CN1107667C - Cis-5,9,12-octade trienic acid derivative and its prepn - Google Patents
Cis-5,9,12-octade trienic acid derivative and its prepn Download PDFInfo
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- CN1107667C CN1107667C CN00110764A CN00110764A CN1107667C CN 1107667 C CN1107667 C CN 1107667C CN 00110764 A CN00110764 A CN 00110764A CN 00110764 A CN00110764 A CN 00110764A CN 1107667 C CN1107667 C CN 1107667C
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- pinolenic acid
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Abstract
The present invention relates to a novel cis-5, 9, 12-calendic acid derivative in a general formula (1), wherein R is alkyl of hydrogen or C1 to C8. The present invention also relates to a preparation method of the derivative.
Description
The present invention relates to a kind of suitable-5,9,12-punicic acid derivative and preparation method thereof.
At present, in import and export and internal trade, the effective constituent in the check pine nut oil does not still have standard substance and compares, and this mixes for strike false making, sell-fake-products activity and discriminating and is forged into very big obstacle.In addition, according to foreign latest, scientist is by tentative experiment, and proving has a kind of material that women breast cancer is had restraining effect in the pine nut oil; By a large amount of mouse tests, this material has blood fat reducing and antiobesity action or the like.Yet, up to the present, people's this material of also not purifying out with pharmaceutical use.
The object of the present invention is to provide and a kind ofly can be used as national material standard product and have the suitable-5,9 of pharmaceutical use, 12-punicic acid derivative and preparation method thereof.
The present invention is suitable-5,9, and 12-punicic acid derivative is represented with following general formula (1):
Wherein R represents the alkyl of hydrogen or C1～C8.
The alkyl of above-mentioned C1～C8 is meant the alkyl of the straight or branched with 1～8 carbon atom, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl and octyl group etc.Preferred derivative of the present invention is that wherein R is formula (1) derivative of the alkyl of hydrogen or C1～C4.Most preferably wherein R is formula (1) derivative of hydrogen or methyl.
Preparation method of the present invention may further comprise the steps successively:
A. pine nut is shelled, pignolia core and anhydrous sodium sulphate mixed grinding powdered with the dynamic lixiviate of sherwood oil 0.5～4 hour, remove by filter residue and remove solvent under reduced pressure in 35～70 ℃.
B. under 10～80 ℃ of conditions, react 0.5～2 hour (nitrogen protection) with 1～5mol/l potassium hydroxide solution and alcohol compound with 2: 1 ratio.Use 1～5mol/l hcl acidifying then, separate mixed fatty acid.
C. with mixed fatty acid: alcohol compound: the mixture of urea=1: 10: 3 is in 35～90 ℃ (nitrogen protection) heating 1～6 hour, slowly cool off thick pinolenic acid.
D. thick pinolenic acid and alcohol compound are pressed 10: 1～20 mixture in 60～90 ℃ of (nitrogen protection) reflux after 0.5～2 hour; steam and remove alcohol compound; add water and use petroleum ether extraction; be washed till neutrality with diluted alkaline; use anhydrous sodium sulfate drying; remove sherwood oil under reduced pressure in 35～70 ℃ (nitrogen protections), get thick pinolenic acid derivative.
E. with thick pinolenic acid derivative through 5～30% Silver Nitrates-silica gel column chromatography, with sherwood oil: ether, acetone, ethyl acetate, chloroform=1: 0～100 are eluent, impurity is separated with it fully, obtain purity at last and be the pure product of pinolenic acid derivative more than 98%.
R is that the derivative of the present invention of hydrogen can R be that the product of C1-C8 is a raw material, makes according to the method acidifying of chemical field routine.
Silica gel column chromatography is to dry gained after adding silica gel behind the water dissolution Silver Nitrate.
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Suitable-5,9, the preparation of 12-punicic acid methyl esters
A. pine nut is shelled, pignolia core and anhydrous sodium sulphate mixed grinding powdered with the dynamic lixiviate of sherwood oil 2 hours, remove by filter residue and remove solvent under reduced pressure in 40 ℃.
