CN1238316C - Process for preparing phenol derivative - Google Patents
Process for preparing phenol derivative Download PDFInfo
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- CN1238316C CN1238316C CN 02135243 CN02135243A CN1238316C CN 1238316 C CN1238316 C CN 1238316C CN 02135243 CN02135243 CN 02135243 CN 02135243 A CN02135243 A CN 02135243A CN 1238316 C CN1238316 C CN 1238316C
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- phenol derivative
- benzene
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Abstract
The present invention relates to a preparation method for a phenol derivative, and the structural formula of the phenol derivative is shown as the following formula, wherein the ratio of a to n or the ratio of b to n is 2 to 7, A represents cyclohexane or benzene, and x represents F or H. The present invention is characterized in that an acetophenone derivative is adopted as a raw material, and the structural formula of the acetophenone derivative is shown as the following formula, wherein the ratio of a' to n or the ratio of b' to n is 2 to 7, A represents the cyclohexane or the benzene, and x represents F or H; furthermore, ammonium persulfate is adopted as an oxidant, a sulphuric acid solution is adopted as a catalyst, and reactions occur in a glacial acetic acid solvent under normal pressures for 5 to 20 hours while the temperature is kept constant at 20 to 50 DEG C. The process of the present invention is a one-step reaction, the yield of obtained raw products can reach more than 97 %, and cost is greatly reduced so that the present invention is favorable for industrialized production.
Description
(1) technical field: the present invention relates to a kind of method of organic compound preparation, especially a kind of preparation method of phenol derivatives.
(2) background technology: phenol derivatives is an industrial preparation liquid crystal and a medical class important intermediate.Used in the past preparation method is complicated, and cost is high again, and using value is not high in industrial production.The great grade of Yang Xin was " Huadong Chemical College journal " 1991 12 interim mentioning
The preparation method.Its method is to use hydrogen peroxide earlier, and ethylene dichloride and trifluoroacetic anhydride prepare peroxy trifluoroacetic acid, according to Bayer-Wei Lie reaction grid, make again
Nucleophilic 1～2 rearrangement reaction takes place under the peroxy trifluoroacetic acid effect, generates
With ethanol, water and sodium hydroxide it is hydrolyzed to again
After adding dense HC acidifying, gained throw out normal hexane recrystallization promptly gets the white object product.In United States Patent (USP) 3992459, announced a kind of preparation
Method, it is consistent that its principle and the great grade of above-mentioned Yang Xin are delivered.Promptly earlier will
Be oxidized to
, get after the hydrolysis treatment again
Above-mentioned preparation method reacts in two steps, and is comparatively complicated, and more main is that raw materials used middle trifluoroacetic anhydride is too expensive, causes production cost too high, is unfavorable for industrial production.
Germany Merk (has introduced among the patent DE2636684
A kind of preparation method of (R is a straight chained alkyl), its method is at oxygenant H
2O
2Under the effect,
(R is a straight chained alkyl) reaction 72 hours generates
(R is a straight chained alkyl) solves with the NaOH solution water again
(R is a straight chained alkyl).This method reaction is two-step reaction, and the reaction times is oversize.
In " J.Or restrains .Chem " (Vo.35, No.9,1970), introduced a kind of method that simple aliphatic ketone generates Fatty Alcohol(C12-C14 and C12-C18).Reaction mechanism also belongs to Bayer-Wei Lie reaction grid, and its method is to use K
2S
2O
8As oxygenant, the decision of the concentration of sulphuric acid soln generates product.As sulphuric acid soln concentration＞70%, then generate alcohol, about 20% as sulphuric acid soln concentration, then generate acid.We once prepared according to this method
Its reaction process is as follows:
This method is because K
2S
2O
8Solubleness is very little in water, be difficult to after the reaction remove from final product, moreover this reaction needs belong to two-step reaction, and the finished product yield to be not high yet with a large amount of NaOH hydrolysis, generally has only 40% (gas-chromatography＞99.5%).
Above-mentioned several preparation methods belong to two-step reaction, handle trouble, are difficult to realize suitability for industrialized production.
