CN101735120A - Synthesis method of thio-menthone perfume - Google Patents
Synthesis method of thio-menthone perfume Download PDFInfo
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- CN101735120A CN101735120A CN200910201221A CN200910201221A CN101735120A CN 101735120 A CN101735120 A CN 101735120A CN 200910201221 A CN200910201221 A CN 200910201221A CN 200910201221 A CN200910201221 A CN 200910201221A CN 101735120 A CN101735120 A CN 101735120A
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Abstract
The invention relates to a synthesis method of thio-menthone perfume, which comprises the steps of: preparation of chloro-menthone, preparation of sodium hydrosulfide, preparation of crude thio-menthone, rectification of the crude thio-menthone and the like. Compared with the prior art, the method is convenient for industrial implementation, less in equipment investment and easy in operation; the technique has highest yield in the preparation of the thio-menthone under the technical condition of normal pressure and normal temperature; meanwhile, the method solves the problems of high equipment investment, strong equipment corrosion, high power consumption, hard operation and the like caused by the technology for preparing the thio-menthone at high pressure and low temperature.
Description
[technical field]
The invention belongs to the spices technical field, more specifically, the present invention relates to a kind of synthetic method of thio-menthone perfume.
[background technology]
The chemical name of thio-menthone (1) be 2-(1-sulfydryl-1-methylethyl)-5-methylcyclohexanone (2-(1-mercapto-1-methylethyl)-5-methyl-cyclohexanone), represented as shown in the formula (1).It is one of important perfume material of perfume industry.Its smell under pure state is not pleasant, but in case after the dilution, but have intensive fruital, blue or green perfume, toast note, slightly some heating installation and sweet gas, even have the note of peppermint, at the preparation black currant, honey peach plays an important role in the food using material such as vegetables.Thio-menthone is at preparation toothpaste local flavor, and the characteristic perfume aspect of daily chemical products also is widely used.The trace of thio-menthone in the tobacco flavor material used notes such as can promoting blue or green, sweet, fruit.The FEMA of thio-menthone is numbered 3177.
Thio-menthone is found in buchu leaves oil (buchu leafoil) the earliest, is found first sulfydryl ketone compounds in the natural essential oil.Thio-menthone has two unsymmetrical carbons respectively at 2,5, and it has 4 isomer, is respectively 2R-trans type (11) as follows; 2S-trans type (12); 2S-cis type (13); 2R-cis type (14).
Along with the progress of modern separation technology and analytical technology, particularly use of the application of cyclodextrin chiral derivative, now various isomer (the Flavour ﹠amp of thio-menthone in the separation essential oil that can be correct as the capillary gas chromatographic column of stationary phase; Fragrance J., 1992, Vol.7 (4), 205-211).The fragrance of the various isomer of thio-menthone is described below:
The sulphur sample note that 2R-trans type intensive band is mould
The black currant note of 2S-trans type green grass or young crops has persistence strongly
The sweet fruital rhythm that the 2S-cis type is soft
2R-cis type intensive is fragrant and sweet, and some pungencys are arranged slightly
Usually, use following isopulegone (2) and pulegone (3), pass through H as raw material
2The electrophilic addition reaction of S prepares thio-menthone.No matter the sulfydryl addition is pulegone or isopulegone on 8, all meets the Markownikoff rule.
Described pulegone (3) is present in the Herba Lysimachiae oil of Spain or Morocco's product; Described isopulegone (2) then can prepare by following synthetic method: geranial (4) prepares isopulegol (5) through cyclization, and then, isopulegol (5) use Jones reagent carries out oxidation and prepares isopulegone (2).
