CN1156468C - Exaltolide preparing process from garlic oil - Google Patents
Exaltolide preparing process from garlic oil Download PDFInfo
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- CN1156468C CN1156468C CNB011327014A CN01132701A CN1156468C CN 1156468 C CN1156468 C CN 1156468C CN B011327014 A CNB011327014 A CN B011327014A CN 01132701 A CN01132701 A CN 01132701A CN 1156468 C CN1156468 C CN 1156468C
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- malania oleifera
- thibetolide
- oleifera oil
- oil
- glyceryl ester
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Abstract
The present invention relates to a method for preparing cyclopentadecanolide from garlic oil. The garlic oil is added in a reaction solvent, and ozone is led into a mixture of the garlic oil. After the ozonization is completed, a reductant is added in an ozonization fatty glyceride intermediate so as to generate pentadeca-carbon containing hydroxy fatty glyceride which has a molecular formula shown as the right formula, wherein the R4, the R5 and the R6 are alkyl with C8 to C18 carbon chains; in the presence of a proper catalyst, products are directly cyclized to generate cyclopentadecanolide containing mixing macrocyclic lactone, and then the cyclopentadecanolide is subsequently separated and purified.
Description
Technical field
The invention belongs to the particularly preparation method field of thibetolide of macrolide.
Background technology
Malania oleifera (Malania oleifera Chun et Lee), the popular name root or bark of Nepal Mallotus for a kind of woody oleiferous plants plant, is distributed in Guangxi and Yunnan.By analysis and identify that the molecular formula of its seed kernel oil fat (being malania oleifera oil) is following glyceride:
Because thibetolide has obtained application more and more widely in pharmaceutical products and senior perfume industry, its production is produced also increasing research.Existing in the literature utilize malania oleifera oil under laboratory condition, produce 15 carbon lactones (with thibetolide be same compound) report (see ＂ chemistry journal ＂ 1987.45 volume 1217-1218, Guo Maodao etc.) (hereinafter to be referred as prior art), the Figure of description of its technological process block-diagram such as the present patent application is shown in Figure 1, its method is malania oleifera oil to be carried out saponification, acidifying and solvent crystallization produce tetracosa carbon-15-olefin(e) acid, be that raw material obtains 15 carbon lactones by ozonize one reduction reaction and polycondensation one depolymerization reaction with this product again, its molecular formula is:
This preparation method has made full use of the natural resources of China, be that the synthesis method of raw material is simplified greatly with cyclododecanone more in the past, also reduced production cost, but, its saponification and acidification reaction cause environmental pollution because producing saponification waste liquid, from mixing-in fat acid extraction and the yield that separates tetracosa carbon-15-olefin(e) acid again only about 30%, add that solvent needs to reclaim, isolated solid needs drying, cause that the whole process of preparation reactions steps is many, operational path length, complicated operation, total yield is low, energy consumption is high, production cost is difficult to lower significantly.We have done as the next one by above-mentioned prior art and have tested: get 300 gram malania oleifera oil (mass content about 30% of tetracosa carbon-15-olefin(e) acid) and carry out saponification and acidifying and obtain 294 gram mixed fatty acids, obtain 35 gram tetracosa carbon-15-olefin(e) acids with the sherwood oil recrystallization, with sherwood oil-ethanol is that solvent carries out ozonize-reduction and obtains 19 gram 15-hydroxyls, 15 carbonic acid, 20 hours polymerization-depolymerization obtains the thick thibetolide of 16.5 grams then, get the thibetolide of 13.5 grams, 98.7% purity after refining, total yield is 13.5/300=4.5%.
Summary of the invention
Technical problem to be solved by this invention is to simplify the technology of producing thibetolide from malania oleifera oil, under the condition that with the suitability for industrialized production is purpose, improve the utilization ratio of effective ingredient in the malania oleifera oil, reduce environmental pollution, produce high-quality thibetolide as much as possible with alap cost.
Main technical schemes of the present invention is: after malania oleifera oil adding reaction solvent is stirred, feed ozone to mixture, after ozonization is finished, add reductive agent to ozonize glyceryl ester intermediate and make reaction generate the hydroxyl glyceryl ester that contains 15 carbon, its molecular formula is:
R wherein
4, R
5, R
6Alkyl for carbochain 8-18
In the presence of appropriate catalyst, the direct cyclisation of this product is generated the mixing macrolide that contains thibetolide, separate the purification thibetolide again.
