CN117820117A - Preparation method of p-acetoxystyrene - Google Patents
Preparation method of p-acetoxystyrene Download PDFInfo
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- CN117820117A CN117820117A CN202310748435.3A CN202310748435A CN117820117A CN 117820117 A CN117820117 A CN 117820117A CN 202310748435 A CN202310748435 A CN 202310748435A CN 117820117 A CN117820117 A CN 117820117A
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- acetoxystyrene
- phosphoric acid
- phenyl
- organic phosphoric
- acetate
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- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 40
- VZOVSXXHXIMTQX-UHFFFAOYSA-N [4-(1-hydroxyethyl)phenyl] acetate Chemical compound CC(O)C1=CC=C(OC(C)=O)C=C1 VZOVSXXHXIMTQX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 13
- FUGYGGDSWSUORM-UHFFFAOYSA-N para-hydroxystyrene Natural products OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical group CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012024 dehydrating agents Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of p-acetoxystyrene, which comprises the following steps: mixing and fully reacting the [4- (1-hydroxyethyl) phenyl ] acetate, the organic phosphoric acid and the polymerization inhibitor to obtain the required parahydroxystyrene. The preparation method of the p-acetoxystyrene realizes the preparation of the p-acetoxystyrene by adopting the organic phosphoric acid as the catalyst for the dehydration reaction of the [4- (1-hydroxyethyl) phenyl ] acetate. Compared with the traditional preparation method of the p-acetoxystyrene, the preparation method of the p-acetoxystyrene does not need a large amount of applied acid and alkaline dehydrating agents, less waste water is generated, and the organic phosphoric acid catalyst can be recycled. Therefore, the preparation method of the p-acetoxystyrene has the advantages of less three wastes, high yield, green and clean property and the like, and has good application value.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of p-acetoxystyrene.
Background
Polymers of p-hydroxystyrene (PHS) and its derivatives are widely used in solid phase synthesis, phase transfer catalysis, permselective membranes, epoxy resin curing agents, radical scavengers and antioxidants, photoresists (also known as photoresists), and the like. 248nm deep ultraviolet photoresist is a mainstream photoresist product in the world at present, and is one of key materials for manufacturing a photoetching integrated circuit and a chip. Wherein, the p-acetoxyl styrene is a core monomer of 248nm photoresist main film forming resin material, thus optimizing the synthesis method and synthesis process condition of the p-acetoxyl styrene has important value.
In the current synthetic route of p-hydroxystyrene, dehydration of [4- (1-hydroxyethyl) phenyl ] acetate under certain conditions is the most important method.
In 1958, corson et al reported a dehydration process of potassium bisulfate or activated alumina as a dehydrating agent, p-tert-butylcatechol as a polymerization inhibitor (J.org.chem.1958, 23,544). Improved processes for the above-described processes are reported in US5151546a and US5245074a by hessian, where the dehydration reaction is carried out in a continuous or semi-continuous manner in a thin film evaporator. Meanwhile, a method of using phosphoric acid as a dehydrating agent is reported in US5041614a patent. CN102795999a patent discloses a method for synthesizing acetoxystyrene by using [4- (1-hydroxyethyl) phenyl ] acetate as dehydrating agent in hydrochloric acid, sulfuric acid, phosphorus trichloride, etc. CN110655462a patent discloses a synthetic method of an alkaline acid binding agent as a dehydrating agent. CN111087303a discloses a method for synthesizing solid acid as dehydrating agent, and preparing p-acetoxystyrene by one-pot boiling in the presence of polymerization inhibitor.
However, the above conventional method for preparing p-hydroxystyrene by dehydrating [4- (1-hydroxyethyl) phenyl ] acetate requires a large amount of acidic and alkaline dehydrating agents, often generates much wastewater, and is less environmentally friendly.
Disclosure of Invention
Based on this, it is necessary to provide a method for producing p-acetoxystyrene which can solve the above-mentioned problems.
A method for preparing p-acetoxystyrene, comprising the following steps:
mixing and fully reacting [4- (1-hydroxyethyl) phenyl ] acetate, organic phosphoric acid and a polymerization inhibitor to obtain the required p-hydroxystyrene, wherein the reaction formula is as follows:
in one embodiment, the organophosphate is a compound having structural formula I or structural formula II:
wherein R is H, phenyl, trifluoromethyl substituted phenyl, ditrifluoromethyl substituted phenyl, halogen substituted phenyl, methyl substituted phenyl or dimethyl substituted phenyl.
