CN103360225A - Method for preparing p-hydroxy phenyl ethyl ketone compound through rearrangement reaction under catalysis of acidic ionic liquid - Google Patents
Method for preparing p-hydroxy phenyl ethyl ketone compound through rearrangement reaction under catalysis of acidic ionic liquid Download PDFInfo
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- CN103360225A CN103360225A CN2013102643078A CN201310264307A CN103360225A CN 103360225 A CN103360225 A CN 103360225A CN 2013102643078 A CN2013102643078 A CN 2013102643078A CN 201310264307 A CN201310264307 A CN 201310264307A CN 103360225 A CN103360225 A CN 103360225A
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- ophenone
- parahydroxyacet
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title abstract description 4
- -1 p-hydroxy phenyl ethyl ketone compound Chemical class 0.000 title abstract description 4
- 238000006462 rearrangement reaction Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940049953 phenylacetate Drugs 0.000 claims abstract description 15
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005618 Fries rearrangement reaction Methods 0.000 claims abstract description 12
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical class CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 claims description 45
- 150000002500 ions Chemical class 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 21
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 2
- KDUWXMIHHIVXER-UHFFFAOYSA-N 2'-hydroxypropiophenone Chemical compound CCC(=O)C1=CC=CC=C1O KDUWXMIHHIVXER-UHFFFAOYSA-N 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- RARSHUDCJQSEFJ-UHFFFAOYSA-N p-Hydroxypropiophenone Chemical compound CCC(=O)C1=CC=C(O)C=C1 RARSHUDCJQSEFJ-UHFFFAOYSA-N 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 10
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007867 post-reaction treatment Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MXJWRABVEGLYDG-UHFFFAOYSA-N bufexamac Chemical compound CCCCOC1=CC=C(CC(=O)NO)C=C1 MXJWRABVEGLYDG-UHFFFAOYSA-N 0.000 description 2
- 229960000962 bufexamac Drugs 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical class CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YABILUBVQMTVNU-UHFFFAOYSA-N FC(F)F.N1=C(C=CC=C1)C Chemical compound FC(F)F.N1=C(C=CC=C1)C YABILUBVQMTVNU-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 239000000924 antiasthmatic agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 239000000731 choleretic agent Substances 0.000 description 1
- 230000001989 choleretic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229960002052 salbutamol Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing a p-hydroxy phenyl ethyl ketone compound through Fries rearrangement reaction under catalysis of an acidic ionic liquid. The method comprises the following steps of: directly adding phenyl acetate to the ionic liquid, wherein the dosage of the ionic liquid is 10%-40% of the mole number of oligomers; next, reacting for 12-18 hours at a temperature ranging from 60 to 120 DEG C, thus obtaining p-hydroxy phenyl ethyl ketone without o-hydroxy phenyl ethyl ketone type product through extraction, drying and reduced pressure distillation. The ionic liquid applied to the method is used as a solvent and a catalyst, and is high in catalytic activity and selectivity; the dosage of the catalyst is low and the reaction yield is high; the use of other organic solvent and toxic catalyst is reduced, so that the corrosivity of the catalyst to equipment is reduced; the aftertreatment is simple and convenient.
Description
Technical field
The present invention relates to the method that a kind of catalysis prepares the parahydroxyacet-ophenone compounds, more particularly, relate to a kind of acidic ion liquid that utilizes and pass through the method that Fries rearrangement reaction catalysis generates the parahydroxyacet-ophenone compounds.
Background technology
The parahydroxyacet-ophenone of present method gained is the important synthon in the organic synthesis, is the important manufacturing important intermediate of Organic Chemicals, pharmaceutical industry and spices.For example, parahydroxyacet-ophenone can be used for the synthetic of medicine intermediate and fodder additives, such as choleretic and the husky butanolamine (Salbutamol) of anti-asthmatic, antiphlogistic drug bufexamac (Bufexamac) etc.
