CN111574380B - Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method - Google Patents
Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method Download PDFInfo
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Abstract
The invention discloses a method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by adopting a reduction coupling reaction based on 4-substituted nitrobenze, which comprises the steps of carrying out catalytic hydrogenation by using hydrogen in the presence of an organic solvent, a noble metal catalyst and strong base to generate corresponding 1, 2-diphenylhydrazine from 4-substituted nitrobenzene, then carrying out rearrangement in a hydrochloric acid-ammonium salt mixed solution, and sequentially carrying out pH regulation, ethyl acetate precipitation, toluene recrystallization, salt acidification and acid precipitation treatment to obtain the 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof; the method has the advantages of cheap and easily-obtained raw materials, simple and convenient operation process, recoverable catalyst for multiple use, mild reaction conditions, high yield and great industrialization prospect.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by a reduction coupling method.
Background
Benzidine compounds are important chemical raw materials and are widely used in the fields of synthesis of pigments and dyes, preparation of polyimide materials, chain extenders in production of polyurethane rubber and fibers and the like. The most widely used benzidine is 4,4 '-diaminobiphenyl and its derivatives, while the synthesis and functional study of its corresponding isomer, 2' -diaminobiphenyl, are relatively lacking, and the current methods for the synthesis of 4,4 '-disubstituted-2, 2' -diaminobiphenyl mainly include Suzuki coupling, see Lee, d.s.; chatterjee, t.; ban, j.; rhee, h.; cho, E.J.simple synthetic method for the functional benzene [ c ] cinanolines.chemistry select 2018,3(7), 2092-; amide oxidative coupling-hydrolysis process, see Weng, y; lan, t.; sun, c.; yang, T.; sua, w.; xie, Y.mechanochemical paladium-catalyzed C (sp2) -H homocoupling of N-arylcarbonates Synthesis of 2,2' -aryldiamines Org.Chem.Front.2018, 5, 2103-2107; and Pd catalyzed dehalogenation coupling, see Chang, y; lee, s.; cho, m.; yoo, b.; rhee, h.; lee, s.; yoon, C.Home of aryl and complexes using palladium/inorganic Communications 2005,35(13), 1851-. However, these synthetic methods use relatively complicated synthetic precursors, have many reaction steps and high cost, and are not suitable for mass production.
Disclosure of Invention
The invention aims to provide a method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl by using 4-substituted nitrobenzene as a raw material based on a reduction coupling method.
Another object of the present invention is to provide a method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride by using 4-substituted nitrobenzene as a raw material based on a reduction coupling method.
Therefore, the technical scheme of the invention is as follows:
the method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl by using 4-substituted nitrobenzene as a raw material based on a reduction coupling method comprises the following preparation steps:
s1, adding 4-substituted nitrobenzene, an organic solvent, 30-45 wt.% of sodium hydroxide solution and a noble metal catalyst into a high-pressure kettle, sealing, then replacing with nitrogen for three times, replacing with hydrogen for three times, controlling the pressure to be 1.0-2.0 Mpa, controlling the temperature to be 45-120 ℃, and reacting for 9-21 h; after the reaction is finished, filtering a reaction product, and layering filtrate to obtain an organic phase, namely 1, 2-diphenyl hydrazine solution;
s2, adding an acidic mixed solution obtained by mixing a strong acid aqueous solution and an ammonium salt aqueous solution into the 1, 2-diphenylhydrazine solution prepared in the step S1, and reacting for 6-19 h at the temperature of 20-60 ℃; filtering the reaction product to obtain a filter cake which is a crude product of 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the crude 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride with water, neutralizing with 32 to 45 wt.% of sodium hydroxide solution to a pH of 7 to 8.5, and filtering to obtain a filter cake, i.e., the crude 5,5 '-disubstituted-2, 2' -diaminobiphenyl;
s4, adding ethyl acetate into the 5,5 '-disubstituted-2, 2' -diaminobiphenyl crude product, heating to 70-75 ℃ to dissolve a filter cake, filtering, concentrating and evaporating the obtained filtrate to obtain a solid crude product; and recrystallizing the solid crude product by using toluene to obtain the 5,5 '-disubstituted-2, 2' -diaminobiphenyl.
The specific chemical reaction formula of the preparation method is as follows:
preferably, in step S1, the chemical formula of the 4-substituted nitrobenzene is:
wherein X is F, Cl, Br, I, CF 3 、COOH、COOR、CONH 2 R OR OR, wherein R is a straight chain alkyl OR a branched chain alkyl with any integer of 1-8 carbon atoms.
