Syntheses and Reactivities of Thiophenetriptycenesulfenic and selenenic acids

噻吩三蝶烯次磺酸和硒酸的合成和反应性

• 批准号: 09640624
• 负责人: ISHII Akihiko
• 金额: $ 1.79万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640624/
• 关键词: sulfenic acid; selenenic acid; thiophenetriptycene; triptycene; selenoseleninate; dimethyldioxirane; oxidation; beta-elimination; セレニド; セレノール; セレノキシド; セレノセレニナ-ト

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.

研究了噻吩三苯磺酸(THTriP-SOH)、亚硒酸(THTriP-SeOH)和三苯基三烯硒酸(TRIP-SeOH)的合成及其反应活性。用二甲基二氧六环(DMD)氧化ThTrip-Se-n-Bu得到相应的氧化硒[ThTrip-Se(O)-n-Bu]。氧化硒的热β消除生成了ThTrip-Se(O)Se-ThTrip，而不是所需的亚硒酸(ThtripSeOH)。结果表明：1.ThTriP-Se(O)Se-ThTrip是第一个可分离的硒硒化合物，其结构经X-射线晶体分析确定。TRIP-Se-n-Bu的合成用DMD氧化TRIP-Se-n-Bu得到了相应的氧化硒[TRIP-Se(O)-n-Bu]，其β消除反应以较高的产率得到了所需的TRIP-SeOH。TRIP-Seoh是第一个分离得到的烷基硒酸，其结构经X-射线衍射法确证。TRIP-SeOH加热TRIP-SeOH在二氯甲烷中的溶液的反应生成亚硒酸酯TRIP-Se(O)Se-TRIP。酸不能加速二聚反应。用Et、C_3N处理TripSe(O)Se-Trip得到了TripSe(O)SeTrip、Trip-Sese-Trip和Trip-SeO_2HEt_3N的混合物，摩尔比为1：1：1。

项目成果

Akihiko Ishii: "Preparation of a Selenenic Acid and Isolation of Selenoseleninates" Journal of Organic Chemistry. 64-4. 1084-1085 (1999)

Akihiko Ishii：“硒酸的制备和硒硒酸盐的分离”有机化学杂志。

Akihiko Ishii: "Preparation of a Selenenic Acid and Isolation of Selenoseleninates" Journal of Organic Chemistry. 64・4. 1084-1085 (1999)

Akihiko Ishii：“硒酸的制备和硒代硒酸盐的分离”有机化学杂志 64・4（1999）。