Sodium benzenethiolate

Operating with sodium benzenethiolate the only reaction observed is the thiophenoxydehalogenation, which is strongly favored by the activation performed by 5-nitro substituent, as previously reported (Scheme 15) (9). 

A -Phenyl-3//-azepin-2-amine (3), obtained in 25% yield by heating 2-methoxy-3//-azepine with aniline at 120 C for four hours,81 in refluxing ethanolic sodium benzenethiolate undergoes displacement of aniline and forms 2-(phenylsulfanyl)-3//-azepine (4).116... 

Cyano-de-diazoniations of the Sandmeyer type have been used for the synthesis of aromatic nitriles for many decades (example Clarke and Reed, 1964), as cyanide ions are comparable to bromide and iodide in many respects. A homolytic cyano-de-diazo-niation that does not use metal ions as reductant or ligand transfer reagent was described by Petrillo et al. (1987). They showed that substituted diazosulfides (XC6H4 — N2 — SC6H5), either isolated or generated in situ from arenediazonium tetrafluoroborates and sodium benzenethiolate, react with tetrabutylammonium cyanide in dimethylsulfoxide under photon stimulation, leading to nitriles (XC6H4CN). The method worked well with eleven benzenediazonium ions substituted in the 3- or 4-position, and was also used for the synthesis of phthalo-, isophthalo-, and tere-... 

Novi and coworkers124 have shown that the reaction of 2,3-bis(phenylsulfonyl)-l,4-dimethylbenzene with sodium benzenethiolate in dimethyl sulfoxide yields a mixture of substitution, cyclization and reduction products when subjected at room temperature to photostimulation by a sunlamp. These authors proposed a double chain mechanism (Scheme 17) to explain the observed products. This mechanism is supported by a set of carefully designed experiments125. The addition of PhSH, a good hydrogen atom donor, increases the percent of reduction products. When the substitution process can effectively compete with the two other processes, the increase in the relative yield of substitution (e.g., with five molar equivalents of benzenethiolate) parallels the decrease in those of both cyclization and reduction products. This suggests a common intermediate leading to the three different products. This intermediate could either be the radical anion formed by electron transfer to 2,3-bis(phenylsulfonyl)-l,4-dimethylbenzene or the a radical formed... 

Treatment of tetrahydroberberine (26) with sodium benzenethiolate (48) or -selenolate (49) in the presence of ruthenium catalyst afforded the C-14—N bond cleavage products 51 or 52 with a phenylthio or phenylseleno group at C-14 (Scheme 12). The latter was converted to the 10-membered amino olefin 53 on treatment with m-chloroperbenzoic acid. 

Scheme 4-21 shows the preparation of L-threitol and L-erythritol.38 Epoxy alcohols (2J ,3iS)-61 and (2S,3/ )-61. generated by asymmetric epoxidation, are exposed to sodium benzenethiolate and sodium hydroxide in a protonic solvent to undergo base-catalyzed rearrangement, yielding the threo-diol 62 and erythro-diol 63, which can then be converted to the corresponding tetraacetate of l-threitol 67 and L-erythritol 69 through subsequent transformations. 

Interaction of substituted arenediazonium salts with potassium O. O-diphenylphosphorodithioates gave a series of solid diazonium salts which decomposed explosively when heated dry [10], The unique failure of diazotised anthranilic acid solutions to produce any explosive sulfide derivatives under a variety of conditions has been investigated and discussed [6]. Preparation of diaryl sulfides from interaction of diazonium and thiophenoxide salts led to violent explosions, attributed to presence of some arenediazo sulfide during subsequent distillation of the diaryl sulfides. Precautions are detailed [11]. A safe method of preparation of diaryl sulfides from diazonium tetralluoroborates and sodium benzenethiolate in DMF is now available [12],... 

Methylbenzo[ ]thiophene is available through the interaction of sodium benzenethiolate and chloroacetone, followed by the cyclization of the initial product by the action of a Lewis acid, zinc chloride (Scheme 7.23c). 

A 100-ml., two-necked flask is fitted with a reflux condenser, a gas inlet, and a magnetic stirrer. The flask is charged with 12.0 ml. (15 1 g, 0 1 mole) of 1-bromo-2,2-dimethylpropane (Note 1), aqueous sodium benzenethiolate (0.1 mole) (Note 2), and 1.67 g (0 0033 mole) of tributylhexadecylphosphonium bromide (Notes 3 and 4) This mixture is heated at 70° with vigorous stirring under... 

Aqueous sodium benzenethiolate was prepared by adding 10.2 ml. (11.0 g., 0.1 mole) of commercial benzenethiol (listed as thiophenol by Aldrich Chemical Company, Inc. and Tridom Chemical Inc.) to an ice-cold solution of 4.0 g. of sodium hydroxide in 25 ml. of water. 