In one embodiment, the organic phosphoric acid is one of the compounds having the following structural formula:
in one embodiment, the molar ratio of the organophosphate to the para [4- (1-hydroxyethyl) phenyl ] acetate is from 0.05 to 0.5:100.
in one embodiment, the molar ratio of the organophosphate to the para [4- (1-hydroxyethyl) phenyl ] acetate is 0.1:100.
in one embodiment, the method further comprises the operation of recovering the organic phosphoric acid in the reactant after the operation of obtaining the parahydroxystyrene.
In one embodiment, the operation of recovering the organic phosphoric acid in the reactant is: the reactant is distilled under reduced pressure, and after the p-acetoxystyrene is distilled off, the volume ratio is 0.5 to 5:10, fully mixing distillation residual liquid and water, regulating the pH to 14, separating to obtain a first aqueous phase and a first organic phase, regulating the pH of the first aqueous phase to 3, adding ethyl acetate into the first aqueous phase for extraction, separating again to obtain a second aqueous phase and a second organic phase after extraction is finished, adding a drying agent into the second organic phase, concentrating under reduced pressure, and recovering to obtain the organic phosphoric acid.
In one embodiment, the polymerization inhibitor is para-tertiary butyl catechol, and the molar ratio of the polymerization inhibitor to the para [4- (1-hydroxyethyl) phenyl ] acetate is from 0.05 to 2:100.
in one embodiment, in the operation of sufficiently reacting the [4- (1-hydroxyethyl) phenyl ] acetate, the organic phosphoric acid and the polymerization inhibitor after mixing, the reaction temperature is 80-100 ℃ and the reaction time is 1-3 h.
In one embodiment, the molar ratio of the polymerization inhibitor to the p [4- (1-hydroxyethyl) phenyl ] acetate is 1:100;
the preparation method of the p-acetoxystyrene realizes the preparation of the p-acetoxystyrene by adopting the organic phosphoric acid as the catalyst for the dehydration reaction of the [4- (1-hydroxyethyl) phenyl ] acetate.
Compared with the traditional preparation method of the p-acetoxystyrene, the preparation method of the p-acetoxystyrene does not need a large amount of applied acid and alkaline dehydrating agents, less waste water is generated, and the organic phosphoric acid catalyst can be recycled.
Therefore, the preparation method of the p-acetoxystyrene has the advantages of less three wastes, high yield, green and clean property and the like, and has good application value.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship between the members, the movement condition, etc. in a specific posture, and if the specific posture is changed, the directional indicators are correspondingly changed.
Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention discloses a preparation method of p-acetoxystyrene, which comprises the following steps:
mixing and fully reacting the [4- (1-hydroxyethyl) phenyl ] acetate, the organic phosphoric acid and the polymerization inhibitor to obtain the required parahydroxystyrene.
The reaction formula of the above reaction is as follows:
the preparation method of the p-acetoxystyrene realizes the preparation of the p-acetoxystyrene by adopting the organic phosphoric acid as the catalyst for the dehydration reaction of the [4- (1-hydroxyethyl) phenyl ] acetate.
Compared with the traditional preparation method of the p-acetoxystyrene, the preparation method of the p-acetoxystyrene does not need a large amount of applied acid and alkaline dehydrating agents, less waste water is generated, and the organic phosphoric acid catalyst can be recycled.
Therefore, the preparation method of the p-acetoxystyrene has the advantages of less three wastes, high yield, green and clean property and the like, and has good application value.
Preferably, the organic phosphoric acid is a compound having the following structural formula I or structural formula II:
wherein R is H, phenyl, trifluoromethyl substituted phenyl, ditrifluoromethyl substituted phenyl, halogen substituted phenyl, methyl substituted phenyl or dimethyl substituted phenyl.
