Disulfide and derivatives

Di(tolyl) -disulfides or Dimethyl-diphenyl-disulfide and Derivatives... 

Carbon disulfide and derivs 2 C60-C61 carbon disulfide monoazide 2 C61 see Azidodithiocarbonic acid 1 A632... 

Halogenation of 2-aminothiazole and derivatives has been reported under a wide variety of experimental conditions in water (161, 405. 406) in aqueous acids (16. 172, 407, 408) in solvents such as chloroform (27. 172), carbon disulfide (162, 166. 320. 409). benzene (165), acetic acid (410-413, 1580). or hydrochloric acid (414) or in 20% sulfuric acid (415-417). 

Disulfides (136) are formed in good yields by oxidation of A-4-thiazoline-2-thiones (135) and derivatives in basic media Scheme 69 (7, 130, 146-151, 317-319). 

When benzaldehyde or its substituted derivatives are added to carbon disulfide and a-aminonitrile, the corresponding 2-mercapto-5-(p-R-benzylideneamino)thiazoles (215), R = hydrogen atom or a propenyl or phenyl group and Ar = aryl, are obtained (Scheme 112) (393, 442, 694). Yields ranged from 40 to 60% (Table II-34b). 

Chemical Properties The formation of salts with acids is the most characteristic reaction of amines. Since the amines are soluble in organic solvents and the salts are usually not soluble, acidic products can be conveniendy separated by the reaction with an amine, the unshared electron pair on the amine nitrogen acting as proton acceptor. Amines are good nucleophiles reactions of amines at the nitrogen atom have as a first step the formation of a bond with the unshared electron pair of nitrogen, eg, reactions with acid anhydrides, haUdes, and esters, with carbon dioxide or carbon disulfide, and with isocyanic or isothiocyanic acid derivatives. 

Similarly, carbon disulfide and propylene oxide reactions are cataly2ed by magnesium oxide to yield episulftdes (54), and by derivatives of diethyUiac to yield low molecular weight copolymers (55). Use of tertiary amines as catalysts under pressure produces propylene trithiocarbonate (56). 

For the most part, thiacyanocarbons are derived from "BAhr s Salt" [18820-77-4] (10), prepared from carbon disulfide and sodium cyanide (61) through the intermediacy of the sodium salt of carbonocyanidodithione acid [33498-03-2] C2NS2Na. 

Acetone Cyanohydrin. This cyanohydrin, also known as a-hydroxyisobutyronitnle and 2-methyUactonitrile [75-86-5], is very soluble in water, diethyl ether, and alcohol, but only slightly soluble in carbon disulfide or petroleum ether. Acetone cyanohydrin is the most important commercial cyanohydrin as it offers the principal commercial route to methacrylic acid and its derivatives, mainly methyl methacrylate [80-62-6] (see Methacrylic acid AND derivatives). The principal U.S. manufacturers are Rohm and Haas Co., Du Pont, CyRo Industries, and BP Chemicals. Production of acetone cyanohydrin in 1989 was 582,000 metric tons (30). 

The irradiation of the thiophene in gas phase yields ethylene, allene, methyl-acetylene, carbon disulfide, and vinylacetylene. No Dewar thiophene or cyclo-propene derivatives were isolated (69CJC2965). The irradiation in liquid phase gave the Dewar thiophene which can be trapped as a Diels-Alder adduct with furan (85JA723). The Dewar thiophene and cyclopropene-3-thiocarbaldehyde can be obtained by irradiation in argon matrices at 10 K (86JA1691). 

Hydrazine 835 underwent ring closure with one carbon cyclizing reagents to afford 837 and/or /V-acyl derivatives 836. The N-acyl derivatives underwent cyclization on treatment with phosphorus oxychloride. They were also prepared by the reaction of hydrazones 838 with thionyl chloride (84JHC1565). Compound 835 underwent ring closure with carbon disulfide and ethyl chloroformate to give 839 (Scheme 169). 

Nitrobenzenediazonium salts [25910-37-6] (ion) N III N+ Sodiiun disulfide, or Sodium poly sulfide See DIAZONIUM SULFIDES AND DERIVATIVES c6h4n3o2z... 

Amidines and amidoximes react with carbon disulfide and a mixture of carbon disulfide and sulfur to afford 5-mercapto-l,2,4-thiadiazole derivatives (see Section 5.08.9.3). 

Aryl-3-phenacylthio-l,2,4-triazoles 122 react with carbon disulfide and aryl isothiocyanates to give 5-aryl-3//-[l,2,4]triazolo[3,4-f][l,2,4]dithiazole-3-thiones and the 3-arylimino derivatives 123 (Equation 35) <1983ABC1017>. 

A Korean team published the synthesis of a mesoionic oxazolopyridazine derivative <1997H(45)2101>. These authors reacted the iV-aminopyridazine dione 345 with carbon disulfide and dicyclohexylcarbodiimide (DGC) to give the product 346 in high yield (70%). 

The l3C chemical shifts of methyl derivatives with sulfur substituents [e.g., SH, -S, -SCH3, -SSCH3, -SSSCHj, -S(0)CH3, -S02CH3, -S(CH3)2+, -SC(0)CH3, -SC(S)CH3, and -SC(S)SCH3] (130,131) and of vicinal and gem-inal bis-sulfides (290) have been reported. Freeman and co-workers have published similar studies on thiols, sulfides, disulfides, and sulfinic and sulfonic acid derivatives (131,132,433) and Tseng and Bowler (434), on thiocarbamates, their S-oxides and S,5-dioxides [R-X-C(0)-NR 2 with X = S, SO, S02]. 

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