Preferably, in step S1, the noble metal catalyst is used in an amount of 0.5 to 1g per 100g of the 4-substituted nitrobenzene; wherein the noble metal catalyst consists of a catalyst carrier and noble metal loaded on the catalyst carrier; wherein the catalyst carrier is active carbon (C) and silicon dioxide (SiO) 2 ) Oxygen, oxygenAluminium (Al) 2 O 3 ) Or a molecular sieve; the noble metal is at least one of palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), thallium (Tl) and iridium (Ir); the weight of the noble metal accounts for 0.5-10% of the total weight of the carrier and the noble metal.
Preferably, in step S1, the organic solvent is xylene, toluene, mesitylene, anisole, diphenyl ether, or tetralin.
In step S1, 30 to 80mL of an organic solvent and 75mL of a sodium hydroxide solution are preferably added to 100g of 4-substituted nitrobenzene.
Preferably, in step S2, in the acidic mixed solution, the mass fraction of the strong acid aqueous solution is 5 to 15%, and the mass fraction of the ammonium salt aqueous solution is 8 to 12%; wherein the strong acid aqueous solution is hydrochloric acid aqueous solution, sulfuric acid aqueous solution or phosphoric acid aqueous solution; the ammonium salt aqueous solution is ammonium chloride aqueous solution, ammonium acetate aqueous solution, ammonium sulfate aqueous solution, ammonium bisulfate aqueous solution, ammonium phosphate aqueous solution, ammonium monohydrogen phosphate aqueous solution or ammonium dihydrogen phosphate aqueous solution.
A method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride, which comprises the following steps: after completing steps S1-S4 in the above preparation of 5,5 '-di-substituted-2, 2' -diaminobiphenyl, steps S5 are performed: adding 5,5 '-disubstituted-2, 2' -diaminobiphenyl into a 5 wt.% hydrochloric acid solution, heating to 85-95 ℃ for complete dissolution, then dropwise adding a 30-35 wt.% concentrated hydrochloric acid solution into the solution while the solution is hot, carrying out acid precipitation for 3-4 h to generate solid precipitates, cooling the mixed solution to room temperature after the solid precipitates are not increased any more, and filtering to obtain 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloric acid.
The specific chemical reaction formula of the preparation method is as follows:
preferably, in step S5, the weight ratio of 5,5 '-di-substituted-2, 2' -diaminobiphenyl to 5 wt.% hydrochloric acid solution is 1:4 to 1: 7; the weight ratio of the 5,5 '-disubstituted-2, 2' -diaminobiphenyl to 30-35 wt.% concentrated hydrochloric acid solution is 1: 5-1: 8.
Preferably, the method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by using 4-substituted nitrobenzene as a raw material through a reduction coupling method comprises the following steps:
s1, adding 200g of 4-substituted nitrobenzene, 60-160 mL of organic solvent, 150mL of 30-45 wt.% sodium hydroxide solution and 1-2 g of 0.5-5 wt.% noble metal catalyst into a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, and controlling the pressure to be 1.0-2.0 Mpa and the temperature to be 45-120 ℃ to react for 9-21 h; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely 1, 2-diphenyl hydrazine solution;
s2, preparing 450-600 g of 20-35 wt.% strong acid aqueous solution, 100-120 g of ammonium salt and 550-650 mL of water to obtain an acid mixture liquid of strong acid and ammonium salt, adding the acid mixture liquid into the 1, 2-diphenylhydrazine solution prepared in the step S1, and reacting for 6-19 h at 20-60 ℃; filtering, wherein a filter cake is a crude product of 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 32 to 45 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7 to 8.5; filtering, wherein a filter cake is a crude product of 5,5 '-disubstituted-2, 2' -diaminobiphenyl;
s4, adding 340-390 mL of ethyl acetate into the filter cake obtained in the step S3, heating to 70-75 ℃ to dissolve the filter cake, filtering insoluble substances, distilling and concentrating the filtrate to recover ethyl acetate for repeated use; adding 190-240 mL of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 5,5 '-disubstituted-2, 2' -diaminobiphenyl;
s5, adding the 5,5 '-disubstituted-2, 2' -diaminobiphenyl obtained in step S4 into 550 to 720mL of 5 wt.% hydrochloric acid, heating to 85 to 95 ℃, and dissolving all the 5,5 '-disubstituted-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dripping 660-800 mL of 30-35 wt.% concentrated hydrochloric acid into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3-4 h, and filtering after the precipitation is complete and the solution is cooled to room temperature to obtain the 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride.
