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Method for preparing cyan aromatic hydrocarbon by using aryl bromide

A technology of cyanoarenes and brominated arenes, which is applied in pharmaceutical and chemical intermediates and related chemical fields, can solve the problems of harsh reaction conditions and high reaction temperature, and achieve the effect of short synthesis route, few reaction steps and convenient operation

Active Publication Date: 2013-01-16
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the cyanation of aryl halides usually requires harsher reaction conditions (higher reaction temperature or some special ligands)

Method used

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  • Method for preparing cyan aromatic hydrocarbon by using aryl bromide
  • Method for preparing cyan aromatic hydrocarbon by using aryl bromide
  • Method for preparing cyan aromatic hydrocarbon by using aryl bromide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Accurately weigh p-bromoacetophenone (99.0 mg, 0.5 mmol), potassium ferrocyanate trihydrate (84.5 mg, 0.2 mmol), palladium acetate (5.6 mg, 0.025 mmol), N, P - Bidentate ligand (12.9 mg, 0.025 mmol), potassium carbonate (138.0 mg, 1.0 mmol) were successively added to a 25 mL Schlenk bottle, acetonitrile (2.0 mL) was added, and placed in a 100 oC oil bath for 24 h . After the reaction, the reaction solution was filtered and spin-dried, and separated through a silica gel chromatography column, and the yield of p-cyanoacetophenone (a) was 85%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.03 (d, J = 8.5 Hz, 2H), 7.77 (d, J = 8.5 Hz, 2H), 2.63 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 196.55, 139.92, 132.53, 128.71, 117.94, 116.41, 26.78.

[0021]

[0022] (a)

Embodiment 2

[0024] Accurately weigh o-bromoaniline (85.5 mg, 0.5 mmol), potassium ferrocyanide trihydrate (84.5 mg, 0.2 mmol), palladium acetate (5.6 mg, 0.025 mmol), N, P - Bidentate ligand (12.9 mg, 0.025 mmol), potassium tert-butoxide (112.3 mg, 1.0 mmol) were successively added to a 25 mL Schlenk bottle, acetonitrile (2.0 mL) was added, and placed in a 100 oC oil bath for reaction 48 h. After the reaction, the reaction solution was filtered and spin-dried, and separated through a silica gel chromatography column, and the yield of p-2-aminobenzonitrile (b) was 62%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.38 (dd, J = 8.0, 1.3 Hz, 1H), 7.35 – 7.29 (m, 1H), 6.78 – 6.68 (m, 2H), 4.41 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 149.53, 133.97, 132.32, 117.96, 117.58, 115.09, 95.98.

[0025]

[0026] (b)

Embodiment 3

[0028] Accurately weigh p-bromoaniline (85.5 mg, 0.5 mmol), potassium ferrocyanide trihydrate (84.5 mg, 0.2 mmol), palladium acetate (5.6 mg, 0.025 mmol), N, P - Bidentate ligand (12.9 mg, 0.025 mmol), sodium carbonate (106.0 mg, 1.0 mmol) were successively added to a 25 mL Schlenk bottle, acetonitrile (2.0 mL) was added, and placed in a 100 oC oil bath for 48 h . After the reaction, the reaction solution was filtered and spin-dried, and separated through a silica gel chromatography column, and the yield of p-aminobenzonitrile (c) was 78%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.40 (d, J= 8.7 Hz, 2H), 6.64 (d, J = 8.7 Hz, 2H), 4.20 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.41, 133.71, 120.14, 114.34, 99.93.

[0029]

[0030] (c)

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Abstract

The invention relates to the technical fields of pharmaceutical chemical intermediates and relevant chemicals, in particular to a method for preparing cyan aromatic hydrocarbons by using aryl bromides. The method comprises the following steps of: a, sequentially adding brominated aromatic hydrocarbons, a cyanogen source, palladium catalyst, ligand and alkali into a reactor, adding organic solvent for reaction, controlling reaction temperature to be 50-200DEG C and reaction time to be 24-48h, wherein the molar ratio of the brominated aromatic hydrocarbons to the cyanogen source is 1: (1-2), the molar ratio of the brominated aromatic hydrocarbons to the palladium catalyst is 1: (0.05-0.1), the molar ratio of the ligand to the palladium catalyst is 1: (1-2) and the molar ratio of the brominated aromatic hydrocarbons to the alkali is 1: (1-20); and b, separating the reaction liquid obtained in the step a through a silica gel column to obtain the cyan aromatic hydrocarbons. The method for preparing cyan aromatic hydrocarbons by using aryl bromides has the advantages that the reaction steps are less, the conditions are moderate and the operation is convenient to conduct; the used cyanogen source is cheap and easy to obtain, the toxicity is lower and the prices of the catalyst and the ligand are low; and the preparation cost can be greatly decreased and the pollution to the surrounding environment is reduced.

Description

technical field [0001] The invention relates to the field of pharmaceutical and chemical intermediates and related chemical technologies, and relates to a method for preparing cyanoarenes from aryl bromides. Background technique [0002] Cyanoarenes are important chemical intermediates and important constituent units of many pharmaceutical and pesticide molecules. Moreover, the introduction of cyano groups can also change some physical and biological properties of aromatic compounds. The classic methods for the preparation of cyanoarenes include direct electrophilic cyanation of arenes (Rosenmund-von Braun reaction), diazotization of aromatic amines followed by cyanation (Sandmeyer reactions), and oxidative cyanation through Ammoxidation reactions. However, the equivalent amount of CuCN is used in the reaction, and a large amount of waste will be generated after the reaction, thus causing serious environmental pollution. In addition, the reaction temperature is extremely h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/08C07C253/14C07C255/56C07C255/58C07C255/52C07C255/57C07C255/50C07C255/51C07C255/54C07D213/84C07D209/08C07D213/85
Inventor 包明冯秀娟于晓强邹涛
Owner DALIAN UNIV OF TECH
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