CN101121649A - Method for preparing functional acetophenone compound - Google Patents
Method for preparing functional acetophenone compound Download PDFInfo
- Publication number
- CN101121649A CN101121649A CNA2007100704387A CN200710070438A CN101121649A CN 101121649 A CN101121649 A CN 101121649A CN A2007100704387 A CNA2007100704387 A CN A2007100704387A CN 200710070438 A CN200710070438 A CN 200710070438A CN 101121649 A CN101121649 A CN 101121649A
- Authority
- CN
- China
- Prior art keywords
- preparation
- organic solvent
- formula
- acetophenone compound
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 acetophenone compound Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- 239000002608 ionic liquid Substances 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 235000014666 liquid concentrate Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 235000019439 ethyl acetate Nutrition 0.000 abstract 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 235000008504 concentrate Nutrition 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- LBWMQVOHFPLVBY-UHFFFAOYSA-N 3,3,3-trifluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)CC(=O)C1=CC=CC=C1 LBWMQVOHFPLVBY-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- SMMIDVLUFMPWFN-UHFFFAOYSA-N 4-nitro-n-[(4-phenyldiazenylphenyl)diazenyl]aniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NN=NC1=CC=C(N=NC=2C=CC=CC=2)C=C1 SMMIDVLUFMPWFN-UHFFFAOYSA-N 0.000 description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical class C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LQASUDVYVOFKNK-UHFFFAOYSA-N 1-(3-fluoro-4-methoxyphenyl)ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1F LQASUDVYVOFKNK-UHFFFAOYSA-N 0.000 description 1
- MIZKCMSSYVUZKD-UHFFFAOYSA-N 2-chloro-5-fluorobenzoic acid Chemical class OC(=O)C1=CC(F)=CC=C1Cl MIZKCMSSYVUZKD-UHFFFAOYSA-N 0.000 description 1
- HYNNNQDQEORWEU-UHFFFAOYSA-N 3-fluoro-4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1F HYNNNQDQEORWEU-UHFFFAOYSA-N 0.000 description 1
- FQXQBFUUVCDIRK-UHFFFAOYSA-N 3-trifluoromethylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C(F)(F)F)=C1 FQXQBFUUVCDIRK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- QICQRRAHXUYAHB-UHFFFAOYSA-N benzene;formonitrile Chemical class N#C.C1=CC=CC=C1 QICQRRAHXUYAHB-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method for a functioned hypnone compound listed in the equation (I): in the ion liquid, the functioned acidum benzoicum listed in the equation (II) is taken esterifying reaction with C1-16 ester to obtain the functioned benzoic ether listed in the equation (III). The functioned benzoic ether is mixed with C1-16 ester under natrium alcohol catalyzer with benzoic ether to obtain the functioned benzoyl acetic ester listed in the equation (IV) after being condensed and then to be extracted by toluene or acetic ester or dichloromethane; after being extracted and condensed, under the acid condition, the material is to be hydrolyzed to obtain the purposed product (I); the molar ratio between alcohol and ether of acidum benzoicum is 1:1 to 3:1 to 3; R listed in the equation (I) and (II) is neighboring, near, contraposition any atom, C1-10 fatty group substituent and C1-16 aromatic series substituent. The technical scheme in the present invention has the advantages of strong composing selectivity, novel process, low cost and easy operation. The solution can be recycled so as not to pollute the environment.
Description
(1) technical field
The present invention relates to a kind of preparation method of functional acetophenone compound.
(2) background technology
Functional acetophenone compound is the important pharmaceutical intermediate of a class, is widely used in fields such as medicine, agricultural chemicals, chemical industry.The preparation method of current functional acetophenone compound mainly contains: 1, the grignard reaction of substituted benzene formonitrile HCN and methyl iodide; 2, substituted benzoic acid is after chloride, and the cadion with methyl iodide reacts again; 3, substituted benzaldehyde and diazomethane reaction; 4, substituted benzene friedel-crafts reaction etc.These synthetic method complicated operations, yield is low, and the three wastes are many.Grignard reaction, cadion, diazomethane potential safety hazard are more, and large-scale industrial is produced difficult.
In recent years, we just are being devoted to utilize the improvement research of green synthesis techniques to traditional technology, in the present invention, with functionalized phenylformic acid is raw material, in the ionic liquid reaction system, through esterification, condensation and three step of hydrolysis cascade reaction, studied the new synthetic method of preparation functional acetophenone compound.Enlarge the source of raw material, simplified technological operation, reduced raw materials cost, improved product yield, reduced the generation of the three wastes.
(3) summary of the invention
The object of the invention is to provide a kind of operational path novelty, meets the preparation method of the functional acetophenone compound of green synthesis techniques.