Conversely to their usual stability and chemical inertness, saturated perfluorocarbons can be susceptible to reductive defluorination in one-electron-transfer reactions. Thus, per-fluorodeeahydronaphthalene is converted by sodium benzenethiolate to octakisfphenylsul-fanyl)naphthalene, attacking first the weaker tertiary C — F bond (see Section 3.5.). Independent of the strong C — C bonds, in hydrocarbon-perfluorocarbon copolymers elimination of hydrogen fluoride takes place above 350 C. 

In contrast, reaction of allylic nitro compounds 4 with sodium benzenethiolate in HMPT leads to rearranged allylic sulfides 5.2... 

A comparison of the suitability of solvents for use in Srn 1 reactions was made in benzenoid systems46 and in heteroaromatic systems.47 The marked dependence of solvent effect on the nature of the aromatic substrate, the nucleophile, its counterion and the temperature at which the reaction is carried out, however, often make comparisons difficult. Bunnett and coworkers46 chose to study the reaction of iodoben-zene with potassium diethyl phosphite, sodium benzenethiolate, the potassium enolate of acetone, and lithium r-butylamide. From extensive data based on the reactions with K+ (EtO)2PO (an extremely reactive nucleophile in Srn 1 reactions and a relatively weak base) the solvents of choice (based on yields of diethyl phenylphosphonate, given in parentheses) were found to be liquid ammonia (96%), acetonitrile (94%), r-butyl alcohol (74%), DMSO (68%), DMF (63%), DME (56%) and DMA (53%). The powerful dipolar aprotic solvents HMPA (4%), sulfolane (20%) and NMP (10%) were found not to be suitable. A similar but more discriminating trend was found in reactions of iodobenzene with the other nucleophilic salts listed above.46 Nearly comparable suitability of liquid ammonia and DMSO have been found with other substrate/nucleophile combinations. For example, the reaction of p-iodotoluene with Ph2P (equation (14) gives 89% and 78% isolated yields (of the corresponding phosphine oxide) in liquid ammonia and DMSO respectively.4 ... 

Polak and Molenaar described a method for the determination of acetylcholine from brain tissue by pyrolysis-gas chromatography-mass spectrometry [200]. The deuterium-labeled acetyl-choline is pyrolytically demethylated with sodium benzenethiolate, followed by quantitative GC-MS analysis. In this method, care must be taken so that the samples do not contain appreciable amounts of choline since exchange of deuterium-labeled groups between acetylcholine and choline during pyrolysis may yield erroneous results. The same authors have also reported a method for the determination of acetylcholine by slow pyrolysis combined with mass fragment analysis on a packed capillary column [201]. 

Treatment of 4-methylphenylthiosulfonato phenyl tellurium with sodium benzenethiolate in methanol afforded phenyl phenylthio tellurium2. 

Hydrazine, lithium triethylborohydride, and sodium benzenethiolate produced the tellurium halides only in low yields3. 

A solution of 0.60 g of NaOH and 1.5 mL of C6H5SH dissolved in 20 mL of methanol saturated with nitrogen may be used in place of solid sodium benzenethiolate. However, the use of this solution has been found to result in a somewhat lower yield of the final product [Cr(CO), C(CH3)(SC6H5 ]. 

The procedure is identical with that given in Sec. C except for the replacement of [Cr(CO)5 C(CH3)(OCH3) ] by [W(CO)5 (C(CH3)(OCH3) ]. Solid sodium benzenethiolate may be replaced by a methanolic solution of Na[SC6H5] generated in situ by the reaction of sodium hydroxide with c6h5sh in methanol with no appreciable decrease in yield of the final product. Yield = 1.6 g (50%). Anal Calcd. for C13H805SW C, 33.88 H, 1.55. Found C, 33.93 H, 2.05. 

Secondary steric effects could become significant in aromatic nucleophilic substitution in activated halogenoben-zenes. This can be ascribed to steric inhibition of resonance. In contrast, secondary steric effects are not important in SNAr reactions of thiophene derivatives this is due to the geometry of five-membered ring derivatives, which strongly lowers the steric interactions between the substituents on the thiophene ring. This has been reconfirmed by kinetic data in methanol on SNAr reactions of the two pairs of substrates 210 and 211 with different nucleophiles (piperidine and sodium benzenethiolate) <1997J(P2)309>. 

A similar reaction with sodium benzenethiolate results in a-phenylthio ketones. Example ... 

Mloston et al. reported that the formation of seven-membered sulfur heterocycles 181 and 182 possibly appears to be the result of a domino reaction involving both the dithiirane 183 and its valence isomer, thiosulfine 184 <2002JOC5690>. Dithiirane 183 is presumed to exist in equilibrium with the thiosulfine 184 and is generated from the reaction of 185 with elemental sulfur in the presence of sodium benzenethiolate. 

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