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Pd-Zn bimetallic catalyst for preparing aromatic cyano compound

A bimetallic catalyst, compound technology, applied in metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, chemical/physical process, etc., can solve the problem of inactive Pd black, low reactivity, easy Poisoning and other problems, to achieve the effect of prolonging the catalytic life, high catalytic activity, and high contact probability

Inactive Publication Date: 2016-11-16
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these homogeneous metal catalysts are difficult to separate, and most of them cannot be recycled and used mechanically. Moreover, the Pd complex of homogeneous catalysts is unstable at higher temperatures, and it is easy to form low-activity or inactive Pd black.
[0005] Because the cost of homogeneous catalysts is too high, which limits its industrial application, research and development of heterogeneous catalytic systems to overcome these disadvantages of homogeneous catalytic systems has become a research hotspot in recent years.
Seki group reported Pd / C as catalyst, PPh 3 as a ligand, and added Zn powder and ZnBr 2 As an additive, the cyanation reaction of halogenated aromatic hydrocarbons is carried out. However, Pd / C is a catalyst with low reactivity, and it is still necessary to add phosphine ligand PPh 3 To promote the reaction, at the same time, Pd / C catalyst is easily poisoned in the cyanation reaction, and zinc powder needs to be added to promote the reduction of high-priced metal atoms to a low-priced state to maintain the stability of the metal catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Palladium acetate (0.025 mmol), zinc acetate (0.025 mmol) and PVP (100 mg) were dissolved in 1.5 mL DMF at room temperature, and stirred until clear and transparent to obtain a metal precursor solution. The reducing agent potassium borohydride (0.15 mmol) was then slowly added to the metal precursor solution with vigorous stirring during the addition of potassium borohydride. Stir for 10 minutes after the addition is complete to obtain a Pd-Zn bimetallic catalyst. Sodium carbonate (0.5mmol) and bromobenzene (0.5mmol) were added to the bimetallic catalyst prepared above, followed by potassium ferrocyanide (0.1mmol) slowly. After adding, fill with nitrogen protection, at 120 O C conditions for 24h. After the reaction was completed, it was lowered to room temperature, and water and ethyl acetate were added. After removing the solvent by rotary evaporation in the organic phase, the product was obtained, and then the catalyst was separated by centrifugal precipitation in ...

Embodiment 2

[0020] Reaction steps are identical with embodiment 1, difference is:

[0021] The reaction substrate is 0.5 mmol nitrobromobenzene, and the yield of p-nitrobenzonitrile is 95%.

Embodiment 3

[0023] Reaction steps are identical with embodiment 1, difference is:

[0024] The amount of zinc acetate used was 0.012mmol, and the yield of benzonitrile was 91.0%.

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PUM

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Abstract

The invention discloses a Pd-Zn bimetallic catalyst for preparing an aromatic cyano compound. The catalyst is prepared by the following steps: uniformly stirring palladium acetate and zinc salt in DMF, adding a certain amount of PVP as a stabilizer, stirring until the solution is clear and transparent, adding a reducing agent KBH4, and stirring for reaction to obtain the Pd-Zn bimetallic catalyst. A reaction process using the Pd-Zn bimetallic nanoparticles as a catalyst does not need additional ligand. The catalyst is at nano level, the probability of contact of catalytic active sites with a reaction substrate is larger, the catalytic activity is higher, and Pd and Zn in the catalyst form an alloy structure to effectively prevent Pd metal poisoning and prolong catalysis life.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of an aromatic cyano compound. Background technique [0002] The general formula of the cyanation product is RCN, and the functional group is cyano (-CN). Aromatic cyanation products are very important intermediates in organic synthesis. It is of great significance in pesticides, dyes, medicines, etc. And it can be used as an intermediate to synthesize many important compounds, such as hydrolysis to prepare acids and amides, and reduction to prepare amines. It is also an important raw material in biology, pharmacy, pesticide chemistry and natural products. Therefore, the cyanation reaction not only plays an important role in theory, but also in practical application. [0003] At present, the preparation of cyanated compounds is mainly prepared by substitution method, among which the halogen substitution method is relatively simple, and is curr...

Claims

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Application Information

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IPC IPC(8): B01J23/60B01J23/89C07C253/14C07C255/50
CPCC07C253/14B01J23/60B01J23/8913B01J23/892B01J23/8926B01J35/40C07C255/50
Inventor 蔡春蔡垚章佳威
Owner NANJING UNIV OF SCI & TECH
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