PRIMARY AND SECONDARY 5-(ALKYLOXY)THIANTHRENIUM PERCHLORATES - CHARACTERIZATION WITH H-1-NMR SPECTROSCOPY, REACTIONS WITH IODIDE AND BROMIDE ION, AND THERMAL-DECOMPOSITION IN SOLUTION

Authors
Citation
Wy. Zhao et Hj. Shine, PRIMARY AND SECONDARY 5-(ALKYLOXY)THIANTHRENIUM PERCHLORATES - CHARACTERIZATION WITH H-1-NMR SPECTROSCOPY, REACTIONS WITH IODIDE AND BROMIDE ION, AND THERMAL-DECOMPOSITION IN SOLUTION, Canadian journal of chemistry, 76(6), 1998, pp. 695-702
Citations number
12
Categorie Soggetti
Chemistry
ISSN journal
00084042
Volume
76
Issue
6
Year of publication
1998
Pages
695 - 702
Database
ISI
SICI code
0008-4042(1998)76:6<695:PAS5P->2.0.ZU;2-M
Abstract
A series of 5-(alkyloxy)thianthrenium perchlorates has been made in wh ich the alkyl group is primary (la-lp) and secondary (2a-2g). Preparat ions were carried out by reaction of the corresponding alkanol with th ianthrene cation radical perchlorate in CH2Cl2 solution followed by pr ecipitation of the perchlorate salt with dry ether. H-1 NMR spectrosco py reveals that the presence of a stereogenic center in the alkyl grou p causes inequivalence in the ordinarily paired protons (e.g., H-4, H- 6) of the thianthrenium ring. Reaction of iodide and bromide ion with primary alkyl-group compounds (e.g., methyl, ethyl, propyl, butyl) gav e the alkyl halide in very good yield and by a second-order kinetic di splacement. The second product was thianthrene 5-oxide (ThO). Rate con stants for some of these reactions are reported. Reaction of secondary alkyl group compounds (e.g., 2-propyl, 2-pentyl, 2-hexyl, and 3-hexyl ) with iodide ion gave good yields of alkyl iodide but also increasing evidence for a side reaction at the sulfonium sulfur, leading to I-2, thianthrene, and secondary alkanol. Decomposition of some compounds a t 100 degrees C in solution (acetonitrile or 1,2-dichloroethane) was s tudied and gave alkene(s) and ThO.