Bis-thiophenols

Recently, a poly(heteroarylene sulfide) formed by the reaction between bis(thiophenols) and bis(6-chlorophe-nyl quinoxalines) has been reported by Hedrick et al. [58]. 

Practically all the above considered reactions for the synthesis of bisfethernaphthalic anhydrides) were employed for preparing bis- thio-ethernaphthalic anhydrides) [92, 93, 107-110] bis-thiophenolates were used instead of alkali metals bis-phenolates ... 

LiCeH4SLi. With dichlorosilanes or dichlorodisilanes, various bis(thiophenols) could be prepared. These thiophenols are useful as hindered ligands. Through reaction of 2-LiCeH4SLi with trichlorosUane, a novel cyclophane silane was prepared. ... 

The enhancement of the electrophilic properties of thaHium(III) ttifluoroacetate makes it a very important thaHation reagent. The products of thaHation, eg, arylthaHium bis(ttifluoracetate), undergo a variety of substitution reactions, yielding iodides, fluorides, nitriles, thiophenols, phenols, and biaryls. 

Acridin wird durch Thiophenol oder Thiokresol zu9,9 -Bi-acridanyl (70% d.Th.) redu-ziert1 ... 

Part C of the present procedure illustrates a mild method for effecting the elimination of thiophenol from thioacetals and thioketals under essentially neutral conditions. The reaction of simple thioacetals and thioketals with bis[copper(I) trifluoro-methanesulfonate] benzene complex in benzene-tetrahydrofuran at room temperature affords vinyl sulfides in high yield (Table I). The reaction presumably occurs by coordination of the thiophilic copper(I) reagent with sulfur, heterolysis to a phenylthio-stabilized... 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

Thiophenol Benzenethiol (8, 9) (108-98-5) 4,4-Bis(phenylthio)-3-methoxy-l-butene Benzene, 1, T-[(2-meth-oxy-3-butenylidene)bis(thio)]bis- (9) (60466-65-1)... 

The bi- and tridentate phosphines dppp (l,3-bis(diphenylphosphino)propane) and dppep (bis (2-diphenylphosphinoethyl)phenylphosphine) have been complexed with Co and their divalent four- and five-coordinated thiophenolate complexes Co(dppp)(SPh)2 and Co(dppep)(SPh)2 have been isolated and structurally characterized.379 Somewhat related to dppp is the bidentate silane Ph2PCH2SiMe2CH2PPh2, which forms high-spin, pseudo-tetrahedral dihalocobalt(II) complexes.380... 

For a liver alcohol dehydrogenase (LADH) model an NS2O coordination sphere is required. The chelating aldehydes are ideal for the formation of this donor set when combined with bis(pentafluoro-thiophenolato)zinc. Structural data on the complexes with one equivalent of 6-methylpyridine-2-carbaldehyde, 6-methoxypyridine-2-carbaldehyde, 2-(dimethylamino)benzal-dehyde) demonstrate that the coordination sphere for LADH has been reproduced to a close approximation and the corresponding alcohol complexes have also been characterized.354 Other thiophenols have been used to form such complexes but have not been structurally characterized.304... 

Dining preparation of thiophenol by addition of a cold solution of potassium O-methyldithiocarbonate to a cold solution of benzenediazonium chloride, a violent explosion accompanied by an orange flash occurred [1], This was attributed to the formation and decomposition of bis(benzenediazo) disulfide. A preparation in which the diazonium solution was added to the xanthate solution proceeded smoothly [2],... 

The oxidative properties of ditelluronium and diselenonium dications are similar to S-S dications. For instance, interaction of thiophenol or 1,2-diphenylhydrazine with either the diselenonium dication 113 or the ditelluronium dication 114 leads to almost quantitative formation of diphenyldisulfide or azobenzene and reduced bis-chalcogenides.113,114,124 Reduction of 113 and 114 with NaBH4 gives the same products as above but proceeds quantitatively via direct electron transfer (Scheme 47).128... 

Homolytic hydrostannation can also be initiated at room temperature by thiophenols, when a trace of oxygen may oxidize the thiol to the ArS radical, which abstracts hydrogen from the stannane to give the stannyl radical (Equation (15)).93 With azoisobutyronitrile (AIBN) initiation, alkynes undergo only monohydrostannation, but with the thiol, simple alkynes show bis(hydrostannation) or bis(stannation). 

Bis-acyl sulphides are obtained in only low yield by the standard reaction of sodium sulphide with an acyl chloride, but the addition of Adogen results in their viable synthesis with yields >70%. Examples using quaternary phosphonium salts provide the optimum yields (> 90%) [63]. Similarly, thiophenols have been benzoylated using benzoyl chloride under basic conditions in the presence of ammonium salts [12]. 

Phenylthioacetylene has been prepared by elimination of thiophenol and dehydrobromination of cis-1,2-bis(phenylthio)ethylene5 and cis-1-bromo-2-phenylthioethylene,2 7 respectively. The latter was obtained by addition of thiophenol to propiolic acid in ethanol and subsequent one-pot bromine addition, decarboxylative dehalogenation, and careful distillation to remove the trans isomer.2.7 on the other hand, cis-1,2-bis(phenylthio)ethylene was prepared by double addition of thiophenol to cis-1,2-dichloroethylene.5a d Although these procedures can provide useful amounts of phenylthioacetylene, they were found to be somewhat less satisfactory in our hands as far as operation and/or overall yields are concerned. Furthermore, we have encountered problems with regard to the reproducibility of one-pot dehydrobrominations of phenylthio-1,2-dibromoethane.6 However, the stepwise execution of the double dehydrobromination, as described in the modified procedure reported here, provides preparatively useful quantities of phenylthioacetylene in a practical manner. 

It is not surprising that chloro esters 1, 2 readily add thiols, catalyzed by sodium thiolates or triethylamine, to give the corresponding 2-(r-organylthiocy-clopropyl)-2-chloroacetates 85,86 (Scheme 22) [15 b, 22b, 27]. This reaction with thiophenol has been used to quantify the Michael reactivity of 1-Me, 2-Me, 3-X in comparison to simple acrylates (see above). With an excess of PhSH, the nucleophilic substitution of the chlorine in 85 a (but not in 85h) proceeded to give the corresponding bis(phenylthio) derivative in 63% yield [15bj. Alkali thiolates (e.g. NaSMe, NaSBn) add smoothly onto 1-Me, 2c-Me and 2p-Me at - 78 °C, because at this temperature subsequent nucleophilic substitution of the chlorine is much slower [7l, 9]. The Michael additions of sodium phenylselenide and sodium arylsulfenates onto 1-Me and their synthetic utility have been discussed above (see Table 1). 

Macrocyclic ligands of biological importance as thiophenolate-containing Schiff-base macrocycles and their amine analogs (see review [138]) and new helical complexes with bis(bidentate) SchifF-base ligand [139] were also described. 

Kita has introduced a novel one-pot preparation of 5-methoxylated indoline 55 and indole 56 derivatives by intermolecular addition followed by cyclization between A-tosylaniline derivatives 53 and activated olefins 54 using phenyliodine(III) bis(trifluoroacetate) (FIFA) <99H511785>. In the reaction of 53 with phenyl vinyl sulfides, indoles were produced directly by the spontaneous elimination of thiophenol. 

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