CN117623948A - Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane - Google Patents
Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane Download PDFInfo
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- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 27
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960000581 salicylamide Drugs 0.000 claims abstract description 24
- SNZAEUWCEHDROX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate Chemical compound O.O.O.FC(F)(F)C(=O)C(F)(F)F SNZAEUWCEHDROX-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000005457 ice water Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 5
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- HLUYHVRRGFKTTM-UHFFFAOYSA-N copper(1+);hypochlorite Chemical compound [Cu+].Cl[O-] HLUYHVRRGFKTTM-UHFFFAOYSA-N 0.000 claims description 4
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 230000035484 reaction time Effects 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- -1 (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane Chemical compound 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which comprises the following steps: s1: under the protection gas, uniformly mixing hexafluoroacetone trihydrate and salicylamide, stirring and heating, controlling Wen Dijia Eton reagent, cooling, quenching with ice water, filtering, washing with water, pulping with ethanol, and drying to obtain a compound (I); s2: and (3) adding the compound (I) obtained in the step (1) into hypochlorite and alkali solution under the protection of gas, stirring, dissolving, heating, reacting, and performing post-treatment after the reaction is finished to obtain the compound (II). The invention has the beneficial effects that: the preparation method disclosed by the invention is novel, easy in raw material acquisition, good in selectivity, low in overall preparation cost, high in yield and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Background
Fluorine-containing polyimide (FPI) is a rigid polymer with a highly regular chemical structure and an imide ring in the main chain, and is a polymer material obtained by melt polycondensation or solution polycondensation reaction of fluorine-containing dianhydride and fluorine-containing diamine to produce fluorine-containing polyamide acid (FPAA) and imidization. The material has the advantages of corrosion resistance, radiation resistance, high and low temperature resistance, excellent mechanical property, better cohesiveness and the like, is widely applied to the fields of electronic power, OLED, aerospace, flame retardance, precision machinery and the like, becomes an irreplaceable high-performance polymer material, and has higher development value. 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) can be used as a polymerization monomer of a novel fluorine-containing polyimide material, can be used as a monomer for preparing a polyimide special high-molecular functional material, and phenolic hydroxyl in the structure can be connected with photosensitive groups such as DNQ through esterification reaction and then polymerized with dianhydride to obtain photosensitive polyimide (PSPI), so that the polyimide has wide application prospect in the fields of display and semiconductors.
The structural formula of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is as follows:
at present, the method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane mainly comprises the steps of nitrifying hexafluorobisphenol A (bisphenol AF) firstly, then hydrogenating or reducing hydrazine hydrate to obtain the product (European patent, EP0895985A2; U.S. Pat. No. 5, 7138103B2, U.S. Pat. No. 5977413A; japanese patent, JP2022152421A, JP6211752B2; chinese patent, CN 115819254A), wherein the raw material hexafluorobisphenol A of the method is expensive, the first-step nitrifying reaction belongs to a high-risk reaction, and if the temperature is controlled improperly and out of control, explosion is generated, and nitric acid or fuming nitric acid used belongs to a strong acid and a strong corrosive reagent; the second step of hydrogenation reduction generally needs high-pressure equipment, belongs to special equipment, also belongs to high-risk reaction, and the hydrogen or hydrazine hydrate used belongs to inflammability and explosiveness, and the metal catalyst used also belongs to inflammability. The method is difficult to be applied to industrial production. In addition, the method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (China patent, CN 111302944A) is obtained by taking halobenzene as a starting material, condensing with hexafluoroacetone gas, hydrolyzing and carrying out catalytic hydrogenation reduction.
Disclosure of Invention
In view of the above, the invention aims to provide a novel preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which has the advantages of simple synthetic route, improved reaction selectivity and product yield, and is suitable for industrial production.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
s1: under the protection gas, uniformly mixing hexafluoroacetone trihydrate and salicylamide, stirring and heating, controlling Wen Dijia Eton reagent, cooling, quenching with ice water, filtering, washing with water, pulping with ethanol, and drying to obtain a compound (I);
s2: under the protection gas, the compound of the formula I obtained in the step S1 undergoes Huffman degradation reaction under the action of hypochlorite and alkali, and the compound (II) 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is obtained after post-treatment;
the synthetic route is as follows:
further, in the step S1, the Eton reagent is added into the mixed solution of hexafluoroacetone trihydrate and salicylamide dropwise under the protection of gas, and the temperature is kept at 100 ℃ for reaction. After the HPLC detection reaction is finished, cooling, quenching by ice water, filtering, washing by water, pulping by ethanol, and drying to obtain the compound (I). By controlling the reaction temperature and the dosage of salicylamide, incomplete reaction of raw material hexafluoroacetone is avoided to the greatest extent.
