化学学报 ›› 2015, Vol. 73 ›› Issue (11): 1203-1206.DOI: 10.6023/A15070459 上一篇    下一篇

研究论文

新型B(C6F5)3/芳香胺盐酸盐体系的应用研究

田冲, 姜亚, Borzov Maxim, 聂万丽   

  1. 天然产物与小分子合成四川省高校重点实验室 乐山师范学院化学学院 乐山 614000
  • 收稿日期:2015-07-04 出版日期:2015-11-15 发布日期:2015-08-18
  • 通讯作者: 聂万丽 E-mail:niewl126@126.com
  • 基金资助:

    项目受四川省教育厅资助科研项目(No. 15ZA0279)和乐山市科技计划项目(No. 14GZD010)资助.

Studies on a Novel Type of B(C6F5)3 and Aromatic Ammonium ChlorideSystem

Tian Chong, Jiang Ya, Borzov Maxim, Nie Wanli   

  1. Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department of LeshanNormal University, Leshan 614000
  • Received:2015-07-04 Online:2015-11-15 Published:2015-08-18
  • Supported by:

    Project support by the Foundation of Sichuan Provincial Department of Education (No. 15ZA0279), Foundation of Leshan Science and Technology plan (No. 14GZD010)

尽管近年来有关受限路易斯酸碱对(FLPs)化学的研究受到了国内外的广泛关注, 但有关芳香胺类FLPs的应用研究却极少涉及. 设计了一种研究芳香胺类FLPs的新型方法, 以芳香胺盐酸盐与路易斯酸三(五氟苯基)硼(BCF)组成新的反应体系, 以氢化硅烷作为氢源. 研究了在计量条件下一系列芳香胺盐酸盐/BCF体系与硅烷的反应特征. 与烷基胺盐酸盐/BCF体系所不同的是, 芳香胺盐酸盐/BCF体系在溶液中与氢化硅烷反应时所形成的芳香硼氢化胺盐[Ar2NH2]+[HBCF]-由于不稳定, 在反应过程中会立即释放出氢气, 并分解为芳胺和BCF. 但是, 恰恰是由于硼氢化芳香胺盐分解后重新产生的BCF, 使得这类体系可用于催化反应, 可作为一种新型高效的非金属催化体系用于硅烷的氯代反应. 本文对在BCF的催化下, 芳香胺盐酸盐与氢化硅烷在不同比例下反应, 制备单氯或二氯代硅烷的反应过程及机理也做了详细地研究. 同时, 根据实际需要, 可在反应结束后向反应体系中通入HCl气体的方法实现原料芳胺盐酸盐的重新利用, 更加绿色环保.

关键词: 受限路易斯酸碱对, 三(五氟苯基)硼, 芳香胺盐酸盐, 氢化硅烷, 氯代硅烷

Although in recent years the frustrated Lewis pairs (FLPs) reactivity towards small molecule activation has been widely concerned, the reports on the FLPs derived from aromatic amines are few. This paper describes a new facile route to the aromatic amine based FLPs starting from aromatic amine hydrochloride/tri(pentafluorophenyl)borane (BCF) as a combined active couple and hydridosilane as a source of the hydride. The reaction characteristics have been studied for a set of the stoichiometrical reactions. The difference between the alkyl amine hydrochloride/BCF and aromatic amine hydrochloride/BCF systems is that after reacting with the silanes the formed aromatic ammonium hydridoborates [Ar2NH2]+[HBCF]- are not thermally stable and immediately release H2 with formation of the corresponding amine and BCF. However, it is precisely because of this fact making this system applicable for a catalytic reaction-a novel efficient chlorination reaction of hydridosilanes, which could be considered as the first example of the nonmetal catalytic reactions of the type, with the aromatic amine hydrochloride as a function of the chlorination reagent and BCF as a catalytic activator. The chlorination products and reaction mechanism have been also explored in detail under different ratios of silanes and aromatic amine hydrochlorides. Remarkably, if required, the initial aromatic amine hydrochloride can be regenerated and recycled by a simple reaction with gaseous HCl. This makes the reaction rather attractive from the viewpoint of “green chemistry”.

Key words: frustrated Lewis pairs, tris(pentafluorophenyl)boron, aromatic ammonium chlorides, hydridosilanes, silane chlorides