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.

研究了噻吩三蝶烯亚磺酸(Thtrip-SOH)、硒酸(Thtrip-SeOH)和三蝶烯硒酸(Trip-SeOH)的合成及反应性。 1．尝试合成Thtrip-SeOH 用二甲基二环氧乙烷(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硒酸盐，并通过X射线晶体学确定了其结构。 2． Trip-SeOH 的合成 Trip-Se-n-Bu 用 DMD 氧化得到相应的氧化硒 [Trip-Se(O)-n-Bu]，其 β-消除以良好的产率产生所需的 Trip-SeOH 。 Trip-SeOH是第一个可分离的链烷硒酸，其结构通过X射线晶体学确定。 3． Trip-SeOH 的反应 加热 Trip-SeOH 的二氯甲烷溶液产生硒硒酸盐 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 : 1。 TripSe(O)SeTrip 的催化水解定量产生 TripSeOH。

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：“硒酸的制备和硒代硒酸盐的分离”有机化学杂志 64・4（1999）。

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。