Methylsulfinylmethide

Carbohydroxy-n-butyl)triphenylphosphonium bromide Sodium methylsulfinylmethide... 

Shemyakin and co-workers, investigating the synthesis of tetracycline antibiotics, found sodium methylsulfinylmethide more satisfactory than sodium hydride, sodium amide, or sodium dispersion for the cyclization of (3) to (4). 

Gardner and co-workers found sodium methylsulfinylmethide a very effective... 

Carey s procedure. The salt is trimethylsulfonium iodide (I), the base is a solution of sodium methylsulfinylmethide (2), prepared by heating a mixture of powdered sodium hydride (0.1 ra.) with excess DMSO with stirring under nitrogen at 75 ... 

Potassium methylsulfinylmethide evidently is the effective species in a tricarbon condensation of p-methoxybenzaldehyde with diphenylmethane and DMSO in the... 

Roberts and Whiting developed a method for effecting the anhydrous hydrolysis of esters and nitriles in DMSO. A solution of sodium methylsulfinylmethide is prepared from sodium hydride and DMSO and titrated with a solution of an appropriate amount of water in DMSO, using triphenylmethane as indicator. This produces a fine suspension of sodium hydroxide which hydrolyzes ethyl benzoate very rapidly at room temperature. As compared with reactions in hydroxylic solvents, rates are enhanced by a factor of 10 -10 . Benzonitrile is hydrolyzed to benzamide. Methyl and ethyl mesitoates are hydrolyzed readily at 25°. 

DMSO in the presence of potassium t-butoxide (potassium methylsulfinylmethide is formed) methylates diolefins and reactive aromatic hydrocarbons, for example "... 

Dimethyl sulfoxide-derived reagent (a). Sodium methylsulfinylmethide, now generally known as Dimsylsodium, [ ch3s(o )=ch2 <—> CH3(s=0)-C H2]Na+ [1, 311, after line... 

Sodium hydroxide, 158 Sodium hypobromite, 383-384 Sodium hypochlorite, 67 Sodium iodide, 166, 384, 461 Sodium isopropoxide, 385 Sodium-lead alloy, 385 Sodium methoxide, 223, 385-386, 418 Sodium 2-methyl-2-butoxide, 138, 386 Sodium methyl phosphorazidate, 386 Sodium methylsulfinylmethide, 130, 166-169, 284... 

ALKYNES Dimethyl sulfoxide-derived reagent (a). Sodium methylsulfinylmethide. 

X-Hydroxy-1 lot, 15triphenyl-phosphonium bromide in a dry nitrogen atmosphere in 6.0 ml dry dimethyl sulfoxide wasadded 3.24 ml (6.5 mmols) of a 2.0M solution of sodium methylsulfinylmethide in dimethyl sulfoxide. To this red ylide solution was added dropwise a solution of 613 mg (1.29 mmols) 2-[50 -hydroxy-30 -(tetrahydropyran-2-yloxy)-2/3-(30 -tetrahydropyran-2-yloxy-4-phenoxy-trans-1-buten-1-yl)cyclopent-10 -yll acetaldehyde, 7-hemiacetal in 5.0 ml dry dimethyl sulfoxide over a period of 20 minutes. 

It also appears possible to alkylate nitrobenzene with the displacement of hydride (or its equivalent) by the use of the anion obtained from deprotonation of methyl-sulfinylmethane (dimethyl sulfoxide [( 113)280]), viz. the methylsulfinylmethide anion (dimsyl anion [CH3SO(CH2) ]. Although the details are not known, the reaction is particularly useful because Friedel-Crafts alkylation of nitrobenzene usually fails. Indeed, the reaction of nitrobenzene with Lewis acids and alkyl (or acyl) halides is so poor that nitrobenzene has occasionally been used as a solvent for the reaction of other arenes with these substrates. It is argued that nitrobenzene is so unreactive because the nitro substituent withdraws electrons, making them unavailable for an incoming electrophile, that is, the ring is deactivated toward electrophilic substitution by the electron-withdrawing substituent. 

Scheme 6.95. A possible pathway for the alkylation of nitrobenzene by the methylsulfinylmethide anion [CH3(SO)CH2 j. Although only para- alkylation to produce 4-nitromethylbenzene (para-nitrotoluene) is shown, ortho- alkylation also occurs. A similar pathway can be written for the latter.

Obtained by reaction of ethyl 2,4-dihy-droxy-6-methyl-benzoate with sodium methylsulfinylmethide [5586] according to [5587]. 

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