Specifically, in the present embodiment, the organic phosphoric acid is one of compounds having the following structural formula:
preferably, in this embodiment, the molar ratio of the organic phosphoric acid to the [4- (1-hydroxyethyl) phenyl ] acetate is 0.05 to 0.5:100.
more preferably, in this embodiment, the molar ratio of the organic phosphoric acid to [4- (1-hydroxyethyl) phenyl ] acetate is 0.1:100.
in this embodiment, the organic solvent may or may not be added in the operation of sufficiently reacting the [4- (1-hydroxyethyl) phenyl ] acetate, the organic phosphoric acid, and the polymerization inhibitor after mixing them.
Specifically, the organic solvent may be toluene.
Preferably, this embodiment further includes an operation of recovering the organic phosphoric acid in the reactant after the operation of obtaining p-hydroxystyrene.
Specifically, the operation of recovering the organic phosphoric acid in the reactant is as follows: the reactant is distilled under reduced pressure, and after the p-acetoxyl styrene is distilled, the volume ratio is 0.5 to 5:10, fully mixing distillation residual liquid and water, regulating the pH value to 14, separating to obtain a first water phase and a first organic phase, regulating the pH value of the first water phase to 3, adding ethyl acetate into the first water phase for extraction, separating again to obtain a second water phase and a second organic phase after the extraction is finished, adding a drying agent into the second organic phase, concentrating under reduced pressure, and recovering to obtain the organic phosphoric acid.
The pH can be adjusted by NaOH solution and HCl solution, and the drying agent can be anhydrous sodium sulfate.
Preferably, in this embodiment, the polymerization inhibitor is p-tert-butylcatechol, and the molar ratio of the polymerization inhibitor to the [4- (1-hydroxyethyl) phenyl ] acetate is 0.05 to 2:100.
more preferably, in this embodiment, the molar ratio of the polymerization inhibitor to [4- (1-hydroxyethyl) phenyl ] acetate is 1:100.
preferably, in the present embodiment, in the operation of mixing and sufficiently reacting [4- (1-hydroxyethyl) phenyl ] acetate, an organic phosphoric acid and a polymerization inhibitor, the reaction temperature is 80 to the reflux temperature, and the reaction time is 1 to 3 hours.
More preferably, in this embodiment, the reaction temperature is from 90℃to 110℃in the operation of mixing [4- (1-hydroxyethyl) phenyl ] acetate, an organic phosphoric acid and a polymerization inhibitor and then refluxing the mixture.
Particularly preferably, in this embodiment, in the operation of mixing [4- (1-hydroxyethyl) phenyl ] acetate, an organic phosphoric acid and a polymerization inhibitor and then refluxing the mixture, the reaction temperature is 90℃and the reaction time is 2 hours.
The following are specific examples.
In specific examples, [4- (1-hydroxyethyl) phenyl ] acetate was prepared by literature methods (J.org.chem.2003, 68, 9340-9347) starting from 4-hydroxyacetophenone. 4-hydroxyacetophenone, organic phosphates A1-A6, p-tert-butylcatechol, dibromomethane, deuterated chloroform, and ethyl acetate were all purchased from Shanghai Taitan technologies Co.
Example 1
180mg (1 mmol) of [4- (1-hydroxyethyl) phenyl ] acetate, 0.2mg of p-tert-butylcatechol and 0.1mol% of organic phosphoric acid were mixed and then reacted catalytically at 90℃for 3 hours to obtain a reaction product.
The above operations are divided into 6 groups, each of which is charged with a different organic phosphoric acid A1 to A6.
After concentrating the reaction under reduced pressure, dibromomethane was added as an internal standard, deuterated chloroform was used as a solvent, and the reaction yields under different conditions were calculated by 1H NMR to give the following table 1.
TABLE 1
Example 2
In a three-necked flask, 18g (0.1 mol) [4- (1-hydroxyethyl) phenyl ] acetate, 34.8mg of binaphthol phosphate (organic phosphoric acid A2) and 16.6mg of p-tert-butylcatechol were charged, and the mixture was stirred at 90℃for 2 hours to obtain a reaction product. The reaction was distilled under reduced pressure to give 14.2g of the product with a yield of 88%.
