CN105037166B - The preparation method of 2,2 2 (4 (4 amino-benzene oxygen) phenyl) HFC-236fas and its intermediate - Google Patents
The preparation method of 2,2 2 (4 (4 amino-benzene oxygen) phenyl) HFC-236fas and its intermediate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract 5
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- FPVZDEONRNIEEJ-UHFFFAOYSA-N 1-[1,1,1,3,3,3-hexafluoro-2-[4-(4-nitrophenoxy)phenyl]propan-2-yl]-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(=CC=3)[N+]([O-])=O)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 FPVZDEONRNIEEJ-UHFFFAOYSA-N 0.000 claims description 25
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 10
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical group [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical group [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- WDWVMZIRIYVNCZ-UHFFFAOYSA-N 1-(1,1,1,3,3,3-hexafluoropropan-2-yl)-4-(4-nitrophenoxy)benzene Chemical compound [N+](=O)([O-])C1=CC=C(OC2=CC=C(C=C2)C(C(F)(F)F)C(F)(F)F)C=C1 WDWVMZIRIYVNCZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000010413 mother solution Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 abstract 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract 2
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LKJWDWUXGCKFPN-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 LKJWDWUXGCKFPN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The preparation method of HFC-236fa intermediate, the intermediate is 2,2 two（4‑（4 nitro-phenoxies) phenyl）HFC-236fa, by 2,2 two（4 hydroxy phenyls）HFC-236fa and para-halo nitrobenzene are reacted in the presence of solvent, catalyst and organic base, obtain 2,2 two（4‑（4 nitro-phenoxies) phenyl）HFC-236fa.The present invention also provides 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The preparation method of HFC-236fa.The method of the present invention uses low-temperature operation, and the first step reacts 95~100 DEG C, and second step, which reacts 20~40 DEG C, can just complete reaction, meanwhile, waste water is not produced in processing procedure, it is environmentally friendly；The method of the present invention can improve product yield, and yield is more than 79.9%, and product purity is high, more than 99.7%；Meanwhile, reduce production cost.
Description
Technical Field
The invention belongs to the technical field of compounds, and particularly relates to a preparation method of 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and an intermediate thereof.
Background
2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (4-BDAF for short), 2-bis (4- (4-aminophenoxy) -hexa-fluoropropane, molecular formula C27H20F6N2O2, structural formula shown in formula (I):
4-BDAF is one of the main raw materials for preparing liquid crystal orientation materials for a thin film transistor liquid crystal display (TFT-LCD), is widely used for preparing fluorine-containing vulcanization accelerator and thermoplastic resin, and is related to WO02100949, WO2004011528 and US 5504128.
The existing preparation methods of 4-BDAF mainly comprise the following steps:
the method comprises the following steps: the reaction formula is as follows
In US4111906, 2-bis (4-hydroxyphenyl) hexafluoropropane and sodium hydroxide are refluxed and dehydrated in N, N-dimethylacetamide and toluene to prepare disodium salt of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, then the disodium salt and p-chloronitrobenzene are reacted at 150 ℃ for 48 hours, the reaction solution is poured into water to precipitate 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is recrystallized and purified by ethanol, and then reduced by an iron powder/hydrochloric acid system to obtain the target product 4-BDAF.
In the method, the reaction temperature is up to 150 ℃, and the reaction time of the disodium salt of the 2,2-bis (4-hydroxyphenyl) hexafluoropropane and the p-chloronitrobenzene is up to 48 hours. And when the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is separated, the solid needs to be filtered out by pouring into water, a large amount of waste water containing N, N-dimethylacetamide is generated, and the method is extremely not suitable for industrial production.
The second method comprises the following steps: the reaction formula is as follows
In US5043478, in comparison with method one, the disodium salt of 2,2-bis (4-hydroxyphenyl) hexafluoropropane was prepared under nitrogen protection and sodium hydroxide was added in portions and reacted with p-chloronitrobenzene at 150 ℃ with a reduction in reaction time of up to 4 hours. However, in the post-treatment of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, the reaction solution is poured into a mixed solution of methanol and water to precipitate 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, and after the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is recrystallized and purified by a mixed solvent of ethyl acetate and methanol, hydrogen is reduced under the catalysis of Pd/C to obtain the target product 4-BDAF.
In this process, the reaction time is also considerably shortened compared with the first process, but the reaction temperature is still as high as 150 ℃. And when the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is separated, the mixture is poured into a mixed solution of methanol and water, and solids are filtered out, so that a large amount of wastewater containing N, N-dimethylacetamide and methanol is generated, and the method is still not suitable for industrial production.
