CN102206148A - Synthesis process of 2-hydroxy-5-nonylacetophenone - Google Patents
Synthesis process of 2-hydroxy-5-nonylacetophenone Download PDFInfo
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- CN102206148A CN102206148A CN2011100924487A CN201110092448A CN102206148A CN 102206148 A CN102206148 A CN 102206148A CN 2011100924487 A CN2011100924487 A CN 2011100924487A CN 201110092448 A CN201110092448 A CN 201110092448A CN 102206148 A CN102206148 A CN 102206148A
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- nonylacetophenone
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Abstract
The invention discloses a synthesis process of 2-hydroxy-5-nonylacetophenone, which comprises adding 4-nonylphenol and anhydrous acetonitrile into an organic solvent, introducing dry hydrogen chloride, adding a catalyst at the same time to perform a reaction for forming nonylphenol ketimine, filtering off nonylphenol ketimine, adding hot water, refluxing to obtain 2-hydroxy-5-nonylacetophenone, extracting the 2-hydroxy-5-nonylacetophenone by using an organic solvent, distilling under reduced pressure to obtain high-purity 2-hydroxy-5-nonylacetophenone. In the process, the synthesis route is short, the 2-hydroxy-5-nonylacetophenone is formed by a one-step reaction instead of the original two-step reaction, the synthesis route is simplified, and the reaction time is short; and the total yield of the process is higher than that of the prior art, the total yield of the synthesis route is over 80 percent, and the purity of the obtained product is more than or equal to 85 percent.
Description
Technical field
The invention belongs to chemical synthesis process, specifically, relate to the technology of a kind of chemosynthesis 2-hydroxyl-5-nonylacetophenone.
Background technology
2-hydroxyl-5-nonylacetophenone, English name: 2-hydroxy-5-nonylacetophenone(HNA), 2-hydroxyl-5-nonylacetophenone prepares metallic copper extraction agent 2-hydroxyl-5-nonylacetophenone oxime (HNAO) by oximation reaction, HNAO is a kind of efficient copper extractant, in hydrometallurgy, have widely and use, mainly from waste printed circuit board, copper mine and electroplating effluent, reclaim copper.
2-hydroxyl-5-nonylacetophenone has synthetic route now:
2-hydroxyl-5-nonylacetophenone synthesis technique is mainly at present:
1, is raw material with the 4-nonyl phenol, in the presence of aluminum trichloride (anhydrous), generates 2-hydroxyl-5-nonylacetophenone with excess acetyl chloride.
2, be raw material with the 4-nonyl phenol, generate magnesium salts, generate 2-hydroxyl-5-nonylacetophenone with the paraldehyde reaction again with the magnesium methylate reaction.
3, be raw material with the 4-nonyl phenol, generate ester with excess acetyl chloride earlier, in the presence of aluminum chloride, carry out Fries then and reset, can generate 2-hydroxyl-5-nonylacetophenone.
Article one, the route reaction by product is more, the bad control of reaction conditions, and yield is lower, and there is big difficulty in the purification aspect; The second route generates gel easily in reaction process, bad processing is bigger to the reaction influence, is not easy to suitability for industrialized production; Article three, use Acetyl Chloride 98Min. when route needs, production operation is relatively more dangerous, generates some by products during rearrangement easily, and difficulty is more during purification.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of to need single step reaction, and the synthesis technique of 2-hydroxyl-5-nonylacetophenone of being improved significantly of yield.
The present invention seeks to realize like this:
4-nonyl phenol and excessive anhydrous acetonitrile are joined in the organic solvent, feeding that the exsiccant hydrogen chloride gas adds simultaneously is that one or more of aluminum chloride, boron trichloride, zinc chloride generate the nonyl phenol ketoimine as catalyst reaction, filter out that the nonyl phenol ketoimine adds hot water, refluxing obtains 2-hydroxyl-5-nonylacetophenone, 2-hydroxyl-5-nonylacetophenone is by organic solvent extraction, organic molten highly purified 2-hydroxyl-5 nonylacetophenone that promptly gets of pressure reducing and steaming.
Reaction scheme is as follows:
Specifically carry out as follows:
(1) organic solvent is added in the exsiccant container, add 4-nonyl phenol and anhydrous acetonitrile then, add catalyzer again, feed the exsiccant hydrogen chloride gas, described catalyzer is aluminum chloride, boron trichloride, zinc chloride or one or more;
(2) step (1) reaction solution is heated to 30～100 ℃, reacted 5～24 hours, reaction solution is cooled to 0～10 ℃ then, separates out the nonyl phenol ketoimine, filters, and uses organic solvent washing;
(3) with the solid transfer after step (2) washing to container, add hot water, reflux, filter, use activated carbon decolorizing;
(4) step (3) filtrate is added in the entry, use water-fast organic solvent extraction, the pressure reducing and steaming organic solvent promptly gets 2-hydroxyl-5 nonylacetophenone.
