CN101570482B - 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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- CN101570482B CN101570482B CN 200910072222 CN200910072222A CN101570482B CN 101570482 B CN101570482 B CN 101570482B CN 200910072222 CN200910072222 CN 200910072222 CN 200910072222 A CN200910072222 A CN 200910072222A CN 101570482 B CN101570482 B CN 101570482B
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- hydroxy
- acid
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- chlorine
- octanol
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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; Be one of main active ingredient of Lac regis apis, account for 2%, have 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 prevent and treat alopecia, have 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 efficient is high, 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 objective of the invention is to realize 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 SULPHOSUCCINIC 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, SULPHOSUCCINIC ACID ESTER and CH again
2Cl
2Solvent stirs in the reactor drum, and CPV observes and follows the tracks of no acetoxyl group octanol reaction terminating; 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, heavily dissolves crystallisation by cooling three days with the Diluted Alcohol of 2 times of amounts, 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 SULPHOSUCCINIC ACID ESTER is a triethoxy phosphine ETHYLE ACETATE;
5, described oxidation-Wittig reaction is not separate out under the midbody 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, mellitus, diabetic complication, high-intensity brainwork and treatments such as manual work, neurasthenia.
(4) embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is further described:
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; Get Formulae II
oxidation then-Wittig reaction and do not separate out Wittig reaction under synthetic intermediate III
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; Tell organic phase, get chemical formula
Each component proportions of present embodiment is: chemical formula
1mol
Silica gel PCC 1.15mol
SULPHOSUCCINIC ACID ESTER 1.3mol
Solvent C H
2Cl
2It is chemical formula
1.5 times (volumes)
Stirring at room is three hours in reactor drum, and 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=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, heavily dissolves crystallisation by cooling three days with the Diluted Alcohol of 2 times of amounts, 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
-), SULPHOSUCCINIC ACID ESTER is a triethoxy phosphine ETHYLE ACETATE, and oxidation-Wittig reaction is not separate out one kettle way reaction under the midbody condition, and the temperature of reaction characteristics is a room temperature in the process method, and the heavily molten Diluted Alcohol liquid of employing is the ethanol of 30%-60%.
Claims (8)
1. 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 SULPHOSUCCINIC 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
IV
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, SULPHOSUCCINIC ACID ESTER and CH again
2Cl
2Solvent stirs in the reactor drum, and CPV observes and follows the tracks of no acetoxyl group octanol reaction terminating; 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 water and strip 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, heavily dissolves crystallisation by cooling three days with the Diluted Alcohol of 2 times of amounts, 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 1 is characterized in that oxygenant is silica gel adsorption pyridinium chloro-chromate PyH in the described oxidizing reaction
+CrO
3Cl
-
4. the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1 is characterized in that described SULPHOSUCCINIC ACID ESTER is a triethoxy phosphine ETHYLE ACETATE.
5. the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1 is characterized in that described oxidation-Wittig reaction is not separate out one kettle way reaction under the midbody condition.
6. the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1 is characterized in that described chemical formula
Consumption 1mol, silica gel PCC consumption 1.15mol, SULPHOSUCCINIC ACID ESTER consumption 1.3mol, solvent C H
2Cl
2Consumption is a chemical formula
1.5 times of volume.
7. the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1 is characterized in that Diluted Alcohol liquid is the ethanol of 30%-60% in the described heavy molten process.
8. the method by the synthetic E-10-hydroxy-2-decylenic acid of ω-chlorine octanol according to claim 1, the temperature that it is characterized in that described reaction conditions is a room temperature.
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| 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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| 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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| CN101570482A CN101570482A (en) | 2009-11-04 |
| CN101570482B true 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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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102267893B (en) * | 2011-06-15 | 2013-06-05 | 嘉兴学院 | Preparation method of royal jelly 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 |
| WO2015171960A1 (en) | 2014-05-08 | 2015-11-12 | Dsm Ip Assets B.V. | Methods and compositions comprising 10-hydroxy-2-decenoic acid |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555351A (en) * | 2001-09-12 | 2004-12-15 | 皮埃尔・波捷 | Process for preparing unsaturated aliphatic hydroxy acids and esters thereof, use in pharmaceutical and/or cosmetic compositions |
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2009
- 2009-06-09 CN CN 200910072222 patent/CN101570482B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555351A (en) * | 2001-09-12 | 2004-12-15 | 皮埃尔・波捷 | Process for preparing unsaturated aliphatic hydroxy acids and esters thereof, use in pharmaceutical and/or cosmetic compositions |
Non-Patent Citations (1)
| Title |
|---|
| Robert Chiron.NEW SYNTHESIS OF ROYAL JELLY ACID.《Journal of Chemical Ecology》.1982,第8卷(第4期),709-713. * |
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