Compared with the prior art, the method for preparing the 5,5 '-disubstituted-2, 2' -diaminobiphenyl and the hydrochloride thereof by using the 4-substituted nitrobenzene as the raw material through the reduction coupling method has the advantages of reasonable reaction route, cheap and easily available raw materials, simple reaction steps, mild reaction conditions and few synthesized precursors, and the method for preparing the 5,5 '-disubstituted-2, 2' -diaminobiphenyl and the hydrochloride thereof by using the 4-substituted nitrobenzene as the raw material through the catalytic hydrogenation reaction has the advantages of high yield and high purity of finished products; in addition, based on the preparation method, the catalyst used in the preparation process can be reused for many times without reducing the catalytic activity, and the organic solvent used in the preparation process can be recycled, so that the aim of effectively reducing the production cost is further fulfilled, and the preparation method has a great industrial prospect.
Drawings
Fig. 1 is a synthesis scheme for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride from 4-substituted nitrobenzene based on a reduction coupling method according to the present invention;
fig. 2 is a nuclear magnetic resonance hydrogen spectrum of 5,5 '-dimethyl-2, 2' -diaminobiphenyl prepared in example 1 of the present invention.
Fig. 3 is a nuclear magnetic resonance hydrogen spectrum of 5,5 '-difluoro-2, 2' -diaminobiphenyl prepared in example 4 of the present invention.
Fig. 4 is a nuclear magnetic resonance hydrogen spectrum of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl prepared in example 8 of the present invention.
Detailed Description
The invention will be further described with reference to the following drawings and specific examples, which are not intended to limit the invention in any way.
Example 1
A method for preparing 5,5 '-dimethyl-2, 2' -diaminobiphenyl and hydrochloride thereof by taking p-nitrotoluene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of paranitrotoluene, 60mL of toluene, 150mL of 30 wt.% sodium hydroxide solution and 2g of 5% Pt/C in a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, and controlling the pressure to be 1.0-1.2 Mpa and the temperature to be 110-115 ℃ for reaction for 9-11 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-methyl phenylhydrazine solution; the molar ratio of the 1, 2-di-p-methyl phenylhydrazine is calculated to be 93 percent according to the analysis of the organic phase by liquid chromatography; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 30 wt.% hydrochloric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 11.25 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acid mixture solution into the 1, 2-di-p-methyl phenylhydrazine solution prepared in the step S1, and carrying out heat preservation reaction at 55-60 ℃ for 6-7 hours; filtering, and layering organic phase toluene from the filtrate for repeated use, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 32 wt.% sodium hydroxide solution to neutralize the mixture until the pH is 7.0 to 7.5; filtering, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of about 95%;
s4, adding the filter cake obtained in the step S3 into 350mL ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, distilling and concentrating the filtrate, and recovering ethyl acetate for repeated use; adding 200mL of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 115g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the toluene in the filtrate can be recycled;
s5, adding the 5,5 '-dimethyl-2, 2' -diaminobiphenyl obtained in step S4 to 600mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃, and dissolving all the 5,5 '-dimethyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and dropwise adding 31 wt.% of concentrated hydrochloric acid 690mL into the hot mixed solution, carrying out acid precipitation for 4.0h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 121g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 2:
a method for preparing 5,5 '-dimethyl-2, 2' -diaminobiphenyl and hydrochloride thereof by taking p-nitrotoluene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of para-nitrotoluene, 120mL of xylene, 150mL of 42 wt.% sodium hydroxide solution and 1.6% Pd/C1.5 g into a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, controlling the pressure to be 1.6-1.8 Mpa and the temperature to be 100-110 ℃, and reacting for 10-12 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-methyl phenylhydrazine solution; the molar ratio of the 1, 2-di-p-methyl phenylhydrazine is calculated to be 91 percent according to the analysis of the organic phase by liquid chromatography; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 30 wt.% hydrochloric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 11.25 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acid mixture solution into the 1, 2-di-p-methyl phenylhydrazine solution prepared in the step S1, and reacting for 8-9 hours at the temperature of 40-45 ℃; filtering, and layering organic phase xylene from filtrate for repeated application, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 45 wt.% sodium hydroxide solution to neutralize the mixture until the pH is 7.5 to 8.0; filtering, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of about 96%;
s4, adding the filter cake obtained in the step S3 into 370ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 190ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 113g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the filtrate xylene can be recycled;
s5, adding the 5,5 '-dimethyl-2, 2' -diaminobiphenyl obtained in step S4 to 600mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃, and dissolving all the 5,5 '-dimethyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dropwise adding 680mL of 33 wt.% concentrated hydrochloric acid into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3.2h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 119g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 3:
a method for preparing 5,5 '-dimethyl-2, 2' -diaminobiphenyl and hydrochloride thereof by taking p-nitrotoluene as a raw material based on a reduction coupling method comprises the following steps:
