CN113429309A - Preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether - Google Patents
Preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether Download PDFInfo
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Abstract
The invention provides a preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether, which comprises the following steps: acylation: adding an acylating agent into 4, 4' -diaminodiphenyl ether for acylation reaction to obtain an acylated product; a nitration step: and cooling the acylation product, and adding nitric acid to carry out nitration reaction to obtain a nitration product. The method directly performs two steps of acylation and nitration on the 4, 4' -diaminodiphenyl ether serving as the raw material in an acylating agent system, does not need to take out an acylate, and has the advantages of simple step, low loss, high purity and high yield.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether.
Background
Polybenzimidazole (PBI) as a novel engineering material still has excellent mechanical property and electrical property at the temperature of more than 400 ℃, and is one of ideal matrix resins of a composite material resistant to high temperature of more than 400 ℃; meanwhile, the coating has excellent performances of wear resistance, radiation resistance, acid and alkali resistance and the like, so that the coating has wide application prospects in various fields, and the application range of the coating is more and more extensive along with the development requirements of production technologies.
The synthesis of PBI is not free of tetraamine monomers. The PBI resin obtained by polymerization using wholly aromatic dibasic acids and dibasic esters tends to have high rigidity, poor solubility, and difficulty in processing. Therefore, in order to improve the properties of PBI resins, flexible groups are often introduced into the tetraamine structure, such as: -CH2-、-SO2-and the like.
The preparation method of 3,3 ', 4,4 ' -tetraaminodiphenyl ether is characterized by using 4,4 ' -diaminodiphenyl ether as raw material, and making it undergo the processes of acetylation, nitration, alkaline hydrolysis, reduction and neutralization so as to obtain the invented product. The intermediate product 3,3 ' -dinitro-4, 4 ' -diacetoxy diphenyl ether is prepared through the conventional process including the steps of reacting 4,4 ' -diaminodiphenyl ether in an acetic acid-acetic anhydride mixed system, cooling, separating, suction filtering, washing, drying, nitrifying in an acetic anhydride system, suction filtering, washing, drying after the nitration is finished, and finally recrystallizing with DMF. The method has the advantages of complicated process steps, low purity and yield and large loss.
Citation 1 discloses a method for synthesizing 3,3 ', 4,4 ' -tetraaminodiphenyl ether and preparing polybenzimidazole resin thereof, wherein 4,4 ' -diaminodiphenyl ether is used as a raw material, and 3,3 ', 4,4 ' -tetraaminodiphenyl ether is synthesized through five steps of acetylation, nitration, alkaline hydrolysis, reduction and neutralization, the total yield is 52.8%, and FT-IR and melting point testing technologies are used for characterizing the total yield. Wherein, after acetylation and nitration, 3 '-dinitro-4, 4' -diacetyl amino diphenyl ether is firstly generated, and the preparation method adopts a two-step method, and has the disadvantages of complicated steps, low purity and yield and large loss.
Citation 2 discloses an improved process for nitration reactions during the synthesis of 3,3 '-dinitro-4, 4' -diacetoxydiphenyl ether. The nitration method comprises the following steps: 40mL of acetic anhydride was added to a three-necked flask placed in an ice-water bath, 8g of DAADPE was added in portions, the electromagnetic stirrer was turned on, and HNO was slowly dropped into the flask using a constant pressure dropping funnel3And ensuring that the temperature in the bottle is lower than 5 ℃, gradually dissolving reactants in the bottle along with the dropwise addition of nitric acid, dropwise adding 8mL of nitric acid, heating to 15 ℃, maintaining the reaction temperature below 25 ℃, pouring the reaction solution into 500mL of ice water after the reaction is carried out for 2 hours, separating out yellow precipitate, filtering, washing with water to be neutral, drying, and recrystallizing by using absolute ethyl alcohol to obtain the 3,3 '-dinitro-4, 4' -diacetamido diphenyl ether (DN-DAADPE). The method is still a two-step preparation method, the steps are complicated, and although the method is improved, the yield is still low and only reaches 88%.