Organic solvent is one or more in ether, tetrahydrofuran (THF), toluene, the chlorobenzene in the above-mentioned steps (1).
Organic solvent is one or more in toluene, trichloromethane, the methylene dichloride in the above-mentioned steps (4).
Above-mentioned technology filters out optimised process by orthogonal test, and proves through replication experiment, and the total recovery of Synthetic 2-hydroxyl-5 nonylacetophenone is stable, all reaches more than 80%, and product purity detects by HPLC, all reaches more than 85%.
Beneficial effect: (1) technology synthetic thread of the present invention is short out, and the present invention has simplified synthetic route with the synthetic step preparation of original two-step reaction 2-hydroxyl-5-nonylacetophenone, and the reaction times shortens.
(2) technology total recovery of the present invention is higher than prior art, and synthetic route total recovery of the present invention reaches more than 80%, the product purity that obtains 〉=85%.
Embodiment
Embodiment 1
In exsiccant 250ml round-bottomed flask, add 4-nonyl phenol 35.2g (0.16mol), 13g (0.32mol) anhydrous acetonitrile, 80ml anhydrous tetrahydro furan, the 4g Zinc Chloride Anhydrous feeds the exsiccant hydrogen chloride gas then, is warming up to 40 ℃ of about 4h of reaction, being cooled to 0 ℃ then and leaving standstill 3h, separate out the safran precipitation, promptly is the nonyl phenol ketoimine, filter, filter cake washs with tetrahydrofuran (THF), filter cake is changed in the there-necked flask of 1L, adds 0.6L hot water, backflow 1h, system becomes yellow solution, and cooling is filtered, filtrate is used decolorizing with activated carbon, product extracts with toluene, and underpressure distillation goes out solvent, gets product 2-hydroxyl-5-nonylacetophenone, yield 82%, purity 87%.
Embodiment 2
In exsiccant 250ml round-bottomed flask, add 4-nonyl phenol 0.2mol, 0.3mol anhydrous acetonitrile, 100ml ether, the 6g aluminum chloride feeds the exsiccant hydrogen chloride gas then, is warming up to 30 ℃ of about 24h of reaction, being cooled to 10 ℃ then and leaving standstill, separate out the safran precipitation, promptly is the nonyl phenol ketoimine, filter, filter cake washs with ether, filter cake is changed in the there-necked flask of 1L, adds 0.7L hot water, backflow 1h, system becomes yellow solution, and cooling is filtered, filtrate is used decolorizing with activated carbon, product extracts with toluene, and underpressure distillation goes out solvent, gets product 2-hydroxyl-5-nonylacetophenone, yield 83%, purity 86%.
Embodiment 3
In exsiccant 250ml round-bottomed flask, add 4-nonyl phenol 0.25mol, 0.32mol anhydrous acetonitrile, the mixed organic solvents of 120ml dry toluene and chlorobenzene, the mixture of 12g aluminum chloride and boron trichloride feeds the exsiccant hydrogen chloride gas then, be warming up to 100 ℃ of about 5h of reaction, being cooled to 5 ℃ then and leaving standstill, separate out the safran precipitation, promptly is the nonyl phenol ketoimine, filter, the filter cake toluene wash changes filter cake in the there-necked flask of 1L, adds 0.7L hot water, backflow 1h, system becomes yellow solution, and cooling is filtered, filtrate is used decolorizing with activated carbon, the product dichloromethane extraction, underpressure distillation goes out solvent, gets product 2-hydroxyl-5-nonylacetophenone, yield 84%, purity 87%.
Claims (4)
1. the synthesis technique of 2-hydroxyl-5-nonylacetophenone, it is characterized in that: 4-nonyl phenol and excessive anhydrous acetonitrile are joined in the organic solvent, feeding that the exsiccant hydrogen chloride gas adds simultaneously is that one or more of aluminum chloride, boron trichloride, zinc chloride generate the nonyl phenol ketoimine as catalyst reaction, filter out that the nonyl phenol ketoimine adds hot water, refluxing obtains 2-hydroxyl-5-nonylacetophenone, 2-hydroxyl-5-nonylacetophenone is by organic solvent extraction, the organic molten highly purified 2-hydroxyl-5-nonylacetophenone that promptly gets of pressure reducing and steaming.
