CN105085268A - Method for enriching natural MeJA (methyl jasmonate) from aglaia odorate oil - Google Patents

Method for enriching natural MeJA (methyl jasmonate) from aglaia odorate oil Download PDF

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CN105085268A
CN105085268A CN201510644527.2A CN201510644527A CN105085268A CN 105085268 A CN105085268 A CN 105085268A CN 201510644527 A CN201510644527 A CN 201510644527A CN 105085268 A CN105085268 A CN 105085268A
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meja
oil
phase solution
solution
extraction
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CN105085268B (en
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李斌
陈亮
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Burton (shanghai) Biotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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Abstract

The invention discloses a method for enriching natural MeJA (methyl jasmonate) from aglaia odorate oil. The method comprises steps as follows: firstly, an extracting solution is prepared, that is, petroleum ether, methanol and water are mixed in the volume ratio being (2-8):(1-7):(0.3-1), the mixture is fully and evenly mixed and then left to stand for layering, upper and lower phases are separately stored in different containers, and an upper-phase solution A and a lower-phase solution B are obtained; then MeJA extraction separation is performed, that is, after the aglaia odorate oil is added to the upper-phase solution A to be dissolved, the lower-phase solution B with the equal volume is added for extraction, the soluble mass-to-volume ratio of the aglaia odorate oil to the upper-phase solution A is 1:(1-10), a lower-phase solution is discharged after layering, the lower-phase solution B is added to the upper-phase solution continuously for extraction once or for multiple times, all lower-phase solutions obtained through extraction each time are mixed, and a MeJA enrichment part is obtained through reduced pressure concentration; finally, the MeJA is subjected to column chromatographic separation and purification. The technology is simple, operation is convenient, the equipment investment is low, and the obtained MeJA compound is high in purity and good in quality.

