57083-06-4

Upstream product

• 5194-50-3 (E,Z)-2,4-hexadiene 
• 118622-94-9 N-(4-methylphenylaminothio)phthalimide 
• 4039-32-1 lithium hexamethyldisilazane 
• 15795-42-3 N-sulfinyl-4-methylaniline 
• 3839-88-1 di-p-tolylsulfur diimide 
• 68-12-2 N,N-dimethyl-formamide 
• 63911-83-1 1,1,1-trimethyl-N-(4-methylphenyl)silanamine 

Downstream Products

• 68777-52-6 N-[(p-phenyl)benzylidene]-p-methylaniline 
• 106-49-0 p-toluidine 
• 60-29-7 diethyl ether 
• 70-29-1 diethyl sulphide 
• 3839-88-1 C₁₄H₁₄N₂S^(1-) 
• 57091-53-9 2,5-di-p-tolyl-1-p-tolylimino-1λ⁴-[1,2,5]thiadiazolidine-3,4-dione 

Relevant academic research and scientific papers

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

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.

Catalytic Imido-Transfer Reactions of Well-Defined Silica-Supported Titanium Imido Complexes Prepared via Surface Organometallic Chemistry

We expand the series of well-defined silica-supported titanium imido complexes of general formula (SiO)Ti(═NtBu)X(py)n prepared via surface organometallic chemistry in order to analyze the effect of the X ligand on their catalytic properties. Two new surface complexes, (SiO)Ti(═NtBu)Cl(py)2 (2s) and (SiO)Ti(═NtBu)Cp(py) (3s), have been prepared and characterized with physicochemical techniques, and their performance in oxo/imido heterometathesis and other catalytic imido-transfer reactions has been studied and compared to that of the previously reported catalyst (SiO)Ti(═NtBu)(Me2Pyr)(py)2 (1s; Me2Pyr = 2,5-dimethylpyrrolyl).

Oxo/Imido heterometathesis reactions catalyzed by a silica-supported tantalum imido complex

Grafting Ta(=NtBu)(CH2CMe2Ph)3 onto the surface of silica partially dehydroxylated at 300°C leads to the formation of the surface imido complex (≡SiO)2Ta(=N tBu)(CH2CMe2Ph) as a major species, which was characterized with EXAFS, 13C CP/MAS NMR, diffuse reflectance FTIR, elemental analyses, and chemical reactivity. The obtained material acts as an efficient heterogeneous catalyst for various oxo/imido heterometathesis transformations: imidation of ketones and DMF with N-sulfinylamines and condensation of N-sulfinylamines into sulfurdiimines and phenyl isocyanate into diphenylcarbodiimide.

Skeletal scrambling of sulphur diimide radical anions

In the presence of a catalytic quantity of alkali metal mixtures of sulphur diimides RNSNR and R'NSNR' (R, R' = Ph, 4-C6H4Me, 4-C6H4OMe, SiMe3, SPh) undergo a rapid scrambling of the R and R' groups.When R and R' are significantly different (e.g., R = Ph,

THE STEREOCHEMICAL OUTCOME OF DIENE ADDITIONS TO THIONITROSOARENES (ArN=S)

Thionitrosoarenes (ArN=S) react efficiently with (E,E)- and (E,Z)-hexadienes to yield 1,2-thiazine adducts in which the stereochemistry of the diene is retained.

SOME KINETIC ASPECTS OF THE ALCOHOLYSIS OF N,N'-DIARYLSULPHURDIIMIDES

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.