s1, 200g of p-nitrotoluene, 160mL of mesitylene, 150mL of 40 wt.% sodium hydroxide solution and 10% Rh/Al were added to a stainless steel autoclave 2 O 3 1.8 g; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, and controlling the pressure to be 1.4-1.6 Mpa and the temperature to be 110-120 ℃ to react for 18-20 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-methyl phenylhydrazine solution; the molar ratio of the 1, 2-di-p-methyl phenylhydrazine is calculated to be 95 percent according to the analysis of the organic phase by liquid chromatography; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 35 wt.% phosphoric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 13.12 wt.% phosphoric acid and 8.33 wt.% ammonium chloride; adding the acidic mixture solution into the 1, 2-di-p-methyl phenylhydrazine solution prepared in the step S1, and reacting for 6-7 hours at the temperature of 50-55 ℃; filtering, and layering filtrate to obtain organic phase mesitylene for repeated application, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 42 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 8.0 to 8.5; filtering, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of about 97%;
s4, adding the filter cake obtained in the step S3 into 340ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 220ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 111g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the filtrate, namely the mesitylene, can be recycled;
s5, adding the 5,5 '-dimethyl-2, 2' -diaminobiphenyl obtained in step S4 to 700mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃, and dissolving all the 5,5 '-dimethyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dropwise adding 720mL of 31 wt.% concentrated hydrochloric acid into the hot mixed solution, carrying out acid precipitation for 3.4h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 115g of 5,5 '-dimethyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 4:
a method for preparing 5,5 '-difluoro-2, 2' -diaminobiphenyl and hydrochloride thereof by taking parafluoronitrobenzene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of p-fluoronitrobenzene, 70mL of anisole, 150mL of 45 wt.% sodium hydroxide solution and 1g of 0.5% Ru/C into a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, controlling the pressure to be 1.5-1.6 Mpa and the temperature to be 80-90 ℃, and reacting for 16-17 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-fluorophenylhydrazine solution; the molar rate of the 1, 2-di-p-fluorophenylhydrazine is calculated to be 90 percent according to the analysis of the organic phase by liquid chromatography; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 600g of 20 wt.% sulfuric acid, 150g of ammonium dihydrogen phosphate and 550mL of water to prepare an acidic mixture liquid of 5.23 wt.% sulfuric acid and 11.53 wt.% ammonium dihydrogen phosphate; adding the acid mixture solution into the 1, 2-di-p-phenylhydrazine solution prepared in the step S1, and reacting for 18-19 hours at the temperature of 30-35 ℃; filtering, and layering organic phase anisole from the filtrate for repeated application, wherein a filter cake is a crude product of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 35 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7.9 to 8.4; filtering to obtain a filter cake which is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl with the purity of about 97%;
s4, adding the filter cake obtained in the step S3 into 390ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 230ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 118g of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the anisole in the filtrate can be recycled;
s5, adding the 5,5 '-difluoro-2, 2' -diaminobiphenyl obtained in step S4 into 610mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all the 5,5 '-difluoro-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dropwise adding 720mL of 35 wt.% concentrated hydrochloric acid into the hot mixed solution, carrying out acid precipitation for 3.6h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 124g of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 5:
a method for preparing 5,5 '-difluoro-2, 2' -diaminobiphenyl and hydrochloride thereof by taking p-fluoronitrobenzene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of parafluoronitrobenzene, 150mL of toluene, 150mL of 37 wt.% sodium hydroxide solution and 4.8% Ir/Al into a stainless steel autoclave 2 O 3 2g of the total weight of the mixture; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, and controlling the pressure to be 1.2-1.3 Mpa and the temperature to be 110-115 ℃ for reaction for 10-12 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-fluorophenylhydrazine solution; the molar ratio of the 1, 2-di-p-fluorophenylhydrazine is 91 percent according to the calculation of a liquid chromatogram analysis organic phase; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 35 wt.% phosphoric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 13.12 wt.% phosphoric acid and 8.33 wt.% ammonium chloride; adding the acid mixture solution into the 1, 2-di-p-phenylhydrazine solution prepared in the step S1, and reacting for 8-9 hours at 55-60 ℃ under heat preservation; filtering, and layering organic phase toluene from the filtrate for repeated use, wherein a filter cake is a crude product of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 38 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7.0 to 7.5; filtering, wherein a filter cake is a crude product of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of about 96%;
s4, adding the filter cake obtained in the step S3 into 350ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 200ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 120g of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the toluene in the filtrate can be recycled;
