31053-92-6

Upstream product

• 103-19-5 di(p-tolyl) disulfide 
• 3174-48-9 p-methylphenoxyl radical 
• 26330-85-8 4-Methyl-benzenethiol anion 
• 877669-19-7 3,7-bis-diethylamino-phenoxazine-10-carbothioic acid S-p-tolyl ester 
• 106-45-6 para-thiocresol 

Downstream Products

• 66729-86-0 C₇H₇S*C₄H₉NO 

Relevant academic research and scientific papers

Synthesis and radiation sensitivity of phenoxazine type color formers including thiol ester protective group

3,7-Bis(N,N-diethylamino)-10-(phenylthio)carbonylphenoxazine (1a) and its analogs (1b-f) were synthesized and the color change after γ irradiation was investigated. The color change of acetonitrile solutions of 1a ([1a] 0 = 1.0 × 10-3 M) after γ irradiation was identified by naked eyes at the dose of 20 Gy. Phenylthio-substituted compound la showed more significant absorbance increase than phenoxy-substituted compound, 3,7-bis(N,N-diethylamino)-10-phenoxycarbonylphenoxazine (2a). The C-S cleavage in la by γ irradiation was revealed to occur more easily than the C-O cleavage in 2a. The sensitivity of the color formers 1a-f) to γ rays was correlated with the stability of the thiyl radicals generated in the reaction.

Thiol radical cations and thiyl radicals as direct products of the free electron transfer from aromatic thiols to n-butyl chloride radical cations

Radical and ionic reactions were observed in the pulse radiolysis of thiophenols (ArSH = thiophenol, o-, m- and p-thiocresol or 2-thionaphthol) in n-butyl chloride solution. The main source of aromatic thiyl radicals is the reaction of butyl radicals with the thiols, which proceeds at 1.0-5.6 x 108 dm3 mol-1 s-1. This radical generation path is completely quenched in the presence of oxygen. Under these conditions, only the electron transfer reaction between n-butyl chloride parent ions and the thiophenols remains and could be well analyzed. It takes place at a rate constant of about 1.5 x 1010 dm3 mol-1 s-1 and takes two parallel paths-common electron transfer yielding thiophenol radical cations and a more complex ionic reaction resulting directly in thiyl radicals. The latter is thought to proceed via an encounter complex geometry, ArSH···ClBu.+, in which electron transfer is directly followed by immediate deprotonation. The thiyl radicals and the thiol radical cations are characterized by their optical absorption spectra and their kinetic properties. Quantum chemical calculations underpin our mechanistic interpretation and provide information about the charge distribution and reactivity of the thiol radical cations.

Reduction potentials and kinetics of electron transfer reactions of phenylthiyl radicals: Comparisons with phenoxyl radicals

The reduction potentials relative to the standard hydrogen electrode (SHE) for a number of para-substituted phenylthiyl radicals (Eo(p-XC6H4S./p-XC6H 4S-)) have been derived from pulse radiolytic studies of electron transfer equilibria which compare their values to those of radicals of known reduction potentials. A ladder combining the reduction potentials for both phenylthiyl and phenoxyl radicals has been established. These reduction potentials have been shown to be self-consistent and are intermediate between those of p-benzosemiquinone radical anion at 0.02 V and phenoxyl radical at 0.79 V. The reduction potential decreases as the electron donating power of the para substituent rises. The substituent effect is, however, much weaker for the phenylthiyl radicals than for their oxygen analogs. These observations demonstrate that the electronic interaction between the sulfur atoms and the aromatic ring system is much less than that which occurs with oxygen atoms. Examination of the rates of electron transfer in terms of the Marcus theory indicates that the reorganization energies of both p-XC6H4O. and p-XC6H4S. radicals are similarly affected by H, CH3, and CH3O substitution. However, the reorganization energies increase substantially for H2N and O- para substituents with the effect being much less for the p-XC6H4S. radicals than for the p-XC6H4O. radicals. These observations are in accord with structural information from spectroscopic and theoretical studies of the radicals which show that in the latter system the substituent groups interact strongly with the aromatic π system.

Substituent Effects on the Free-radical Addition Reactions of Arylthiyl Radicals with Arylacetylenes

Absolute rate constants for addition reactions of arylthiyl radicals (YC6H4S.) to arylacetylenes (XC6H4CCH) have been determined by a flash-photolysis method.The rate constants (in dm3 mol-1 s-1) vary from 1.

Kinetic Study for Spin-Trapping Reactions of Thiyl Radicals with Nitroso Compounds

The rate constants for the reactions of para-substituted benzenethiyl radicals with nitroso compounds have been determined by flash photolysis.For the benzenethiyl radical the rate constants (M-1 s-1) decreased in the order pentameth