Studies on the Highly Nucleophilic Triphenylphosphines and their Derivatives

高亲核性三苯基膦及其衍生物的研究

• 批准号: 62550633
• 负责人: WADA Masanori
• 金额: $ 1.28万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550633/
• 关键词: 2, 6-Dimethoxyphenyl; Tertiary phosphine; Phosphine oxide; Phosphine sulfide; Hydroxyphosphonium salt; Hydrothiophosphonium salt; Benzenethiol; 金属抽出; 2,6ジメトキシフェニル; 親核剤; 3級ホスホニウム塩; 4級ホスホニウム塩; アミン付加体

1. Tris(2.6-dimethoxyphenyl)phosphine oxide. {2,6-(MeO)_2C_6H_3}_3P=O, is highly soluble in water and reacts with acids to form stable hydroxy phosphonium salts. [{2,6-(MeO_2C_6H_3}_3P-OH]X (X= C10_4, BF_4). The salt (X= C10_4) formed stable 1:1 adducts, [{2,6-(MeO)_2C_6H_3}_3P=O, HNR_3]C10_4, with a variety of amines.2. Tris(2,6-dimethoxyphenyl)phosphine sulfide. {2,6-(MeO)_2C_6H_3}_3P=S, reacted with acids to form protonated salts. of which thermolysis in the absence or presence of triphenylphosphine resulted in the un-usual desulfurization to give the tertiary phosphonium salt.3. 2,6-Dimethoxybenzenethiol is a non-smelling, air-stable crystal-line compound with stronger nucleophilicity towards alkyl halides than phSH; the crystallinity of several types of derivative ArSR (R=H, Ar, SAr, CH_2CH_2SAr, CH_2CH_2CH_2SAr) is in the order of Ar=Ph < 2-MeOC_6H_4 < 2.6-(MeO)_2C_6H_3.4. {2,4,6-(MeO)_3C_6H_2}_3P, {2,6-(MeO)_2C_6H_3}_3P and their onium salts were found to be excellent extractants for particular metal ions such as Ca^<3+>and Au^<3+> in hydrochloric acid solution.

1.三（2，6-二甲氧基苯基）氧化膦。{2，6-（MeO）_2C_6H_3}_3P=O，易溶于水，与酸反应生成稳定的羟基鏻盐。[{2，6-（MeO_2C_6H_3}_3P-OH]X（X= C10_4，BF_4）.盐（X= C10_4）与多种胺形成稳定的1：1加合物[{2，6-（MeO）_2C_6H_3}_3P=O，HNR_3]C10_4.三（2，6-二甲氧基苯基）硫化膦。{2，6-（MeO）_2C_6H_3}_3P=S与酸反应生成质子化盐。其中在不存在或存在三苯基膦的情况下的热交换导致不常见的脱硫，得到叔鏻盐。2，6-二甲氧基苯乙胺是一种无臭、空气稳定的晶体化合物，对卤代烷的亲核性比phSH强，几种衍生物ArSR（R=H，Ar，SAr，CH_2CH_2SAr，CH_2CH_2CH_2SAr）的结晶度顺序为Ar=Ph < 2-MeOC_6H_4 < 2.6-（MeO）_2C_6H_3.4。在盐酸溶液中，{2，4，6-（MeO）_3C_6H_2}_3P、{2，6-（MeO）_2C_6H_3}_3P及其鎓盐对Ca^<3+>、Au^<3+>等金属离子有良好的萃取性能。

项目成果

Yuko Yamashouji.: Analytical Sciences. 4. 431-432 (1988)

Yuko Yamashouji.：分析科学。

Masanori Wada.: Chem.Express. 3. 471-474 (1988)

和田正德：Chem.Express。

Masanori Wada.: Chem.Express. 4. (1989)

和田正德：Chem.Express。

Yuko Yamashoji: "Selective Solvent Extraction of Various Metal Ions with Tris(2,6-dimethoxyphenyl)phosphine from Hydrochloric Acid Solutions" Analytical Sciences. 4. 431-432 (1988)

Yuko Yamashoji：“用三(2,6-二甲氧基苯基)膦从盐酸溶液中选择性溶剂萃取各种金属离子”分析科学。

Masanori Wada.: Chem.Express. 4. 109-111 (1989)

和田正德：Chem.Express。