CN114085158B - Synthesis method of 4,4' -diaminodiphenyl ether - Google Patents
Synthesis method of 4,4' -diaminodiphenyl ether Download PDFInfo
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Abstract
The invention discloses a synthetic method of 4,4' -diaminodiphenyl ether, which comprises the following steps: the 4,4' -diaminodiphenyl ether is synthesized by taking diphenyl ether, hydrogen peroxide, ammonia water and bromide as starting materials through one-step reaction in the presence of a solvent, a catalyst and a ligand. The invention solves the technical problems of high temperature and high pressure, poor selectivity and low yield of the reaction condition in the existing synthesis process of 4,4' -diaminodiphenyl ether; the Mannich alkali ligand has strong electricity supply and large steric hindrance, and can coordinate with copper salt to obviously improve the catalysis effect of copper salt; the adopted bromide salt can lead the diphenyl ether to carry out oxidation bromination reaction to generate a 4,4' -dibromodiphenyl ether intermediate; the synthesis process can be completed at room temperature, and has the advantages of mild reaction conditions, good selectivity, simple post-treatment and purification, high yield and good product quality.
Description
Technical Field
The invention belongs to the technical field of fine chemical organic materials, and particularly relates to a synthetic method of 4,4' -diaminodiphenyl ether.
Background
The 4,4' -diaminodiphenyl ether is an important fine chemical intermediate, can be industrially used for synthesizing engineering plastics polyimide, polyetherimide, polyester imide and other high-temperature resistant polymeric materials, and can also be used as raw materials and cross-linking agents for synthesizing high-performance heat-resistant epoxy resin polyurethane and other synthetic polymers; and can be used for replacing benzidine with cancerogenic function to produce azo dye, reactive dye and perfume. Therefore, the research on the synthesis of 4,4' -diaminodiphenyl ether has important significance. Industrially, the synthesis of 4,4' -diaminodiphenyl ether mainly has the following two routes.
Route one: patent CN112876367a reports a synthesis method of 4,4' -diaminodiphenyl ether, which uses diphenyl ether as raw material, mixes aromatic ether with nitric acid to make nitration reaction under the catalysis of solid acid, then makes hydrogenation reduction reaction, synthesizes diaminodiphenyl ether mixture in two steps, and has yield of 78-88%, and the specific process route is as follows:
route two: patent CN112062683 reports a method for synthesizing 4,4 '-diaminodiphenyl ether, which takes paranitrochlorobenzene as a raw material, inorganic base and catalyst exist for hydrolysis reaction, then the obtained 4,4' -nitrodiphenyl ether is added into water, acid is added, 10% palladium carbon is added, hydrogen is replaced, then the temperature is raised to 140-170 ℃ and the pressure is maintained for 0.2MPa for hydrogenation reaction for 4 hours, a diaminodiphenyl ether mixture is synthesized in two steps, the yield is 96%, and the specific process route is as follows:
the above synthetic route has certain disadvantages or drawbacks. Wherein, route one: in the reaction process, a large amount of 2,2' -dinitrodiphenyl ether is generated due to the electronic effect of the nitration reaction, so that the reaction selectivity is poor, a diaminodiphenyl ether mixture is obtained, the separation and purification difficulty is high, a large amount of nitric acid is used in the reaction process, and the pollution is serious; route two: although the reaction yield is high and the selectivity is good, the conditions of high temperature and high pressure are needed in the reaction process, the equipment investment is large, the safety risk is high, and the high temperature and high pressure are needed in the hydrogenation reaction in the reaction process, so that the hydrogenation catalyst is limited to be applied to the industrial large scale.
In the past, technicians have continuously studied the synthesis method of 4,4 '-diaminodiphenyl ether in order to obtain new, more economical, green and efficient synthesis method of 4,4' -diaminodiphenyl ether.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a method for synthesizing 4,4 '-diaminodiphenyl ether, which can solve the technical problems of high temperature and high pressure, poor selectivity and low yield of reaction conditions in the existing synthesis process of 4,4' -diaminodiphenyl ether.