Further, in step S1, the molar ratio of hexafluoroacetone trihydrate to salicylamide as raw materials is 1.0: (2.2-4.0). In this range, hexafluoroacetone reacts most completely and the yield is highest.
Further, in the step S1, the Eton reagent is dripped into a hexafluoroacetone trihydrate and salicylamide system under the protection gas at the temperature of 80-100 ℃, and the system is stirred at the temperature of 100+/-5 ℃ after the dripping is finished.
Preferably, in step S1, the dripping time is controlled to be 0.5-2h.
Preferably, in step S1, the system is kept at 100.+ -. 5 ℃ for 1-3h.
The hypochlorite in step S2 includes sodium hypochlorite, potassium hypochlorite, copper hypochlorite, calcium hypochlorite, and lithium hypochlorite.
The alkali in the step S2 comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate and potassium carbonate.
The hypochlorite solution is sodium hypochlorite solution, and the alkali solution is sodium hydroxide solution;
in step S2, the molar ratio of compound (i), hypochlorite and base is 1.0: (1.1-3.0): (2.2-4.0).
Further, in the step S2, the compound (I) is added into hypochlorite and aqueous alkali, stirred and dissolved, and heated to 80 ℃ for reaction for 4-6 hours.
Preferably, in step S2, the system is kept at 80.+ -. 5 ℃ for 4-6h.
Further, in both step S1 and step S2, the shielding gas is an inert gas, preferably nitrogen.
Further, the post-treatment in the step S2 comprises the steps of cooling, pH adjustment, filtration, water washing and drying to obtain the compound (II) 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Compared with the prior art, the preparation method of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane has the following advantages:
according to the invention, hexafluoroacetone trihydrate and salicylamide are used as main raw materials, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane is obtained through dehydration condensation reaction, and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is obtained through Huffman degradation reaction, so that the main raw materials are cheap and easy to obtain, the reaction steps are simple and safe, the preparation method is easy to realize, the reaction selectivity is higher, the side reaction is less, and the reaction yield is high.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The present invention will be described in detail with reference to examples.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to examples.
The synthetic route of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is as follows:
example 1:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:2.2 adding hexafluoroacetone trihydrate (100 g,1.0 eq) to a 1L four-necked flask under nitrogen protection, adding salicylamide (137.1 g,2.2 eq) under stirring, heating to 80deg.C, and dropwise adding Eton's reagent (94.4 g, containing 7.5% P) 2 O 5 ) After the completion of the 1-hour dripping, the reaction is stirred at the temperature of 100 ℃ for 2 hours. After the reaction is detected by HPLC, the temperature is reduced to 40 ℃, the reaction solution is slowly poured into 1000mL of ice water, stirred and quenched, filtered, washed with water, pulped by ethanol and dried to obtain 181.5g of compound (I) 2, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane with the yield: 94.6%. MS M/z 421 (M)-H) -
The hydrogen nuclear magnetic resonance spectrum is as follows:
1 H NMR(600MHz,DMSO-d 6 ,δppm):6.98(d,2H),7.35(d,2H),7.68(s,2H),7.98(s,4H),11.11(s,2H).
in the reaction, in order to completely react the substrate hexafluoroacetone, the salicylamide is excessive, the reaction temperature is 100 ℃, and the raw materials are completely reacted to the greatest extent.
Step (2): the molar ratio of the compound (I), sodium hypochlorite and sodium hydroxide is 1.0:1.1:2.2 to a 1L four-necked flask under the protection of nitrogen gas, 10% aqueous sodium hypochlorite solution (351.9 g,1.1 eq) was added, sodium hydroxide (37.8 g,2.2 eq) was added under stirring, and finally compound (I) (181.5 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃to react for 5 hours. After the reaction is detected by HPLC, the temperature is reduced to 20 ℃, hydrochloric acid is added dropwise to adjust the pH value to be between 5 and 6, the mixture is filtered, washed by water and dried to obtain 144.0g of the compound 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane shown in the formula II, and the yield is: 91.5%. MS M/z 365 (M-H) -
The hydrogen nuclear magnetic resonance spectrum is as follows:
1 H NMR(600MHz,DMSO-d 6 ,δppm):4.66(s,4H),6.45(d,2H),6.59(s,2H),6.69(d,2H),10.06(s,2H).
in the reaction, in order to completely react the compound of the formula I, sodium hypochlorite and sodium hydroxide are excessive, the reaction temperature is 80 ℃, and the raw materials are completely reacted to the greatest extent.