Citation 3 discloses a method for synthesizing and characterizing 3,3 ', 4, 4' -tetraaminodiphenyl ether, wherein 3,3 '-dinitro-4, 4' -diacetyl aminodiphenyl ether is synthesized first and is prepared by a step-by-step method, and the nitration step specifically comprises adding 26mL of acetic anhydride into a three-necked flask, placing the three-necked flask in an ice-water bath, starting an electromagnetic stirrer, and slowly dripping 60% concentrated HNO (HNO) by using a constant-pressure dropping funnel312mL, the temperature in the reaction bottle is lower than 10 ℃, the temperature is raised to 15 ℃ after the dropwise addition, the (II) (8.0g, 0.028mol) is added in batches, the reaction temperature is maintained below 15 ℃, after the reaction is carried out for 2 hours, the reaction solution is slowly poured into 500mL of ice water, yellow precipitate is separated out, the yellow precipitate is filtered, washed to be neutral by water, dried and recrystallized by absolute ethyl alcohol, and 8.8g of the compound (III) is obtained.
In view of the technical problems in the prior art, it is an urgent need to solve the above problems by developing a simple and easy preparation method that can improve the yield.
Disclosure of Invention
Problems to be solved by the invention
In view of the problems in the prior art, the invention aims to provide a preparation method of 3,3 '-dinitro-4, 4' -diacetoxydiphenyl ether, which has the advantages of simple process flow, less solvent consumption, low loss, high product purity and high yield.
Means for solving the problems
The invention provides a preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether, which comprises the following steps:
acylation: adding an acylating agent into 4, 4' -diaminodiphenyl ether for acylation reaction to obtain an acylated product;
a nitration step: and cooling the acylation product, and adding nitric acid to carry out nitration reaction to obtain a nitration product.
In the preparation method according to the present invention, in the acylating step, the acylating agent includes acetic acid, acetic anhydride, or a mixture of acetic acid and acetic anhydride, preferably acetic acid.
The production method according to the present invention, wherein, in the acylation step, the acetic acid is glacial acetic acid; and/or the presence of a gas in the gas,
in the mixed solution of acetic acid and acetic anhydride, the mass ratio of acetic anhydride to acetic acid is 1: 5-35, preferably 1: 10-20.
According to the preparation method, in the acylation step, the mass ratio of the 4, 4' -diaminodiphenyl ether to the acylating agent is 1: 10-20, and preferably 1: 11-15.
The preparation method provided by the invention is characterized in that the acylation reaction temperature is 80-115 ℃, preferably 105-115 ℃; the acylation time is 2-10 hours, preferably 7-10 hours.
According to the preparation method, in the nitration step, the temperature after cooling is-5-30 ℃, and preferably 10-30 ℃; and/or
The mass fraction of the nitric acid is 60-98%.
The preparation method provided by the invention is characterized in that the molar ratio of the 4, 4' -diaminodiphenyl ether to the nitric acid is 1: 2.1-4, and preferably 1: 2.4-3.
According to the preparation method, in the nitration step, the temperature of the added nitric acid is-5-30 ℃, preferably 10-30 ℃, and the temperature is kept for 1-2 hours; then heating to 40-70 ℃, preferably 60-70 ℃, and then preserving heat for 4-10 hours, preferably 6-8 hours.
The preparation method according to the present invention, wherein after the nitration step, a post-treatment step is further included, and preferably, the post-treatment step includes a recrystallization step.
According to the preparation method, in the recrystallization treatment, the solvent used is ethanol and/or dimethylformamide.
ADVANTAGEOUS EFFECTS OF INVENTION
The method directly performs two steps of acylation and nitration on the 4, 4' -diaminodiphenyl ether serving as the raw material in an acylating agent system, does not need to take out an acylate, and has the advantages of simple step, low loss, high purity and high yield.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3% or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
In the present specification, if the expression "normal temperature", "room temperature", etc. appears, it may generally mean 10 to 40 ℃.
