1,7-Dithioxo Systems. Synthetic Routes to Bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) Sulfide

Synthetic routes to bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) sulfide have been studied. The title compound can be obtained by reaction of 3-chloro-5,5-dimethyl-2-cyclohexenethione with sodium thiosulfate and by condensation of 3-mercapto-5,5-dimethyl-2-cyclohexenethione. The reaction of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sulfide with hydrogen sulfide and hydrogen chloride yields 3-oxo-3'-thioxobis(5,5-dimethyl-1-cyclohexenyl) sulfide.     

Hydrolysis of Bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] Sulfide Diperchlorate

Hydrolysis of bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] sulfide diperchlorate, as well as of bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) sulfide, in the system MeCN-Et₃N yields a mixture of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sulfide and isomeric 5,5-dimethyl-3-oxo-1-cyclohexenyl 3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide. The structure of the products and their ratio were established by ¹H and ¹³C NMR and IR spectroscopy.     

1,7-Dithioxo systems. Reaction of bis(5,5-dimethyl-3-thioxo-cyclohex-1-en-1-yl) sulfide with amines

Reactions of amines (N,N-dimethylethane-1,2-diamine, benzylamine, aniline) with bis(5,5-dimethyl-3-thioxocyclohex-1-en-1-yl) sulfide result in cleavage of the sulfide bond and formation of the corresponding 3-amino-5,5-dimethylcyclohex-2-ene-1-thiones. Aminolysis of bis(5,5-dimethyl-3-oxocyclohex-1-en-1-yl) sulfide occurs at the carbonyl groups with conservation of the divinyl sulfide fragment.     

Gas-phase pyrolysis of bis(phenylthio) acetylene

Conclusions The main products of the gas-phase pyrolysis of bis(phenylthio)acetylene in either benzene or toluene at 560° are diphenyl sulfide, thiophenol, and acetylene. Benzothiophene and thianthrene are also formed here. The yield of diphenyl sulfide increases when bis (phenylthio)acetylene is copyrolyzed with chlorobenzene (580°).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.5, pp. 1188–1190, May, 1983.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

Useful and accessible organometallic precursors for preparation of zinc sulfide and indium sulfide thin films via solution pyrolysis (printing) method

Polycrystalline β-zinc sulfide thin films were prepared by solution pyrolysis of an ethylzinc isopropylthiolate–zinc bis(dibutyldithiocarbamate) combined precursor (EtZnSiPr–Zn(S₂CNnBu₂)₂) in chloroform solution on glass or silicon(111) substrates at 300°C. Homogeneous but amorphous indium sulfide thin films were obtained from butylindium bis(isopropylthiolate) (nBuInSiPr₂) in P-xylene on these substrates at 300°C similarly. The sulfide thin films obtained were characterized by means of X-ray photoelectron spectroscopy (XPS), X-ray fluorescence Microanalysis, scanning electron microscopy (SEM) and optical band gap measurements.     

Synthesis of 2-mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles

2-Mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles were synthesized by reduction of bis(3,3′-nitro-2,2′-thienyl) and bis(2,2′-nitrobenzo[b]thien-3,3′-yl) disulfides, respectively, with sodium hydrosulfite or sodium sulfide in the presence of carbon disulfide.     

Synthesis and some reactions of bis(triphenylstannyl)carbodiimide, N′-(triphenylstannyl)-N′-tritylcarbodiimide,and (triphenylstannyl)cyanamide

Some methods for preparing bis(triphenylstannyl)carbodiimide (I), N-(triphenylstannyl)-N′-tritylcarbodiimide (II), and (triphenylstannyl)cyanamide are described. (I) was found to react with 1,3-disubstituted thioureas in refluxing acetonitrile or toluene to give bis(triphenyltin) sulfide and the corresponding N,N′-disubstituted-N″-cyanoguanidine. Some evidence for a diorganocarbodiimide intermediate in this reaction was found. The reaction of(I) with thiourea in refluxing acetonitrile was found to give bis(triphenyltin) sulfide,(triphenylstannyl)cyanamide and unchanged thiourea. The reaction of (I) with cyanamide gave (triphenylstannyl)cyanamide. (Triphenylstannyl)cyanamide was found to react with bis(triphenyltin) oxide in refluxing acetonitrile to give (I). (Triphenylstannyl)cyanamide was found to disproportionate in refluxing benzene to give (I) and dicyandiamide. (II) was found to be more hydrolytically stable than (I). The SnN bonds in both (I) and (II) were found to be readily cleaved by acetic acid. It was found that triphenyltin iodide and triphenyltin chloride can be conveniently prepared in good yield by the reaction of bis(triphenyltin) oxide with either calcium iodide or calcium chloride in refiuxing acetonitrile.     

