CN101570482A - Method for synthesizing jelly acid by omega-chlorine octanol - Google Patents
Method for synthesizing jelly acid by omega-chlorine octanol Download PDFInfo
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- CN101570482A CN101570482A CN 200910072222 CN200910072222A CN101570482A CN 101570482 A CN101570482 A CN 101570482A CN 200910072222 CN200910072222 CN 200910072222 CN 200910072222 A CN200910072222 A CN 200910072222A CN 101570482 A CN101570482 A CN 101570482A
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- hydroxy
- chlorine
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Abstract
The invention provides a method for synthesizing jelly acid by omega-chlorine octanol. Omega-chlorine octanol is adopted, acetylated, treated by oxidation-Witting phosphate ester reaction, hydrolyzed, acidized, and prepared by refined treatment. The invention has the advantages of simple and reasonable preparation process, low cost, high efficiency, good executability at room temperature and wide application range. The prepared theta-10-hydroxy-2-caproleic acid can be used for treating arteriosclerosis, cerebral infarction, coronary heart disease, blood stagnant disease with highly thick blood, hyperlipoidemia, immunologic function deficiency, radiotherapy, chemotherapy, old and weak people, patients with chronic diseases, various kinds of infectious hepatitis, hepatocirrhosis, diabetes, complications of diabetes, high-intensity brainwork and physical labour, neurasthenia, and the like.
Description
(1) technical field
The present invention relates to a kind of E-10-hydroxy-2-decylenic acid chemical preparation technology, be specifically related to a kind of method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol.
(2) background technology
The chemical name of E-10-hydroxy-2-decylenic acid is that anti-form-1 0-hydroxyl-2-decylenic acid (E-10-Hydroxy-2-Decenoic Acid) is called for short E-10-HAD, it is one of main active ingredient of Lac regis apis, account for 2%, has multiple physiologically active, the effect of antibiotic, sterilization, strong human body and multiple cancer cells such as strongly inhibited lymphatic cancer, mammary cancer, can also strengthen body immune function, effectively control alopecia, has the cell regeneration effect, damage due to treatment acute radiation injury and the chemical substance, and the synergistic agent that also can be used as makeup.
(3) summary of the invention
The object of the present invention is to provide a kind of preparation process simple, reasonable, cost is low, and the efficient height can carry out under the room temperature, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol applied widely.
The object of the present invention is achieved like this: the general chemical formula of E-10-hydroxy-2-decylenic acid:
The general Formula I of E-10-hydroxy-2-decylenic acid of the present invention is to adopt ω-chlorine octanol, through acetylize, and oxidation-Wittig phosphoric acid ester reaction, hydrolysis, acidifying, refinement treatment is produced, and reaction is undertaken by following:
Get Formulae II rear oxidation-Wittig reaction and do not separate out Wittig reaction under synthetic intermediate III, the IV condition, acidication is handled, and adds ω-chlorine octanol, Potassium ethanoate and PEG200ml, and stirring at room adds cold water flush away PEG, tells organic phase, gets chemical formula
Add silica gel PCC, phosphoric acid ester and CH again
2Cl
2Solvent, stir in the reactor, CPV observes and follows the tracks of no acetoxyl group octanol reaction terminating, and elimination silica gel PCC adds water sepn and goes out organic phase, decompression and solvent recovery, add in the organic phase with the volume of ethanol liquid and NaOH 20% aqueous solution, 30 ℃ were stirred decompression recycling ethanol 5 hours, with but 0 ℃ of material liquid cooling, add 30%H
2SO
4Or hydrochloric acid is used CH to PH3-4
2Cl
2Extract twice, merge and add the 20%NaOH aqueous solution in the organic phase to PH=8-9, add counter the quenching of water and get twice, merge water, decompression steams CH
2Cl
2, add hydrochloric acid to PH=4.5-5, crystallisation by cooling 3 days is told coarse crystal, drains surface water, with the heavy molten crystallisation by cooling of Diluted Alcohol of 2 times of amounts three days, 50 ℃ of dryings of product 24 hours, the white crystal E-10-hydroxy-2-decylenic acid of fusing point 64.5-64.8, yield 80%.
The present invention also has some technical characterictics like this:
1, described acylating agent is a Potassium ethanoate;
2, described PEG is a polyglycol ether;
3, described oxygenant is silica gel adsorption chlorine Lip river acid pyridinium salt (PyH
+CrO
3Cl
-);
4, described phosphoric acid ester is a triethoxy phosphine ethyl acetate;
5, described oxidation-Wittig reaction is not separate out under the intermediate condition-reaction of pot method;
6, the temperature of described reaction conditions is a room temperature;
7, Diluted Alcohol liquid is the ethanol of 30%-60% in the described heavy molten process.