(3) summary of the invention: the objective of the invention is to overcome the deficiency of above-mentioned prior art and a kind of two-step reaction that changes is provided is single step reaction, belong to synthesis under normal pressure, conversion unit there is not particular requirement, simple to operate, the product yield height, raw materials used price is low, and product cost is descended significantly, help industrial production, have the process for preparing phenol derivative of actual application value.
Purpose of the present invention can reach by following measure: process for preparing phenol derivative, phenol derivatives structural formula are following formula a or b:
N=2～7, A: hexanaphthene or benzene
X=F or H
Its characteristics are to make raw material with acetophenone derivs, and the acetophenone derivs structural formula is following formula a ' or b ':
N=2～7, A: hexanaphthene or benzene
X=F or H
With ammonium persulphate is oxygenant, and sulphuric acid soln is made catalyzer, in the Glacial acetic acid solvent, and under the normal pressure, 20～50 ℃ of insulation reaction 5～20 hours.
Purpose of the present invention can reach by following measure: process for preparing phenol derivative, its benzene feedstock ethanone derivatives gas-chromatography＞70%, preferably benzene feedstock ethanone derivatives gas-chromatography＞85%.The mole number of ammonium persulphate oxygenant is 2-6 a times of benzene feedstock ethanone derivatives mole number.The mole number of catalyst sulfuric acid solution is 1-3 a times of benzene feedstock ethanone derivatives mole number, and the sulphuric acid soln mass concentration is 50%-75%.Solvent Glacial acetic acid mole number is at least 8 times of benzene feedstock ethanone derivatives mole number.
Compared with the prior art the present invention has following positively effect: the present invention becomes two-step reaction and is single step reaction, and is simple to operate, and the reaction times is short: the yield height; Because take the cheap cost of phenol derivatives that makes of cost of material to reduce greatly, help suitability for industrialized production.
(5) embodiment: following detailed description the present invention also provides several embodiment:
Reaction mechanism of the present invention: with 4-(4 '-n-propyl cyclohexyl) methyl phenyl ketone is that raw material production 4-(4 '-n-propyl cyclohexyl) phenol is example, and its reaction mechanism is as follows:
Among the present invention, the reaction mechanism of phenol derivatives preparation is identical with 4-(4 '-n-propyl cyclohexyl) phenol all.
Process for preparing phenol derivative is applicable to:
4-(4 '-alkyl-cyclohexyl) phenol, wherein carbon atom is 2～7
4-alkyl biphenyl phenol, wherein carbon atom is 2～7
4-fluorine xenol
2,4-DfBP phenol
The invention belongs to synthesis under normal pressure, selecting Glacial acetic acid for use is reaction solvent, adds acetophenone derivs and ammonium persulphate, drips sulphuric acid soln, and 20～50 ℃ of insulation reaction 5～20 hours add the water hydrolysis, filter, and drip washing promptly gets the thick product of target product to neutral.Use the toluene recrystallization, can get gas-chromatography and be the target product elaboration more than 99.7%, roll over hundred yields more than 85%.
Embodiment 1:
Add 230 grams (1 mole) in 2 liters of reaction flasks
(chromatography of gases: 94.52%), 108C gram (18 moles) Glacial acetic acid and 684 gram (3 moles) ammonium persulphates, stir, be cooled to 10～15 ℃, drip the sulphuric acid soln of preparing by 196 gram (2 moles) vitriol oils and 108 gram (6 moles) water, 10～40 ℃ of dropping temperatures, drip to finish in about 2 hours, and dropwised, in 20～50 ℃ of insulation reaction 5～20 hours, follow the tracks of and detect, extremely
COCH
3Till reacting completely.Insulation is finished, and adds 500 gram water, stirs 30 minutes, filters,, drain to neutral with water wash, oven dry, obtain product 201 grams, gas-chromatography: 95.38%, yield: 98.5%.With 612 gram toluene recrystallizations, obtain product 182 grams, chromatography of gases again: 99.83%, yield: 89.8%, fusing point: 132.5～133.9 ℃.