The third method comprises the following steps: the reaction formula is as follows
Zhang build et al (liquid crystal and display, 2009,3,345-349) used a method in which 2,2-bis (4-hydroxyphenyl) hexafluoropropane and sodium hydroxide are first reacted in N, N-dimethylacetamide at 70-80 ℃ to form the disodium salt of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, then p-chloronitrobenzene is dripped at 140 ℃ for 5 hours of reaction, after the reaction is finished, most of N, N-dimethylacetamide is recovered by reduced pressure distillation, the rest materials are poured into water, 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is precipitated, and after 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane is recrystallized with a mixed solvent of ethanol and toluene, and (3) under the catalysis of Pd/C, reducing hydrogen to obtain the target product 4-BDAF.
Although most of the N, N-dimethylacetamide is recovered, the recovered N, N-dimethylacetamide contains moisture and cannot be recovered and reused. And the reaction temperature is up to 140 ℃. But also still generates a large amount of waste water, which is not suitable for industrial production.
Disclosure of Invention
The invention mainly aims to solve the defects of the preparation process of the 4-BDAF and provide a preparation method of the 4-BDAF and an intermediate thereof, which has high yield, easy operation and environmental protection.
Through diligent efforts of the inventor, the inventor finds that in the preparation process of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, a solvent with a lower boiling point is selected, and the reaction can be conveniently carried out in the presence of a proper alkali and a catalyst, so that the reaction condition is mild, the operation is convenient to control, and the product yield and the product content are high. The 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane produced by this step can be conveniently reduced to 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane.
The reaction route is as follows:
the invention provides a preparation method of a 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate, wherein the 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate is 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, and 2,2-bis (4-hydroxyphenyl) hexafluoropropane and para-halogenated nitrobenzene are reacted in the presence of a solvent, a catalyst and an organic base to obtain 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane; wherein,
the solvent is one or a mixture of two of dimethoxyethane and toluene; such solvents have low boiling points and are easy to recover. The two can be mixed in any proportion, and the preferable proportion is as follows: dimethoxyethane: the weight ratio of toluene is 20-80: 80-20.
The catalyst is selected from cuprous iodide, anhydrous nickel chloride or palladium dichloride.
Preferably, the p-halogenated nitrobenzene is p-chloronitrobenzene or p-fluoronitrobenzene.
Preferably, the organic base is selected from sodium tert-butoxide or potassium tert-butoxide.
Preferably, the temperature of the reaction is 95-105 ℃.
Preferably, 2-bis (4-hydroxyphenyl) hexafluoropropane, p-nitrohalogenated benzene, a solvent, a catalyst and an organic base are added into a reaction vessel at one time, the temperature is raised for reaction for 5 to 7 hours, a generated by-product is distilled off at any time in the reaction process, the temperature is reduced after the reaction is finished, the catalyst is removed by filtration, a mother liquor is rectified to recover the solvent, the residual solid is a crude product of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, and the crude product is recrystallized to obtain a refined product of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane.
The invention also provides a preparation method of the 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, which comprises the following steps:
(1) preparing a 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate, i.e., 2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, according to the process of any one of claims 1 to 4;
(2) adding the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane prepared in the step (1) into ethyl acetate, and reducing the mixture by using hydrogen in the presence of Pd/C to prepare the 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane.
Preferably, in the step (2), the pressure of the reduction reaction is 0.05 MPa.
Preferably, in the step (2), the temperature of the reduction reaction is 20-40 ℃.
The pressure is lower, the temperature is lower, the reaction condition is mild, the operation is simple and convenient, and the cost is lower.
The method adopts low-temperature operation, the reaction can be completed at 95-100 ℃ in the first step and 20-40 ℃ in the second step, and meanwhile, no wastewater is generated in the treatment process, so that the method is environment-friendly; the method can improve the product yield, the yield is over 79.9 percent, and the product purity is high and is over 99.7 percent; meanwhile, the production cost is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an HPLC chromatogram of the final product of example 1 of the present invention.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
Example 1
A1000 mL three-neck bottle is prepared, a mechanical stirring and distilling device is arranged, 33.6g (0.1mol) of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 200 mL of dimethoxyethane, 23.06g (0.24mol) of sodium tert-butoxide, 0.5g of cuprous iodide and 34.66g (0.22mol) of p-chloronitrobenzene are added, the mixture is slowly heated to 95-105 ℃ under the protection of nitrogen, the reaction is started, and the tert-butyl alcohol generated in the reaction process is gradually evaporated. After the temperature is kept for 6 hours, the reaction is finished, the temperature is reduced to 25 ℃, cuprous iodide and generated sodium chloride are removed by filtration, mother liquor is rectified and concentrated to recover dimethoxyethane, 180ml is obtained, the residual solid in the bottle is a crude product of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, and the crude product is recrystallized by using a mixed solvent of 800 ml of ethanol and 200 ml of ethyl acetate to obtain 52.02g of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane. HPLC 99.5%, mp159.5 ℃; the yield thereof was found to be 90%.
