CN102659536A - Method for synthesizing o-hydroxy phenyl ether - Google Patents
Method for synthesizing o-hydroxy phenyl ether Download PDFInfo
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- CN102659536A CN102659536A CN2012101809921A CN201210180992A CN102659536A CN 102659536 A CN102659536 A CN 102659536A CN 2012101809921 A CN2012101809921 A CN 2012101809921A CN 201210180992 A CN201210180992 A CN 201210180992A CN 102659536 A CN102659536 A CN 102659536A
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- phosphoric acid
- activated carbon
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- pyrocatechol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for synthesizing o-hydroxy phenyl ether. In the method, catechol is used as a raw material and diethyl carbonate is used as an alkylating agent; and activated carbon load type phosphoric acid is used as catalyst in synthetic reaction. The activated carbon load type phosphoric acid which is low in price and easy to prepare is used as catalyst, and o-hydroxy phenyl ether compounds can be prepared by catalytic synthesis; and the catalyst is easily separate and recovered, and can be repeatedly used for a plurality of times. The synthesis method has the advantages of being easy in obtaining of raw material, low in cost, simple and convenient in operation, mild in reaction condition, less in pollution, high in yield and the like, and is easy in industrial production.
Description
Technical field
The invention belongs to the chemical intermediate synthesis technical field, especially relate to the compound method of 2-ethoxy-phenol compounds.
Background technology
2-ethoxy-phenol is important fine-chemical intermediate, is widely used in the synthesis technique of medicine, spices (vanillin food grade,1000.000000ine mesh, synthetic musk etc.), fuel, makeup, oxidation inhibitor and stopper.Particularly methyl catechol (formal name used at school ortho-hydroxyanisole) and ethyl wood phenol (formal name used at school 2-ethoxy-phenol) has bigger consumption as the raw material of synthesis of vanillin.At present, its working method mainly contains the monoalkylation method of o-phenetidine diazonium salt catalytic oxidation and pyrocatechol and alkyl esters or halogenated alkane.These reactions exist that technological process is numerous and diverse, seriously corroded, have shortcomings such as severe toxicity, contaminate environment.For avoiding these shortcomings, there is bibliographical information to adopt green chemical industry material carbon diethyl phthalate as alkylating reagent, have characteristics such as nontoxic, non-corrosiveness, but its catalyzer is selected Al for use
1P
aX
b, preparation is relatively complicated, and cost is high.We improve on this basis and adopt activated carbon loaded type phosphoric acid is catalyzer, has characteristics such as efficient, that cost is low, reaction conditions is gentle, and catalyzer is separable.
Summary of the invention
Technical problem to be solved by this invention provides the method for the synthesizing 2-ethoxy-phenol that a kind of yield is high, three-waste pollution is few.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is following:
A kind of method of synthesizing 2-ethoxy-phenol is a raw material with the pyrocatechol, is alkylating reagent with the diethyl carbonate, and building-up reactions is a catalyzer with activated carbon loaded type phosphoric acid.
Wherein, the reaction mol ratio of pyrocatechol and diethyl carbonate is 1:1～6, preferred 1:2～3.
Wherein, the adding quality of described activated carbon loaded type phosphoric acid is 1～15% of a pyrocatechol quality, preferred 5～10%.
Wherein, described building-up reactions is at 150 ~ 300 ℃ of following stirring reaction 2 ~ 10h, preferably at 200 ℃ of following stirring reaction 5h.
Wherein, the concrete compound method of activated carbon loaded type phosphoric acid catalyst of the present invention can be referring to document [Han Bo, Jiang Haijin; Jia Xiaowei; Gu Xiaohui. the research [J] of the synthetic 1-benzyl-2-Phenylbenzimidazole of activated carbon loaded phosphoric acid catalyzed, use chemical industry, 2011; 40 (9): 1553-1555], concrete grammar is following:
Take by weighing the 2g gac, wash 1,2 time, suction filtration is placed on 115 ℃ of granular active carbons of drying to constant mass in the baking oven, is soaked in the 10mL massfraction and is 30h in 16% the phosphoric acid solution, suction filtration, and washing is to neutral.110 ℃ of dry 5h put into loft drier and cool off then.Weighing gets the 2.12g solid catalyst, is 6% through the load quality mark of calculated activity charcoal.Regulate phosphate aqueous solution concentration, can make the load quality fractional catalyzer of different activities charcoal.
