CN104109109B - A kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone - Google Patents
A kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone Download PDFInfo
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- CN104109109B CN104109109B CN201410213035.3A CN201410213035A CN104109109B CN 104109109 B CN104109109 B CN 104109109B CN 201410213035 A CN201410213035 A CN 201410213035A CN 104109109 B CN104109109 B CN 104109109B
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- sulfydryl
- malaysia
- ketone
- pulegone
- sodium sulfide
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Abstract
The present invention relates to a kind of method utilizing pulegone and sulfide to prepare edible essence 8 sulfydryl Malaysia ketone, the method uses sodium sulfide, Potassium monosulfide. or ammonium sulfide to make raw material, not only avoid toxic gas H than prior art2The use of S, it is thus also avoided that numerous and diverse many more manipulations, processing safety is high, environmentally friendly.And this technique becomes the 8 sulfydryl Malaysia ketone productivity produced high, processing step is simple, and reaction condition is gentle, it is adaptable to industrialized production, solves the deficiency that prior art productivity is low.
Description
Technical field
The present invention relates to a kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone, belong to
In edible essence preparing technical field.
Background technology
Essence has been widely applied to as a kind of special high power concentrated additive affecting food taste and flavor
The every field of food production, it can make up the fragrance defect of food itself, give the former flavour that Partial Food is lively, strengthen
The fragrance of food, covers the bad breath of food, and these advantages of essence make it be increasingly becoming the emphasis of people's research.Along with existing
For the development of analytical technology and updating of analysis means, the structure of more and more aroma substances is identified out, especially
It is that so content such as sulfur-containing compound is small but after composition indispensable to odor type be found, compound essence and natural essence
Fragrance be more nearly so that compound essence industry has obtained development at full speed, food flavor has become as modern food
The indispensable important component part of industry.
In existing flavorant, Sulfur-containing flavor occupies very important status, and Sulfur-containing flavor is often the micro-of food
The fragrant composition of amount, along with the development of analytical technology, increasing sulfur-containing compound is detected in food, such as Fructus Ananadis comosi
In containing methanthiol, 3-methyl mercaptomethyl propionate, 3-methyl mercapto ethyl propionate etc.；Containing thio acetate, sulfur in hami melon
For propyl valerate etc.；Containing more than 40 kind of sulfur-containing compound in the coffee roasted；Containing thio-ether type compounds kind more than 30 in Bulbus Allii Cepae；
Containing sulphur compound kind more than 160 etc. in beef aroma volatile.Sulfur-containing flavor fragrance threshold value is low, characteristic is strong, consumption is little,
Can be widely used for the allotment of edible essence especially meat flavor essence, the quality and class improving essence is had important function, produces
Product price often in extremely several ten thousand yuan of every kilogram of thousand of units, has obvious economic benefit.Owing to Sulfur-containing flavor has that consumption is little, sells
The feature that valency is high, odor characteristic is strong, is increasingly subject to the attention of people.
Thio-alcohol flavor compounds is the Sulfur-containing flavor that a class is important, is also the important centre synthesizing other Sulfur-containing flavors
Body, is the class spice grown up since 20 century 70s, is mostly the micro constitutent of food, and in food, content exists
10-6 or 10-9 level.The sulfur alcohol compound of low concentration has the fragrance such as coffee, Oleum sesami, Herba Alii fistulosi Bulbus Allii Radix Raphani, tropical fruit (tree), barbecue.Sulfur
The preparation method of alcohol is a lot, and conventional method be to react with thiourea with alcohol or alkyl halide to generate S-alkyl for different sulfate, then
Prepare with alkali effect.React generation S-alkyl for different sulfate with alcohol or alkyl halide and thiourea, then prepare mercaptan with alkali effect.
8-sulfydryl Malaysia ketone is a kind of thio-alcohol spice, be the exploitation of Abroad in Recent Years company a kind of important source material kind it
One, it has strong fruital taste, slightly sweet gas, is configuration tropical fruit (tree) and the requisite composition of Cortex Cinnamomi type fruit flavor,
The configuration food flavor such as black currant, honey peach plays an important role.
The chemical name of 8-sulfydryl Malaysia ketone is: 2-(1-sulfydryl-1-Methylethyl)-5-methyl cyclohexanone；2-(1-
Mercapto-1-methylethyl)-5-methyl-cyclohe-xanone, molecular formula is C10H18OS, relative molecular mass
It is 186.1078.
About the preparation of 8-sulfydryl Malaysia ketone, reported in literature Lewis acid such as alchlor is had to induce, but 8-sulfydryl Malaysia
The yield of ketone is only 9%, and in product, transisomer is 43%, and cis-isomer is 7% separately to have 39% raw material unconverted.Givandan
Company applies for a patent for 1973, prepares 8-sulfydryl Malaysia ketone with autoclave pressure, first pulegone is put in autoclave pressure, then with
Autoclave pressure is cooled to-75 DEG C together, is passed through liquid H in the case of-75 DEG C2S, increases to the volume of metering, is then shut off pressure
Still, reacts 16 hours, it is stated that having the yield of 73%, trans and cis ratio is 4:1, but this technique industrially produces tired
Difficulty is bigger.
Summary of the invention
It is low that the technical problem that present invention mainly solves is to provide a kind of production cost, and reaction raw materials utilizes fully, and product is pure
Degree height, and it is applicable to the synthetic method of the 8-sulfydryl Malaysia ketone of industrialized production, to overcome hydrogen sulfide method productivity low and to pollute
With the problem of murder by poisoning.
It is as follows that the present invention realizes process:
A kind of synthetic method of 8-sulfydryl Malaysia ketone, it is characterised in that: with pulegone, sodium sulfide, Potassium monosulfide. or sulfur
Change ammonium is reaction raw materials, prepares with water, methanol or ethanol for reaction dissolvent.
Above-mentioned preparation method specifically includes following steps:
(1) pulegone, sulfide with water at 50 DEG C ~ 80 DEG C reactions, pulegone with the mol ratio of sodium sulfide are
1:1～1:2.5, preferably 1:1.5 ~ 1.9, more preferably 1:1.8；
(2) above-mentioned reactant mixture hydrochloric acid is acidified, is cooled to room temperature, adjust pH value to neutral, filter precipitation, 30 ~ 50
DEG C warm water washing filter cake, obtains 8-sulfydryl Malaysia ketone crude product, and warm water temperature is preferably 35 DEG C ~ 40 DEG C；
(3) Methanol+Water that 8-sulfydryl Malaysia ketone crude product volume ratio is 1:1 is carried out recrystallization, filter, dry
Dry obtain target product.
In above-mentioned steps (1), pulegone is 1:1.5 ~ 1.9 with the mol ratio of sulfide, and reaction temperature is 60 DEG C ~ 80
DEG C, preferably 60 DEG C ~ 70 DEG C.
Above-mentioned steps (1) can add catalyst Friedel-Crafts catalyst or zeolite molecular sieve.
Advantages of the present invention: the 1. present invention uses pulegone and sodium sulfide reaction, it is to avoid use toxic gas
H2S, it is to avoid numerous and diverse many more manipulations, environmental protection.2. the present invention is using water, methanol or ethanol as reaction dissolvent, does not only has
Effect reduces production cost, and environmental pollution is little, and processing safety is high, environmental friendliness.Target product productivity the most of the present invention
Height, processing step is simple, and reaction condition is gentle, and product purity is high, it is not necessary to complicated purification process, it is adaptable to industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited solely to following enforcement
Example.
