CN113636938A - Preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) - Google Patents
Preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) Download PDFInfo
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- -1 perfluoropropane-2, 2-diyl Chemical group 0.000 title claims abstract description 74
- VPZRVYLJWAJQRE-UHFFFAOYSA-N 2-prop-2-enoxyaniline Chemical compound NC1=CC=CC=C1OCC=C VPZRVYLJWAJQRE-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 72
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 125000005336 allyloxy group Chemical group 0.000 claims abstract description 36
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- NMRDKGOPQYFYTD-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-nitrophenyl)propan-2-yl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C([N+]([O-])=O)=C1 NMRDKGOPQYFYTD-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 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 abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 87
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000006396 nitration reaction Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007867 post-reaction treatment Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012992 electron transfer agent Substances 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
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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 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), which relates to the technical field of chemical intermediate synthesis and comprises the following steps: dissolving 4,4 '- (hexafluoroisopropylidene) diphenol in glacial acetic acid and nitric acid to react to obtain 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, dissolving the product in acetonitrile, adding potassium carbonate and 3-bromopropylene to react to obtain 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); reacting 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene), iron powder and ammonium chloride to obtain 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline); the synthesis route has mild reaction conditions, simple reaction and post-treatment process operation, low reaction risk coefficient and low production cost, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of chemical intermediate synthesis, and particularly relates to a preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline).
Background
5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) is an important organic synthesis intermediate, has a wide application prospect, is mainly used for a cross-linking agent of epoxy resin, can generate claisen rearrangement at high temperature or under the condition of a catalyst to form diallyl bisphenol, and is applied to high-end application technologies including an adhesive on the surface of a semiconductor wafer, a light-resistant material, an impact-resistant prepreg, a molding of a fiber reinforced structural member, a mixed material for preventing high temperature and chemical corrosion, a high-temperature coating film, water proofing, corrosion proofing and the like. The compound synthesized in the prior art has the defects of severe reaction conditions, low process yield and incapability of industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), which does not adopt a high-toxicity reagent, has the overall reaction temperature not exceeding 100 ℃, has mild reaction conditions, effectively improves the process yield compared with the prior art, and is suitable for industrial mass production.
In order to achieve the above purpose, the invention provides the following technical scheme: the preparation process of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) includes the following steps:
the specific synthesis steps comprise:
1) carrying out nitration reaction on 4, 4' - (hexafluoroisopropylidene) diphenol in a compound (1) in a first organic solvent to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane;
2) reacting the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane with 3-bromopropene in a second organic solvent in a basic environment to obtain a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene);
3) under the action of a reducing agent, the compound (3)5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacts with a mixed solution of ammonium chloride to obtain a target product compound (4)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline).
Further, the reaction process of the step 1) is as follows: dissolving a compound (1), 4' - (hexafluoroisopropylidene) diphenol in a first organic solvent, dropwise adding nitric acid into the solution when the temperature of the solution reaches 25-35 ℃, and stirring until the reaction is finished; after the reaction is finished, pouring the reaction liquid into ice water, filtering, washing a filter cake with water, and drying to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane; wherein the first organic solvent is glacial acetic acid.
Further, the reaction process of the step 2) is as follows: adding a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane into a second organic solvent, sequentially adding potassium carbonate and 3-bromopropylene into the solution, heating the reaction solution to 75-85 ℃, and fully reacting; after the reaction is finished, filtering the reaction solution; spin-drying the filtrate to obtain oil, adding water and ethyl acetate, and separating; extracting the water phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating to obtain a compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); wherein the second organic solvent is acetonitrile.
Further, the reaction process of the step 3) is as follows: adding a reducing agent into ethanol, sequentially adding ammonium chloride and water to obtain an ammonium chloride mixed solution, and heating to 75-85 ℃; dropwise adding an ethanol solution in which a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is dissolved into the ammonium chloride mixed solution, and fully reacting; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, washing a filter cake with ethanol, concentrating and drying the filtrate to obtain a target product compound (4), namely 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline); wherein the reducing agent is iron powder.
Further, an ethanol solution in which the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is dissolved in the step 3) is gradually added dropwise to the ammonium chloride mixed solution under the condition that the reaction temperature is controlled to be 78 to 83 ℃.