In carrying out ozonize and reduction reaction process, the solvent that is added is single or mixes sherwood oil, dehydrated alcohol, nonyl alcohol, aliphatic saturated hydrocarbon such as the hexane of use, heptane, octane etc. that usage quantity is: solvent: malania oleifera oil=0～10 (mass ratio); The temperature of reaction of ozonize is controlled at-10～40 ℃.The reductive agent that uses has POTASSIUM BOROHYDRIDE, sodium borohydride etc., and usage quantity is: malania oleifera oil: reductive agent=2.0～7 (mass ratio).The catalyzer that uses in hydroxyl glyceryl ester cyclization process can be one or more the mixture in sodium hydroxide, potassium hydroxide, salt of wormwood, plumbous oxide, lead monoxide, methanolizing metallic compound, the dealing with alcohol metallic compound etc., temperature of reaction is controlled at 150～250 ℃, vacuum tightness is at 1～50mmHg, and the usage quantity of catalyzer is: catalyzer is 0.1%～10% (mass ratio) of malania oleifera oil.
The present invention produces the method for thibetolide from malania oleifera oil, compared with the prior art, has significantly reduced reactions steps, has simplified technological process, has reduced energy consumption, and the total yield height, and production cost significantly reduces.
Description of drawings
Fig. 1 is a production technique skeleton diagram of producing the prior art of thibetolide from malania oleifera oil.
Fig. 2 is a production technique skeleton diagram of producing thibetolide from malania oleifera oil of the present invention.
Embodiment
Embodiment 1:
2400 gram malania oleifera oil (mass content about 30% of tetracosa carbon-15-olefin(e) acid) mix with 5600 gram sherwood oils puts into the gas liquid reaction still, feeding ozone down in 20 ℃ reacts, after being reacted to terminal point, under 25 ℃ of stirrings, slowly drip the aqueous solution that contains 800 gram POTASSIUM BOROHYDRIDE, 4 hours reaction times.Regulate PH=6～7 with sulfuric acid then, standing demix is got and is obtained 2100 gram hydroxyl glyceryl ester after oil reservoir heating steaming desolventizes.The 240 gram hydroxyl glyceryl ester of getting are wherein put into there-necked flask, add 18 gram sodium methylates, and reacting by heating liquid to 180～230 ℃ under vacuum tightness 3～10mmHg reacts and obtained product 188 in 12 hours and restrain.By obtaining the thibetolide of 48 grams, 98.5% purity behind rectifying and the alcohol crystal.Total yield is (2100/2400) * (48/240)=17.5%.
Embodiment 2:
300 gram malania oleifera oil (mass content about 50% of tetracosa carbon-15-olefin(e) acid) mix with 1000 gram sherwood oils and 500 gram ethanol puts into the gas liquid reaction still, feeding ozone down in 10 ℃ reacts, after being reacted to terminal point, under 25 ℃ of stirrings, slowly drip the aqueous solution that contains 65 gram POTASSIUM BOROHYDRIDE, between 4 hours reaction times.Regulate PH=6～7 with sulfuric acid then, standing demix is got and is obtained 265 gram hydroxyl glyceryl ester after oil reservoir heating steaming desolventizes.The 180 gram hydroxyl glyceryl ester of getting are wherein put into reactor, add 7 gram sodium methylates, and reacting by heating liquid to 180～230 ℃ under vacuum tightness 3～10mmHg add glycerine and carry distillation secretly as entrainment agent, reacts to obtain product 130 in 12 hours and restrain.By obtaining the thibetolide of 59 grams, 98.5% purity behind rectifying and the alcohol crystal.Total yield is (265/300) * (59/180)=30%.
Embodiment 3:
The manufacture method of hydroxyl glyceryl ester is with embodiment 2.Get 180 gram hydroxyl glyceryl ester and put into reactor, add 9 gram sodium methylates, reacting by heating liquid to 180～230 ℃ under vacuum tightness 3～10mmHg add glycerine and carry distillation secretly as entrainment agent, reacts to obtain product 136 in 16 hours and restrain.By obtaining the thibetolide of 61 grams, 98.5 purity behind rectifying and the alcohol crystal.Total yield is (61/180)=33.9%.