Embodiment 1
In reactor, add 300 grams of pulegones, 250 grams of sodium sulfide and 1000 grams of water, be uniformly mixed, heating
To 60 DEG C ~ 70 DEG C, it is being stirred continuously lower reaction 15 hours.Then by above-mentioned reactant mixture dilute, it is acidified with hydrochloric acid
To neutral, being cooled to room temperature, filter, filter cake temperature is 35 DEG C ~ 40 DEG C warm water washings, obtains 280 grams of 8-sulfydryl Malaysia ketone thick
Product.
Adding 280 grams of 8-sulfydryl Malaysia ketone crude products in reaction vessel, being subsequently adding 400 grams of alcohol refluxs will after 4 hours
Solution is cooled to room temperature, separates out solid, refilters, be dried the solid being filtrated to get to constant weight, obtain end product 8-sulfydryl horse
Carrying out ketone 170 grams, yield is 46%, is better than the reported in literature of existing synthesis under normal pressure.
The constants of nuclear magnetic resonance of the 8-sulfydryl Malaysia ketone prepared is:
1H-NMR(300MHz,DMSO)δ:2.53(m,1H)；2.30(m,1H); 2.14(m,1H); 1.99(m,1H);
1.90(m,2H); 1.64(m,2H); 1.51(s,1H); 1.49(s,6H); 0.96(d,3H);
13C-NMR(75MHz, DMSO) δ: 219.1; 59.4; 52.3; 36.2; 34.0; 31.6; 29.5;
20.5; HRMS (ESI) for (M+H)+: calcd 187.1157, found 187.1153。
Embodiment 2
In reactor, add 300 grams of pulegones, 280 grams of sodium sulfide and 1000 grams of methanol, be uniformly mixed, add
Heat, to 60 DEG C ~ 70 DEG C, adds 5g zinc chloride (Friedel-Crafts catalyst), is being stirred continuously lower reaction 15 hours.Then
By above-mentioned reactant mixture dilute, it being acidified to neutrality with hydrochloric acid, be cooled to room temperature, filter, filter cake temperature is 35 DEG C ~
40 DEG C of warm water washings, obtain 320 grams of 8-sulfydryl Malaysia ketone crude products.
Adding 320 grams of 8-sulfydryl Malaysia ketone crude products in reaction vessel, being subsequently adding 400 grams of alcohol refluxs will after 4 hours
Solution is cooled to room temperature, separates out solid, refilters, be dried the solid being filtrated to get to constant weight, obtain end product 8-sulfydryl horse
Carrying out ketone 240 grams, yield is 65%.
Embodiment 3
In reactor, add 300 grams of pulegones, 320 grams of sodium sulfide and 1200 grams of ethanol, be uniformly mixed, add
Heat, to 60 DEG C ~ 70 DEG C, is being stirred continuously lower reaction 15 hours.Then by above-mentioned reactant mixture dilute, with hydrochloric acid acid
Changing to neutral, be cooled to room temperature, filter, filter cake temperature is 35 DEG C ~ 40 DEG C warm water washings, obtains 290 grams of 8-sulfydryl Malaysia ketone
Crude product.
Adding 290 grams of 8-sulfydryl Malaysia ketone crude products in reaction vessel, being subsequently adding 400 grams of alcohol refluxs will after 4 hours
Solution is cooled to room temperature, separates out solid, refilters, be dried the solid being filtrated to get to constant weight, obtain end product 8-sulfydryl horse
Carrying out ketone 200 grams, yield is 54%.
Embodiment 4
The impact on target product yield of the different rate of charges of investigation pulegone and sodium sulfide, result is as shown in table 1:
Reaction condition is: 120 grams of water, and reaction temperature is 50 DEG C～80 DEG C, and other reaction condition is with embodiment 1, and result shows to be worked as
When the weight ratio of pulegone and sodium sulfide is 1:0.93, when i.e. mol ratio is 1:1.8, target product yield is the most preferable.