For reaching goal of the invention, benzene is invented by the following technical solutions:
A kind of preparation method: in ionic liquid suc as formula functional acetophenone compound shown in (I), carrying out esterification suc as formula the alcohol of functionalized phenylformic acid shown in (II) and C1～6 must be suc as formula the functionalized benzoic ether shown in (III), described functionalized benzoic ether makes suc as formula the functionalized Benzoylacetic acid ester shown in (IV) through condensation in the presence of the catalyzer sodium alkoxide with the ester of C1～6 again, hydrolysis under acidic conditions again makes target product (I); Described phenylformic acid is 1: 1～3: 1～3 with alcohol and ester amount of substance ratio, R shown in formula (I), (II) be adjacent,, contraposition arbitrary atom, the aliphatics substituting group of C1～10 and the aromatic substituents of C1～16.
Ionic liquid of the present invention is 1-alkyl-3-Methylimidazole hexafluorophosphate or 1-alkyl-3-methyl imidazolium tetrafluoroborate, and the alkyl described in 1-alkyl-3-Methylimidazole hexafluorophosphate and the 1-alkyl-3-methyl imidazolium tetrafluoroborate is the alkyl of C1～C18.
The method of the invention may further comprise the steps:
1) esterification: the alcohol of functionalized phenylformic acid shown in the adding formula (II) and C1～6 in ionic liquid, in 60～200 ℃ of reactions 1～20 hour reaction solution, described ion liquid consumption is a functionalized phenylformic acid shown in every mole of formula (II) with 100～1000 milliliters of ionic liquids;
2) condensation reaction: in step 1) gained reaction solution, add the ester and the catalyzer sodium alkoxide of C1～6, reacted 1～20 hour, concentrate concentrated solution;
3) hydrolysis reaction: in step 2) add diluted acid in the gained concentrated solution, reaction is hydrolyzed, use organic solvent extraction after the hydrolysis, described organic solvent is toluene or ethyl acetate or methylene dichloride, gets functional acetophenone compound shown in the formula (I) behind the organic layer extraction liquid concentrate drying.
Step 1) of the present invention and step 2) described reaction carries out under 60～200 ℃ of temperature separately, is preferably 100～160 ℃.Described reaction time of esterification is preferably 5～10 hours.The preferred alcohol of described step 1) esterification is ethanol.
Described step of condensation 2) ester of Jia Ruing is an ethyl acetate.
The described diluted acid of described step 3) hydrolysis reaction is recommended as hydrochloric acid or sulfuric acid, and the consumption of described diluted acid is generally 10～30% diluted acid.The recommendation consumption of organic solvent be the same volume consumption of reaction system.
Present method is strong to target compound synthetic selectivity, preparation technology's novelty, and cost is low, and is easy to operate, the recyclable utilization of solvent, environmental pollution is little.
(4) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.
The preparation of embodiment .1 m-trifluoromethyl methyl phenyl ketone
With m-trifluoromethylbenzoic acid 19 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating, 60 ℃ of reactions 20 hours, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 20 hours.After reaction finishes, cooling, with toluene 50 milliliters * 3 extractions, the toluene layer extraction liquid concentrates, and adds 30% dilute hydrochloric acid hydrolysis, uses 20 milliliters of extractions of toluene again, and the dry extraction in the dense place of toluene layer extraction liquid makes product 17 grams, yield 90%.198～202 ℃ of boiling points, purity 〉=98%, MS (m/z): 188 (M
+).
Embodiment .2 is to the preparation of trifluoromethyl acetophenone
Will be to trifluoromethylbenzoic acid 19 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stir, reflux, reacted 1 hour, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 1 hour.After reaction finishes, cooling, toluene 50 milliliters * 3 extractions concentrate, and add 30% dilute hydrochloric acid hydrolysis, and 30 milliliters of extractions of toluene make product 17.1 grams, yield 91%.30～32 ℃ of fusing points, purity 〉=98%, MS (m/z): 188 (M
+).
Embodiment .3 3, the preparation of 5-two (trifluoromethyl) methyl phenyl ketone
With 3,5-two (trifluoromethyl) phenylformic acid 25.8 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating 100 ℃ of reactions 4 hours, adds the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours, after reaction finishes, cooling, ethyl acetate 50 milliliters * 3 extractions, concentrate, the dilute sulphuric acid hydrolysis of adding 30%, 20 milliliters of extractions of ethyl acetate make product 20.7 grams, yield 82%.185～188 ℃ of boiling points, purity 〉=98%, MS (m/z): 256 (M
+).