In order to achieve the above object, the present invention provides a method for synthesizing 4,4' -diaminodiphenyl ether, comprising: the method is characterized in that diphenyl ether, hydrogen peroxide, ammonia water and bromide are used as starting materials, and 4,4' -diaminodiphenyl ether is synthesized through one-step reaction in the presence of a catalyst and a ligand, wherein the reaction formula is as follows:
in one embodiment of the present invention, the catalyst is a copper salt.
The copper salt is used as a catalyst in the reaction process, and the intermediate 4,4 '-dibromodiphenyl ether generated in the catalytic reaction process and ammonia water undergo a C-N coupling reaction to generate 4,4' -diaminodiphenyl ether.
In one embodiment of the present invention, the copper salt is selected from any one of copper iodide, copper chloride, copper bromide, copper oxide, copper sulfate, copper chloride, copper acetate, and copper trifluoroacetate.
In one embodiment of the invention, the ligand is a Mannich base ligand.
The Mannich alkali ligand has strong electricity supply and large steric hindrance, and can obviously improve the catalytic activity and the reaction conversion rate by coordinating with copper salt.
In one embodiment of the present invention, the Mannich base ligand is a Mannich base ligand having the following structural formula:
in one embodiment of the present invention, the bromide salt is sodium bromide or potassium bromide.
The bromide salt has synergistic effect with oxidant in the reaction process and has oxidizing bromination reaction with diphenyl ether to produce 4,4 '-dibromodiphenyl ether, and the intermediate is key to preparing 4,4' -diamino diphenyl ether.
In one embodiment of the present invention, the solvent is selected from any one or more of halogenated hydrocarbons, halogenated aromatic hydrocarbons, and cyclic ethers.
In an embodiment of the present invention, the halogenated alkane is dichloromethane and/or dichloroethane.
In one embodiment of the present invention, the halogenated aromatic hydrocarbon is o-dichlorobenzene and/or chlorobenzene.
In one embodiment of the present invention, the cyclic ether is tetrahydrofuran and/or dioxane.
In one embodiment of the present invention, the molar ratio of the ammonia water to the diphenyl ether is 1:1 to 10:1.
In one embodiment of the present invention, the molar ratio of the bromide salt to the diphenyl ether is 0.05:1 to 0.2:1.
In an embodiment of the present invention, a molar ratio of the hydrogen peroxide to the diphenyl ether is 1:1-3:1.
In one embodiment of the present invention, the mass ratio of the solvent to the diphenyl ether is 5:1 to 10:1.
In one embodiment of the present invention, the molar ratio of the catalyst to the diphenyl ether is 0.05:1 to 0.2:1.
In one embodiment of the present invention, the molar ratio of the Mannich base ligand to the diphenyl ether is 0.05:1 to 0.2:1.
In one embodiment of the present invention, the above-mentioned one-step reaction is followed by a crystallization step to obtain 4,4' -diaminodiphenyl ether.
Compared with the prior art, the invention has the following advantages:
(1) The Mannich alkali ligand adopted by the invention is a specific ligand specifically selected for a reaction system, has strong power supply and large steric hindrance, coordinates with copper salt, and can obviously improve the catalysis effect of the copper salt; if no ligand or a conventional ligand such as 1, 10-phenanthroline is added in the reaction process, the reaction can not be basically carried out.
(2) The bromide salt adopted by the invention can lead the diphenyl ether to carry out oxidation bromination reaction to generate 4,4 '-dibromodiphenyl ether intermediate, and then carry out C-N coupling reaction with ammonia water to generate 4,4' -diaminodiphenyl ether under the action of copper and ligand.
(3) The raw materials of diphenyl ether, ammonia water and hydrogen peroxide adopted by the invention are cheap and easy to obtain, and the 4,4' -diaminodiphenyl ether with high purity is synthesized by adopting a one-step method in the presence of the catalyst and the ligand, so that the method has the advantages of short reaction step, convenient operation, easily obtained raw materials, low production cost and environmental friendliness, and is easy for large-scale industrial production.
