当前位置：
X-MOL 学术
›
Z. Anorg. Allg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Ishikawa's Reagent – a Valuable Source for Fluoroorganic Iminium Salts
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2020-07-17 , DOI: 10.1002/zaac.202000198 Mira Keßler 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Berthold Hoge 1
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2020-07-17 , DOI: 10.1002/zaac.202000198 Mira Keßler 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Berthold Hoge 1
Affiliation
|
We herein report on iminium salts derived from Ishikawa's reagent Et2N‐CF2‐CHF‐CF3. The reaction with P(C2F5)3F2 afforded [Et2N=CF‐CHF‐CF3][P(C2F5)3F3] as an ionic liquid. The fluorine atom in the cation in α position to the nitrogen atom is labile towards nucleophilic substitution as demonstrated by the reaction with SnCl2 where an exchange of the fluorine by a chlorine atom took place. Upon contact with water the fluorine atom is substituted by a hydroxyl group. The reaction of Ishikawa's reagent with P(C2F5)2F afforded the zwitterionic [P(C2F5)2F3{C(NEt2)(CHF‐CF3)}]. Most likely [Et2N=CF‐CHF‐CF3][P(C2F5)2F2] was formed transiently. The anion is obviously sufficiently nucleophilic to attack the susceptible α‐fluorine atom of the cation. During several months Ishikawa's reagent loses hydrogen fluoride, which reacts with glass producing SiF4 which abstracts a fluoride ion from Ishikawa's reagent affording [Et2N=CF‐CHF‐CF3][SiF5].
中文翻译：
石川试剂–氟有机亚胺盐的重要来源
我们在此报告了源自Ishikawa试剂Et 2 N-CF 2 -CHF-CF 3的亚胺盐。与P（C 2 F 5）3 F 2反应，得到[Et 2 N = CF-CHF-CF 3 ] [P（C 2 F 5）3 F 3 ]，为离子液体。与SnCl 2的反应表明，位于氮原子α位的阳离子中的氟原子对亲核取代反应不稳定。其中氯原子与氟发生了交换。与水接触时，氟原子被羟基取代。石川试剂与P（C 2 F 5）2 F的反应得到两性离子[P（C 2 F 5）2 F 3 {C（NEt 2）（CHF-CF 3）}。最有可能[Et 2 N = CF-CHF-CF 3 ] [P（C 2 F 5）2 F 2]是瞬时形成的。阴离子显然具有足够的亲核性，可以攻击阳离子中易受影响的α-氟原子。在几个月的时间里，石川的试剂损失了氟化氢，它与玻璃反应生成SiF 4，该SiF 4从石川的试剂中提取了氟离子，从而提供了[Et 2 N = CF-CHF-CF 3 ] [SiF 5 ]。
更新日期：2020-07-17
中文翻译：
石川试剂–氟有机亚胺盐的重要来源
我们在此报告了源自Ishikawa试剂Et 2 N-CF 2 -CHF-CF 3的亚胺盐。与P（C 2 F 5）3 F 2反应，得到[Et 2 N = CF-CHF-CF 3 ] [P（C 2 F 5）3 F 3 ]，为离子液体。与SnCl 2的反应表明，位于氮原子α位的阳离子中的氟原子对亲核取代反应不稳定。其中氯原子与氟发生了交换。与水接触时，氟原子被羟基取代。石川试剂与P（C 2 F 5）2 F的反应得到两性离子[P（C 2 F 5）2 F 3 {C（NEt 2）（CHF-CF 3）}。最有可能[Et 2 N = CF-CHF-CF 3 ] [P（C 2 F 5）2 F 2]是瞬时形成的。阴离子显然具有足够的亲核性，可以攻击阳离子中易受影响的α-氟原子。在几个月的时间里，石川的试剂损失了氟化氢，它与玻璃反应生成SiF 4，该SiF 4从石川的试剂中提取了氟离子，从而提供了[Et 2 N = CF-CHF-CF 3 ] [SiF 5 ]。
京公网安备 11010802027423号