CN104087627A - Method for preparing gram-level high-purity natural thiosulfinate - Google Patents
Method for preparing gram-level high-purity natural thiosulfinate Download PDFInfo
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Abstract
The invention relates to a method for preparing gram-level high-purity natural thiosulfinate, belonging to the technical field of compound preparation. The method comprises the following steps: preparing an allium tissue homogenate containing active alliinase, keeping the temperature, washing off endogenous thiosulfinate generated in the tissue homogenate with an organic solvent, preparing exogenous ACSO into a solution, adding the solution into the tissue homogenate, keeping the temperature to generate single thiosulfinate or mixed thiosulfinates, and finally, purifying to obtain the product. The method has the advantages of mild reaction conditions, high product purity, high reaction yield, high cleanness and environmental protection, is simple to operate, and conforms to green technological requirements. The purity of the prepared pure thiosulfinate is sufficient for manufacturing drugs and especially diallyl thiosulfinate (garlicin). The research indicates that the garlicin has the maximum antibacterial, antihypertensive, anticancer, antioxidation and other activities in thiosulfinate.
Description
Technical field
The present invention relates to a kind of gram method for rank high-purity natural thiosulfinate of preparing, product can be applicable to food, and makeup, in healthcare products or medicine, belong to compound preparing technical field.
Background technology
Epidemiology proves, the edible ill risk that is rich in allium and can greatly reduces numerous disease, for example bacterium, fungi, virus infection.In addition, edible allium also has anti-oxidant, cancer cell specific induction of apoptosis, the effects such as killing off tumor cells.These plants comprise more than the 700 kind of allium liliaceous plants such as garlic, green onion, ginger, hotbed chives.
The health efficacy of allium is given the credit to a class material---the thiosulfinate (TS) that in allium, allinase catalysis alkylthio (alkenyl) Cys sulfoxide ACSO forms.
ACSO comprises MCSO, ECSO, PCSO, 2-PeCSO, 1-PeCSO, and BCSO, concrete structure is as follows.
Thiosulfinate (TS), general structure can be represented by RSS (O) R ', (R, R '=methyl, ethyl, propyl group, allyl group, propenyl, butyl), concrete structure formula is as implied above.
In allium, alliin (ACSO) and allinase lay respectively in the tenuigenin and enchylema of tissue, once plant tissue destroyed, the two contact, generate rapidly highly active sulfenic acid, bimolecular sulfenic acid can dewater rapidly and form the thiosulfinate of 1 molecule.The TS generating is mixture, forms mechanism as follows.
1) allinase catalysis alkylthio (alkenyl) halfcystine sulfoxide (ACSO) forms the sulfenic acid of high reaction activity; Wherein, R=methyl, ethyl, propyl group, allyl group, propenyl, butyl;
2) sulfenic acid that two molecular reactions 1 form carries out dehydrating condensation, forms a part thiosulfinate (TS).Wherein, R
1and R
2=methyl, ethyl, propyl group, allyl group, propenyl, butyl;
R
1=R
2time, form symmetrical thiosulfinate (TS); R
1≠ R
2, form asymmetric thiosulfinate.
(structural formula is: CH at present the research of thiosulfinate mainly to be concentrated on to garlicin (Allicin)
2=CH-CH
2-S (O) S-CH
2-CH=CH
2, be abbreviated as AllS (O) SAll) and aspect.Garlicin is considered to the main source of allium physiologically active.Research is found, also can be produced other a small amount of thiosulfinate in allium.For example methyl-allyl group-thiosulfinate (CH
2=CH-CH
2-S (O) S-CH
3) and allyl group-methyl-thiosulfinate (CH
3-S (O) S-CH
2-CH=CH
2) etc.Thiosulfinate under native state is mixture.Concrete structure formula as the formula (2).
Garlicin formal name used at school GIUCOSinoate (Allicin), is the representative of thiosulfinate in garlic, and content is in 70% left and right.After garlic fragmentation, form garlicin by allinase catalysis alliin.Under garlicin normal temperature, be pale yellow oily liquid body, character is unstable, can be degraded to single sulphur, two sulphur, three sulfenyl oxygen sulfur compounds.The inadequate specification of domestic garlicin concept, the product of a lot of so-called garlicin working methods is the degraded product of garlicin in fact.