The invention provides a preparation method of 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether, which comprises the following steps:
acylation: adding an acylating agent into 4,4 '-diaminodiphenyl ether for acylation reaction to obtain an acylation product 4, 4' -diacetyl aminodiphenyl ether;
a nitration step: and cooling the acylation product, and adding nitric acid to carry out nitration reaction to obtain the nitration product 3,3 '-dinitro-4, 4' -diacetyl amido diphenyl ether.
The specific reaction formula is as follows:
acylation:
a nitration step:
the invention adopts a one-pot method to prepare the 3,3 '-dinitro-4, 4' -diacetoxy diphenyl ether, and has the advantages of simple process flow, little solvent consumption, low loss, high product purity and high yield.
Acylation step
The acylation step of the invention comprises adding an acylating agent into 4,4 '-diaminodiphenyl ether to carry out acylation reaction, thereby obtaining an acylation product of 4, 4' -diacetoxydiphenyl ether.
In some specific embodiments, in the acylation step, the acylating agent comprises acetic acid, acetic anhydride or a mixture of acetic acid and acetic anhydride, and the inventors of the present invention found that when acetic acid is used as the acylating agent, the finally prepared nitrated product 3,3 '-dinitro-4, 4' -diacetoxydiphenyl ether is obtained in a higher yield, and that the use of acetic acid as the acylating agent facilitates the production in a plant and reduces the operation cost. Therefore, acetic acid is preferably used as the acylating agent in the present invention.
In the present invention, in the acylation step, the acetic acid is glacial acetic acid. Glacial acetic acid is preferably used as an acylating agent, and is particularly a reaction solvent and a reaction reagent, participates in the reaction and can give an amino protecting group; in addition, glacial acetic acid can be used as a reaction solvent in the subsequent nitration reaction, so that an acylation product does not need to be taken out to participate in the next reaction, but the next reaction can be directly carried out, and the procedure can be saved.
Further, in the present invention, a mixed solution of acetic acid and acetic anhydride may be used as the acylating agent, and the present inventors have found that the reaction rate can be increased by adding a certain amount of acetic anhydride. Wherein in the mixed solution of acetic acid and acetic anhydride, the mass ratio of acetic anhydride to acetic acid is 1: 5-35, preferably 1: 10-20, for example: 1:7, 1:8, 1:12, 1:15, 1:18, 1:22, 1:25, 1:28, etc. When the mass ratio of acetic anhydride to acetic acid is 1: 5-35, the rapid preparation of the acylation product is facilitated.
In some specific embodiments, in view of the fact that the acylation reaction can be efficiently performed, the mass ratio of the 4, 4' -diaminodiphenyl ether to the acylating agent in the acylation step is 1:10 to 20, preferably 1:11 to 15, for example: 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, etc.
Further, the reaction conditions for the acylation reaction in the present invention are not particularly limited, and may be some reaction conditions commonly used in the art. Specifically, in order to increase the purity and/or yield of the acylation product after the acylation reaction, the acylation reaction temperature is 80-115 ℃, preferably 105-115 ℃, such as 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ and the like; the acylation time is 2-10 hours, preferably 7-10 hours, for example: 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, etc.
Nitration step
The nitration step comprises the steps of cooling the acylation product, and adding nitric acid for nitration reaction to obtain the nitration product 3,3 '-dinitro-4, 4' -diacetyl amido diphenyl ether.
In the present invention, the mass fraction of the nitric acid used in the nitration step may be preferably 60% to 98%. Thereby facilitating the nitration step.
In some specific embodiments, the acylation product is subjected to a temperature reduction treatment in order to facilitate the nitration step, and generally, the temperature after the temperature reduction is-5 to 30 ℃, preferably 10 to 30 ℃, such as-2 ℃, 5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃ and the like. Further, in order to enable the reaction to proceed orderly, the molar ratio of the 4, 4' -diaminodiphenyl ether to the nitric acid is 1:2.1 to 4, preferably 1:2.4 to 3, for example: 1:2.2, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.1, 1:3.3, 1:3.5, 1:3.6, 1:3.8, etc. The invention can make the nitration reaction more complete by using a little excessive nitric acid for reaction.
