CN101525294B - Method for preparing 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl - Google Patents
Method for preparing 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl Download PDFInfo
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Abstract
The invention relates to the technical field of fine chemistry industry, in particular to a method for preparing 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl. Under the conditions of nitrogen protection and inorganic aqueous alkali exising, alcohol and aromatic hydrocarbon are used as a mixed solvent; meta-nitro benzotrifluoride is prepared into 3,3'-bis(trifluoromethyl) diphenyl hydrazine by a one-step method of zinc dust reductive coupling; reaction liquid is directly used for rearrangement reaction after acidification and filtration, the rearrangement reaction of the 3,3'- bis(trifluoromethyl) diphenyl hydrazine is carried out under the conditions of 0-40 DEG C and inorganic acid, the reaction time is 3 hours to 18 hours; then the solvent is recovered by separating liquid, and a water phase and an organic phase are separated; the pH value of the water phase is regulated into 8 to 12 by inorganic base; after suction filtration, water scrubbing and recrystallization, clear crystal is dried in high vacuum at 40 to 85 DEG C for 12 hours to 24 hours to obtain the 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl. The method solves the problem of large solvent consumption in the prior production art.
Description
Affiliated technical field
The present invention relates to the fine chemical technology field, specifically a kind of 2,2 '-two (trifluoromethyl)-4,4 '-preparation method of benzidine.
Background technology
2,2 '-two (trifluoromethyl)-4,4 '-benzidine (being called for short TFMB, lower same) is the important source material of synthesized high-performance aromatic polyimide resin.With the synthetic polyimide resin of TFMB have that thermostability is high, good insulating, the performance such as wear-resistant, anti-aging, have broad application prospects in fields such as Materials science.Existing synthetic method mainly is divided into two classes: one, by metal (zinc, copper, magnesium) linked reaction prepare 2,2 '-two (trifluoromethyl)-4,4 '-dinitrobenzene biphenyl, again by the synthetic TFMB of reduction reaction.Although the method total recovery is high, there is severe reaction conditions, difficulty is high, aftertreatment is complicated and the high in cost of production shortcoming, is difficult to use in suitability for industrialized production.Two, at first take m-nitryl benzotrifluoride as raw material by prepare 3,3 in the alkaline reduction coupling '-two (trifluoromethyl) hydrazo-benzene (be called for short TFMPHA, lower with), TFMPHA again in the presence of mineral acid position rotaring rearrangement obtain TFMB.For example: J.Chem.Soc.1953, the 1994-1998 reported first drip aqueous sulfuric acid (volume ratio 1: 1) in the ethanolic soln of TFMPHA position rotaring rearrangement prepare TFMB, but yield only has 10%.J.Polym.Sci., PartA:Polym.Chem.1999,937-957 have reported that also dripping the concentrated hydrochloric acid position rotaring rearrangement in the ethanolic soln of TFMPHA prepares TFMB, but yield also only is 17%.Although this class methods yield is low, because synthesis technique is simple, cost is relatively low, is expected to for actual production.WO2006048935A1 improves the technique of above-mentioned two pieces of bibliographical informations, drips the aqueous sulfuric acid position rotaring rearrangement in the toluene solution of TFMPHA and prepares TFMB, makes the rearrangement reaction yield reach 30%.But its synthesis technique solvent consumption is large, and intermediate TFMPHA need to could be used for position rotaring rearrangement through aftertreatments such as solvent evaporated, and production cost still can not effectively reduce.Recently, JP2007246427 reported under the Ultrasonic Conditions, in the time of-20 ℃, drips the aqueous sulfuric acid position rotaring rearrangement in the toluene solution of TFMPHA and prepares TFMB.But because appliance arrangement is special and need low temperature, technique is amplified difficulty, can't be applied to large-scale industrialization production.In the post-processed of product, need in the method that in existing technology, adopts to use a large amount of solvents to extract and recrystallization
Summary of the invention
The technical problem to be solved in the present invention is: for the large problem of solvent consumption in the technique in existing the production, provide a kind of solvent consumption little, product purity high 2,2 '-two (trifluoromethyl)-4,4 '-preparation method of benzidine.