Further, the amount ratio of the compound (1)4, 4' - (hexafluoroisopropylidene) diphenol reacted with nitric acid in the step 1) is 1: (2-15).
Further, the dropping of nitric acid into the solution comprises at least two stages, respectively:
in the first stage, when the temperature of a first organic solvent in which a compound (1), 4' - (hexafluoroisopropylidene) diphenol is dissolved is 28-29 ℃, 5-10 percent of the total amount of nitric acid is dripped into the solution to initiate reaction;
and in the second stage, after the dropwise addition in the first stage is finished, controlling the temperature of the reaction liquid of the compound (1), 4' - (hexafluoroisopropylidene) diphenol and nitric acid to be 25-35 ℃, and dropwise adding the residual nitric acid into the reaction liquid.
Further, the amount ratio of the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane reacted with 3-bromopropene in the step 2) is 1: (2-6).
Further, the amount ratio of the substances of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacted with ammonium chloride in the step 3) is 1: (0.1-2.0).
Further, the amount ratio of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacted with the iron powder in the step 3) is 1: (8-15).
According to the technical scheme, the technical scheme of the invention has the following beneficial effects:
the invention discloses a preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), which comprises the steps of firstly adopting reaction conditions of an optimized preparation process, particularly selecting a reaction solvent and reactants, so that the reaction conditions are mild, and the reaction risk coefficient is reduced; secondly, the post-reaction treatment and purification modes are simplified, so that the reaction operation is simple, the preparation difficulty of the target product is greatly reduced, the product yield is improved, and the aims of reducing the production cost and realizing industrial mass production are fulfilled; the specific preparation process comprises the following steps: dissolving 4,4 '- (hexafluoroisopropylidene) diphenol in glacial acetic acid and nitric acid to react to obtain 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, dissolving the product in acetonitrile, adding potassium carbonate and 3-bromopropylene to react to obtain 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene), iron powder and ammonium chloride were reacted to give 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline).
The comprehensive yield of the target product of the preparation method disclosed by the invention under the preferable reaction condition is more than 80% through research and calculation; in addition, the method has the advantages of less consumption of reaction solvent, no need of column chromatography, great reduction of a large amount of solvents used for purification, very important promotion effect on reduction of environmental pollution, energy conservation and emission reduction, and environmental friendliness.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane according to the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) which is a compound (3) of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the target compound of the invention, 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The use of "first," "second," and similar terms in the description and claims of the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Similarly, the singular forms "a," "an," or "the" do not denote a limitation of quantity, but rather denote the presence of at least one, unless the context clearly dictates otherwise. The terms "comprises," "comprising," or the like, mean that the elements or items listed before "comprises" or "comprising" encompass the features, integers, steps, operations, elements, and/or components listed after "comprising" or "comprising," and do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Based on the fact that a cross-linking agent of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) used for epoxy resin in the prior art has a wide application prospect, the disclosed synthetic method has the technical problems of severe reaction conditions, high reaction risk coefficient, low product yield and incapability of industrial production; the invention aims to disclose a new method for preparing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), and the synthesis route provided by the method has the advantages of mild reaction conditions, low reaction risk coefficient, simple post-reaction treatment and purification processes, high product yield and remarkably reduced production cost.
The preparation process of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) includes the following steps:
the specific synthesis steps comprise:
1) carrying out nitration reaction on 4, 4' - (hexafluoroisopropylidene) diphenol in a compound (1) in a first organic solvent to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane; specifically, the compound (1), 4' - (hexafluoroisopropylidene) diphenol, is dissolved in glacial acetic acid, nitric acid is dripped into the solution when the temperature of the solution reaches 25-35 ℃, and the solution is stirred until the reaction is completed; after the reaction is finished, pouring the reaction liquid into ice water, filtering, washing a filter cake with water, and drying to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane; wherein, the amount ratio of the compound (1)4, 4' - (hexafluoroisopropylidene) diphenol to the substance reacted with nitric acid is 1: (2-15).