Description

A kind of method of the natural methyl jasmonate of enrichment from oil of aglaia odorate
Technical field
The invention belongs to chemical technology field, relate to the method for the natural methyl jasmonate of separation and concentration from oil of aglaia odorate medicinal extract.
Background technology
Methyl jasmonate, Chinese: methyl jasmonate, pentenyl cyclopentanone-3-methyl acetate, English name: Methyljasmonate, writes a Chinese character in simplified form: MeJA, chemical name: 2-(1R, 2R)-3-ketone group-2-((Z)-2-heptene) NSC 60134 methyl esters, 2-((1R, 2R)-3-oxo-2-((Z)-pent-2-enyl) cyclopentyl) acetate, CAS:1211-29-6, molecular formula: C 13h 20o 3, molecular weight: 224.3, structural formula is:
Methyl jasmonate, colourless to weak yellow liquid, boiling point: higher than 300 DEG C, density: 1.02; Flash-point: 156 DEG C, refractive index 20 DEG C: 1.473-1.477; Water-soluble hardly, be dissolved in ethanol and oils, strong, soft and happy jasmin, more lasting than methyl dihydrojasmonate fragrance.Natural be present in Spanish jasmin, Tunisia Rosmarinus officinalis, pepper, spearmint, in tree orchid and tealeaves.Can be widely used in manually preparing jasmin quintessence oil, also may be used in jasmine perfume base, making essence have the characteristic perfume of natural Flower of Arabian Jasmine, but price is more expensive at present, be now mainly used in the formulas such as high-grade perfume fragrance, cosmetic essence.Current chemosynthesis circuit is a lot, but all very complicated.
Methyl jasmonate is a kind of micromolecular compound with several functions.Methyl jasmonate occupies an important position in essence and flavoring agent field, and the flowers and plants with strong lasting similar jasmin quintessence oil are fragrant and fragrant and sweet, are generally used in the cosmetics of super quality because it is expensive.Meanwhile, jasmonate class is novel plant hormone, can the aging of involved in plant organ, induction its secondary metabolites content, the induction physiological process such as fruit maturation, anti-freezing injury.In addition, good anti-tumor activity is shown at field of medicaments jasmonate and derivative thereof, although its effect in oncotherapy and antitumor mechanism also need to further investigate widely, but normal cell tissue toxicity can be reduced react compared with existing chemotherapeutic, and also have certain curative effect to the tumour cell of many resistances, both can also can as preventive usage as therapeutic medication.
In view of the huge Development volue that jasmonate is potential, finding the more natural phant of content or developing new preparation method to become the top priority of jasmonate research.
The traditional preparation method of jasmonate is chemosynthesis, the equal more complicated of synthesis technique step, and product is the mixture of isomer, and individual isomer is difficult to obtain, and is chemical.
The methyl jasmonate of plant origin is single configuration methyl jasmonate, and is natural methyl jasmonate.Current natural methyl jasmonate is present in plants essential oil or medicinal extract or absolute oil usually, and as oil of aglaia odorate volatile component 86 kinds, methyl jasmonate accounts for about 4.5%.Routine techniques such as distillation, column chromatography etc. are difficult to the methyl jasmonate that separation energy obtains high-content.
Summary of the invention
For the problems referred to above that prior art exists, the object of this invention is to provide a kind of simple, and the preparation method that natural methyl jasmonate content is high.
For achieving the above object, the present invention adopts following technical scheme: a kind of method of the natural methyl jasmonate of enrichment from oil of aglaia odorate, comprises the steps:
Step 1, extraction liquid is prepared
Get sherwood oil, methyl alcohol, water, according to volume ratio 2-8:1-7:0.3-1 mixing, fully stratification after mixing, is separately stored in upper and lower phase in different vessels, obtains phase solution A and lower phase B solution;
Step 2, MeJA extracting and separating
After oil of aglaia odorate being added the dissolving of upper phase solution A, add isopyknic lower phase B solution extraction, the mass volume ratio that wherein orchid oil and upper phase solution A are dissolved is 1:1-10, lower phase solution is released after layering, upper phase solution continues to add lower phase B solution and to extract 1 time or repeatedly, merge all lower phase solution of each extraction, concentrating under reduced pressure obtains the enrichment positions C of MeJA;
Step 3, column chromatographic isolation and purification MeJA
Step 2 is extracted after the MeJA enrichment positions C obtained adds silica gel mixed sample and be splined on silica gel column chromatography, wherein enrichment positions C is 1:1-2 with mixing sample silica gel ratio, with petroleum ether-ethyl acetate system gradient elution, when elutriant ratio is 5-40:1, collect elutriant, concentrating under reduced pressure obtains the enrichment positions D of MeJA after purifying.
As optimization, in described step 1, sherwood oil, methyl alcohol, water, according to volume ratio 5:4:1;
The mass volume ratio that in described step 2, orchid oil and upper phase solution A are dissolved is 1:5;
In described step 3 when elutriant ratio is 20:1, collect elutriant, concentrating under reduced pressure obtains the enrichment positions D of MeJA after purifying.
The present invention is found by research, and two-phase extraction system contributes to concentration and separation methyl jasmonate from oil of aglaia odorate.Further research finds, the three components two-phase extraction system be made up of sherwood oil, methyl alcohol, water is more conducive to the enrichment of methyl jasmonate.Find further, sherwood oil, methyl alcohol, water three components are two-layer up and down according to being divided into after the mixing of certain ratio, and upper strata is upper phase solution A, and lower floor is lower phase B solution again.Find further, jointly from oil of aglaia odorate, extract methyl jasmonate by upper phase solution A and lower phase B solution, concentration and separation effect is best again.Find further, oil of aglaia odorate first adds phase solution A again, then adds lower phase B solution, and effect of extracting is better than oil of aglaia odorate and first adds lower phase B solution, adds the extraction of phase solution A.Because when oil of aglaia odorate mixes with 1:5 mass volume ratio with lower phase B solution, if oil of aglaia odorate first adds lower phase B solution, so oil of aglaia odorate is difficult to dissolve completely in lower phase B solution, and when thus adding phase solution A subsequently, extraction efficiency is poor.Phase B solution volume under certain increase is until the oil of aglaia odorate added dissolves, and one is increase B solution cost, and two is need to increase more solution A to extract, thus increases solution A cost, and three is that wastewater flow rate increases along with solution A and B solution increase.Find further, the amount that lower phase B solution adds in upper phase solution A, too much or very fewly all should be unfavorable for two-phase laminated flow by equal-volume as far as possible, thus causes enriched product quantity few, and content is low again.