The Fries rearrangement method be the most frequently used preparation to hydroxyaryl ketone compounds approach, the catalyzer that traditional Fries rearrangement method is selected is AlCl
3, the protonic acid homogeneous catalyst such as the Lewis acid such as fluoroform sulphonate or trifluoromethanesulfonic acid.Yet these catalyzer self have higher toxicity and volatility, and instrument and equipment is had severe corrosive; The consumption of catalyzer is excessive, and the costliness of price is not suitable for industrial production; May produce corrosive gases and a large amount of waste liquid in the post-reaction treatment process, cause serious environmental pollution; The simultaneous reactions system need to be carried out in the high carcinogenic solvents such as chlorobenzene at benzene, therefore the people is known from experience and causes very major injury.
In recent years, along with the aggravation of environmental problem, the researchist has turned to the visual field solid acid catalyst and the loaded catalyst of high-efficiency cleaning.Successively there are the catalyzer such as molecular sieve, acid clay, heteropolyacid, Zeo-karb, binary solid acid to be used for the Fries rearrangement reaction.It is lower that this type of catalyzer obtains the parahydroxyacet-ophenone productive rate, and the adjacency pair position selectivity of product is relatively poor.
In the past few decades, ionic liquid (ionic liquid) is because its unique character more and more receives people's concern.It is low, non-volatile that ionic liquid often has a fusing point, liquid journey wide ranges, and Heat stability is good, dissolving power is strong, and character is adjustable, and nonflammable grade is different from the character of conventional solvent.Jitendra
[1]With Katkevica etc.
[2]Improved the transformation efficiency that Fries resets with ionic liquid as solvent or catalyzer, but the less stable of this type of ionic liquid.Yet adopt Br nsted acid ion liquid catalyst Fries to reset the method for preparing the parahydroxyacet-ophenone compounds and yet there are no report.
Reference:
[1]?Jitendra?R.?Harjani,?Susheel?J.?Nara,?Manikroa?M.?Salunkhe,?Fries?rearrangement?in?ionic?melts.?Tertahedron?Lett.,?2001,?42,?1979-1981。
[2]?S.?Katkevica,?A.?Zicmanis,?P.?Mekss,?Imidazolium?and?Pyridinium?Salts–Solvents?Influencing?the?Rate?and?Direction?of?the?Fries,?Beckmann,?and?Claisen?Rearrangements.?Chemistry?of?Heterocyclic?Compounds,?2010,?46(2),?158-169。
Summary of the invention
The objective of the invention is large for the catalyst toxicity that exists in the current techniques, corrodibility is high, environmental pollution is serious, poor catalyst stability and the deficiency such as be difficult to reuse, and a kind of acidic ionic liquid catalysts of resetting preparation parahydroxyacet-ophenone compounds for Fries is provided.This catalyzer has the advantages such as higher catalytic activity, selectivity and stability.
Reaction expression is:
R is methyl, methoxyl group, bromine, chlorine, the benzene of different the position of substitution.
Technical scheme of the present invention is: prepare the processing method of parahydroxyacet-ophenone compounds with IL presence of acidic ionic liquid catalyst Fries rearrangement reaction, may further comprise the steps:
(1) use phenylacetate as reactant, as catalyzer, do not need to add other solvent with acidic ion liquid, the acidic ion liquid consumption is 10%～400% mol of phenylacetate;
(2) be to be 12-18h in the 60-120 ℃ lower reaction times in temperature of reaction, after reaction finished, directly thin up was used ethyl acetate extraction, drying, and underpressure distillation obtains parahydroxyacet-ophenone.White crystal, fusing point are 109-110 ℃.
The described acidic ionic liquid catalysts of described step (1) is Br nsted acidic ion liquid.
Described Br nsted acidic ion liquid is imidazoles Br nsted acidic ion liquid, pyridines Br nsted acidic ion liquid, quaternary ammonium salt Br nsted acidic ion liquid or quaternary phosphonium salt Br nsted acidic ion liquid;
The negatively charged ion of described Br nsted acidic ion liquid is the trifluoromethanesulfonic acid root, changes cationic kind and all has catalytic effect, and still along with the change of cation type, the productive rate of parahydroxyacet-ophenone is also along with change.
