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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- isothymol
- karvon
- carvacrol
- water
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000006227 byproduct Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 10
- 239000005973 Carvone Substances 0.000 title abstract 7
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 title abstract 6
- 235000007746 carvacrol Nutrition 0.000 title abstract 6
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 title abstract 6
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 238000004064 recycling Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- DSTPUJAJSXTJHM-UHFFFAOYSA-N isothymol Natural products CC(C)C1=CC(C)=CC=C1O DSTPUJAJSXTJHM-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 235000010755 mineral Nutrition 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910001577 potassium mineral Inorganic materials 0.000 claims description 3
- 235000002770 Petroselinum crispum Nutrition 0.000 claims description 2
- 240000009164 Petroselinum crispum Species 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 150000007822 carvacrol derivatives Chemical class 0.000 abstract 3
- 238000003916 acid precipitation Methods 0.000 abstract 1
- 150000007529 inorganic bases Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011027 product recovery Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- JOAADLZWSUDMHZ-ZHACJKMWSA-N (ne)-n-(2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ylidene)hydroxylamine Chemical compound CC(=C)C1CC=C(C)\C(=N\O)C1 JOAADLZWSUDMHZ-ZHACJKMWSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475449A CN101475449A (en) | 2009-07-08 |
| CN101475449B true CN101475449B (en) | 2011-08-24 |
Family
ID=40836240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100290997A Active CN101475449B (en) | 2009-01-21 | 2009-01-21 | Method for preparing carvacrol by recycling carvone synthesis by-product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475449B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 with 8-hydroxycarvone |
-
2009
- 2009-01-21 CN CN2009100290997A patent/CN101475449B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475449A (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101607888B (en) | Alpha-keto-leucine-calcium preparation method | |
| CN102086427B (en) | Process for producing conjugated linoleic acid by using rubber seed oil | |
| CN101284772B (en) | Synthetic method of D-(+)-2-chloro-propanoyl chloride | |
| CN113493428A (en) | Method for synthesizing vitamin C tetraisopalmitate | |
| CN101475449B (en) | Method for preparing carvacrol by recycling carvone synthesis by-product | |
| CN103408475B (en) | The preparation method of liquid antioxidant 4,6-bis-(pungent thiomethyl) ortho-cresol | |
| CN101781236B (en) | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea | |
| EP3045444A1 (en) | Method of preparing vanillin | |
| CN103130657B (en) | Synthetic method of 2-chloro-4-aminophenol | |
| CN104817436A (en) | Method for preparing high-purity ethylhexylglycerin | |
| CN101143829A (en) | Method for producing 2,6-dichloro-4-trifluoromethylaniline | |
| CN103254058A (en) | Process for synthesizing 2, 3, 3, 3-tetrafluoropropionic acid | |
| CN102775443B (en) | The synthetic method of Chlorpyrifos 94 | |
| CN102757455B (en) | Preparation method of cyclopropylboronic acid | |
| CN111807877A (en) | DL-p-hydroxyphenylhydantoin and production process of urea sulfate/ammonium sulfate thereof | |
| CN113666837B (en) | Preparation method of 1, 4-dimethyl pentylamine hydrochloride | |
| CN101973860A (en) | Method for preparing 2,3-butanedione from paraformaldehyde | |
| CN114044747A (en) | Synthetic method of o-methylthiobenzonitrile | |
| CN111333571A (en) | Method for synthesizing vitamin B6 triisopalmitate | |
| CN104591989B (en) | The preparation method of 5 [(4 chlorphenyl) methyl] 2,2 cyclopentanone dimethyls | |
| CN100516016C (en) | Process for the preparation of malonic ester | |
| CN101538233B (en) | Preparation method of thiogeraniol | |
| CN101941930B (en) | Preparation method of 3-mercaptopropionic acid | |
| CN102643188B (en) | Method for preparing 5-bromovalerate | |
| CN112174801B (en) | Method for coproducing glycolic acid and 1,1,1, 2-tetrafluoroethane by one-pot method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
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. |