B. under 30 ℃ of conditions, react 1 hour (nitrogen protection) with 2mol/l potassium hydroxide solution and methyl alcohol with 2: 1 ratio.Use the 4mol/l hcl acidifying then, separate mixed fatty acid.
C. with mixed fatty acid: methyl alcohol: the mixture of urea=1: 10: 3 is in 70 ℃ (nitrogen protection) heating 2 hours, slowly cool off thick pinolenic acid.
D. thick pinolenic acid and methyl alcohol after 1 hour, steam and remove methyl alcohol in 90 ℃ of (nitrogen protection) reflux by 10: 20 mixture, add water and use petroleum ether extraction; be washed till neutrality with diluted alkaline; use anhydrous sodium sulfate drying, remove sherwood oil under reduced pressure, get thick pinolenic acid methyl esters in 40 ℃ (nitrogen protections).
E. with thick pinolenic acid methyl esters through 10% Silver Nitrate-silica gel column chromatography (silica gel column chromatography is to dry gained after adding silica gel behind the water dissolution Silver Nitrate), with sherwood oil: ether, acetone, ethyl acetate, chloroform=1: 5 are eluent, impurity is separated with it fully, obtain purity at last and be the pure product of pinolenic acid methyl esters more than 98%.
Embodiment 2
Suitable-5,9, the preparation of 12-punicic acid ethyl ester
A. pine nut is shelled, pignolia core and anhydrous sodium sulphate mixed grinding powdered with the dynamic lixiviate of sherwood oil 2 hours, remove by filter residue and remove solvent under reduced pressure in 40 ℃.
B. under 30 ℃ of conditions, react 1 hour (nitrogen protection) with 2mol/l potassium hydroxide solution and ethanol with 2: 1 ratio.Use the 4mol/l hcl acidifying then, separate mixed fatty acid.
C. with mixed fatty acid: ethanol: the mixture of urea=1: 10: 3 is in 70 ℃ (nitrogen protection) heating 2 hours, slowly cool off thick pinolenic acid.
D. thick pinolenic acid and ethanol after 1 hour, steam and remove ethanol in 90 ℃ of (nitrogen protection) reflux by 10: 20 mixture, add water and use petroleum ether extraction; be washed till neutrality with diluted alkaline; use anhydrous sodium sulfate drying, remove sherwood oil under reduced pressure, get thick pinolenic acid ethyl ester in 40 ℃ (nitrogen protections).
E. with thick pinolenic acid ethyl ester through 10% Silver Nitrate-silica gel column chromatography (silica gel column chromatography is to dry gained after adding silica gel behind the water dissolution Silver Nitrate), with sherwood oil: ether, acetone, ethyl acetate, chloroform=1: 5 are eluent, impurity is separated with it fully, obtain purity at last and be the pure product of pinolenic acid ethyl ester more than 98%.
Embodiment 3
Suitable-5,9, the preparation of 12-punicic acid propyl ester
A. pine nut is shelled, pignolia core and anhydrous sodium sulphate mixed grinding powdered with the dynamic lixiviate of sherwood oil 2 hours, remove by filter residue and remove solvent under reduced pressure in 40 ℃.
B. under 30 ℃ of conditions, react 1 hour (nitrogen protection) with 2mol/l potassium hydroxide solution and propyl alcohol with 2: 1 ratio.Use the 4mol/l hcl acidifying then, separate mixed fatty acid.
C. with mixed fatty acid: propyl alcohol: the mixture of urea=1: 10: 3 is in 70 ℃ (nitrogen protection) heating 2 hours, slowly cool off thick pinolenic acid.
D. thick pinolenic acid and propyl alcohol after 1 hour, steam and remove propyl alcohol in 90 ℃ of (nitrogen protection) reflux by 10: 20 mixture, add water and use petroleum ether extraction; be washed till neutrality with diluted alkaline; use anhydrous sodium sulfate drying, remove sherwood oil under reduced pressure, get thick pinolenic acid propyl ester in 40 ℃ (nitrogen protections).
