Methyl reaction with sulfuryl chloride

R R2CHOH -> RlR2CHCl. This transformation can be effected with retention of configuration in two steps conversion to the methyl xanthate followed by reaction with sulfuryl chloride (equation I). 

An interesting application of the reaction with sulfuryl chloride consisted in the synthesis of a fully chlorinated hexoside.27 Treatment of methyl 2-chloro-2-deoxy-/3-D-galactopyranoside with sulfuryl chloride and pyridine in chloroform, followed by heating of the product with an excess of pyridinium chloride, afforded a tetrachloride, presumably methyl 2,3,4,6-tetrachloro-2,3,4,6-tetradeoxy-/3-D-allopy-ranoside. 

E. Reaction of methyl pentofiuanosides with sulfuryl chloride ... 

E. Reaction of Methyl Pentofuranosides with Sulfuryl Chloride ... 

In the absence of a 2-alkyl group, other methyl groups may become chlorinated on prolonged reaction with sulfuryl chloride but yields are usually low for example, 6-methylflavone (475) is chlorinated both at C-3 and in the methyl group (71T4837). 

The reaction of methyl glycopyranosides with sulfuryl chloride has also provided a route to 6-chloro (and other monochloro, dichloro, and trichloro) derivatives. 44 Schlubach and Wagenitz 44 observed that reaction of /3-d-galactopyranose pentaacetate with hydrogen bromide affords a 1,6-dibromo derivative which they converted into crystalline D-fucose in two steps. 

Pure diastereoisomers of 0,0-dinucleoside-0-methyl thiophosphate 36a,b Rp and Sp are readily available (21a,b), and their reaction with sulfuryl chloride fluoride is either fully stereoselective (36a, Rp) or highly selective (36b, Sp) (22). 

Preparative Methods benzyl alcohol plus aqueous formaldehyde and hydrogen chloride gas - reaction of benzyl methyl ether with boron trichloride cleavage of benzyloxymethyl methyl sulfide with sulfuryl chloride. ... 

This activation of the ortho position is most strikingly illustrated in the reactivity of 2,5-dimethylthiophene, which competitive experiments have shown to undergo the SnCb-catalyzed Friedel-Crafts reaction more rapidly than thiophene and even 2-methylthiophene. The influence of the reagent on the isomer distribution is evident from the fact that 2-methoxythiophene is formylated and bromi-nated (with A -bromosuccinimide) only in the 5-position. Similarly, although 3-bromo-2-methylthiophene has been detected in the bromi-nation of 2-methylthiophene with bromine, only the 5-isomer (besides some side-chain bromination) is obtained in the bromination of alkylthiophenes with A -bromosuccinimide. ° However, the mechanism of the latter type of bromination is not established. No lines attributable to 2-methyl-3-thiocyanothiophene or 2-methyl-3-chIoro-thiophene could be detected in the NMR spectra of the substitution products (5-isomers) obtained upon thiocyanation with thiocyanogen or chlorination with sulfuryl chloride. 2-Methyl- and 2-ethyl-thiophene give, somewhat unexpectedly, upon alkylation with t-butyl chloride in the presence of Feds, only 5-t-butyl monosubstituted and... 

Dichloromethyl methyl ether has been prepared by the chlorination of chlorodimethyl ether in the liquid5-4 or gas phase,5 by the reaction of chlorodimethyl ether with sulfuryl chloride and benzoyl peroxide,6 7 and by the treatment of methyl formate with phosphorus pentachloride.8-10... 

---