Embodiment .4 2, the preparation of 4-two chloro-5-fluoro acetophenones
With 2,4-two chloro-5-fluorobenzoic acids 20.9 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating was 60 ℃ of reactions 4 hours, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours.After reaction finishes, cooling, methylene dichloride 50 milliliters * 3 extractions concentrate, and add 30% dilute sulphuric acid hydrolysis, and 20 milliliters of extractions of methylene dichloride make product 18.2 grams, yield 88%.30 ℃ of fusing points, purity 〉=98%, MS (m/z): 207 (M
+).
The preparation of embodiment .5 o-hydroxyacetophenone
With salicylic acid 13.8 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating, 120 ℃ of reactions 6 hours, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours.After reaction finishes, cooling, toluene 50 milliliters * 3 extractions concentrate, and add 30% dilute sulphuric acid hydrolysis, and 20 milliliters of extractions of toluene make product 12.2 grams, yield 90%.109～110 ℃ of fusing points, purity 〉=98%, MS (m/z): 136 (M
+).
The preparation of the adjacent thiophenyl methyl phenyl ketone of embodiment .6
With adjacent thiophenyl phenylformic acid 23 grams (0.1 mole), ethanol 14 grams (0.3 mole), 100 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating, 200 ℃ of reactions 1 hour, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours.After reaction finishes, cooling, toluene 50 milliliters * 3 extractions concentrate, and add 30% dilute sulphuric acid hydrolysis, and 20 milliliters of extractions of toluene make product 19.6 grams, yield 84%.70～72 ℃ of fusing points, purity 〉=98%, MS (m/z): 228 (M
+).
The preparation of embodiment .7 p-methoxy-acetophenone
With anisic acid 15.2 grams (0.1 mole), ethanol 14 grams (0.3 mole), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating, 120 ℃ of reactions 10 hours, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours.After reaction finishes, cooling, methylene dichloride 50 milliliters * 3 extractions concentrate, and add 30% dilute sulphuric acid hydrolysis, and 20 milliliters of extractions of methylene dichloride make product 13.6 grams, yield 89%.36～38 ℃ of fusing points, purity 〉=98%, MS (m/z): 150 (M
+).
The preparation of embodiment .8 3-fluoro-4-methoxyacetophenone
With 3-fluoro-4-methoxybenzoic acid 17 grams (0.1 mole), ethanol 14 grams (0.3 mole), 100 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, stirring heating, 100 ℃ of reactions 20 hours, add the sodium ethylate of ethyl acetate 18 grams (0.2 mole) and catalytic amount, continue reaction 4 hours.After reaction finishes, cooling, toluene 50 milliliters * 3 extractions concentrate, and add 30% dilute sulphuric acid hydrolysis, and 20 milliliters of extractions of toluene make product 15 grams, yield 90%.90～91 ℃ of fusing points, purity 〉=98%, MS (m/z): 168 (M
+).
Claims (7)
1. preparation method suc as formula functional acetophenone compound shown in (I), it is characterized in that described method is in ionic liquid, carrying out esterification suc as formula the alcohol of functionalized phenylformic acid shown in (II) and C1～6 must be suc as formula the functionalized benzoic ether shown in (III), described functionalized benzoic ether makes suc as formula the functionalized Benzoylacetic acid ester shown in (IV) through condensation in the presence of the catalyzer sodium alkoxide with the ester of C1～6 again, use organic solvent extraction again, described organic solvent is toluene or ethyl acetate or methylene dichloride, after the organic solvent layer extraction liquid concentrates, hydrolysis under acidic conditions makes target product (I); Described phenylformic acid is 1: 1～3: 1～3 with the alcohol of C1～6 and the ester amount of substance ratio of C1～6, R shown in the formula respectively do for oneself the neighbour,, contraposition arbitrary atom or the aliphatics substituting group of C1～10 or the aromatic substituents of C1～16.
2. the preparation method of functional acetophenone compound as claimed in claim 1, it is characterized in that described ionic liquid is 1-alkyl-3-Methylimidazole hexafluorophosphate or 1-alkyl-3-methyl imidazolium tetrafluoroborate, the alkyl described in 1-alkyl-3-Methylimidazole hexafluorophosphate and the 1-alkyl-3-methyl imidazolium tetrafluoroborate is the alkyl of C1～C18.
