Methanesulfonyl Chloride chlorination

Manufacture. Methanesulfonyl chloride is made commercially either by the chlorination of methyl mercaptan or by the sulfochlorination of methane. The product is available in 99.5% assay purity by Elf Atochem NA in the United States or by Elf Atochem SA in Europe. 

Manufacture. Methanesulfonic acid is made commercially by oxidation of methyl mercaptan by chlorine in aqueous hydrochloric acid to give methanesulfonyl chloride which is then hydrolyzed to MSA. 

Activity is also retained when the hydroxyl group at the 21 position is replaced by chlorine. Reaction of corticoid 44 with methanesulfonyl chloride proceeds preferentially at the 21-hydroxyl (45) due to the hindered nature of the 11-alcohol. Replacement of the mesylate by means of lithium chloride in DMF affords clobetasol propionate (46) a similar sequence starting with the 17- butyrate ester 47, via mesylate 48, should give clobetasone butyrate, (49) [11]. 

Methanesulfonyl chloride has been prepared by the chlorination of methyl thiocyanate, S-methylthiourethan, sodium methyl thiosulfate or S-methylisothiuronium sulfate from sodium methanesulfonate by the action of phosphorus penta-chloride, phosphorus oxychloride, or benzotrichloride from methanesulfonic acid by the action of phosphorus pentachloride or by the reaction of methylmagnesium iodide with sulfuryl chloride. ... 

The hydroxy group of l-(2-hydroxyethyl)thieno[3,4-d]pyrimidine-2,4(3//)-dione 344 was chlorinated with thionyl chloride in a mixture of pyridine and chloroform, or mesylated with methanesulfonyl chloride in pyridine. No ring chlorination was observed under these conditions. The resulting l-(2-chloro or 2-methanesulfonylethyl) derivative 365 was cyclized to l,2-dihydrooxazolo[2,3-6]thieno[3,4-d]pyrimidin-5-one 366 with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (89H985). A similar transformation of 3-(2-hydroxyethyl)thieno[3,4-d]pyrimidine-2(l//),4-diones 333a,b into the 3-(2-chloroethyl) derivatives 367 with thionyl chloride occurred in chlo-... 

Another useful method to convert thioureas into carbodiimides involves their reaction with reactive chlorine compounds, such as SOCI2, SO2CI2, SCI2 or S2CI2, The use of the sulfur chlorides involves chloroformamidines as intermediates (see Section 2.2.6). The reaction of thioureas 11 with methanesulfonyl chloride in methylene chloride in the presence of triethylamine/DMAP (4-dimethylaminopyridine) at room temperature produces carbodiimides 12 in 85-100% yield... 

Anthranilic diamides, D11-D17, were prepared in good yield by the reaction of an amine, R5NH2, with benzoxazinones 35 as shown in Figure 6. Synthesis of the benzoxazinones was accomplished by sequential treatment of 34 with one equivalent of triethylamine and methanesulfonyl chloride, followed by the anthranilic acid 33, and then followed by a second equivalent of triethylamine and methanesulfonyl chloride. The intermediate 4-chloro-6-mefhyl-anthranilic acid 33 = Cl) was prepared by chlorination of 6-methylanfhranilic acid with... 

Ishii X, Ishizu A., Nakano I, Chlorination of cellulose with methanesulfonyl chloride in /VJV-dimethylformamide and chloral, Carbohyd. Res., 59, 1977,155-163. 

Sato X, Koizumi J., Ohno Y, Endo X, An improved procedure for the preparation of chlorinated cellulose with methanesulfonyl chloride in a dimethylformamide-chloral-pyridine mixture, J. Polyrru Sci A. Polym. Chem., 28, 1990,2223-2227. 

Synthesis of dienyl chloride 2.349, the dithiane coupling partner for dithiane aldehyde 2.338, was accomplished in five steps from commercially available cis-2-butene-l,4-diol (Scheme 2.72). To this end, monosilylation of 2.344 as the TBS ether and this allyl alcohol was then oxidized with accompanying Zto E isomerization by PCC [122] to afford the enal 2.346 in 73 % yield. a,]S-unsaturated ester 2.347 was accessed by the Still—Gennari modification [219] of the Homer-Wads worth-Emmons olefination in good yield and selectivity (92 %, Z/E — 16 1). Reduction of the resulting ester 2.347 to produce allyl alcohol 2.348, in turn was chlorinated by treatment with LiCl and methanesulfonyl chloride to furnish the requisite dienyl chloride 2.349. 

The preparation of dienyl chloride 2334 for the cyanohydrin alkylation was achieved in a two-step sequence from the known ester 2,355. Reduction of 2355 and chlorination by treatment with LiCl and methanesulfonyl chloride furnished the dienyl chloride 2.334 (Scheme 2.78). 

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