And (3) carrying out nuclear magnetic hydrogen spectrum detection on the prepared product, wherein the nuclear magnetic hydrogen spectrum result is as follows: 1H NMR (400 MHz, CDCl 3) delta 7.50-7.40 (m, 2H), 7.17-7.05 (m, 2H), 6.80-6.65 (m, 1H), 5.76 (dd, J=17.7, 2.7Hz, 1H), 5.29 (dd, J=11.2, 2.6Hz, 1H), 2.31 (s, 3H).
By combining the nuclear magnetic resonance hydrogen spectrum results, it can be confirmed that the prepared product is p-acetoxystyrene.
The residue was added with 5mL of water, the pH was adjusted to 14 by adding 0.1N NaOH aqueous solution, the aqueous phase was separated by a separating funnel, the organic phase was washed again with 5mL of water, and the aqueous phase was further separated. The two aqueous phases were combined and 1N HCl aqueous solution was added dropwise to a pH of 3. 3mL of ethyl acetate was used for extraction, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure to recover 29.0mg of the organic phosphoric acid A2 catalyst.
Example 3
In a three-necked flask, 18g (0.1 mol) [4- (1-hydroxyethyl) phenyl ] acetate, 29.0mg of the organic phosphoric acid A2 catalyst recovered in example 2 and 16.6mg of p-tert-butylcatechol were charged, and the reaction was stirred at 90℃for 3 hours to obtain a reaction product. The reaction was distilled under reduced pressure to give 12.5g of p-acetoxystyrene with a yield of 77%.
The prepared product is p-acetoxystyrene through nuclear magnetic hydrogen spectrum characterization.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the p-acetoxystyrene is characterized by comprising the following steps:
mixing and fully reacting [4- (1-hydroxyethyl) phenyl ] acetate, organic phosphoric acid and a polymerization inhibitor to obtain the required p-hydroxystyrene, wherein the reaction formula is as follows:
2. the method for preparing p-acetoxystyrene according to claim 1, wherein the organic phosphoric acid is a compound having the following structural formula I or structural formula II:
wherein R is H, phenyl, trifluoromethyl substituted phenyl, ditrifluoromethyl substituted phenyl, halogen substituted phenyl, methyl substituted phenyl or dimethyl substituted phenyl.
3. The method for producing p-acetoxystyrene according to claim 1, wherein the organic phosphoric acid is one of compounds having the following structural formula:
4. the method for producing p-acetoxystyrene according to claim 3, wherein the molar ratio of the organic phosphoric acid to the [4- (1-hydroxyethyl) phenyl ] acetate is 0.05 to 0.5:100.
5. the method for producing p-acetoxystyrene according to claim 4, wherein the molar ratio of the organic phosphoric acid to the [4- (1-hydroxyethyl) phenyl ] acetate is 0.1:100.
6. the method for producing p-acetoxystyrene according to claim 4, further comprising an operation of recovering the organic phosphoric acid in the reactant after the operation of obtaining p-hydroxystyrene.
7. The method for producing p-acetoxystyrene according to claim 6, wherein the operation of recovering the organic phosphoric acid in the reactant is: the reactant is distilled under reduced pressure, and after the p-acetoxystyrene is distilled off, the volume ratio is 0.5 to 5:10, fully mixing distillation residual liquid and water, regulating the pH to 14, separating to obtain a first aqueous phase and a first organic phase, regulating the pH of the first aqueous phase to 3, adding ethyl acetate into the first aqueous phase for extraction, separating again to obtain a second aqueous phase and a second organic phase after extraction is finished, adding a drying agent into the second organic phase, concentrating under reduced pressure, and recovering to obtain the organic phosphoric acid.
8. The method for producing p-acetoxystyrene according to any one of claims 1 to 7, wherein the polymerization inhibitor is p-tert-butylcatechol, and the molar ratio of the polymerization inhibitor to the [4- (1-hydroxyethyl) phenyl ] acetate is 0.05 to 2:100.
9. the method for producing p-acetoxystyrene according to claim 8, wherein in the step of mixing and sufficiently reacting [4- (1-hydroxyethyl) phenyl ] acetate, an organic phosphoric acid and a polymerization inhibitor, the reaction temperature is 80 to 100 ℃ and the reaction time is 1 to 3 hours.
10. The method for producing p-acetoxystyrene according to claim 9, wherein a molar ratio of the polymerization inhibitor to the [4- (1-hydroxyethyl) phenyl ] acetate is 1:100.
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