The technical solution adopted for the present invention to solve the technical problems is: a kind of 2; 2 '-two (trifluoromethyl)-4; 4 '-preparation method of benzidine; under nitrogen protection; under the inorganic base aqueous solution existence condition; pure and mild aromatic hydrocarbons is as mixed solvent, by zinc powder reduction coupling single stage method prepare 3,3 '-two (trifluoromethyl) hydrazo-benzene; reaction solution is acidified; be directly used in rearrangement reaction after the filtration; 3,3 '-rearrangement reaction of two (trifluoromethyl) hydrazo-benzene is at 0～40 ℃, and mineral acid carries out under existing; 3～18 hours reaction times; then separatory reclaims solvent, isolates water and organic phase, it is characterized in that: described water is regulated the pH value with mineral alkali; suction filtration; washing; recrystallization; dry 2,2 '-two (trifluoromethyl)-4,4 '-benzidine.
Reaction principle of the present invention is schematically as follows:
Water described in the present invention is regulated the pH value and is preferably 9～10.
The mixed solvent of the pure and mild aromatic hydrocarbons described in the present invention, alcohol is one or both or the two or more alcohol mixtures in methyl alcohol, ethanol or the Virahol, aromatic hydrocarbons is one or both or the two or more BTX aromatics in benzene, toluene or the dimethylbenzene, alcohol is 5: 1～1: 5 with the mass ratio of aromatic hydrocarbons, preferred 2: 1～1: 2 of the mass ratio of alcohol and aromatic hydrocarbons.
The mixed solvent of the alcohol described in the present invention and aromatic hydrocarbons and the mass ratio of m-nitryl benzotrifluoride are 1: 1～10: 1, preferred 3: 1～7: 1 of the mixed solvent of alcohol and aromatic hydrocarbons and the mass ratio of m-nitryl benzotrifluoride, described zinc powder and m-nitryl benzotrifluoride mol ratio are 2: 1～10: 1, preferred 2: 1～6: 1 of institute's zinc powder and m-nitryl benzotrifluoride mol ratio, the mol ratio of described mineral alkali and m-nitryl benzotrifluoride is 0.1: 1～0.8: 1, preferred 0.2: 1～0.7: 1 of the mol ratio of mineral alkali and m-nitryl benzotrifluoride.
Mineral alkali described in the present invention is the aqueous sodium hydroxide solution of mass concentration 10%～50% or the potassium hydroxide aqueous solution of mass concentration 10%～50%.
Mineral acid described in the present invention and 3,3 '-mol ratio of two (trifluoromethyl) hydrazo-benzene is 1: 1～10: 1.
Mineral acid described in the present invention is that concentrated hydrochloric acid or mass concentration are 20%～70% aqueous sulfuric acid.Under 0 ℃, mineral acid adds in the reaction soln in the dropping mode, reacts 3～18 hours 0～40 ℃ of lower continuation after dripping.
After rearrangement reaction finishes, add suitable quantity of water in reaction solution, its mass ratio with m-nitryl benzotrifluoride is 0.3: 1～2: 1, makes the vitriol of TFMB or hydrochloride be dissolved in separatory behind water and the pure mixed phase fully.Water is with sodium hydroxide or the potassium hydroxide aqueous solution neutralization of concentration 10～50% (w/w), suction filtration, and gained TFMB solid washes with water to pH=8～9, with the aqueous solution recrystallization of toluene or alcohol, clear crystal under 50 ℃ of high vacuum dry 24 hours.
The invention has the beneficial effects as follows: 2,2 '-two (trifluoromethyl)-4,4 '-preparation method of benzidine has following advantage: 1, solvent load is few, and production cost is low.Reductive coupling reaction is compared with existing method, and solvent load greatly reduces, and rearrangement reaction do not need additionally to add other solvent again, and linked reaction liquid is directly used in rearrangement reaction after acidifying, simple filtration.
