been examined using thermovolatilization analysis and radiochemical assay. The yields of methyl chloride and hydrogen chloride agree with predictions made from sequence distribution calculations. The thermal degradation of a number of chlorine-containing polymers, poly(vinyl chloride), chlorinated polyethylene, chlorosulphonated polyethylene, polychloroprene, poly-epichlorhydrin, and co- and ter-polymers of epichlorhydrin has been compared and structural effects elucidated. ... 

C9H1gNaOe f Sodium 2-methyl-6-endo-hydroxybicyclo[2.2.1]heptane-2-endo-carboxylate trihydrate, 43B, 233 C10CI12O3S, Undecachloro-pentacyclo-[5.3.0.0 .0 .O ]-decan-5-chlorosulphonate, 32B, 146 CtoHsClyr Heptachlor, 39B, 136... 

As an example of surface-modified latex particles via chemical reactions, there is the work of Imbert-Laurenceau et al. [130] PS particles functionalized by various amino acids were prepared in three steps by modifying chemically the surface of cross-linked PS particles. First, phenyl groups of PS were chlorosulphonated by reaction with an excess of monochlorosulfonic acid. Second, The PS-SO2CI was condensed with various amino acid methyl esters in order to obtain the different functionalized particles. Third, ester groups were hydrolyzed by successive washing of the particles with different aqueous solutions of NaOH. The final particles are able to strongly interact with antiviral antibodies. Due to these biospecific interactions, the functionalized particles are candidates to be used in vaccinal approach as virus-like polymers or as affinity matrix for the purification of antiviral antibodies. 

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