CN114149335B - Synthesis method of 4,4' -diaminodiphenyl ether by taking parachloroaniline as starting material - Google Patents
Synthesis method of 4,4' -diaminodiphenyl ether by taking parachloroaniline as starting material Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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Abstract
The invention discloses a method for synthesizing 4,4' -diaminodiphenyl ether, which comprises the following steps: the method is characterized in that p-chloroaniline is used as a starting material, and 4,4' -diaminodiphenyl ether is synthesized through one-step reaction in the presence of water, alkali, a catalyst and a ligand. The bisoxamide ligand adopted by the invention has strong electricity supply and large steric hindrance, and is coordinated with copper salt, so that the catalytic effect is obviously improved; 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, the adopted hydroxide salt alkali plays an important role in the process of preparing the 4,4 '-diaminodiphenyl ether by taking the parachloroaniline as a starting material, and other types of alkali such as potassium carbonate are added in the reaction process, the reaction can not be carried out, and the technical problems that the reaction condition needs high temperature and high pressure, the selectivity is poor and the yield is low in the existing synthesis process of the 4,4' -diaminodiphenyl ether can be solved.
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 that a diaminodiphenyl ether mixture is synthesized by two steps of nitration and hydrogenation reaction by taking diphenyl ether as a raw material and perfluorinated sulfonic acid resin as a catalyst, and the yield is 78-88%.
Route two: patent CN112062683A reports that p-nitrochlorobenzene is used as a raw material, and a diaminodiphenyl ether mixture is synthesized by two steps of hydrolysis and hydrogenation reaction in the presence of inorganic base and a catalyst, and the yield is 96%.
The above synthetic route has certain disadvantages or drawbacks. Wherein, the liquid crystal display device comprises a liquid crystal display device,
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 difficulties are great, 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 a new synthesis method of 4,4' -diaminodiphenyl ether which is more economical, green, good in selectivity and high in yield.
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 steps of: synthesizing 4,4' -diaminodiphenyl ether by taking parachloroaniline as a starting raw material through one-step reaction in the presence of water, alkali, a catalyst and a ligand; the reaction formula is as follows:
in one embodiment of the present invention, the catalyst is a copper compound.
In one embodiment of the present invention, the copper-based compound is selected from any one or more of a copper-based compound, an inorganic copper salt, an organic copper salt, and the like.
In one embodiment of the present invention, the cuprous compound is selected from any one of cuprous iodide, cuprous chloride, cuprous bromide, and cuprous oxide.
In one embodiment of the present invention, the inorganic copper salt is selected from any one of copper sulfate and copper chloride.
In one embodiment of the present invention, the organic copper salt is selected from any one of copper acetate and copper trifluoroacetate.
In one embodiment of the invention, the ligand is a bisoxamide ligand.
The dithiooxamide ligand has strong electricity supply and large steric hindrance, and can obviously improve the catalytic effect in the synthesis reaction by coordinating with copper salt.
In one embodiment of the present invention, the above-mentioned bisoxamide ligand has the following structural formula:
in one embodiment of the present invention, the base is a hydroxide base.
In an embodiment of the present invention, the hydroxide base is selected from any one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and tetrabutylammonium hydroxide.
In one embodiment of the present invention, the molar ratio of the p-chloroaniline to the base, the catalyst, the ligand and the water is 1:1-3:0.01-0.1:0.01-0.1:5-10.
In one embodiment of the present invention, the molar ratio of the p-chloroaniline to the base, the catalyst, the ligand and water is 1:1-2:0.03-0.07:0.3-0.07:6-8.
In one embodiment of the present invention, the reaction temperature of the above-mentioned one-step reaction is 100 to 180 ℃.
In one embodiment of the present invention, the reaction temperature is 130 to 150 ℃.
In one embodiment of the present invention, the reaction pressure of the above-mentioned one-step reaction is 1.5MPa to 6MPa.
In one embodiment of the present invention, the reaction pressure is 2.0MPa to 4.5MPa.
In one embodiment of the invention, the reaction time is from 6 to 24 hours.
In one embodiment of the invention, the reaction time is 8 to 15 hours.
In one embodiment of the present invention, the above-mentioned one-step reaction is followed by a crystallization step to obtain high-purity 4,4' -diaminodiphenyl ether.
