Methyl 4-tolyl sulfide

In accord with their character as salts, these products are soluble in water but insoluble in ether. The reaction is general in the aliphatic series, but aromatic sulfides behave differently for instance, methyl tolyl sulfide is methylated to the sulfonium salt by dimethyl sulfate but not by methyl iodide.307,308 Alcohol, acetone, benzene, or nitromethane is often used as solvent. Reaction of sufficiently reactive components occurs at room temperature. Formation of sulfonium salts is often appreciably increased by adding an equivalent amount of a metal salt 309... 

Methyl -tolyl sulfone has been prepared by oxidation of methyl -tolyl sulfide with hydrogen peroxide or ruthenium tetroxide, by alkylation of sodium -toluenesulfinate with methyl iodide or with methyl potassium sulfate, by decarboxylation of -tolylsulfonylacetic acid, by thermal decomposition of tetramethylammonium -toluenesulfinate, " by reaction of cw-bis-(j >-tolylsulfonyl)-ethene with sodium hydroxide (low yield), by the reaction of methanesulfonyl chloride with toluene in the presence of aluminum chloride (mixture of isomers)by... 

A graphite electrode modified chemically with L-phenylalanine gave an ee of 9.7% in the reduction of phenylglyoxalic acid into mandelic acid and an ee of 2.5% in the oxidation of methyl / -tolyl sulfide into its sulfoxide Later this oxidation reaction was improved... 

Oxidation. Huoromethyl /7-tolyl sulfide, which can be oxidized to fluoromethyl /7-tolyl sulfoxide with (V-bromo-succinimide in methanol, is synthesized by the reaction of chloromethyl />-tolyl sulfide with potassium fluoride in the presence of 18-crown-6 (eq 11). Chloromethyl />-tolyl sulfoxide can be S3mthesized by a one-pot operation from methyl />-tolyl sulfide with silver(I) nitrate and sulfuryl chloride via the intermediacy of chloromethyl p-tolyl sulfide (eq 12). ... 

More recently, Bolm and coworkers extended their original work on the Schiff-base ligands to iron-catalyzed reactions [5, 32]. With the use of ligand (S)-14 they obtained high ee in the oxidation of various sulfides. In the original report the yields of sulfoxide were moderate (up to 44%), and sulfoxides could be obtained in up to 90% ee. The reaction was later improved by the addition of additives, and with benzoic acid as additive methyl tolyl sulfide was oxidized to the (S)-sulfoxide in 78% yield and 92% ee [32b]. The highest ee obtained with the improved procedure was 96%, but then the yield was more moderate. 

Imamoto and Koto131 prepared some interesting chiral oxidants (104) by the reaction of iodosyl benzene with tartaric anhydride. Methyl p-tolyl sulfide (105) was oxidized by 104c to the sulfoxide in 80% yield with 40% e.e. Methyl p-tolyl, o-tolyl and o-anisyl sulfides (105-107) were oxidized by 104a to their sulfoxides with the enantiomeric purities shown. 

Komori and Nonaka132,133 electrochemically oxidized methyl, isopropyl, n-butyl, isobutyl, r-butyl and cyclohexyl phenyl sulfides (108) and cyclohexyl p-tolyl sulfide (109) to their sulfoxides using a variety of polyamino acid-coated electrodes to obtain the range of e.e. values shown in parentheses. The highest enantiomeric purities were obtained using an electrode doubly coated with polypyrrole and poly(L-valine), an electrode which also proved the most durable of those prepared. 

SCH2COOEt) ° and with methyl methylsulfinylmethyl sulfide (MeSCH2SOMe) or methylthiomethyl p-tolyl sulfone (MeSCH2S02C6H4Me) (to give ArCH2-SMe), in each case with a Lewis acid catalyst. 

Of several procedures for the stereoselective oxidation of sulfides using organometallic complexes, two adaptations of Kagan s original process have gained prominence. In the first method the diol (36) is reacted with Ti(0 Pr)4 to form the catalyst. With cumyl hydroperoxide as the stoichiometric oxidant, methyl para-tolyl sulfide was converted into the optically active sulfoxide in 42 % yield (98 % ee)[109]. 

Structural information on aromatic donor molecule binding was obtained initially by using H NMR relaxation measurements to give distances from the heme iron atom to protons of the bound molecule. For example, indole-3-propionic acid, a structural homologue of the plant hormone indole-3-acetic acid, was found to bind approximately 9-10 A from the heme iron atom and at a particular angle to the heme plane (234). The disadvantage of this method is that the orientation with respect to the polypeptide chain cannot be defined. Other donor molecules examined include 4-methylphenol (p-cresol) (235), 3-hydroxyphenol (resorcinol), 2-methoxy-4-methylphenol and benzhydroxamic acid (236), methyl 2-pyridyl sulfide and methylp-tolyl sulfide (237), and L-tyrosine and D-tyrosine (238). Distance constraints of between 8.4 and 12.0 A have been reported (235-238). Aromatic donor proton to heme iron distances of 6 A reported earlier for aminotriazole and 3-hydroxyphenol (resorcinol) are too short because of an inappropriate estimate of the molecular correlation time (239), a parameter required for the calculations. Distance information for a series of aromatic phenols and amines bound to Mn(III)-substituted HRP C has been published (240). 

The crude product (10 g) is diluted with 4 mL of a solvent mixture (ethyl acetate/cyclohexane = 9 1). This solution is poured onto a column (75-mm diameter) filled with 120 g of silica gel (Merck 230-400 mesh) for flash chromatography. Elution is performed under gravity and requires 200 mL of the above solvent system, followed by 200 mL of ethyl acetate. 2-Phenyl-2-propanol mixed with methyl p-tolyl sulfide is eluted in the first fraction ( 150 mL, monitored by TLC). The subsequent fractions are collected ( 300 mL)... 

Methyl p-tolyl sulfide, available from Aldrich Chemical Company, Inc., was distilled (bp 95°C, 18 mm) before use. 

Methyl p-tolyl sulfide Sulfide, methyl p-tolyl (8) Benzene, l-raethyl-4-(methylthio)- (9) (623-13-2)... 

Methyl-p-tolyl sulfide Methyl-p-tolyl sulfone S [99]... 

Little work has been done in this area with Ru catalysts. CM-A-[Ru(0)(py)(bpy)3] V water-CH3CN was used for the stoicheiometric oxidation of methyl-p-tolyl sulfide to (R)-methyl-p-tolyl sulfoxide with an e.e. of ca 15% [121],... 

Enantioselective Oxidation of Sulfides Synthesis of (-)-(S)-Methyl -Tolyl Sulfoxide... 

In 1997, Chmielewski and coworkers investigated the oxidation of methyl phenyl sulfide and methyl p-tolyl sulfide with chiral carbohydrate hydroperoxides, which have been... 

In Studying asymmetric oxidation of methyl p-tolyl sulfide, employing Ti(OPr-/)4 as catalyst and optically active alkyl hydroperoxides as oxidants, Adam and coworkers collected experimental evidence on the occurrence of the coordination of the sulfoxide to the metal center. Therefore, also in this case the incursion of the nucleophilic oxygen transfer as a mechanism can be invoked. The authors also used thianthrene 5-oxide as a mechanistic probe to prove the nucleophilic character of the oxidant. 

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