Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Catalytic preparation process for aromatic nitrile or heteroaromatic nitrile

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

Inactive Publication Date: 2014-07-02
ZHEJIANG UNIV
View PDF2 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] In a 100-liter reactor, 25 liters of water, 32.5 kilograms of p-methoxybromobenzene, 14.5 kilograms of potassium ferrocyanide, 2 kilograms of nano-cuprous iodide, 5.7 kilograms of potassium iodide, and 18.7 liters of N,N'-dimethyl iodide were added successively. Ethylenediamine, closed and stirred at 160 ° C for 40 hours, the reaction was terminated, the nano-cuprous iodide was recovered by suction filtration, the organic phase was separated from the filtrate, and the organic phase was subjected to vacuum fractionation to recover N,N'-dimethylethylenediamine amine, and p-methoxybenzonitrile was obtained in 96% yield as a 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 reaction kettle, add 5 liters of water, 30 moles of p-bromobiphenyl, 5.1 moles of potassium ferrocyanide, 1.5 moles of nano-cuprous iodide, 1 kilogram of potassium iodide (6 moles, 0.2 equivalents), 2.64 kilograms of N, N'-Dimethylethylenediamine (30 mol, 1.0 equivalent), the reaction was closed and stirred at 165 ° C for 48 hours, the reaction was terminated, the nano-cuprous iodide was recovered by suction filtration, the organic phase was separated from the filtrate, and the organic phase was subjected to reduced pressure fractionation N,N'-dimethylethylenediamine can be recovered, and the residue is recrystallized from ethanol to obtain p-cyanobiphenyl, yield 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] 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 were successively added to the 100-liter reaction kettle. '-dimethylethylenediamine, the reaction was closed and stirred at 160 ° C for 48 hours, the reaction was terminated, the nano-cuprous iodide was recovered by suction filtration, the organic phase was separated from the filtrate, and the organic phase was subjected to reduced pressure fractionation to recover N,N'-di Methylethylenediamine, the residue was subjected to high vacuum fractionation to obtain liquid crystal intermediate 4-cyano-4'-ethylbiphenyl, yield 90%, mp73~74 ℃, 1 H NMR ( 400 MHz CDCl 3 ): 1.28 (m, 3H), 2.74 (m, 2H), 7.36~7.85 (m, 8H) ppm.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

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 an aromatic nitrile or a heteroaromatic nitrile. Background technique [0002] Aromatic nitrile or heteroaromatic nitrile compounds are important fine chemicals, which can be hydrolyzed to produce acids or reduced to amines, and are widely used in the fields of medicine, pesticides, dyes, and plastic auxiliaries; for example, the antidepressant citalopram is the key Intermediate 5-cyanophthalide, key intermediate of antihypertensive drugs, sartan biphenyl, intermediate of hydralazine, o-cyanobenzaldehyde, intermediate of new herbicide, 2-cyanopyridine, liquid crystal material 4 '-Alkyl-4-cyanobiphenyl, etc. are all compounds containing a cyano group. The industrially used process for the preparation of aromatic nitriles is mainly the aminooxidation of substituted toluene by reacting methyl aromatic compounds with ammo...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
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
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com