s5, adding the 5,5 '-difluoro-2, 2' -diaminobiphenyl obtained in step S4 to 640mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all of the 5,5 '-difluoro-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) 780mL of 32 wt.% concentrated hydrochloric acid is dropwise added into the mixed solution while the mixed solution is hot, the mixed solution is subjected to acid precipitation for 3.8 hours, and after the precipitation is completed and the temperature is reduced to room temperature, the mixed solution is filtered to obtain 126g of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 6:
a method for preparing 5,5 '-difluoro-2, 2' -diaminobiphenyl and hydrochloride thereof by taking parafluoronitrobenzene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of p-fluoronitrobenzene, 125mL of mesitylene, 150mL of 35 wt.% sodium hydroxide solution and 1.5g of (2.5% Rh +0.5Pd)/C into a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, controlling the pressure to be 1.4-1.6 Mpa and the temperature to be 110-120 ℃, and reacting for 19-21 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-fluorophenylhydrazine solution; the molar ratio of the 1, 2-di-p-fluorophenylhydrazine is 93 percent according to the calculation of a liquid chromatogram analysis organic phase; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 600g of 20 wt.% sulfuric acid, 120g of ammonium monohydrogen phosphate and 550mL of water to prepare an acidic mixture liquid of 9.44 wt.% sulfuric acid and 9.44 wt.% ammonium monohydrogen phosphate; adding the acidic mixture solution into the 1, 2-di-p-phenylhydrazine solution prepared in the step S1, and reacting for 6-7 hours at the temperature of 50-55 ℃; filtering, and layering filtrate to obtain organic phase mesitylene for repeated application, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl hydrochloride;
s3, pulping the 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 36 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 8.0 to 8.5; filtering, wherein a filter cake is a crude product of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of about 95%;
s4, adding the filter cake obtained in the step S3 into 340ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 220ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 117g of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the filtrate, namely the mesitylene, can be recycled;
s5, adding the 5,5 '-difluoro-2, 2' -diaminobiphenyl obtained in step S4 to 600mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all of the 5,5 '-difluoro-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dropwise adding 35 wt.% concentrated hydrochloric acid 760mL into the hot mixed solution, carrying out acid precipitation for 3.2h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 123g of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 7:
a method for preparing 5,5 '-difluoro-2, 2' -diaminobiphenyl and hydrochloride thereof by taking p-fluoronitrobenzene as a raw material based on a reduction coupling method comprises the following steps:
s1, 200g of parafluoronitrobenzene, 68mL of anisole, 150mL of 38 wt.% sodium hydroxide solution and (1.5% Ru + 1.0% Ir)/SiO 2 1.7 g; after the autoclave is sealed, replacing the autoclave by nitrogen for three times, then replacing the autoclave by hydrogen for three times, and controlling the pressure to be 1.5-1.6 Mpa and the temperature to be 80-90 ℃ for reaction for 20-21 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely the 1, 2-di-p-fluorophenylhydrazine solution; the molar ratio of the 1, 2-di-p-fluorophenylhydrazine is calculated to be 92 percent according to the analysis of the organic phase by liquid chromatography; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 30 wt.% hydrochloric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 11.25 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acid mixture solution into the 1, 2-di-p-phenylhydrazine solution prepared in the step S1, and reacting for 10-11 hours at the temperature of 20-25 ℃; filtering, and layering organic phase anisole from the filtrate for repeated application, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl hydrochloride;
s3, pulping the 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 38 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7.9 to 8.4; filtering, wherein a filter cake is a crude product of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of about 97%;
s4, adding the filter cake obtained in the step S3 into 380ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 230ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 115g of 5,5 '-difluoro-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the toluene in the filtrate can be recycled;
s5, adding the 5,5 '-difluoro-2, 2' -diaminobiphenyl obtained in step S4 into 550mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all of the 5,5 '-difluoro-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) adding 770mL of 36 wt.% concentrated hydrochloric acid dropwise into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3.6 hours, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 121g of 5,5 '-difluoro-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 8:
a method for preparing 5,5 '-diisopropyl-2, 2' -diaminobiphenyl and hydrochloride thereof by using isopropyltoluene as a raw material based on a reduction coupling method comprises the following steps:
s1, 200g of p-cymene, 76mL of diphenyl ether, 150mL of 34 wt.% sodium hydroxide solution and (1.5% Pt + 1.2% Ir + 1.3% Ru)/SiO 2 1.6 g; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, controlling the pressure to be 1.9-2.0 Mpa and the temperature to be 80-90 ℃, and reacting for 22-23 hours; filtering the reaction product, and demixing the filtrate to obtain an organic phase 1, 2-bisP-isopropylphenylhydrazine solution; the molar ratio of 1, 2-di-p-isopropylphenylhydrazine calculated according to the liquid chromatography analysis of the organic phase is 92 percent; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 32 wt.% hydrochloric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture of 12 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acidic mixture solution into the 1, 2-di-p-isopropylphenylhydrazine solution prepared in the step S1, and reacting for 12-13 hours at the temperature of 40-45 ℃; filtering, and layering organic phase diphenyl ether from the filtrate for repeated use, wherein a filter cake is a crude product of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 40 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7.0 to 7.5; filtering, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl with the purity of about 95%;