Described Br nsted acidic ion liquid general structure is expressed as follows:
R1 in the following formula, R2, R3, R4 is for cationic four substituting groups in the ionic liquid select carbon number at alkane or the aromatic hydrocarbons of 1-14;
The present invention prepares parahydroxyacet-ophenone technique with tradition and compares, and have the following advantages: it is strong that acidic ion liquid is done catalyst stability, non-volatile, and catalytic activity is high, and selectivity is single-minded; Do not need to add other solvent in the reaction process; During post-reaction treatment, do not need hcl acidifying, simple and convenient.Reaction system does not need to add other solvent, and ionic liquid serves as reaction solvent simultaneously; During post-reaction treatment, do not need to add the acidifyings such as hydrochloric acid, directly extraction, drying, underpressure distillation can obtain parahydroxyacet-ophenone; Products therefrom is parahydroxyacet-ophenone compounds and generating without the o-hydroxyacetophenone compounds, and reaction preference is high.
Embodiment
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, and under the scope of described aim, change is included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add 5mmol's
N-ethyl imidazol(e) fluoroform sulphonate ionic liquid, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 18%.
Embodiment 2
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the 2-picoline fluoroform sulphonate ionic liquid of 5mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 16%.
Embodiment 3
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the tri-n-octyl amine fluoroform sulphonate ionic liquid of 5mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 40%.
Embodiment 4
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 5mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 54%.
Embodiment 5
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 5mmol, stopped reaction behind 60 ℃ of lower stirring reaction 18h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 53%.
Embodiment 6
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 5mmol, stopped reaction behind 120 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 40%.
Embodiment 7
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 2.5mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 36%.
Embodiment 8
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 10mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 75%.
Embodiment 9
Experimental technique: the phenylacetate of 5mmol is added in the 25mL single port flask, add the two fluoroform sulphonate ionic liquids of triphenylphosphine of 15mmol, stopped reaction behind 60 ℃ of lower stirring reaction 12h.Add the dilution of 2mL water, behind 2mL ethyl acetate extraction three times, with the anhydrous MgSO of ethyl acetate layer
4Drying, underpressure distillation obtains parahydroxyacet-ophenone, and yield is 63%.
Claims (4)
1. presence of acidic ionic liquid catalyst Fries rearrangement reaction prepares the method for parahydroxyacet-ophenone compounds, it is characterized in that the Fries rearrangement reaction of presence of acidic ionic liquid catalyst phenylacetate, carries out according to following step:
(1) use phenylacetate as reactant, as catalyzer, the ionic liquid consumption is 10%～400% mol of phenylacetate with the acidic ion liquid of imidazoles or quaternary ammonium salt or quaternary alkylphosphonium salt;
(2) be to be 12-18h in the 60-120 ℃ lower reaction times in temperature of reaction, after reaction finished, directly thin up was used ethyl acetate extraction, drying, and underpressure distillation obtains parahydroxyacet-ophenone, and white crystal, fusing point are 109-110 ℃.
2. presence of acidic ionic liquid catalyst Fries rearrangement reaction prepares the method for parahydroxyacet-ophenone compounds as claimed in claim 1, it is characterized in that described acidic ionic liquid catalysts is Br nsted acidic ion liquid.
3. presence of acidic ionic liquid catalyst Fries rearrangement reaction prepares the method for parahydroxyacet-ophenone compounds as claimed in claim 2, it is characterized in that described Br nsted acidic ion liquid is imidazoles Br nsted acidic ion liquid, pyridines Br nsted acidic ion liquid, quaternary ammonium salt Br nsted acidic ion liquid or quaternary phosphonium salt Br nsted acidic ion liquid.