Gas-phase Reaction of 2-Chlorothiophene with Hydrogen Sulfide in the Presence of Alcohols

The effect of methanol and ethanol on the route of the gas-phase reaction of 2-chlorothiophene with hydrogen sulfide, leading to 2-thiophenethiol and to bis(2-thienyl) sulfide, has been investigated. It was found that methanol significantly enhances this reaction and increases its selectivity for the thiol at higher temperatures than without the initiator. The optimal conditions were achieved at 570°C in the presence of 10 mole % of methanol when the conversion of the 2-chlorothiophene in the reaction with hydrogen sulfide reaches 98% and the yield of the thiophenethiol (43%) exceeds that of the bis(2-thienyl)sulfide (31%). In the absence of methanol the 2-thiophenethiol is formed only at 510-540°C in just 17% yield, the basic reaction product being the indicated sulfide (52% yield); the conversion of the 2-chlorothiophene does not exceed 54%.     

Molecular addition compounds. 17. Borane and chloroborane adducts with organic sulfides for hydroboration

The following sulfides have been examined as borane carriers in comparison with dimethyl sulfide and 1,4-oxathiane: tert-butyl methyl sulfide, isoamyl methyl sulfide, ethyl isoamyl sulfide, tert-butyl isoamyl sulfide, diisoamyl sulfide, tetrahydrothiophene, tetrahydro-thiopyran, thioanisole, 3-ethylthiotetrahydrofuran, bis(3-tetrahydrofuryl) sulfide, and bis(2-methoxyethyl) sulfide. Their complexing ability toward borane increases in the following order: thioanisole < ether-sulfides < dialkyl sulfides < dimethyl sulfide. Borane adducts of the sulfides are liquids above 0 degrees C. The thioanisole adduct loses diborane at room temperature. The reactivity of the adducts toward 1-octene increases in the reversed order of the complexing ability of the sulfides. Diisoamyl sulfide has a mild, ethereal, agreeable aroma, its synthesis is economical and the borane adduct, 4.2 M in BH3, is stable over prolonged periods at room temperature. The sulfide can be recovered from hydroboration-oxidation products by distillation. Consequently, diisoamyl sulfide is a new promising borane carrier. Bis(2-methoxyethyl) sulfide, easily synthesized from the low cost thiodiethanol, is three times more soluble in water than 1,4-oxathiane. Its borane adduct is 6.0 M in BH3 and can substitute for more expensive borane-1,4-oxathiane in hydroboration reactions. Applications of these new borane adducts in the synthesis of mono- and dichloroborane adducts was also studied. The equilibrium ratios observed for the new chloroborane adducts were similar to that observed for dimethyl sulfide adducts. However, the hydroboration of 1-octene with these new chloroborane adducts are much faster than the corresponding adducts of dimethyl sulfide, which are currently used extensively.     

Preconcentration of gold,silver, palladium,platinum, and ruthenium with organophosphorus extractants

Extraction of noble metals in acid media with new tertiary phosphines and phosphine chalcogenides was examined. Tristyrylphosphine, tristyrylphosphine sulfide tris(2-phenylethyl)phosphine oxide, tris-(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)[2-(propylthio)ethyl]phosphine oxide, bis(2-phenylethyl)-[2-(butylthio)ethyl]phosphine oxide, and tris[2-(butylthio)ethyl]phosphine oxide were used as extractants. The suitability of the extractants for determination of Au, Ag, and Pd in rock and ore samples was elucidated.     

High refractive index materials: A structural property comparison of sulfide‐ and sulfoxide‐containing polyamides

High‐refractive‐index polyamides (PAs) are developed by incorporation of sulfide‐ or sulfoxide linkages and chlorine substituents. The PAs are synthesized through the polycondensation of two novel diamine monomers, 2,2′‐sulfide‐bis(4‐chloro‐1‐(4‐aminophenoxy) phenyl ether (3a) and 2,2′‐sulfoxide‐bis(4‐chloro‐1‐(4‐aminophenoxy) phenyl ether (3b), with various aromatic diacids (a–e). The ortho‐sulfide or sulfoxide units, pendant chlorine groups, and flexible ether linkages in the diamine monomers endowed the obtained PAs with excellent solubilities in organic solvents. The resulting PAs showed high thermal stability, with 10% weight loss temperatures exceeding 415 °C under nitrogen and 399 °C in air atmosphere. The combination of chlorine substituents, sulfide or sulfoxide linkages, and ortho‐catenated structures provided polymers with high transparency along with high refractive index values of up to 1.7401 at 632.8 nm and low birefringences (<0.0075). The structure–property relationships of the analogous PAs containing sulfide or sulfoxide linkages were also studied in detail by comparing the results. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2867–2877     

