CN106187715A - A kind of synthetic method of 4 butoxy phenol - Google Patents
A kind of synthetic method of 4 butoxy phenol Download PDFInfo
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- CN106187715A CN106187715A CN201610493959.2A CN201610493959A CN106187715A CN 106187715 A CN106187715 A CN 106187715A CN 201610493959 A CN201610493959 A CN 201610493959A CN 106187715 A CN106187715 A CN 106187715A
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- hydroquinone
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- butoxy phenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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Abstract
The invention provides the synthetic method of a kind of 4 butoxy phenol; first in two hydroxyls of hydroquinone is protected with acetyl group; ester exchange reaction is utilized to make the monohydroxy that is converted into of hydroquinone almost equivalent protect product; then react with butyl halide and make unprotected hydroxyl become ether, then hydrolysis removes acetyl group protection and obtained 4 butoxy phenol of high yield.The method controls simple, stable yield, and synthetic product simple crystallization purity in aqueous just reaches more than 98%.
Description
Technical field
The invention belongs to technical field of chemical synthesis, be specifically related to the synthetic method of a kind of 4-butoxy phenol.
Background technology
4-butoxy phenol, molecular formula C10H14O2, molecular weight 166.2；Chemical formula, it is synthesis local
The intermediate of anesthetics pramocaine.Mostly the synthetic method of existing document report 4-butoxy phenol is with hydroquinone and halo
Butane reacts in the presence of acid binding agent, and chemical formula is as follows:
。
Although the yield of existing document report is higher, but in the feelings of the special installation not using costliness in large-scale production
Under condition, the actual recovery of 4-butoxy phenol is difficult to more than 60%.This is due to two hydroxyl reaction poor selectivity of hydroquinone,
Can generate two hydroxyls in course of reaction and all form the by-product of ether, chemical formula is,
Quite a few hydroquinone generates by-product and is consumed, and also have impact on product quality while reducing yield；It is thus desirable to
Find the higher synthetic method generated with minimizing by-product of a kind of yield.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides the synthetic method of a kind of 4-butoxy phenol, first will be to benzene
In two hydroxyls of diphenol one protects with acetyl group, utilizes what ester exchange reaction made hydroquinone almost equivalent to be converted into single hydroxyl
Base protection product, then reacts with butyl halide and makes unprotected hydroxyl become ether, then hydrolysis removes acetyl group protection and obtained height
Yield and high-quality 4-butoxy phenol.The method controls simple, stable yield, and synthetic product is the simplest
Crystallization purity just reaches more than 98%.
The present invention is to be realized by following technical scheme:
The synthetic method of a kind of 4-butoxy phenol, first reacts hydroquinone and chloroacetic chloride, then in the absence of a solvent
React hydrolysis again with butyl bromide and generate 4-butoxy phenol.
Chemical formula is:
The mol ratio of hydroquinone and chloroacetic chloride is 1:0.9-1.
Hydroquinone and chloroacetic chloride react particularly as follows: chloroacetic chloride heats to 50 ~ 60 DEG C in the absence of a solvent,
Add hydroquinone, be gradually heating to 100 DEG C, and be incubated 3h at 100 ~ 110 DEG C, cool to 80-90 DEG C.
After hydroquinone and chloroacetic chloride react in the absence of a solvent, add organic solvent, add carbonate as tiing up
Acid agent, to be back to raw material reaction complete with butyl bromide.Carbonate is the ratio of sodium carbonate or potassium carbonate, carbonate and hydroquinone
Example is 0.7 ~ 1.5.
Hydroquinone and chloroacetic chloride are reacted in the absence of a solvent, after then reacting with butyl bromide, is filtered to remove
Inorganic salt, adds methanol and the aqueous solution of alkali or ethanol and the aqueous hydrolysis of alkali after recycling design, water consumption is hydroquinone
3 ~ 4 times of weight.
Hydroquinone and chloroacetic chloride are reacted in the absence of a solvent, then reacts with butyl bromide after terminating, filter
Removing inorganic salt, add the aqueous hydrolysis of alkali, water consumption is 3 ~ 4 times of hydroquinone weight.