The at present existing part garlic healthcare products in market, as garlic powder, garlicin oral liquid, garlicin injection, due to the course of processing and preservation condition improper, its main component is all garlicin degraded products.Research shows, garlicin degraded product physiologically active, far away from garlicin itself, still can show strong bacteriostasis efficacy even if garlicin is diluted to 50,000/concentration.
In view of thiosulfinate (TS) particularly garlicin at antibacterial anti-infective, reducing blood-fat, raising body immunity, the outstanding health-care effect of anticancer aspect.Allicin goods have the very strong market competitiveness.Particularly, in markets such as Europe, the United States and Japan, the product relevant to garlicin is quite burning hot.At present, because the TS taking garlicin as representative is unstable, and lack the method for a large amount of production TS a kind of, on market, there is no commodity garlicin.Therefore work out a kind of method that can produce in a large number highly purified TS and there are wide market outlook.
The preparation method of thiosulfinate (TS) generally has extraction and synthesizes two kinds of approach at present.Wherein extraction method generally adopts organic solvent lixiviate allium or its crushing and beating is filtered to extraction thiosulfinate, then purifies through approach such as post separation, membrane sepn, as patent CN1465283A; Or extract separately respectively alliin (ACSO) and allinase and make preparation, as patent CN 1491722A.Its advantage is that products therefrom is natural product, and biological activity is high; Shortcoming is complex steps, and product purity is low, is the mixture of TS; Next is that garlicin nature content is low, and extraction yield is lower, is generally no more than 0.3g/100g(allicin/100g garlic), cause production to be difficult to meet the need of market.
The synthesis method of thiosulfinate (TS) comprises synthesis method and semi-synthesis method; Synthesis method generally adopts the sulfide oxidation that TS is corresponding to obtain, as directly obtained garlicin with diallyl disulphide through hydrogen peroxide oxidation.This method output is large, and productive rate is high, but product is not natural product, and biological activity the unknown does not meet the demand of product back to nature.The general allinase effect that adopts synthetic alliin and extraction of semi-synthesis method generates allicin, or adopts enzyme immobilization technology.This method is loaded down with trivial details, need to extract allinase or immobilization allinase, has greatly improved production cost, has reduced formation efficiency.
In view of the foregoing, be necessary to propose new method to preparing TS, i.e. preparation has that output is large, preparation flow Simple temperature and, the TS natural product, particularly natural allicin (Allicin) of product purity high.Allicin product both can be used for foodstuff additive, also can be for makeup, healthcare products and pharmaceuticals.The natural TS product of high purity high yield can impel new industrial chain to form, and improves the added value of allium, spurs economic growth.
Summary of the invention
The object of the invention is to overcome above-mentioned weak point, provide one to prepare a gram method for rank high-purity natural thiosulfinate (TS).
Technical scheme provided by the invention:
The invention discloses the preparation method of a kind of following general formula natural compounds thiosulfinate (TS):
Formula (1).
Wherein, R
1, R
2the one of represent methylidene, ethyl, propyl group, allyl group, propenyl, butyl.R
1=R
2time, form symmetrical thiosulfinate (TS), as R
1=R
2=-CH
2-CH=CH
2form the representative garlicin (CH of TS
2=CH-CH
2-S (O) S-CH
2-CH=CH
2); R
1≠ R
2time, form asymmetric thiosulfinate.Concrete structure is as shown in table 1.
The structure of the thiosulfinate producing in table 1 allium
The invention provides the symmetrical thiosulfinate (R of preparation
1=R
2) method, also provide preparation asymmetric thiosulfinate (R
1≠ R
2) method.Concrete thiosulfinate prepared by the present invention comprises the cited compound of formula (2):
Formula (2).
The inventive method comprises following basic step:
1) tissue homogenate of the allium that preparation contains active allinase; 2) tissue homogenate was incubated after for some time, washes away the endogenous thiosulfinate producing in tissue homogenate with suitable organic solvent; 3) external source alkylthio (alkenyl)-halfcystine sulfoxide (ACSO) wiring solution-forming is added in tissue homogenate, insulation for some time is to produce single thiosulfinate or to mix thiosulfinate; 4) utilize suitable solvent extraction to go out products therefrom.