3. the preparation method of functional acetophenone compound as claimed in claim 1, it is characterized in that said method comprising the steps of: 1) esterification: the alcohol of functionalized phenylformic acid shown in the adding formula (II) and C1～6 in ionic liquid, stir, in 60～200 ℃ of reactions 1～20 hour reaction solution, described ion liquid consumption is a functionalized phenylformic acid shown in every mole of formula (II) with 100～1000 milliliters of ionic liquids;
2) condensation reaction: the ester and the catalyzer sodium alkoxide that in step 1) gained reaction solution, add C1～6, stir, in 60～200 ℃ of reactions 1～20 hour, cooling back organic solvent extraction, described organic solvent is toluene or ethyl acetate or methylene dichloride, the organic solvent layer extraction liquid concentrate concentrated solution;
3) hydrolysis reaction: in step 2) add 30% dilute hydrochloric acid or sulfuric acid in the gained concentrated solution, reaction is hydrolyzed, use organic solvent extraction after the hydrolysis again, described organic solvent is toluene or ethyl acetate or methylene dichloride, gets functional acetophenone compound shown in the formula (I) behind the organic layer extraction liquid concentrate drying.
4. as the preparation method of functional acetophenone compound as described in the claim 3, it is characterized in that the described reaction time of esterification of step 1) is 5～10 hours.
5. as the preparation method of functional acetophenone compound as described in the claim 3, it is characterized in that the alcohol that the step 1) esterification adds C1～6 is ethanol.
6. as the preparation method of functional acetophenone compound as described in the claim 3, it is characterized in that the ester that the step 1) condensation reaction adds C1～6 is an ethyl acetate.
7. as the preparation method of functional acetophenone compound as described in the claim 3, it is characterized in that described step 2) the consumption of organic solvent be 150 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710070438A CN101121649B (en) | 2007-08-01 | 2007-08-01 | Method for preparing functional acetophenone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710070438A CN101121649B (en) | 2007-08-01 | 2007-08-01 | Method for preparing functional acetophenone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101121649A true CN101121649A (en) | 2008-02-13 |
| CN101121649B CN101121649B (en) | 2010-05-26 |
Family
ID=39084173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710070438A Expired - Fee Related CN101121649B (en) | 2007-08-01 | 2007-08-01 | Method for preparing functional acetophenone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101121649B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044231A (en) * | 2011-10-15 | 2013-04-17 | 徐州师范大学 | Preparation method of 3, 5-dibromo-2, 4-dihydroxyacetophenone |
-
2007
- 2007-08-01 CN CN200710070438A patent/CN101121649B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044231A (en) * | 2011-10-15 | 2013-04-17 | 徐州师范大学 | Preparation method of 3, 5-dibromo-2, 4-dihydroxyacetophenone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101121649B (en) | 2010-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101450943A (en) | Method for synthesizing drug pranlukast from tetrahydrofuran path | |
| CN102911022A (en) | Method for artificially synthesizing natural curcumin compound | |
| CN105237503A (en) | Method for preparing baicalein | |
| CN103694119A (en) | Preparation method of ethyl 4,4,4-trifluoroacetoacetate | |
| CN101121649B (en) | Method for preparing functional acetophenone compound | |
| CN105439824A (en) | Synthesis method of piceatannol | |
| CN102267911A (en) | Synthesis method of methyl salicylate | |
| CN103232345B (en) | Synthesis method of 8-hydroxyl ethyl caprylate | |
| CN105294415A (en) | Preparation method of 3-halogenated fluorenone compound | |
| CN105348037A (en) | Synthetic method of directly coupling aryl halide by aromatic hydrocarbon Grignard reagent in the presence of recycled modified palladium-charcoal | |
| Kabalka et al. | Thermal and microwave hydrolysis of organotrifluoroborates mediated by alumina | |
| CN103449994A (en) | Purifying process of cyclobutanone | |
| CN103755657B (en) | A kind of preparation method of Rivaroxaban intermediate | |
| CN103288628B (en) | Citric acid hydrogen peroxide oxidation prepares the method for 1,3-��-ketoglutaric acid diester and intermediate thereof | |
| CN102786429A (en) | Synthesis method of tolfenamic acid | |
| CN103012081B (en) | 4-iodophenylether derivative preparation method | |
| CN102070426B (en) | Method for synthesizing flocumafen intermediate | |
| CN108047114B (en) | Halogenated trifluoromethyl pyrrole derivative and preparation method and application thereof | |
| CN104876806A (en) | Novel method for synthesizing bisoprolol importance intermediate | |
| CN104529726A (en) | Preparation method of hydroxyacetophenone | |
| CN103613479B (en) | Preparation method of aromatic carboxylic acid compounds | |
| CN102351834B (en) | Economic, practical, and environment friendly method for preparing norathyriol | |
| CN114195638B (en) | Preparation method of phenyl o-hydroxybenzoate | |
| CN103508987A (en) | Method for synthetizing 2,3-disubstituted dihydrobenzofuran | |
| CN107880011A (en) | The synthetic method of Shandong agate Kato key intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100526 Termination date: 20120801 |