CN114085158A - Synthetic method of 4, 4' -diaminodiphenyl ether - Google Patents
Synthetic method of 4, 4' -diaminodiphenyl ether Download PDFInfo
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- CN114085158A CN114085158A CN202111422455.9A CN202111422455A CN114085158A CN 114085158 A CN114085158 A CN 114085158A CN 202111422455 A CN202111422455 A CN 202111422455A CN 114085158 A CN114085158 A CN 114085158A
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- diphenyl ether
- diaminodiphenyl ether
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003446 ligand Substances 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 3
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005893 bromination reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 2, 2' -dinitrodiphenyl ether Chemical compound 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C213/02—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthesis method of 4, 4' -diaminodiphenyl ether, which comprises the following steps: diphenyl ether, hydrogen peroxide, ammonia water and bromide salt are used as initial raw materials, and the 4, 4' -diaminodiphenyl ether is synthesized 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 reaction conditions in the existing synthesis process of 4, 4' -diaminodiphenyl ether; the Mannich alkali ligand has strong power supply and large steric hindrance, and can be coordinated with copper salt to remarkably improve the catalytic effect of the copper salt; the adopted bromide salt can lead diphenyl ether to carry out oxidation bromination reaction to generate a 4, 4' -dibromo diphenyl 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 synthesis method of 4, 4' -diaminodiphenyl ether.
Background
4, 4' -diaminodiphenyl ether is an important fine chemical intermediate, can be industrially used for synthesizing high-temperature resistant polymer materials such as engineering plastics polyimide, polyetherimide, polyesterimide and the like, and can also be used as a raw material and a cross-linking agent for synthesizing high polymers such as high-performance heat-resistant epoxy resin polyurethane and the like; meanwhile, the method can also be used for replacing benzidine with carcinogenic effect to produce azo dyes, reactive dyes, perfumes and other fields. Therefore, the research on the synthesis of the 4, 4' -diaminodiphenyl ether is of great significance. Industrially, the synthesis of 4, 4' -diaminodiphenyl ether has the following two main routes.
Route one: patent CN112876367A reports a method for synthesizing 4, 4' -diaminodiphenyl ether, which takes diphenyl ether as raw material, under the catalysis of solid acid, aromatic ether and nitric acid are mixed for nitration reaction, then hydrogenation reduction reaction is carried out, diaminodiphenyl ether mixture is synthesized in two steps, yield is 78-88%, and the specific process route is as follows:
and a second route: patent CN112062683 reports a synthesis method of 4,4 '-diaminodiphenyl ether, which takes p-nitrochlorobenzene as a raw material, and inorganic base and catalyst exist for hydrolysis reaction, then adds the obtained 4, 4' -nitrodiphenyl ether into water, adds acid and 10% palladium carbon, replaces hydrogen, then heats up to 140-:
the above synthetic routes have certain disadvantages or drawbacks. Wherein, route one: in the reaction process, a large amount of 2, 2' -dinitrodiphenyl ether can be generated due to the electronic effect of nitration reaction, so that the reaction selectivity is poor, a diaminodiphenyl ether mixture is obtained, the separation and purification difficulty is high, and a large amount of nitric acid is used in the reaction process, so that the pollution is serious; and a second route: although the reaction yield is high and the selectivity is good, the reaction process needs high temperature and high pressure, the equipment investment is large, the safety risk is high, and the condition that the hydrogenation reaction needs high temperature and high pressure in the reaction process limits the large-scale application of the hydrogenation reaction in industry.
Technical personnel continuously research the synthesis method of 4,4 '-diaminodiphenyl ether so as to obtain a new economic, 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 skilled 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: diphenyl ether, hydrogen peroxide, ammonia water and bromide are used as initial raw 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 an intermediate 4,4 '-dibromodiphenyl ether generated in the catalytic reaction process and ammonia water generate C-N coupling reaction to generate 4, 4' -diaminodiphenyl ether.
In one embodiment of the present invention, the copper salt is any one selected from cuprous iodide, cuprous chloride, cuprous bromide, cuprous oxide, cupric sulfate, cupric chloride, cupric acetate, and cupric trifluoroacetate.
In an embodiment of the present invention, the ligand is a Mannich base ligand.
The Mannich base ligand has strong power supply and large steric hindrance, and can obviously improve catalytic activity and reaction conversion rate by being coordinated with copper salt.
In one embodiment of the present invention, the Mannich base ligand is a Mannich base ligand having a structural formula as follows:
in an embodiment of the present invention, the bromide salt is sodium bromide or potassium bromide.
The bromide salt and oxidant produce synergistic reaction in the reaction process, and produce oxidation bromination reaction with diphenyl ether to produce 4,4 '-dibromo diphenyl ether, and the intermediate is key for preparing 4, 4' -diamino diphenyl ether.