(4) The synthesis process can be completed at room temperature, and has the advantages of mild reaction conditions, good selectivity, simple post-treatment and purification, high yield and good product quality.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1: synthesis method of 4,4' -diaminodiphenyl ether
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.8g of cuprous iodide (99%, 0.03 mol), 12.1g of ligand L2 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring at room temperature for reaction, stirring at 600rpm, and keeping the temperature for reaction for 6hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 57.3g of 4,4 '-diaminodiphenyl ether, wherein the content of the 4,4' -diaminodiphenyl ether is 99.8 percent, and the yield is 95.2 percent;
wherein, the structural formula of the ligand L2 is as follows:
example 2: synthesis method of 4,4' -diaminodiphenyl ether
A2000 mL reaction flask was charged with 516g of methylene chloride (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 204.0g of aqueous ammonia (25%, 3 mol), 3.1g of sodium bromide (99%, 0.03 mol), 4.1g of copper chloride (99%, 0.03 mol), 12.1g of ligand L2 (99%, 0.03 mol), and 51.0g of hydrogen peroxide (30%, 0.45 mol); stirring at room temperature for reaction at 600rpm after feeding, and keeping the temperature for reaction for 12hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 58.1g of 4,4 '-diaminodiphenyl ether, wherein the content of the 4,4' -diaminodiphenyl ether is 99.8 percent, and the yield is 96.5 percent;
wherein, the structural formula of the ligand L2 is as follows:
example 3: synthesis method of 4,4' -diaminodiphenyl ether
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.8g of cuprous iodide (99%, 0.03 mol), 8.0g of ligand L1 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 24hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 35.5g of 4,4 '-diaminodiphenyl ether, wherein the content of the 4,4' -diaminodiphenyl ether is 99.2 percent, and the yield is 58.6 percent;
wherein, the structural formula of the ligand L1 is as follows:
example 4: synthesis method of 4,4' -diaminodiphenyl ether
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 4.3g of cuprous oxide (99%, 0.03 mol), 8.0g of ligand L1 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 12hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 32.1g of 4,4 '-diaminodiphenyl ether, wherein the content of the 4,4' -diaminodiphenyl ether is 99.1 percent, and the yield is 52.9 percent;
wherein, the structural formula of the ligand L1 is as follows:
example 5: synthesis method of 4,4' -diaminodiphenyl ether
258g of o-dichlorobenzene (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of ammonia water (25%, 1.5 mol), 3.1g of sodium bromide (99%, 0.03 mol), 4.8g of copper sulfate (99%, 0.03 mol), 8.0g of ligand L1 (99%, 0.03 mol) and 68.0g of hydrogen peroxide (30%, 0.6 mol) are added into a 1000mL reaction flask; after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 18hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 34.3g of 4,4' -diaminodiphenyl ether, wherein the content is 99.2 percent, and the yield is 56.7 percent;
wherein, the structural formula of the ligand L1 is as follows:
example 6: synthesis method of 4,4' -diaminodiphenyl ether
A1000 mL reaction flask was charged with 258g of chlorobenzene (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.5g of copper acetate (99%, 0.03 mol), 12.1g of ligand L2 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 12hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 56.3g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8 percent, and the yield is 93.6 percent;
wherein, the structural formula of the ligand L2 is as follows:
example 7: synthesis method of 4,4' -diaminodiphenyl ether
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.4g of copper trifluoroacetate (99%, 0.03 mol), 12.1g of ligand L2 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and preserving heat and reacting for 8hr; after the reaction is finished, separating liquid, washing with water, recovering solvent from an organic layer, and crystallizing by methanol to obtain 58.3g of 4,4 '-diaminodiphenyl ether, wherein the content of the 4,4' -diaminodiphenyl ether is 99.8 percent, and the yield is 96.8 percent;
wherein, the structural formula of the ligand L2 is as follows:
comparative example 1
The only difference between this comparative example and the reaction conditions and parameters of example 1 is that comparative example 1 did not incorporate ligand L2.
