REACTIONS OF p-HYDROXYPHENYL- AND p-PHENOLATOTHIANIUM COMPOUNDS

Article abstract of DOI:10.1007/BF00513160

p-Hydroxyphenylthianium perchlorate reacts with OH^- to give bis(p-phenolatothianium) dihydrate,in which the oxygen atoms of the zwitter ions are tied up in an eight-membered ring by hydrogen bonds with the H2O molecules.The unit cell of the perchlorate consists of two cations and two anions bonded by linear and forked hydrogen bonds. p-Hydroxyphenylthianium perchlorate reacts with a concentrated solution of KOH in methanol to give 1-(p-hydroxyphenyl)-1'-(p-phenolato)bisthianium perchlorate,which is also obtained by the reaction of p-hydroxyphenylthianium perchloratewith bis(p-phenolatothianium) dihydrate and of the latter with HClO4. 1-(p-Hydroxyphenyl)-1'-(p-phenolato)bisthianium chloride hydrate and 1-(p-phenolato)thianiumbisphenol, respectively, were obtained by the reaction of bis(p-phenolatothianium) dihydrate with p-hydroxyphenylthianium chloride or with C6H5OH.Under the influence of picric or perchloric acid, 1-(p-hydroxyphenyl)-1'-(p-phenolato)bisthianium perchlorate is converted to p-hydroxyphenylthianium picrate or its perchlorate, respectively, while reaction with OH^- gives bis(p-phenolatothianium) dihydrate, and heating with piperidine gives p-hydroxyphenyl ω-piperidinoamyl sulfide.When bis(p-phenolatothianium) dihydrate is heated, it undergoes dehydration and polymerization to <-OC6H4S(CH2)5->n; depending on the conditions, n=2, 3, 14, or 25. p-Hydroxyphenyl ω-piperidinoamyl sulfide is formed when II is heated with piperidine.