CN100450987C - Synthesis of isodecyl isoamyl dienol - Google Patents
Synthesis of isodecyl isoamyl dienol Download PDFInfo
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- CN100450987C CN100450987C CNB2006100056498A CN200610005649A CN100450987C CN 100450987 C CN100450987 C CN 100450987C CN B2006100056498 A CNB2006100056498 A CN B2006100056498A CN 200610005649 A CN200610005649 A CN 200610005649A CN 100450987 C CN100450987 C CN 100450987C
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- dienol
- isodecyl
- isoamyl
- eggplant
- alcohol
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Abstract
The present invention discloses a process of preparing isodecyl isoamyl dienol, which has the steps that high purity solanesol with the contents of 96% is used as raw material and reacts with ethyl acetoacetate through halogenation to obtain solane acetone which then reacts with selfmade vinylmagnesium chloride to obtain isodecyl isoamyl dienol. The process has the total yield of 48 % by accounting in solanesol.
Description
Patent of the present invention is to divide an application, and original applying number is: 200410040400.1; Original application day is: on August 6th, 2004; The original application denomination of invention is: a kind of extracting method of high-purity solanesol.
Technical field:
The present invention relates to the synthetic of a kind of isodecyl isoamyl dienol.
Background technology:
The English name of eggplant Buddhist nun alcohol is Solanesol, it is the main intermediate of synthesizing coenzyme Q 10 and multiprenylmenaquinone and the important intermediate of making some anti-allergy agent, anti-ulcerative drug, hypolipidemic, anticarcinogen, mainly being present in animal viscera and the plant leaf, is height with content in the tobacco.The method of extracting eggplant Buddhist nun alcohol from tobacco has multiple, it as the patent No. 94107849.3 the method for from the tobacco of extracting nicotine, extracting eggplant Buddhist nun alcohol, be to be raw material with the tobacco of extracting nicotine, through oven dry, pulverizing, with the Cs---G2 fat alkane is solvent extraction, concentrated extracting solution, add the soda ash solution saponification, remove and anhydrate and solvent, handle with the mixed solvent of ketone and alcohol, cooling, separate out eggplant Buddhist nun alcohol, with the eggplant Buddhist nun alcohol that this method is extracted, purity can only reach 90%, purity is low, does not reach the requirement of pharmacy.
Summary of the invention:
The purpose of this invention is to provide a kind of eggplant Buddhist nun alcohol purity height of purification, the method for extraction of high purity solanesol alcohol that production cost is low, and as raw material through halo, make eggplant Thessaloniki acetone with the methyl aceto acetate reaction, the latter obtains the isodecyl isoamyl dienol synthetic method with homemade chlorovinyl reactive magnesium again.
The synthetic method of isodecyl isoamyl dienol of the present invention is finished like this: the extracting method of high-purity solanesol is to be raw material with the thick cream of eggplant Buddhist nun alcohol, through saponification solvent extraction blending means, through saponification → extraction → crystallization → recrystallization → removal of impurities → steps such as chromatography, obtain content at last and be 96% high-purity solanesol, yield 48-55%; The synthetic method that it is characterized in that isodecyl isoamyl dienol is that the eggplant Buddhist nun alcohol with 96% content is raw material, through halo, react with methyl aceto acetate, make eggplant Thessaloniki acetone again, the latter and the reaction of chlorovinyl Grignard reagent, the synthetic isodecyl isoamyl dienol that obtained calculates with eggplant Buddhist nun alcohol, the three-step reaction total recovery is that 48% extracting method adopts saponification one solvent extraction synthetic method, and used solvent is industrial methanol, ethanol, 6
#Oil, molten Ji consumption is 20-40 times during saponification, the mixed solvent alcohol oil rate is 95～98: 5～2, saponification temperature 40-80 ℃ of time 2-6h, decolouring simultaneously, adding assistant, cooling, precipitation, centrifugation after the saponification; Saponification post crystallization gained eggplant Buddhist nun alcohol is through the organic solvent recrystallization, and coarse crystallization is separated through removal of impurities, last column chromatography purification, but described impurity-removing method vacuum filtration, membrane filtration, clear are filtered, are added diatomite and help filter or clarify tubular type centrifuging; Filtered liquid after the processing concentrates upper prop and separates, and behind the primary column chromatography, product purity can reach 〉=90%, twice column chromatography for separation, and eggplant Buddhist nun alcohol purity just can reach 96%; The eggplant Buddhist nun alcohol of 96% content is through halo, acetonylization obtains eggplant Thessaloniki acetone, and then the feature of synthetic isodecyl isoamyl dienol is to have adopted the reaction of homemade chlorovinyl Grignard reagent and eggplant Thessaloniki acetone, adds the protophobe hydrolysis and obtains isodecyl isoamyl dienol, and yield can reach 80%; The reaction of vinylchlorid Grignard reagent and eggplant Thessaloniki acetone, solvent are anhydrous tetrahydro furan, temperature of reaction between+40-100 ℃, and protophobe comprises the water and the aqueous solution, pure and mild alcoholic solution, organic-inorganic acid solution.