Reaction equation of the present invention is following:
The present invention has following tangible advantage:
1, the present invention be prone to preparation with cheapness the catalyzer of activated carbon loaded type phosphoric acid as catalyzer, catalysis synthesizing 2-ethoxy-phenol compounds, catalyzer is easy to Separation and Recovery, and can be repeatedly used.
2, compound method raw material of the present invention is easy to get, and cost is low, easy and simple to handle, reaction conditions is gentle, pollute less, the yield advantages of higher, is easy to suitability for industrialized production.
Embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described content of embodiment only is used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Embodiment 1: activated carbon loaded type phosphoric acid preparation.
Take by weighing the 2g gac, wash 1,2 time, suction filtration is placed on 115 ℃ of granular active carbons of drying to constant mass in the baking oven, is soaked in the 10mL massfraction and is 30h in 16% the phosphoric acid solution, suction filtration, and washing is to neutral.110 ℃ of dry 5h put into loft drier and cool off then.Weighing gets the 2.12g solid catalyst, is 6% through the load quality mark of calculated activity charcoal.
Embodiment 2: activated carbon loaded type phosphoric acid preparation.
Take by weighing the 2g gac, wash 1,2 time, suction filtration is placed on 115 ℃ of granular active carbons of drying to constant mass in the baking oven, is soaked in the 10mL massfraction and is 30h in 28% the phosphoric acid solution, suction filtration, and washing is to neutral.110 ℃ of dry 5h put into loft drier and cool off then.Weighing gets the 2.20g solid catalyst, is 10% through the load quality mark of calculated activity charcoal.
Embodiment 3: activated carbon loaded type phosphoric acid preparation.
Take by weighing the 2g gac, wash 1,2 time, suction filtration is placed on 115 ℃ of granular active carbons of drying to constant mass in the baking oven, is soaked in the 10mL massfraction and is 30h in 45% the phosphoric acid solution, suction filtration, and washing is to neutral.110 ℃ of dry 5h put into loft drier and cool off then.Weighing gets the 2.30g solid catalyst, is 15% through the load quality mark of calculated activity charcoal.
Embodiment 4: activated carbon loaded type phosphoric acid preparation.
Take by weighing the 2g gac, wash 1,2 time, suction filtration is placed on 115 ℃ of granular active carbons of drying to constant mass in the baking oven, is soaked in the 10mL massfraction and is 30h in 64% the phosphoric acid solution, suction filtration, and washing is to neutral.110 ℃ of dry 5h put into loft drier and cool off then.Weighing gets the 2.42g solid catalyst, is 21% through the load quality mark of calculated activity charcoal.
Embodiment 5: the preparation 2-ethoxy-phenol.
Successively add 2g 6% activated carbon loaded type phosphoric acid, 24g pyrocatechol (0.22mol), 78g diethyl carbonate (0.56mol) at reactor drum; After stirring, closed reactor, elevated temperature are controlled at 200 ℃; Behind the reaction 4h, filter the filtrating efficient liquid phase chromatographic analysis; The pyrocatechol transformation efficiency is 57.2%, and the 2-ethoxy-phenol selectivity is 93.3%.
Embodiment 6: the preparation 2-ethoxy-phenol.
Successively add 2g 10% activated carbon loaded type phosphoric acid at reactor drum, 24g pyrocatechol (0.22mol), 78g diethyl carbonate (0.56mol) is after stirring; Closed reactor, elevated temperature are controlled at 200 ℃, behind the reaction 4h, filter; Filtrating 10ml washing twice, oil phase separates through silica gel column chromatography, obtains product; Efficient liquid phase chromatographic analysis, pyrocatechol transformation efficiency are 65.1%, and the 2-ethoxy-phenol selectivity is 90.3%.
Embodiment 7: the preparation 2-ethoxy-phenol.
Successively add 2g 15% activated carbon loaded type phosphoric acid at reactor drum, 24g pyrocatechol (0.22mol), 78g diethyl carbonate (0.56mol) is after stirring; Closed reactor, elevated temperature are controlled at 200 ℃, behind the reaction 4h, filter; Filtrating 10ml washing twice, oil phase separates through silica gel column chromatography, obtains product; Efficient liquid phase chromatographic analysis, pyrocatechol transformation efficiency are 70.5%, and the 2-ethoxy-phenol selectivity is 83.3%.
