CN110156613B - Synthetic method of 3, 3-diaminodiphenol hydrochloride - Google Patents
Synthetic method of 3, 3-diaminodiphenol hydrochloride Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention provides a synthetic method of 3, 3-diaminodiphenol hydrochloride, which comprises the following steps: adding raw materials 4, 4-diphenol and a reaction solvent into a reaction container, stirring, dropwise adding concentrated nitric acid under an ice bath, carrying out nitration reaction for 1-4 hours under the ice bath after dropwise adding, and then carrying out aftertreatment to obtain an intermediate 3, 3-dinitrodiphenol; adding 3, 3-dinitrodiphenol, activated carbon, ferrous sulfate heptahydrate and absolute ethyl alcohol into a reaction container, refluxing at 80 ℃, dropwise adding hydrazine hydrate, performing reduction reaction for 7-12 hours in a refluxing state after dropwise adding, and performing post-treatment on reaction liquid to obtain a product 3, 3-diaminodiphenol hydrochloride; the invention has the advantages of easy control of reaction process parameters, low energy consumption, no generation of highly toxic byproducts, good yield, high purity and high industrial feasibility.
Description
(I) the technical field
The invention relates to a method for synthesizing 3, 3-diaminodiphenol hydrochloride
(II) background of the invention
The PBO monomer 3, 3-diaminodiphenol hydrochloride shown in the formula (1) provides raw materials for preparing hydroxyl modified poly-p-Phenylene Benzobisoxazole (PBO) polymers by polymerization, and can also be used as raw materials for preparing heat-resistant materials, adhesives and aerospace materials.
At present, the main synthetic method of 3, 3-diaminodiphenol hydrochloride comprises the following steps:
4, 4-diphenol is taken as raw material (Samuel Guieu. synthosis AND CHARACTERIZATION OF LINEAR AND MACROCYCLIC LIGANDS WITH MULTIPLE HEMIALLEN POCKETS [ J ]. Synthetic Communications, 2012, 42: 3177-3186) to carry out nitration AND reduction reaction to prepare the target product, but the defects OF poor reaction safety, more by-products, difficult product separation, low yield AND the like exist, therefore, the route is not adopted; the target product is prepared by nitration and reduction reaction of 4, 4-biphenol (Qiang Liu, Hailun Borjigin, Donald R.Paul et al, Gas coatings properties of thermal conductivity predicted (TR) isomers and the aromatic polyimide precursors [ J ], Journal of Membrane Science, 2016, 518: 88-99.) as raw material. But the materials required by the reaction are expensive, the time is long, and the industrial production capacity is poor.
In view of the above-mentioned situation for synthesizing 3, 3-diaminodiphenol hydrochloride, we have searched for a new method for industrially easily synthesizing 3, 3-diaminodiphenol hydrochloride more reasonably.
Disclosure of the invention
The invention aims to provide a safe synthesis method which is feasible in industry, high in yield, short in synthesis steps, easy in obtaining of raw materials, high in reaction selectivity, free of generation of highly toxic byproducts, high in atom utilization rate and capable of preparing high-purity 3, 3-diaminodiphenol hydrochloride.
The technical scheme of the invention is as follows:
a synthetic method of 3, 3-diaminodiphenol hydrochloride comprises the following steps:
(1) adding 4, 4-diphenol serving as a raw material and a reaction solvent into a reaction container, stirring, dropwise adding 65-68 wt% of concentrated nitric acid under an ice bath (0-10 ℃, preferably 0-5 ℃), carrying out nitration reaction for 1-4 hours (preferably 2-3 hours) under an ice bath after dropwise adding is finished, and then carrying out aftertreatment to obtain an intermediate 3, 3-dinitrodiphenol;
the mass ratio of the 4, 4-biphenol to nitric acid is 1: 2-4, preferably 1: 2-2.2;
the reaction solvent is toluene and glacial acetic acid with the volume ratio of 1: 1.2-2 (preferably 1: 1.2-1.5) of a mixed solvent;
the volume consumption of the reaction solvent is 10-20 mL/g, preferably 12-16 mL/g, based on the mass of 4, 4-biphenol;
the post-treatment method comprises the following steps: after the reaction is finished, cooling the reaction liquid to room temperature (20-30 ℃), performing suction filtration, washing a filter cake with water and methanol, drying, and then performing vacuum filtration on the filter cake with toluene and N, N-dimethylformamide in a volume ratio of 1: refining the 0.875 mixed solvent, heating and refluxing for 20-30 min, cooling to room temperature, and filtering to obtain an intermediate 3, 3-dinitrobiphenol (yellow solid);
