CN104109109A - Method for preparing edible essence 8-mercaptomenthone from pulegone and sodium sulfide - Google Patents
Method for preparing edible essence 8-mercaptomenthone from pulegone and sodium sulfide Download PDFInfo
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- CN104109109A CN104109109A CN201410213035.3A CN201410213035A CN104109109A CN 104109109 A CN104109109 A CN 104109109A CN 201410213035 A CN201410213035 A CN 201410213035A CN 104109109 A CN104109109 A CN 104109109A
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Abstract
The invention relates to a method for preparing edible essence 8-mercaptomenthone from pulegone and sodium sulfide. The method utilizes sodium sulfide, potassium sulfide or ammonium sulfide as a raw material. Compared with the prior art, the method does not use toxic gas H2S, is free of multiple complicated processes, has high operation safety and is environmentally friendly. The method has a high 8-mercaptomenthone yield, simple processes and mild reaction conditions, is suitable for industrial production and solves the problems of a low yield of the prior art.
Description
Technical field
The present invention relates to a kind of method of utilizing pulegone and sodium sulphite to prepare food flavour 8-sulfydryl Malaysia ketone, belong to food flavour preparing technical field.
Background technology
Essence has been widely applied to the every field of foodstuff production as a kind of special high power concentrated additive that affects food mouthfeel and local flavor, it can make up the fragrance defect of food itself, give Partial Food lively former flavour, strengthen the fragrance of food, cover the bad breath of food, these advantages of essence make it day by day become the emphasis of people's research.Along with the development of modern analytical technique and updating of analysis means, the structure of more and more aroma substances is out identified, especially content is small but after the indispensable composition of odor type is found like this for sulfocompound etc., the fragrance of compound essence and natural essence is more approaching, thereby make compound essence industry obtain development at full speed, food flavor(ing) has become the indispensable important component part of modern food industry.
In existing flavouring agent, Sulfur-containing flavor occupies very important status, Sulfur-containing flavor is the fragrant composition of trace of food often, development along with analytical technology, increasing sulfocompound is detected in food, as contained thiomethyl alcohol, 3-methyl mercaptomethyl propionate, 3-methylthio group ethyl propionate etc. in pineapple; In hami melon, contain thio acetate, sulfo-propyl valerate etc.; In the coffee roasting, contain more than 40 kind of sulfocompound; In onion, contain thio-ether type compounds kind more than 30; In beef volatile aroma composition, contain sulphur compound kind more than 160 etc.Sulfur-containing flavor fragrance threshold value is low, characteristic is strong, consumption is little, can be widely used in the especially allotment of meat flavour essence of food flavour, to improving quality and the class of essence, have vital role, product price often, at every kilogram several thousand yuan to several ten thousand yuan, has obvious economic benefit.Because Sulfur-containing flavor has, consumption is little, price is high, odour characteristics is strong, is day by day subject to people's attention.
Thio-alcohol flavor compounds is the important Sulfur-containing flavor of a class, is also the important intermediate of synthetic other Sulfur-containing flavors, is the class spices having grown up since 20 century 70s, is mostly the trace ingredients of food, and in food, content is in 10-6 or 10-9 level.The sulfur alcohol compound of lower concentration has the fragrance such as coffee, sesame oil, green onion garlic radish, tropical fruit, barbecue.The preparation method of mercaptan is a lot, and conventional method is to react with thiocarbamide and generate S-alkyl different vitriol of generation with alcohol or haloalkane, and then effect makes with alkali.With alcohol or alkyl halide, react generate S-alkyl different vitriol of generation with thiocarbamide, then effect makes mercaptan with alkali.
8-sulfydryl Malaysia ketone is a kind of thio-alcohol spices, it is one of a kind of important source material kind of Abroad in Recent Years company exploitation, it has strong fruital taste, sweet gas slightly, be configuration tropical fruit and the requisite composition of Chinese cassia tree type fruit flavor, in the food spices such as configuration black currant, honey peach, play an important role.
The chemical name of 8-sulfydryl Malaysia ketone is: 2-(1-sulfydryl-1-methylethyl)-5-methylcyclohexanone; 2-(1-mercapto-1-methylethyl)-5-methyl-cyclohe-xanone, molecular formula is C
10h
18oS, relative molecular mass is 186.1078.
About the preparation of 8-sulfydryl Malaysia ketone, have reported in literature to induce with Lewis acid as alchlor, but the yield of 8-sulfydryl Malaysia ketone is only 9%, in product, trans-isomer(ide) is 43%, cis-isomeride is 7% separately to have 39% raw material unconverted.Givandan company applies for a patent for 1973, with autoclave pressure, prepares 8-sulfydryl Malaysia ketone, first pulegone is put into autoclave pressure, is then cooled to-75 ℃ together with autoclave pressure, in-75 ℃ of situations, passes into liquid H
2s, is increased to the volume of metering, and then closing presure still, reacts 16 hours, allegedly has 73% yield, and trans and ratio cis is 4:1, but this technique is larger in industrial production difficulty.
summary of the invention
It is low that the technical problem that the present invention mainly solves is to provide a kind of production cost, and reaction raw materials utilization is abundant, and product purity is high, and be applicable to the synthetic method of the 8-sulfydryl Malaysia ketone of suitability for industrialized production, to overcome hydrogen sulfide method productive rate low and pollution and murder by poisoning problem.
Implementation procedure of the present invention is as follows:
A synthetic method for 8-sulfydryl Malaysia ketone, is characterized in that: with pulegone, sodium sulphite, potassium sulphide or ammonium sulfide are reaction raw materials, take water, methyl alcohol or ethanol to prepare as reaction solvent.
Above-mentioned preparation method specifically comprises the following steps:
(1) pulegone, sulfide react at 50 ℃ ~ 80 ℃ with water, and the mol ratio of pulegone and sodium sulphite is 1:1～1:2.5, is preferably 1:1.5 ~ 1.9, more preferably 1:1.8;
(2) by above-mentioned reaction mixture hcl acidifying, be cooled to room temperature, adjust pH is to neutral, and filtering-depositing, 30 ~ 50 ℃ of warm water washing leaching cakes, obtain 8-sulfydryl Malaysia ketone crude product, and warm water temperature is preferably 35 ℃ ~ 40 ℃;
(3) Methanol+Water that is 1:1 by 8-sulfydryl Malaysia ketone crude product by volume ratio carries out recrystallization, filters, the dry target product that obtains.
In above-mentioned steps (1), the mol ratio of pulegone and sulfide is 1:1.5 ~ 1.9, and temperature of reaction is 60 ℃ ~ 80 ℃, is preferably 60 ℃ ~ 70 ℃.
Above-mentioned steps can add catalyzer Friedel-Crafts catalyzer or zeolite molecular sieve in (1).
Advantage of the present invention: 1. the present invention adopts pulegone and sodium sulphite reaction, has avoided use toxic gas H
2s, has avoided numerous and diverse multistep operation, environmental protection.2. the present invention is usingd water, methyl alcohol or ethanol as reaction solvent, not only effectively reduce production cost, and environmental pollution is little, and processing safety is high, environmental friendliness.3. target product productive rate of the present invention is high, and processing step is simple, and reaction conditions is gentle, and product purity is high, and the purification process without complicated, is applicable to suitability for industrialized production.
embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
In reactor, add 300 grams of pulegones, 250 grams of sodium sulphite and 1000 grams of water, be uniformly mixed, and is heated to 60 ℃ ~ 70 ℃, under constantly stirring, reacts 15 hours.Then by above-mentioned reaction mixture thin up, with hcl acidifying, to neutral, be cooled to room temperature, filter, filter cake temperature is 35 ℃ ~ 40 ℃ warm water washings, obtains 280 grams of 8-sulfydryl Malaysia ketone crude products.
In reaction vessel, add 280 grams of 8-sulfydryl Malaysia ketone crude products, then add 400 grams of alcohol refluxs, after 4 hours, solution is cooled to room temperature, separate out solid, refilter, the solid drying that filtration is obtained is to constant weight, obtain 170 grams of final product 8-sulfydryl Malaysia ketone, 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 preparing 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 sulphite and 1000 grams of methyl alcohol, be uniformly mixed, and is heated to 60 ℃ ~ 70 ℃, adds 5g zinc chloride (Friedel-Crafts catalyzer), under constantly stirring, reacts 15 hours.Then by above-mentioned reaction mixture thin up, with hcl acidifying, to neutral, be cooled to room temperature, filter, filter cake temperature is 35 ℃ ~ 40 ℃ warm water washings, obtains 320 grams of 8-sulfydryl Malaysia ketone crude products.
