4- Benzylthio

Aus a-Acylamino-thiocarbonsaure-amiden sind 4-Mercapto-imidazole zuganglich. Diese werden vorzugsweise nicht selbst isoliert, sondern in situ zu Bis-[4-imidazolyl]-disulfanen oxidiert oder zu 4-Benzylthio-imidazolen alkyliert308. 

Dinitrobenzenesulfenamide,(02N)2 CsH,.S.NH2 mw 215-24, N 19.50%. Yel crysts(from ethanol), mp 119.0-205°. Can be prepd by cleavage of 4--benzylthio-1,3-dinitrobenzene with chlorine. Its expl props were not detd... 

Figure 3 Bond lengths (pm) and bond angles for 4-benzylthio-3-iodo-1/-/-2-benzopyran.

Benzylthio-l,5-naphthyridine 1-oxide underwent oxidation to give 4-benzylsulfonyl-l,5-naphthyridine 1-oxide (4) (30% H202, AcOH, 20°C, 2 days 63%).814... 

Pyl et al. developed a two-stage synthesis of l-aminoimidazoline-2-thionesfrom 2-amino-4-benzylthio-l,3,4-thiadiazole(Eq. (16)] (63LA113). This method is somewhat similar to the previous one and has preparative importance because of good yields. 

On the other hand, the Birch reduction of 2-propylthiophen again led to regioselective ring-opening, giving 2,4-benzylthio-3-heptene in 72% yield. ... 

Methyl iodide, in the presence of NaOMe in abs. MeOH at room temperature, transforms 3,4-dihydro-1,2,3-benzotriazin-4-thione into 4-methoxy-l,2,3-benzotriazine 222 (64%) <1986J(P1)1249>. The same reagent at reflux temperature is reported to methylate thiones at sulfur, for example, to generate 4-methylthio-l,2,3-benzotriazine 227 (79%) <1971JHC785>. 4-Benzylthio-, 4-phenacylthio-, and 4-ethoxycarbonylmethylthio-l,2,3-benzotriazines have been prepared similarly <1971JHC785>. 

A soln. of 3-acetylamino-l-methyl-4-benzylthio-5-benzylthiomethyl-3-pyrrolin-2-one and diloranil in benzene refluxed 0.5 hr. 3-acetylamino-l-methyl-4-benzyl-thio-5-benzylthiomethylene-3-pyrrolin-2-one. Y 82%. F. e., also with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone, s. K. Hagio and N. Yoneda, Chem. Ind. 1974, 494 thiophenes from 2,5-dihydrothiophenes s. J. M. McIntosh and H. Khalil, Can. J. Chem. 53, 209 (1975) thioenol- from thio-ethers with sulfuryl chloride s. S. Iriudiijima et al., Agr. Biol. Chem. (Tokyo) 40, 1031 (1976). 

Ethyl orthoformate added with vigorous stirring to a suspension of 2,5-diamino-4-(benzylthio)-6-hydrazinopyrimidine in aq. HCl, and the product isolated after 3 hrs. 7-amino-5-(benzylthio)pyrimido[5,4-e]-a5-triazine. Y 76-85%. C. Temple, Jr., C. L. Kussner, and J. A. Montgomery, J. Org. Chem. 36, 3502 (1971). 

K-thiocyanate added at room temp, to a soln. of the startg. m. in anhydrous acetone, and stirred overnight > 5,5-diphenyl-4-benzylthio-3-oxazolin-2-thione. Y 90%. F. e. s. D. N. Harpp and P. Mathiaparanam, J. Org. Chem. 36, 2886 (1971). 

C19H23CI3O3S, (IS,5S)-6,6-Dimethyl-2-((2S)-3,3,3-trichloro-2-tosyl-oxypropyl)bicyclo[3.1.1]hept-2-ene, 44B, 178 Cl9H2nBrN03, 2-Bromo-3-methoxy-5-hydroxy-5,6,7,8,9,10,13,14-octahyd-ro-8-methyl-10,13-N-acetylaminomethano-phenanthrene, 39B, 148 Cl9H24S, 4-Benzylthio-2,6-dimethyl-endo-tricyclo[5.2,1,0 ]dec-3-ene, 45B, 186... 

Treatment of thiophene-3-carboxylic acid with five equivalents sodium in liquid ammonia and ethanol, and then benzyl bromide, produced a ring-opened product (Z)-4-benzylthio-2-methyl-3-butenoic acid in 51% yield. Similarly, the Birch... 

A hydroxyl functional group can also be tolerated thus, Birch reaction and alkylation of 2-(a-hydroxylbenzyl)thiophene-3-carboxylic acid resulted in the formation of the over-reduced product, (Z)-4-benzylthio-2-(2-phenylethyl)-3-butenoic acid, in 48% yield (Scheme 125) [140]. 

As depicted in Scheme 126, when substituted thien-3-ylacetic acid 124 was allowed to react with five equivalents of sodium in liquid ammonium in the presence of ethanol, to which three equivalents of ammonium chloride and benzyl bromide were added subsequently, 4-benzylthio-2,3-diethyl-3-hexenoic acid was obtained with a yield of 72%. In a similar manner, 4-benzylthio-3-ethyl-3-octenoic acid was obtained in 82% yield [140]. 

Dibenzyl dithiooxaldiimidate and p-nitrobenzaldehyde refluxed 1 hr. in benzene 5-amino-4-benzylthio-2-p-nitrophenyloxazole. Y 83%. F. e., also 5-alkylidene-amino analogs, s. A. R. Martin and R. Ketcham, J. Org. Chem. 31, 3612 (1966). 

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