Embodiment 4:
The manufacture method of hydroxyl glyceryl ester is with embodiment 2.Get 180 gram hydroxyl glyceryl ester and put into reactor, add 8 gram sodium methylates and 0.5 gram salt of wormwood, reacting by heating liquid to 180～210 ℃ under vacuum tightness 1～3mmHg add glycerine and carry distillation secretly as entrainment agent, reacts to obtain product 140 in 12 hours and restrain.By obtaining the thibetolide of 65 grams, 98.5% purity behind rectifying and the alcohol crystal.Total yield is (65/180)=36.1%.
Claims (5)
1, a kind of method of producing thibetolide from malania oleifera oil, it is characterized in that behind the malania oleifera oil adding reaction solvent, feed ozone to the malania oleifera oil mixt, make reaction generate the hydroxyl glyceryl ester that contains 15 carbon to ozonize glyceryl ester intermediate adding reductive agent after finishing ozonize, its molecular formula is:
In the presence of appropriate catalyst, the direct cyclisation generation of this product is contained the mixing macrolide that encircles ten five-esters, separate the purification thibetolide again.
2, the method for producing thibetolide from malania oleifera oil as claimed in claim 1, when it is characterized in that preparing ozonize glyceryl ester intermediate, the solvent that ozonization added is one or more mixtures in sherwood oil, dehydrated alcohol, nonyl alcohol, aliphatic saturated hydrocarbon such as hexane, heptane, the octane etc.; The mass ratio of usage quantity is: solvent: malania oleifera oil=0～10.
3, claim 1 or the 2 described methods of producing thibetolide from malania oleifera oil, it is characterized in that the reductive agent that the reduction of ozonize glyceryl ester intermediate is used is a kind of of sodium borohydride, POTASSIUM BOROHYDRIDE, the mass ratio of usage quantity is: malania oleifera oil: reductive agent=2.0～7.
4, as claimed in claim 1 or 2ly produce the method for thibetolide, it is characterized in that the catalyzer that uses is one or more the mixture in sodium hydroxide, potassium hydroxide, salt of wormwood, plumbous oxide, lead monoxide, methanolizing metallic compound, the dealing with alcohol metallic compound etc. in hydroxyl glyceryl ester cyclization process from malania oleifera oil; Temperature of reaction is controlled at 150-250 ℃, vacuum tightness 1～50mmHg, and the mass ratio of catalyzer usage quantity is: catalyzer is 0.1%～10% of a malania oleifera oil.
5, as claimed in claim 3ly produce the method for thibetolide, it is characterized in that the catalyzer that uses is one or more the mixture in sodium hydroxide, potassium hydroxide, salt of wormwood, plumbous oxide, lead monoxide, methanolizing metallic compound, the dealing with alcohol metallic compound etc. in hydroxyl glyceryl ester cyclization process from malania oleifera oil; Temperature of reaction is controlled at 150-250 ℃, vacuum tightness 1～50mmHg, and the mass ratio of catalyzer usage quantity is: catalyzer is 0.1%～10% of a malania oleifera oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011327014A CN1156468C (en) | 2001-09-03 | 2001-09-03 | Exaltolide preparing process from garlic oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011327014A CN1156468C (en) | 2001-09-03 | 2001-09-03 | Exaltolide preparing process from garlic oil |
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| CN1349988A CN1349988A (en) | 2002-05-22 |
| CN1156468C true CN1156468C (en) | 2004-07-07 |
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| CNB011327014A Expired - Fee Related CN1156468C (en) | 2001-09-03 | 2001-09-03 | Exaltolide preparing process from garlic oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365290A (en) * | 2017-08-10 | 2017-11-21 | 王显权 | The method that Malania Oleifera Oil prepares pentadacanolide |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100575350C (en) * | 2007-06-29 | 2009-12-30 | 浙江工业大学 | A kind of Macrocyclic glyceride and its production and application with anti-oxidant activity |
| CN106565662B (en) * | 2016-10-26 | 2019-05-21 | 西南林业大学 | Macrocyclic musk-pentadacanolide method is prepared using Malania Oleifera Oil |
| CN107569411A (en) * | 2017-08-04 | 2018-01-12 | 杨宇明 | A kind of plant source Moschus cosmetics and preparation method thereof |
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2001
- 2001-09-03 CN CNB011327014A patent/CN1156468C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365290A (en) * | 2017-08-10 | 2017-11-21 | 王显权 | The method that Malania Oleifera Oil prepares pentadacanolide |
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Granted publication date: 20040707 Termination date: 20120903 |