Nucleophilic Substitution on S₄N₄. Reactions with Benzylamines

Abstract

Reactions of benzylamines with tetrasulfur tetranitride lead to benzylidenimine polysulfides, ammonia, N-benzylidene benzylamines, and some free sulfur. The stoichiometric equation has been established. The reaction is quite sensitive to structural changes and appears limited to ring substituted benzylamines. The benzylidenimine polysulfides undergo thermal decomposition to sulfur and triphenyl-s-triazine and react with benzylamine to give benzylammonium polysulfides, ammonia, and N-benzylidene benzylamine. The benzylammonium polysulfides decompose in air to sulfur, hydrogen sulfide, and benzylammonium thiosulfate.

Geochemical Explication of Sulfur Organics Characterized by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry on Sulfur-Rich Heavy Oils in Jinxian Sag, Bohai Bay Basin, Northern China

“…There are several reaction pathways possible for inorganic sulfur entering into organic/biological molecules with the generation of some possible/specific structures: , (1) incorporating into the cateniform compounds in the form of H 2 S, leading to the generation of thiols; (2) adding onto double bonds, such as isoprenoids, by elemental sulfur, H 2 S, HS – , etc., resulting in the generation of S 1 -type compounds, such as thiols, that can cyclize to form thioethers and be further dehydrogenated to form thiophenic compounds; (3) reacting between complex polysulfides and organic matter; hereinto, the former was formed by the reaction between sulfides and elemental sulfur or as the intermediate products of H 2 S oxidation, leading to the formation of S 2 - and S 3 -type compounds; and (4) entering into the structure of organic compounds through sulfate assimilation, in which OS- and OS 2 -type compounds can also be formed as redox products with sulfate.substitution reactions normalR− CH 2 −OH + normalH 2 normalS → normalR− CH 2 −SH + normalH 2 normalO addition reactions normalR− CH CH normal−R ′ + normalH 2 normalS → normalR− CH 2 CH ( SH ) CH normal−R ′ complex sulfide reactions 2 RR ′ NH + normalS n → RR ′ normalN− normalS n − 1 −NRR ′ + normalH 2 normalS normalH 2 normalS + ( n − 1 ) normalS + 2 RR ′ NH → …”

“…It can be seen that almost 20 peaks appeared in this narrow mass range of no more than 0.3 Da and all are identified as OSCs. Because the compounds detected in the mass spectrum correspond to the ions of the methylsulfonium salt, the most abundant peak labeled as C 27 H 41 S should be originated from a compound with a molecular formula of C 26 13 C contributions because the natural abundance of 13 C is only 1.1% relative to the corresponding 12 C species and limited dynamic range of approximately 10 3 offered by the FT-ICR mass spectrometer.…”

Crystal and Molecular Structure of Benzylidenimine Tetrasulfide, (C6H5CHN)2S4

“…In 2, the internal bond is 2.066(2) A while in benzylidenimine it is 2.083(4) A and in 4 it is 2.076(1). These lengths compare to a S-S bond length of2.048 (2) A in (29,30) elemental S,.…”

“…Only in the recent cases are differences groups; it has also been isolated from the reaction in sulfur-sulfur bond lengths clearly outside the of benzylamine with sulfur in the presence of lead experimental errors in the measurements. oxide (2,3), from the decomposition of N-benzylIn view of the interest in bond length alternaheptasulfurimide (4), from the reaction of sulfur tion in organotetrasulfides and to resolve any monochloride (5,6), or disulfur trichloride (5) residual uncertainty in the structure of 1, we have with benzylamine and from the decomposition of determined the crystal and molecular structure of benzylamine disulfide (6). At least four alternate this material.…”