Find further, two-phase extracting process combines with simple silica gel column chromatography again, can remove other compositions in enriched substance further, improves the content of methyl jasmonate in enriched substance.And single method such as two-phase extraction or column chromatography all can not significantly improve enriched product methyl jasmonate content.
Relative to prior art, tool of the present invention has the following advantages:
1, the present invention adopt double solvents enrichment and column chromatography to combine method purifying oil of aglaia odorate in methyl jasmonate compound, separation degree is good, and gained methyl jasmonate compound purity is high, and quality is good; Methyl jasmonate enriching and purifying successful, improves the effective concentration of methyl jasmonate.
2, the invention provides the new way of a separation and concentration methyl jasmonate from plant, the plant origin containing methyl jasmonate enriches, and technique is simple, and easy to operate, facility investment is few, has a good application prospect.
Embodiment
Below the present invention is described in further detail.
The present invention extracts methyl jasmonate through processing steps such as extraction liquid preparation, extracting and separating, column chromatographies, concentration effect methyl jasmonate single-component content from tree orchid essential oil brings up to more than 90% from 4.5%, methyl jasmonate enriching and purifying successful, improve the effective concentration of methyl jasmonate, present invention process is easy, bioaccumulation efficiency is high, and facility investment is few, has a good application prospect.In addition, the present invention proposes the method for the natural methyl jasmonate of separation and concentration from oil of aglaia odorate medicinal extract, the raw material sources that natural methyl jasmonate compound separation extracts preparation are enriched, be conducive to the flavouring exploitation of natural methyl jasmonate compound, also be conducive to alleviating because natural methyl jasmonate price is high simultaneously, and limit a difficult problem for the development and application research of natural methyl jasmonate compound.
Embodiment 1: a kind of method of the natural methyl jasmonate of enrichment from oil of aglaia odorate, comprises the steps:
Step 1, extraction liquid is prepared
Get sherwood oil (100ml), methyl alcohol (80ml), water (20ml), mix according to volume ratio 5:4:1, stratification after abundant mixing, is separately stored in upper and lower phase in different vessels, obtains phase solution A and lower phase B solution.
Step 2, MeJA extracting and separating
Get oil of aglaia odorate 6g, adding phase solution A on 30mL is transferred in separating funnel after dissolving, add isopyknic lower phase B solution extraction, lower phase solution is released after layering, upper phase solution continues to add lower phase B solution (30 milliliters) extraction 2 times, merge all lower phase solution of each extraction, concentrating under reduced pressure obtains the enrichment positions C of MeJA.Detect for GC after the enrichment positions C of MeJA of taking a morsel adds dichloromethane solvent dilution and analyze, result display methyl jasmonate accounts for 44.2%, light yellow transparent liquid.
Step 3, column chromatographic isolation and purification MeJA
Step 2 is extracted the MeJA enrichment positions C obtained to add 1 times after the silica gel mixed sample of enrichment positions C quality and be splined on silica gel column chromatography, with petroleum ether-ethyl acetate system gradient elution, when elutriant ratio is 20:1, collect elutriant, concentrating under reduced pressure obtains the enrichment positions D of MeJA, colourless transparent liquid.Get MeJA enrichment positions D and add q. s. methylene chloride dissolved dilution on a small quantity, analyze after crossing 0.22 μm of organic phase filter membrane for GC, result display methyl jasmonate accounts for 90%.
Provide the comparative example of the natural methyl jasmonate method of embodiment 1 enrichment below:
Comparative example 1: silica gel column chromatography concentration and separation MeJA
Step 1, loading
Choose 30 × 250mm chromatography column, dry method loads 200-300 order silica gel 50g, paves rear decompression and bleeds silica gel is loaded closely, then get the direct loading of oil of aglaia odorate 5g.
Step 2, wash-out
Adsorb completely on a silica gel column until sample, use normal hexane, normal hexane-methylene dichloride 1:1 (volume ratio), methylene dichloride, each 300mL wash-out of ethyl acetate successively.Collect dichloromethane eluant, concentrating under reduced pressure obtains the enrichment positions D of MeJA, colourless transparent liquid.
Step 3, Analysis and Identification
Get MeJA enrichment positions D and add q. s. methylene chloride dissolved dilution on a small quantity, analyze after crossing 0.22 μm of organic phase filter membrane for GC, result display methyl jasmonate accounts for 18.23%.
Comparative example 2: alumina column chromatography concentration and separation MeJA
Step 1, loading
Get in aluminum oxide 100g to 250ml beaker, add after sherwood oil (200ml) is stirred to bubble-free and pour glass chromatography column into, after natural subsidence compacting, get Aglaia odorata oil 10g 10mL sherwood oil dilution loading.
Step 2, wash-out
After sample adsorbs completely, priority sherwood oil, sherwood oil-methylene dichloride 1:1 (volume ratio), methylene dichloride, each 400mL wash-out of ethyl acetate, collect each section of flow point, sherwood oil-methylene dichloride 1:1 (volume ratio) and methylene dichloride position are merged, concentrating under reduced pressure obtains the enrichment positions D of MeJA, colourless transparent liquid.
Step 3, Analysis and Identification
Get the enrichment positions D of MeJA on a small quantity with suitable methylene dichloride dissolved dilution, analyze for GC after crossing 0.22 μm of organic phase filter membrane, result display methyl jasmonate accounts for 35.1%.
Embodiment 2-6, adopts the method identical with embodiment 1, unlike the proportioning of parameter, concrete as table 1:
Table 1
The detection method of the content of the enrichment positions D methyl jasmonate of the MeJA that embodiment 2-6 obtains is identical with embodiment 1, and detected result is as table 2.
Table 2
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.

