チオホスホニウム塩構造を有するロタキサンの合成と構造
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概要
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Generally, dialkylthiophosphonium salts cannot be isolated in desulfurization of disulfide with tertiary phosphine. Recently we have found that stable dialkylthiophosphonium salt-type [2]rotaxane is isolated by the reaction of [3]rotaxane having a disulfide moiety with hexamethylphosphorous triamide. In this paper, we wish to report the synthesis, structure and reactivity of the thiophosphonium salt. A bisammonium salt having a disulfide moiety and a crown ether were dissolved in a mixed solvent CH<SUB>3</SUB>CN/CHCl<SUB>3</SUB> (3/7). 10 mol% of benzenethiol was added to the solution, which was allowed to stand for 3 days at 50°C and further 1 week at room temperature, giving [3]rotaxane in 89 % yield. The [3]rotaxane reacted with HMPT in dichloromethane at room temperature for 32h to give [2]rotaxane having thiophosphonium salt structure in 58 % yield. The [2]rotaxane was characterized by <SUP>1</SUP>H NMR, FAB MS spectrum and X-ray crystallography. In the reaction of the [2]rotaxane with nucleophiles such as Grignard reagent and thiolate, attack only at P atom by the nucleophiles was observed. This is probably because both S and the neighboring C atoms are sterically protected by the crown ether.
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