CN115925560B - Preparation method of 4,4' -diaminodiphenyl ether - Google Patents
Preparation method of 4,4' -diaminodiphenyl ether Download PDFInfo
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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 17
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 claims abstract description 11
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 5
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 239000010413 mother solution Substances 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 4,4' -diaminodiphenyl ether, belonging to the technical field of organic synthesis. The preparation method comprises the steps of taking 4-nitro-fluorine/chlorobenzene as a raw material, firstly generating hydroxamate with acetylhydroxylamine, then substituting with water to obtain 4-nitrophenol, then forming ether with the 4-nitro-fluorine/chlorobenzene under the action of a catalyst to obtain 4,4 '-dinitrodiphenyl ether, and finally reducing nitro to obtain the 4,4' -diaminodiphenyl ether. The process has the advantages of rapid reaction, proper temperature, continuous operation and easy mass production.
Description
Technical Field
The invention relates to a preparation method of 4,4' -diaminodiphenyl ether, belonging to the technical field of organic synthesis.
Background
4,4 '-Diaminodiphenyl ether, english name 4,4' -oxybisbenzenamine, CAS:101-80-4, molecular formula C 12H12N2 O, molecular weight 200.24, used for preparing heat-resistant plastics such as polyimide resin, polymaleimide resin, polyamideimide resin, polyesterimide resin, epoxy resin, polyurethane, etc., and also used as cross-linking agent. Also belongs to pharmaceutical intermediates. Polyimide resins are widely used in PI films and graphite films, which are basic materials in high-tech fields such as 5G equipment, aerospace industry, military industry, etc.
4,4 '-Diaminodiphenyl ether is generally produced by reduction of 4,4' -dinitrodiphenyl ether. At present, the synthesis of 4,4 '-dinitrodiphenyl ether is mainly a condensation method of p-nitrochlorobenzene and p-nitrophenol or a one-step condensation method of p-nitrochlorobenzene, but the existing condensation method has the defects of high reaction temperature, long time, easy byproduct generation and the like, and the synthesis of 4,4' -diaminodiphenyl ether is mainly an iron powder reduction method, a hydrazine hydrate method and a catalytic hydrogenation method. The iron powder reduction method has the advantages of large consumption of iron powder, high production cost, more three wastes, good quality of products produced by the hydrazine hydrate reduction method, high price, high cost, high toxicity and higher requirements on production equipment. The Pd/C or Raney nickel catalytic hydrogenation method has high product purity and high yield, but Pd/C is easy to poison in the catalytic hydrogenation process, and the application effect cannot be achieved.
Aiming at the defects of the method, the method has the advantages of short condensation time, less impurities, recycling of some mother liquor or catalyst, and more convenient industrialized production by optimizing and preparing the raw material proportion so as to meet the increasing market demands.
Disclosure of Invention
In order to overcome the technical defects, the 4-nitro-fluorine/chlorobenzene is taken as a raw material, firstly, hydroxamate is generated with acetohydroxylamine, then water is used for substitution to obtain 4-nitrophenol, then the 4-nitrophenol and the 4-nitro-fluorine/chlorobenzene are subjected to ether formation under the action of a catalyst to obtain 4,4 '-dinitrodiphenyl ether, and finally, the nitro is reduced to obtain the 4,4' -diaminodiphenyl ether. The process has the advantages of rapid reaction, proper temperature, continuous operation and easy mass production.
The preparation method of the 4,4' -diaminodiphenyl ether comprises the following steps:
The first step: mixing 4-nitro-fluorine/chlorobenzene, potassium carbonate, acetylhydroxylamine and an organic solvent, heating to 60-90 ℃ for reaction, then adding water and dilute acid for hydrolysis, performing simple post-treatment, and then mixing with potassium carbonate, a catalyst and DMF for reaction to obtain 4,4' -dinitrodiphenyl ether;
And a second step of: mixing 4,4 '-dinitrodiphenyl ether, raney nickel, DMF and triethylamine, and carrying out high-pressure hydrogenation to obtain 4,4' -diaminodiphenyl ether.
Further, in the above technical scheme, in the first step, the organic solvent is selected from dimethyl sulfoxide or sulfolane.
Further, in the above technical solution, in the first step, the catalyst is selected from cuprous iodide.
