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One-pot aromatic nitrile synthesis method adopting Fe (III) porphyrin for catalyzing nitrite to oxidize aromatic olefin

A technology of porphyrin catalyzing nitrite and nitrite, which is applied in the fields of organic chemical synthesis and pharmaceutical intermediates, can solve the problems of harsh reaction conditions, low yield and the like, and achieves easy controllable operation, reduced production cost, and mild reaction conditions. Effect

Inactive Publication Date: 2018-01-19
YUANJIANG HUALONG CATALYST TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The existing method for synthesizing aryl nitrile compounds from aryl olefins has defects such as harsh reaction conditions and low yield. A method for synthesizing aromatic nitriles with high yield by salt one-step reaction, the method has wide and easy-to-obtain raw material sources, is environmentally friendly, low in price, simple in operation, environment-friendly, and conducive to industrial production

Method used

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  • One-pot aromatic nitrile synthesis method adopting Fe (III) porphyrin for catalyzing nitrite to oxidize aromatic olefin
  • One-pot aromatic nitrile synthesis method adopting Fe (III) porphyrin for catalyzing nitrite to oxidize aromatic olefin
  • One-pot aromatic nitrile synthesis method adopting Fe (III) porphyrin for catalyzing nitrite to oxidize aromatic olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Synthesis of Benzonitrile

[0054] Add 0.4 mmol styrene, 2 mmol sodium nitrite, 1 mg metallic iron (Ⅲ) porphyrin, and 4.5 ml acetonitrile solvent to the reaction test tube, heat and stir at 70°C under air atmosphere, and add dropwise within the first 0.5 hours 0.5 milliliters of formic acid, after reacting for 4 hours, stop heating and stirring, cool to room temperature, obtain crude product through rotary evaporator, then separate and purify by column chromatography, obtain target product, the eluent of column chromatography used is petroleum ether and ethyl acetate Esters mixed solvents. The structure of benzonitrile is shown in the following formula:

[0055]

[0056] The compound is a colorless liquid with a yield of 84%, and its NMR data are as follows:

[0057] 1 H NMR (400MHz, CDCl 3 )δ7.60(dd, J=12.0,7.6Hz,3H),7.45(t,J=7.8Hz,2H); 13 CNMR (101MHz, CDCl 3 )δ132.82, 132.05, 129.16, 118.82, 112.28.

Embodiment 2

[0059] Synthesis of p-methylbenzonitrile

[0060] Add 0.4 mmol of p-methylstyrene, 2 mmol of sodium nitrite, 0.5 mg of metal iron (Ⅲ) porphyrin, and 4.5 ml of acetonitrile solvent into the reaction test tube, heat and stir at 70°C under air atmosphere, gradually within the first 0.5 hours Add 0.5 milliliters of formic acid drop by drop, after reacting for 4 hours, stop heating and stirring, cool to room temperature, obtain the crude product by rotary evaporator, then separate and purify by column chromatography to obtain the target product, the eluent of column chromatography used is petroleum ether mixed solvent with ethyl acetate. The structure of p-methylbenzonitrile is shown in the following formula:

[0061]

[0062] The compound is a colorless liquid with a yield of 87.26%, and its NMR data are as follows:

[0063] 1H NMR (400MHz, CDCl3) δ7.54 (d, J = 8.1Hz, 2H), 7.26 (d, J = 2.1Hz, 2H), 2.42 (s, 3H); 13C NMR (101MHz, CDCl3) δ 143.71, 132.06 ,129.85,119.18,109.33,2...

Embodiment 3

[0065] Synthesis of m-methylbenzonitrile

[0066] Add 0.4 mmol of m-methylstyrene, 2 mmol of sodium nitrite, 2 mg of metal iron (Ⅲ) porphyrin, and 4.5 ml of acetonitrile solvent into the reaction test tube, heat and stir at 70°C under air atmosphere, gradually within the first 0.5 hours Add 0.5 milliliters of formic acid drop by drop, after reacting for 4 hours, stop heating and stirring, cool to room temperature, obtain the crude product by rotary evaporator, then separate and purify by column chromatography to obtain the target product, the eluent of column chromatography used is petroleum ether mixed solvent with ethyl acetate. The m-methylbenzonitrile structure is shown in the following formula:

[0067]

[0068] The compound is a colorless liquid with a yield of 71.23%, and its NMR data are as follows:

[0069] 1 H NMR (400MHz, CDCl 3 )δ7.45(d, J=4.7Hz, 2H), 7.41(d, J=7.7Hz, 1H), 7.35(t, J=5.9Hz, 1H), 2.39(s, 3H); 13 C NMR (101MHz, CDCl 3 )δ139.23, 133.64, 132.50...

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Abstract

The invention discloses a one-pot aromatic nitrile synthesis method adopting Fe (III) porphyrin for catalyzing nitrite to oxidize aromatic olefin. According to the method, in an air atmosphere and anorganic carboxylic acid solution system, aromatic nitrile compounds or aromatic heterocyclic nitrile compounds are generated from aromatic alkene compounds or aromatic heterocyclic alkene compounds and nitrite under the catalysis of Fe (III) porphyrin by one-step reaction. The method has the advantages as follows: 1) reaction conditions are mild, operation is simple and easy to control, and yieldis higher; 2) an efficient Fe (III) porphyrin catalyst instead of a toxic CN negative ion reagent is adopted, so that environmental pollution is reduced; 3) raw materials, the nitrogen source, an acidreagent and the like are cheap and easily available, the production cost is obviously reduced, and the method can be popularized and applied to industrial production.

Description

technical field [0001] The invention relates to a method for synthesizing aromatic nitriles, in particular to a method for synthesizing aromatic nitriles in one pot by catalyzing Fe(III) porphyrin to oxidize aromatic olefins with nitrite; it belongs to the technical fields of pharmaceutical intermediates and organic chemical synthesis. Background technique [0002] Aryl olefins are a class of unsaturated aromatic compounds containing carbon-carbon double bonds, which are mainly obtained from petroleum raw materials. For example, typical styrene is obtained by catalytic dehydrogenation or co-oxidation of petrochemical raw material ethylbenzene. These methods are Very mature and industrialized production process, so styrene is a cheap raw material. Aromatic nitrile compounds are very important intermediates for the synthesis of pesticides, aliphatic amines or benzoic acids, and can be used as solvents for nitrile rubber, resins, polymers and coatings. In addition, benzonitril...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/00C07C253/02C07C255/50C07C255/54C07C255/52C07C255/55C07D333/38B01J31/22C01B21/24C01B21/36
Inventor 刘强何维郭欣郭灿城
Owner YUANJIANG HUALONG CATALYST TECH
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