Methyl thiobenzoate

Methyl thiobenzoate Benzoic acid, thio-, S-methyl ester (8) Ben-zenecarbothioic acid, S-methyl ester (9), (5925-68-8)... 

Although electrophilic carbenes react with the sulfur atom of CS double bonds, dimethoxycarbene reacts at the carbon atom.10 A review commentary covers the limited range of literature available covering 2,2,4,4-tetramethyl-l,3-cyclobutanedithione, diarylthiones, o-methyl thiobenzoate, methyl dithiobenzoate, and dimethyl xanthate. 

MIDETRIETHYLAMINE, 58, 122 Methyl thiobenzoate, 58, 41,43 Methyl vinyl ketone, 58, 162, 163, 164, 167 Moffat oxidation, 56, 99 Monochloroborane diethyletherate, 58,... 

Monotbio-j -diketones. Acetophenone added slowly with stirring to a suspension of NaNHg in ether, after 15 min. an ethereal soln. of 0-methyl thiobenzoate added, stirred 3 hrs., and allowed to stand overnight monothiodibenzoyl-methane. Y 68%. E. Uhlemann and H. Muller, Ang. Gh. 77, 172 (1965) with Li, also from dithiocarboxylic acid esters, and f. method, s. E. Uhlemann and H. Muller, J. pr. 30, 163 (1965). 

CuHigBrNOS 4-Athoxy-3-methyl-thiobenzoe saure-[3-brom-anilid] 12, 635. 

Benzoyl methyl dithiolcarbonate heated at 80-90° with COS-evolution methyl thiobenzoate. Y 94%. F. e., also from acyl trithiocarbonates, s. H. Yoshida, T. Ogata, and S. Inokawa, Bull. Chem. Soc. Japan 44, 1949 (1971). 

C9H10OS 4-methyl-thiobenzoic acid O-methyl ester 5977-80-0... 

C10H12OS 4-methyl-thiobenzoic acid O-ethyl ester 26028-04-6... 

C11H14OS 4-methyl-thiobenzoic acid O-isopropyl ester 83078-40-4... 

A water-cooled mixture of allylbenzene and O-methyl thiobenzoate irradiated 10 days with a 400 w. high-pressure Hg-lamp under CO in a sealed Pyrex vessel, evaporated under reduced pressure, and the residue diromatographed on silica-gel with -hexane as eluent phenethyl phenyl ketone. Y ca. 100%. - An allylic methylene group is necessary for the reaction. F. e. s. A. Ohno, T. Koizumi, and Y. Akazaki, Tetrah. Let. 7972, 4993. 

Protected 3-methyl-D-cystein (257 Scheme 3.94), a structural unit of the peptide antibiotics nisin and subtilin, has been synthesized through the ring-opening of the aziridinecarbamide 254 with thiobenzoic acid (255) [143, 144]. The reaction took place overnight at room temperature and in methylene chloride to give 256 in greater than 95% yield. 

Potassium 4-chloro-3,5-dinitrobenzene-sulfonate, 31, 46 Potassium cyanate, 31, 9 Potassium cyanide, 30,84 32,31,63 37,47 Potassium ethyl malonate, 37, 34 Potassium ethyl xanthate, 30, 56 Potassium fluoride, 36, 40 Potassium iodide, 30, 34 31, 31, 66 Potassium metal, 37, 29, 30 Potassium methyl sulfate, 31, 73 Potassium nitrate, 31, 46 Potassium 1-nitropropylnitronate, 37, 24 Potassium oxalate, 34, 83 Potassium permanganate, 30, 87 31, 59 Potassium sulfide, 32, 103 Potassium thiobenzoate, 32, 101 Potassium thiocyanate, 32, 39, 40 Prins reaction, 33, 72 Propane, 1, 3-dibromo-2, 2-Ws-(bromo-methyl)-, 31, 82... 

Displacement reactions on methyl 6-deoxy-2,3-0-isopropylidene-a-D-(L)-mannopyranoside 4-sulphonates with ionic nucleopliiles such as acetate benzoate azide and thiobenzoate > take place... 

The synthesis of four out of eight possible stereoisomers of 3-methyllanthionine [(25,35,67 ), (25,37 ,67 ), (25,35,65), (25,37 ,65)] has been achieved using the reaction of Z-protected 3-methyl-D-cysteine with d- or L-3-chloroalanine in yields of 35—53% J64 The methyl-D-cys-teine stereoisomers were obtained by two routes. Firstly from (25,35)-threonine via O-tosylation and subsequent inversion of configuration by nucleophilic attack with thiobenzoic acid. The resulting derivative was debenzoylated and oxidized to the respective cystine derivative prior to the reduction with Zn/HCl to give the eryt/u-o-3-methyl-D-cysteine... 

These include thiobenzoates, thiocarbonylimidazolides, and phenyl thionocarbonate esters.6 The S-methyl xanthate ester is a particularly convenient intermediate to prepare because of its ease of formation and the low cost of the reagents. Its use is precluded, however, by the presence of base-labile protecting groups and, in such cases, the thiocarbonylimidazolide or phenyl thionocarbonate ester will generally prove satisfactory. Additional methods for the radical deoxygenation of alcohols are described in a review by Hartwig.7... 

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). 

In a similar way, the reaction of xanthates under radical conditions leads to products and selectivities that are totally different from those in thermal rearrangements. The radical transformation usually furnishes unsubstituted hydrocarbons as reaction products. The major accomplishment of the reaction is the deoxygenation of secondary alcohols to furnish the corresponding hydrocarbons when tributylstannane is used with 0-cycloalkyl thiobenzoates or S-methyl dithiocarbamates [13]. However, the rearranged product may be observed as a byproduct [14,15]. 

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