the volume consumption of the mixed solvent of the toluene and the N, N-dimethylformamide is 13-17 mL/g based on the mass of the raw material 4, 4-biphenol;
it should be noted that: the nitration reaction is an exothermic reaction, local overheating can be caused by the too fast dropping of the concentrated nitric acid (the dropping time of the concentrated nitric acid is recommended to be controlled within 10-15 min), and side reactions are increased, while on the other hand, the side reactions can be caused by the too long reaction time after the completion of the dropping of the nitric acid, so that the purity of the product is reduced, and the industrial application is not facilitated;
(2) adding the 3, 3-dinitrodiphenol, the activated carbon, ferrous sulfate heptahydrate and absolute ethyl alcohol obtained in the step (1) into a reaction container, refluxing at 80 ℃, dropwise adding hydrazine hydrate, carrying out reduction reaction for 7-12 h (preferably 9-10 h) in a reflux state after dropwise adding, and then carrying out post-treatment on reaction liquid to obtain a product, namely 3, 3-diaminodiphenol hydrochloride;
the mass ratio of the 3, 3-dinitrobiphenol to the activated carbon to the ferrous sulfate heptahydrate is 1: 0.3-0.5: 0.1 to 0.2;
the mass ratio of the 3, 3-dinitrobiphenol to the hydrazine hydrate is 1: 4-8, preferably 1: 4-6;
the volume consumption of the absolute ethyl alcohol is 10-20 mL/g, preferably 12-15 mL/g, based on the mass of the 3, 3-dinitrobiphenol;
the post-treatment method comprises the following steps: after the reaction is finished, filtering the reaction solution while the reaction solution is hot, taking a filter cake, dissolving the filter cake in 5 wt% of dilute hydrochloric acid, filtering, taking a filtrate, adding stannous chloride to dissolve the filtrate, adjusting the pH value to 1-3 by using hydrochloric acid (36-38 wt%), standing for 6-16 h, performing suction filtration, and performing vacuum drying on the filter cake to obtain a product, namely 3, 3-diaminodiphenol hydrochloride (white solid);
the volume consumption of the 5 wt% dilute hydrochloric acid is 8-15 ml/g, preferably 10-12 ml/g, based on the mass of the 3, 3-dinitrobiphenol;
the mass ratio of the stannous chloride to the 3, 3-dinitrodiphenol is 1: 8-15, preferably 1: 8 to 10.
Compared with the prior art, the invention has the following beneficial effects: the reaction process parameters are easy to control, the energy consumption is low, no toxic by-products are generated, the yield is good, the purity is high, and the industrial feasibility is high.
(IV) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1
5.00g of 4, 4-biphenol, 25mL of toluene and 35mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, stirred, 3.8mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2.5h, the reaction is cooled to room temperature, suction filtration is carried out, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 98.65%, and the yield is 92.23% based on 4, 4-biphenol.
FT-IR(KBr，cm -1 )：3224(s)、3090(s)、1520(s)、1310(s)、1239(s)。
1 H-NMR(DMSO，δ，ppm)：11.13(s,2H,OH),8.14(d,2H,J1/42.4Hz),7.86(dd,2H,J1/48.6Hz,J1/42.4Hz),7.20(d,2H,J1/48.6Hz)。
ESI-MS：[M+H] - ＝275.0。
Sequentially adding 1g of 3, 3-dinitrobiphenol (DNDHBP), 0.30g of activated carbon, 0.10g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol into a 250mL four-neck flask with a thermometer and a spherical condenser, refluxing and stirring at 80 ℃, slowly dropwise adding 1mL of hydrazine hydrate, stopping reaction after 9 hours, carrying out hot filtration, dissolving a filter cake in 12mL of 5 wt% dilute hydrochloric acid, filtering to remove impurities, adding 0.10g of stannous chloride, stirring and dissolving, then adding concentrated hydrochloric acid, adjusting the pH to about 1-3, standing overnight, carrying out suction filtration, carrying out vacuum drying on the filter cake to obtain a white solid product, namely 3, 3-diaminobiphenol hydrochloride, wherein the HPLC analysis mass fraction is 93.15%, and the yield is 88.31% by taking 3, 3-dinitrobiphenol as a meter
FT-IR(KBr，cm -1 )：3371(s)、3291(s)、2954(s)、1600.3(s)、1219(s)。
1 H-NMR(DMSO，δ，ppm)：8.92(s,2H,OH),4.51(s,4H,NH2).
ESI-MS：[M+H] + ＝217.1。
HPLC analysis conditions for 3, 3-dinitrobiphenol and 3, 3-diaminobiphenol hydrochloride: ODS C 18 Column, 6.0 × 150mm, mobile phase: 40/60(V/V), 254nm detection wavelength, flow rate 1.0 ml/min.
