Chloromethyl sulfones

Further substitution of 2,4-disubstituted and most 2,3-disubstituted thiophenes occurs in the free a-position, except when a - -M-substituent in the 3-position strengthens the 4-directing power of a —1—M-sub-stituent in the 2-position. Thus methyl 3-methyl-2-thiophenecar-boxylate is brominated in the 4-position and 3-brorao-2-thiophene-aldehyde is nitrated in the 4-position. Recent investigations on the chloromethylation, sulfonation, mercuration, and nitration of 2,4-di-chlorothiophene, which without proof are assumed to occur in the 5-position serves as examples of the reactivity of a 2,4-disubstituted thiophene. Formylation with iV,A-dimethylformamide and... 

The cycloaddition reaction of the allenyl chloromethyl sulfone 130c was successfully applied to an iterative ring-annulation procedure [115]. 

The products 179 and 180 result from VNS on 2-nitropyrrole with chloromethyl sulfones <1995T8339>. 3-Nitropyrrole is attacked only at G(2). 

The products of VNS of 2-nitro- and 3-nitropyrroles with chloromethyl sulfones are depicted in Equations 207 and 208, respectively <1995T8339>. When R =Ts, pyrrole 827 (83% yield) was the only reaction product, but in the case of l-(methoxymethyl)-2-nitro-l//-pyrrole a mixture of pyrroles 826 and 827 (14%), with predominance of 5-substituted isomer 826 (74%), was obtained. Electron-donating alkyl substituents direct the reaction exclusively to position 5 with formation of pyrroles 826 in 68-93% yields. Erom the reaction of l-methyl-3-nitropyrrole with chloromethyl sulfones 2-substituted products 828 were isolated. 

A related approach uses a Darzens-type reaction to prepare aziridines <2001M849, 2002M1071>. Chloromethyl sulfones and sulfonamides were deprotonated with powdered KOH in DMSO. Addition of this carbanion to the more electrophilic C=N bond followed by aziridine ring formation provides aziridine 135 (Equation 32). No information was provided on the relative stereochemistry of the aziridine. 

CHLOROMETHYL SULFONE (124-63-0) Combustible liquid (flash point >212°F/ >100°C). Reacts with water, acid, or acid fumes, forming hydrochloric acid. Violent reaction with ammonia, caustics, strong oxidizers. Aqueous solution incompatible with sulfuric acid, ammonia, aliphatic amines, alkanolamines, bases, isocyanates, alkylene oxides, epichlorohydrin. Attacks metals in the presence of moisture. 

AI3-52234 Chloromethyl sulfone EINECS 204-706-1 HSDB 5605 Mesyl chloride Methanesulfonic acid chloride Methanesulfonyl chloride Methanesulfuryl chloride Methanesulphonyl chloride Methyl sulfochloride Methylsulfonyl chloride NSC 16039 UN3246. Liquid bp = 162, bpii = 55 d = 1.4805 insoluble in H2O, soluble in EtOH, EtzO. 

Allenyl chloromethyl sulfoxide (57) reacts with m-CPBA to furnish allenyl chloromethyl sulfone (58) (eq 21). The enethi-olizahle thioketone (59) has been oxidized to the ( )-sulfine (60) (eq 22). The 2 -deoxy-4-pyrimidinone (62) has been prepared by reacting the 2-thiop3Timidine nucleoside (61) with m-CPBA (eq 23). Thioamides have been transformed to the amides in high yields. ... 

In search for new antiparasitic agents active against Trichomonas vaginalis, a number of 4-(arylsulfonylmethyl)-5-nitroimidazole derivatives have been prepared via the VNS reaction of 4-nitroimidazoles with substituted aryl chloromethyl sulfones (Scheme 32) [124]. 

A similar reaction of compound 17 with phenyl(chloromethyl)sulfone 18, as a vicarious nucleophile, affords 3-sulfonylindole 19 [29] (Scheme 12). 

Crosslinked polystyrene (copolymer with divinyl benzene) is now a favorite support material. Perhaps the main reason for choosing crosslinked polystyrene is that it can be functionalized in many ways. It can be nitrated, chloromethylated, sulfonated, lithiated, carboxylated, and acylated. The greatest use has been made of the chloromethylated and lithiated derivatives. This is because these two derivatives can react with nucleophilic and electrophilic reagents, respectively, resulting in a wide range of functionalized polymers. See Section 8.4.3 for an illustration. 

Synonyms Chloromethyl sulfone Mesyl chloride Methylsulfonyl chloride MSC... 

Methylene compounds from chloromethyl sulfones GHSO2GH2GI -> G GHg... 

SMA resins may be chemically modified by a host of other reactions, such as nitration, reduction, chloromethylation, " sulfon-ation, " " grafting with intermediates such as E-caprolactam, " and treatment with alkyl tin compounds. The latter organometallic copolymers exhibit... 

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