s4, adding the filter cake obtained in the step S3 into 390ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 240ml of toluene into the obtained solid, heating to dissolve the solid, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 145g of 5,5 '-dimethyl-2, 2' -difluorobiphenyl with the purity of more than 99%, wherein the toluene in the filtrate can be recycled;
s5, adding the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl obtained in step S4 into 720mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃, and dissolving all the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) dripping 660mL of 30 wt.% concentrated hydrochloric acid into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3.9h, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 151g of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 9:
a method for preparing 5,5 '-diisopropyl-2, 2' -diaminobiphenyl and hydrochloride thereof by using isopropyl toluene as a raw material based on a reduction coupling method comprises the following steps:
s1, adding 200g of p-cymene, 60mL of xylene, 150mL of 40 wt.% sodium hydroxide solution and (1.5% Pd + 0.5% Ru + 0.7% Ir)/C2 g into a stainless steel autoclave; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, and controlling the pressure to be 1.6-1.8 Mpa and the temperature to be 100-110 ℃ for reaction for 12-14 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely a 1, 2-di-p-isopropylphenylhydrazine solution; the molar ratio of 1, 2-di-p-isopropylphenylhydrazine calculated according to the analysis of the organic phase by liquid chromatography is 91 percent; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 30 wt.% hydrochloric acid, 100g of ammonium phosphate and 650mL of water to prepare an acidic mixture liquid of 11.25 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acid mixture liquid into the 1, 2-di-p-isopropylphenylhydrazine solution prepared in the step S1, and carrying out heat preservation reaction at 40-45 ℃ for 9-10 hours; filtering, and layering filtrate to obtain an organic phase of xylene for repeated application, wherein a filter cake is a crude product of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 37 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 7.6 to 8.0; filtering, wherein a filter cake is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl with the purity of about 95%;
s4, adding the filter cake obtained in the step S3 into 370ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 190ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 146g of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the filtrate toluene can be recycled;
s5, adding the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl obtained in step S4 into 700mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and dropwise adding 800mL of 32 wt.% concentrated hydrochloric acid into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3.5 hours, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 152g of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
Example 10:
a method for preparing 5,5 '-diisopropyl-2, 2' -diaminobiphenyl and hydrochloride thereof by using isopropyl toluene as a raw material based on a reduction coupling method comprises the following steps:
s1, a stainless steel autoclave was charged with 200g of p-cymene, 80mL of mesitylene, 150mL of 31 wt.% sodium hydroxide solution, and (2.9% Pd + 0.7% Ru)/SiO 2 2g of the total weight of the mixture; after the autoclave is sealed, replacing the autoclave with nitrogen for three times, then replacing the autoclave with hydrogen for three times, controlling the pressure to be 1.4-1.6 Mpa and the temperature to be 110-120 ℃, and reacting for 17-19 hours; filtering the reaction product, and layering the filtrate to obtain an organic phase, namely a 1, 2-di-p-isopropylphenylhydrazine solution; the molar ratio of 1, 2-di-p-isopropylphenylhydrazine calculated according to the liquid chromatography analysis of the organic phase is 93 percent; the catalyst solid obtained by filtering can be repeatedly reused;
s2, weighing 450g of 30 wt.% hydrochloric acid, 100g of ammonium chloride and 650mL of water to prepare an acidic mixture liquid of 11.25 wt.% hydrochloric acid and 8.33 wt.% ammonium chloride; adding the acid mixture liquid into the 1, 2-di-p-isopropylphenylhydrazine solution prepared in the step S1, and carrying out heat preservation reaction at 50-55 ℃ for 6-7 hours; filtering, and layering filtrate to obtain organic phase mesitylene for repeated application, wherein a filter cake is a crude product of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride filter cake obtained in step S2 with water, and adding 35 wt.% sodium hydroxide solution to neutralize the filter cake until the pH is 8.0 to 8.5; filtering to obtain a filter cake which is a crude product of 5,5 '-dimethyl-2, 2' -difluorobiphenyl with the purity of about 95%;
s4, adding the filter cake obtained in the step S3 into 340ml of ethyl acetate, heating to 85-95 ℃ to dissolve the filter cake, filtering insoluble substances, and distilling and concentrating the filtrate to recover ethyl acetate for reuse; adding 220ml of toluene into the obtained solid, heating and dissolving, naturally cooling to 20-30 ℃ to obtain crystals, and filtering to obtain 147g of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl with the purity of more than 99%, wherein the filtrate toluene can be recycled;
s5, adding the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl obtained in step S4 into 680mL of 5 wt.% hydrochloric acid, heating to 85-95 ℃ to dissolve all the 5,5 '-diisopropyl-2, 2' -diaminobiphenyl in the hydrochloric acid solution; and (3) adding 740mL of 35 wt.% concentrated hydrochloric acid dropwise into the mixed solution while the mixed solution is hot, carrying out acid precipitation for 3 hours, and filtering after the precipitation is complete and the temperature is reduced to room temperature to obtain 153g of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl hydrochloride with the purity of more than 99%.
