- Interaction of 1,3λ4δ2,2,4-benzodithiadiazines with neutral and charged S-electrophiles: SCl2, C6F5SCl, and NS2+
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[Figure not available: see fulltext.] Reactions of 1,3λ4δ2,2,4-benzothiadiazines with SCl2, C6F5SCl, and [NS2][SbF6] leading to 1,2,3-benzodithiazolium salts (Herz salts) were in
- Makarov, Alexander Yu.,Bagryanskaya, Irina Yu.,Zhivonitko, Vladimir V.
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- Convenient Synthesis of Symmetrical Polyfluorinated Diphenyl Sulfides
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Abstract: Thermal properties of decafluorodiphenyl disulfide in the pure state and in the presence of copper and iron metals have been studied. A procedure has been proposed for the synthesis of symmetrical poly-fluorinated diaryl sulfides from diaryl dis
- Bredikhin, R. A.,Maksimov, A. M.,Nikul’shin, P. V.,Platonov, V. E.
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p. 1921 - 1930
(2022/01/24)
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- Copper(I) nitrosyls from reaction of copper(II) thiolates with S-nitrosothiols: Mechanism of NO release from RSNOs at Cu
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S-nitrosothiols (RSNOs) serve as ready sources of biological nitric oxide activity, especially in conjunction with copper centers. We report a novel pathway for the generation of NO within the coordination sphere of copper model complexes from reaction of copper(II) thiolates with S-nitrosothiols. Reaction of tris(pyrazolyl)borate copper(II) thiolates iPr2TpCu-SR (R = C 6F5 or CPh3) with tBuSNO leads to formation of iPr2TpCu(NO) and the unsymmetrical disulfide RS-S tBu. Quantum mechanical investigations with B3LYP-D3/6-311G(d) suggest formation of a κ1-N-RSNO adduct iPr2TpCu(SR) (R′SNO) that precedes release of RSSR′ to deliver iPr2TpCu(NO). This process is reversible; reaction of iPr2TpCu(NO) (but not iPr2TpCu(NCMe)) with C 6F5S-SC6F5 forms iPr2TpCu-SC6F5. Coupled with the facile, reversible reaction between iPr2TpCu(NO) and C6F 5SNO to give iPr2TpCu-SC6F5 and 2 equiv NO, we outline a new, detailed catalytic cycle for NO generation from RSNOs at Cu.
- Zhang, Shiyu,Celebi-Oelcuem, Nihan,Melzer, Marie M.,Houk,Warren, Timothy H.
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p. 16746 - 16749
(2013/12/04)
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- HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXVII. REACTIONS OF ALKANETHIONES WITH THE CHLORINE DERIVATIVES OF BENZENE, THIOPHENE, AND NAPHTHALENE
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Alkanethiols react effectively with chlorobenzene, its derivatives, 1-chloronaphthalene, and 2-chlorothiophene at 600-660 deg C with the preferential formation of the corresponding aromatic or heteroatomic thiols.Ethanethiol is most reactive.When it is used instead of hydrogen sulfide in reactions with chlorobenzene or its 4-substituted derivatives, the yield of the aromatic thiols, from which the phenylthiyl radicals are generated with greater difficulty, increases more sharply than the yield of the thiophenols, which generate the more stable 4-XC6H4S radicals.The side products of the reactions are the corresponding diaryl sulfides, thiophene, benzothiophene, and toluene.
- Voronkov, M. G.,Deryagina, E. N.,Sukhomazova, E. N.
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p. 755 - 760
(2007/10/02)
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- HIGH TEMPERATURE ORGANIC SYNTHESIS. XIX. MECHANISM OF HIGH-TEMPERATURE REACTION OF AROMATIC CHLORINE DERIVATIVES WITH HYDROGEN SULFIDE
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Quantum-chemical calculations were made in the CNDO/2 approximation for para-substituted chlorobenzene and thiophenol, and the x-ray fluorescence Kα and Kβ spectra of the sulfur in the latter were obtained.The electronic structure parameters of these compounds were compared with their reactivity in high-temperature processess.The reactivity of 4-substituted chlorobenzenes in reaction with hydrogen sulfide in the gas phase correlates with the electron density at the chlorine atom of the chlorine derivative.The direction of this process (the formationof the corresponding thiophenol or diaryl sulfide) is determined by the ability of the thiophenol formed at the first stage to generate sufficiently stable phenylthiyl radicals.The latter are stabilized by a mechanism of ?-conjugation, and the stability increases with increase in the ?-donating character of the para substituent in the aromatic ring. ?-Accepting substituents destabilize the phenylthiyl radicals, increasing the selectivity of the process leading to the production of the respective thiophenol.
- Voronkov, M. G.,Deryagina, E. N.,Dolenko, G. N.,Ivanova, G. M.,Sukhomazova, E. N.,et. al.
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p. 2095 - 2101
(2007/10/02)
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