The Chemistry of Hydrochalcogenides

氢硫属化物的化学

• 批准号: 15550027
• 负责人: ISHII Akihiko
• 金额: $ 2.43万
• 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: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550027/
• 关键词: selenoselenenic acid; diselenide; selenoseleninate; selenol; triselenide; selenoester; hydrolysis; 9-トリプチシル基; ジセレノラート塩; スルフェン酸; チオセレネン酸; トリプチシル基

The synthesis of triptycene-9-selenoselenenic acid (TripSeSeH;Trip denotes 9-triptycyl hereafter) was investigated.1.Synthesis of diselenides, TripSeSeC(O)R.1.1.The reaction of Se-9-triptycyl triptycene-9-selenoseleninate [TripSe(O)SeTrip] with selenocarboxylic acids [RC(O)SeH] yielded the desired TripSeSeC(O)R in high yields. p-Tolyl and benzyl groups were employed as the substituent R.1.2.Selenol, TripSeH, was treated with a base, and the resulting TripSe^-was allowed to react with elemental selenium, followed by quenching the mixture with methyl iodide to give the corresponding diselenide (TripSeSeMe). This result indicated the formation of TripSeSe. When the mixture was quenched with acid, TripSeH was recovered. Using elemental sulfur, instead of selenium, led to the formation of TripSeSH in 15% yield. Diselenides, TripSeSe(O)-p-Tol and TripSeSeC(O)Me were prepared by quenching the mixture with benzoyl chloride and acetyl chloride, respectively.2.Hydrolysis of TripSeSeC(O)RHydrolysis of TripSeSeC(O)-p-Tol was carried out under acidic or basic conditions to give the selenol (TripSeH) and the triselenide (TripSeSeSeTrip) as the main products. Hydrolysis of TripSeSeC(O)Me with perchloric acid in a mixed solvent of dichloromethane and ethanol at 40℃ gave a similar mixture of TripSeH and TripSeSeSeTrip in a ration of 1:1. TripSeSeSeTrip would be formed by a dimerization of intermediary generated TripSeSeH accompanying with elimination of H_2Se. The formation of TripSeH suggests the deselenation of TripSeSeH.

1.二硒化合物TripSeC(O)R.1.1的合成。Se-9-Triptycyl-9-Selenoselenate[TripSe(O)SeTrip]与硒羧酸[RC(O)Seh]反应，高产率地得到了所需的TripSeSeC(O)R。以对甲苯基和苯基为取代基，用碱处理TripSeH，生成的TripSe^-与元素硒反应，然后用碘甲烷淬灭混合物，得到相应的二硒醚(TripSeMe)。这一结果表明了TripSeSe的形成。当混合物用酸淬灭时，TripSeH被回收。用元素硫代替了硒，以15%的产率生成了TripSeSH。分别用苯甲酰氯和乙酰氯淬灭得到TripSeSeC(O)-p-Tol和TripSeSeC(O)Me。2.TripSeC(O)-Tol在酸性或碱性条件下进行水解，得到主要产物为硒醇(TripSeH)和三硒醚(TripSeSeTrip)。TripSeSeC(O)Me与高氯酸在二氯甲烷和乙醇的混合溶剂中以40℃的温度进行水解，得到类似的TripSeH和TripSeSeTrip的混合物，比例为1：1。TripSeSeSeTrip将中间产物TripSeSeH进行二聚反应，同时消除H_2Se。TripSeH的形成表明TripSeSeH的脱盐作用。

项目成果

Synthesis and Hydrolysis of p-Toluoyl and Acetyl 9-Triptycyl Diselenides : A Study on Generation of Triptycene-9-selenenoselenoic Acid

对甲苯酰基和乙酰基9-三蝶酰基二硒化物的合成与水解：三蝶烯-9-硒代硒酸的生成研究

• 期刊: Heteroatom Chemistry (印刷中)
• 作者: Akihiko Ishii;Yuichiro Mori;Rei Uchiumi
• 通讯作者: Rei Uchiumi