Anti-form-1 0-hydroxyl-2-decylenic acid that method of the present invention is produced can be used for: behind arteriosclerosis, cerebral infarction, coronary heart disease, high thick stasis mass formed by blood stasis, hyperlipidemia, immunodeficiency disease, various cancer operation back, the radiation and chemotherapy, oldaged physically weak person, chronic, various infectious hepatitis, liver cirrhosis, diabetes, diabetic complication, high-intensity brainwork and treatments such as manual work, neurasthenia.
(4) embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments:
The general chemical formula of E-10-hydroxy-2-decylenic acid of the present invention is:
Above-mentioned chemical formula i compound is to be derived by ω-chlorine octanol, and classical way is:
Present embodiment adopts:
Characteristics of the present invention: Formula I is by ω-chlorine octanol, ω-Ji acidylate, gets Formulae II
Synthetic intermediate III is not separated out in oxidation then-Wittig reaction
Wittig reaction under the condition, acidication is handled and is produced.Reaction is undertaken by following:
Operation: in the 3000ml there-necked flask, add 130 ℃/11mmHg of boiling point ω-chlorine octanol 646 grams, Potassium ethanoate 540 grams, PEG200ml, stirring at room 4 hours adds cold water flush away PEG, tells organic phase, gets chemical formula
Each component proportions of present embodiment is: chemical formula
1mol
Silica gel PCC 1.15mol
Phosphoric acid ester 1.3mol
Solvent C H
2Cl
2It is chemical formula
1.5 times (volumes)
Stirring at room is three hours in reactor, CPV observes and follows the tracks of no acetoxyl group octanol reaction terminating, elimination PCC, add water sepn and go out organic phase, decompression and solvent recovery adds in the organic phase with the volume of ethanol liquid and NaOH 20% aqueous solution, 30 ℃ were stirred 5 hours, decompression recycling ethanol with but 0 ℃ of material liquid cooling, adds 30%H
2SO
4Or hydrochloric acid is used CH to PH3-4
2Cl
2Extract twice, merge and add the 20%NaOH aqueous solution in the organic phase to PH=g-9, add counter the quenching of water and get twice, merge water, decompression steams CH
2Cl
2, add hydrochloric acid to PH=4.5-5, crystallisation by cooling 3 days is told coarse crystal, drains surface water, with the heavy molten crystallisation by cooling of Diluted Alcohol of 2 times of amounts three days, 50 ℃ of dryings of product 24 hours, the white crystal E-10-hydroxy-2-decylenic acid of fusing point 64.5-64.8, yield 80%.
Acylating agent is a Potassium ethanoate in the present embodiment, and PEG is a polyglycol ether, and the oxygenant of employing is silica gel adsorption chlorine Lip river acid pyridinium salt (PyH
+CrO
3Cl
-), phosphoric acid ester is a triethoxy phosphine ethyl acetate, and oxidation-Wittig reaction is not separate out one kettle way reaction under the intermediate condition, and the temperature of reaction characteristics is a room temperature in the processing method, the ethanol that the molten Diluted Alcohol liquid of the weight of employing is 30%-60%.
Claims (10)
1, a kind of method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol, the general chemical formula of E-10-hydroxy-2-decylenic acid:
It is characterized in that the general Formula I of E-10-hydroxy-2-decylenic acid is to adopt ω-chlorine octanol, through acetylize, oxidation-Wittig phosphoric acid ester reaction, hydrolysis, acidifying, refinement treatment is produced, and reaction is undertaken by following:
2, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1 is characterized in that Formulae II
Do not separate out synthetic intermediate III through oxidation-Wittig reaction
Wittig reaction under the condition, acidication is handled, and adds ω-chlorine octanol, acylating agent and PEG 200ml, and stirring at room adds cold water flush away PEG, tells organic phase, gets chemical formula
Add silica gel PCC, phosphoric acid ester and CH again
2Cl
2Solvent, stir in the reactor, CPV observes and follows the tracks of no acetoxyl group octanol reaction terminating, and elimination silica gel PCC adds water sepn and goes out organic phase, decompression and solvent recovery, add in the organic phase with the volume of ethanol liquid and NaOH 20% aqueous solution, 30 ℃ were stirred decompression recycling ethanol 5 hours, with but 0 ℃ of material liquid cooling, add 30%H
2SO
4Or hydrochloric acid is used CH to PH3-4
2Cl
2Extract twice, merge and add the 20%NaOH aqueous solution in the organic phase to PH=8-9, add counter the quenching of water and get twice, merge water, decompression steams CH
2Cl
2, add hydrochloric acid to PH=4.5-5, crystallisation by cooling 3 days is told coarse crystal, drains surface water, with the heavy molten crystallisation by cooling of Diluted Alcohol of 2 times of amounts three days, 50 ℃ of dryings of product 24 hours, the white crystal E-10-hydroxy-2-decylenic acid of fusing point 64.5-64.8, yield 80%.
3, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 2 is characterized in that described acylating agent is a Potassium ethanoate.
4, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 3 is characterized in that described PEG is a polyglycol ether.
5, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 4 is characterized in that oxygenant is silica gel adsorption chlorine Lip river acid pyridinium salt PyH in the described oxidizing reaction
+CrO
3Cl
-
6, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 5 is characterized in that described phosphoric acid ester is a triethoxy phosphine ethyl acetate.
7, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 6 is characterized in that described oxidation-Wittig reaction is not separate out under the intermediate condition-reaction of pot method.
8, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 7 is characterized in that described chemical formula
Consumption 1mol, silica gel PCC consumption 1.15mol, phosphoric acid ester consumption 1.3mol, solvent C H
2Cl
2Consumption is a chemical formula
1.5 times of volume.
9, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 8 is characterized in that Diluted Alcohol liquid is the ethanol of 30%-60% in the described heavy molten process.
10, the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 9, the temperature that it is characterized in that described reaction conditions is a room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910072222 CN101570482B (en) | 2009-06-09 | 2009-06-09 | Method for synthesizing jelly acid by omega-chlorine octanol |
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|---|---|---|---|
| CN 200910072222 CN101570482B (en) | 2009-06-09 | 2009-06-09 | Method for synthesizing jelly acid by omega-chlorine octanol |
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| CN101570482B CN101570482B (en) | 2012-12-26 |
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|---|---|---|---|
| CN 200910072222 Expired - Fee Related CN101570482B (en) | 2009-06-09 | 2009-06-09 | Method for synthesizing jelly acid by omega-chlorine octanol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206151A (en) * | 2010-03-30 | 2011-10-05 | 上海灏翔生物科技有限公司 | Synthetic method of royaljelly acid |
| CN102267893A (en) * | 2011-06-15 | 2011-12-07 | 嘉兴学院 | Preparation method of royal jelly acid |
| CN104215722A (en) * | 2013-06-05 | 2014-12-17 | 江苏中谱检测有限公司 | Quick determination method of artificial decenoic acid |
| CN104622861A (en) * | 2014-12-26 | 2015-05-20 | 石家庄康诺生物技术有限公司 | Application of E-10-hydroxy-2-decenoic acid in medicines or health products for preventing and treating chemical liver injuries |
| CN104825435A (en) * | 2015-03-25 | 2015-08-12 | 石家庄康诺生物技术有限公司 | An application of E-10-hydroxy-2-decenoic acid in preparation of medicines or healthcare products for hepatic disease |
| US10004711B2 (en) | 2014-05-08 | 2018-06-26 | Dsm Ip Assets B.V. | Methods and compositions comprising 10-hydroxy-2-decenoic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2829491B1 (en) * | 2001-09-12 | 2005-09-30 | Diverchim | PROCESS FOR THE PREPARATION OF UNSATURATED FATTY HYDROXY ACIDS AND THEIR ESTERS, THEIR USE AS ANTI-COLLAGENASE AGENT |
-
2009
- 2009-06-09 CN CN 200910072222 patent/CN101570482B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206151A (en) * | 2010-03-30 | 2011-10-05 | 上海灏翔生物科技有限公司 | Synthetic method of royaljelly acid |
| CN102206151B (en) * | 2010-03-30 | 2013-04-17 | 上海灏翔生物科技有限公司 | Synthetic method of royaljelly acid |
| CN102267893A (en) * | 2011-06-15 | 2011-12-07 | 嘉兴学院 | Preparation method of royal jelly acid |
| CN102267893B (en) * | 2011-06-15 | 2013-06-05 | 嘉兴学院 | Preparation method of royal jelly acid |
| CN104215722A (en) * | 2013-06-05 | 2014-12-17 | 江苏中谱检测有限公司 | Quick determination method of artificial decenoic acid |
| CN104215722B (en) * | 2013-06-05 | 2016-04-13 | 江苏中谱检测有限公司 | The method for quick of artificial decylenic acid |
| US10004711B2 (en) | 2014-05-08 | 2018-06-26 | Dsm Ip Assets B.V. | Methods and compositions comprising 10-hydroxy-2-decenoic acid |
| CN104622861A (en) * | 2014-12-26 | 2015-05-20 | 石家庄康诺生物技术有限公司 | Application of E-10-hydroxy-2-decenoic acid in medicines or health products for preventing and treating chemical liver injuries |
| CN104622861B (en) * | 2014-12-26 | 2019-08-06 | 石家庄康诺生物技术有限公司 | Application of the E-10- hydroxyl -2- decylenic acid in the drug of prevention and treatment chemical liver |
| CN104825435A (en) * | 2015-03-25 | 2015-08-12 | 石家庄康诺生物技术有限公司 | An application of E-10-hydroxy-2-decenoic acid in preparation of medicines or healthcare products for hepatic disease |
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| Publication number | Publication date |
|---|---|
| CN101570482B (en) | 2012-12-26 |
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