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Method for epoxidation of cyclooctene catalyzed by calixarene ammonium perrhenate

A technology of cyclooctene ring and calix perrhenate, applied in the field of organic catalysis, can solve the problems of difficulty in recycling, high cost of use and high cost of ionic liquid

Inactive Publication Date: 2017-06-20
LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

NH 4 ReO 4 / C is used as a catalyst for cyclohexane dehydrogenation and ethanol dehydrogenation; KReO 4 / SiO 2 It is also a catalyst in a series of hydrogenation; the above-mentioned rhenium and some of its compounds used for catalysis are all inorganic compounds, but the metal organic compounds and catalytic properties of rhenium were developed very late, and the metal organic compounds of rhenium are more representative For example, methyl rhenium trioxide (MTO), which is a new type of efficient transition metal organic catalyst, can catalyze a variety of organic synthesis reactions, such as olefin epoxidation, oxidation of C-H and Si-H, oxidation of aromatic compounds , the self-metathesis reaction of olefins, allyl aldehydes, ethers, silanes and unsaturated carboxylic acid esters and the olefination of aldehydes, etc. (Chem Rev, 1997,97(8):3197-3264.Rare Metal,2006,25(6 ): 411-421. Molecular Catalysis, 2010,24(3): 241-246.), but methyl rhenium trioxide is expensive, the cost of use is relatively high, and it is a homogeneous reaction, so it is difficult to recycle, although it can The purpose of repeated use is achieved through the load, but the problem of high cost of use still cannot be solved
There is also a report on the use of rhenium ionic liquids to catalyze the epoxidation of olefins (CN 101735175.A), but the ionic liquids also have the problem of high cost

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] 1. Catalyst 1 (n=4, R=-C 2 h 5 ) preparation

[0018] Take 0.2 mmol of calix[4]arene diethylamine mannich base and 0.8 mmol of ammonium perrhenate, and dissolve them in 5 mL of 1 mol / L hydrochloric acid and 5 mL of distilled water, respectively. The hydrochloric acid solution of calix[4]arene diethylamine mannich base was added dropwise to the ammonium perrhenate aqueous solution under stirring, a white solid was formed, stirred for 30 minutes, filtered, and vacuum-dried to obtain 0.34 g of a white solid with a yield of 93.1 %.

[0019] 2. Catalytic cyclooctene epoxidation

[0020] Into a 25 mL round bottom flask, add 1 mmol cyclooctene and 3 mmol 30% H 2 o 2 , 6.0×10 -3 One mmol of the above catalyst was dissolved in 5mL N,N-dimethylformamide and added to the reaction flask, stirred in a water bath at 40°C for 4h, after the reaction was completed, a small amount of MnO 2 Decompose H 2 o 2 , until no bubbles are produced, and then use anhydrous MgSO 4 0.06g dr...

Embodiment 2

[0022] 1. Catalyst 1 (n=6, R=-C 2 h 5 ) preparation

[0023] Take calix[6]arene diethylamine mannich base 0.2mmol, ammonium perrhenate 0.2mmol, respectively dissolve in 5mL 1mol L -1 hydrochloric acid and distilled water. Add calix[6]arene diethylamine mannich base solution dropwise to ammonium perrhenate aqueous solution under stirring, a white solid is formed, stir for 30 minutes, filter, and vacuum dry to obtain 0.51 g of white solid with a yield of 90.4%.

[0024] 2. Catalytic cyclooctene epoxidation

[0025] Into a 25 mL round bottom flask, add 1 mmol cyclooctene and 3 mmol 30% H 2 o 2 , 6.0×10 - 3 One mmol of the above catalyst was dissolved in 5mL N,N-dimethylformamide and added to the reaction flask, stirred in a water bath at 40°C for 4h, after the reaction was completed, a small amount of MnO 2 Decompose H 2 o 2 , until no bubbles are generated; then use anhydrous MgSO 4 0.05g dry reaction system, then filter, and the filtrate is qualitatively analyzed by ...

Embodiment 3

[0027] 1. Catalyst 1 (n=8, R=-C 2 h 5 ) preparation

[0028] Take 0.2mmol of calix[8]arene diethylamine mannich base and 0.2mmol of ammonium perrhenate, dissolve them in 5mL of 1mol·L -1 hydrochloric acid and distilled water. Add calix[8]arene diethylamine mannich base solution dropwise to ammonium perrhenate aqueous solution under stirring, a white solid is formed, stir for 30 min, filter, and vacuum dry to obtain 0.6591 g of white solid with a yield of 89.5%.

[0029] 2. Catalytic cyclooctene epoxidation

[0030] Into a 25 mL round bottom flask, add 1 mmol cyclooctene and 3 mmol 30% H 2 o 2 , 6.0×10 -3 One mmol of the above catalyst was dissolved in 5mL N,N-dimethylformamide and added to the reaction flask, stirred in a water bath at 40°C for 4h, after the reaction was completed, a small amount of MnO 2 Decompose H 2 o 2 , until no bubbles are generated, and then use anhydrous MgSO 4 0.07g dried reaction system, then filtered, the filtrate was qualitatively analyze...

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Abstract

The invention relates to a method for catalyzing epoxidation of cyclooctene by calixarene ammonium salt of perrhenic acid. The method comprises the following steps: by taking calixarene ammonium salt of perrhenic acid as a catalyst, 30% H2O2 as an oxidizing agent and N,N-dimethylformamide as a solvent, catalyzing epoxidation reaction of cyclooctene, wherein the reaction is a homogeneous reaction; after reaction, adding a small amount of MnO2 to decompose H2O2 till no bubbles are generated, then drying a reaction system by anhydrous MgSO4, and determining the reaction transformation rate through qualitative and quantitative analysis of gas chromatography; extracting a product by normal hexane, distilling water and most organic matters at a reduced pressure from other solution, and then adding methanol, wherein the precipitated catalyst can be repeatedly used.

Description

technical field [0001] The present invention relates to the field of organic catalysis, in particular to a method for the epoxidation of cyclooctene catalyzed by a calixarene ammonium perrhenic acid, specifically, using the calixarene ammonium perrhenic acid as a catalyst, and using H 2 o 2 As an oxidizing agent, it catalyzes the epoxidation of cyclooctene. Background technique [0002] Rhenium (Re) is the latest important element discovered in the rare element (RSE) group. It is a rare and expensive non-ferrous metal and one of the extremely important raw materials in the modern high-tech field. It has its own catalytic properties, high temperature resistance, Excellent properties such as corrosion resistance, ductility, formability and carburization resistance. In the electronic structure of rhenium, the 5 electrons of the unsaturated 4d layer are easy to release, and the 2 electrons of the 6s layer are easy to participate in the interaction to form a covalent bond. In a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D301/12C07D303/04B01J31/02
CPCY02P20/584
Inventor 陈平臧树良周明东吴爽武秋朋张亚洲
Owner LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY