CN101475449B - Method for preparing carvacrol by recycling carvone synthesis by-product - Google Patents
Method for preparing carvacrol by recycling carvone synthesis by-product Download PDFInfo
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- CN101475449B CN101475449B CN2009100290997A CN200910029099A CN101475449B CN 101475449 B CN101475449 B CN 101475449B CN 2009100290997 A CN2009100290997 A CN 2009100290997A CN 200910029099 A CN200910029099 A CN 200910029099A CN 101475449 B CN101475449 B CN 101475449B
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- isothymol
- karvon
- carvacrol
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Abstract
The invention discloses a method for recovering and preparing carvacrol from byproducts of synthetic carvone. The method is characterized in that fractions rich in carvacrol in the production for synthesizing food-grade L-carvone are taken as raw materials; inorganic base is adopted to react with carvacrol in the fractions to prepare carvacrol salt; the carvacrol salt is dissolved in water and separated from unreacted carvone; carvacrol salt aqueous solution is subjected to acid precipitation by use of inorganic acid and is rectified to prepare carvacrol; and finished carvone products can be obtained by distilling the unreacted carvone. The method has the advantages of digesting the byproducts in carvone synthesis and preparing carvacrol from the byproducts, along with mild conditions, convenient operation, easiness for industrial implementation and good economic and social benefit.
Description
Technical field
The present invention relates to a kind of flavor compounds synthesising by-product and handle and reclaim the method for high added value by product, by-product recovery is produced the method for isothymol in the specifically synthetic Karvon.
Background technology
Isothymol is the staple product that is used for industries such as spices, foodstuff additive, fodder additives, oxidation inhibitor, sanitary disinfecting agent, wormer, sanitas, deodorization agent, medicine intermediate, and market outlook are wide.Isothymol has heat-clearing, dampness elimination, drive away summer heat, induce sweat, regulate the flow of vital energy extremely strong sterilization, a bacteriostatic action, has the Chinese medicine additive of safety, efficient, green, no incompatibility.
Isothymol is a kind of colourless to weak yellow liquid, 237 ℃ of boiling points, and structural formula is:
In Karvon is produced, carvoxime is under acidic conditions, hydrolysis reaction takes place make the Karvon product, the intramolecular rearrangement reaction takes place in Karvon in the sour environment lower section, further be converted into isothymol, account for 5% of Karvon amount, and the boiling point of isothymol and Karvon only differs 7.5 ℃, and separating difficulty is big, so have the fraction and the Karvon wherein that much are rich in isothymol also can't be converted into product in Karvon production, cause great waste, also cause serious environmental issue.
Summary of the invention
The objective of the invention is: the method that provides by-product recovery in the synthetic Karvon to produce isothymol, the by product during the digestion Karvon is synthetic, and produce isothymol by by product, enhance productivity.
Technical solution of the present invention is: with the fraction that is rich in isothymol in the production of synthesised food level L-Karvon is raw material, adopt the isothymol reaction in mineral alkali and the fraction to make the Sheep's-parsley phenates, phenates is water-soluble, separate with unreacted Karvon, the phenates aqueous solution makes isothymol by mineral acid acid out, rectifying again, and unreacted Karvon can get the Karvon finished product through distillation.
By-product recovery is produced in the method for isothymol in the synthetic Karvon of the present invention, and reaction equation is as follows:
Concrete steps of the present invention are as follows: under nitrogen protection, add the fraction that is rich in isothymol in the reactor, stirring and water-bath cooling drip inorganic alkali solution down, the mass ratio of isothymol and alkali is 1.8-2.8: 1, the control rate of addition, dropwises by holding temperature 30-40 ℃, continue to react half an hour, standing demix; Organic phase makes Karvon through full each salt solution washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath cooling, and it is 5～7 that dropping inorganic acid solution is adjusted pH value, the control rate of addition, and holding temperature 20-30 ℃, standing demix, organic phase saturated common salt solution washing, rectification under vacuum makes isothymol.
By-product recovery is produced in the method for isothymol in a kind of Karvon production of the present invention, and mineral alkali is sodium hydroxide or potassium hydroxide, and mineral acid is sulfuric acid or hydrochloric acid.
Method mild condition of the present invention, easy to operate, be easy to suitability for industrialized production, product yield height, quality better, alternative natural isothymol.
Embodiment
Below in conjunction with concrete example, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
Under nitrogen protection, adding 100 gram isothymol mass content are 83.2% fraction in the 500ml flask, and stirring and water-bath cooling be dropping 280 gram mass concentration 15% sodium hydroxide solution down, 33 ℃ of holding temperatures, dripped in about 4 hours, and continued to react half an hour, standing demix; Organic phase makes Karvon 13 grams with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath; dripping mass concentration 10% hydrochloric acid soln adjustment pH value is 5.0; the control rate of addition; 25 ℃ of holding temperatures; standing demix, organic phase saturated common salt solution washing, rectification under vacuum make 80.4 gram isothymols; content 99.35%, yield 96.6%.
Embodiment 2
Under nitrogen protection, adding 100 gram isothymol mass content are 86.2% fraction in the 500ml flask, and stirring and water-bath cooling be dropping 250 gram mass concentration 15% sodium hydroxide solution down, 35 ℃ of holding temperatures, dripped in about 4.5 hours, and continued to react half an hour, standing demix; Organic phase makes Karvon 12 grams with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath, and dripping 10% hydrochloric acid soln adjustment pH value is 6.0, the control rate of addition; 20 ℃ of holding temperatures, standing demix, organic phase saturated common salt solution washing; rectification under vacuum makes 82.7 gram isothymols, content 99.45%, yield 95.9%.
Embodiment 3
Under nitrogen protection, adding 100 gram isothymol mass content are 85.7% fraction in the 500ml flask, and stirring and water-bath cooling be dropping 280 gram mass concentration 17% potassium hydroxide solution down, 32 ℃ of holding temperatures, dripped in about 5 hours, and continued to react half an hour, standing demix; Organic phase makes 12.3 gram Karvons with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath, and dripping mass concentration 10% hydrochloric acid soln adjustment pH value is 5.5, the control rate of addition; 22 ℃ of holding temperatures, standing demix, organic phase saturated common salt solution washing; rectification under vacuum makes 83.1 gram isothymols, content 99.43%, yield 97%.
Embodiment 4
Under nitrogen protection, adding 100 gram isothymol mass content are 86.1% fraction in the 500ml flask, and stirring and water-bath cooling be dropping 220 gram mass concentration 14% potassium hydroxide solution down, 38 ℃ of holding temperatures, dripped in about 5.5 hours, and continued to react half an hour, standing demix; Organic phase makes 11.8 gram Karvons with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath; dripping mass concentration 11% sulphuric acid soln adjustment pH value is 6.5; the control rate of addition; 20 ℃ of holding temperatures; standing demix, organic phase saturated common salt solution washing, rectification under vacuum make 83.7 gram isothymols; content 99.36%, yield 97.2%.
Embodiment 5
Under nitrogen protection, adding 120 gram isothymol mass content are 84.9% fraction in the 500ml flask, and stirring and water-bath cooling be dropping 280 gram mass concentration 19% sodium hydroxide solution down, 30 ℃ of holding temperatures, dripped in about 5.5 hours, and continued to react half an hour, standing demix; Organic phase makes Karvon 15.7 grams with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath; dripping mass concentration 12% hydrochloric acid soln adjustment pH value is 6.4; the control rate of addition; 28 ℃ of holding temperatures; standing demix, organic phase saturated common salt solution washing, rectification under vacuum make 99.1 gram isothymols; content 99.44%, yield 97.3%.
Embodiment 6
Under nitrogen protection, adding 230 gram isothymol mass content are 84.3% fraction in the 1000ml flask, and stirring and water-bath cooling be Dropwise 5 70 gram mass concentration 13% potassium hydroxide solution down, 40 ℃ of holding temperatures, dripped in about 6 hours, and continued to react half an hour, standing demix; Organic phase makes 32.8 gram Karvons with saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath; dripping mass concentration 13% sulphuric acid soln adjustment pH value is 7.0; the control rate of addition; 30 ℃ of holding temperatures; standing demix, organic phase saturated common salt solution washing, rectification under vacuum make 189.5 gram isothymols; content 99.48%, yield 97.7%.
Claims (3)
1. from the by product of synthetic Karvon, reclaim the method for producing isothymol, it is characterized in that: with the fraction that is rich in isothymol in the production of synthesised food level L-Karvon is raw material, adopt the isothymol reaction in mineral alkali and the fraction to make the Sheep's-parsley phenates, phenates is water-soluble, separate with unreacted Karvon, the phenates aqueous solution makes isothymol with mineral acid acid out, rectifying again, and unreacted Karvon can get the Karvon finished product through distillation; Wherein, mineral alkali is sodium hydroxide or potassium hydroxide, and mineral acid is sulfuric acid or hydrochloric acid.
2. the method for producing isothymol that reclaims from the by product of synthetic Karvon according to claim 1 is characterized in that reaction equation is as follows:
3. the method for producing isothymol that from the by product of synthetic Karvon, reclaims according to claim 1, it is characterized in that concrete steps are as follows: under nitrogen protection, add the fraction that is rich in isothymol in the reactor, stirring and water-bath cooling drip inorganic alkali solution down, and the mass ratio of isothymol and alkali is 1.8-2.8: 1, and the control rate of addition, holding temperature 30-40 ℃, dropwise, continue to react half an hour, standing demix; Organic phase makes Karvon through saturated common salt water washing, rectifying; Water is under nitrogen protection, stirring and ice-water bath cooling, and it is 5～7 that dropping inorganic acid solution is adjusted pH value, the control rate of addition, and holding temperature 20-30 ℃, standing demix, organic phase saturated common salt solution washing, rectification under vacuum makes isothymol; Wherein, mineral alkali is sodium hydroxide or potassium hydroxide, and mineral acid is sulfuric acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100290997A CN101475449B (en) | 2009-01-21 | 2009-01-21 | Method for preparing carvacrol by recycling carvone synthesis by-product |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100290997A CN101475449B (en) | 2009-01-21 | 2009-01-21 | Method for preparing carvacrol by recycling carvone synthesis by-product |
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| CN101475449A CN101475449A (en) | 2009-07-08 |
| CN101475449B true CN101475449B (en) | 2011-08-24 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058829B (en) * | 2012-12-26 | 2014-10-15 | 淮安万邦香料工业有限公司 | Method for manufacturing carvacrol by carvone composite foot oil |
| CN105523897A (en) * | 2015-12-30 | 2016-04-27 | 淮安万邦香料工业有限公司 | A synthetic method of carvacrol |
| CN112479826B (en) * | 2021-01-07 | 2022-04-12 | 江苏宏邦化工科技有限公司 | Method for synthesizing carvacrol by using 8-hydroxy carvone |
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Effective date of registration: 20190107 Address after: 223005 No. 16 Shilian Avenue, Salinized New Materials Industrial Park, Suhuai High-tech Zone, Huaian City, Jiangsu Province Patentee after: Jiangsu Hongbang Chemical Technology Co., Ltd Address before: 223300 No. 216 East Changjiang Road, Huaiyin District, Huaian City, Jiangsu Province Patentee before: Huaian Wanbang Aromatic Chemicals Co., Ltd. |