In an embodiment of the present invention, the solvent is selected from one or more of halogenated alkanes, halogenated aromatic hydrocarbons, and cyclic ethers.
In one 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 an 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, the molar ratio of the hydrogen peroxide to the diphenyl ether is 1:1 to 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 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 beneficial effects:
(1) the Mannich base ligand adopted by the invention is a specific type of ligand specially selected for a reaction system, has strong power supply and large steric hindrance, is coordinated with copper salt, and can obviously improve the catalytic 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 carried out basically.
(2) The bromide salt adopted by the invention can lead diphenyl ether to carry out oxidation bromination reaction to generate 4,4 '-dibromo diphenyl ether intermediate, and further generate C-N coupling reaction with ammonia water under the action of copper and ligand to generate 4, 4' -diaminodiphenyl ether.
(3) The raw materials of diphenyl ether, ammonia water and hydrogen peroxide adopted by the invention are cheap and easy to obtain, and the high-purity 4, 4' -diaminodiphenyl ether is synthesized by adopting a one-step method under the condition of existence of a catalyst and a ligand, so that the method has the advantages of short reaction step, convenience in operation, easy obtainment of 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 provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1: synthesis method of 4, 4' -diaminodiphenyl ether
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.8g of cuprous iodide (99%, 0.03mol), 12.1g of ligand L2 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring at room temperature for reaction, stirring at the rotating speed of 600rpm, and keeping the temperature for reaction for 6 hours; after the reaction is finished, liquid separation and water washing are carried out, the organic layer is crystallized by methanol after the solvent is recovered, and 57.3g of 4, 4' -diaminodiphenyl ether with the content of 99.8 percent and the yield of 95.2 percent is obtained;
wherein the structural formula of the ligand L2 is as follows:
example 2: synthesis method of 4, 4' -diaminodiphenyl ether
516g of dichloromethane (99%), 51.6g of diphenyl ether (99%, 0.3mol), 204.0g of ammonia water (25%, 3mol), 3.1g of sodium bromide (99%, 0.03mol), 4.1g of copper chloride (99%, 0.03mol), 12.1g of ligand L2 (99%, 0.03mol) and 51.0g of hydrogen peroxide (30%, 0.45mol) are added into a 2000mL reaction bottle; after the feeding is finished, stirring at room temperature for reaction, stirring at the rotating speed of 600rpm, and keeping the temperature for reaction for 12 hours; after the reaction is finished, liquid separation and water washing are carried out, the organic layer is crystallized by methanol after the solvent is recovered, and 58.1g of 4, 4' -diaminodiphenyl ether with the content of 99.8 percent and the yield of 96.5 percent is obtained;
wherein the structural formula of the ligand L2 is as follows:
example 3: synthesis method of 4, 4' -diaminodiphenyl ether
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.8g of cuprous iodide (99%, 0.03mol), 8.0g of ligand L1 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 24 hours; after the reaction is finished, liquid separation and water washing are carried out, the organic layer is crystallized by methanol after the solvent is recovered, and 35.5g of 4, 4' -diaminodiphenyl ether with the content of 99.2 percent and the yield of 58.6 percent is obtained;
wherein the structural formula of the ligand L1 is as follows:
example 4: synthesis method of 4, 4' -diaminodiphenyl ether
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 4.3g of cuprous oxide (99%, 0.03mol), 8.0g of ligand L1 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 12 hours; after the reaction is finished, liquid separation and water washing are carried out, the solvent is recovered from the organic layer, and 32.1g of 4, 4' -diaminodiphenyl ether with the content of 99.1 percent and the yield of 52.9 percent is obtained by methanol crystallization;
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%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.1g of sodium bromide (99%, 0.03mol), 4.8g of copper sulfate (99%, 0.03mol), 8.0g of ligand L1 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 18 hours; after the reaction is finished, liquid separation and water washing are carried out, the organic layer is crystallized by methanol after the solvent is recovered to obtain 34.3g of 4, 4' -diaminodiphenyl ether with the content of 99.2 percent and the yield of 56.7 percent;
wherein, the junction of ligand L1The structure formula is as follows:
example 6: synthesis method of 4, 4' -diaminodiphenyl ether
258g of chlorobenzene (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.5g of copper acetate (99%, 0.03mol), 12.1g of ligand L2 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 12 hours; after the reaction is finished, liquid separation and water washing are carried out, the organic layer is crystallized by methanol after the solvent is recovered, and 56.3g of 4, 4' -diaminodiphenyl ether is obtained, the content of which 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
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.4g of copper trifluoroacetate (99%, 0.03mol), 12.1g of ligand L2 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 8 hours; after the reaction is finished, liquid separation and water washing are carried out, the solvent is recovered from the organic layer, and then methanol is used for crystallization to obtain 58.3g of 4, 4' -diaminodiphenyl ether with the content of 99.8 percent and the yield of 96.8 percent;
wherein the structural formula of the ligand L2 is as follows:
comparative example 1
This comparative example compares the reaction conditions and parameters of example 1 with the only difference that comparative example 1 did not incorporate ligand L2.
