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Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex

A ferrocenylimide ring palladium and a synthesis method are applied in the synthesis field of aromatic nitriles and derivatives thereof, and can solve the problems of waste of transition metals, high toxicity, environmental pollution and the like, and achieve mild reaction conditions and reaction specificity. Strong, wide range of raw material effects

Inactive Publication Date: 2010-05-12
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, substituted aromatic nitriles are mostly catalyzed by KCN, NaCN, CuCN or Zn(CN) 2 It is synthesized as a nitrile source, but KCN and NaCN are highly toxic and have potential environmental pollution; CuCN and Zn(CN) 2 Will cause equivalent transition metal waste, etc.; now K 4 [Fe(CN) 6 ] is the synthetic method of nitrile source, must also use ligand-assisted chelation except need catalyst, and this synthetic method needs to use special and expensive bisphosphine ligand; And with Pd(OAc) 2 As a catalyst synthesis method, the reaction substrate has great limitations. Generally, only brominated aromatic compounds are used.

Method used

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  • Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex
  • Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex
  • Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex

Examples

Experimental program
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Effect test

Embodiment 1

[0023] Embodiment 1, the synthesis of benzonitrile: under the protection of inert gas (such as high-purity nitrogen), add 0.22mmol (93mg) K 4 [Fe(CN) 6 ]3H 2 O, 0.0025 mmol (2.3 mg) of catalyst (Y=CH 3 Z=CH 3 ), 1mmol (106mg) of sodium carbonate and 1ml of N,N-dimethylacetamide solvent, replace the reaction tube with nitrogen for 4 times, under the protection of slightly positive pressure nitrogen, add 1mmol (105μl) of bromobenzene with a syringe, and then Heat to 120° C. with an oil bath under magnetic stirring, and react for 3 hours. Remove the oil bath, water bath down to room temperature; add 3ml of water, and extract three times with 3ml of dichloromethane, combine the organic phase and wash with anhydrous MgSO 4 Dry for 30 minutes, filter; concentrate in a rotary evaporator, and use 10:1 petroleum ether / ethyl acetate as a developing solvent to separate the residue by silica gel thin-layer chromatography. 96 mg of pure benzonitrile was obtained (purity>98%, colorless...

Embodiment 2

[0024] Embodiment 2, the synthesis of p-methylbenzonitrile: under the protection of inert gas (such as high-purity nitrogen), add 0.22mmol (93mg )K 4 [Fe(CN) 6 ]3H 2 O, 0.0025 mmol (2.3 mg) of catalyst (Y=CH 3 Z=CH 3 ), 0.5mmol (83mg) of sodium carbonate and 1ml of N,N-dimethylacetamide solvent, replace the reaction tube with nitrogen for 4 times, under the protection of slightly positive pressure nitrogen, add 1mmol of p-methylbromobenzene with a syringe, and then Heat to 120° C. with an oil bath under magnetic stirring, and react for 3 hours. Remove the oil bath, water bath down to room temperature; add 3ml of water, and extract three times with 3ml of dichloromethane, combine the organic phase and wash with anhydrous MgSO 4 Dry for 30 minutes, filter; concentrate in a rotary evaporator, and use 10:1 petroleum ether / ethyl acetate as a developing solvent to separate the residue by silica gel thin-layer chromatography. 96 mg of pure product p-toluonitrile (purity>98%, co...

Embodiment 3

[0025] Example 3, the synthesis of 2-methylbenzonitrile: under the protection of an inert gas (such as high-purity nitrogen), add 0.22 mmol ( 93mg) K 4 [Fe(CN) 6 ]3H 2 O, 0.0025 mmol (2.3 mg) of catalyst (Y=CH 3 Z=CH 3 ), 5mmol (530mg) of sodium carbonate and 5ml of N,N-dimethylacetamide solvent, replace the reaction tube with nitrogen for 4 times, under the protection of slight positive pressure nitrogen, add 1mmol of 2-methylbromobenzene with a syringe, and then Heat to 120° C. with an oil bath under magnetic stirring, and react for 3 hours. Remove the oil bath, water bath down to room temperature; add 3ml of water, and extract three times with 3ml of dichloromethane, combine the organic phase and wash with anhydrous MgSO 4 Dry for 30 minutes, filter; concentrate in a rotary evaporator, and use 10:1 petroleum ether / ethyl acetate as a developing solvent to separate the residue by silica gel thin-layer chromatography. 111 mg of pure product 2-methylbenzonitrile was obtai...

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Abstract

The invention pertains to the synthesizing technology field of organic intermediate, relating to a synthesizing method of derivative of aryl nitrie by the catalysis of cyclopalladated ferrocenyliminecomplex; the preparation steps are that: catalyst, potassium ferrocyanide and alkali are dissolved into an organic solvent, then halonitroaromatic compound is added to be reacted in the protection ofnitrogen, and is cooled down to room temperature after the reaction is completed, the product can be acquired after the mixture being washed with water, extracted, dried, concentrated and purified. The reaction uses the universal catalyst, wherein Y is H or CH3; Z is H, CH3, OCH3 or OC2H5. The invention has the advantages of mild reaction conditions, universal material scope, good reaction specificity, high yielding and free of environmental pollution.

Description

technical field [0001] The invention belongs to the technical field of synthesis of organic intermediates, and relates to a synthesis method of aromatic nitriles with various substituents and derivatives thereof. Background technique [0002] Substituted aromatic nitriles and their derivatives are important intermediates in medicine, pesticides, dyes, chemicals, etc. They can be used to synthesize arylamines, amides, carboxylic acids, carboxylic acid esters, imidazoles, etc. through changes in nitrile groups, and have a wide range of applications. At present, substituted aromatic nitriles are mostly catalyzed by KCN, NaCN, CuCN or Zn(CN) 2 It is synthesized as a nitrile source, but KCN and NaCN are highly toxic and have potential environmental pollution; CuCN and Zn(CN) 2 Will cause equivalent transition metal waste, etc.; now K 4 [Fe(CN) 6 ] is the synthetic method of nitrile source, must also use ligand-assisted chelation except need catalyst, and this synthetic method ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C253/14C07C255/50C07C255/52C07C255/51C07C255/54C07C255/58C07C255/56C07D213/85B01J31/12B01J31/22
Inventor 段征吴养洁程绎南李挺
Owner ZHENGZHOU UNIV