Syntheses and Reactivities of Thiophenetriptycenesulfenic and selenenic acids

研究了噻吩三烯基亚砜（Thtrip-SOH）、亚硒酸（Thtrip-SeOH）和三烯基亚硒酸（Trip-SeOH）的合成及其反应活性。Thtrip-Se-n-Bu与二甲二氧环（DMD）氧化得到相应的硒氧化物[Thtrip-Se(O)-n-Bu]。硒氧化物的热β消除得到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酸盐，其结构由x射线晶体学测定。Trip-Se-n-Bu与DMD氧化得到相应的硒氧化物[Trip-Se(O)-n-Bu]，其β -消去得到所需的Trip-SeOH，产率很高。Trip-SeOH是第一个可分离的烷烃二烯酸，并通过x射线晶体学测定了其结构。在二氯甲烷中加热Trip-SeOH溶液，制得硒酸盐Trip-Se(O)Se-Trip。酸不加速二聚化。用Et^c_3N处理Trip-Se(O)Se-Trip得到TripSe(O)SeTrip、Trip-SeSe-Trip和Trip-SeO_2HEt_3N的混合物，其摩尔比为1:1。酸催化水解TripSe(O)SeTrip定量得到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.