2, intermediate and the finished product separation and purification are easy, and technique is simple.Intermediate TFMPHA need not extra aftertreatment, purifying, even reaction solvent does not need underpressure distillation to remove; The finished product are separated out from water by the pH value of regulating its vitriol or hydrochloride, and filtration obtains, and processing ease is fit to the mass-producing batch production.
3, adopt admixture solvent to carry out rearrangement reaction, by changing reactant and the partition ratio of product in two phase reaction liquid, greatly improved the yield of rearrangement reaction.Present method total recovery 30～50%, product purity are easy to suitability for industrialized production up to 99.9%.
Embodiment
Embodiment 1
Under the room temperature nitrogen protection; to agitator is housed; add successively the 75g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 100g toluene; 73g methyl alcohol; 40% aqueous sodium hydroxide solution 18.5g; and in above-mentioned reaction solution, drip the 51g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4.5h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 30% dilution heat of sulfuric acid is regulated pH value to 5～6; remove by filter zinc powder and solid insoluble, divide the washing filter residue three times with 117g toluene, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, slowly drip 56% sulphuric acid soln 196g, 1h drips off, and continues at room temperature to react 4.5h, adds 40g water, separatory, lower floor's water 0 ℃ of lower neutralization, is regulated pH value to 9～10 with 40% aqueous sodium hydroxide solution, there is faint yellow solid to separate out, suction filtration, washing, head product 45g toluene recrystallization, obtain white crystal 16.8g, overall yield is 40% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 2
Under the room temperature nitrogen protection; to agitator is housed; add successively the 75g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 100g toluene; 73g methyl alcohol; 40% aqueous sodium hydroxide solution 18.5g; and in above-mentioned reaction solution, drip the 51g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4.5h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 50% dilution heat of sulfuric acid is regulated pH value to 3～4; remove by filter zinc powder and solid insoluble, divide the washing filter residue three times with 80g toluene, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, slowly drip 58% sulphuric acid soln 200g, 1h drips off, continue at room temperature to react 4.5h, add 40g water, separatory, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 20.5g with 55g toluene recrystallization, overall yield is 48% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 3
Under the room temperature nitrogen protection; to agitator is housed; add successively the 40g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 40g toluene; 30g methyl alcohol; 40% aqueous sodium hydroxide solution 11g; and in above-mentioned reaction solution, drip the 30g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 40% sulphuric acid soln is regulated pH value to 5～6; remove by filter zinc powder and solid insoluble, wash several times filter residue with 70g toluene and 20g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip 56% sulphuric acid soln 120g, 1h drips off, continuation adds 20g water, separatory at 0 ℃ of lower reaction 8h, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 8.8g with 20g toluene recrystallization, overall yield is 35% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 4
Under the room temperature nitrogen protection; to agitator is housed; add successively the 120g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 135g toluene; 95g methyl alcohol; 40% aqueous sodium hydroxide solution 37g; and in above-mentioned reaction solution, drip the 100g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 5h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 56% sulphuric acid soln is regulated pH value to 4～5; remove by filter zinc powder and solid insoluble, wash several times filter residue with 230g toluene and 33g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip 60% sulphuric acid soln 400g, 1h drips off, continue at room temperature to react 8h, add 70g water, separatory, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 41.9g with 105g toluene recrystallization, overall yield is 50% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 5