In reaction vessel, add 320 grams of 8-sulfydryl Malaysia ketone crude products, then add 400 grams of alcohol refluxs, after 4 hours, solution is cooled to room temperature, separate out solid, refilter, the solid drying that filtration is obtained, to constant weight, obtains 240 grams of final product 8-sulfydryl Malaysia ketone, and yield is 65%.
Embodiment 3
In reactor, add 300 grams of pulegones, 320 grams of sodium sulphite and 1200 grams of ethanol, be uniformly mixed, and is heated to 60 ℃ ~ 70 ℃, under constantly stirring, reacts 15 hours.Then by above-mentioned reaction mixture thin up, with hcl acidifying, to neutral, be cooled to room temperature, filter, filter cake temperature is 35 ℃ ~ 40 ℃ warm water washings, obtains 290 grams of 8-sulfydryl Malaysia ketone crude products.
In reaction vessel, add 290 grams of 8-sulfydryl Malaysia ketone crude products, then add 400 grams of alcohol refluxs, after 4 hours, solution is cooled to room temperature, separate out solid, refilter, the solid drying that filtration is obtained, to constant weight, obtains 200 grams of final product 8-sulfydryl Malaysia ketone, and yield is 54%.
Embodiment 4
The impact of the different feed ratio of investigation pulegone and sodium sulphite on target product yield, result is as shown in table 1:
reaction conditions is: 120 grams, water, and temperature of reaction is 50 ℃～80 ℃, and other reaction conditions is with embodiment 1, and result shows that when mol ratio is 1:1.8, target product yield is the most desirable when the weight ratio of pulegone and sodium sulphite is 1:0.93.
Embodiment 5
Investigate the impact of differential responses temperature on target product productive rate, result is as shown in table 2:
Reaction conditions is: 120 grams, water, and the reaction times is 15 hours, and other reaction conditions is with embodiment 1, and result shows that target product yield is the most desirable when the temperature of reaction of pulegone and sodium sulphite is 60 ℃.
Integrated survey, utilize pulegone and sodium sulphite to prepare reacting of food flavour 8-sulfydryl Malaysia ketone, the weight ratio feeding intake when pulegone and sodium sulphite is 1:0.93, be that mol ratio is 1:1.8, with ethanol, make solvent, temperature of reaction is 60 ℃, and the reaction times is that under the condition of 15 hours, target product yield is the most desirable.
Claims (5)
1. a synthetic method for 8-sulfydryl Malaysia ketone, is characterized in that: with pulegone, sodium sulphite, potassium sulphide or ammonium sulfide are reaction raw materials, take water, methyl alcohol or ethanol to prepare as reaction solvent.
2. the synthetic method of 8-sulfydryl Malaysia ketone according to claim 1, is characterized in that comprising the following steps:
(1) pulegone, sodium sulphite, potassium sulphide or ammonium sulfide react at 50 ℃ ~ 80 ℃ with water, and the mol ratio of pulegone and sulfide is 1:1～1:2.5;
(2) by above-mentioned reaction mixture hcl acidifying, be cooled to room temperature, adjust pH is to neutral, and filtering-depositing, 30 ~ 50 ℃ of warm water washing leaching cakes, obtain 8-sulfydryl Malaysia ketone crude product;
(3) Methanol+Water that is 1:1 by 8-sulfydryl Malaysia ketone crude product by volume ratio carries out recrystallization, filters, the dry target product that obtains.
3. the synthetic method of 8-sulfydryl Malaysia ketone according to claim 2, is characterized in that: in step (1), the mol ratio of pulegone and sulfide is 1:1.5 ~ 1.9.
4. the synthetic method of 8-sulfydryl Malaysia ketone according to claim 2, is characterized in that: step adds catalyzer Friedel-Crafts catalyzer or zeolite molecular sieve in (1).
5. the synthetic method of 8-sulfydryl Malaysia ketone according to claim 2, is characterized in that: step (1) temperature of reaction 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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