2) Reacting the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane with 3-bromopropene in a second organic solvent in a basic environment to obtain a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); specifically, a compound (2), 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane is added into acetonitrile, potassium carbonate and 3-bromopropylene are sequentially added into the solution, and then the reaction solution is heated to 75-85 ℃ for full reaction; after the reaction is finished, filtering the reaction solution; spin-drying the filtrate to obtain oil, adding water and ethyl acetate, and separating; extracting the water phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating to obtain a compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); wherein the mass ratio of the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane to the 3-bromopropene is 1: (2-6).
3) Under the action of a reducing agent, reacting a compound (3)5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) with a mixed solution of ammonium chloride to obtain a target product compound (4), namely 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline); specifically, a reducing agent is added into ethanol, then ammonium chloride and water are sequentially added to obtain an ammonium chloride mixed solution, and then the temperature is raised to 75-85 ℃; dropwise adding an ethanol solution in which a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is dissolved into the ammonium chloride mixed solution, and fully reacting; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, washing a filter cake with ethanol, concentrating and drying the filtrate to obtain a target product compound (4), namely 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline); wherein the reducing agent is iron powder, and the mass ratio of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) to the substances reacted with ammonium chloride and iron powder is 1: (0.1-2.0): (8-15).
The preparation of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) disclosed in the present invention will be described in more detail with reference to specific examples.
The starting materials and reagents used in the examples of the present invention are commercially available, and in the present document, "at room temperature" means a temperature range of 10 ℃ to 30 ℃.
Example 1
The first step of synthesizing the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane
The compound (1), 4' - (hexafluoroisopropylidene) diphenol (130g, 0.387mol, 1eq), was added to 930mL of glacial acetic acid (975g, 16.24mol, 42eq), after the starting materials were dissolved, the reaction system was heated to 28 ℃ to 29 ℃, generally 29 ℃, which is the temperature at which the pilot reaction was initiated, and nitric acid (85.3g, 1.353mol, 3.5eq) was started. In order to reduce the danger coefficient of the reaction, the reaction is initiated firstly, and the dropping process of the nitric acid at least comprises two stages; firstly, dripping 5-10% of the total amount of nitric acid into the solution to initiate reaction, namely, slowly raising the temperature of the reaction solution when about 9g of nitric acid is dripped, raising the temperature to 32 ℃ and then not raising the temperature, and further, continuously dripping the residual nitric acid in the second stage; the reaction solution was slightly heated up to 34 ℃ during the dropwise addition. After the dropwise addition, the reaction process was monitored by LCMS and HPLC, and the reaction was carried out for 2.5 h. Pouring the reaction solution into ice water with the volume 2 times that of the reaction solution, separating out a large amount of solid, filtering, and washing a filter cake with water. The filter cake was dried in an oven at 50 ℃ to obtain 148.3g of compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, yield 90%, HPLC purity 95%.
The nuclear magnetic resonance hydrogen spectrum of the compound (2), 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane is shown in figure 1,1H NMR(600MHz,CDCl3)δ10.69(s,1H),8.22(d,J＝2.2Hz,1H),7.55(dd,J＝9.0,1.7Hz,1H),7.24(d,J＝9.1Hz,1H)。
the second step of synthesis of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene)
In a 5L reaction flask, compound (2), 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane (201g, 0.472mol, 1eq) was added to 3L acetonitrile and dissolved; potassium carbonate (390.7g, 2.83mol, 6eq) was added. Then, dropwise adding a compound 3-bromopropylene (147.2g, 1.226mol, 2.6eq), and after the dropwise adding is finished, heating to reflux, wherein the reaction temperature is in a range of 75-85 ℃; after the reaction was refluxed overnight, the reaction was filtered through celite pad after completion of the reaction by LCMS and HPLC, and the fluorescence was reduced by washing the filter cake with acetonitrile and ethyl acetate until the plate was spotted. And (3) adding about 1.3L of water into the filtrate during quick drying, adding about 1.0L of ethyl acetate, extracting for 2 times by using ethyl acetate after separating liquid, washing the organic phase once by using salt solution, drying by using anhydrous sodium sulfate, and carrying out rotary drying to obtain a black sticky solid, wherein the yield is about 220g, and the HPLC purity is 95%.