In one embodiment of the present invention, the crystals are alcohol crystals.
In one embodiment of the present invention, the alcohol crystal is a methanol crystal.
Compared with the prior art, the invention has the following beneficial effects:
(1) The dithiooxamide ligand is a specific type ligand specifically selected for a reaction system, has strong power supply and large steric hindrance, coordinates with copper salt, and remarkably improves the catalytic effect; if no ligand or a conventional ligand such as 1, 10-phenanthroline is added in the reaction process, the reaction can not be carried out basically.
(2) The hydroxide alkali adopted by the invention plays an important role in the process of preparing 4,4' -diaminodiphenyl ether by taking parachloroaniline as a starting material, and other types of alkali such as potassium carbonate are added in the reaction process, so that the reaction cannot be carried out.
(3) Compared with the prior art, the method has the advantages of short reaction steps, easily obtained raw materials, convenient operation, low production cost, environmental friendliness and the like, and is easy for large-scale industrial production.
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
The method comprises the following steps: into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 40.4g of sodium hydroxide (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol), 16.7g of bisoxamide ligand L1 (99%, 0.05 mol); after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 12 hours, and the pressure is 2.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 45.2g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8%, and the total molar yield is 90.2%.
Wherein, the structural formula of the bisoxamide ligand L1 is as follows:
example 2: synthesis method of 4,4' -diaminodiphenyl ether
Into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 84.8g of potassium hydroxide (99%, 1.5 mol), 2.5g of catalyst cuprous chloride (99%, 0.025 mol) and 8.0g of bisoxamide ligand L2 (99%, 0.025 mol); after the material is fed, the temperature is raised to 150 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 6 hours, and the pressure is 3.8MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 45.9g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8%, and the total molar yield is 91.6%.
Wherein, the structural formula of the bisoxamide ligand L2 is as follows:
example 3: synthesis method of 4,4' -diaminodiphenyl ether
Into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 262.1g of tetrabutylammonium hydroxide (99%, 1.0 mol), 8.1g of copper sulfate (99%, 0.05 mol), 16.7g of bisoxamide ligand L1 (99%, 0.05 mol); after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 24 hours, and the pressure is 2.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 41.4g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8%, and the total molar yield is 82.6%.
Wherein, the structural formula of the bisoxamide ligand L1 is as follows:
example 4: synthesis method of 4,4' -diaminodiphenyl ether
The method comprises the following steps: into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 40.4g of sodium hydroxide (99%, 1.0 mol), 7.2g of cuprous oxide (99%, 0.05 mol), 16.7g of bisoxamide ligand L1 (99%, 0.05 mol); after the material is fed, the temperature is raised to 110 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 20 hours, and the pressure is 1.6MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 30.5g of 4,4' -diaminodiphenyl ether, wherein the content is 99.2%, and the total molar yield is 60.5%.
Wherein, the structural formula of the bisoxamide ligand L1 is as follows:
example 5: synthesis method of 4,4' -diaminodiphenyl ether
The method comprises the following steps: into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 262.1g of tetrabutylammonium hydroxide (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol), 16.7g of bisoxamide ligand L1 (99%, 0.05 mol); after the material is fed, the temperature is raised to 160 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 10 hours, and the pressure is 4.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 45.7g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8 percent, and the total molar yield is 91.2 percent. Is the total molar yield
Wherein, the structural formula of the bisoxamide ligand L1 is as follows:
example 6: synthesis method of 4,4' -diaminodiphenyl ether
The method comprises the following steps: into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 24.2g of lithium hydroxide (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol), 16.0g of bisoxamide ligand L2 (99%, 0.05 mol); after the material is fed, the temperature is raised to 160 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 15 hours, and the pressure is 4.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 43.3g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8%, and the total molar yield is 86.3%. Is the total molar yield
Wherein, the structural formula of the bisoxamide ligand L2 is as follows:
example 7: synthesis method of 4,4' -diaminodiphenyl ether
The method comprises the following steps: into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 56.7g of potassium hydroxide (99%, 1.0 mol), 9.2g of copper acetate (99%, 0.05 mol), 16.0g of bisoxamide ligand L2 (99%, 0.05 mol); after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 10 hours, and the pressure is 2.3MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, recovering the solvent from the organic layer, and crystallizing by methanol to obtain 44.2g of 4,4' -diaminodiphenyl ether, wherein the content is 99.8%, and the total molar yield is 88.2%.