E. with thick pinolenic acid propyl ester through 10% Silver Nitrate-silica gel column chromatography (silica gel column chromatography is to dry gained after adding silica gel behind the water dissolution Silver Nitrate), with sherwood oil: ether, acetone, ethyl acetate, chloroform=1: 5 are eluent, impurity is separated with it fully, obtain purity at last and be the pure product of pinolenic acid propyl ester more than 98%.
Embodiment 4
Suitable-5,9, the preparation of 12-punicic acid
The product adding 1mol/lKOH (1: 10) of the foregoing description was reacted 1 hour, add 10mol/lHCL and be acid, reacted 1 hour, add Petroleum ether extraction, get pure pinolenic acid.
Claims (1)
1, a kind of suitable-5,9, the preparation method of 12-punicic acid derivative, it may further comprise the steps successively:
A. pine nut is shelled, pignolia core and anhydrous sodium sulphate mixed grinding powdered with the dynamic lixiviate of sherwood oil 0.5～4 hour, remove by filter residue and remove solvent under reduced pressure in 35～70 ℃;
B. under 10～80 ℃ of conditions, reacted 0.5～2 hour with 2: 1 ratio with 1～5mol/l potassium hydroxide solution and alcohol compound, use 1～5mol/l hcl acidifying then, separate mixed fatty acid;
C. with mixed fatty acid: alcohol compound: the mixture of urea=1: 10: 3 is in 35～90 ℃ of heating 1～6 hour, slowly cool off thick pinolenic acid;
D. thick pinolenic acid and alcohol compound are pressed 10: 1～20 mixture in 60～90 ℃ of reflux after 0.5～2 hour, steam and remove alcohol compound, add water and use petroleum ether extraction, be washed till neutrality with diluted alkaline, use anhydrous sodium sulfate drying, remove sherwood oil under reduced pressure in 35～70 ℃, thick pinolenic acid derivative;
E. with thick pinolenic acid derivative through 5～30% Silver Nitrates-silica gel column chromatography, with sherwood oil: ether, acetone, ethyl acetate, chloroform=1: 0～100 are eluent, impurity is separated with it fully, obtain purity at last and be the pure product of pinolenic acid derivative more than 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110764A CN1107667C (en) | 2000-08-03 | 2000-08-03 | Cis-5,9,12-octade trienic acid derivative and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110764A CN1107667C (en) | 2000-08-03 | 2000-08-03 | Cis-5,9,12-octade trienic acid derivative and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1337389A CN1337389A (en) | 2002-02-27 |
| CN1107667C true CN1107667C (en) | 2003-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN00110764A Expired - Fee Related CN1107667C (en) | 2000-08-03 | 2000-08-03 | Cis-5,9,12-octade trienic acid derivative and its prepn |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262076B (en) * | 2014-09-04 | 2016-04-13 | 宁波大红鹰生物工程股份有限公司 | A kind of method utilizing Silver Nitrate silica gel chromatography purification plant origin squalene |
| CN105175243B (en) * | 2015-07-15 | 2017-02-22 | 长春万成生物电子工程有限公司 | Method for purifying pinolenic acid from pine seed oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6163610A (en) * | 1984-09-05 | 1986-04-01 | Nisshin Oil Mills Ltd:The | Cosmetic |
| JPS61238729A (en) * | 1985-04-16 | 1986-10-24 | Nippon Oil & Fats Co Ltd | Agent for lowering cholesterol |
-
2000
- 2000-08-03 CN CN00110764A patent/CN1107667C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6163610A (en) * | 1984-09-05 | 1986-04-01 | Nisshin Oil Mills Ltd:The | Cosmetic |
| JPS61238729A (en) * | 1985-04-16 | 1986-10-24 | Nippon Oil & Fats Co Ltd | Agent for lowering cholesterol |
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| CN1337389A (en) | 2002-02-27 |
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