108-98-5 Benzenethiol

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). 

Addition Reactions. The addition of nucleophiles to quinones is often an acid-catalyzed, Michael-type reductive process (7,43,44). The addition of benzenethiol to 1,4-benzoquinone (2) was studied by A. Michael for a better understanding of valence in organic chemistry (45). The presence of the reduced product thiophenyUiydroquinone (52), the cross-oxidation product 2-thiophenyl-1,4-benzoquinone [18232-03-6] (53), and multiple-addition products such as 2,5-(bis(thiophenyl)-l,4-benzoquinone [17058-53-6] (54) and 2,6-bis(thiophenyl)-l,4-benzoquinone [121194-11-4] (55), is typical ofmany such transformations. 

Benzyl chloride reacts with alkaH hydrogen sulfides, sulfides, and polysulfides to yield benzenethiol, dibenzyl sulfide, and dibenzyl polysulfide, respectively. With sodium cyanate it forms benzyl isocyanate (20). 

C6H6S BENZENETHIOL 114.974 9.1284E-02 6.0204E-05 147.61 290 C7H5N BENZONITRILE 217.638 1.3974E-01 1.5912E-05 260.87... 

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-... 

The experiments with 2-(3-butenyloxy)benzenediazonium ions (10.55, Z = 0, n = 2, R=H) and benzenethiolate showed a significant shift of the product ratio in favor of the uncyclized product 10.57. They also indicated that the covalent adduct Ar — N2 — SC6H5 is formed as an intermediate, which then undergoes homolytic dissociation to produce the aryl radical (Scheme 10-83). Following the bimolecular addition of the aryl radical to a thiolate ion (Scheme 10-84), the chain propagation reaction (Scheme 10-85) yielding the arylphenylsulfide is in competition with an alternative route leading to the uncyclized product 10.57. 

Bromo-2-(t-butylsulfonyl)propene (79) reacts with nucleophiles such as lithium benzenethiolate, lithium enolates and Grignard reagents to give a, /(-unsaturated sulfones, which undergo nucleophilic addition of lithium cuprates (equation 68)58. 

When benzenethiol is used as a quenching acid, and the resulting reaction mixture (containing 123 or 125) is added into another cuprate solution, a bis-addition product (124 or 126) can be obtained, as illustrated in equation 9781. 

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... 

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