The chemical structures of the 5,5 '-disubstituted-2, 2' -diaminobiphenyl and its hydrochloride salt prepared in examples 1 to 10 were verified by nuclear magnetic resonance. Wherein the content of the first and second substances,
taking the nuclear magnetic resonance hydrogen spectrum of 5,5 '-dimethyl-2, 2' -diaminobiphenyl prepared in example 1 as an example, as shown in fig. 2, in the nuclear magnetic resonance hydrogen spectrum, a single peak at δ ═ 2.29ppm is assigned to a characteristic peak of methyl; the single peak at δ ═ 3.62ppm is attributed to the amino group attached to the aromatic ring; two doublets and one singlet in the unsaturated region δ ═ 7.26 to 6.71ppm belong to the carbons on the benzene ring, where δ ═ 7.26ppm is the characteristic solvent peak of deuterated chloroform, indicating that 5,5 '-dimethyl-2, 2' -diaminobiphenyl was produced.
The analysis results of the nuclear magnetic resonance hydrogen spectrum spectra of 5,5 '-dimethyl-2, 2' -diaminobiphenyl prepared in example 2 and example 3 are the same as those of example 1, i.e., 5 '-dimethyl-2, 2' -diaminobiphenyl is effectively synthesized.
Taking the nuclear magnetic resonance hydrogen spectrum of 5,5 '-difluoro-2, 2' -diaminobiphenyl prepared in example 4 as an example, as shown in fig. 3, in the nuclear magnetic resonance hydrogen spectrum, a single peak at δ ═ 3.62ppm is attributed to a characteristic peak of amino group; the single peak at δ 7.26ppm is attributed to the characteristic solvent peak of deuterated chloroform; the three multiplets in the unsaturated region δ -6.94-6.71 ppm are attributed to carbons on the benzene ring, indicating that 5,5 '-difluoro-2, 2' -diaminobiphenyl was produced.
The analysis results of the nuclear magnetic resonance hydrogen spectrum spectra of 5,5 '-difluoro-2, 2' -diaminobiphenyl prepared in example 5, example 6 and example 7 are all the same as in example 4, i.e., 5 '-difluoro-2, 2' -diaminobiphenyl was efficiently synthesized.
Taking the nuclear magnetic resonance hydrogen spectrum of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl prepared in example 8 as an example, as shown in fig. 4, in the nuclear magnetic resonance hydrogen spectrum, a double peak at δ ═ 1.25 to 1.23ppm belongs to a characteristic peak of a methyl group, and the double peak and a multiple peak at δ ═ 2.90 to 2.80ppm together form a characteristic peak of an isopropyl group; a single peak at δ of 3.61ppm is attributed to a characteristic peak of the amino group; two double peaks and one multiple peak in the unsaturated region δ -7.07-6.73 ppm are attributed to carbons on the benzene ring, thus it can be illustrated that 5,5 '-diisopropyl-2, 2' -diaminobiphenyl is produced.
The analysis results of the nuclear magnetic resonance hydrogen spectrum spectra of 5,5 '-diisopropyl-2, 2' -diaminobiphenyl prepared in example 9 and example 10 are the same as those of example 8, i.e., 5 '-diisopropyl-2, 2' -diaminobiphenyl is effectively synthesized.