The nuclear magnetic resonance hydrogen spectrum of the compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is shown in fig. 2, 1H NMR (400MHz, cdcl3) δ 7.87(s,2H),7.52(d, J ═ 9.0Hz,2H),7.19 to 7.09(m,2H),6.12 to 5.95(m,2H),5.50(d, J ═ 17.2Hz,2H),5.37(d, J ═ 10.5Hz,2H),4.78 to 4.69(m, 4H).
The third step synthesizes compound (4)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline)
Iron powder (124.4g, 2.22mol, 10eq) was added to 1.69L of ethanol, and ammonium chloride (5.94g, 0.111mol, 0.5eq) and 337.2mL of water were added in this order to obtain an ammonium chloride mixed solution, at which time the mixed solution was warmed from 12 ℃ to 16 ℃, and then the mixed solution was warmed to 78 ℃ by heating under reflux. The compound (3), 5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) (112.4g, 0.222mol, 1eq) was dissolved in 560mL of ethanol, and then an ethanol solution of the compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) was dropped into the reaction mixture, the temperature of the reaction mixture was controlled to 78 to 83 ℃, and the temperature of the reaction mixture slightly increased during the dropping process, generally not more than 2 ℃. After the end of the dropwise addition of the compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene), the reaction was monitored by HPLC, which generally showed completion within 1.5 h. Wherein, the iron powder, the ammonium chloride and the water are added in the ethanol in sequence to improve the reaction activity and keep the reaction continuously.
In the third step, the reaction time is controlled not to exceed 1h, with the aim of reducing the formation of impurities. Meanwhile, in the reaction of the step, ammonium chloride is used as an electrolyte to participate in the reaction, and in the synthesis process, the high-concentration ammonium chloride is more beneficial to electron transfer and reducing agents, namely, iron powder is beneficial to reduction of reaction substrates to promote forward progress of the reaction; meanwhile, the ammonium chloride can provide certain acidity to prevent reaction byproducts from attaching to the surface of the reducing agent, such as iron oxide from attaching to the surface of iron powder, so that the reaction rate is increased and the reaction is kept continuously; therefore, the reaction is carried out by adopting a feeding mode of dropwise adding an ethanol solution of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) into an ammonium chloride mixed solution.
After completion of the reaction was detected, heating was stopped, the reaction solution was filtered through celite at room temperature, and the filter cake was washed with ethyl acetate. The filtrate was added with about 4L of water and brine, and about 1.5L of ethyl acetate, and after standing and separating the layers. The aqueous phase was extracted with 1L of ethyl acetate and the aqueous phase spotted onto the plate until no fluorescence was present. The organic phases were combined, washed 5 times with saturated brine, and the organic phase was dried over sodium sulfate to give about 86.5g of the target compound, 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), 87% yield and 98% purity by HPLC.
The NMR spectrum of the compound (4), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) is shown in FIG. 3,1H NMR(400MHz,cdcl3)δ6.74(dd,J＝23.9,8.7Hz,6H),6.15–5.97(m,2H),5.45–5.36(m,2H),5.28(dd,J＝10.5,1.1Hz,2H),4.56(d,J＝5.2Hz,4H),3.79(s,4H)。
example 2
The first step of synthesizing the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane
The compound (1), 4' - (hexafluoroisopropylidene) diphenol (130g, 0.387mol, 1eq), was added to 930mL of glacial acetic acid (975g, 16.24mol, 42eq), after the starting materials were dissolved, the reaction system was heated to 29 ℃ and nitric acid (48.7g, 0.773mol, 2.0eq) was started to be added in portions. The temperature of the reaction solution begins to rise slowly when about 4.87g of the first batch is dripped, the temperature does not rise after rising to 32 ℃, the nitric acid is dripped continuously in the second batch, and the temperature of the reaction solution rises slightly in the dripping process to 34 ℃ at most. After the addition was complete, the reaction was monitored by LCMS and HPLC for about 2.5 hours and worked up. Pouring the reaction solution into ice water with the volume 2 times that of the reaction solution, separating out a large amount of solid, filtering, and washing a filter cake with water. The filter cake was dried in an oven at 50 ℃ to obtain 121.5g of the compound (2), 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, in 73.7% yield and 95% purity.
