Alkaline ionic liquid and its prepn process and application

A basic ion and liquid technology, applied in the field of basic ionic liquid and its preparation, can solve the problems of poor solubility, limited use, difficult activation, etc., to achieve activity and stability promotion, good thermal stability, ultra-low vapor pressure effect

Inactive Publication Date: 2007-03-21
EAST CHINA NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the shortcoming of this reaction has the following aspects: 1. the catalyst system is unstable, and after a fresh catalyst is used once, palladium black is often precipitated—catalyst deactivation; It can be effectively carried out, and the cheap substrates chlorinated aromatic hydrocarbons and brominated aromatic hydrocarbons are difficult to activate; ③The use of alkali-using organic bases or inorganic bases as acid-binding agents, forming a large number of by-products sodium salts, potassium salts or ammonium salts, these by-products The accumulation of salt will gradually poison and deactivate the transition m

Method used

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  • Alkaline ionic liquid and its prepn process and application
  • Alkaline ionic liquid and its prepn process and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-12

[0036] The following examples will specifically describe the present invention, but not to further limit the present invention; all examples are operated according to the above reaction conditions and steps.

[0037] The synthesis steps of basic ionic liquid BIL1-12 are as follows. Synthesis of BIL1-4: N-methylimidazole and excess chlorobutane were refluxed in toluene for 48 hours to obtain the chloride salt of 1-butyl-3-methylimidazole. Use this chloride salt with NH 4 OAc, NH 4 HCO 3 , (NH 4 ) 2 CO 3 After ion exchange reaction with PhCOONa in acetonitrile solution, filter, remove solvent, and vacuum dry to obtain the corresponding basic ionic liquids BIL-1, 2, 3, 4, wherein BIL-4 is a white solid at room temperature. Synthesis of BIL5-12: N-methylimidazole and 2-chlorotriethylamine, 1-(2-chloroethyl)piperidine, N-(2-chloroethyl)morpholine, 1-(2-chloro Ethyl)pyrrolidine hydrochloride was refluxed in toluene for 24 hours to give the corresponding chloride salt as a sol...

Embodiment 13-27

[0040] The embodiment has investigated different acid-binding agents (traditional base NaHCO 3 、Et 3 N, the Heck coupling reaction result (table 1) of palladium-catalyzed bromobenzene and ethyl acrylate under the effect of basic ionic liquid BIL1-12)——the palladium catalyst precursor used is palladium dichloride (PdCl 2 ), the phosphine ligand is 1-butyl-3-methylimidazolium triphenylphosphine monosulfonate ([BMIM][TPPMS]), the reaction temperature is 140° C., and the reaction time is 3 hours. The results in Table 1 show that the coupling reaction is carried out in alkaline ionic liquids, the catalyst system is very stable, there is no palladium black to separate out, and the selectivity is also very good, but the conversion rate of bromobenzene is different because of the structure and composition of the ionic liquid.

[0041] Preface

No

Acid Binder

solvent

Bromobenzene conversion rate

(%)

Ethyl cinnamate selectivity

(%)

...

Embodiment 28-41

[0046] Embodiment has investigated in BIL-7 alkaline ionic liquid, four factors such as reaction temperature, palladium catalyst concentration and phosphine ligand and palladium catalyst molar ratio, and BIL-7 ionic liquid consumption etc. Heck coupling to bromobenzene and ethyl acrylate The effect of the linkage reaction.

[0047] Preface

No

temperature(℃)

Bromobenzene conversion rate

(%)

Ethyl cinnamate selectivity

(%)

1

50

5

99

2

90

31

99

3

140

43

98

4 *

200

46

98

[0048] a Bromobenzene 12mmol, ethyl acrylate 12mmol, basic ionic liquid BIL-718mmol, catalyst precursor PdCl 2 0.12mmol; PdCl 2 / [BMIM][TPPMS]=1 / 2 (molar ratio); reaction time 3 hours.

[0049] * Palladium black precipitation

[0050] Preface

No

PdCl 2 / PhBr

(mol%)

Bromobenzene conversion rate

(%)

Ethyl cinnamate s...

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PUM

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Abstract

The present invention is one kind of alkaline ionic liquid and its preparation process and application in Pd catalyzed C-C and C-N coupling reaction, and belongs to the field of new material and fine chemical technology. The alkaline ionic liquid consists of two parts, cation A+ and anion B-. The cation A+ precursor is imidazole, pyridine, etc; and the anion B- is alkaline group X- or non-alkaline group Y-. The alkaline ionic liquid is prepared through the first quaternizing with alkyl halide as the quaternizing reagent to obtain ion type halide; and the subsequent ion exchange to obtain the target alkaline ionic liquid. The alkaline ionic liquid of the present invention may act as acid-binding agent and can avoid formation of sticky inorganic salt to facilitate reuse.

Description

technical field [0001] The invention relates to an alkaline ionic liquid and its preparation method, as well as its application in palladium-catalyzed carbon-carbon and carbon-nitrogen coupling reactions, belonging to the field of new materials and fine chemicals. Background technique [0002] The carbon-carbon / carbon-nitrogen coupling reaction under the action of the transition metal palladium compound catalyst plays an important role in organic synthetic chemistry. It is an effective means for preparing many fine chemicals and pharmaceutical intermediates, and can be applied to drugs, pesticides , dyes, daily chemicals and polymers. However, the shortcoming of this reaction has the following aspects: 1. the catalyst system is unstable, and after a fresh catalyst is used once, palladium black is often precipitated—catalyst deactivation; It can be effectively carried out, and the cheap substrates chlorinated aromatic hydrocarbons and brominated aromati...

Claims

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Application Information

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IPC IPC(8): C07D233/58C07D233/61B01J31/02B01J31/24B01J31/28
Inventor 刘晔路勇李敏吴海虹何鸣元
Owner EAST CHINA NORMAL UNIVERSITY
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