2. according to the synthesis technique of the described 2-hydroxyl of claim 1-5-nonylacetophenone, it is characterized in that: carry out as follows:
(1) organic solvent is added in the exsiccant container, add 4-nonyl phenol and anhydrous acetonitrile then, add catalyzer again, feed the exsiccant hydrogen chloride gas, described catalyzer is aluminum chloride, boron trichloride, zinc chloride or one or more;
(2) step (1) reaction solution is heated to 30～100 ℃, reacted 5～24 hours, reaction solution is cooled to 0～10 ℃ then, separates out the nonyl phenol ketoimine, filters, with the used organic solvent washing of reaction;
(3) with the solid transfer after step (2) washing to container, add hot water, reflux, filter, use activated carbon decolorizing;
(4) step (3) filtrate is added in the entry, use water-fast organic solvent extraction, the pressure reducing and steaming organic solvent promptly gets 2-hydroxyl-5-nonylacetophenone.
3. according to the synthesis technique of the described 2-hydroxyl of claim 1-5-nonylacetophenone, it is characterized in that: organic solvent is one or more in ether, tetrahydrofuran (THF), toluene, the chlorobenzene in the described step (1).
4. according to the synthesis technique of the described 2-hydroxyl of claim 1-5-nonylacetophenone, it is characterized in that: organic solvent is one or more in toluene, trichloromethane, the methylene dichloride in the described step (4).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100924487A CN102206148A (en) | 2011-04-13 | 2011-04-13 | Synthesis process of 2-hydroxy-5-nonylacetophenone |
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| CN2011100924487A CN102206148A (en) | 2011-04-13 | 2011-04-13 | Synthesis process of 2-hydroxy-5-nonylacetophenone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731278A (en) * | 2012-06-12 | 2012-10-17 | 清华大学 | Technique for synthesizing 2-hydroxy-5-tert octyl acetophenone |
| CN103570518A (en) * | 2012-07-20 | 2014-02-12 | 江苏英力科技发展有限公司 | Preparation method of 2, 4-dimethoxyacetophenone |
| CN112250597A (en) * | 2020-11-02 | 2021-01-22 | 安徽绿色谷创客空间股份有限公司 | Green synthesis method of 2-hydroxy-5-nonyl acetophenone oxime |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485695A (en) * | 1974-02-06 | 1977-09-14 | Corning Glass Works | Systems for transmitting optical wave energy |
| US5300689A (en) * | 1992-03-20 | 1994-04-05 | Henkel Corporation | Oximation process |
| WO2004054954A1 (en) * | 2002-12-18 | 2004-07-01 | Cytec Technology Corp. | Process for the purification of hydroxyaryl-aldhydes and ketones and their use in the production of hydroxyaryl oxime derivatives |
-
2011
- 2011-04-13 CN CN2011100924487A patent/CN102206148A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485695A (en) * | 1974-02-06 | 1977-09-14 | Corning Glass Works | Systems for transmitting optical wave energy |
| US5300689A (en) * | 1992-03-20 | 1994-04-05 | Henkel Corporation | Oximation process |
| WO2004054954A1 (en) * | 2002-12-18 | 2004-07-01 | Cytec Technology Corp. | Process for the purification of hydroxyaryl-aldhydes and ketones and their use in the production of hydroxyaryl oxime derivatives |
Non-Patent Citations (4)
| Title |
|---|
| MICHIHISA YATO, TOMOHIKO OHWADA, KOICHI SHUDO: "Requirements for Houben-Hoesch and Gattermann reactions. Involvement of diprotonated cyanides in the reactions with benzene", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 冯成: "萃取剂2-羟基-5-壬基苯乙酮肟的合成研究及其类似物的设计与合成", 《中国优秀硕士学位论文数据库 工程科技Ⅰ辑》 * |
| 李效军 等: "萃取剂2-羟基-5-壬基苯乙酮肟的合成", 《天津化工》 * |
| 高鸿宾主编: "《实用有机化学辞典》", 31 July 1997, 北京高等教育出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731278A (en) * | 2012-06-12 | 2012-10-17 | 清华大学 | Technique for synthesizing 2-hydroxy-5-tert octyl acetophenone |
| CN103570518A (en) * | 2012-07-20 | 2014-02-12 | 江苏英力科技发展有限公司 | Preparation method of 2, 4-dimethoxyacetophenone |
| CN103570518B (en) * | 2012-07-20 | 2015-08-19 | 江苏英力科技发展有限公司 | One prepares the method for 2,4-dimethoxy-acetophenone |
| CN112250597A (en) * | 2020-11-02 | 2021-01-22 | 安徽绿色谷创客空间股份有限公司 | Green synthesis method of 2-hydroxy-5-nonyl acetophenone oxime |
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Application publication date: 20111005 |