Example 2:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:2.5 adding hexafluoroacetone trihydrate (100 g,1 eq) into a 1L four-necked flask under the protection of nitrogen, adding salicylamide (155.8 g,2.5 eq) under stirring, heating to 80 ℃, and dropwise adding Eton reagent (118.0 g containing 7.5% P) at 80-100 DEG C 2 O 5 ) After the completion of the 1-hour dripping, the reaction is stirred at the temperature of 100 ℃ for 2 hours. After the HPLC detection reaction is finished, the temperature is reduced to 40 ℃, and the reaction solution is slowly poured in1000mL of ice water, stirring and quenching, filtering, washing with water, pulping with ethanol and drying to obtain 189.2g of 2, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane compound (I), yield: 98.6%.
Step (2): the molar ratio of the compound (I), sodium hypochlorite and sodium hydroxide is 1.0:1.5:2.5, to a 1L four-necked flask under the protection of nitrogen gas, 10% aqueous sodium hypochlorite solution (500.3 g,1.5 eq) was added, sodium hydroxide (44.8 g,2.5 eq) was added under stirring, and finally compound (I) (189.2 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃to react for 5 hours. After the reaction is detected by HPLC, the temperature is reduced to 20 ℃, hydrochloric acid is added dropwise to adjust the pH value to be between 5 and 6, the mixture is filtered, washed by water and dried to obtain 159.8g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane compound shown in the formula II, and the yield is: 97.4%.
Example 3:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:3.0, adding hexafluoroacetone trihydrate (100 g,1 eq) into a 1L four-necked flask under the protection of nitrogen, adding salicylamide (186.9 g,3 eq) under stirring, heating to 80 ℃, and dropwise adding Eton reagent (141.6 g containing 7.5% P) at a temperature of 80-100 DEG C 2 O 5 ) After the completion of the 1-hour dripping, the reaction is stirred at the temperature of 100 ℃ for 2 hours. After the reaction is detected by HPLC, the temperature is reduced to 40 ℃, the reaction solution is slowly poured into 1000mL of ice water, stirred and quenched, filtered, washed with water, pulped by ethanol and dried to obtain 185.2g of compound (I) 2, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane with the yield: 96.5%.
Step (2): the molar ratio of compound (i), calcium hypochlorite and potassium hydroxide is 1.0:2.0:3.0, 500g of water and calcium hypochlorite (125.4 g,2.0 eq) were added to a 2L four-necked flask under nitrogen protection, potassium hydroxide (73.8 g,3.0 eq) was added under stirring, and finally compound (I) (185.2 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃for reaction for 5 hours. After the reaction is detected by HPLC, the temperature is reduced to 20 ℃, hydrochloric acid is added dropwise to adjust the pH value to be between 5 and 6, the mixture is filtered, washed by water and dried to obtain 158.1g of the compound 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane shown in the formula II, and the yield is: 98.4%.
Example 4:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:3.5 adding hexafluoroacetone trihydrate (100 g,1 eq) into a 1L four-necked flask under the protection of nitrogen, adding salicylamide (218.1 g,3.5 eq) under stirring, heating to 80 ℃, and dropwise adding Eton reagent (188.8 g containing 7.5% P) at 80-100 DEG C 2 O 5 ) After the completion of the 1-hour dripping, the reaction is stirred at the temperature of 100 ℃ for 2 hours. After the reaction is detected by HPLC, the temperature is reduced to 40 ℃, the reaction solution is slowly poured into 1000mL of ice water, stirred and quenched, filtered, washed with water, pulped by ethanol and dried to obtain 173.9g of 2, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane compound (I), and the yield is: 90.6%.
Step (2): the molar ratio of the compound (I), the copper hypochlorite and the ammonium hydroxide is 1.0:2.5:3.5, 500g of water and copper hypochlorite (171.4 g,2.5 eq) were added to a 2L four-necked flask under nitrogen protection, ammonium hydroxide (50.5 g,3.5 eq) was added with stirring, and finally compound (I) (173.9 g,1.0 eq) was added, and the mixture was dissolved with stirring and heated to 80℃for reaction for 5 hours. After the reaction is detected by HPLC, the temperature is reduced to 20 ℃, hydrochloric acid is added dropwise to adjust the pH value to be between 5 and 6, the mixture is filtered, washed by water and dried to obtain 144.0g of the compound 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane shown in the formula II, and the yield is: 95.5%.