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.8g of cuprous iodide (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 6 hours; after the reaction is finished, liquid separation and water washing are carried out, an organic layer is sampled and subjected to GC-MS analysis, and the generation of the product 4, 4' -diaminodiphenyl ether is not detected.
Comparative example 2
This comparative example compares the reaction conditions and parameters of example 1 with the only difference that the ligand added in comparative example 2 is 1, 10-phenanthroline instead of ligand L2.
Adding 258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 3.6g of potassium bromide (99%, 0.03mol), 5.8g of cuprous iodide (99%, 0.03mol), 6.0g of 1, 10-phenanthroline (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 6 hours; after the reaction is finished, liquid separation and water washing are carried out, an organic layer is sampled and subjected to GC-MS analysis, and the generation of the product 4, 4' -diaminodiphenyl ether is not detected.
As can be seen from comparative examples 1 and 2, the ligand in the invention is important for the reaction, the adopted ligand is a specific type of ligand specially selected for the reaction system, the Mannich base ligand has strong power supply and large steric hindrance, and is coordinated with copper salt, so that the catalytic effect is obviously improved. During the reaction, no ligand or conventional ligand (such as 1, 10-phenanthroline in comparative example 2) is added, and the reaction can not be carried out basically.
Comparative example 3
This comparative example compares the reaction conditions and parameters of example 1, except that no sodium bromide was added in comparative example 3.
258g of tetrahydrofuran (99%), 51.6g of diphenyl ether (99%, 0.3mol), 102.0g of ammonia water (25%, 1.5mol), 5.8g of cuprous iodide (99%, 0.03mol), 12.1g of ligand L2 (99%, 0.03mol) and 68.0g of hydrogen peroxide (30%, 0.6mol) are added into a 1000mL reaction bottle; after the feeding is finished, stirring and reacting at room temperature, wherein the stirring speed is 600rpm, and keeping the temperature for reacting for 6 hours; after the reaction is finished, liquid separation and water washing are carried out, an organic layer is sampled and subjected to GC-MS analysis, and the generation of the product 4, 4' -diaminodiphenyl ether is not detected.
It can be seen from comparative example 3 that the bromide salt is also important for the reaction, the addition of the bromide salt enables the diphenyl ether to undergo oxidative bromination reaction to form a 4,4 '-dibromodiphenyl ether intermediate, which in turn undergoes a C-N coupling reaction with ammonia water under the action of copper and a ligand to form 4, 4' -diaminodiphenyl ether, and the reaction cannot proceed without the bromide salt added during the reaction (comparative example 3).
The foregoing descriptions of specific exemplary embodiments of the present invention have been 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 certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and 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 synthetic method of 4, 4' -diaminodiphenyl ether is characterized by comprising the following steps: diphenyl ether, hydrogen peroxide, ammonia water and bromide are used as initial raw 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:
2. the method of claim 1, wherein the catalyst is a copper salt.
3. The method of claim 2, wherein 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.
4. The synthetic method of claim 1 wherein said ligand is a Mannich base ligand.
5. The synthetic method according to claim 4, wherein the Mannich base ligand is a Mannich base ligand of the formula:
6. the method of synthesis of claim 1, wherein the bromide salt is sodium bromide or potassium bromide.
7. The synthesis method according to claim 1, wherein the solvent is selected from one or more of halogenated alkane, halogenated aromatic hydrocarbon and cyclic ether.
8. The synthesis process according to claim 7, characterized in that 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.
9. The synthesis method of claim 1, wherein the molar ratio of the ammonia water to the diphenyl ether is 1:1-10: 1; the molar ratio of the bromide salt to the diphenyl ether is 0.05:1-0.2: 1; the molar ratio of the hydrogen peroxide to the diphenyl ether is 1:1-3: 1; the mass ratio of the solvent to the diphenyl ether is 5:1-10: 1; the molar ratio of the catalyst to the diphenyl ether is 0.05:1-0.2: 1; the molar ratio of the Mannich alkali ligand to the diphenyl ether is 0.05:1-0.2: 1.
10. The synthesis process of claim 1, wherein 4, 4' -diaminodiphenyl ether is obtained in one step through crystallization.
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| CN115724751A (en) * | 2022-11-28 | 2023-03-03 | 中钢集团南京新材料研究院有限公司 | Method for preparing 4,4' -diaminodiphenyl ether by using aniline as raw material |
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| CN115724751A (en) * | 2022-11-28 | 2023-03-03 | 中钢集团南京新材料研究院有限公司 | Method for preparing 4,4' -diaminodiphenyl ether by using aniline as raw material |
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