Embodiment 8: the preparation 2-ethoxy-phenol.
Successively add 2g 21% activated carbon loaded type phosphoric acid at reactor drum, 24g pyrocatechol (0.22mol), 78g diethyl carbonate (0.56mol) is after stirring; Closed reactor, elevated temperature are controlled at 200 ℃, behind the reaction 4h, filter; Filtrating 10ml washing twice, oil phase separates through silica gel column chromatography, obtains product; Efficient liquid phase chromatographic analysis, pyrocatechol transformation efficiency are 75.3%, and the 2-ethoxy-phenol selectivity is 70.3%.
Embodiment 11: the preparation 2-ethoxy-phenol.
With the preparation method of embodiment 5, the reaction mol ratio of different is pyrocatechol and diethyl carbonate is 1:1, and the adding quality of activated carbon loaded type phosphoric acid is 1% of a pyrocatechol quality, and described building-up reactions is at 150 ℃ of following stirring reaction 10h.
Embodiment 12: the preparation 2-ethoxy-phenol.
With the preparation method of embodiment 5, the reaction mol ratio of different is pyrocatechol and diethyl carbonate is 1:6, and the adding quality of activated carbon loaded type phosphoric acid is 15% of a pyrocatechol quality, and described building-up reactions is at 300 ℃ of following stirring reaction 2h.
Claims (4)
1. the method for a synthesizing 2-ethoxy-phenol is a raw material with the pyrocatechol, is alkylating reagent with the diethyl carbonate, it is characterized in that, building-up reactions is a catalyzer with activated carbon loaded type phosphoric acid.
2. the method for synthesizing 2-ethoxy-phenol according to claim 1 is characterized in that, the reaction mol ratio of pyrocatechol and diethyl carbonate is 1:1～6.
3. the method for synthesizing 2-ethoxy-phenol according to claim 1 is characterized in that, the adding quality of described activated carbon loaded type phosphoric acid is 1～15% of a pyrocatechol quality.
4. the method for synthesizing 2-ethoxy-phenol according to claim 1 is characterized in that, described building-up reactions is at 150 ~ 300 ℃ of following stirring reaction 2 ~ 10h.
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| CN2012101809921A CN102659536A (en) | 2012-06-04 | 2012-06-04 | Method for synthesizing o-hydroxy phenyl ether |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349026A (en) * | 2016-08-24 | 2017-01-25 | 安徽金邦医药化工有限公司 | Synthesis technology of o-hydroxy phenyl ethyl ether |
| CN107814691A (en) * | 2017-11-01 | 2018-03-20 | 贝利化学（张家港）有限公司 | A kind of method for synthesizing guaethol |
| CN115197052A (en) * | 2022-07-29 | 2022-10-18 | 常州大学 | Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033177A (en) * | 2007-04-11 | 2007-09-12 | 江苏工业学院 | Method of synthesizing 2-ethoxy-phenol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033177A (en) * | 2007-04-11 | 2007-09-12 | 江苏工业学院 | Method of synthesizing 2-ethoxy-phenol |
Non-Patent Citations (2)
| Title |
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| 朱小梅等: "气相合成邻甲（乙）氧基苯酚催化剂的研究进展", 《化工进展》 * |
| 潘春柳等: "负载型磷酸催化剂上合成邻羟基苯乙醚", 《石油化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349026A (en) * | 2016-08-24 | 2017-01-25 | 安徽金邦医药化工有限公司 | Synthesis technology of o-hydroxy phenyl ethyl ether |
| CN107814691A (en) * | 2017-11-01 | 2018-03-20 | 贝利化学（张家港）有限公司 | A kind of method for synthesizing guaethol |
| CN107814691B (en) * | 2017-11-01 | 2020-07-28 | 贝利化学（张家港）有限公司 | Method for synthesizing ethylguaiacol |
| CN115197052A (en) * | 2022-07-29 | 2022-10-18 | 常州大学 | Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis |
| CN115197052B (en) * | 2022-07-29 | 2023-11-03 | 常州大学 | Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite |
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Application publication date: 20120912 |