Methyl sulfonylation

Mizutani and coworkers57a confirmed the presence of polychloro(methylsulfonyl)biphenyls (159-170) as sulfur-containing metabolites of chlorobiphenyls (Cl-BP) in the feces of mice based on both GLC-mass spectrometry and chemical derivatization. In some cases comparison with authentic samples (161 and 162) was also made. When preparing 161 and 162,2,5-dichloro-3-(methylsulfonyl)aniline, 2,5-dichloro-l-iodo-3-(methylsulfonyl)benzene and 2,2, 5,5 -tetrachloro-3,3 -bis(methyl-sulfonyl)biphenyl were also obtained and their four peak El mass spectra reported572. Similar data were given for the corresponding 4-substituted intermediates, which were involved in the preparation of 162. Also 2,4, 5-trichloro-2 -(methylsulfonyl)-biphenyl was prepared and its four peak mass spectra given. Metabolites 163 and 164 were also identified by comparison with the authentic standards. 

Residues of PCBs in animal tissues include not only the original congeners themselves, but also hydroxy metabolites that bind to cellular proteins, for example, transthyretin (TTR Klasson-Wehler et al. 1992 Brouwer et al. 1990 Fans et al. 1993). Small residues are also found of methyl-sulfonyl metabolites of certain PCBs (Bakke et al. 1982, 1983). These appear to originate from the formation of glutathione conjugates of primary epoxide metabolites, thus providing further evidence of the existence of epoxide intermediates. Further biotransformation, including methylation, yields methyl-sulfonyl products that are relatively nonpolar and persistent. 

Janak K, G Becker, A Colmsjo, C Ostman, M Athanasiadou, K Valters, A Bergman (1998) Methyl sulfonyl polychlorinated biphenyls and 2,2-bis(4-chlorophenyl)-l,l-dichloroethene in gray seal tissues determinated by gas chromatography with electron capture detection and atomic emission detection. Environ Toxicol Chem 17 1046-1055. 

Stereoselective Synthesis of 2,2-Disubstituted 1-Fluoro Olefins (E)-[[Fluoro(2-phenylcyclohexylidene)methyl]sulfonyl]benzene. 

Intramolecular displacement of primary sulfonyloxy or halide groups in derivatives of D-mannitol can also be brought about under basic conditions, albeit in low yield. Treatment of l,6-di-0-(methyl-sulfonyl)-D-mannitol (78), or the corresponding dichloride derivative, with sodium methoxide gave 2,5 3,6-dianhydro-D-glucitol74 (79). Treatment of the latter with hydrochloric acid at 100° in a sealed tube gave the 6-chloro-6-deoxy derivative (80), which was converted into the known 2,5-anhydro-l,6-di-0-benzoyl-D-glucitol45 47 (32). The sequence 78-80 is of interest in the context of C-/3-D-nucleoside precursors, but it suffers from the fact that yields are low. 

C14H24N4O7S 5-Azido-5-deoxy-l,2-0-isopropylidene-3-0-(methyl-sulfonyl)-/3-L-idofuranuronic N,N-diethylamide (AZDMIF10)91,92... 

METHYL]SULFONYL]BENZENE AND (Z)-[2-(FLUOROMETHYLENE)CYCLOHEXYL] BENZENE... 

E)-[[Fluoro(2-phenylcyclohexylidene)methyl]sulfonyl]benzene Benzene, [[fluoro(2-phenylcyclohexylidene)methyl]sulfonyl]-, (E)-( )- (12) (135790-01-1)... 

J. R. McCarthy, D. P. Matthews, and J. P. Paolini 216 STEREOSELECTIVE SYNTHESIS OF 2,2-DISUBSTITUTED 1-FLUOROALKENES (E)-[[FLUORO-(2-PHENYLCYCLOHEXYLIDENE)-METHYL]SULFONYL]BENZENE AND (Z)-[2-(FLUOROMETHYLENE)-CYCLOHEXYL]BENZENE... 

It is evident that some leeway is available in the substituents tolerable in the m-position. The bronchodilator sulfonterol (28) is descended from this observation. Chloromethylanisole (29) is reacted with methylmereaptan to give 30, and the newly introduced group is oxidized to the methyl-sulfonyl moiety of 31 with hydrogen peroxide. Ether cleavage, acetylation and Fries rearrangement of the phenolic acetate produces 32, which is next brominated with pyrrolidinone hydrobromide tribromide and then oxidized to the glyoxal (33) with dimethyl sulfoxide. 

IV 7-Diethylamino-8-methyl-4-methyl-sulfonyl-3-phenyl-3H-( imidazo[4,5-d] -1,2-diazocm 46% Schmp. 204-206°... 

The combinatorial reactions chosen for the novel amines were amide bond formation and sulfonamide formation. The novel carboxylic acids were derivatized to simple amides. For the amine reactions, we chose two simple carboxylic acids (propionic acid and benzoic acid) and two simple sulfonyl chlorides (methyl-sulfonyl chloride and benzenesulfonyl chloride) as the capping groups. Propyl amine and benzylamine were chosen as the capping groups to react with the novel carboxylic acids. Because only one reactant will be variable, these combinatorial libraries were essentially 1 x N libraries, where the one reactant was a simple reactant and the N component is the novel amines or acids. 

Attempts66 to prepare the 2,3-anhydride from methyl 3-0-(methyl-sulfonyl)-/3-maltoside, using M sodium methoxide, resulted in the corresponding 3,6-anhydride 43. To circumvent the formation of 43, the reaction was performed with methyl 3-0-(methylsulfonyl)-6,6 -di-0-trityl-/3-maltoside. The desired product, methyl 2,3-anhydro-4-0-(2,3,4-tri-0-acetyl-6-0-trityl-a-D-glucopyranosyl)-6-0-trityl-/3-D-allopyrano-side (44), was obtained in 72% yield. Attempted detritylation of 44 by brief treatment with hydrogen bromide in glacial acetic acid, followed by conventional acetylation, gave methyl 2,6,2, 3, 4, 6 -hexa-0-acetyl-... 

Chloramphenicol, thiamphenicol, and florfenicol are broad-spectrum antibacterials with closely related chemical structures (Fig. 3.2). In thiamphenicol, the p-nitro group on the benzene ring of chloramphenicol is replaced with a methyl sulfonyl group. In florfenicol, the hydroxyl group on the side chain of thiamphenicol is replaced with a fluorine. They are all potent antibacterial agents acting... 

The corresponding methyl derivative 1 c is available in 90 % yield upon treatment of bis(methyl-sulfonyl)amine in acetonitrile with 10% fluorine in nitrogen.91... 

Miscellaneous compounds l-(3-Chloroallyl)-3,5,7-triaza-l-azoniaadamantane chloride 2,3,5,6-Tetrachloro-4-(methyl-sulfonyl)pyridine... 

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