Examples 2 to 5
Examples 2 to 5, using the same operation procedure as in example 1, and performing tests with different parameters according to the parameter ranges described in the present invention, it can be seen that the purities of 3, 3-dinitrobiphenol and 3, 3-diaminobiphenol hydrochloride obtained under these process conditions are all above 90%, and the net yields of 3, 3-dinitrobiphenol and 3, 3-diaminobiphenol hydrochloride are both above 80% and above 90%, and both can be applied to industrial synthesis of 3, 3-dinitrobiphenol and 3, 3-diaminobiphenol hydrochloride.
Example 2
5.00g of 4, 4-biphenol, 30mL of toluene and 40mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, the mixture is stirred, 3.8mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2.5h, the mixture is cooled to room temperature, the filtration is carried out, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 98.15%, and the yield is 91% and 17% in terms of 4, 4-biphenol.
1g of 3, 3-dinitrobiphenol (DNDHBP), 0.30g of activated carbon, 0.10g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, reflux stirring is carried out at 80 ℃, 0.9mL of hydrazine hydrate is slowly dripped in, the reaction is stopped after 9 hours, heat filtration is carried out, a filter cake is dissolved in 12mL of 5 wt% diluted hydrochloric acid, impurities are removed by filtration, 0.10g of stannous chloride is added, stirring and dissolving are carried out, then concentrated hydrochloric acid is added, the pH is adjusted to about 1-3, the mixture is kept stand overnight, suction filtration is carried out, the filter cake is vacuum-dried, a white solid product 3, 3-diaminobiphenol hydrochloride is obtained, the HPLC analysis mass fraction is 91.13%, and the yield is 84.31% by taking 3, 3-dinitrobiphenol as a meter.
Example 3
5.00g of 4, 4-biphenol, 25mL of toluene and 35mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, the mixture is stirred, 4mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2.5h, the mixture is cooled to room temperature, the mixture is filtered, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 97.75%, and the yield is 90.88% based on the 4, 4-biphenol.
Sequentially adding 1g of 3, 3-dinitrobiphenol (DNDHBP), 0.30g of activated carbon, 0.10g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol into a 250mL four-neck flask with a thermometer and a spherical condenser, refluxing and stirring at 80 ℃, slowly dropwise adding 1mL of hydrazine hydrate, stopping reaction after 9 hours, carrying out hot filtration, dissolving a filter cake in 12mL of 5 wt% dilute hydrochloric acid, filtering to remove impurities, adding 0.10g of stannous chloride, stirring and dissolving, then adding concentrated hydrochloric acid, adjusting the pH to about 1-3, standing overnight, carrying out suction filtration, carrying out vacuum drying on the filter cake to obtain a white solid product, namely 3, 3-diaminobiphenol hydrochloride, wherein the HPLC analysis mass fraction is 92.19%, and the yield is 88.31% by taking 3, 3-dinitrobiphenol as a meter
Example 4
5.00g of 4, 4-biphenol, 25mL of toluene and 35mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, the mixture is stirred, 3.8mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2h, the mixture is cooled to room temperature, the mixture is filtered, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 96.81%, and the yield is 91.03% based on 4, 4-biphenol.
Sequentially adding 1g of 3, 3-dinitrobiphenol (DNDHBP), 0.30g of activated carbon, 0.10g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol into a 250mL four-neck flask with a thermometer and a spherical condenser, refluxing and stirring at 80 ℃, slowly dropwise adding 1mL of hydrazine hydrate, stopping reaction after 8 hours, carrying out hot filtration, dissolving a filter cake in 12mL of 5 wt% dilute hydrochloric acid, filtering to remove impurities, adding 0.10g of stannous chloride, stirring and dissolving, then adding concentrated hydrochloric acid, adjusting the pH to about 1-3, standing overnight, carrying out suction filtration, carrying out vacuum drying on the filter cake to obtain a white solid product, namely 3, 3-diaminobiphenol hydrochloride, wherein the HPLC analysis mass fraction is 90.28%, and the yield is 83.61% by taking 3, 3-dinitrobiphenol as a meter
Example 5
5.00g of 4, 4-biphenol, 20mL of toluene and 30mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, the mixture is stirred, 3.8mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2.5h, the mixture is cooled to room temperature, the filtration is carried out, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 95.17%, and the yield is 90.53% based on 4, 4-biphenol.