It is 96% high-purity solanesol that technology of the present invention can be extracted content, has the yield height, the advantage that cost is low.While can also be a raw material with this high-purity solanesol, reacts through halo, with methyl aceto acetate to make eggplant Thessaloniki acetone, and the latter obtains isodecyl isoamyl dienol with homemade chlorovinyl reactive magnesium again, and total recovery counts 48% with eggplant Buddhist nun alcohol.
Embodiment:
The extraction of embodiment 1 1.1 high-purity solanesols (96%)
The thick eggplant Buddhist nun of 100g alcohol (content 17%), alkaline saponification in (methyl alcohol, sherwood oil 95: 5) in the 1000ml mixed organic solvents, in 4 hours reaction times, 60 ℃ of temperature of reaction are after reaction is finished, adding 1500ml mixed solvent and discoloring agent again continues to stir 1 hour, cooling precipitation, centrifugation, filtered liquid separate the crystallization that obtains-25 ℃ of-0 ℃ of crystallizations, use above-mentioned mixed solvent recrystallization again, getting content is the eggplant Buddhist nun alcohol of 50-75%.The latter is with non-machine organic solvent dissolution, with the removal of impurities of tubular type clarification filtration, filtrate concentrates carries out column chromatography purification and separates, and elutriant can get content through condensing crystal and be 〉=90% eggplant Buddhist nun alcohol, can obtain content on the secondary behind the column purification and be 96% high-purity solanesol 9.5g, yield is 55%.
1.2 the preparation of isodecyl isoamyl dienol
Get 96% eggplant Buddhist nun alcohol 100g, be dissolved among the 160ml exsiccant DMF, under cryosel is bathed, slowly add PCl
313ml, reaction 2-5h uses petroleum ether extraction, Na
2CO
3The aqueous solution and NaCl water washing, Na
2SO
4Drying, concentrate eggplant Thessaloniki chlorine 92.3g, mass yield 92%.
92g eggplant Thessaloniki chlorine is dissolved in the 150ml sherwood oil, slowly drips in the solution of 130ml anhydrous (including 5.8gNa) sodium ethylate liquid and 36ml methyl aceto acetate, behind the reaction 5-10h, add the hydrolysis of NaOH solution, use solvent extraction, Na
2SO
4Drying, concentrate the thick ketone of eggplant Thessaloniki, thick ketone is through recrystallization, separate content 〉=78% eggplant Thessaloniki acetone 63g, mass yield is 68%.
Getting 63g eggplant Thessaloniki ketone is dissolved among the anhydrous THF of 65ml, slowly splash among the THF that contains saturated chlorovinyl magnesium Grignard reagent 300ml and carry out grignard reaction, be reflected under the temperature control state and carry out, behind the time 3-6h, hydrolysis, hydrolyzate solvent extraction, drying, condensing crystal, filter, vacuum-drying gets isodecyl isoamyl dienol 51g, (yield 80.9%).Product is a white crystal
The extraction of embodiment 2 2.1. high-purity solanesols (96%).
The thick eggplant Buddhist nun of 100g alcohol (content 17%), alkaline saponification in (ethanol, sherwood oil 95: 5) in the 1000ml mixed organic solvents, reaction times 6h, 70 ℃ of temperature of reaction are after reaction is finished, adding 1200ml mixed solvent and discoloring agent again continues to stir 1 hour, cooling precipitation, centrifugal powder from, filtered liquid separates the crystallization that obtains 0-15 ℃ of following crystallization, use above-mentioned mixed solvent recrystallization again, getting content is the eggplant Buddhist nun alcohol of 50-75%.The latter is dissolved with non-polar organic solvent, adopt the vacuum filtration removal of impurities, carry out column chromatography purification after filtrate concentrates and separate, can to reach content be 90% eggplant Buddhist nun alcohol to elutriant through concentrating post crystallization, can obtain content on the secondary behind the column purification and be 96% high-purity solanesol 8.2g, yield is 48%.
2.2 the preparation of isodecyl isoamyl dienol
Get 95% eggplant Buddhist nun alcohol 100g, be dissolved in the 160ml exsiccant ether, under cryosel is bathed, slowly add PBr3,14ml, reaction 2-5h uses petroleum ether extraction, Na
2CO
3The aqueous solution and NaCl water washing, Na
2SO
4Drying, concentrate eggplant Thessaloniki bromine 95g, mass yield 95%.
95g eggplant Thessaloniki bromine is dissolved in the 150ml sherwood oil, slowly drip in the solution of 130ml sodium ethylate and 36ml methyl aceto acetate, behind the reaction 5-10h, add the hydrolysis of NaOH solution, use solvent extraction, drying, concentrate the thick ketone of eggplant Thessaloniki, thick ketone is through recrystallization, or gets content 78% eggplant Thessaloniki acetone 63g with chromatographic separation, and mass yield is 68%.