In summary, the synthetic route provided by the present application enables the preparation of 5,5 '-disubstituted-2, 2' -diaminobiphenyl and its hydrochloride salt, and has high yield and purity of the finished product.
Claims (7)
1. The method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl by a reduction coupling method is characterized by comprising the following steps:
s1, adding 4-substituted nitrobenzene, an organic solvent, 30-45 wt.% of sodium hydroxide solution and a noble metal catalyst into a high-pressure kettle, sealing, and then performing nitrogen replacement three times and hydrogen replacement three times, wherein the pressure is controlled to be 1.0-2.0 Mpa, the temperature is controlled to be 45-120 ℃, and the reaction is performed for 9-21 hours; after the reaction is finished, filtering a reaction product, and layering filtrate to obtain an organic phase, namely 1, 2-diphenyl hydrazine solution;
s2, adding an acidic mixed solution obtained by mixing a strong acid aqueous solution and an ammonium salt aqueous solution into the 1, 2-diphenylhydrazine solution prepared in the step S1, and reacting for 6-19 h at the temperature of 20-60 ℃; filtering the reaction product to obtain a filter cake which is a crude product of 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride;
s3, pulping the crude 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride with water, neutralizing with 32 to 45 wt.% of sodium hydroxide solution to a pH of 7 to 8.5, and filtering to obtain a filter cake, i.e., the crude 5,5 '-disubstituted-2, 2' -diaminobiphenyl;
s4, adding ethyl acetate into the 5,5 '-disubstituted-2, 2' -diaminobiphenyl crude product, heating to 70-75 ℃ to dissolve a filter cake, filtering, concentrating and evaporating the obtained filtrate to obtain a solid crude product; and recrystallizing the solid crude product by using toluene to obtain the 5,5 '-disubstituted-2, 2' -diaminobiphenyl.
2. The method according to claim 1, wherein in step S1, the 4-substituted nitrobenzene has the chemical formula:
wherein X is F, Cl, Br, I, CF 3 、COOH、COOR、CONH 2 R OR OR, wherein R is straight-chain alkyl OR branched-chain alkyl with carbon number being any integer of 1-8.
3. The method according to claim 1, wherein in step S1, 30 to 80mL of the organic solvent and 75mL of the sodium hydroxide solution are added per 100g of the 4-substituted nitrobenzene; wherein the organic solvent is xylene, toluene, mesitylene, anisole, diphenyl ether or tetralin.
4. The method according to claim 1, wherein in step S1, the noble metal catalyst is used in an amount of 0.5 to 1g per 100g of the 4-substituted nitrobenzene; wherein the noble metal catalyst is composed of a catalyst carrier and a noble metal carried on the catalyst carrier; wherein, the catalyst carrier is active carbon, silicon dioxide, alumina or molecular sieve; the noble metal is at least one of palladium, platinum, ruthenium, rhodium and iridium; the weight of the noble metal accounts for 0.5-10% of the total weight of the carrier and the noble metal.
5. The method according to claim 1, wherein in step S2, the acidic mixture comprises 5 to 15% by mass of the strong acid aqueous solution and 8 to 12% by mass of the ammonium salt aqueous solution; wherein the strong acid aqueous solution is hydrochloric acid aqueous solution; the ammonium salt aqueous solution is ammonium chloride aqueous solution, ammonium acetate aqueous solution, ammonium sulfate aqueous solution, ammonium bisulfate aqueous solution, ammonium phosphate aqueous solution, ammonium monohydrogen phosphate aqueous solution or ammonium dihydrogen phosphate aqueous solution.
6. A method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloride by using the method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl according to any one of claims 1 to 5, wherein after steps S1 to S4 are completed, step S5 is performed: adding 5,5 '-disubstituted-2, 2' -diaminobiphenyl into a 5 wt.% hydrochloric acid solution, heating to 85-95 ℃ for complete dissolution, then dropwise adding 30-35 wt.% concentrated hydrochloric acid solution into the solution while the solution is hot, carrying out acid precipitation for 3-4 h to generate solid precipitates, cooling the mixed solution to room temperature after the solid precipitates are not increased any more, and filtering to obtain the 5,5 '-disubstituted-2, 2' -diaminobiphenyl hydrochloric acid.
7. The method according to claim 6, wherein in step S5, the weight ratio of 5,5 '-disubstituted-2, 2' -diaminobiphenyl to 5 wt.% hydrochloric acid solution is 1:4 to 1: 7; the weight ratio of the 5,5 '-disubstituted-2, 2' -diaminobiphenyl to 30-35 wt.% concentrated hydrochloric acid solution is 1: 5-1: 8.
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