Described pulegone carbon-carbon double bond is powerful δ-key and relative more weak π-key, and π bonding electron commute is polarized and electrophilic addition reaction takes place; Its two keys have bigger steric hindrance again, electrophilic reagent H simultaneously
2S electronegativity among the S is less relatively, and the weak positive polarity deficiency that H has is so that the π bond polarization of pulegone, so electrophilic addition reaction is difficult to carry out.Firmenich company in 1969 proposes to prepare thio-menthone with the autoclave pressure of sealing in its patent application (GB 2 152 015).This patent application discloses following preparation method: earlier pulegone is added in the autoclave pressure, be cooled to-80 ℃ then, at the H of-80 ℃ following feeding required dosages
2S, the closing presure still carried out electrophilic addition reaction 48 hours, then the H of excessive separation then
2S, the yield of thio-menthone is 70% like this, trans and ratio cis is 3: 2.Yet this method is at industrial performance difficulty, and existing problems are a lot, for example: 1, essential wanting greatly, medium-sized steel autoclave pressure equipment, facility investment is big; 2, the H in the technology
2S is very severe to the corrosion of steel equipment, the maintenance of equipment and Abschreibungskosten height; 3, the processing requirement temperature of reaction will reach-80 ℃, needs a large amount of energy consumptions; 4, big, temperature will reach-80 ℃ in the medium-sized autoclave pressure, also is inconvenient in design, can increase the manufacturing cost and the operation easier of equipment.Document (Flavour ﹠amp; Fragrance J., 1993, Vol.8 (5) 289-294) reports, uses for example aluminum chloride Lowis acid to induce, and helps H like this
2The electrophilic addition of S, but the yield of thio-menthone only is 9%.
Therefore, the inventor has carried out lot of experiments at the problems that exist in the prior art, has designed brand-new synthetic route, has finished the present invention.
[summary of the invention]
[technical problem that will solve]
The synthetic method that the purpose of this invention is to provide a kind of thio-menthone perfume.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to the synthetic method of thio-menthone perfume.
The step of this method is as follows:
The preparation of A, chloro piperitone
The pennyroyal mint that adds 20-30 weight part 70-90 weight % isopulegone in the flask that the alkali lye device for absorbing tail gas is housed is slightly oily, feeds dry HCl gas then up to saturated, obtains chloro piperitone solution;
The preparation of B, sulfhydrylation sodium
The dehydrated alcohol that in the there-necked flask that agitator, built-in temperature meter, reflux exchanger, dropping funnel are housed, adds the 100-140 weight part, add 3.0-4.0 weight part sodium Metal 99.5 then, reflux, treat all cool to room temperature again after the dissolving of sodium Metal 99.5, perhaps use commercially available 8-12 weight % industrial alcohol sodium solution, feed H then
2S gas up to pH=7-8, obtains the sulfhydrylation sodium solution;
The preparation of C, thick thio-menthone
With step B) the sulfhydrylation sodium solution that obtains is cooled to below 10 ℃ or 10 ℃, the past then steps A that wherein drips) the chloro piperitone solution of preparation, at room temperature continue reaction 1-3 hour after dripping again, add the 80-120 weight parts water then and 80-120 weight part ether washs extraction, be separated, separating ether uses the saturated common salt solution washing to neutral mutually, rotate vacuum again and boil off ether, steam surplus liquid and carry out reduced pressure distillation, collect the 72-92 ℃/1kp gold-plating branch of 9-11 weight part, gas chromatographic analysis, this thick cut contain 22-28 weight % thio-menthone, unreacted isopulegone and pulegone;
The smart gold-plating of D, thick thio-menthone
The 80-120 weight part is at step C) the described thick cut that obtains carries out smart gold-plating, collects 88-92 ℃/1kp gold-plating and divides about 20-28 weight part, and this cut is the target product thio-menthone.With the isopulegone that reacts away is base of calculation, and the product yield is 17%, is better than existing synthesis under normal pressure preparation technology's yield; Also avoided simultaneously high pressure, the difficulty of low temperature preparation technology on industrial production is implemented.
A preferred embodiment of the invention, described alkali lye is selected from the alkali lye of sodium ethylate, sodium methylate or sodium isopropylate.
The concentration of described alkali lye is the 0.5-2.0 mol.
Preferably, the concentration of described alkali lye is the 1.0-1.5 mol.
More preferably, the concentration of described alkali lye is the 1.2-1.3 mol.
According to another kind of preferred implementation of the present invention, feed H
2The flow of S gas is 40-100ml/min.
Preferably, described feeding H
2The flow of S gas is 50-70ml/min.
More preferably, described feeding H
2The flow of S gas is 60-80ml/min.
According to another kind of preferred implementation of the present invention, water and ether divide and wash extraction 1-3 time in step C.
According to another kind of preferred implementation of the present invention, the rotation vacuum boils off ether and underpressure distillation is carried out under pressure 3.0-0.5KPa in step C.
In the present invention, collect 72-76 ℃/1kp gold-plating and divide 50-60 weight part in step D, this gold-plating is divided into isopulegone, returns use.
Also collect 78-82 ℃/1kp gold-plating and divide 12-16 weight part in step D, this gold-plating is divided into pulegone, returns use.
The present invention will be described in detail belows.
From thermodynamic (al) angle, H
2The addition reaction of S and pulegone is difficult to carry out.The present invention has adopted a kind of circuitous synthetic method, carries out electrophilic addition with the HCl of close electric better effects if, prepares thio-menthone with the sulfhydryl ion nucleophilic substitution reaction then.
The electronegativity of chlorion compares H among the HCl
2The electronegativity of sulfonium ion wants big among the S, and the hydrogen atom among the HCl has more positive charge, carries out electrophilic addition easily.In pulegone (3), feed HCl, generate 8-chloro piperitone (6), be added dropwise to then and contain SH
-In the ionic solion, carry out nucleophilic substitution reaction.Because the chlorine in the chloro piperitone is tertiary carbon chlorine, the nucleophilic substitution reaction type is generally the Sn1 course, and promptly chlorion is left away in advance, and the tertiary carbon electronics carries out SP
3Hydridization becomes a plane, owing to sterically hindered reason, SH
-Ion is always from top attack tertiary carbon ion, produce equatorial bond, and the methyl of stable piperitone structure also is equatorial bond usually, so synthetic thio-menthone majority is a transconfiguration, the ratio of common trans thio-menthone (11) and cis thio-menthone (13) is 4: 1:
The chloro piperitone is added dropwise in the protonic solvent that contains sulfhydryl ion, since the inducing action of 3 carbonyls, the H of 4 carbon
+Proton is actually the reactive hydrogen of a β position, very easily combines with other basic groups in nucleophilic group and the solvent and leaves away, and produces 4,8 elimination product, i.e. E
1Eliminate reaction mechanism, be returned to the raw material pulegone.Feed excessive H with the NaOH aqueous solution
2S gas, pH are 7-8, are added dropwise to the chloro piperitone then, have only micro-thio-menthone to produce, and still are the raw material pulegone in a large number.Produce a large amount of reasons of eliminating reaction product, except having the β reactive hydrogen, itself has alkalescence solvent, and the lyate ion volume is again little, easily combines with hydrogen ion and leaves away.
Though 4 proton is very easy to leave away, alkaline reagents owing to the sterically hindered reason of having living space, also has certain degree of difficulty to the attack of proton.The reaction system of the aqueous solution, the volume of water molecules is less relatively, easily attacks 4 protons and generates the elimination reaction product.The present invention uses ethanol to be reaction solvent, although the second alcohol and water is alkaline almost equal, their PKa is respectively 15.9 and 15.75, but the alcoholic acid volume is greater than water, because steric effect and 4 s' proton in conjunction with relative difficult, also reduces to some extent so eliminate the product of reaction.The present invention feeds H in ethanolic soln
2S drips the chloro piperitone then to pH=7-8, obtains thio-menthone at last, and yield is 16%, is better than the bibliographical information of existing synthesis under normal pressure.
The synthetic method step of thio-menthone perfume of the present invention is as follows:
The preparation of A, chloro piperitone
The pennyroyal mint that adds 20-30 weight part 70-90 weight % isopulegone in the flask that the alkali lye device for absorbing tail gas is housed is slightly oily, feeds dry HCl gas then up to saturated, obtains chloro piperitone solution.
The operable alkali lye device for absorbing tail gas of the present invention for example is that the inverted triangle funnel is attached on the alkali lye storage tank.
Described alkali lye is selected from the alkali lye of sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide.Preferably, described alkali lye is selected from the alkali lye of sodium hydroxide, potassium hydroxide or calcium hydroxide.More preferably, described alkali lye is selected from the alkali lye of sodium hydroxide or potassium hydroxide.
The concentration of described alkali lye is the 3.0-7.0 mol.
Preferably, the concentration of described alkali lye is the 3.5-6.5 mol.
More preferably, the concentration of described alkali lye is the 4.0-6.0 mol.
In the present invention, can adopt the chloro piperitone content of gravimetric analysis method detection in resultant chloro piperitone solution.Constantly increase when constant according to chloro piperitone content, can determine to feed HCl gas and reach capacity.
The preparation of B, sulfhydrylation sodium
The dehydrated alcohol that in the there-necked flask that agitator, built-in temperature meter, reflux exchanger, dropping funnel are housed, adds the 100-140 weight part, add 3.0-4.0 weight part sodium Metal 99.5 then, reflux is treated all cool to room temperature again after the dissolving of sodium Metal 99.5, feeds H then
2S gas up to pH=7-8, obtains the sulfhydrylation sodium solution.
In the present invention, the granularity of sodium Metal 99.5 is not crucial, but considers that from dissolution rate the granularity of sodium Metal 99.5 is 0.5-2.5mm preferably.More preferably, the granularity of sodium Metal 99.5 is 1.0-1.Smm.
Sodium Metal 99.5 all is dissolved in the resulting solution of dehydrated alcohol and can adopts general method of cooling to cool off, and for example cools off with water coolant or ice cube.
In the present invention, feed H
2The flow of S gas is 40-100ml/min.
Preferably, described feeding H
2The flow of S gas is 50-90ml/min.
More preferably, described feeding H
2The flow of S gas is 60-80ml/min.
The preparation of C, thick thio-menthone
With step B) the sulfhydrylation sodium solution that obtains is cooled to below 10 ℃ or 10 ℃, can adopt common method of cooling cooling sulfhydrylation sodium solution, for example refrigerated water chuck cooling.Then, toward wherein dripping steps A) the chloro piperitone solution of preparation, rate of addition can be controlled at the 1-2ml/ branch.Drip this mixture of relief and rise to room temperature naturally, at room temperature continue reaction 1-3 hour again, preferably at room temperature continue reaction 2 hours.
Reaction finishes the back toward wherein adding the 80-120 weight parts water and 80-120 weight part ether washs extraction, can divide and wash extraction 1-3 time.Be separated thereafter, separating ether uses the saturated common salt solution washing to neutral mutually, rotate vacuum again and boil off ether, steam surplus liquid and carry out reduced pressure distillation, collect the 72-92 ℃/1kp gold-plating branch of 9-11 weight part, gas chromatographic analysis: this thick cut contains 22-28 weight % thio-menthone, and unreacted isopulegone and pulegone.
The rotation vacuum boils off ether and reduced pressure distillation is carried out under pressure 3.0-0.5KPa in this step C, preferably pressure 2.0-0.6KPa, more preferably pressure 1.3-0.7KPa.
The rotation vacuum boils off ether and uses the rotary vacuum evaporator of selling in the market, and for example Looye company is with the rotary vacuum evaporator of trade(brand)name ZX98-1Rotarapor sale.
Reduced pressure distillation can be carried out with general glass column still.
Collected product adopts the method for gas chromatographic analysis and gas chromatography mass spectrometry analysis to carry out the qualitative and quantitative analysis during reduced pressure distillation.
Mass spectrometric analysis method is adopted in described qualitative analysis.
Gas chromatographic analysis is adopted in described quantitative analysis.
The analytical instrument of using is Agilent 6890N gas chromatograph; Agilent 7683 automatic samplers, Agilent 6890N-5873N gas chromatograph-mass spectrometer.
The gaschromatographic mass spectrometric analysis condition:
GC conditions: with He is carrier gas, constant current flow velocity 1.0ml/min, 250 ℃ of injector temperatures, heating schedule 60-280 ℃, 8 ℃/min of temperature rise rate, splitting ratio 29.0: 1.Quantitatively detect the peak area integration with FID.
Mass spectrum condition: interface temperature: 280 ℃, electron-bombardment energy: 70eV, the EI ion source temperature: 230 ℃, the quadrupole temperature: 150 ℃, full scan scope: m/z 50-550.
The smart gold-plating of D, thick thio-menthone
The 80-120 weight part is at step C) the described thick cut that obtains carries out smart gold-plating, and the present invention can use general glass fractionate to carry out when the smart gold-plating of thick thio-menthone.
