Benzyl methyl disulfide

Benzyl 2-methylcrotonate Benzyl trans-2-methyl crotonate. See Benzyl tiglate Benzyl methyl disulfide. See Methyl benzyl disulfide... 

Synonyms Benzyl methyl disulfide Uses Synthetic flavoring agent in foods... 

Aminophenyl disulfide Cystine, 2-Nitrophenyl disulfide Methyl disulfide, p-tolyl disulfide Benzyl disulfide Naphthothiophenes (NTH)... 

In addition, manganese oxide oxidizes benzylic methyl or methylene to carbonyl [814] and cleaves the carbon bonds of vicinal diols [577, 522]. It converts amines into imines [577, 525] tertiary amines into secondary amines [572], formamides [526, 527, 525], or ketones aromatic primary amines [575, 525] and hydrazo compounds [525] into azo compounds hy-droxylamines into nitroso [576] or nitro compounds [525] hydrazones into diazo compounds [520] phosphines into phosphine oxides [575] thiols into disulfides [576] and sulfides into sulfoxides [541]. 

Water with aniline, benzene, benzyl alcohol, carbon disulfide, carbon tetrachloride, chloroform, cyclohexane, cyclohexanol, cyclohexanone, diethyl ether, ethyl acetate, isoamyl alcohol, methyl ethyl ketone, nitromethane, tributyl phosphate or toluene. 

Historically, this represents the first thiophene synthesis, when Laurent obtained tetraphenylthiophene by heating polymeric thiobenzaldehyde in 1844. Almost any aromatic methyl derivative can be converted to tetraphenylthiophene, which is thermodynamically the most stable thiophene, by heating with sulfur. Toluene, phenylacetic acid, benzyl alcohol, benzyl sulfide or disulfide, benzyl sulfonate or even sodium thiobenzoate have been converted to tetraphenylthiophene under these conditions (52HC(3)l). 

This reaction sequence was applied to 2-methyl-6-tert-butylphenol, and it was found that bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide can be produced in an over-all yield greater than 90% in pilot-plant scale reactions. Since the reaction mother liquor, after removal of the product, contains sodium dimethyldithiocarbamate, it can be recycled and neutralized, thus regenerating carbon disulfide and dimethylamine for reuse in preparing the intermediate. In essence, therefore, the over-all reaction consumes only 2,6-dialkylphenol, formaldehyde, and sodium sulfide. The scope of this reaction sequence was demonstrated by preparing bis (3,5-dialky 1-4-hydroxy benzyl) sulfides from a number of phenols ranging from 2,6-dimethylphenol to 2,6-di-ferf-butylphenol (20). 

Irradiation of a benzene solution of 5-phenyl Af-benzoylformyl-A-p-tolylthiocar-bamate 48a (Scheme 23) gave 5-phenyl-5-phenylthio-3-p-tolyloxazolidine-2,4-dione 49a in 61% yield accompanied by oxazolidine-2,4-dione dimer (15%), p-tolyl isocyanate (22%), and diphenyl disulfide [29]. Photolysis of 48a in the solid state gave oxazolidine-2,4-dione 49a in 96% yield. For the N-methyl derivative, 48b, compared to the solution photochemistry in which only 8% of oxazolidinedi-one 49b was obtained with a complex mixture, radical cyclization proceeds selectively to give oxazolidinedione in 75% yield in the solid state. Whereas N-p-tolyl and A-methyl derivatives, 48a and 48b, formed achiral crystals, the N-benzyl derivative 48c crystallized in chiral space group P2. Photolysis of the chiral... 

The 4-hydroxyl of 8,9-0-isopropylidene derivative 4b has been protected as its 4-t-butyl-dimethyl-silyl ether 4e. Then, the 7-hydroxyl has been converted to its xantate ester 4f, by deprotonation with butyl litium, treatment with carbon disulfide and alkylation with methyl iodide. Deoxygenatiobn of the 7-position has been accomplished by heating with tributyl-tin hydride in xylenes. Then, the cleavage of acetonide and of silyl ether, by heating in 80% acetic acid, followed by hydrogenolysis to remove the benzyl ester, afford 7-deoxy-Neu%Ac-ctMe Im. 

Ethoxymethylenamino- 2-methyl-1,2,3-triazole-5-carbonitrile (90) (also its 1-methyl and 3-benzyl analogs), when refluxed with ethanolic sodium hydrogen sulfide for 10 h, produced 8-methyl-, 7-methyl-, and 9-ben-zyl-8-azapurine-6-thione in 83 - 97% yields. 4-Amino-1,2,3-triazole-5-car-bonitrile and its 2-methyl and 9-benzyl derivatives were refluxed (2 h) with potassium 0-ethyldithiocarbonate in dimethylformamide (or alternatively with carbon disulfide in pyridine) to produce 8-azapurine-X6-dithione (or its respective alkyl derivatives) in 88-95% yields. ... 

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