Getting 63g eggplant Thessaloniki ketone is dissolved among the anhydrous THF of 65ml, slowly splashing into 300ml contains among the THF of saturated chlorovinyl magnesium Grignard reagent, carry out grignard reaction, be reflected under the temperature control state and carry out, behind the time 3-6h, hydrolysis, hydrolyzate solvent extraction, drying, condensing crystal filters, vacuum-drying gets isodecyl isoamyl dienol 51g, (yield 80.9%).Product is white crystal mp29-30 ℃
The extraction of embodiment 3 3.1. high-purity solanesols (96%)
The thick eggplant Buddhist nun of 100g alcohol (content 17%), alkaline saponification in (methyl alcohol, sherwood oil 98: 2) in the 1000ml mixed organic solvents, reaction times 2h, 80 ℃ of temperature of reaction are after reaction is finished, adding 1500ml mixed solvent and discoloring agent again continues to stir 1 hour, cooling precipitation, centrifugation, filtered liquid separate the crystallization that obtains 0-10 ℃ of following crystallization, use above-mentioned mixed solvent recrystallization again, getting content is the eggplant Buddhist nun alcohol of 50-75%.The latter is dissolved with non-polar organic solvent, clarification filtration.Filtering in centrifugal minute is assorted, carries out column chromatography purification after filtrate concentrates and separates, and elutriant should can to reach content be 90% eggplant Buddhist nun alcohol through concentrating post crystallization, can obtain content on the secondary behind the column purification and be 96% high-purity solanesol 9.2g, and yield is 54%.
3.2 the preparation of isodecyl isoamyl dienol
Get 96% eggplant Buddhist nun alcohol 100g, be dissolved in the 500ml exsiccant ether, under cryosel is bathed, slowly add PBr3,14ml, reaction 2-5h uses petroleum ether extraction, Na
2CO
3The aqueous solution and NaCl water washing, Na
2SO
4Drying, concentrate eggplant Thessaloniki bromine 96g, mass yield 96%.96g eggplant Thessaloniki bromine is dissolved in the 150ml sherwood oil, slowly drip in the solution of 130ml sodium ethylate and 36ml methyl aceto acetate, behind the reaction 5-10h, add the hydrolysis of NaOH solution, use solvent extraction, drying, concentrate the thick ketone of eggplant Thessaloniki, thick ketone is through getting content 85% eggplant Thessaloniki acetone 60g with chromatographic separation, mass yield is 62.5%.Getting 63g eggplant Thessaloniki ketone is dissolved among the anhydrous THF of 65ml, slowly splashing into 300ml contains among the THF of saturated chlorovinyl magnesium Grignard reagent, carry out grignard reaction, be reflected under the temperature control state and carry out, behind the time 3-6h, hydrolysis, hydrolyzate solvent extraction, drying, condensing crystal filters, vacuum-drying gets isodecyl isoamyl dienol 51g, (yield 85%).Product is a white crystal.
Claims (2)
1, a kind of isodecyl isoamyl dienol is synthetic, the synthetic method that it is characterized in that isodecyl isoamyl dienol is that the eggplant Buddhist nun alcohol with 96% content is raw material, through halo, react with methyl aceto acetate, make eggplant Thessaloniki acetone again, the latter and the reaction of chlorovinyl Grignard reagent, add the protophobe hydrolysis and obtain isodecyl isoamyl dienol, solvent is anhydrous tetrahydro furan, temperature of reaction between+40-100 ℃, the synthetic isodecyl isoamyl dienol that obtained, calculate with eggplant Buddhist nun alcohol, the three-step reaction total recovery is 48%.
2, isodecyl isoamyl dienol according to claim 1 is synthetic, and feature is that protophobe is water, aqueous solution, alcohol, contains solution, organic acid soln or the inorganic acid solution of alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100056498A CN100450987C (en) | 2004-08-06 | 2004-08-06 | Synthesis of isodecyl isoamyl dienol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100056498A CN100450987C (en) | 2004-08-06 | 2004-08-06 | Synthesis of isodecyl isoamyl dienol |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100404001A Division CN100417632C (en) | 2004-08-06 | 2004-08-06 | Method for extraction of high purity solanocupsin and synthesis of isodecyl dienol and isoprenol |
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| CN1821197A CN1821197A (en) | 2006-08-23 |
| CN100450987C true CN100450987C (en) | 2009-01-14 |
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| CNB2006100056498A Expired - Fee Related CN100450987C (en) | 2004-08-06 | 2004-08-06 | Synthesis of isodecyl isoamyl dienol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100381413C (en) * | 2006-09-14 | 2008-04-16 | 浙江大学 | Preparation of high purity solanesol |
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Non-Patent Citations (2)
| Title |
|---|
| 癸异戊二烯醇的合成研究. 王超杰等.精细化工，第17卷第9期. 2009 |
| 癸异戊二烯醇的合成研究. 王超杰等.精细化工，第17卷第9期. 2009 * |
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