52.02g of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, 600 ml of ethyl acetate and 8g of 5% palladium carbon are added into a stainless steel hydrogenation kettle, and after nitrogen replacement, the reaction is finished after hydrogen reduction reaction is carried out for 6 hours at 30 ℃ under the pressure of 0.05 MPa. The reaction was stopped, after nitrogen displacement, the material was taken out, the catalyst was removed by filtration, ethyl acetate was removed by concentration under reduced pressure, the resulting solid was recrystallized from 5-fold ethanol to give 42.43g of white crystals, HPLC 99.8%, yield 91.0% at mp162.5 ℃ and HPLC chromatogram of the product is shown in FIG. 1. The method for calculating the content using the spectrum is shown in table 1.
TABLE 1 method of content calculation using HPLC profile
The total yield of the two-step reaction is 81.9%.
Example 2
The procedure is as in example 1, except that the solvent used is 180ml of dimethoxyethane recovered in example 1, and 20 ml of fresh dimethoxyethane is added and worked up to give 41.95g of 2,2-bis (4- (4-aminophenoxyphenyl)) hexafluoropropane in 99.8% HPLC with a yield of 90.0%.
Example 3 to example 18
In examples 3 to 18, except for one or more of the kind of halogenated nitrobenzene, the kind of solvent, the kind of catalyst, and the kind of base in the production of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane; the other specific parameters, the amounts and the preparation method are the same as those of the example 1, and the specific conditions are shown in the table 2:
table 2 examples 3 to 18
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
- A process for the preparation of a 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate, said 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate being 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, characterized in that: reacting 2,2-bis (4-hydroxyphenyl) hexafluoropropane with para-halogenated nitrobenzene in the presence of a solvent, a catalyst and an organic base to obtain 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane; wherein,the solvent is one or a mixture of two of dimethoxyethane and toluene;the catalyst is selected from anhydrous nickel chloride;the organic base is selected from sodium tert-butoxide or potassium tert-butoxide.
- 2. The method of claim 1, wherein: the p-halogenated nitrobenzene is p-chloronitrobenzene or p-fluoronitrobenzene.
- 3. The method of claim 1, wherein: the reaction temperature is 95-105 ℃.
- 4. A method according to any one of claims 1-3, characterized in that: adding 2,2-bis (4-hydroxyphenyl) hexafluoropropane, para-halogenated nitrobenzene, a solvent, a catalyst and an organic base into a reaction container at one time, heating for reaction for 5-7 hours, evaporating a generated byproduct at any time in the reaction process, cooling after the reaction is finished, filtering to remove the catalyst, rectifying a mother solution to recover the solvent, obtaining a residual solid which is a crude product of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, and recrystallizing the crude product to obtain a refined product of 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane.
- A process for producing 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, characterized in that: the method comprises the following steps:(1) preparing a 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane intermediate, i.e., 2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane, according to the method of any one of claims 1 to 4;(2) adding the 2,2-bis (4- (4-nitrophenoxy) phenyl) hexafluoropropane prepared in the step (1) into ethyl acetate, and reducing the mixture by using hydrogen in the presence of Pd/C to prepare the 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane.
- 6. The method of claim 5, wherein: in the step (2), the pressure of the reduction reaction is 0.05 MPa.
- 7. The method of claim 5, wherein: in the step (2), the temperature of the reduction reaction is 20-40 ℃.
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| CN201510392457.6A CN105037166B (en) | 2015-07-06 | 2015-07-06 | The preparation method of 2,2 2 (4 (4 amino-benzene oxygen) phenyl) HFC-236fas and its intermediate |
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| CN201510392457.6A CN105037166B (en) | 2015-07-06 | 2015-07-06 | The preparation method of 2,2 2 (4 (4 amino-benzene oxygen) phenyl) HFC-236fas and its intermediate |
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| CN105037166B true CN105037166B (en) | 2017-07-14 |
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