Syntheses and Reactivities of Thiophenetriptycenesulfenic and selenenic acids

研究了噻吩三蝶烯磺酸（Thrip-SOH）、三蝶烯硒酸（Thrip-SeOH）和三蝶烯硒酸（Trip-SeOH）的合成及反应性. Thtrip-Se（O）-n-Bu与二甲基二氧杂环丙烷（DMD）反应生成相应的硒氧化物[Thtrip-Se（O）-n-Bu]。硒氧化物的热β-消除产生Thtrip-Se（O）Se-Thtrip，而不是所需的硒酸（ThtripSeOH）。Thtrip-Se（O）Se-Thtrip是第一个可分离的硒代硒酸盐，其结构经X射线晶体学测定.用DMD氧化Trip-Se-n-Bu得到相应的硒氧化物[Trip-Se（O）-n-Bu]，其β-消除以良好的产率产生所需的Trip-SeOH。Trip-SeOH是第一个分离得到的链亚硒酸，其结构经X-射线晶体学测定. Trip-SeOH的反应加热Trip-SeOH在二氯甲烷中的溶液产生硒代硒酸盐Trip-Se（O）Se-Trip。酸不能加速二聚反应。用Et^c_3N处理Trip-Se（O）Se-Trip得到TripSe（O）SeTrip、Trip-SeSe-Trip和Trip-SeO_2 HEt_3 N的混合物，其摩尔比为1：1：1。酸催化水解TripSe（O）SeTrip定量地产生TripSeOH。

Syntheses and reactivities of thiophenetriptycenesulfenic (Thtrip-SOH) and selenenic acids (Thtrip-SeOH) and triptycneneselenenic acid (Trip-SeOH) were investigated.1. Attempted synthesis of Thtrip-SeOH The oxidation of Thtrip-Se-n-Bu with dimethyldioxirane (DMD) gave the corresponding selenoxide [Thtrip-Se(O)-n-Bu] . The thermal beta-elimination of the selenoxide yielded Thtrip-Se(O)Se-Thtrip, instead of the desired selenenic acid (ThtripSeOH). Thtrip-Se(O)Se-Thtrip is the first isolable selenoseleninates and the structure was determined by X-ray crystallography.2. Synthesis of Trip-SeOH The oxidation of Trip-Se-n-Bu with DMD gave the corresponding selenoxide [Trip-Se(O)-n-Bu], the beta-elimination of which yielded the desired Trip-SeOH in a good yield. Trip-SeOH is the first isolable alkancselenenic acid and the structure was determined by X-ray crystallography.3. Reactions of Trip-SeOH Heating a solution of Trip-SeOH in dichloromethane yielded the selenoseleninate, Trip-Se(O)Se-Trip. The dimerization was not accelerated by an acid. The treatment of Trip-Se(O)Se-Trip with Et^c_3N furnished a mixture of TripSe(O)SeTrip, Trip-SeSe-Trip, and Trip-SeO_2HEt_3N, the molar ratio of which was 1 : 1 : 1. Acid-catalized hydrolysis of TripSe(O)SeTrip gave TripSeOH quantitatively.