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.8g of cuprous iodide (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 6hr; after the reaction, separating liquid, washing the organic layer, sampling the organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
Comparative example 2
The only difference between this comparative example and the reaction conditions and parameters of example 1 is that the ligand added in comparative example 2 is 1, 10-phenanthroline instead of ligand L2.
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of ammonia water (25%, 1.5 mol), 3.6g of potassium bromide (99%, 0.03 mol), 5.8g of cuprous iodide (99%, 0.03 mol), 6.0g of 1, 10-phenanthroline (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol) are added into a 1000mL reaction flask; after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 6hr; after the reaction, separating liquid, washing the organic layer, sampling the organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
As is clear from comparative examples 1 and 2, the ligand in the invention is critical to the reaction, the ligand adopted is a specific type of ligand specifically selected for the reaction system, and the Mannich alkali ligand has strong electricity supply and large steric hindrance, coordinates with copper salt, and has obviously improved catalytic effect. The reaction can not be carried out basically without adding ligand or adding conventional ligand (such as 1, 10-phenanthroline in comparative example 2).
Comparative example 3
The only difference between this comparative example and the reaction conditions and parameters of example 1 is that comparative example 3 does not add sodium bromide.
A1000 mL reaction flask was charged with 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3 mol), 102.0g of aqueous ammonia (25%, 1.5 mol), 5.8g of cuprous iodide (99%, 0.03 mol), 12.1g of ligand L2 (99%, 0.03 mol), 68.0g of hydrogen peroxide (30%, 0.6 mol); after the material is fed, stirring and reacting at room temperature, stirring at 600rpm, and keeping the temperature and reacting for 6hr; after the reaction, separating liquid, washing the organic layer, sampling the organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
As can be seen from comparative example 3, the bromide salt is also critical to the reaction, and the addition of the bromide salt can lead the diphenyl ether to undergo oxidation bromination reaction to generate 4,4 '-dibromodiphenyl ether intermediate, and then undergo C-N coupling reaction with ammonia water under the action of copper and ligand to generate 4,4' -diaminodiphenyl ether, and the reaction cannot be carried out without adding the bromide salt in the reaction process (comparative example 3).
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A method for synthesizing 4,4' -diaminodiphenyl ether, the method comprising: the method is characterized in that diphenyl ether, hydrogen peroxide, ammonia water and bromide are used as starting materials, and 4,4' -diaminodiphenyl ether is synthesized through one-step reaction in the presence of a solvent, a catalyst and a ligand, wherein the reaction formula is as follows:
the catalyst is copper salt;
the ligand is Mannich alkali ligand;
the Mannich base ligand is of the following structural formula:
the bromide salt is sodium bromide or potassium bromide;
the copper salt is selected from any one of cuprous iodide, cuprous chloride, cuprous bromide, cuprous oxide, cupric sulfate, cupric chloride, cupric acetate and cupric trifluoroacetate;
the solvent is selected from any one or more of halogenated alkane, halogenated aromatic hydrocarbon and cyclic ether;
the halogenated alkane is dichloromethane and/or dichloroethane; the halogenated aromatic hydrocarbon is o-dichlorobenzene and/or chlorobenzene; the cyclic ether is tetrahydrofuran and/or dioxane.
2. The method of claim 1, wherein the molar ratio of ammonia to diphenyl ether is 1:1 to 10:1.
3. The synthetic method of claim 1 wherein the molar ratio of bromide salt to diphenyl ether is from 0.05:1 to 0.2:1.
4. The method according to claim 1, wherein the molar ratio of hydrogen peroxide to diphenyl ether is 1:1-3:1.
5. The synthetic method of claim 1 wherein the mass ratio of solvent to diphenyl ether is from 5:1 to 10:1.
6. The synthetic method of claim 1 wherein the molar ratio of catalyst to diphenyl ether is from 0.05:1 to 0.2:1.
7. The synthetic method of claim 1 wherein the molar ratio of Mannich base ligand to diphenyl ether is from 0.05:1 to 0.2:1.
8. The synthesis method according to claim 1, wherein the 4,4' -diaminodiphenyl ether is obtained by a crystallization step after the one-step reaction.
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