Example 5:
a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the following steps:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:4.0, into a 1L four-necked flask under the protection of nitrogen gas, hexafluoroacetone trihydrate (100 g,1 eq) and salicylamide (249.3 g,4.0 eq) are added under stirring, the temperature is raised to 80 ℃, and Eton reagent (188.8 g, containing 7.5% P) is added dropwise at a temperature of 80-100 DEG C 2 O 5 ) After the completion of the 1-hour dripping, the reaction is stirred at the temperature of 100 ℃ for 2 hours. After the HPLC detection reaction is finished, the temperature is reduced to 40 ℃, the reaction solution is slowly poured into 1000mL of ice water, stirred and quenched, filtered,washing with water, beating with ethanol, drying to give compound (I) 170.6g of 2, 2-bis (3-carbamoyl-4-hydroxyphenyl) hexafluoropropane, yield: 88.9%.
Step (2): the molar ratio of the compound (I), the lithium hypochlorite and the potassium carbonate is 1.0:3.0:4.0, 500g of water and lithium hypochlorite (70.8 g,3.0 eq) were added to a 2L four-necked flask under nitrogen protection, potassium carbonate (223.3 g,4.0 eq) was added under stirring, and finally compound (I) (170.6 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃for reaction for 5 hours. After the reaction is detected by HPLC, the temperature is reduced to 20 ℃, hydrochloric acid is added dropwise to adjust the pH value to be between 5 and 6, the mixture is filtered, washed by water and dried to obtain 142.8g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane compound shown in the formula II, and the yield is: 96.5%.
Comparative example 1:
step (1): the molar ratio of hexafluoroacetone trihydrate to salicylamide is 1.0:2.5 into a 1L four-necked flask under the protection of nitrogen, hexafluoroacetone trihydrate (100 g,1 eq) and salicylamide (155.8 g,2.5 eq) were added under stirring, the temperature was raised to 100℃and the reaction was stirred at 100℃for 2h. No compound (i) was formed by HPLC.
Comparative example 2:
step (2): the molar ratio of compound (I) to sodium hydroxide is 1.0:2.5, 500g of water was added to a 1L four-necked flask under nitrogen protection, sodium hydroxide (23.7 g,2.5 eq) was added under stirring, and finally compound (I) (100 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃to react for 5 hours. No compound (ii) was formed by HPLC.
Comparative example 3:
step (2): the molar ratio of compound (I) to sodium hypochlorite is 1.0:1.5, to a 1L four-necked flask under the protection of nitrogen gas, 10% sodium hypochlorite solution (264.4 g,1.5 eq) was added under stirring, and finally compound (I) (100 g,1.0 eq) was added, and the mixture was dissolved under stirring and heated to 80℃to react for 5 hours. HPLC showed 25% formation of compound (II).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is characterized in that: the method comprises the following steps:
s1: under the protection gas, uniformly mixing hexafluoroacetone trihydrate and salicylamide, stirring and heating, controlling Wen Dijia Eton reagent, cooling, quenching with ice water, filtering, washing with water, pulping with ethanol, and drying to obtain a compound (I);
s2: adding the compound (I) obtained in the step (1) into hypochlorite and alkali solution under the protection gas, stirring, dissolving, heating, reacting, and performing post-treatment after the reaction is finished to obtain a compound (II);
2. the method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the molar ratio of hexafluoroacetone trihydrate to salicylamide in step S1 is 1.0: (2.2-4.0).
3. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: dropwise adding the Eton reagent into a hexafluoroacetone trihydrate and salicylamide system at 80-100 ℃ under the protection gas, and stirring the system at 100+/-5 ℃;
in the step S1, the Eton reagent is added in a dropwise adding mode, and the dropwise adding speed is the same;
the dripping time is 0.5-2h.
4. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the temperature of the Wen Dijia Eton reagent is controlled to be 80-100 ℃ in the step S1.
5. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the reaction time of hexafluoroacetone trihydrate and salicylamide in the step S1 is 1-3h.
6. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the hypochlorite in step S2 includes sodium hypochlorite, potassium hypochlorite, copper hypochlorite, calcium hypochlorite, and lithium hypochlorite.
7. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the alkali in the step S2 comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate and potassium carbonate.
8. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the molar ratio of compound (i), hypochlorite and base in step S2 is 1.0: (1.1-3.0): (2.2-4.0).
9. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the reaction temperature of the temperature-rising reaction in the step S2 is 80+/-5 ℃;
the temperature-rising reaction time in the step S2 is 4-6h.
10. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the shielding gas in the step S1 and the step S2 is inert gas, and the preferable shielding gas is nitrogen;
the post-treatment in the step S2 comprises the steps of cooling, pH adjustment, filtration, water washing and drying to obtain the compound (II) 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
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