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Synthetic method of aryl cyanide in water solution

A synthesis method and cyanide technology, which are used in the preparation of cyanide reactions, chemical instruments and methods, chemical/physical processes, etc., can solve the problems of harsh reaction conditions, damage, functional groups cannot be retained, etc., and achieve easy separation and reduce environmental protection. Pollution problems, the effect of reducing the use of organic solvents

Inactive Publication Date: 2010-06-02
NANJING UNIV OF TECH
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Problems solved by technology

However, these methods (comprising the use of aqueous solution) that adopt potassium ferrocyanide as the cyanide reagent all need relatively harsh reaction conditions, for example, the reaction temperature is greater than 140 ° C, so that many functional groups cannot be retained in the aryl cyanide reaction, which is easy destroyed

Method used

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  • Synthetic method of aryl cyanide in water solution
  • Synthetic method of aryl cyanide in water solution
  • Synthetic method of aryl cyanide in water solution

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: the synthesis of benzonitrile

[0023] 1.1 Add 2ml of water and 1,4-dioxane to a 25ml Schlenk test tube, the mixture (volume ratio 1:1), then add chlorobenzene (1mmol, 102μL), K 4 [Fe(CN) 6 ] (0.25mmol, 92.1mg), K 2 CO 3 (0.25mmol, 34.5mg), XPhosSO 3 Na(2%mol, 10.5mg), Pd(OAc) 2 (1%mol, 2.2mg), reacted at 110°C for 10h, and the yield of benzonitrile was 93.6% (determined by gas chromatography).

[0024]

[0025] 1.2 Add 2ml of water and 1,4-dioxane to a 25ml Schlenk test tube, the mixture (volume ratio 1.5:0.5), then add chlorobenzene (1mmol, 102μL), K 4 [Fe(CN) 6 ] (0.20mmol, 73.7mg), K 2 CO 3 (0.25mmol, 34.5mg), XPhosSO 3 Na(2%mol, 10.5mg), Pd(OAc) 2 (1%mol, 2.2mg), reacted at 110°C for 10h, and the yield of benzonitrile was 83.2% (determined by gas chromatography).

[0026] 1.3 Add 2ml of water and 1,4-dioxane to a 25ml Schlenk test tube, the mixed solution (volume ratio 1.2:0.8), then add chlorobenzene (1mmol, 102μL), K 4 [Fe(CN) 6 ] (0...

Embodiment 2

[0031] Embodiment 2: the synthesis of 2-methylbenzonitrile

[0032] 2.1 Add 2ml of water and 1,4-dioxane mixture (volume ratio 1:1) to a 25ml Schlenk test tube, then add o-chlorotoluene (1mmol, 117μL), K 4 [Fe(CN) 6 ] (0.25mmol, 92.1mg), K 2 CO 3 (0.25mmol, 34.5mg), XPhosSO 3 Na(3%mol, 15.7mg), Pd(OAc) 2 (1.5%mol, 3.3mg), reacted at 120°C for 10h, and the yield of 2-methylbenzonitrile was 97% (determined by gas chromatography).

[0033]

[0034] 2.2 Add 2ml of water and N,N-dimethylformamide to a 25ml Schlenk test tube to form a mixed solution (volume ratio 1.5:0.5), then add o-chlorotoluene (1mmol, 117μL), K 4 [Fe(CN) 6 ] (0.25mmol, 92.1mg), K 2 CO 3 (0.25mmol, 34.5mg), XPhosSO 3 Na(3%mol, 15.7mg), Pd(OAc) 2 (1.5%mol, 3.3mg), reacted at 120°C for 10h, and the yield of 2-methylbenzonitrile was 60% (determined by gas chromatography).

[0035] 2.3 Add 2ml of water and 1,4-dioxane mixture (volume ratio 1:1) to a 25ml Schlenk test tube, then add o-tolyl-4-methylbenze...

Embodiment 3

[0037] Embodiment 3: the synthesis of 4-methoxybenzonitrile

[0038] 3.1 Add 2ml of water and 1,4-dioxane mixture (volume ratio 1:1) to a 25ml Schlenk test tube, then add 4-chloroanisole (1mmol, 123μL), K 4 [Fe(CN) 6 ] (0.25mmol, 92.1mg), K 2 CO 3 (0.25mmol, 34.5mg), XPhosSO 3 Na(3%mol, 15.7mg), Pd(OAc) 2 (1.5%mol, 3.3mg), reacted at 120°C for 10h, and the yield of 4-methoxybenzonitrile was 96% (determined by gas chromatography).

[0039]

[0040] 3.2 Add 2ml of water and ethanol (volume ratio 1.5:0.5) to a 25ml Schlenk test tube, then add 4-chloroanisole (1mmol, 123μL), K 4 [Fe(CN) 6 ] (0.5mmol, 184.2mg), K 2 CO 3 (0.5mmol, 69.0mg), XPhosSO 3 Na(2%mol, 10.5mg), Pd(OAc) 2 (0.5% mol, 1.1 mg), reacted at 120°C for 10 h, and the yield of 4-methoxybenzonitrile was 45.1% (determined by gas chromatography).

[0041] 3.3 Add 2ml of water and 1.0mmol of tetrabutylammonium bromide mixture to a 25ml Schlenk test tube, then add 4-bromoanisole (1mmol, 125μL), K 4 [Fe(CN) 6...

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Abstract

The invention relates to a synthetic method of an aryl cyanide in a water solution, which comprises the following steps: adding an aryl compound, a ferrocyanide and a phase transfer agent into an alkaline water solution, or adding the aryl compound and the ferrocyanide into a mixed solution of alkaline water and an organic solution; controlling the reaction temperature at 30 DEG C-140 DEG C; and synthesizing the aryl cyanide by catalytic coupling of a metal palladium catalyst. In the invention, the non-toxic environment-friendly ferrocyanide is used as a cyanide source for synthesizing the aryl cyanide, and water is used as an environment-friendly solvent to substitute the virulent cyanide and the organic solvent in the prior art, thereby solving the problem of environment pollution in the process of synthesizing the aryl cyanide. In the invention, good solubility of the ferrocyanide in the water and the strong polarity of the ferrocyanide are used, thereby greatly promoting the generation of the aryl cyaniding reaction, the cyaniding reaction can be finished at lower temperature (30 DEG C-140 DEG C), the reaction yield is high, and the application range of the aryl cyaniding reaction is improved.

Description

technical field [0001] The invention relates to a palladium-catalyzed green method for synthesizing aryl cyanide, in particular to a method for synthesizing aryl cyanide in an aqueous solution in which aryl chloride aryl sulfonate is coupled with non-toxic ferrocyanide. Background technique: [0002] Benzonitrile compounds are important components of many chemical products, such as dyes, herbicides, pharmaceuticals and many natural compounds. At the same time, benzonitrile is also an important intermediate in organic synthesis, which can be converted into a series of functional substances, such as Acids, amides, aldehydes, ketones, oximes, etc. There are many methods for synthesizing benzonitrile. The early methods are Rosenmund-von Braun reaction and Sandmeyer reaction, which use stoichiometric CuCN and cause heavy metal pollution. In order to overcome this disadvantage, chemists have developed some nitrilation reagents, such as: KCN, NaCN, TMSCN (Trimethylsilyl cyanide). ...

Claims

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Application Information

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IPC IPC(8): C07C253/16C07C253/14C07C255/50C07C255/54B01J31/24
Inventor 黄军陈晓蓉张渊张俊丽
Owner NANJING UNIV OF TECH
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