Prepare a gram method for rank high-purity natural thiosulfinate, concrete steps are as follows:
(1) preparation of tissue homogenate: by the peeling of fresh allium, clean, add the ratio of the solution of 20-90mL to mix in every 100g allium under room temperature, at 0-40 DEG C, plant tissue is broken into tissue homogenate with machine mixer or crusher;
Described solution is deionized water or 0.1-0.5mM, the phosphate buffered saline buffer of pH5-7;
(2) extraction: the tissue homogenate of step (1) gained is at room temperature incubated to 0.1-2h, then crosses leaching filtrate; Under room temperature, wash gained filtrate 1-2 time with organic solvent extraction, extraction time is 5min-2h; The process of extraction can adopt centrifugal or ionization acceleration phase separation;
Described organic solvent is the one in methylene dichloride, anhydrous diethyl ether, ethyl acetate, ethanol, normal hexane, tetracol phenixin or chloroform;
(3) preparation of thiosulfinate: get external source alkylthio synthetic or that separating-purifying goes out from allium (alkenyl) halfcystine sulfoxide ACSO and be made into the solution that mass volume ratio is 10%-20%, then join in the extraction liquid water layer of step (2) gained, at 0-40 DEG C of insulation 0.5-2h, ensure that allinase catalysis ACSO is complete;
(4) extract purifying: the reaction solution that step (3) is obtained carries out product extraction, can carry out purifying to obtain final product gram rank high-purity natural thiosulfinate for mixing thiosulfinate.
In step (1), allium is one or more of the allium liliaceous plants such as garlic, chive, ginger, onion, hotbed chives.Broken temperature in step (1) is 20-35 DEG C.In step (1), the object of crushing and beating is in order to discharge alliin and the allinase in allium, makes it produce thiosulfinate.
The described soaking time of step (2) is 0.5-1.5h.Be to allow alliin in the abundant catalysis plant tissue of allinase in tissue by the object of tissue homogenate insulation, make it change thiosulfinate into.The source of allinase can be separating-purifying and obtaining from allium, and in fresh plant tissue, allinase content is higher.The object of organic solvent washing is for the endogenous thiosulfinate producing in step (1) is removed by extraction.
ACSO in step (3) is (±)-S-methyl-Cys sulfoxide (MCSO); (±)-S-ethyl-Cys sulfoxide (ECSO); (±)-S-propyl group-Cys sulfoxide (PCSO); (±)-S-propenyl-Cys sulfoxide (2-PeCSO); (±)-SACS (1-PeCSO); One or more of (±)-S-butyl-Cys sulfoxide (BCSO).
When described ACSO add-on is a kind of, prepare pure symmetrical thiosulfinate; When ACSO add-on is several, prepares and comprise corresponding symmetry and asymmetrical thiosulfinate mixture;
Described ACSO be synthesize or from allium prepared by separating-purifying; ACSO is pure ACSO crystal, pure ACSO lyophilize product wiring solution-forming or high purity ACSO nature extracting solution; ACSO sterie configuration can be left-handed L or dextrorotation D, or the mixture of two kinds of configurations;
Synthetic ACSO can be synthesized into through oxygenant oxidation via corresponding deoxidation (±)-S-methyl-Cys sulfoxide ACS;
The concentration of ACSO is that mass volume ratio is 10%-20%.
The described purification process of step (4) is for extraction, filtration, centrifugal, positive and reverse-phase chromatography, the one in ion-exchange.
When step (4) adopts the Methods For Purification extracting, step is: adopt organic solvent to extract step (3) gained reaction solution, extraction liquid adopts siccative to be dried; After having extracted, logical nitrogen or helium flow, flow velocity is 0.5-50L/min, and the solvent in extraction liquid is evaporated, temperature is 10-40 DEG C, obtains final product gram rank high-purity natural thiosulfinate; Described organic solvent is one or more in methylene dichloride, chloroform, anhydrous diethyl ether, ethyl acetate, ethanol, normal hexane, benzene; Described siccative is the one in Calcium Chloride Powder Anhydrous, anhydrous magnesium sulfate, anhydrous sodium sulphate, Vanadium Pentoxide in FLAKES, anhydrous potassium sulfate, Anhydrous potassium carbonate.
Described vaporization temperature is 10-40 DEG C.
Beneficial effect of the present invention: first by insulation for some time, allinase effect substrate A CSO endogenous allium is all converted into endogenous thiosulfinate in the inventive method, by suitable organic solvent, endogenous thiosulfinate Ex-all is retained to the activity of allinase, then add respectively different types of external source ACSO(MCSO, ECSO, PCSO, 2-PeCSO, 1-PeCSO, BCSO), can in tissue homogenate, make allinase be translated into corresponding thiosulfinate.
The thiosulfinate purity that the present invention makes is high, by adding different types of external source alliin ACSO, can utilize allinase to be separately converted to natural thiosulfinate, also can be by adding mixing ACSO to obtain mixing thiosulfinate.
The thiosulfinate output that the present invention makes is large, because allinase and alliin are swift in response, to a certain degree in, can strengthen the content of thiosulfinate by strengthening the amount of garlic zymolyte alliin, experimental results show that and can reach a gram rank.
The thiosulfinate that the present invention makes is different from the product that chemical synthesis makes, and in the present invention, thiosulfinate is to obtain by the natural allinase catalysis in allium, and product has natural sex.
The inventive method reaction conditions gentleness, easy and simple to handle, product purity is high, reaction yield is high, clean environment firendly, meets friendly process requirement.
The pure thiosulfinate purity that the present invention makes is enough to be used in medicine manufacture, particularly GIUCOSinoate (garlicin), there are some researches show that it is antibacterial, reducing blood-fat, anticancer, anti-oxidant isoreactivity be the highest in thiosulfinate.
Brief description of the drawings
GIUCOSinoate described in Fig. 1 embodiment 1
1h
nMR figure.
Embodiment
Following example will describe thiosulfinate preparation method in detail, and prepare preferred compound of the present invention, can prepare other the pure thiosulfinates in a lot of the present invention and mix thiosulfinate but technician understands this preparation method.
The present invention is not subject to the restriction of following embodiment, can determine concrete embodiment according to the technical scheme of the invention described above and practical situation.
Embodiment 1: prepare GIUCOSinoate (garlicin)
(1) take 100g peeling garlic bulb, under room temperature, it is mixed with 20mL deionized water, at 0 DEG C, Garlic Tissue is broken into homogenate with machine mixer or crusher, making beating 5min, makes tissue homogenate.
(2) homogenate of step (1) gained Garlic Tissue is at room temperature incubated to 1h, with Coarse Mesh Gauze filtration, gets filtrate.Under room temperature, the washed with dichloromethane filtrate of use equivalent 2 times is washed 20min at every turn, to ensure that extraction completely.Filtrate after washing has enough enzymic activitys to be converted into thiosulfinate with catalysis external source ACSO.Washing process can adopt centrifugal or ionization acceleration phase separation.
(3) get 4g external source allyl cysteine sulfoxide ((±) 2-PeCSO) and be dissolved in 40mL deionized water, be made into ACSO solution.2-PeCSO solution is added in the extraction liquid water layer of step (2) gained, at 30 DEG C of insulation 1.5h, ensure that allinase catalysis 2-PeCSO is complete.
(4) extract with the thiosulfinate that 100mL methylene dichloride obtains step (3).Extraction liquid anhydrous magnesium sulfate drying.Under nitrogen gas stream, the solvent in extraction liquid to be evaporated, vaporization temperature is 30 DEG C.Obtain final product GIUCOSinoate (garlicin, AllS (O) SAll) 1.98g, molar yield is 98%.
The GIUCOSinoate of above-described embodiment is added to CDCl
3dissolve, carry out
1h NMR Structural Identification, as shown in Figure 1.Nucleus magnetic resonance condition is: Bruker AV300 nuclear magnetic resonance spectrometer, and 300MHz:AllS-(O) SAll:
δ5.87-6.04 (2H,
m, C=CHC-), 5.20-5.49 (4H, m, CH
2=CC), 3.70-3.93 (4H, m ,-CH
2-).
Embodiment 2: prepare diethyl thiosulfinate
(1) take 100g peeling garlic bulb, under room temperature, it is mixed with 90mL deionized water, at 4 DEG C, Garlic Tissue is broken into homogenate with machine mixer or crusher, making beating 5min, makes tissue homogenate.
(2) homogenate of step (1) gained Garlic Tissue is at room temperature incubated to 1h, with Coarse Mesh Gauze filtration, gets filtrate.Under room temperature, the washed with dichloromethane filtrate of use 100mL 2 times is washed 15min at every turn, to ensure that extraction completely.Filtrate after washing has enough enzymic activitys to be converted into thiosulfinate with catalysis external source ACSO.Washing process can adopt centrifugal or ionization acceleration phase separation.
(3) get 3.6g external source S-ethyl-Cys sulfoxide ((±) ECSO) and be dissolved in 30mL deionized water, be made into ECSO solution.ECSO solution is added in the extraction liquid water layer of step (2), at 30 DEG C of insulation 1.5h, ensure that allinase catalysis ECSO is complete.