Further, in the above technical scheme, in the first step, the molar ratio of the 4-nitro-fluorine/chlorobenzene, potassium carbonate, acetylhydroxylamine, potassium carbonate to the catalyst is 1:2.0-2.5:1.2-1.5:1.2-1.5:0.02-0.05.
Further, in the technical scheme, in the second step, the Raney nickel is 4.0-7.5% of the weight of the 4,4' -dinitrodiphenyl ether, and the high pressure is 0.5-1.2Mpa.
Advantageous effects of the invention
A. In the first step, by optimizing the molar ratio of the acetylhydroxylamine to the potassium carbonate, more than half of the p-nitrochloro/fluorobenzene is ensured to be p-nitrophenol, the further recondensation is carried out, the control point in the reaction is clearer, and the large-scale production is facilitated.
B. the mother liquor purified in the first step and the second step can be repeatedly used, so that the atom utilization rate is increased, the cost is further reduced, and the yield is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following specific examples. These examples should be construed as merely illustrative of the present invention and not limiting the scope of the present invention. Various changes and modifications to the present invention may be made by one skilled in the art after reading the description herein, and such equivalent changes and modifications are intended to fall within the scope of the present invention as defined in the appended claims. Synthesis of 4,4' -diaminodiphenyl ether
Example 1
Under the protection of nitrogen, 15.8g (0.1 mol) of 4-nitrochlorobenzene, 62.2g (0.45 mol) of potassium carbonate, 22.5g (0.3 mol) of acetylhydroxylamine and 150mL of dimethyl sulfoxide are added into a reaction bottle and mixed, the temperature is raised to 80 ℃ for reaction for 2 hours, acetonitrile water is sampled and added for dilution, the raw materials are cooled to 10-15 ℃,10 mL of water, 200mL of MTBE and 50mL of n-heptane are added, 2M hydrochloric acid is added dropwise for regulating pH=4-5, standing and layering are carried out, an upper organic phase is reserved, the water is washed, the organic phase is concentrated to the residual volume under reduced pressure, 12.6g of p-nitrophenol is obtained by pulping by adding n-heptane, the yield is 90.6%, and HPLC:98.9%.
Example 2
Under the protection of nitrogen, 15.8g (0.1 mol) of 4-nitrochlorobenzene, 27.6g (0.2 mol) of potassium carbonate, 11.3g (0.15 mol) of acetylhydroxylamine and 100mL of dimethyl sulfoxide are added into a reaction bottle and mixed, the temperature is raised to 80 ℃ for reaction for 2 hours, acetonitrile water is added for sampling to dilute, and the raw material is remained for 46%. It is preferable to keep more than half of the raw materials to react with the p-nitrophenol.
With 4-nitrochlorobenzene as 1.0eq, other raw materials react in different proportions as follows:
Example 3
Under the protection of nitrogen, 14.1g (0.1 mol) of 4-nitrofluorobenzene, 27.6g (0.2 mol) of potassium carbonate, 9.0g (0.12 mol) of acetylhydroxylamine and 100mL of dimethyl sulfoxide are added into a reaction bottle for mixing, the temperature is raised to 80 ℃ for reaction for 2 hours, acetonitrile water is added for sampling for dilution, and the raw material is 45 percent remained. It is preferable to keep more than half of the raw materials to react with the p-nitrophenol.
With 1.0eq of 4-nitrofluorobenzene, other raw materials react in different proportions as follows:
Example 4
Under the protection of nitrogen, 141g (1 mol) of 4-nitrofluorobenzene, 276.4g (2 mol) of potassium carbonate, 90.1g (1.2 mol) of acetylhydroxylamine and 1000mL of sulfolane are added into a reaction bottle to be mixed, the temperature is raised to 80 ℃ for reaction for 2 hours, acetonitrile water is added for sampling for dilution, and the raw material is remained by 46%. Cooling to 10-15deg.C, adding 100mL of water, 100mL of MTBE 850mL of n-heptane, dropwise adding 2M hydrochloric acid to adjust pH=4-5, standing for layering, retaining upper organic phase, washing with water, and concentrating the organic phase under reduced pressure until no fluid is present. Then 103.7g (0.75 mol) of potassium carbonate, 4.8g (0.025 mol) of CuI and 700mL of DMF are added, the temperature is raised to 100 ℃ for reaction for 3 hours, the temperature is reduced to 45 ℃, the filtration is carried out, the temperature of filtrate is reduced to 0-5 ℃, solid is separated out, 108.8g of 4,4' -dinitrodiphenyl ether is obtained by filtration, the mother liquor can be sleeved in condensation reaction, the yield is 83.6%, and the HPLC is 98.8%. 1HNMR(400MHz,DMSO-d6 ) Delta, 8.36-8.32 (m, 4H), 7.21-7.16 (m, 4H).
