CN105523897A - A synthetic method of carvacrol - Google Patents
A synthetic method of carvacrol Download PDFInfo
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- CN105523897A CN105523897A CN201511011195.0A CN201511011195A CN105523897A CN 105523897 A CN105523897 A CN 105523897A CN 201511011195 A CN201511011195 A CN 201511011195A CN 105523897 A CN105523897 A CN 105523897A
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- CN
- China
- Prior art keywords
- isothymol
- polynite
- montmorillonite
- reaction
- synthetic method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
Abstract
A synthetic method of carvacrol is provided. The method includes a first step of adding montmorillonite that is a catalyst into an organic solvent under stirring to mix the montmorillonite and the solvent, heating to 130-160 DGE C, adding carvone dropwise, and allowing the carvone to be isomerized under the conditions, with the mass ratio of the montmorillonite to the carvone being 25-100:500-1000, and the mass ratio of the organic solvent to the carvone being 50-500:500-2000, and a second step of monitoring the reaction through gas chromatography (GC), filtering after the reaction is completed, collecting the solid catalyst, and subjecting a filtrate to vacuum rectification to obtain a finished carvacrol product. Traditional methods adopt sulfuric acid and other strong acids, and compared with the traditional methods, the method is advantageous in that (1) the montmorillonite is small in using amount and is of a catalytic amount, (2) after-treatment is convenient, neutralization is not needed, and the finished product can be obtained only by filtering to remove the montmorillonite and then rectifying, and (3) the montmorillonite filtered after the reaction is completed can be recycled and reused so that the method is economical and environmental friendly. Reaction conditions of the method are mild, the synthetic process of the method is green, and the method is particularly suitable for industrial production.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of chemical synthesis process, specifically refer to a kind of synthetic method of isothymol.
Technical background
Isothymol is the colourless extremely faint yellow stiff oily liquids having thymol smell, and as a kind of conventional foodstuff additive and perfume compound, it has the feature of hypotoxicity, natural sex, is approved for safe foodstuff additive at US and European.Natural isothymol is mainly present in multiple Labiatae class plant, as Thymus vulgaris, wild marjoram etc.Isothymol has function and application widely and is worth.It is by destroying and changing membrane structure or the mycelial structure of pathogenic bacterium or effectively suppress conidial activity, to bacterium, yeast, fungi, insect and mite class, all there is good growth-inhibiting effect, there is well antibacterial, insecticidal effect.It is the effective constituent that Thymus vulgaris is promoting blood circulation and removing blood stasis, and the kinase whose signal transduction pathway of RhoA/Rho-joined through G13 albumen lotus root by mediation antithromboxin, realizes platelet activation.These effects make it widely as natural bacteriostatic sanitas, are applied in the products such as food, medicine, makeup.
At present, it is take ortho-methyl phenol as raw material that the synthetic method of isothymol mainly contains two kinds: one, by synthesizing isothymol with the Friedel-Crafts reaction of Virahol or 2-halogenopropane.As with Zr-Al-SiO
2composite catalyst catalysis Virahol and ortho-methyl phenol Reactive Synthesis isothymol (JournalofChemicalTechnologyandBiotechnology, 2009,84,1499-1508), but the temperature of this reaction needs 180 DEG C, and yield is lower, is only 73%; Using Aluminium Trichloride as Catalyst ortho-methyl phenol and 2 cbloropropane isopropyl chloride Reactive Synthesis isothymol is described in US Patent No. 2286953, also the method promoting ortho-methyl phenol and 2 cbloropropane isopropyl chloride Reactive Synthesis isothymol with aluminum chloride or iron trichloride is disclosed on this basis in patent CN1488615, but it is excessive all to there is catalyst levels in these methods, produce the pollution problem of a large amount of aluminium salt and molysite solid waste.Two is take Karvon as raw material, carries out aromizing synthesis isothymol under the effect of strong acid.As patent CN101475448 reports with organic acid or mineral acid for Primary Catalysts, PEG-400 or PEG-600 is the example that cocatalyst promotes Karvon intramolecular rearrangement synthesis isothymol.In addition, the method being converted into isothymol with the Karvon in sulfuric acid catalysis Karvon pin oil is reported in patent CN103058829.But all used a large amount of organic acids or inorganic acid in these two inventions, not only higher to the requirement of conversion unit, post-reaction treatment all needs to neutralize with a large amount of alkali lye, creates a large amount of waste liquids, adds environmental protection pressure.
Therefore, research and develop that a kind of reaction conditions is gentle, simple to operate, the synthetic method of green non-pollution isothymol is significant.
Summary of the invention
For traditional isothymol production technique and shortcoming and the deficiency of having reported synthetic method, the invention provides a kind of is raw material with Karvon, by the aromatization of polynite catalysis, and the method for green high-efficient synthesis isothymol.
The present invention is achieved through the following technical solutions:
The synthetic method of isothymol, is characterized in that comprising the steps:
Under step one, stirring, catalyzer polynite is added in organic solvent and mix, when being warming up to 130 ~ 160 DEG C, drip Karvon, with this understanding, Karvon generation isomerization reaction, the mass ratio of described polynite and Karvon is 25 ~ 100:500 ~ 1000; The mass ratio of described organic solvent and Karvon is 50 ~ 500:500 ~ 2000;
Step 2, reaction process are monitored by gas-chromatography (GC), and after reaction terminates, filter, collect solid catalyst, filtrate decompression rectifying obtains isothymol finished product.
Reaction equation is as follows:
。
Described catalyzer polynite pale yellow powder, specific surface area is 20 ~ 240m
2/ g.
Described polynite recycles at least one times; Rectifying gained recycled solvent.
Described polynite recycles 3 ~ 5 times and still has good catalytic effect.