Adding acid after having hydrolyzed to neutralize, cooling crystallize obtains 4-butoxy phenol, and acid is hydrochloric acid, sulphuric acid, phosphoric acid, nitre
Any in acid, formic acid, acetic acid.
Alkali is at least one in sodium hydroxide, potassium hydroxide, Lithium hydrate, calcium hydroxide.
The beneficial effects of the present invention is: in two hydroxyls of hydroquinone is first protected by the present invention with acetyl group,
Utilize ester exchange reaction to make the monohydroxy that is converted into of hydroquinone almost equivalent protect product, then react with butyl halide and make not
The hydroxyl of protection becomes ether, then hydrolysis removes acetyl group protection and obtained the 4-butoxy phenol of high yield.The method controls simple,
Stable yield, and synthetic product simple crystallization purity in aqueous just reaches more than 98%.
Accompanying drawing illustrates:
Fig. 1 show the liquid chromatogram of embodiment 2 product.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, in order to those skilled in the art knows more about
The present invention, but and it is not so limited the present invention.
Embodiment 1
Chloroacetic chloride 39.2Kg(499.4mol) put into enamel reaction still heat to 50 ~ 60 DEG C, add hydroquinone 55Kg
(500mol), gradually heat up and make hydrogen chloride gas stably discharge, be finally warming up to 100 DEG C, and be incubated 3h at 100 ~ 110 DEG C.Fall
Temperature, to 80 DEG C, adds 71.9Kg(525mol) n-butyl bromide, continues to be cooled to 50 DEG C and adds 300Kg acetone, be cooled to room temperature and add
103.7Kg(750.4mol) potassium carbonate, is warming up to be back to the monitoring of efficient liquid phase and determines fall after the reaction completely of acetyl hydroquinone
Temperature, filters, and filtrate adds 22.4Kg(560mol) alkali liquor backflow 5h that sodium hydroxide and 165Kg water are made, add 6Kg hydrochloric acid
Rear recovery acetone, under nitrogen protection, gradually cooling separates out crystallization, sucking filtration, washing, and solid is dried and obtained off-white color crystallization
74Kg.Yield 89.1%.Mp64 ~ 65 DEG C, liquid phase purity 98.1%.
Embodiment 2
Chloroacetic chloride 35.5Kg(452mol) put into enamel reaction still heat to 50 ~ 60 DEG C, add hydroquinone 55Kg
(500mol), gradually heat up and make hydrogen chloride gas stably discharge, be finally warming up to 100 DEG C, and be incubated 3h at 100 ~ 110 DEG C.Fall
Temperature, to 90 DEG C, adds 150Kg toluene and is cooled to room temperature and adds 69.1Kg(500mol) potassium carbonate and 72Kg(525.5mol) bromine fourth
Alkane, temperature rising reflux band water is to not having water to take out of.Cooling, filters, and filtrate decompression is steamed to no longer there being toluene to steam addition 200Kg first
Alcohol, 22.4Kg(560mol) alkali liquor backflow 4h that sodium hydroxide and 220Kg water are made, add 6Kg HCl recovery methanol, nitrogen is protected
Protecting gradually cooling and separate out crystallization, sucking filtration, washing, 50 ~ 55 DEG C of drying of solid obtain off-white color crystallization 72.2Kg.Yield 87.0%.
Mp64 ~ 65 DEG C, liquid phase purity 98.8%.The present embodiment product liquid chromatogram is as shown in Figure of description Fig. 1.