Embodiment 2:
In 2 liters of reaction flasks, add 272 grams (1 mole)
(chromatography of gases: 95.24%), 1080 gram (18 moles) Glacial acetic acid and 684 gram (3 moles) ammonium persulphates, stirring is cooled to 10～15 ℃, the sulphuric acid soln that dropping is prepared by 196 gram (2 moles) vitriol oils and 108 gram (6 moles) water, 10～40 ℃ of control dropping temperatures dripped complete in about 2 hours, dropwise, in 20～50 ℃ of insulation reaction 5～20 hours, follow the tracks of and detect, to C
5H
11-
Till reacting completely.Insulation is finished, and adds entry 500 grams, stirs 30 minutes, filters,, drain to neutral with water wash, oven dry, obtain product 244 grams, gas-chromatography: 96.86%, yield: 99.2%.With 738 gram toluene recrystallizations, obtain product 224 grams, gas-chromatography again: 99.86%, yield: 91.1%, fusing point: 139.1～140.2 ℃.
Hydrogen nuclear magnetic resonance spectrum: δ=0.89396～0.93906 (m, 3H, CH
3)
δ＝0.99024～189312(txd，17H，
δ＝2.41907～2.45977(m，1H，
δ＝4.2～4.4(s，1H，-OH)
δ=6.75075～7.11068 (m, 4H, C
6H
4) the nuclear magnetic resonance of carbon spectrum: δ=13.9,22.5,26.4,32.0,33.5,34.4,37.1,37.2,43.5,76.4,76.8,77.2,114.8,127.6,140.1,153.2.
Embodiment 3:
In 2 liters of reaction flasks, add 238 grams (1 mole)
(gas-chromatography: 96.56%), 1080 gram (18 moles) Glacial acetic acid and 684 gram (3 moles) ammonium persulphates, stirring is cooled to 10～15 ℃, dropping is by 196 gram (2 moles) vitriol oils and 108 gram (6 moles) sulphuric acid solns that water was made into, 10～40 ℃ of control dropping temperatures are finished, are dropwised for about 2 hours, in 20～50 ℃ of insulation reaction 5～20 hours, follow the tracks of and detect extremely
Till reacting completely.Insulation is finished, and adds 500 gram water, stirs 30 minutes, filters,, drain to neutral with water wash, oven dry, obtain product 208 grams, gas-chromatography: 97.37%, yield: 98.1%.With 636 gram toluene recrystallizations, obtain product 196 grams, gas-chromatography again: 99.81%, yield: 92.5%, fusing point: 146.7～148.0 ℃.
Embodiment 4:
In 2 liters of reaction flasks, add 214 grams (1 mole)
(gas-chromatography: 95.73%), 1080 gram (18 moles) Glacial acetic acid and 684 gram (3 moles) ammonium persulphates, stirring is cooled to 10～15 ℃, drip 196 gram (2 moles) vitriol oils and 108 gram (6 moles) sulphuric acid solns that water was made into, 10～40 ℃ of control dropping temperatures are finished for about 2 hours, dropwise, in 20～50 ℃ of insulation reaction 5～20 hours, follow the tracks of inspection then, extremely
COCH
3Till reacting completely.Be incubated and finish, add 500 gram water, stirred 30 minutes, filter, extremely neutral with water wash, drain, oven dry, obtain product 116 grams, gas-chromatography: 96.58%, yield: 98.3%, with 354 gram toluene recrystallizations, obtain product 109 grams, gas-chromatography again: 99.92%, yield: 92.4%.Mass spectrum: molecular ion peak (m/z)=188 (M
+)
Embodiment 5:
In 2 liters of reaction flasks, add 232 grams (1 mole)
(gas-chromatography: 94.73%), 1080 gram (18 moles) Glacial acetic acid and 684 gram (3 moles) ammonium persulphates, stirring is cooled to 10～15 ℃, drip 196 gram (2 moles) vitriol oils and 108 gram (6 moles) sulphuric acid solns that water was made into, 10～40 ℃ of control dropping temperatures are finished for about 2 hours, dropwise, in 20～50 ℃ of insulation reaction 5～20 hours, follow the tracks of and detect, extremely
Claims (7)
1, process for preparing phenol derivative, phenol derivatives structural formula are following formula a or b:
A: hexanaphthene or benzene
X=F or H
It is characterized in that making raw material with acetophenone derivs, the acetophenone derivs structural formula is following formula a ' or b ':
With ammonium persulphate is oxygenant, and sulphuric acid soln is made catalyzer, in the Glacial acetic acid solvent, and under the normal pressure, 20～50 ℃ of insulation reaction 5～20 hours.