Embodiment 5
Investigating the impact on target product productivity of the differential responses temperature, result is as shown in table 2:
Reaction condition is: 120 grams of water, and the response time is 15 hours, and other reaction condition is with embodiment 1, and result shows to be worked as
When the reaction temperature of pulegone and sodium sulfide is 60 DEG C, target product yield is the most preferable.
Integrated survey, utilizes pulegone and sodium sulfide to prepare the reaction of edible essence 8-sulfydryl Malaysia ketone, when coming into leaves
The weight ratio that menthone and sodium sulfide feed intake be 1:0.93, i.e. mol ratio be 1:1.8, with ethanol as solvent, reaction temperature is 60
DEG C, under conditions of the response time is 15 hours, target product yield is the most preferable.
Claims (4)
1. the synthetic method of a 8-sulfydryl Malaysia ketone, it is characterised in that comprise the following steps:
(1) pulegone, sodium sulfide and water the mol ratio of 50 DEG C ~ 80 DEG C reactions, pulegone and sodium sulfide be 1:1～
1:2.5；
(2) above-mentioned reactant mixture hydrochloric acid is acidified, is cooled to room temperature, adjust pH value to neutral, filter precipitation, 30 ~ 50 DEG C of temperature
Water washing filter cake, obtains 8-sulfydryl Malaysia ketone crude product；
(3) Methanol+Water that 8-sulfydryl Malaysia ketone crude product volume ratio is 1:1 is carried out recrystallization, filter, be dried
To target product.
The synthetic method of 8-sulfydryl Malaysia ketone the most according to claim 1, it is characterised in that: in step (1), pulegone
It is 1:1.5 ~ 1.9 with the mol ratio of sodium sulfide.
The synthetic method of 8-sulfydryl Malaysia ketone the most according to claim 1, it is characterised in that: step (1) adds catalyst
Friedel-Crafts catalyst or zeolite molecular sieve.
The synthetic method of 8-sulfydryl Malaysia ketone the most according to claim 1, it is characterised in that: step (1) reaction temperature is 60
℃~80℃。
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| CN201410213035.3A CN104109109B (en) | 2014-05-21 | 2014-05-21 | A kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone |
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| CN201410213035.3A CN104109109B (en) | 2014-05-21 | 2014-05-21 | A kind of method utilizing pulegone and sodium sulfide to prepare edible essence 8-sulfydryl Malaysia ketone |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3819712A (en) * | 1969-09-10 | 1974-06-25 | Givaudan Corp | Mercapto-or alkylthio-substituted terpenoids |
| EP0277688A2 (en) * | 1987-01-30 | 1988-08-10 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for preparing thiol compounds |
| CN101735120A (en) * | 2009-12-16 | 2010-06-16 | 华宝食用香精香料（上海）有限公司 | Synthesis method of thio-menthone perfume |
| CN101801922A (en) * | 2007-09-20 | 2010-08-11 | 昭和电工株式会社 | Method of producing beta-mercaptocarboxylic acids |
-
2014
- 2014-05-21 CN CN201410213035.3A patent/CN104109109B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3819712A (en) * | 1969-09-10 | 1974-06-25 | Givaudan Corp | Mercapto-or alkylthio-substituted terpenoids |
| EP0277688A2 (en) * | 1987-01-30 | 1988-08-10 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for preparing thiol compounds |
| CN101801922A (en) * | 2007-09-20 | 2010-08-11 | 昭和电工株式会社 | Method of producing beta-mercaptocarboxylic acids |
| CN101735120A (en) * | 2009-12-16 | 2010-06-16 | 华宝食用香精香料（上海）有限公司 | Synthesis method of thio-menthone perfume |
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Effective date of registration: 20170329 Address after: Room 210043, building 1-026, Datong Ecological Industrial Park, Bagua street, Qixia District, Jiangsu, Nanjing, China, B Patentee after: Nanjing best medical technology Co., Ltd. Address before: 710021 Shaanxi city of Xi'an province Weiyang University Park Patentee before: Shaanxi University of Science and Technology |
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