Claims (2)

1. the method for the natural methyl jasmonate of enrichment from oil of aglaia odorate, is characterized in that, comprise the steps:
Step 1, extraction liquid is prepared
Get sherwood oil, methyl alcohol, water, according to volume ratio 2-8:1-7:0.3-1 mixing, fully stratification after mixing, is separately stored in upper and lower phase in different vessels, obtains phase solution A and lower phase B solution;
Step 2, MeJA extracting and separating
After oil of aglaia odorate being added the dissolving of upper phase solution A, add isopyknic lower phase B solution extraction, the mass volume ratio that wherein orchid oil and upper phase solution A are dissolved is 1:1-10, lower phase solution is released after layering, upper phase solution continues to add lower phase B solution and to extract 1 time or repeatedly, merge all lower phase solution of each extraction, concentrating under reduced pressure obtains the enrichment positions C of MeJA;
Step 3, column chromatographic isolation and purification MeJA
Step 2 is extracted after the MeJA enrichment positions C obtained adds silica gel mixed sample and be splined on silica gel column chromatography, wherein enrichment positions C is 1:1-2 with mixing sample silica gel ratio, with petroleum ether-ethyl acetate system gradient elution, when elutriant ratio is 5-40:1, collect elutriant, concentrating under reduced pressure obtains the enrichment positions D of MeJA after purifying.
2. the method for the natural methyl jasmonate of enrichment from oil of aglaia odorate as claimed in claim 1, it is characterized in that, in described step 1, sherwood oil, methyl alcohol, water, according to volume ratio 5:4:1;
The mass volume ratio that in described step 2, orchid oil and upper phase solution A are dissolved is 1:5;
In described step 3 when elutriant ratio is 20:1, collect elutriant, concentrating under reduced pressure obtains the enrichment positions D of MeJA after purifying.
CN201510644527.2A 2015-09-30 2015-09-30 A kind of method being enriched with natural methyl jasmonate from oil of aglaia odorate Active CN105085268B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109718574A (en) * 2018-12-14 2019-05-07 山东省中医药研究院 A method of target component in orientation fast enriching Chinese medicine especially mulberry leaf

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03284618A (en) * 1990-03-30 1991-12-16 Shiseido Co Ltd Oriental orchid-like perfume composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03284618A (en) * 1990-03-30 1991-12-16 Shiseido Co Ltd Oriental orchid-like perfume composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
R. PORAT ET AL.: "Examination of the possible involvement of lipoxygenase and jasmonates in pollination-induced senescence of Phalaenopsis and Dendrobium orchid flowers", 《PHYSIOLOGIA PLANTARUM》 *
张峻松等: "《树兰花挥发性成分的提取及鉴定》", 《色谱》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109718574A (en) * 2018-12-14 2019-05-07 山东省中医药研究院 A method of target component in orientation fast enriching Chinese medicine especially mulberry leaf
CN109718574B (en) * 2018-12-14 2021-04-16 山东省中医药研究院 Method for directionally and rapidly enriching target components in traditional Chinese medicine, particularly mulberry leaves

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