1g of 3, 3-dinitrodiphenol (DNDHBP), 0.40g of activated carbon, 0.20g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser, reflux stirring is carried out at 80 ℃, 1mL of hydrazine hydrate is slowly dripped in, reaction is stopped after 9 hours, heat filtration is carried out, a filter cake is dissolved in 12mL of 5 wt% dilute hydrochloric acid, impurities are removed by filtration, 0.10g of stannous chloride is added, stirring and dissolving are carried out, then concentrated hydrochloric acid is added, the pH value is adjusted to be about 1-3, standing is carried out overnight, suction filtration is carried out, the filter cake is dried in vacuum, a white solid product 3, 3-diaminodiphenol hydrochloride is obtained, the HPLC analytical mass fraction is 90.68%, and the yield is 81.91% by taking 3, 3-dinitrodiphenol as the standard.
Examples 7 to 8
The preparation process of example 1 was used, and tests were carried out under conditions other than the parameters described in the present invention, and the results showed that the obtained product had a poor effect.
Example 7
5.00g of 4, 4-biphenol, 30mL of toluene and 20mL of glacial acetic acid are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, the mixture is stirred, 6.5mL of nitric acid (65 wt%) is dropwise added at 5 ℃ in an ice bath, then the reaction is stopped after 2.5h, the mixture is cooled to room temperature, the mixture is filtered, water and methanol are respectively used for washing a filter cake, the filter cake is dried, 40mL of toluene and 35mL of N, N-dimethylformamide are used for refining, the temperature is reduced to room temperature after 20-30 min at the reflux temperature, a yellow product 3, 3-dinitrobiphenol is obtained by filtration, the HPLC analysis mass fraction is 74.25%, and the yield is 63.43% based on 4, 4-biphenol.
1g of 3, 3-dinitrobiphenol (DNDHBP), 0.30g of activated carbon, 0.10g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser tube, reflux stirring is carried out at 50 ℃, 1mL of hydrazine hydrate is slowly dripped, the reaction is stopped after 12 hours, heat filtration is carried out, a filter cake is dissolved in 12mL of 5 wt% diluted hydrochloric acid, impurities are removed by filtration, 0.10g of stannous chloride is added, stirring and dissolving are carried out, then concentrated hydrochloric acid is added, the pH value is adjusted to about 1-3, the mixture is kept stand overnight, suction filtration is carried out, the filter cake is dried in vacuum, a white solid product 3, 3-diaminobiphenol hydrochloride is obtained, the HPLC analysis mass fraction is 63.11%, and the yield is 59.26% by taking 3, 3-dinitrobiphenol as a meter.
Example 8
Adding 4, 4-biphenol 5.00g and glacial acetic acid 60mL into a 250mL four-neck flask provided with a thermometer and a spherical condenser, stirring, dropwise adding nitric acid 3.8mL (65 wt%) at normal temperature, reacting for 2.5h, stopping, cooling to room temperature, performing suction filtration, washing filter cakes with water and methanol respectively, drying the filter cakes, refining with toluene 40mL and N, N-dimethylformamide 35mL, cooling to room temperature after refluxing for 20-30 min, filtering to obtain a yellow product 3, 3-dinitrobiphenol, analyzing the mass fraction by HPLC (high performance liquid chromatography) 72.65%, and obtaining the yield of 60.73% based on 4, 4-biphenol.
1g of 3, 3-dinitrodiphenol (DNDHBP), 0.20g of activated carbon, 0.30g of ferrous sulfate heptahydrate and 15mL of absolute ethyl alcohol are sequentially added into a 250mL four-neck flask provided with a thermometer and a spherical condenser, reflux stirring is carried out at 80 ℃, 1mL of hydrazine hydrate is slowly dripped in, reaction is stopped after 9 hours, heat filtration is carried out, a filter cake is dissolved in 12mL of 5 wt% dilute hydrochloric acid, impurities are removed by filtration, 0.10g of stannous chloride is added, stirring is carried out for dissolution, then concentrated hydrochloric acid is added, the pH is adjusted to be about 1-3, standing is carried out overnight, suction filtration is carried out, the filter cake is vacuum-dried, a white solid product 3, 3-diaminodiphenol hydrochloride is obtained, the HPLC analysis mass fraction is 55.12%, and the yield is 51.82% by taking 3, 3-dinitrodiphenol as the reference.