In some embodiments, in order to make the nitration step more complete, the temperature at which the nitric acid is added in the nitration step is between-5 ℃ and 30 ℃, preferably between 10 ℃ and 30 ℃, such as-2 ℃, 5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃ and the like; and then preserving the heat for 1-2 hours, for example: 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, etc.; then heating to 40-70 deg.C, preferably 60-70 deg.C, such as 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, etc.; and preserving the heat for 4-10 hours, preferably 6-8 hours, for example: 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, etc.
According to the invention, one amino group in the acylation product can be quickly protected at low temperature by keeping the temperature of-5-30 ℃ for 1-2 hours, and the rest amino group can be partially protected. By maintaining the temperature at a lower temperature for a period of time, the occurrence of side reactions can be reduced.
Further, after the heat preservation is carried out for 1-2 hours at the temperature of-5-30 ℃, the temperature is raised to 40-70 ℃, the heat preservation is carried out for 4-10 hours, the rest part of amino groups can be protected, the time of acylation reaction is shortest, and the occurrence of side reaction can be reduced. If the temperature after the temperature rise is too high, a small amount of nitration products are decomposed or byproducts are generated.
In some embodiments, the nitration step is followed by a post-treatment step. The present invention is not particularly limited with respect to the post-treatment, and may be post-treatment steps generally employed in the art, such as: and (3) carrying out post-treatment steps of separation, washing, drying, recrystallization, classification, packaging and the like.
The present invention is not particularly limited with respect to the separation, and may be some separation means commonly used in the art, for example: filtration, centrifugation, and the like. The washing may be carried out using water and/or an organic solvent such as a low-boiling hydrocarbon, an alcohol, an ether, or a ketone, and is preferably carried out using water. The drying may be carried out under conditions of heat and/or reduced pressure to obtain a dried product.
Further, in order to obtain 3,3 '-dinitro-4, 4' -diacetoxydiphenyl ether with higher purity, it is preferable that the post-treatment of the present invention includes recrystallization. The treatment method of recrystallization is not particularly limited in the present invention, and may be any treatment method commonly used in the art, for example: at a certain temperature, the solvent is used to dissolve the nitration product and then the temperature is reduced, thereby separating out the 3,3 '-dinitro-4, 4' -diacetyl amido diphenyl ether with higher purity.
Specifically, in the recrystallization treatment, the solvent used is ethanol and/or Dimethylformamide (DMF), and Dimethylformamide (DMF) is preferably used.
The amount of the solvent used is not particularly limited, and may be the amount commonly used in the art, and specifically, the mass ratio of the nitration product to the solvent may be 1: 3-10; for example: 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, etc. The temperature for recrystallization is not particularly limited in the present invention, and generally, the temperature may be raised to 80 to 120 ℃ to elute, and the temperature of the elution may be 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or the like. After dissolving and clearing, cooling to-5-30 ℃ for recrystallization; the recrystallization temperature may be-2 deg.C, 5 deg.C, 8 deg.C, 10 deg.C, 12 deg.C, 15 deg.C, 18 deg.C, 20 deg.C, 22 deg.C, 25 deg.C, 28 deg.C, etc.
In the invention, after the nitration reaction is finished, after post-treatment separation, washing and drying, the purity of the obtained nitration product can reach more than 95%, and the yield can reach more than 90%; after post-treatment and recrystallization, the purity of the obtained recrystallized product can reach more than 98 percent, the yield can reach more than 95 percent, and the total yield of the two-step reaction can reach more than 85 percent. Therefore, the method of the invention not only has simple steps, but also can improve the purity and yield of the product.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
350g of glacial acetic acid and 30g of 4,4 '-diaminodiphenyl ether are added into a 500mL four-neck flask, the temperature is increased to 110 ℃ for reaction for 7 hours, and an acylation product of the 4, 4' -diacetoxydianiline is obtained, the medium-controlled purity is 98.81%, and the yield of the step is 98%. The temperature is reduced to 20 ℃ so as to carry out nitration reaction.