Collected 88-92 ℃/1kp gold-plating branch during the essence gold-plating, adopted above-mentioned analytical procedure to carry out the qualitative and quantitative analysis, the analytical results of its thio-menthone is as follows:
MS：m/z：186(M+，24)，153(26)，152(13)，135(9)，123(5)，112(59)，109(62)，97(25)，81(37)，75(46)，69(100)，67(33)，41(89)。
Can determine that by above-mentioned analytical results this cut is the target product thio-menthone, the 20-28 weight part.
Simultaneously, collected 72-76 ℃/1kp gold-plating branch, adopted above-mentioned analytical procedure to carry out the qualitative and quantitative analysis, the analytical results of its isopulegone is as follows:
MS：m/z：152(M+，62)，137(30)，125(1)，121(2)，119(3)，109(93)，95(31)，81(100)，69(46)，68(60)，67(97)，53(35)，41(76)。
Can determine that by above-mentioned analytical results this gold-plating is divided into isopulegone, the 50-60 weight part can return use.
Also collect 78-82 ℃/1kp gold-plating branch, adopt above-mentioned analytical procedure to carry out the qualitative and quantitative analysis, the analytical results of its pulegone is as follows:
MS：m/z：152(M+，100)，137(32)，123(7)，121(5)，119(4)，109(55)，95(23)，81(94)，69(31)，68(21)，67(69)，55(21)，41(34)。
Can determine that by above-mentioned analytical results this gold-plating is divided into pulegone, the 12-16 weight part can return use.
[beneficial effect]
Compared with prior art, the inventive method is convenient to industrial implementation, and facility investment is little, and easy handling is existing normal pressure, the highest technology of preparation thio-menthone yield under the normal temperature processing condition; Avoided high pressure simultaneously, low temperature technique prepares the problem that thio-menthone brings, for example: 1, essential wanting greatly, medium-sized steel autoclave pressure equipment, facility investment is big; 2, the H in the technology
2S is very severe to the corrosion of steel equipment, the maintenance of equipment and Abschreibungskosten height; 3, the processing requirement temperature of reaction will reach-80 ℃, needs a large amount of energy consumptions; 4, big, temperature will reach-80 ℃ in the medium-sized autoclave pressure, also is inconvenient in design, can increase the manufacturing cost and the operation easier of equipment.
[embodiment]
Embodiment 1
The pennyroyal mint of the isopulegone (23g) of adding 25ml content 80 weight % is slightly oily in the flask that the alkali lye device for absorbing tail gas is housed.Feed HCl gas with flow 70ml/min then, up to saturated, the reaction solution 6g that increases weight approximately,, carry out the next step at once.In addition agitator is being housed, adds the 120ml dehydrated alcohol in the interior 500ml there-necked flask that thermometer, reflux exchanger, dropping funnel be set, adding the sodium Metal 99.5 3.5g that is cut into small pieces then, treating in the backflow that sodium Metal 99.5 all dissolves, cool to room temperature feeds H
2S gas is up to PH=7.5.The solution of sulfhydrylation sodium is cooled to 10 ℃, toward wherein dripping freshly prepd chloro piperitone solution, dripped off in about one hour then, at room temperature stirred again 2 hours.After reaction finishes, add 100ml water and 100ml ether and wash extraction, be separated, separate ether and use the saturated common salt water washing mutually to neutral.Rotate vacuum again and steam ether, steam surplus liquid and carry out underpressure distillation, collect 72-92 ℃/1kp gold-plating and divide about 10g, gas chromatographic analysis: include thio-menthone 25%, unreacted isopulegone 59% and pulegone 16%, the theoretical yield of reaction is 19%.
Above-mentioned thick steaming liquid can carry out smart gold-plating by fractionating column.Drop into the thick oil that 100g obtains previously, collect 72-76 ℃/1kp gold-plating and divide about 55g, adopt previously described methods analyst to be defined as the raw material isopulegone, it can return and feed intake; Collect 78-82 ℃/1kp gold-plating and divide about 14g, adopt previously described methods analyst to be defined as pulegone, it also can return and feed intake; Collect 88-92 ℃/1kp gold-plating and divide about 24g; Adopt previously described methods analyst to be defined as the target product thio-menthone.Other has a small amount of distillation residue.
The finished product yield is 17% as calculated.