The second step of synthesis of the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene)
In a 5L reaction flask, compound (2), 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane (201g, 0.472mol, 1eq) was added to 3L acetonitrile, the mixture was dissolved, potassium carbonate (390.7g, 2.83mol, 6eq) was added, compound 3-bromopropene (113g, 0.943mol, 2eq) was added dropwise, after completion of the addition, the mixture was heated to reflux, the reaction was overnight, the mixture was filtered through celite after the completion of the reaction by LCMS and HPLC, and the fluorescence was reduced when the cake was washed to the spot plate with acetonitrile and ethyl acetate. And (3) adding about 1.3L of water into the filtrate during quick drying, adding about 1.0L of ethyl acetate, extracting for 2 times by using ethyl acetate after separating liquid, washing the organic phase once by using salt water, drying by using anhydrous sodium sulfate, and spin-drying to obtain a black sticky solid with the yield of about 185g and the purity of 95%.
The third step synthesizes compound (4)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline)
Iron powder (124.4g, 2.22mol, 10eq) was added to 1.69l of ethanol, ammonium chloride (11.88g, 0.222mol, 1eq) was added, and 337.2mL of water were added, whereupon the reaction solution was warmed from 12 ℃ to 16 ℃ and then heated to reflux (78 ℃). The compound (3), 5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) (112.4g, 0.222mol, 1eq) was dissolved in 560mL of ethanol, and then a mixture of the compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) and ethanol was dropped into the reaction mixture, the temperature of the reaction mixture was controlled to 78 to 83 ℃, and the temperature of the reaction mixture slightly increased during the dropping process, generally not more than 2 ℃. After the completion of dropwise addition of the compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene), completion of the reaction was monitored by HPLC.
After completion of the reaction was detected, heating was stopped, and the reaction mixture was filtered through celite at about 30 ℃ to wash the filter cake with ethyl acetate. The filtrate was added with about 4L of water and brine, and about 1.5L of ethyl acetate, and after standing and separating the layers. The aqueous phase was extracted with 1L ethyl acetate and spotted on a plate until no fluorescence was observed. The organic phases were combined, washed 5 times with saturated brine, and the organic phase was dried over sodium sulfate to give about 63g of the compound (4), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline), yield 63%, purity 98%.
Examples 3, 4 differ from example 1 only in the amount ratio of the substance in which the compound (1)4, 4' - (hexafluoroisopropylidene) diphenol reacts with nitric acid; examples 5, 6 differ from example 1 only in the amount ratio of the substance in which the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane is reacted with 3-bromopropene; examples 7 and 8 differ from example 1 only in the amount ratio of the substances in which the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is reacted with ammonium chloride; examples 9 and 10 differ from example 1 only in the amount ratio of the substance in which the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacts with iron powder; the target products obtained in the examples are shown in table 1 below.
TABLE 1 reaction conditions for the preparation of Compound (4) and product yield
Examples 2 to 4 the amount of nitric acid used was changed from example 1; in example 3, the amount of nitric acid is increased, the obtained reaction yield is not much different from that of example 1, however, the increase of the amount of nitric acid increases the risk of the reaction and reduces the safety factor of the reaction; example 4 reduces the amount of nitric acid used, reduces the reaction rate of the electrophilic substitution reaction, and reduces the reaction yield.
Examples 5 and 6 varied the amount of 3-bromopropene compared to example 1; in example 5, compared with example 1, the amount of 3-bromopropylene is reduced, the reaction rate of the reaction is slowed down, and the reaction yield is reduced; example 6 compared with example 1, the amount of 3-bromopropene is increased, the occurrence of side reactions is promoted, and the reaction yield is also reduced.
Examples 7 to 8 the amount of ammonium chloride was changed from example 1; in example 7, the amount of ammonium chloride is reduced, which is not beneficial to electron transfer in the reaction, and the acidity provided by the ammonium chloride in the amount is not enough to avoid the adhesion of iron oxide on the iron surface, so that the forward progress of the reaction is hindered, and the reaction yield is reduced; in example 8, the amount of ammonium chloride used was further increased in addition to example 1, so that the side reaction of the reaction was increased, the reaction was complicated, and the reaction yield was lowered.