In the system, 25g of concentrated nitric acid with the mass fraction of 98% is dripped, after the dripping is finished, the temperature is kept for 1.5 hours at 20 ℃, the temperature is slowly increased to 60 ℃, the temperature is kept for 7 hours, the purity of the sample is controlled to be 93.46%, after the reaction is finished, the temperature is reduced to about 20 ℃, and the nitration product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether is obtained by suction filtration, washing and drying, wherein the purity of the finished product is 95.41%, and the yield of the step is 91.4%.
60g of the nitrated product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether and 360g of Dimethylformamide (DMF) are added into a 500mL flask, the temperature is raised to 100 ℃, after all the nitrated product is dissolved, the temperature is slowly lowered to about 20 ℃, and the mixture is filtered, washed and dried to obtain a recrystallized product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether with the purity of 98.57 percent and the yield of the step is 96.93 percent.
Example 2:
350g of glacial acetic acid and 30g of 4,4 '-diaminodiphenyl ether are added into a 500mL four-neck flask, the temperature is raised to 60 ℃, 10g of acetic anhydride is added dropwise, the temperature is raised to 110 ℃ after the addition is finished, the reaction is carried out for 4 hours, the acylation product 4, 4' -diacetoxydiphenyl ether is obtained, the medium-controlled purity is 98.17%, and the yield of the step is 98%. The temperature is reduced to 20 ℃ so as to carry out nitration reaction.
In the system, 25g of concentrated nitric acid with the mass fraction of 98% is dripped, after the dripping is finished, the temperature is kept for 1.5 hours at 20 ℃, the temperature is slowly increased to 60 ℃, the temperature is kept for 8 hours, the purity of the sample is controlled to be 91.26%, and the nitration product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether is obtained by suction filtration, washing and drying, wherein the purity of the finished product is 95.34%, and the yield of the step is 91.4%.
60g of the nitrated product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether and 360g of Dimethylformamide (DMF) are added into a 500mL flask, the temperature is raised to 100 ℃, after all the nitrated product is dissolved, the temperature is slowly lowered to about 20 ℃, and the mixture is filtered, washed and dried to obtain a recrystallized product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether with the purity of 98.43 percent and the yield of 96.39 percent.
Example 3
350g of glacial acetic acid and 30g of 4,4 '-diaminodiphenyl ether are added into a 500mL four-neck flask, the temperature is increased to 110 ℃ for reaction for 7 hours, and the acylation product 4, 4' -diacetoxydianiline is obtained, the medium-controlled purity is 98.61%, and the yield of the step is 98%. The temperature is reduced to 20 ℃ so as to carry out nitration reaction.
In the system, 28.35g of concentrated nitric acid with the mass fraction of 98% is dripped, after the dripping is finished, the temperature is kept for 1.5 hours at 20 ℃, the temperature is slowly increased to 60 ℃, the temperature is kept for 7 hours, the sampling central control purity is 93.46%, after the reaction is finished, the temperature is reduced to about 20 ℃, and the nitration product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether is obtained by suction filtration, washing and drying, wherein the finished product purity is 96.11%, and the yield of the step is 91.6%.
60g of the nitrated product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether and 360g of Dimethylformamide (DMF) are added into a 500mL flask, the temperature is raised to 100 ℃, after all the nitrated product is dissolved, the temperature is slowly lowered to about 20 ℃, and the mixture is filtered, washed and dried to obtain a recrystallized product 3,3 '-dinitro-4, 4' -diacetyl amino diphenyl ether with the purity of 99.01 percent and the yield of 96.81 percent.
Comparative example 1
Adding 350g of glacial acetic acid and 30g of 4, 4' -diaminodiphenyl ether into a 500mL flask, uniformly stirring at 40 ℃, then raising the temperature to 60 ℃, adding 40g of acetic anhydride, controlling the temperature to be not higher than 75 ℃, after finishing dripping, raising the temperature to 100 ℃, reacting for 4 hours, sampling, after the reaction is finished, cooling, and separating out pink solid.