Claims (9)
1. A synthetic method of 3,3 '-diamino-4, 4' -biphenol hydrochloride is characterized by comprising the following steps:
(1) adding raw materials 4,4' -biphenol and a reaction solvent into a reaction container, stirring, dropwise adding concentrated nitric acid under ice bath, carrying out nitration reaction for 1-4 h under ice bath after dropwise adding, and then carrying out aftertreatment to obtain an intermediate 3,3' -dinitro-4, 4' -biphenol;
the mass ratio of the 4,4' -biphenol to the nitric acid is 1: 2-4;
the reaction solvent is toluene and glacial acetic acid with the volume ratio of 1: 1.2-2 of a mixed solvent;
(2) adding the 3,3 '-dinitro-4, 4' -biphenol obtained in the step (1), activated carbon, ferrous sulfate heptahydrate and absolute ethyl alcohol into a reaction container, refluxing at 80 ℃, dropwise adding hydrazine hydrate, performing reduction reaction for 7-12 hours in a refluxing state after dropwise adding, and performing post-treatment on reaction liquid to obtain a product, namely 3,3 '-diamino-4, 4' -biphenol hydrochloride;
the mass ratio of the 3,3 '-binitro-4, 4' -biphenol to the activated carbon to the ferrous sulfate heptahydrate is 1: 0.3-0.5: 0.1 to 0.2;
the mass ratio of the 3,3 '-dinitro-4, 4' -biphenol to the hydrazine hydrate is 1: 4-8;
the post-treatment method comprises the following steps: after the reaction is finished, filtering the reaction solution while the reaction solution is hot, taking a filter cake, dissolving the filter cake in 5 wt% of dilute hydrochloric acid, filtering, taking a filtrate, adding stannous chloride to dissolve the filtrate, adjusting the pH value to 1-3 with hydrochloric acid, standing for 6-16 h, performing suction filtration, and performing vacuum drying on the filter cake to obtain a product, namely 3,3 '-diamino-4, 4' -biphenol hydrochloride; the volume consumption of the 5 wt% diluted hydrochloric acid is 8-15 ml/g based on the mass of the 3,3 '-dinitro-4, 4' -biphenol; the mass ratio of the stannous chloride to the 3,3 '-dinitro-4, 4' -biphenol is 1: 8-15.
2. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (1), the time of the nitration reaction is 2-3 h.
3. The method for synthesizing 3,3' -diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in step (1), the mass ratio of the 4,4' -biphenol to the nitric acid is 1: 2 to 2.2.
4. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (1), the reaction solvent is toluene and glacial acetic acid in a volume ratio of 1: 1.2 to 1.5.
5. The method for synthesizing 3,3' -diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (1), the volume usage of the reaction solvent is 10 to 20mL/g based on the mass of 4,4' -biphenol.
6. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (1), the post-treatment method is: after the reaction is finished, cooling the reaction liquid to room temperature, performing suction filtration, washing a filter cake with water and methanol, drying, and then performing vacuum filtration on the filter cake with toluene and N, N-dimethylformamide in a volume ratio of 1: refining the 0.875 mixed solvent, heating and refluxing for 20-30 min, cooling to room temperature, and filtering to obtain an intermediate 3,3 '-dinitro-4, 4' -biphenol; the volume usage of the mixed solvent of toluene and N, N-dimethylformamide is 13-17 mL/g based on the mass of the raw material 4,4' -biphenol.
7. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in step (2), the time of the reduction reaction is 9-10 hours.
8. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (2), the mass ratio of the 3,3 '-dinitro-4, 4' -biphenol to the hydrazine hydrate is 1: 4 to 6.
9. The method for synthesizing 3,3 '-diamino-4, 4' -biphenol hydrochloride according to claim 1, wherein in the step (2), the volume usage amount of the absolute ethyl alcohol is 10 to 20mL/g based on the mass of the 3,3 '-dinitro-4, 4' -biphenol.
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| CN1426390A (en) * | 2000-04-25 | 2003-06-25 | 日本化药株式会社 | Process for producing bis (4-hydroxy-3-nitrophenyl) compound |
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| CN103664685A (en) * | 2013-11-20 | 2014-03-26 | 山西大同大学 | BHNAPPDP and preparation method and application thereof |
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