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Synthesis method of ruthenium carbene catalyst

A carbene catalyst and a synthesis method technology are applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., and can solve the problems of complicated post-processing and unfavorable industrial production, etc. Achieve the effect of easy availability of raw materials, convenient raw materials and simple operation

Pending Publication Date: 2020-07-31
SHANGHAI RES INST OF CHEM IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This method utilizes excess styrene to carry out olefin exchange reaction (20 equivalents), and aftertreatment is more complicated, is unfavorable for industrialized production

Method used

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  • Synthesis method of ruthenium carbene catalyst
  • Synthesis method of ruthenium carbene catalyst
  • Synthesis method of ruthenium carbene catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Embodiment 1: the synthesis of Grubbs catalyst

[0044] Step 1)C 6 h 5 CH=PPh 3 preparation of

[0045] Add 20.7g triphenylphosphine (PPh 3 ) and 50ml of toluene, stirred at 40°C for 0.5 hours until triphenylphosphine was completely dissolved, slowly added 6.8g of benzyl bromide (C 6 h 5 CH 2 Br), keep a constant temperature of 40°C for 4 hours, the reaction solution gradually becomes cloudy, and it is observed that a large amount of white solids are formed in the reaction system. Suction filtration, washing obtains white solid [C 6 h 5 CH 2 -PPh 3 ]Br about 16.5g, yield 96%. 1 H NMR (C 6 D. 6 ,500M):δ7.63-7.70(m,6H),7.01-7.71(m,7H),6.92-6.96(m,6H),6.67-6.69(m,1H),2.85(d,1H),; 31 P NMR (C 6 D. 6 ,200M):δ7.9(s,PCy 3 ).

[0046] Get 100ml Schlenk reaction bottle and add 4.32g [C 6 h 5 CH 2 -PPh 3 ]Br, replace the air 3 times, inject 40ml of anhydrous ether, inject 7.5ml of n-butyllithium-n-hexane solution (1.6M) into the above system under the condit...

Embodiment 2

[0054] Compared with Example 1, most of them are the same, and the benzyl bromide in step 2) is replaced with benzyl chloride, and white solid [C 6 h 5 CH 2 -PPh 3 ]Cl about 10.3g, yield 67%. 1 H NMR (C 6 D. 6 ,500M):δ7.69-7.75(m,9H),7.58-7.61(m,6H),7.18-7.20(m,1H),7.07-7.10(m,4H),5.45(d,2H),; 31 P NMR (C 6 D. 6 ,200M):δ23.6(s,PCy 3 ).

[0055] Get 100ml Schlenk reaction bottle and add 3.88g [C 6 h 5 CH 2 -PPh 3 ]Cl, replace the air 3 times, inject 40ml of anhydrous ether, inject 7.5ml of n-butyllithium-n-hexane solution (1.6M) into the above system under ice-water bath conditions, stir at room temperature for 2 hours, and the reaction solution gradually becomes orange-red The reaction was stopped, and the orange-red liquid was obtained by vacuum filtration, which was C 6 h 5 CH=PPh 3 , the reaction solution can be directly put into the next reaction. 31 P NMR (C 6 D. 6 ,200M):δ9.7(s,PCy 3 ).

[0056] Further complexation reaction with triphenylphosphine r...

Embodiment 3

[0058] Compared with Example 1, most of them are the same, and the reaction medium dichloromethane in step 2) is replaced with methyl tetrahydrofuran.

[0059] Take another 100ml Schlenk reaction bottle, and add 4.5g RuCl to the glove box 2 (PPh 3 ) 3 , add 50ml of dry methyl tetrahydrofuran under nitrogen atmosphere, and slowly add the C prepared in step (1) under the condition of -30°C 6 h 5 CH=PPh 3 (2 times equivalent, in [C 6 h 5 CH 2 -PPh 3 ] X meter, X=Cl or Br), the color of the reaction solution gradually deepens, and 5.6gPCy is added after stirring for 2 hours 3 , return to room temperature and stir for 1 hour, and the reaction ends. The reaction solvent was removed under vacuum, recrystallized, washed, and filtered to obtain Grubbs I catalyst, 1.7 g, yield 41%.

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Abstract

The invention relates to a synthesis method of a ruthenium carbene catalyst, which comprises the following steps: (1) adding benzyl halide and triphenylphosphine into a reactor, reacting in a medium,and reacting the obtained reaction product under the action of a strong alkali to obtain a first intermediate product; (2) reacting the first intermediate product with triphenylphosphine ruthenium chloride in a solvent, replacing triphenylphosphine with tricyclohexylphosphine, filtering and washing to obtain a ruthenium carbene complex precursor; and (3) carrying out a complex addition reaction onthe ruthenium carbene complex precursor and a functional ligand to obtain the target product that is the ruthenium carbene catalyst. Compared with the prior art, the method has the characteristics ofcapability of efficiently controlling the reaction speed, short preparation period, simplicity in operation, stable process, environmental friendliness, good atom economy and the like, and has a relatively great application prospect in the aspect of industrial amplification.

Description

technical field [0001] The invention belongs to the technical field of ruthenium carbene catalyst preparation and relates to a ruthenium carbene catalyst. Background technique [0002] Transition metal carbene complexes have attracted great research interest because of their unique structures, reaction characteristics and applications in organic synthesis and catalytic reactions. Metal carbenes can be regarded as free radical metal complexes formed by complexing free state carbenes with metals. Free carbene is a kind of unstable intermediate with short life and high activity, but after complexing with metal to form metal carbene, the stability is improved, and the corresponding reactivity is also improved. Since the first metal carbene complex came out, people have developed many methods for synthesizing metal carbene, which can be roughly divided into three categories: 1. From metal-carbon bond conversion; 2. Carbene source addition to metal complexation 3. Transformation...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/24
CPCB01J31/181B01J31/2409B01J2531/821
Inventor 杨维成罗勇段高坤刘建方超立乔新峰乔拟春付宏伟李秀君
Owner SHANGHAI RES INST OF CHEM IND
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