Structure and properties of bis{[2-(4-<Emphasis Type="Italic">tert</Emphasis>-butyl)phen]ethyl}phosphine sulfide

Previously unknown bis[2-(4-tert-butyl)phen]ethylphosphine sulfide is obtained with a high yield from 4-tert-butyl styrene, red phosphorus, and elemental sulfur. Using single crystal XRD, multinuclear NMR, IR, and UV spectroscopy, it is found that the phosphorus atom is four-coordinated in the bis[2-(4-tert-butyl)phen]ethylphosphine sulfide molecule (regardless of the phase state of the compound: crystal, solution). By the example of phosphorylation of bis[2-(4-tert-butyl)phen]ethylphosphine sulfide acetylene in the KOH-DMSO system it is shown that the reaction proceeds by double addition with the participation of phosphorus-centered nucleophiles.     

Allylic Sulfones Containing Triene Moieties as Key Synthons for Carotenoid Synthesis

An efficient synthetic method for the allylic sulfone 2 containing a conjugated triene moiety has been proposed involving i) coupling of allylic sulfones 4 with the C₅ bromoallylic sulfide 5 , ii) base‐promoted dehydrosulfonation in the presence of allylic sulfide, and iii) selective oxidation of the resulting trienyl sulfide to the corresponding sulfone. Total synthesis of lycopene starting from the C₁₅ allylic sulfone 2b has been described, where the new C₁₀ bis(chloroallylic) sulfone 11 proved to be a useful substitute for the C₁₀ bis(chloroallylic) sulfide 3 , which did not require the problematic chemoselective sulfur oxidation in a conjugated polyene.     

Synthesis of new electron-donor compounds: Bis(2-thia-1,3-propylenedithio)teterathiafulvalene and bis(2-oxo-1,3-propylenedithio)tetrathiafulvalene

1,3-Dithiole-2-thione derivatives, which are starting compounds for the synthesis of new electron donors of the tetrathiafulvalene class, viz., bis(2-thia-1,3-propylendithio)tetrathiafulvalene and bis(2-oxo-1,3-propylendithio)tetrathiafulvalene, were obtained by the reaction of bis(tetraalkylamonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)zincates with 1,3-dichlorodimethyl sulfide and 1,3- dibromoacetone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 471–474, April, 1990.     

Conformational mobility and intramolecular rearrangements of bis(3-thioxo-1-phenylpropenyl) sulfide

Possible intramolecular transformations of bis(3-thioxo-1-phenylpropenyl) sulfide were studied by the quantum-chemical semiempirical AM1 method. A group of the most stable, potentially spectroscopically discernible rotamers was distinguished. A possibility of intramolecular rearrangements giving thiirane structures was considered. The ability of bis(3-thioxo-1-phenylpropenyl) sulfide for spontaneous trimerization was evaluated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2255–2261, December, 1999.     

Generation of bis(pentafluorophenyl)borane-dimethyl sulfide complex as a solution of hexane and its application to hydroboration of alk-1-yne with pinacolborane

A solution of bis(pentafluorophenyl)borane-dimethyl sulfide complex in hexane was generated by redistribution between tris(pentafluorophenyl)borane and borane-dimethyl sulfide complex. In the resulting solution a stoichiometric hydroboration of alk-1-yne with pinacolborane proceeded well at room temperature to afford (E)-alk-1-enylboronic acid pinacol ester in high yield. Bis(pentafluorophenyl)borane-dimethyl sulfide complex served as a mediator for the hydroboration.     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

High-Temperature Synthesis of Thiophene from Bis(2-chloroethyl) Sulfide

Gas-phase reaction of bis(2-chloroethyl) sulfide (Yperite) with acetylene at 550–700°C leads to formation of thiophene in 45% yield, the conversion of the initial sulfide being complete. The yield of thiophene reaches 63–68% in the thermolysis of a mixture of acetylene, bis(2-chloroethyl) sulfide, and lower organic disulfides.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 910–912.Original Russian Text Copyright © 2005 by Voronkov, Levanova, Sukhomazova, Russavskaya, Deryagina, Korchevin.     

Chlorination of secondary phosphine chalcogenides with carbon tetrachloride in the absence of bases

The interaction of bis(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)phosphine selenide and bis[2-(2-phenyl)propyl]phosphine selenide with carbon tetrachloride under heating (80°C, 8–20 h) leads to the formation of the corresponding chlorophosphine chalcogenides with the yield of 80–90%.