Disulfides synthesis

Cogan, D. A. Liu, G. Kim, K. Backes, B. J. Ellman, J. A., Catalytic Asymmetric Oxidation of fert-Butyl Disulfide. Synthesis of tert-Butanesulfinamides, terf-Butyl Sulfoxides, and fert-Butane-sulfmimines / Am. Chem. Soc. 1998, 32, 8011. 

Hydrogen cyanide Carbon disulfide Synthesis gas (CO/H2) Chlorinated methanes Single cell protein... 

Liu, S.-G. Liu. H. Bandyopadhyay. K. Gao. Z. Echegoyen. L. Dithia-crown-annelated tetrathiafulvalene disulfides Synthesis, electrochemistry, self-assembled films, and metal ion recognition. J. Org. Chem. 2000,... 

Thiol and Disulfide Synthesis. Reaction of 2-tetrahydrofu-ranyl(thiomethyl)lithium with tert-butyldimethylchlorosilane, followed by n-BuLi and a second equivalent of t-butyldimethyl-chlorosilane followed by hydrolysis of the adduct with sil-ver(I) nitrate or mercury(II) chloride followed hy hydrogen sulfide or hydrogen chloride gives bis(f-butyldimethylsilyl)-methanethiol (t-BuMe2Si)2CHSH 91%) (eq 1). ... 

Yamazaki N, Tomioka T, Higashi F (1975) Trisubstituted ureas and thioureas from hexa-alkylphosphorous triamides, primary amines, and carbon dioxide or carbon disulfide. Synthesis 384—385... 

Su Y-Z, Niu Y-P, Xiao Y-Z et al (2004) Novel conducting polymer poly[bis(phenylamino) disulfide] synthesis, characterization, and properties. J Polym Sci, Part A Polym (Them 42 (10) 2329-2339... 

Trofimov, B.A., L.N. Sobenina, A.I. Mikhaleva et al. 2000. Reaction of pyrrole anions with carbon disulfide. Synthesis of pyrrole-3-carbodithioates. Tetrahedron 56 7325-7329. 

Enders D, Rembiak A, Liebich JX. Direct organocatalytic a-sulfenyaltion of aldehydes and ketones with tetramethylth-iuram disulfide. Synthesis 2011 281-286. 

Togo, H., Muraki, T., and Yokoyama, M., Preparation of adamantyl sulfides with [bis(l-adaman-tanecarboxy)iodo]arenes and disulfides. Synthesis, 115, 1995. 

Diallylsulfonium salts undergo intramolecular allylic rearrangement with strong bases to yield 1,5-dienes after reductive desulfurization. The straight-chain 1,5-dienes may be obtained by double sulfur extrusion with concomitant allylic rearrangements from diallyl disulfides. The first step is achieved with phosphines or phosphites, the second with benzyne. This procedure is especially suitable for the synthesis of acid sensitive olefins and has been used in oligoisoprene synthesis (G.M. Blackburn, 1969). 

The thiazole ring can be obtained directly by other methods, but they have limited application. An example is the synthesis of Cook and Heilbron using a-aminonitriles or a-aminoamides and carbon disulfide (or thioacid derivatives) as reactants of type II. 

This type of synthesis, which was investigated by Cook and Heilbron (323) and Takahashi (393, 394) between 1947 and 1953, gives 5-aminothiazoles variously substituted in the 2-position by reacting an aminonitrile with salts and esters of dithioacids, carbon disulfide, carbon oxysulfide, and isothiocyanates under exceptionally mild conditions. 

Although a variety of oxidizing agents are available for this transformation it occurs so readily that thiols are slowly converted to disulfides by the oxygen m the air Dithiols give cyclic disulfides by intramolecular sulfur-sulfur bond formation An example of a cyclic disulfide is the coenzyme a lipoic acid The last step m the laboratory synthesis of a lipoic acid IS an iron(III) catalyzed oxidation of the dithiol shown... 

Synthesis from Thiohydantoins. A modification (71) of the Bucherer-Bergs reaction consisting of treatment of an aldehyde or ketone with carbon disulfide, ammonium chloride, and sodium cyanide affords 2,4-dithiohydantoias (19). 4-Thiohydantoias (20) are available from reaction of amino nitriles with carbon disulfide (72). Compounds (19) and (20) can be transformed iato hydantoias. 

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

Nitromethane also is used in the synthesis of the antiulcer dmg, ranitidine [66357-35-5]. A two-step process utilizing nitromethane, carbon disulfide, potassium hydroxide, and dimethyl sulfate yields l,l-bis(methylthio)-2-nitroethene [13623-94 ] which reacts further to produce ranitidine. 

Phosphorothioates. All three synthetic approaches appHcable to unmodified oligonucleotides can be adapted for synthesis of phosphorothioates (11) (33,46). If all of the phosphodiester linkages in an oligonucleotide are to be replaced with phosphorothioates, the ff-phosphonate method for coupling, followed by oxidation with Sg in carbon disulfide and triethylamine in the final step, is the most straightforward method. 

The synthesis of poly(arylene sulfide)s via the thermolysis of bis(4-iodophenyl) disulfide has been reported (78). The process leads to the formation of PPS and elemental iodine. This process presumably occurs analogously to that reported by Eastman Chemical Company. 

Fluorinated and Ghlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The Hterature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl haHdes, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal haHde catalysts, such as... 

Cysteine [52-90 ] is a thiol-bearing amino acid which is readily isolated from the hydrolysis of protein. There ate only small amounts of cysteine and its disulfide, cystine, in living tissue (7). Glutathione [70-18-8] contains a mercaptomethyl group, HSCH2, and is a commonly found tripeptide in plants and animals. Coenzyme A [85-61-0] is another naturally occurring thiol that plays a central role in the synthesis and degradation of fatty acids. 

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