Under the room temperature nitrogen protection; to agitator is housed; add successively the 400g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 400g toluene; 300g methyl alcohol; 40% aqueous sodium hydroxide solution 110g; and in above-mentioned reaction solution, drip the 300g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 5h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 56% sulphuric acid soln is regulated pH value to 4～5; remove by filter zinc powder and solid insoluble, wash several times filter residue with 500g toluene and 100g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip 56% sulphuric acid soln 1200g, 2h drips off, continue at room temperature to react 8h, add 200g water, separatory, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 103g with 250g toluene recrystallization, overall yield is 41% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 6
Under the room temperature nitrogen protection; to agitator is housed; add successively the 38g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 40g toluene; 29g methyl alcohol; 40% aqueous sodium hydroxide solution 11g; and in above-mentioned reaction solution, drip the 30g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4h, solution is become colorless by redness, is cooled to 0 ℃; dripping concentration is that 40% sulphuric acid soln is regulated pH value to 5～6; remove by filter zinc powder and solid insoluble, divide the washing filter residue three times with 50g toluene and 8g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip 40% sulphuric acid soln 170g, 1h drips off, and continues at room temperature to react 8h, separatory, lower floor's water 0 ℃ of lower neutralization, is regulated pH value to 9～10 with 40% aqueous sodium hydroxide solution, has faint yellow solid to separate out, continue at room temperature to stir 2h suction filtration, washing, head product 19g toluene recrystallization, obtain white crystal 8.1g, overall yield is 32% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 7
Under the room temperature nitrogen protection; to agitator is housed; add successively the 38g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 40g toluene; 30g methyl alcohol; 40% aqueous sodium hydroxide solution 11g; and in above-mentioned reaction solution, drip the 30g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4h, solution is become colorless by redness, is cooled to 0 ℃; drip concentrated hydrochloric acid and regulate pH value to 5～6; remove by filter zinc powder and solid insoluble, wash several times filter residue with 30g toluene and 16g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip concentrated hydrochloric acid 100g, 2h drips off, continue at room temperature to react 8h, add 40g water, separatory, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 9.6g with 20g toluene recrystallization, overall yield is 38% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Embodiment 8
Under the room temperature nitrogen protection; to agitator is housed; add successively the 380g active zinc powder in the reaction flask of dropping funnel and reflux condensing tube; 400g toluene; 290g methyl alcohol; 40% aqueous sodium hydroxide solution 110g; and in above-mentioned reaction solution, drip the 300g m-nitryl benzotrifluoride; the control rate of addition is kept 68 ℃ of interior temperature; dropwise; be incubated 68 ℃; vigorous stirring backflow 4h, solution is become colorless by redness, is cooled to 0 ℃; drip concentrated hydrochloric acid and regulate pH value to 5～6; remove by filter zinc powder and solid insoluble, wash several times filter residue with 400g toluene and 110g methyl alcohol, merge gained filtrate; need not further aftertreatment, be directly used in rearrangement reaction.
In the reaction flask that agitator and dropping funnel are housed, add above-mentioned filtrate, under 0 ℃, drip concentrated hydrochloric acid 900g, 2h drips off, continue at room temperature to react 8h, add 400g water, separatory, lower floor's water neutralizes under 0 ℃ with 40% aqueous sodium hydroxide solution, regulate pH value to 9～10, have faint yellow solid to separate out, continue at room temperature to stir 2h, suction filtration, washing, head product obtains white crystal 75.4g with 165g toluene recrystallization, overall yield is 30% take m-nitryl benzotrifluoride as benchmark, and purity is 99.9%.
Claims (7)
1. one kind 2; 2 '-two (trifluoromethyl)-4; the preparation method of 4 '-benzidine; under nitrogen protection; under the inorganic base aqueous solution existence condition; pure and mild aromatic hydrocarbons is as mixed solvent, and m-nitryl benzotrifluoride prepares 3 by zinc powder reduction coupling single stage method, 3 '-two (trifluoromethyl) hydrazo-benzene; reaction solution is acidified; be directly used in rearrangement reaction after the filtration; 3,3 '-two (trifluoromethyl) hydrazo-benzene rearrangement reaction is at 0～40 ° of C, and mineral acid carries out under existing; 3～18 hours reaction times; then separatory reclaims solvent, isolates water and organic phase, it is characterized in that: described water is regulated pH value to 8～12 with mineral alkali; suction filtration; washing; recrystallization; white crystal drying under 40～65 ℃ of high vacuum got 2,2 '-two (trifluoromethyl)-4,4 '-benzidine in 12～24 hours.