4. presence of acidic ionic liquid catalyst Fries rearrangement reaction prepares the method for parahydroxyacet-ophenone compounds as claimed in claim 3, the negatively charged ion that it is characterized in that described Br nsted acidic ion liquid is the trifluoromethanesulfonic acid root, and described Br nsted acidic ion liquid general structure is expressed as follows:
R1 in the following formula, R2, R3, R4 is for cationic four substituting groups in the ionic liquid select carbon number at alkane or the aromatic hydrocarbons of 1-14.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896810A (en) * | 2014-04-04 | 2014-07-02 | 湖南迪诺制药有限公司 | Synthesis method of bufexamac |
| CN105130781A (en) * | 2015-08-20 | 2015-12-09 | 上海应用技术学院 | Preparation method of 2-hydroxyacetophenone |
| CN105661040A (en) * | 2016-02-29 | 2016-06-15 | 湖南晶天科技实业有限公司 | Feed additive and feed |
| CN106167449A (en) * | 2016-07-24 | 2016-11-30 | 遵义师范学院 | A kind of synthetic method of parahydroxyacet-ophenone |
| CN109180447A (en) * | 2018-10-18 | 2019-01-11 | 大连大学 | A kind of synthetic method of parahydroxyacet-ophenone class compound |
| CN109369322A (en) * | 2018-12-18 | 2019-02-22 | 大连大学 | A kind of acidic ion liquid [PPh3][TfOH]2The method that catalysis prepares cyclohexyl benzene |
| CN109369359A (en) * | 2018-12-24 | 2019-02-22 | 浙江工业大学 | A method of preparing parahydroxyacet-ophenone |
| KR20200082514A (en) * | 2018-12-28 | 2020-07-08 | 노승호 | Method for preparing p-Hydroxyacetophenone and cosmetic composition containing p-Hydroxyacetophenone |
| CN115368226A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Hydroxy arone and preparation method thereof |
-
2013
- 2013-06-28 CN CN201310264307.8A patent/CN103360225B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| JITENDRA R. HARJANI ET AL: "Fries rearrangement in ionic melts", 《TETRAHEDRON LETTERS》 * |
| 吕丽莉: "乙酸苯酯 Fries重排反应的研究", 《万方学位论文数据库》 * |
| 姜红波: "咪唑类离子液体及其催化有机重排反应", 《化工时刊》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896810A (en) * | 2014-04-04 | 2014-07-02 | 湖南迪诺制药有限公司 | Synthesis method of bufexamac |
| CN103896810B (en) * | 2014-04-04 | 2015-09-16 | 湖南迪诺制药有限公司 | The synthetic method of bufexamac |
| CN105130781A (en) * | 2015-08-20 | 2015-12-09 | 上海应用技术学院 | Preparation method of 2-hydroxyacetophenone |
| CN105661040A (en) * | 2016-02-29 | 2016-06-15 | 湖南晶天科技实业有限公司 | Feed additive and feed |
| CN106167449A (en) * | 2016-07-24 | 2016-11-30 | 遵义师范学院 | A kind of synthetic method of parahydroxyacet-ophenone |
| CN106167449B (en) * | 2016-07-24 | 2018-07-03 | 遵义师范学院 | A kind of synthetic method of parahydroxyacet-ophenone |
| CN109180447A (en) * | 2018-10-18 | 2019-01-11 | 大连大学 | A kind of synthetic method of parahydroxyacet-ophenone class compound |
| CN109369322A (en) * | 2018-12-18 | 2019-02-22 | 大连大学 | A kind of acidic ion liquid [PPh3][TfOH]2The method that catalysis prepares cyclohexyl benzene |
| CN109369359A (en) * | 2018-12-24 | 2019-02-22 | 浙江工业大学 | A method of preparing parahydroxyacet-ophenone |
| KR20200082514A (en) * | 2018-12-28 | 2020-07-08 | 노승호 | Method for preparing p-Hydroxyacetophenone and cosmetic composition containing p-Hydroxyacetophenone |
| KR102195387B1 (en) * | 2018-12-28 | 2020-12-24 | 노승호 | Method for preparing p-Hydroxyacetophenone |
| CN115368226A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Hydroxy arone and preparation method thereof |
| CN115368226B (en) * | 2021-05-19 | 2024-05-28 | 中国石油化工股份有限公司 | Hydroxy aryl ketone and preparation method thereof |
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