The result is as follows for its thio-menthone product analysis:
MS：m/z：186(M+，24)，153(26)，152(13)，135(9)，123(5)，112(59)，109(62)，97(25)，81(37)，75(46)，69(100)，67(33)，41(89)。
Claims (8)
1. the synthetic method of a thio-menthone perfume is characterized in that the step of this method is as follows:
The preparation of A, chloro piperitone
The pennyroyal mint that adds 20-30 weight part 70-90 weight % isopulegone in the flask that the alkali lye device for absorbing tail gas is housed is slightly oily, feeds dry HCl gas then up to saturated, obtains chloro piperitone solution;
The preparation of B, sulfhydrylation sodium
The dehydrated alcohol that in the there-necked flask that agitator, built-in temperature meter, reflux exchanger, dropping funnel are housed, adds the 100-140 weight part, add 3.0-4.0 weight part sodium Metal 99.5 then, reflux, treat all cool to room temperature again after the dissolving of sodium Metal 99.5, perhaps use commercially available 8-12 weight % industrial alcohol sodium solution, feed H then
2S gas up to pH=7-8, obtains the sulfhydrylation sodium solution;
The preparation of C, thick thio-menthone
With step B) the sulfhydrylation sodium solution that obtains is cooled to below 10 ℃ or 10 ℃, the past then steps A that wherein drips) the chloro piperitone solution of preparation, at room temperature continue reaction 1-3 hour after dripping again, add the 80-120 weight parts water then and 80-120 weight part ether washs extraction, be separated, separating ether uses the saturated common salt solution washing to neutral mutually, rotate vacuum again and boil off ether, steam surplus liquid and carry out reduced pressure distillation, collect the 72-92 ℃/1kp gold-plating branch of 9-11 weight part, gas chromatographic analysis: this thick cut contains 22-28 weight % thio-menthone, and unreacted isopulegone and pulegone;
The smart gold-plating of D, thick thio-menthone
The 80-120 weight part is at step C) the described thick cut that obtains carries out smart gold-plating, collects 88-92 ℃/1kp gold-plating and divides about 20-28 weight part, and this cut is the target product thio-menthone.
2. method according to claim 1 is characterized in that described alkali lye is selected from sodium ethylate, sodium methylate, the alkali lye of sodium isopropylate.
3. method according to claim 1 and 2, the concentration that it is characterized in that described alkali lye are the 0.5-2.0 mol.
4. method according to claim 1 is characterized in that feeding H
2The S gas flow is 40-100ml/min.
5. method according to claim 1 is characterized in that water and ether divide in step C to wash extraction 1-3 time.
6. method according to claim 1 is characterized in that in step C the rotation vacuum boils off ether and reduced pressure distillation is carried out under pressure 3.0-0.5KPa.
7. method according to claim 1 is characterized in that collecting 72-76 ℃/1kp gold-plating and divides 50-60 weight part in step D, this gold-plating is divided into isopulegone, returns use.
8. method according to claim 1 is characterized in that collecting 78-82 ℃/1kp gold-plating and divides 12-16 weight part in step D, this gold-plating is divided into pulegone, returns use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109110A (en) * | 2014-05-21 | 2014-10-22 | 陕西科技大学 | Preparation method of edible essence 8-mercaptomenthone |
| CN104109109A (en) * | 2014-05-21 | 2014-10-22 | 陕西科技大学 | Method for preparing edible essence 8-mercaptomenthone from pulegone and sodium sulfide |
-
2009
- 2009-12-16 CN CN200910201221A patent/CN101735120A/en active Pending
Non-Patent Citations (2)
| Title |
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| 施友钟等: "硫代薄荷酮合成的新方法", 《2000年中国香料香精学术研讨会论文集》 * |
| 秦雯: "薄荷的研究概况与进展", 《海淀走读大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109110A (en) * | 2014-05-21 | 2014-10-22 | 陕西科技大学 | Preparation method of edible essence 8-mercaptomenthone |
| CN104109109A (en) * | 2014-05-21 | 2014-10-22 | 陕西科技大学 | Method for preparing edible essence 8-mercaptomenthone from pulegone and sodium sulfide |
| CN104109110B (en) * | 2014-05-21 | 2016-08-24 | 陕西科技大学 | A kind of preparation method of edible essence 8-sulfydryl Malaysia ketone |
| CN104109109B (en) * | 2014-05-21 | 2016-09-14 | 陕西科技大学 | A kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone |
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Application publication date: 20100616 |