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Method for preparing phenylaniline

A technology of aminobiphenyl and basebiphenyl, which is applied in the field of preparation of aminobiphenyl, and can solve problems such as increased cost, difficulty in cleaning, and environmental pollution by iron powder

Active Publication Date: 2011-05-25
CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The preparation methods of aminobiphenyls mentioned in the prior art all use noble metal palladium as a catalyst, which increases the cost and is not suitable for large-scale industrial production
In addition, after the preparation of nitrobiphenyl, it is necessary to use a large amount of iron powder to reduce the nitro group to amino group. The existence of a large amount of iron powder will pollute the environment and make it difficult to clean.

Method used

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  • Method for preparing phenylaniline
  • Method for preparing phenylaniline
  • Method for preparing phenylaniline

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preparation example Construction

[0049] The invention provides a preparation method of aminobiphenyl, comprising:

[0050] a) The benzonitrile shown in formula II, the phenylboronic acid shown in formula III, the first basic compound and the nickel catalyst are mixed in the first solvent to carry out the Suzuki coupling reaction to obtain the cyanobiphenyl shown in formula IV ;

[0051] b) mixing the cyanobiphenyl with a second basic compound and hydrogen peroxide in a second solvent, and hydrolyzing the cyanobiphenyl to obtain amidobiphenyl shown in formula V;

[0052] c) mixing the amidobiphenyl with the third basic compound and sodium hypohalite in a third solvent to undergo a Hofmann degradation reaction to obtain the aminobiphenyl represented by formula I.

[0053]

[0054]

[0055] Among them, R 1 is chlorine, bromine, iodine, sulfonate, carbonate or alkyl ester; R 2 is alkyl, alkoxy, cyano, amido or hydrogen; R 3 is chlorine, bromine or iodine; R 4 is alkyl, alkoxy, cyano, amido or hydrogen. ...

Embodiment 1

[0083] Under a nitrogen atmosphere, mix 0.7819g (5mmol) of 4-chlorophenylboronic acid, 1.0318g (7.5mmol) of o-chlorobenzonitrile, 3.1840g (15mmol) of anhydrous potassium phosphate, 0.0054g (0.01mmol) of nickel chloride, and Add 1,3-bis(diphenylphosphine)propane at an equimolar ratio of nickel to the reactor, add 20 g of dioxane to the reactor, react at 100°C for 6 h under a nitrogen atmosphere, and quench with saturated brine. The reaction was quenched, extracted with dichloromethane, dried, separated on silica gel, and the dichloromethane was evaporated to obtain 1.0149 g of 4'-chloro-2-cyanobiphenyl with a yield of 82.8%. The hydrogen spectrum and the carbon spectrum of the 4'-chloro-2-cyanobiphenyl prepared in embodiment 1 are:

[0084] 1 H NMR (CDCl 3 , 600MHz) δ: 7.26(m, 6H), 7.64(t, J=7.5Hz, 1H), 7.77(d, J=7.7Hz, 1H)); 13 C NMR (CDCl 3 , 150MHz) δ: 111.3, 118.4, 127.9, 129.0 (2C), 129.9, 130.1 (2C), 132.9, 133.8, 135.1, 136.5, 144.2;

Embodiment 2

[0086] Under a nitrogen atmosphere, mix 1.5637g (10mmol) of 4-chlorophenylboronic acid, 1.3757g (10mmol) of o-chlorobenzonitrile, 6.0681g (30mmol) of anhydrous potassium phosphate, 0.0108g (0.02mmol) of nickel chloride and Add 1,3-bis(diphenylphosphine)propane with an equimolar ratio of nickel into the reactor, add 40g of dioxane into the reactor, react at 100°C for 8h under a nitrogen atmosphere, and quench with saturated saline Reaction, extraction with dichloromethane, drying, separation on silica gel, evaporation of dichloromethane to obtain 2.0200 g of 4'-chloro-2-cyanobiphenyl with a yield of 82%. The hydrogen spectrum and the carbon spectrum of the 4'-chloro-2-cyanobiphenyl prepared in embodiment 2 are:

[0087] 1 H NMR (CDCl 3 , 600MHz) δ: 7.26(m, 6H), 7.64(t, J=7.5Hz, 1H), 7.77(d, J=7.7Hz, 1H)); 13 C NMR (CDCl 3 , 150MHz) δ: 111.3, 118.4, 127.9, 129.0 (2C), 129.9, 130.1 (2C), 132.9, 133.8, 135.1, 136.5, 144.2;

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Abstract

The invention provides a method for preparing phenylaniline, which comprises the following steps: mixing cyanophenyl shown in the formula II, first alkaline compounds, nickel catalysts and borophenylic acid shown in the formula III or borophenylic esters shown in the formula VI to carry out suzuki coupling reaction for obtaining cyanobiphenyl shown in the formula IV; mixing the cyanobiphenyl, second alkaline compounds and oxyful, and hydrolyzing the cyanobiphenyl to obtain amido biphenyl shown in the formula V; and mixing the amido biphenyl, third alkaline compounds and sodium hypohalite to generate Hofmann degradation reaction for obtaining phenylaniline shown in the formula I, wherein R1 is chlorine, bromine, iodine, sulphonic acid ester radicals, carbonic ether radicals or alkyl ester radicals; R2 is alkyl, alkoxy, cyano, amido or hydrogen; R3 is chlorine, bromine or iodine; and R4 is alkyl, alkoxy, cyano, amido or hydrogen. The preparing method provided by the invention has the advantages of mild condition, low cost, cleanness and environment protection.

Description

technical field [0001] The invention relates to the field of compound synthesis, in particular to a preparation method of aminobiphenyl. Background technique [0002] The aminobiphenyl shown in formula I is an important intermediate, which is widely used in the fields of medicine and pesticide manufacturing, especially as a raw material for the production of boscalid fungicides. The currently commercialized boscalids The fungicide is Boscalid produced by BASF, Germany. The boscalid fungicide prepared by using aminobiphenyl as a raw material has the characteristics of mild reaction conditions and few side effects. [0003] [0004] So far, the synthesis of aminobiphenyl is as follows: [0005] Adv.Synth.Catal.2009,351,649-655 has reported a kind of boron tetrafluoride salt that adopts o-nitrodiazobenzene as raw material, and metal palladium / activated carbon is catalyst, and reaction makes nitrobiphenyl, and then in Under iron powder reduction, the nitrobiphenyl is reduc...

Claims

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Application Information

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IPC IPC(8): C07C211/52C07C209/56
Inventor 韩福社李水明孙凤一
Owner CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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