Thio ... s. a. Alkylthio

Alkylthio, arylthio, and thioxo. The thioxo group in pyrimidine-2,4-dithione can be displaced by amines, ammonia, and amine acetates, and this amination is specific for the 4-position in pyrimidines and quinazolines. 2-Substitution fails even when a 5-substituent (cf. 134) sterically prevents reaction of a secondary amine at the 4-position. Acid hydrolysis of pyrimidine-2,4-dithione is selective at the 4-position. 2-Amination of 2-thiobarbituric acid and its /S-methyl derivative has been reported. Under more basic conditions, anionization of thioxo compounds decreases the reactivity 2-thiouracil is less reactive toward hot alkali than is the iS-methyl analog. Hydrazine has been reported to replace (95°, 6 hr, 65% 3deld) the 2-thioxo group in 5-hexyl-6-methyl-2-thiouracil. Ortho and para mercapto- or thio- azines are actually in the thione form. ... 

Allyl p-tolyl sulphoxide 535 reacts with sodium methoxide in methanol by initial prototropic isomerization and subsequent addition of methanol to give 536 (equation 333). Protic solvents are photochemically incorporated by the open chain olefinic bond of trans methyl )S-styryl sulphoxide 537 in a Markovnikov regiospecificity (equation 334). Mercaptanes and thiophenols add to vinyl sulphoxides in a similar manner (compare also Reference 604 and Section IV.B.3) to give fi-alkylthio(arylthio)ethyl sulphoxides 538 (equation 335). Addition of deuteriated thio-phenol (PhSD) to optically active p-tolyl vinyl sulphoxide is accompanied by a low asymmetric a-induction not exceeding 10% (equation 336) . Addition of amines to vinyl sulphoxides proceeds in the same way giving )S-aminoethyl sulphoxides in good to quantitative yields depending on the substituents at the vinyl moiety When optically active p-tolyl vinyl sulphoxides are used in this reaction, diastereoisomeric mixtures are always formed and asymmetric induction at the p- and a-carbon atoms is 80 20 (R = H, R = Me) and 1.8 1 (R = Me, R = H), respectively (equation 337) ... 

Nucleophilic replacement reactions (by AcS, Ph CO S , MeS , and PhCHaS") with methyl 0-toluene-p-sulphonyl-L-lactate and sodium L-2-chloropropionate give 2-acylthio- and 2-alkylthio-D-propionic acids and esters. Extensive racemization accompanies the use of excess thio-acetate or thiobenzoate, due to further 5 2 replacement reactions, as observed for LiAlH4 reduction of L-(2-methylthio)propionic acid or its methyl ester. Diborane reduction gives optically pure L-(2-methylthio)-propanol, however. This work includes a new synthesis of ( + )-2-mercaptopropionic acid, though by known methods, and establishes the D configuration for this isomer. 

Trifluoroacetic acid added with shaking during 5 min. to a soln. of 3-O-benzoyI-1,2 5,6-di-O-isopropylidene-a-D-glucofuranose in chloroform-ethanethiol, and stirred 3 days at room temp. -> ethyl 4-0-benzoyI-2,3,6"tri-S-ethyl-l,2,3,6-tetra-thio-a-D-mannopyranoside. Y 40%. - The alkylthio groups are first introduced at C-1 and then relayed as follows C-l- -C-2- C-3->-C-6. G. S. Bethell and R. J. Perrier, Soc. Perkin I 1973, 1400. 

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