The pink solid is post-treated, filtered, washed and dried to obtain a pink powdery solid with the purity of 99.84 percent and the yield of 50.7 percent.
Adding 400g of glacial acetic acid and 40g of pink powdery solid 4, 4' -diacetyl amino diphenyl ether into a 500mL flask, keeping the temperature in a reaction bottle at a low temperature (ice bath), starting stirring, dropwise adding 44.0g of 60% concentrated nitric acid, keeping the temperature at 20 ℃ for 1.5 hours after the dropwise adding is finished, slowly raising the temperature to 60 ℃, keeping the temperature for 7 hours, controlling the purity of 93.16% in sampling, after the reaction is finished, performing suction filtration, washing and drying to obtain 48.2g of solid, wherein the purity is 96.23%, and the yield is 91.4%. Recrystallizing with DMF, washing with water, and oven drying to obtain final product with purity of 98.12% and yield of 96.48%.
Wherein, DMF mother liquor can be used indiscriminately, the mother liquor is filtered out each time and is washed by water after being stored, and the loss amount is complemented when the next batch is used indiscriminately by calculation. In comparative example 1, a large amount of the acylate was dissolved in acetic acid, and the loss was too large.
Comparative example 2
Adding 350g of glacial acetic acid and 30g of 4, 4' -diaminodiphenyl ether into a 500mL flask, uniformly stirring at 40 ℃, then raising the temperature to 60 ℃, adding 40g of acetic anhydride, controlling the temperature to be not higher than 75 ℃, after the dropwise addition is finished, raising the temperature to 100 ℃, reacting for 4 hours, sampling, adding 150g of water after the end point, cooling to room temperature, carrying out suction filtration, washing and drying to obtain pink powdery solid with the purity of 99.78% and the yield of 97.82%.
Adding 400g of glacial acetic acid and 40g of pink powdery solid 4, 4' -diacetyl amino diphenyl ether into a 500mL flask, keeping the temperature in a reaction bottle at a low temperature (ice bath), starting stirring, dropwise adding 44.0g of 60% concentrated nitric acid, keeping the temperature at 20 ℃ for 1.5 hours after the dropwise adding is finished, slowly raising the temperature to 60 ℃, keeping the temperature for 7 hours, controlling the purity of a sample to be 93.48%, after the reaction is finished, performing suction filtration, washing and drying to obtain 48.3g of solid with the purity of 96.36% and the yield of 91.6%. Recrystallizing with DMF, washing with water, and oven drying to obtain final product with purity of 98.78% and yield of 97.22%.
Wherein, DMF mother liquor can be used indiscriminately, the mother liquor is filtered out each time and is washed by water after being stored, and the loss amount is complemented when the next batch is used indiscriminately by calculation. In the acylation product post-treatment of the comparative example 2, although water is added to reduce the loss of the acylation product in acetic acid, the loss of acetic acid is increased, and the waste acid treatment pressure at the later stage is increased.
Comparative example 3
Adding 350g of glacial acetic acid and 30g of 4, 4' -diaminodiphenyl ether into a 500mL flask, uniformly stirring at 40 ℃, then raising the temperature to 60 ℃, adding 40g of acetic anhydride, controlling the temperature to be not higher than 75 ℃, after finishing dripping, raising the temperature to 100 ℃, reacting for 4 hours, sampling, cooling after reaction, and separating out pink solid.
And cooling the reacted materials to about 20 ℃, and performing suction filtration to obtain mother liquor and pink solid. Mother liquor is indiscriminately used, namely the mother liquor is used as a reaction solvent for the next batch of reaction, and glacial acetic acid is used for supplementing enough; the pink solid is washed by a proper amount of water and dried to obtain a pink powdery solid with the purity of 99.51 percent and the yield of 98.12 percent.