Wherein, the structural formula of the bisoxamide ligand L2 is as follows:
comparative example 1: synthesis method of 4,4' -diaminodiphenyl ether
This comparative example 1 is identical to example 1, except that the oxamide ligand L1 is not used.
Into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 40.4g of sodium hydroxide (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol); after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 12 hours, and the pressure is 2.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, sampling an organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
Comparative example 2: synthesis method of 4,4' -diaminodiphenyl ether
This comparative example 1 is the same as example 1, except that the ligand used is not L1 but 1, 10-phenanthroline.
322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 40.4g of sodium hydroxide (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol) and 10.0g of 1, 10-phenanthroline (99%, 0.05 mol) are added into a 1L autoclave; after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 12 hours, and the pressure is 2.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, sampling an organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
Comparative example 3: synthesis method of 4,4' -diaminodiphenyl ether
This comparative example 1 is identical to example 1, with the only difference that the alkali sodium hydroxide is used in place, but potassium carbonate is used.
Into a 1L autoclave were charged 322g of water, 64.4g of p-chloroaniline (99%, 0.5 mol), 139.4g of potassium carbonate (99%, 1.0 mol), 9.6g of cuprous iodide (99%, 0.05 mol), 16.7g of ligand L1 (99%, 0.05 mol); after the material is fed, the temperature is raised to 130 ℃, the stirring speed is 600rpm, the heat preservation reaction is carried out for 12 hours, and the pressure is 2.2MPa; after the reaction is finished, cooling, adding ethyl acetate into the kettle material for extraction, washing, sampling an organic layer for GC-MS analysis, and detecting no product 4,4' -diaminodiphenyl ether.
Thus, the hydroxide alkali plays an important role in the process of preparing 4,4' -diaminodiphenyl ether by taking parachloroaniline as a starting material, and other types of alkali such as potassium carbonate are added in the reaction process, so that the reaction cannot be carried out.
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 (10)
1. A method for synthesizing 4,4' -diaminodiphenyl ether, which is characterized by comprising the following steps: synthesizing 4,4' -diaminodiphenyl ether by taking parachloroaniline as a starting raw material through one-step reaction in the presence of water, alkali, a catalyst and a ligand; the reaction formula is as follows:
the catalyst is a copper compound, and the copper compound is selected from any one or more of cuprous compounds, inorganic copper salts and organic copper salts;
the alkali is hydroxide alkali;
the ligand is a bisoxamide ligand, and the structural formula of the bisoxamide ligand is as follows:
2. the synthesis method according to claim 1, wherein the cuprous compound is selected from any one of cuprous iodide, cuprous chloride, cuprous bromide and cuprous oxide, the inorganic copper salt is selected from any one of cupric sulfate and cupric chloride, and the organic copper salt is selected from any one of cupric acetate and cupric trifluoroacetate.
3. The method according to claim 1, wherein the hydroxide base is selected from any one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, tetrabutylammonium hydroxide.
4. The method of claim 1, wherein the molar ratio of p-chloroaniline to base, catalyst, ligand and water is 1:1-3:0.01-0.1:0.01-0.1:5-10.
5. The synthetic method of claim 1 wherein the one-step reaction is carried out at a reaction temperature of 100-180 ℃.
6. The synthetic method of claim 1 wherein the reaction temperature is 130-150 ℃.
7. The synthetic method according to claim 1, wherein the reaction pressure of the one-step reaction is 1.5MPa to 6MPa; the reaction time is 6-24h.
8. The synthetic method according to claim 1, wherein the reaction pressure is 2.0MPa to 4.5MPa; the reaction time is 8-15h.
9. The synthetic method according to claim 1, wherein the one-step reaction is followed by a crystallization step to obtain high purity 4,4' -diaminodiphenyl ether, the crystallization being alcohol crystallization.
10. The synthetic method of claim 9 wherein the alcohol crystals are methanol crystals.
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