2-Chloro-1,3,5-trithiane and 2-Chloro-1,3-dithiane. Their Ionic Dissociation and Reactions with Nucleophiles
- 1 February 1976
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 49 (2) , 553-558
- https://doi.org/10.1246/bcsj.49.553
Abstract
2-Chlorol,3,5-trithiane and 2-chloro-1,3-dithiane have been prepared by chlorination of the corresponding polythianes with N-chlorosuccinimide. These chlorides afford various substitution products when treated with nucleophiles, whereas nuclear substitution of the aromatic ring occurs when the chlorides are treated with phenol or N,N-dimethylaniline. 1H NMR spectra of these chlorides show remarkable solvent dependence which is explained by assuming ionic dissociation of the chlorides to produce polythianyl cation and chloride anion. Free energies of activation for the dissociation in various solvents indicate that the dissociation of 2-chloro-1,3,5-trithiane is more sluggish than that of 2-chloro-1,3-dithiane. The results are attributed to the difference in availability of electrons on the sulfur atoms in two systems.This publication has 15 references indexed in Scilit:
- Anomeric Effect Involving Carboxyl and Ethynyl Group in Sulfur-Containing HeterocyclesBulletin of the Chemical Society of Japan, 1975
- Equilibrium ion pair acidities of dithianes in cyclohexylamineJournal of the American Chemical Society, 1975
- Formation and Conformation of Benzoyloxylated Sulfur-containing HeterocyclesBulletin of the Chemical Society of Japan, 1974
- Reaction of 1,3-dithienium fluoroborate with 1,3-dienes. Synthesis of .DELTA.3-cyclopenten-1-onesJournal of the American Chemical Society, 1972
- Correction. Conformational Studies on Pyranoid Sugar Derivatives. The Conformational Equilibria of the D-Aldopentopyronose Tetraacetates and TetrabenzoatesThe Journal of Organic Chemistry, 1971
- Conformational studies on pyranoid sugar derivatives by n.m.r. spectroscopy. Conformational equilibria of the peracetylated and some perbenzoylated methyl d-aldopentopyranosides in solutionCarbohydrate Research, 1971
- Conformational studies on pyranoid sugar derivatives by n.m.r. spectroscopy. The conformational equilibria of the 1,2-trans peracetylated aldopentopyranosyl benzoates and perbenzoylated aldopentopyranosyl acetates in solutionCarbohydrate Research, 1971
- Synthesis of α‐substituted cyclic sulfidesJournal of Heterocyclic Chemistry, 1969
- Conformational and Configurational Studies on Some Acetylated Aldopyranosyl Halides1,2The Journal of Organic Chemistry, 1965
- Ionization Equilibria of Derivatives of Triphenylchloromethane in Liquid Sulfur DioxideJournal of the American Chemical Society, 1951