Adding 400g of glacial acetic acid and 40g of pink powdery solid 4, 4' -diacetyl amino diphenyl ether into a 500mL flask, keeping the temperature in a reaction bottle at a low temperature (ice bath), starting stirring, dropwise adding 44.0g of 60% concentrated nitric acid, keeping the temperature at 20 ℃ for 1.5 hours after the dropwise adding is finished, slowly raising the temperature to 60 ℃, keeping the temperature for 7 hours, controlling the purity of 93.92% in sampling, after the reaction is finished, performing suction filtration, washing and drying to obtain 48.5g of solid, wherein the purity is 95.93%, and the yield is 92.1%. Recrystallizing with DMF, washing with water, and oven drying to obtain final product with purity of 98.57% and yield of 96.37%.
Note: the DMF mother liquor can be used indiscriminately, the mother liquor is filtered out each time and is washed by water after being stored additionally, and the loss is complemented when the next batch is used indiscriminately by calculation. In comparative example 3, although the product dissolved in acetic acid was reduced and the loss of the acetic acid solvent was reduced as compared with comparative example 1 and comparative example 2, the loss was still excessive as compared with examples 1 to 3 of the present application.
Comparison of Performance test results
The data of the above examples are compared, and are shown in the following table 1:
TABLE 1
As can be seen from Table 1, in examples 1-3 of the present invention, the amounts of acetic acid, acetic anhydride and nitric acid used are relatively low, and after the nitration reaction is completed, the purity of the obtained nitrated product can reach more than 95% and the yield can reach more than 90% after post-treatment separation, washing and drying; after post-treatment and recrystallization, the purity of the obtained recrystallized product can reach more than 98 percent, the yield can reach more than 95 percent, and the total yield of the two-step reaction can reach more than 85 percent. Therefore, the method of the invention not only has simple steps and saves raw materials, but also can improve the purity and yield of the product.
In comparative examples 1 to 3, a large amount of acetic acid, acetic anhydride and nitric acid was used, and the raw material consumption was too high and the loss was too large.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A preparation method of 3,3 '-dinitro-4, 4' -diacetoxyl diphenyl ether is characterized by comprising the following steps:
acylation: adding an acylating agent into 4, 4' -diaminodiphenyl ether for acylation reaction to obtain an acylated product;
a nitration step: and cooling the acylation product, and adding nitric acid to carry out nitration reaction to obtain a nitration product.
2. The method according to claim 1, wherein in the acylating step, the acylating agent comprises acetic acid, acetic anhydride, or a mixture of acetic acid and acetic anhydride, preferably acetic acid.
3. The production method according to claim 2, wherein in the acylating step, the acetic acid is glacial acetic acid; and/or the presence of a gas in the gas,
in the mixed solution of acetic acid and acetic anhydride, the mass ratio of acetic anhydride to acetic acid is 1: 5-35, preferably 1: 10-20.
4. The production method according to any one of claims 1 to 3, wherein in the acylating step, the mass ratio of 4, 4' -diaminodiphenyl ether to the acylating agent is 1:10 to 20, preferably 1:11 to 15.
5. The process according to any one of claims 1 to 4, wherein the acylation reaction temperature is 80 to 115 ℃, preferably 105 to 115 ℃; the acylation time is 2-10 hours, preferably 7-10 hours.
6. The production method according to any one of claims 1 to 5, wherein in the nitration step, the temperature after the temperature reduction is-5 to 30 ℃, preferably 10 to 30 ℃; and/or
The mass fraction of the nitric acid is 60-98%.
7. The method according to any one of claims 1 to 6, wherein the molar ratio of 4, 4' -diaminodiphenyl ether to nitric acid is 1:2.1 to 4, preferably 1:2.4 to 3.
8. The preparation method according to any one of claims 1 to 7, wherein in the nitration step, the temperature of adding nitric acid is-5 ℃ to 30 ℃, preferably 10 ℃ to 30 ℃, and the temperature is kept for 1 to 2 hours; then heating to 40-70 ℃, preferably 60-70 ℃, and then preserving heat for 4-10 hours, preferably 6-8 hours.
9. The process according to any one of claims 1 to 8, wherein the nitration step is followed by a post-treatment step, preferably the post-treatment comprises a recrystallization step.
10. The method according to claim 9, wherein the solvent used in the recrystallization process is ethanol and/or dimethylformamide.
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