Example 5
52G (0.2 mol) of 4,4 '-dinitrodiphenyl ether, 5.2g (wet weight) of skeletal nickel, 1mL of triethylamine and 600mL of DMF are added into a high-pressure reaction kettle, after three times of hydrogen replacement, the pressure is increased to 1Mpa, then the temperature is gradually increased to 45-55 ℃, after the pressure is kept at 1Mpa and hydrogen is not consumed, nitrogen is replaced for three times, the catalyst is filtered, the filtrate is decompressed and concentrated to remove DMF, and methanol is added for recrystallization to obtain 33.4g of 4,4' -diaminodiphenyl ether, the yield is 83.4%, and the HPLC is 99.5%. 1HNMR(400MHz,DMSO-d6 ) Delta, 6.83-6.75 (m, 8H), 6.13 (s, 4H).
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (1)
1. A method for preparing 4,4' -diaminodiphenyl ether, which is characterized by comprising the following steps:
Under the protection of nitrogen, 141g of 4-nitrofluorobenzene, 276.4g of potassium carbonate, 90.1g of acetylhydroxylamine and 1000mL of sulfolane are added into a reaction bottle to be mixed, the temperature is raised to 80 ℃ for reaction for 2 hours, acetonitrile water is added for dilution, the residual raw material is cooled to 10-15 ℃, 100mL of water, 150mL of MTBE 850mL and n-heptane are added, 2M hydrochloric acid is added dropwise to regulate pH to be 4-5, the mixture is stood for layering, an upper organic phase is reserved, water washing is carried out, and the organic phase is concentrated to no fluid under reduced pressure; then adding 103.7g of potassium carbonate, 4.8g of CuI and 700mL of DMF, heating to 100 ℃ for reaction for 3 hours, cooling to 45 ℃, filtering, cooling filtrate to 0-5 ℃, separating out solid, filtering to obtain 108.8g of 4,4' -dinitrodiphenyl ether, and sleeving a mother solution in the condensation reaction;
52g of 4,4 '-dinitrodiphenyl ether, 5.2g of skeleton nickel, 1mL of triethylamine and 600mL of DMF are added into a high-pressure reaction kettle, after three times of hydrogen replacement, the mixture is pressurized to 1Mpa, then the temperature is gradually increased to 45-55 ℃, after the pressure is kept at 1Mpa and hydrogen is not eaten, the mixture is replaced by nitrogen for three times, the catalyst is filtered, the filtrate is decompressed, concentrated to remove DMF, and 33.4g of 4,4' -diaminodiphenyl ether is obtained by adding methanol for recrystallization.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827586A (en) * | 2006-04-17 | 2006-09-06 | 常州市阳光精细化工有限公司 | Process for preparing 4,4'-diamino diphenyl ether |
| RU2671581C1 (en) * | 2017-12-28 | 2018-11-02 | Федеральное государственное унитарное предприятие "Институт химических реактивов и особо чистых химических веществ Национального исследовательского центра "Курчатовский институт" | Method of obtaining dinitroprotective diphenyl and triphenyl ethers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0739376B2 (en) * | 1985-03-04 | 1995-05-01 | 三井東圧化学株式会社 | Method for producing dinitrodiphenyl ethers |
| CN112062683B (en) * | 2020-09-24 | 2022-07-01 | 青岛科技大学 | Synthesis method of 4, 4-aminodiphenyl ether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827586A (en) * | 2006-04-17 | 2006-09-06 | 常州市阳光精细化工有限公司 | Process for preparing 4,4'-diamino diphenyl ether |
| RU2671581C1 (en) * | 2017-12-28 | 2018-11-02 | Федеральное государственное унитарное предприятие "Институт химических реактивов и особо чистых химических веществ Национального исследовательского центра "Курчатовский институт" | Method of obtaining dinitroprotective diphenyl and triphenyl ethers |
Non-Patent Citations (1)
| Title |
|---|
| Direct Conversion of Haloarenes to Phenols under Mild, Transition-Metal-Free Conditions;atrick S. Fier，Kevin M. Maloney;Org. Lett.;2244−2247 * |
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