51290-79-0Relevant articles and documents
Dual Mechanisms of Bimolecular Nucleophilic Subtitution of a Heterobenzylic Bromide Related to Thiamin
Zoltewicz, John A.,Uray, Georg
, p. 1370 - 1375 (1989)
4-Amino-5-(bromomethyl)-1,2-dimethylpyrimidinium ion at 25 deg C in 0.9 M KCl made to an ionic strength of 1 M with buffers react with hydroxide ion with a rate constant 725 M-1s-1.Evidence for an intermediate is found in the large common ion rate retarding effect of added bromide ion.An addition-elimination mechanism (SN(AE)) involving the addition of hydroxide ion to give a pseudobase intermediate followed by loss of bromide ion is advanced.Chloride ion reacts by an SN2 mechanism (5.9E-5 M-1s-1).When 2-thiopyridone acts as a nucleophile by the SN2 mechanism, its sulfur atom is heterobenzylated with a rate constant of 0.28 M-1s-1 (31 deg C).Two different bimolecular mechanisms of nucleophilic substitution are thereby observed.
Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
, p. 13029 - 13032 (2020/11/07)
A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
Promoting Effect of Crystal Water Leading to Catalyst-Free Synthesis of Heteroaryl Thioether from Heteroaryl Chloride, Sodium Thiosulfate Pentahydrate, and Alcohol
Ma, Xiantao,Yu, Jing,Yan, Ran,Yan, Mengli,Xu, Qing
supporting information, p. 11294 - 11300 (2019/09/12)
It is observed the crystal water in sodium thiosulfate pentahydrate (Na2S2O3·5H2O) can promote its multicomponent reaction with heteroaryl chlorides and alcohols, providing a facile, green, and specific synthesis of unsymmetrical heteroaryl thioethers via one-step formation of two C-S bonds under catalyst-, additive-, and solvent-free conditions. Mechanistic studies suggest that the crystal water in Na2S2O3·5H2O is crucial in generating the key thiol intermediates and byproduct NaHSO4, which then catalyzes the dehydrative substitution of alcohols with thiols to afford thioethers.