Examples 9 and 10 the amount of iron powder was changed from example 1; in example 9, the amount of iron powder used was reduced, the rate of the main reaction was reduced, and the occurrence of side reactions was promoted, increasing impurities, and decreasing the reaction yield; in example 10, the amount of iron powder was increased, and since the amount of iron powder was increased, part of the product remained on the cake during filtration, which made it difficult to clean the cake, and the reaction yield was lowered, and the difficulty of the post-reaction treatment was increased.
In summary, the preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) disclosed by the invention has the advantages of mild overall reaction conditions, low reaction risk coefficient and simple post-reaction treatment and purification processes; under the preferable reaction conditions, as in example 1, the side reaction impurities are less, the comprehensive yield of the product reaches more than 80%, and the product purity is high.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (10)
1. The preparation method of 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) is characterized by comprising the following synthetic route:
the specific synthesis steps comprise:
1) carrying out nitration reaction on 4, 4' - (hexafluoroisopropylidene) diphenol in a compound (1) in a first organic solvent to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane;
2) reacting the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane with 3-bromopropene in a second organic solvent in a basic environment to obtain a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene);
3) under the action of a reducing agent, the compound (3)5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacts with a mixed solution of ammonium chloride to obtain a target product compound (4)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline).
2. The method for preparing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 1, wherein the reaction process of the step 1) is:
dissolving a compound (1), 4' - (hexafluoroisopropylidene) diphenol in a first organic solvent, dropwise adding nitric acid into the solution when the temperature of the solution reaches 25-35 ℃, and stirring until the reaction is finished; after the reaction is finished, pouring the reaction liquid into ice water, filtering, washing a filter cake with water, and drying to obtain a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane; wherein the first organic solvent is glacial acetic acid.
3. The method for preparing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 1, wherein the reaction process of the step 2) is:
adding a compound (2), namely 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane into a second organic solvent, sequentially adding potassium carbonate and 3-bromopropylene into the solution, heating the reaction solution to 75-85 ℃, and fully reacting; after the reaction is finished, filtering the reaction solution; spin-drying the filtrate to obtain oil, adding water and ethyl acetate, and separating; extracting the water phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating to obtain a compound (3), 5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene); wherein the second organic solvent is acetonitrile.
4. The method for preparing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 1, wherein the reaction process of the step 3) is:
adding a reducing agent into ethanol, sequentially adding ammonium chloride and water to obtain an ammonium chloride mixed solution, and heating to 75-85 ℃; dropwise adding an ethanol solution in which a compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) is dissolved into the ammonium chloride mixed solution, and fully reacting; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, washing a filter cake with ethanol, concentrating and drying the filtrate to obtain a target product compound (4), namely 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline); wherein the reducing agent is iron powder.
5. The process for producing 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 4, wherein the ethanol solution containing the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) dissolved in the step 3) is gradually added dropwise to the ammonium chloride mixed solution while controlling the reaction temperature to 78 to 83 ℃.
6. The process for producing 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 2, wherein the amount ratio of the substance obtained by reacting the compound (1)4, 4' - (hexafluoroisopropylidene) diphenol with nitric acid in the step 1) is 1: (2-15).
7. The process for preparing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 2, wherein the dropwise addition of nitric acid to the solution comprises at least two stages, each of which is:
in the first stage, when the temperature of a first organic solvent in which a compound (1), 4' - (hexafluoroisopropylidene) diphenol is dissolved is 28-29 ℃, 5-10 percent of the total amount of nitric acid is dripped into the solution to initiate reaction;
and in the second stage, after the dropwise addition in the first stage is finished, controlling the temperature of the reaction liquid of the compound (1), 4' - (hexafluoroisopropylidene) diphenol and nitric acid to be 25-35 ℃, and dropwise adding the residual nitric acid into the reaction liquid.
8. The process for producing 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 3, wherein the amount ratio of the substance obtained by reacting the compound (2)2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane with 3-bromopropene in the step 2) is 1: (2-6).
9. The method for producing 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 4, wherein the amount ratio of the substance obtained by reacting 5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) with ammonium chloride in the compound (3) in the step 3) is 1: (0.1-2.0).
10. The method for preparing 5,5'- (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) aniline) according to claim 4, wherein the amount ratio of the substance in the step 3) in which the compound (3)5,5' - (perfluoropropane-2, 2-diyl) bis (2- (allyloxy) nitrobenzene) reacts with iron powder is 1: (8-15).
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