Claims (10)
1. the synthetic method of a 4-butoxy phenol, it is characterised in that first by hydroquinone and chloroacetic chloride at solvent-free bar
React under part, then react hydrolysis again with butyl bromide and generate 4-butoxy phenol.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 1, it is characterised in that hydroquinone and acetyl
The mol ratio of chlorine is 1:0.9-1.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 2, it is characterised in that hydroquinone and acetyl
The mol ratio of chlorine is 1:1.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 1, it is characterised in that hydroquinone and acetyl
Chlorine reacts particularly as follows: chloroacetic chloride heats to 50 ~ 60 DEG C in the absence of a solvent, adds hydroquinone, gradually heats up
To 100 DEG C, and it is incubated 3h at 100 ~ 110 DEG C, cools to 80-90 DEG C.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 1, it is characterised in that hydroquinone and acetyl
After chlorine reacts in the absence of a solvent, adding organic solvent, addition carbonate is as acid binding agent, with butyl bromide back flow reaction
To reaction completely.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 5, it is characterised in that carbonate is sodium carbonate
Or potassium carbonate, carbonate is 0.7 ~ 1.5 with the ratio of hydroquinone.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 1, it is characterised in that by hydroquinone and second
Acyl chlorides reacts in the absence of a solvent, after then reacting with butyl bromide, is filtered to remove inorganic salt, adds first after recycling design
Alcohol and the aqueous solution of alkali or ethanol and the aqueous hydrolysis of alkali, water consumption is 3 ~ 4 times of hydroquinone weight.
The synthetic method of a kind of 4-butoxy phenol the most according to claim 1, it is characterised in that by hydroquinone and second
Acyl chlorides reacts in the absence of a solvent, after then reacting with butyl bromide, is filtered to remove inorganic salt, adds the aqueous solution water of alkali
Solving, water consumption is 3 ~ 4 times of hydroquinone weight.
9. according to the synthetic method of the arbitrary described a kind of 4-butoxy phenol of claim 7 or 8, it is characterised in that hydrolyzed
Adding acid after one-tenth to neutralize, cooling crystallize obtains 4-butoxy phenol, and acid is in hydrochloric acid, sulphuric acid, phosphoric acid, nitric acid, formic acid, acetic acid
A kind of.
10. according to the synthetic method of the arbitrary described a kind of 4-butoxy phenol of claim 7 or 8, it is characterised in that alkali is hydrogen
At least one in sodium oxide, potassium hydroxide, Lithium hydrate, calcium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652167A (en) * | 2017-10-25 | 2018-02-02 | 武汉纺织大学 | A kind of synthetic method of 3 butoxy phenol |
| CN114805038A (en) * | 2022-04-28 | 2022-07-29 | 荆州市天翼精细化工开发有限公司 | Synthetic method of poly (p-phenylene ethylene) photoelectric material intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205174A (en) * | 2006-12-21 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing p-alkoxy phenol |
| CN104030893A (en) * | 2014-06-09 | 2014-09-10 | 上海应用技术学院 | Method for preparing 4-methyl catechol |
-
2016
- 2016-06-30 CN CN201610493959.2A patent/CN106187715B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205174A (en) * | 2006-12-21 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing p-alkoxy phenol |
| CN104030893A (en) * | 2014-06-09 | 2014-09-10 | 上海应用技术学院 | Method for preparing 4-methyl catechol |
Non-Patent Citations (2)
| Title |
|---|
| PEGGY M. PADURARU, ET AL.: "Synthesis of Substituted Alkoxy Benzene Minilibraries, for the Discovery of New Insect Olfaction or Gustation Inhibitors", 《JOURNAL OF COMBINATORIAL CHEMISTRY》 * |
| 舒学军 等: "相转移催化合成对苯乙炔聚合物发光材料中间体4-丁氧基苯酚的研究(Ⅰ)", 《中山大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652167A (en) * | 2017-10-25 | 2018-02-02 | 武汉纺织大学 | A kind of synthetic method of 3 butoxy phenol |
| CN114805038A (en) * | 2022-04-28 | 2022-07-29 | 荆州市天翼精细化工开发有限公司 | Synthetic method of poly (p-phenylene ethylene) photoelectric material intermediate |
| CN114805038B (en) * | 2022-04-28 | 2023-11-03 | 荆州市天翼精细化工开发有限公司 | Synthesis method of poly (p-phenylene ethylene) photoelectric material intermediate |
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Denomination of invention: A synthetic method of 4-butoxyphenol Effective date of registration: 20220616 Granted publication date: 20190222 Pledgee: Shandong Pingyuan Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG CHENGHUI SHUANGDA PHARMACEUTICAL CO.,LTD. Registration number: Y2022980007784 |
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