Complex Syntheses Using Electronic Charge and Softness of Organothallium Crown-ether Complexes

利用电子电荷和有机铊冠醚配合物的柔软度合成配合物

• 批准号: 03640518
• 负责人: KAWASAKI Yoshikane
• 金额: $ 1.34万
• 依托单位: Osaka Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640518/
• 关键词: Organothallium; Monophenylthallium; Crown-ether Complexes; Electrophilic reaction; Cleavage of Si-C Bond; フェニルタリウムイオン; クラウンエ-テル; フェノ-ル; アニリン; 求電子置換反応

The reaction of [Phenylthallium(III)(18-crown-6)] diperchlorate,[PhTl^<III>(18-crown-6)](ClO_4)_2 (1 a) with phenol gives [phenyl(4'-hydroxyphenyl)tnallium(III)(18-crown-6)]diperchlorate (2). The complex 1 a reacts also with alkylphenols, methoxyphenols, catechol, resorcinol, and pyrogallol to give thallated product exclusively at the para position of the electron-donating group(OH or OCH3) without suffering from reduction of thallium(III). No reaction takes place with 4-methylphenol, benzene, toluene, Electrophilic thallation of diphenylamine, diphenylmethylamine and triphenylamine with 1 a gives compounds of the type [PhArTl^<III>(18-crown-6)](ClO_4) (Ar=4'-phenylamino)phenyl, 4'-(methylphenylamino)phenyl, and 4'-(diphenylamino)phenyl, respectively). Similar reaction of five-membered heterocycls, such as pyrrole, furan and thiophene and their derivatives, was observed at mild condition. On the other hand the reaction of 1 a with imidazole resulted in coordination of imidazole nitrogen to the thallium ion without substitution at the ring.Reactions of 1 a with Me_3SiR(R=PhCH_2, Et, Ph, CH=CH_2, SiMe_3 OSiMe_3) proceeded at 60ﾟC to provide exclusively [phenylmethylthallium(III)(18-crown-6)]perchlorate in good yield to excellent yield. Cleavage of the Me-Si bond in tetramethylsilane using 1 a also occurred at room temperature.

[苯基铊（Ⅲ）（18-冠-6）]二高氯酸盐，[PhTl^<III>（18-冠-6）]（ClO_4）_2（1a）与苯酚反应生成[苯基（4 ′-羟基苯基）铊（Ⅲ）（18-冠-6）]二高氯酸盐（2）。配合物1a还与烷基酚、甲氧基酚、邻苯二酚、间苯二酚和连苯三酚反应，仅在给电子基团（OH或OCH 3）的帕拉得到铊化产物，而不遭受铊（III）的还原。二苯胺、二苯甲胺和三苯胺与1a亲电加成，分别得到[PhArTl<III>（18-冠-6）]（ClO_4）（Ar= 4 ′-苯氨基）苯基、4 ′-（甲基苯氨基）苯基和4 ′-（二苯氨基）苯基）。吡咯、呋喃、噻吩等五元杂环化合物及其衍生物在温和条件下也有类似的反应。1a与Me_3SiR（R=PhCH_2，Et，Ph，CH=CH_2，SiMe_3OSiMe_3）在60 ℃下反应，以高产率得到[苯甲基铊（III）（18-冠-6）]高氯酸盐。使用Ia的四甲基硅烷中的Me-Si键的裂解也在室温下发生。

项目成果

F.Kakiuchi, S.Murai, and Y.Kawasaki: "Electrophilic Thallation of Thiopheene Derivertives and Furan with Phenylthallium(III) 18-Crown-6 Diperchlorate" Organometallics. 11. 4352-4355 (1992)

F.Kakiuchi、S.Murai 和 Y.Kawasaki：“噻吩衍生物和呋喃与苯基铊 (III) 18-Crown-6 二高氯酸盐的亲电铊化”有机金属化合物。

垣内 史敏.村井 真二 川崎 吉包: "Electrophilic Thallation of Thiophene Derivatives and Furan with Phenylthallium(3) 18-Crown-6 Diperchlorato" Organometallics. 11. 4352-4356 (1992)

Fumitoshi Kakiuchi。Shinji Murai、Yoshikazu Kawasaki：“噻吩衍生物和呋喃与苯基铊的亲电铊化(3) 18-Crown-6 二氯酸”11。4352-4356 (1992)。

垣内 史敏,大江 浩一,茶谷 直人,黒沢 英夫,村井 真二,川崎 吉包: "Electrophilic Thallation of Aniline Derivatives and Nitrogen Hetrocycles with Phenylthallium(III)18ーCrounー6 Diperchlorate" Organometallics. 11. 752-756 (1992)

Fumitoshi Kakiuchi、Koichi Oe、Naoto Chatani、Hideo Kurosawa、Shinji Murai、Yoshikazu Kawasaki：“苯胺衍生物和氮杂环与苯基铊(III)18-Croun-6二高氯酸盐的亲电铊化”有机金属学11。752-756(1992)。

F.Kakiuchi, K.Ohe, N.Chatani, H.Kurosawa, and S.Murai: "Electrophilic Thallation of Aniline Derivatives and Nitrogen Hetero- cyles with Phenylthallium(III) 18-Crown-6 Diperchlorate" Organometallics. 11. 752-756 (1992)

F.Kakiuchi、K.Ohe、N.Chatani、H.Kurosawa 和 S.Murai：“苯胺衍生物和氮杂环与苯基铊 (III) 18-Crown-6 二高氯酸盐的亲电铊化”有机金属。

垣内 史敏,古田 清敬,村井 真二,川崎 吉包: "Highly Selective Methyl Transfer from Methylsilanes to Phenylthallium(3) Crown Ether Comploxes" Organometallics. 12. 15-16 (1993)

Fumitoshi Kakiuchi、Kiyotaka Furuta、Shinji Murai、Yoshikazu Kawasaki：“从甲基硅烷到苯基铊 (3) 冠醚络合物的高度选择性甲基转移”有机金属学 12. 15-16 (1993)。