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Method for catalyzing green cyanation of halogenated aromatic hydrocarbons by supported Pd complex

A halogenated aromatic hydrocarbon, supported technology, applied in the field of chemical industry and two-phase catalysis, can solve the problems of strong corrosion, restricting wide application, and difficult post-processing

Active Publication Date: 2019-02-15
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of the traditional Rosenmund-von Braun method and the Sandmeyer method is that the use of stoichiometric cuprous cyanide will produce an equivalent amount of heavy metal waste to pollute the environment
In addition, the disadvantage of the Rosenmund-von Braun method is that the reaction needs to be carried out at high temperature (150-250°C)
The problem with the ammoxidation method is that the reaction conditions are harsh (high temperature and high pressure) and the use of a large excess of ammonia
At present, the traditional cyanation reagents (CuCN, NaCN, KCN, etc.) 4 [Fe(CN) 6 ]·3H 2 O is an ideal source of green cyanide, but K 4 [Fe(CN) 6 ]·3H 2 O is easily soluble in water and difficult to dissolve in organic solvents, so it is often necessary to use high-boiling point and high-polarity organic solvents such as NMP, DMA, DMF, etc. as a cyanide source, which brings great difficulties to post-processing.
The homogeneous Pd catalyst has the characteristics of high catalytic activity and mild reaction conditions, and is the most commonly used catalyst in the cyanation reaction of halogenated aromatic hydrocarbons. However, due to the high price of Pd metal and the difficulty of separation and recovery, its wide application is restricted.

Method used

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  • Method for catalyzing green cyanation of halogenated aromatic hydrocarbons by supported Pd complex
  • Method for catalyzing green cyanation of halogenated aromatic hydrocarbons by supported Pd complex
  • Method for catalyzing green cyanation of halogenated aromatic hydrocarbons by supported Pd complex

Examples

Experimental program
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Effect test

Embodiment 1

[0034] Preparation of supported ligand I and its method for catalyzing the green cyanation of halogenated aromatic hydrocarbons:

[0035] (1) Preparation of CH 3 O-(CH 2 CH 2 O) 6 -CH 2 CH 2 OTs: CH 3 O-(CH 2 CH 2 O) 6 -CH 2 CH 2 OH (2.5466g, 7.25mmol), NaOH (0.5800g, 20.30mmol) were dissolved in deionized water (15mL) and tetrahydrofuran (15mL), and stirred in an ice-water bath for 0.5h. p-Toluenesulfonyl chloride (TsCl, 1.7273g, 9.06mmol) was dissolved in tetrahydrofuran (20mL) and added dropwise to the reaction system. The stirring reaction was continued for 2h, and then warmed to room temperature for 24h. After the reaction was completed, deionized water (20 mL) was added, extracted with dichloromethane (25 mL×3), the organic phase was washed with saturated brine (15 mL×2), anhydrous Na 2 SO 4 Dry, filter, and remove the organic solvent under reduced pressure to obtain a crude product, which was separated and purified by column chromatography (developing solve...

Embodiment 2

[0041] Preparation of supported ligand Ⅱ and its method for catalyzing the green cyanation of halogenated aromatic hydrocarbons:

[0042] (1) Preparation of N-(MPEG)-3-bromo-2-phenylindole (MPEG=CH 3 O-(CH 2 CH 2 O) 6 -CH 2 CH 2 -): Under nitrogen protection, 2-phenylindole (868.5mg, 3.19mmol), CH 3 O-(CH 2 CH 2 O) 6 -CH 2 CH 2 OTs (534.4mg, 1.06mmol), NaOH (255.2mg, 6.38mmol) were dissolved in anhydrous DMF (30mL), stirred at 80°C for 48h. After the reaction, DMF was removed by rotary evaporation, deionized water (30 mL) was added, extracted with dichloromethane (20 mL×3), the organic phase was washed with saturated brine (15 mL), anhydrous Na 2 SO 4 Dry, filter, and remove the solvent under reduced pressure to obtain a crude product, which was separated and purified by column chromatography (developing solvent, dichloromethane: anhydrous methanol = 10:1) to obtain 621.1 mg of a yellow-brown oily liquid with a yield of 97%.

[0043] (2) Preparation of Ligand II: ...

Embodiment 3

[0047] Supported Ligand II Catalyzed Recycling Method for Green Cyanylation of Halogenated Aromatics:

[0048] (1) Supported ligand II catalyzes cyanation of halogenated aromatic hydrocarbons: same as step (2) in Example 2.

[0049] (2) will K 4 [Fe(CN) 6 ]·3H 2 O (31.7mg, 0.075mmol) was dissolved in deionized water (2mL) and anhydrous acetonitrile (0.5mL), and added to the reaction system after dissolution, and reacted for 3h. After the reaction, take out the toluene layer while it is hot, and extract the reaction solution twice with toluene (5mL), combine the toluene phases, take out 0.5mL and add anhydrous Na 2 SO 4 Dry, filter, yield 58% by GC. The toluene in the remaining toluene phase was removed by rotary evaporation, isopropanol (2 ml) was added to the residue to dissolve, and extracted with n-hexane. Then the isopropanol was removed by rotary evaporation to obtain the catalyst, and the next catalytic reaction was continued.

[0050] (3) The second cycle method:...

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Abstract

The invention provides a method for catalyzing green cyanation of halogenated aromatic hydrocarbons by a supported Pd complex and belongs to the technical field of chemical engineering and catalysis.According to the method disclosed by the invention, a series of supported Pd catalysts are synthesized, and applied to a reaction for catalyzing cyanation of halogenated aromatic hydrocarbons. The method disclosed by the invention has the advantages that the preparation method of the series of supported ligands is simple, the cost is low, the Pd complex can realize complete transformation of bromobenzene, and the catalyst can be recycled for three times. The cyanide source used in the reaction is non-toxic yellow prussiate of potash, the reaction can be completed in a methylbenzene-water two-phase catalytic system, use of a high-boiling-point high-polarity organic solvent is avoided, and the whole reaction system is green and environmental-friendly.

Description

technical field [0001] The invention belongs to the technical field of chemical industry and two-phase catalysis, and relates to two-phase catalysis for the cyanation reaction of halogenated aromatic hydrocarbons, in particular to a method for catalyzing the green cyanation of halogenated aromatic hydrocarbons by using such supported Pd complexes. Background technique [0002] Aromatic nitriles are a very important class of organic compounds, and are important components of dyes, herbicides, insecticides, pesticides, medicines and natural products. Drugs containing cyano functional groups account for a considerable proportion of clinical drugs. The physical and chemical properties of small molecule drugs can be adjusted by introducing cyano groups, thereby improving the bioavailability of drugs. In the pesticide molecule, the cyano group is also an indispensable group. Since the cyano group is an active group with special electrical and structural characteristics, it is of...

Claims

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Application Information

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IPC IPC(8): C07F9/50C07F9/572B01J31/24C07C255/50C07C253/14
CPCB01J31/2404B01J2531/0213B01J2531/824C07C253/14C07F9/5022C07F9/5728C07C255/50Y02P20/584
Inventor 王万辉吴有根韩东包明
Owner DALIAN UNIV OF TECH
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