(4) extract with the thiosulfinate that 150mL methylene dichloride obtains step (3).Extraction liquid anhydrous sodium sulfate drying.Under nitrogen gas stream, the solvent in extraction liquid to be evaporated, vaporization temperature is 25 DEG C.Obtain final product diethyl thiosulfinate (EtS (O) SEt) 1.0g, molar yield is 67%.
The diethyl thiosulfinate of above-described embodiment is added to CDCl
3dissolve, carry out
1h NMR Structural Identification.Nucleus magnetic resonance condition is: Bruker AV300 nuclear magnetic resonance spectrometer, and 300MHz:
δ3.05-3.24 (4H,
m,-CH
2s (O) SCH
2-), 1.48 (3H,
t,
j=7.5 Hz, CH
3cS (O)-), 1.42 (3H,
t,
j=7.5 Hz, CH
3cSS (O)-).
Embodiment 3: prepare dipropyl thiosulfinate (garlicin)
(1) take 100g peeling onion bulb stem, under room temperature, it is mixed with 70mL deionized water, at 0 DEG C, Garlic Tissue is broken into homogenate with machine mixer or crusher, the 10min that pulls an oar, makes tissue homogenate.
(2) homogenate of step (1) gained onion tissues is at room temperature incubated to 1h, with Coarse Mesh Gauze filtration, gets filtrate.Under room temperature, the washed with dichloromethane filtrate of use 100mL 2 times is washed 20min at every turn, to ensure that extraction completely.Filtrate after washing has enough enzymic activitys to be converted into thiosulfinate with catalysis external source ACSO.Washing process can adopt centrifugal or ionization acceleration phase separation.
(3) get 2g external source S-propyl group-Cys sulfoxide ((±) PCSO) and be dissolved in 20mL deionized water, be made into PCSO solution.PCSO solution is added in the extraction liquid water layer of step (2), at 30 DEG C of insulation 1.5h, ensure that allinase catalysis PCSO is complete.
(4) extract with the thiosulfinate that 120mL anhydrous diethyl ether obtains step (3).Extraction liquid anhydrous sodium sulfate drying.Under nitrogen gas stream, the solvent in extraction liquid to be evaporated, vaporization temperature is 25 DEG C.Obtain final product dipropyl thiosulfinate (PrS (O) SPr) 0.6g, molar yield is 65%.
The dipropyl thiosulfinate of above-described embodiment is added to CDCl
3dissolve, carry out
1h NMR Structural Identification.Nucleus magnetic resonance condition is: Bruker AV300 nuclear magnetic resonance spectrometer, and 300MHz:
δ3.03-3.22 (4H,
m,-CH
2s (O) SCH
2-), 1.77-1.96 (4H,
m,-CH
2cS (O) SCCH
2-), 1.10 (3H,
t,
j=7.5Hz, CH
3cCS (O)-), 1.05 (3H,
t,
j=7.5 Hz, CH
3cCSS (O)-).
Embodiment 4: prepare dimethyl thiosulfinate
(1) take 100g peeling onion bulb stem, under room temperature, it is mixed with 90mL deionized water, at 0 DEG C, Garlic Tissue is broken into homogenate with machine mixer or crusher, the 10min that pulls an oar, makes tissue homogenate.
(2) homogenate of step (1) gained onion tissues is at room temperature incubated to 1h, with Coarse Mesh Gauze filtration, gets filtrate.Under room temperature, the ethyl diacetate wash filtrate of use 100mL 2 times washs 15min at every turn, to ensure that extraction completely.Filtrate after washing has enough enzymic activitys to be converted into thiosulfinate with catalysis external source ACSO.Washing process can adopt centrifugal or ionization acceleration phase separation.
(3) get 3.2g external source S-methyl-Cys sulfoxide ((±) MCSO) and be dissolved in 20mL deionized water, be made into MCSO solution.MCSO solution is added in the extraction liquid water layer of step (2), at 25 DEG C of insulation 1.5h, ensure that allinase catalysis MCSO is complete.
(4) extract with the thiosulfinate that 150mL anhydrous diethyl ether obtains step (3).Extraction liquid anhydrous magnesium sulfate drying.Under nitrogen gas stream, the solvent in extraction liquid to be evaporated, vaporization temperature is 25 DEG C.Obtain final product dimethyl thiosulfinate (MeS (O) SMe) 0.5g, molar yield is 42%.