2,, it is characterized in that benzene feedstock ethanone derivatives complexion spectrum is greater than 70% according to the described process for preparing phenol derivative of claim 1.
3,, it is characterized in that benzene feedstock ethanone derivatives complexion spectrum is greater than 85% according to the described process for preparing phenol derivative of claim 1.
4, according to the described process for preparing phenol derivative of claim 1, the mole number that it is characterized in that the ammonium persulphate oxygenant is 2-a times of benzene feedstock ethanone derivatives mole number.
5, according to the described process for preparing phenol derivative of claim 1, the mole number that it is characterized in that catalyst sulfuric acid solution is 1-3 a times of benzene feedstock ethanone derivatives mole number.
6,, it is characterized in that the sulphuric acid soln mass concentration is 50%-75% according to claim 1 or 5 described process for preparing phenol derivative.
7,, it is characterized in that the Glacial acetic acid mole number is at least 8 times of benzene feedstock ethanone derivatives mole number according to the preparation method of the described phenol derivatives of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135243 CN1238316C (en) | 2002-06-27 | 2002-06-27 | Process for preparing phenol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135243 CN1238316C (en) | 2002-06-27 | 2002-06-27 | Process for preparing phenol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1463961A CN1463961A (en) | 2003-12-31 |
| CN1238316C true CN1238316C (en) | 2006-01-25 |
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ID=29744250
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02135243 Expired - Lifetime CN1238316C (en) | 2002-06-27 | 2002-06-27 | Process for preparing phenol derivative |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560553C (en) * | 2007-01-19 | 2009-11-18 | 烟台九目化学制品有限公司 | The preparation method of phenol analog derivative |
| CN104961629A (en) * | 2015-05-19 | 2015-10-07 | 烟台蓓丰医药科技有限公司 | Synthetic method of pentafluorophenol |
| JP2020512384A (en) * | 2017-03-30 | 2020-04-23 | マーケット ユニバーシティー | Substituted (4'-hydroxyphenyl) cycloalkane and (4'-hydroxyphenyl) cycloalkene compounds and methods of their use as selective agonists of estrogen receptor beta isoforms to improve memory consolidation |
| CN112341320A (en) * | 2020-11-02 | 2021-02-09 | 烟台丰鲁精细化工有限责任公司 | Novel synthesis method of p- (trans-4-hydroxycyclohexyl) phenol |
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2002
- 2002-06-27 CN CN 02135243 patent/CN1238316C/en not_active Expired - Lifetime
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Owner name: FINE CHEMICAL INDUSTRY CO. Free format text: FORMER NAME OR ADDRESS: YANTAI WANRUN FINE CHEMICALS CO., LTD. |
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Address after: No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong province (Wang Jihua) Patentee after: Yantai Valiant Fine Chemicals Co.,Ltd. Address before: No. 11 Wuzhishan Road, Yantai Development Zone, Shandong, China Patentee before: Valiant Fine Chemicals Co.,Ltd. Yantai |
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Owner name: CHINA ENERGY CONSERVATION VALIANT CO., LTD. Free format text: FORMER NAME: |
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Address after: 264006 Shandong city of Yantai Province Economic and Technological Development Zone Wuzhi Mountain Road No. 11 Patentee after: VALIANT Co.,Ltd. Address before: 264006 No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong province (Wang Jihua) Patentee before: Yantai Valiant Fine Chemicals Co.,Ltd. |
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Granted publication date: 20060125 |