2. 2,2 '-two (trifluoromethyl)-4 according to claim 1, the preparation method of 4 '-benzidine is characterized in that: it is 9～10 that described water is regulated the pH value.
3. according to claim 12,2 '-two (trifluoromethyl)-4, the preparation method of 4 '-benzidine, it is characterized in that: the mixed solvent of described pure and mild aromatic hydrocarbons, alcohol is one or both or the two or more alcohol mixtures in methyl alcohol, ethanol or the Virahol, aromatic hydrocarbons is one or both or the two or more BTX aromatics in benzene, toluene or the dimethylbenzene, and alcohol is 2:1～1:2 with the mass ratio of aromatic hydrocarbons.
4. according to claim 1 or 3 described 2,2 '-two (trifluoromethyl)-4, the preparation method of 4 '-benzidine is characterized in that: the mixed solvent of described alcohol and aromatic hydrocarbons and the mass ratio of m-nitryl benzotrifluoride are 3:1～7:
1, described zinc powder and m-nitryl benzotrifluoride mol ratio are 2:1～6:1, and the mol ratio of described mineral alkali and m-nitryl benzotrifluoride is 0.2:1～0.7:1.
5. according to claim 1 or 4 described 2,2 '-two (trifluoromethyl)-4, the preparation method of 4 '-benzidine is characterized in that: described mineral alkali is the aqueous sodium hydroxide solution of mass concentration 10%～50% or the potassium hydroxide aqueous solution of mass concentration 10%～50%.
6. 2,2 '-two (trifluoromethyl)-4 according to claim 1, the preparation method of 4 '-benzidine is characterized in that: described mineral acid and 3, the mol ratio of 3 '-two (trifluoromethyl) hydrazo-benzene is 1:1～10:1.
7. according to claim 1 or 6 described 2,2 '-two (trifluoromethyl)-4, the preparation method of 4 '-benzidine is characterized in that: described mineral acid is that concentrated hydrochloric acid or mass concentration are 20%～70% aqueous sulfuric acid.
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| CN102417459B (en) * | 2011-08-29 | 2014-03-05 | 天津市筠凯化工科技有限公司 | Preparation method of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl |
| CN102675665B (en) * | 2012-04-23 | 2014-05-07 | 常州市阳光药业有限公司 | Colorless transparent polyimide film preparation method |
| CN105384648B (en) * | 2015-09-30 | 2017-12-29 | 常州市阳光药业有限公司 | 2,2 ' is double（Methoxyl group）The preparation method of 4,4 ' benzidines |
| CN105198753B (en) * | 2015-09-30 | 2017-06-27 | 常州市阳光药业有限公司 | 2,2 ' is double（Trifluoromethoxy）The preparation method of 4,4 ' benzidines |
| CN109232273A (en) * | 2018-10-23 | 2019-01-18 | 烟台海川化学制品有限公司 | The preparation method of bis- (trifluoromethyl) -4,4 '-benzidines of one kind 2,2 ' - |
| CN111574380B (en) * | 2020-02-19 | 2022-09-09 | 天津科技大学 | Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method |
| CN113024385B (en) * | 2021-03-16 | 2022-08-16 | 西安瑞联新材料股份有限公司 | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl |
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| JP2006265129A (en) * | 2005-03-23 | 2006-10-05 | Air Water Inc | Method for producing 3,3'-bis(trifluoromethyl)hydrazobenzene |
| JP2007246427A (en) * | 2006-03-15 | 2007-09-27 | Wakayama Seika Kogyo Kk | Method for producing 4,4'-diaminobiphenyl derivative |
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| JP2006265129A (en) * | 2005-03-23 | 2006-10-05 | Air Water Inc | Method for producing 3,3'-bis(trifluoromethyl)hydrazobenzene |
| JP2007246427A (en) * | 2006-03-15 | 2007-09-27 | Wakayama Seika Kogyo Kk | Method for producing 4,4'-diaminobiphenyl derivative |
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