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Catalytic preparation process for aromatic nitrile or heteroaromatic nitrile

A technology for catalytic preparation and heteroaromatic nitrile, which can be used in cyanide reaction preparation, organic chemistry, formation/introduction of cyano groups, etc., and can solve the problems of no industrially applied catalytic method, high technical cost, and difficulty in large-scale production. , to achieve the effect of short reaction process, wide substrate range and mild reaction conditions

Inactive Publication Date: 2013-01-30
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There have been reports in the literature using potassium ferrocyanide as a palladium-catalyzed cyanation substitution method (Chem. Commun. 2004, 1388-1389) or a copper-catalyzed cyanation method using microwave radiation, but due to technical Due to high cost or difficulty in large-scale production, there is no catalytic method for industrial application

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] In a 100-liter reactor, add 25 liters of water, 32.5 kg of p-methoxybromobenzene, 14.5 kg of potassium ferrocyanide, 2 kg of nano-cuprous iodide, 5.7 kg of potassium iodide, and 18.7 liters of N,N'-dimethyl N, N'-dimethylethylenediamine can be recovered by vacuum fractionation of the organic phase. amine, and p-methoxybenzonitrile was obtained in 96% yield, white solid, mp 52-53 °C; 1 H NMR (CDCl 3 ): 3.87 (s, 3H), 6.92-6.99 (m, 2H), 7.57-7.64 (m, 2H); EI-MS m / z : 133 (M+, 100).

Embodiment 2

[0015] In a 100-liter reactor, add 5 liters of water, 30 moles of p-bromobiphenyl, 5.1 moles of potassium ferrocyanide, 1.5 moles of nano-cuprous iodide, 1 kg of potassium iodide (6 moles, 0.2 equivalents), 2.64 kg of N, N'-Dimethylethylenediamine (30 moles, 1.0 equivalents), reacted at 165°C for 48 hours with closed stirring, ended the reaction, recovered nano-cuprous iodide by suction filtration, separated the organic phase from the filtrate, and fractionated the organic phase under reduced pressure N,N'-dimethylethylenediamine can be recovered, and the residue is recrystallized from ethanol to obtain p-cyanobiphenyl with a yield of 70%, white solid, mp 81-82 °C; 1 H NMR (CDCl 3 ): 7.39-7.53 (m, 3H), 7.56-7.62 (m, 2H), 7.66-7.75 (m, 4H); EI-MS m / z : 179 (M + , 100).

Embodiment 3

[0017] Add 5 liters of water, 30 moles of 4-iodo-4'-ethylbiphenyl, 5.2 moles of potassium ferrocyanide, 3 moles of nano-cuprous iodide, 6 moles of potassium iodide, 24 moles of N,N '-Dimethylethylenediamine, reacted under closed stirring at 160°C for 48 hours, ended the reaction, recovered nano-cuprous iodide by suction filtration, separated the organic phase from the filtrate, and recovered the N,N'-di Methylethylenediamine, the residue was subjected to high vacuum fractionation to obtain the liquid crystal intermediate 4-cyano-4'-ethylbiphenyl, the yield was 90%, mp73~74 ℃, 1 H NMR ( 400 MHz CDCl 3 ):1. 28 (m ,3 H ) ,2. 74 (m, 2H) ,7.36~7. 85 (m, 8H) ppm.

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Abstract

The invention discloses a catalytic preparation process for aromatic nitrile or heteroaromatic nitrile. According to the process, water is used as a reaction solvent, nanometer cuprous iodide, potassium iodide and N,N'-dimethylethylenediamine are used as a combined catalyst, substituted aryl halide or heteroaryl halide reacts with potassium ferrocyanide at a temperature of 150 to 170 DEG C for 24 to 48 h, and purification is carried out to obtain corresponding aromatic nitrile or heteroaromatic nitrile. Compared with synthetic methods in the prior art, the catalytic preparation process provided by the invention has the following advantages: (1) reaction conditions are mild; (2) reaction process flow is short; (3) a cheap nontoxic cyanated reagent is used, and a wide range of substrates can be used; and (4) industrial-grade aromatic nitrile or heteroaromatic nitrile is easy to use and is more economic and environment-friendly.

Description

technical field [0001] The invention relates to a preparation method of an organic synthesis intermediate, in particular to a catalytic preparation process of aromatic nitrile or heteroaromatic nitrile. Background technique [0002] Aromatic nitrile or heteroaromatic nitrile compounds are important fine chemicals, which can be hydrolyzed to prepare acids or reduced to amines, and are widely used in the fields of medicine, pesticides, dyes, and plastic additives; for example, the antidepressant citalopram is the key Intermediate 5-cyanophthalide, antihypertensive drug key intermediate sartan biphenyl, hydralazine drug intermediate o-cyanobenzaldehyde, new herbicide piceridine intermediate 2-cyanopyridine, liquid crystal material 4 '-Alkyl-4-cyanobiphenyl, etc. are compounds containing cyano groups. The industrially used process for the preparation of aromatic nitriles is primarily the amination of substituted toluenes by reacting methylaromatic compounds with ammonia and oxy...

Claims

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Application Information

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IPC IPC(8): C07B43/08C07C253/14C07C255/54C07C255/50C07D215/50C07D213/84
Inventor 毛侦军赵彦彦全丽丽林旭锋
Owner ZHEJIANG UNIV
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