The dimethyl thiosulfinate of above-described embodiment is added to CDCl
3dissolve, carry out
1h NMR Structural Identification.Nucleus magnetic resonance condition is: Bruker AV300 nuclear magnetic resonance spectrometer, and 300MHz:
δ3.00 (3H,
s, CH
3s (O)-), 2.69 (3H,
s, CH
3sS (O)-).
Embodiment 5: preparation mixes asymmetric thiosulfinate
(1) take 100g peeling garlic bulb, under room temperature, it is mixed with 90mL deionized water, at 0 DEG C, Garlic Tissue is broken into homogenate with machine mixer or crusher, making beating 10min, makes tissue homogenate.
(2) homogenate of step (1) gained Garlic Tissue is at room temperature incubated to 1h, with Coarse Mesh Gauze filtration, gets filtrate.Under room temperature, the ethyl diacetate wash filtrate of use 100mL 2 times washs 15min at every turn, to ensure that extraction completely.Filtrate after washing has enough enzymic activitys to be converted into thiosulfinate with catalysis external source ACSO.Washing process can adopt centrifugal or ionization acceleration phase separation.
(3) get 3-4g external source S-methyl-Cys sulfoxide ((±) MCSO) and SACS ((±) 2-PeCSO) is dissolved in 50mL deionized water, be made into and mix ACSO solution.ACSO solution is added in the extraction liquid water layer of step (2), at 25 DEG C of insulation 2h, ensure that allinase catalysis ACSO is complete.
(4) extract with the thiosulfinate that 150mL anhydrous diethyl ether obtains step (3).Extraction liquid anhydrous magnesium sulfate drying.Under nitrogen gas stream, the solvent in extraction liquid to be evaporated, vaporization temperature is 25 DEG C.Obtain final product mixing thiosulfinate (MeS (O) SMe, AllS (O) SAll, MeS (O) SAll, AllS (O) SMe).
Claims (8)
1. prepare a gram method for rank high-purity natural thiosulfinate, it is characterized in that step is as follows:
(1) preparation of tissue homogenate: by the peeling of fresh allium, clean, add the ratio of the solution of 20-90mL to mix in every 100g allium under room temperature, at 0-40 DEG C, plant tissue is broken into tissue homogenate with machine mixer or crusher;
Described solution is deionized water or phosphate buffered saline buffer;
(2) extraction: the tissue homogenate of step (1) gained is at room temperature incubated to 0.1-2h, then crosses leaching filtrate; Under room temperature, wash gained filtrate 1-2 time with organic solvent extraction, extraction time is 5min-2h;
Described organic solvent is the one in methylene dichloride, anhydrous diethyl ether, ethyl acetate, ethanol, normal hexane, tetracol phenixin or chloroform;
(3) preparation of thiosulfinate: get external source alkylthio synthetic or that separating-purifying goes out from allium (alkenyl) halfcystine sulfoxide ACSO and be made into the solution that mass volume ratio is 10%-20%, then join in the extraction liquid water layer of step (2) gained, at 0-40 DEG C of insulation 0.5-2h, ensure that allinase catalysis ACSO is complete;
(4) extract purifying: the reaction solution that step (3) is obtained carries out product extraction, carry out purifying to obtain final product gram rank high-purity natural thiosulfinate for mixing thiosulfinate.
2. the method for preparation gram rank high-purity natural thiosulfinate according to claim 1, is characterized in that: allium is one or more of garlic, chive, ginger, onion, hotbed chives allium liliaceous plant in step (1).
3. the method for preparing according to claim 1 gram rank high-purity natural thiosulfinate, is characterized in that: the broken temperature in step (1) is 20-35 DEG C.
4. the method for preparing according to claim 1 gram rank high-purity natural thiosulfinate, is characterized in that: the described soaking time of step (2) is 0.5-1.5h.
5. the method for preparing according to claim 1 gram rank high-purity natural thiosulfinate, is characterized in that: the ACSO in step (3) is (±)-S-methyl-Cys sulfoxide MCSO; (±)-S-ethyl-Cys sulfoxide ECSO; (±)-S-propyl group-Cys sulfoxide PCSO; (±)-S-propenyl-Cys sulfoxide 2-PeCSO; (±)-SACS 1-PeCSO; One or more in (±)-S-butyl-Cys sulfoxide BCSO.
