Copper thiophenol

Copper (I) thiophenolate [1192-40-1] M 172.7, m ca 280°, pKj 6.62 (for PhS ). The Cu salt can be extracted from a thimble (Soxhlet) with boiling MeOH. It is a green-brown powder which gives a yellow-green soln in pyridine. Wash with EtOH and dry in a vacuum. It can be ppted from a pyridine soln by addition of H2O, collect ppte, wash with EtOH and dry in a vacuum. [Synthesis 662 1974, J Am Chem Soc 79 170 1957-, Chem Ber 90 425 1957.]... 

Benzenesulfonyl chloride, 4-methyl- [p-Tol-uenesulfonyl chloride], 55, 57, 59 Benzenethiol [Phenol, thio-], 55, 122 Benzenethiol, copper(I) salt [Thiophenol, copper(I) salt], 55, 123 Benzenethiol, lithium salt [Thiophenol, lithium salt], 55, 1 22 Benzoic acid, 2-amino- [Anthramlic acid], p bromination of, 55, 23... 

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. ... 

CENTRAL RING CONTAINING ONE HETEROATOM Reaction of 2-bromobenzoic acid (1) with chloroSulfonic acid proceeds to afford the sulfonyl chloride 2 treatment with dimethylamine leads to the corresponding sulfonamide (3). Condensation of bromoacid 3 with the anion from thiophenol in the presence of copper powder results in displacement of halogen by sulfur... 

The 1,6-addition reaction can also be conducted with catalytic amounts of copper however, very carefully controlled reaction conditions were required to minimize the competitive 1,2-addition reaction [122]. Using 3-5mol% of copper (2-dimethylamino-methy)thiophenolate (160) suspended in diethyl ether, simultaneous addition of the substrate 157 and an organolithium reagent 158 at 0 °C resulted in the formation of various substituted /i-allenylcarboxylatcs 159 (Scheme 3.82). The yields from the catalytic reactions were comparable to those from analogous stoichiometric procedures. 

It is not surprising that in attempted AICI3 catalysis of the reaction between thiophenol and various lactones, considerable amounts of thianthrene were obtained from a side reaction (81JOC5163). A low yield of thianthrene itself was obtained by converting o-bromobenzene thiol into its copper derivative (66JOC4071), but a good yield of thianthrene-2,3,7,8-tetracarboxylic acid 83 was observed from a hot reaction between 84 with cuprous oxide in DMF (82MI5). The saturated o-chlorobenzene thiols, 85... 

Bringing the complex formed between copper, tribenzylphosphine (PBz) and thiophenolate (SPh) in the solid state into contact with a gas containing... 

Iodothiophene was coupled with thiophenol in the presence of a copper-neocuproin catalyst to give 2-phenylthio-thiophene in excellent yield. (6.84.)114... 

Thionyl chloride, 55, 27 Thiophenol, 58, 144 Thiophenol, copper(I) salt, 55, 123 Thiophenol, lithium salt, 55, 122 Toluene, 56,86,58,125 Toluene, p-bromo-, 56, 86 Toluene, 4-bromo-, 55,49 Toluene, p-chloro-, 56, 86 Toluene, a-cyclohexyhdene-, 56, 105 Toluene, a (2 hydroxycyclohexyhdene)-, 56,105... 

A regio- and stereocontrolled copper catalyzed allylic alkylation has been recently reported [219]. With the thiophenolate copper catalyst 150, the Grignard-coupling reaction provided only the y-allylated product in quantitative yield, albeit with modest enantioselectivity (Eq. 8E.33). 

The ability to polymerize readily via selective oxidation utilizing the abundant and cheap oxidant 02 often represents a desirable low-cost method for upgrading the value of a raw material. The most successful example is the oxidative polymerization of 2,6-dimethylphenol to yield poly(2,6-dimethyl-l,4-phenylene ether) with copper-amine catalysts under an 02 atmosphere at room temperature. Thiophenol also has a labile hydrogen but is rapidly oxidized to yield thermodynamically stable diphenyl disulfide. This formation is based on the more facilitated formation of S—S bond through radical coupling [82] in comparison with the formation of C—S—C bond through the coupling with the other molecules in the para position (Eq. 9). 

Thiophenol Phosphoric acid Acetyl chloride Hydrogen chloride Chlorophosphate Hydrogen chloride Dicyclohexylcarbodiimide Copper iodide Diethyl chlorophosphate... 

Benzothiepines 69 have been synthesised by a gold-catalysed rearrangement of homopropargyl arylsulfoxides 68 <07JACS4160>. The dibenzothiepine 71 was synthesised by intramolecular Friedel-Crafts acylation of a diarylsulfide 70 which was formed by the copper mediated substitution of an appropriately substituted aryl derivative with thiophenol... 

The copper-catalyzed cross coupling reaction of thiophenol and aryl halide was also studied by ESl-MS. In this study, reported in 2011, three anionic complexes were assigned as key intermediates, Analysis of the same mixture by positive ion mode ESI revealed only the potassium adducts of thiophenol. An anionic... 

A variety of organophosphine transition-metal complexes have been used for the detection of SO2 [149]. Cook et al. used triphenyl- and tribenzyl phosphine compounds as ligands bound to Cu and Mn. Varying the ligand affects the Lewis acid strength of the metal complex, and hence, its ability to bind SO2. One complex (bis(tribenzylphosphine)copper(II) thiophenolate — [Cu(PBz3)2)SPh]) exhibited a reversible response to SO2 that was linear in the range of lO-KKK) mg/L. 

Arylboronic acids, (ArB(OH)2, react with thiols and copper(II) acetate to give the corresponding alkyl aryl sulfide. " Arylboronic acids also react with N-methylthiosuccinimide, with a copper catalyst, to give the aryl methyl sulfide. " " In the presence of a palladium catalyst, thiophenols react with diaryliodonium salts. 

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