- Rapid and effective synthesis of diarylsulfur diimides from substituted anilines and sulfur monochloride
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A one-pot and effective procedure has been developed for the synthesis of symmetrical diarylsulfur diimides from anilines, sulfur monochloride, and DABCO in good yields (70-90%). A plausible mechanism for this transformation has been proposed. Georg Thiem
- Konstantinova, Lidia S.,Lysov, Kirill A.,Rakitin, Oleg A.
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supporting information
p. 655 - 658
(2013/04/10)
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- SOME KINETIC ASPECTS OF THE ALCOHOLYSIS OF N,N'-DIARYLSULPHURDIIMIDES
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Kinetic determinations (at 22 deg C) show that the ethanolysis of N,N'-diarylsulphurdiimides 1 - 9, catalysed by anhydrous copper(II) chloride, obeys a first-order rate law with respect to N,N'-diarylsulphurdiimide.The logarithm of the observed first-order rate constants (at the same concentration of the catalyst) can be correlated with the Hammett ? substituent constants.The ethanolysis rate of 1 - 9 is increased by the electron-withdrawing effect of the substituents linked to the aromatic rings of N,N'-diarylsulphurdiimide.The observed first-order rate constant of the CuCl2-catalysed ethanolysis of N,N'-bis(p-tolyl)sulphurdiimide, 3, is directly proportional to the catalyst concentration: kobs = k2.The second-order rate constants, k2, of the alcoholysis of 3 were measured in four alcohols different from ethanol.These constants seem to be a function of the polarity of the reaction medium and of the steric hindrance of the alcohol.Finally, it was ascertained that the catalysing power of CuCl2 in the ethanolysis of 3 is higher than that of NiCl2 and CoCl2.
- Carpanelli, Corrado,Gaiani, Giovanni
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p. 503 - 506
(2007/10/02)
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- One-electron Reduction of Di-imidosulphur Compounds, S(NR)2, and some Complexes of Group 6A Metal Carbonyl Derivatives containing S(NR)2 Ligands: Studies of the Radical Products by Electron Spin Resonance Spectroscopy
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Reduction of the di-imidosulphur compounds, S(NR)2 (R=But, Ph, 4-MeC6H4, or 4-O2NC6H4), in 1,2-dimethoxyethane solution with a potassium mirror in vacuo gives fairly stable solutions of the corresponding anion radicals - which have been studied by e.s.r. spectroscopy.The frozen-solution e.s.r. spectrum of Kt)2> has also been recorded.Isotropic coupling constants A(14N), A(1H) and, for R=But, A(33S) have been deduced and analysed in terms of the electronic structures of the radicals using empirical electron-density relationships.Some CNDO/2 and INDO calculations have been made and the experimental and calculated electron-spin densities compared.Variable-temperature e.s.r. measurements have given no indication of the presence of distinct geometric isomers of the anions in solutions.The model calculations suggest that the E/E conformation is most stable and that interconversion to give the E/Z or Z/Z forms is unlikely.The experimental evidence in all cases indicates the two nitrogen atoms to be magnetically equivalent.Alkali-metal isotropic coupling constants A(MI) for the species MIt)2> (MI=7Li, 23Na, or 39K) have been estimated and indicate that the metal-anion interaction increases in the order K t)2)> (M=Cr, Mo, or W) produces the corresponding anions with well defined isotropic e.s.r. spectra.Values for A(14N) and A(M) (M=95/97Mo or 183W) have been deduced and the spectra analysed.The results suggest that the unpaired electron is located mainly in the S(NBut)2 ligand.CNDO/2 calculations for the chromium anion are consistent with this observation.Attempts to produce - have been unsuccesful except for M=Cr, when an unstable species is formed.A tentative analysis of the e.s.r. spectrum of this radical anion is presented.
- Hunter, John A.,King, Boyd,Lindsell, W. Edward,Neish, Margaret A.
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p. 880 - 887
(2007/10/02)
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