6. the method for preparing according to claim 5 gram rank high-purity natural thiosulfinate, is characterized in that: when described ACSO add-on is a kind of, prepare pure symmetrical thiosulfinate; When ACSO add-on is several, prepares and comprise corresponding symmetry and asymmetrical thiosulfinate mixture;
Described ACSO be synthesize or from allium prepared by separating-purifying; ACSO is pure ACSO crystal, pure ACSO lyophilize product wiring solution-forming or high purity ACSO nature extracting solution; ACSO sterie configuration can be left-handed L or dextrorotation D, or the mixture of two kinds of configurations;
Synthetic ACSO can be synthesized into through oxygenant oxidation via corresponding deoxidation (±)-S-methyl-Cys sulfoxide ACS;
The concentration of ACSO is that mass volume ratio is 10%-20%.
7. the method for preparing according to claim 1 gram rank high-purity natural thiosulfinate, is characterized in that: the described purification process of step (4) is extraction, filters, centrifugal, positive and reverse-phase chromatography, the one in ion-exchange.
8. prepare according to claim 7 the method for gram rank high-purity natural thiosulfinate, it is characterized in that step (4) adopt extraction Methods For Purification time step be: adopt organic solvent step (3) gained reaction solution is extracted, extraction liquid adopt siccative be dried; After having extracted, logical nitrogen or helium flow, flow velocity is 0.5-50L/min, and the solvent in extraction liquid is evaporated, temperature is 10-40 DEG C, obtains final product gram rank high-purity natural thiosulfinate;
Described organic solvent is one or more in methylene dichloride, chloroform, anhydrous diethyl ether, ethyl acetate, ethanol, normal hexane, benzene;
Described siccative is the one in Calcium Chloride Powder Anhydrous, anhydrous magnesium sulfate, anhydrous sodium sulphate, Vanadium Pentoxide in FLAKES, anhydrous potassium sulfate, Anhydrous potassium carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105461604A (en) * | 2015-12-24 | 2016-04-06 | 青岛自然珍萃生物科技有限公司 | Preparing method of high purity allicin |
| CN112592765A (en) * | 2020-12-25 | 2021-04-02 | 青岛博恩高科生物技术有限公司 | Preparation method of garlic essential oil |
| CN114916561A (en) * | 2022-05-27 | 2022-08-19 | 山东大学 | Biopesticide for preventing and treating crop pathogenic bacteria |
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| CN101591587A (en) * | 2009-04-28 | 2009-12-02 | 江苏大学 | A kind of method of extracting onion essential oil through ultrahigh pressure regulation of alliinase reaction |
| CN101748166A (en) * | 2010-01-12 | 2010-06-23 | 南京泽朗医药科技有限公司 | Method for preparing garlicin |
| CN102382020A (en) * | 2010-08-31 | 2012-03-21 | 成都菊乐制药有限公司 | Method for simultaneously extracting alliin and garlic enzyme from garlic |
| CN103484233A (en) * | 2013-09-17 | 2014-01-01 | 暨南大学 | Method and device for preparing garlic oil with racemate alliin as raw materials |
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| CN101591587A (en) * | 2009-04-28 | 2009-12-02 | 江苏大学 | A kind of method of extracting onion essential oil through ultrahigh pressure regulation of alliinase reaction |
| CN101748166A (en) * | 2010-01-12 | 2010-06-23 | 南京泽朗医药科技有限公司 | Method for preparing garlicin |
| CN102382020A (en) * | 2010-08-31 | 2012-03-21 | 成都菊乐制药有限公司 | Method for simultaneously extracting alliin and garlic enzyme from garlic |
| CN103484233A (en) * | 2013-09-17 | 2014-01-01 | 暨南大学 | Method and device for preparing garlic oil with racemate alliin as raw materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461604A (en) * | 2015-12-24 | 2016-04-06 | 青岛自然珍萃生物科技有限公司 | Preparing method of high purity allicin |
| CN112592765A (en) * | 2020-12-25 | 2021-04-02 | 青岛博恩高科生物技术有限公司 | Preparation method of garlic essential oil |
| CN114916561A (en) * | 2022-05-27 | 2022-08-19 | 山东大学 | Biopesticide for preventing and treating crop pathogenic bacteria |
| CN114916561B (en) * | 2022-05-27 | 2022-11-18 | 山东大学 | Biopesticide for preventing and treating crop pathogenic bacteria |
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