Described solvent, including, but not limited to dimethylbenzene, chlorobenzene or methyl-phenoxide, can also comprise dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc., and the effect of solvent prevents from reacting very exothermic, plays shock absorption.
Beneficial effect of the present invention is:
(1) polynite consumption is little, is catalytic amount;
(2) convenient post-treatment, need not carry out neutralization reaction, as long as carry out rectifying after excessively filtering polynite can obtain finished product;
(3) reaction is filtered the polynite obtained afterwards and be can be recycled, economic environmental protection.
(4) this invention reaction conditions is gentle, simple to operate;
(5) synthesis technique environmental protection, whole technique produces without the three wastes, is very applicable to suitability for industrialized production.
Embodiment
Specific embodiment of the invention step is as follows:
Embodiment one:
In 1000mL reactor, add 100g dimethylbenzene and 20g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, under room temperature, (it is 100 ~ 200g/min that rate of addition controls) drips Karvon 600g fast, 150 DEG C of reactions 4 ~ 5 hours are warmed up to after dripping off, GC monitoring reaction terminates rear mistake and filters polynite, the first decompression and solvent recovery of filtrate, further rectifying obtains the isothymol finished product 590g that content is greater than 99%, yield 98.3%.
Again dropping in 1000mL reactor by reclaiming the polynite 19g obtained above, adding 100g dimethylbenzene (comprise and reclaim dimethylbenzene 90g) afterwards, fast drop Karvon 600g under room temperature, after dripping off, being warmed up to 150 DEG C of reactions about 5 hours.GC shows after reaction terminates and carries out aftertreatment according to mode above, and rectification under vacuum obtains the isothymol finished product 593g that content is greater than 99%, yield 98.8%.The polynite of reclaiming by this step reuses 5 times, and result shows polynite 5 recycleds in this synthesis technique, and catalytic efficiency does not obviously reduce, and product average yield is 98.5%.
Embodiment two:
In 1000mL reactor, add 100g dimethylbenzene and 30g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, fast drop Karvon 600g under room temperature, be warmed up to 160 DEG C of reactions 2 ~ 3 hours after dripping off, GC monitoring reaction terminates rear mistake and filters polynite, the first decompression and solvent recovery of filtrate, further rectifying obtains the isothymol finished product 595g that content is greater than 99%, yield 99%.
Embodiment three:
In 1000mL reactor, add 150g methyl-phenoxide and 40g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, quick Karvon 600g under room temperature, be warmed up to 150 DEG C of reactions 2 hours after dripping off, GC monitors after reaction terminates and carries out aftertreatment according to mode above, and rectification under vacuum obtains the isothymol finished product 590g that content is greater than 99%, yield 98.3%.
Embodiment four:
In 1000mL reactor, add 200g chlorobenzene and 30g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, fast drop Karvon 600g under room temperature, be warmed up to 150 DEG C of reactions 3 hours after dripping off, GC monitors after reaction terminates and carries out aftertreatment according to mode above, and rectification under vacuum obtains the isothymol finished product 588g that content is greater than 99%, yield 98%.
Embodiment five:
In 1000mL reactor, add 100g toluene and 50g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, fast drop Karvon 600g under room temperature, be warmed up to 160 DEG C of reactions 0.5 hour after dripping off, GC monitors after reaction terminates and carries out aftertreatment according to mode above, and rectification under vacuum obtains the isothymol finished product 591g that content is greater than 99%, yield 98.3%.
Embodiment six:
In 1000mL reactor, add 150g toluene and 70g polynite, the specific surface area of described polynite is 20 ~ 240m
2/ g, fast drop Karvon 500g under room temperature, be warmed up to 130 DEG C of reactions 5 ~ 6 hours after dripping off, GC monitors after reaction terminates and carries out aftertreatment according to mode above, and rectification under vacuum obtains the isothymol finished product 480g that content is greater than 99%, yield 96%.
Claims (6)
1. the synthetic method of isothymol, is characterized in that comprising the steps:
Under step one, stirring, catalyzer polynite is added in organic solvent and mix, when being warming up to 130 ~ 160 DEG C, drip Karvon, with this understanding, Karvon generation isomerization reaction; The mass ratio of described polynite and Karvon is 25 ~ 100:500 ~ 1000, and the mass ratio of described organic solvent and Karvon is 50 ~ 500:500 ~ 2000;
After step 2, reaction terminate, filter, collect solid catalyst, filtrate decompression rectifying obtains isothymol finished product.
2. the synthetic method of isothymol according to claim 1, is characterized in that reaction equation is as follows:
。
3. the synthetic method of isothymol according to claim 1, is characterized in that: the specific surface area of described catalyzer polynite is 20 ~ 240m
2/ g; Described polynite at least recycles once after reclaiming.
4. the synthetic method of the isothymol according to claim 1 or 3, is characterized in that: described catalyzer polynite recycles 3 ~ 5 times.
5. the synthetic method of isothymol according to claim 1, is characterized in that: described solvent comprises dimethylbenzene, chlorobenzene or methyl-phenoxide.
6. the synthetic method of isothymol according to claim 1, is characterized in that: described rectifying gained recycled solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511011195.0A CN105523897A (en) | 2015-12-30 | 2015-12-30 | A synthetic method of carvacrol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511011195.0A CN105523897A (en) | 2015-12-30 | 2015-12-30 | A synthetic method of carvacrol |
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| CN105523897A true CN105523897A (en) | 2016-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201511011195.0A Pending CN105523897A (en) | 2015-12-30 | 2015-12-30 | A synthetic method of carvacrol |
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| CN (1) | CN105523897A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851479A (en) * | 2019-01-17 | 2019-06-07 | 亿如科技(北京)有限公司 | A kind of chemical synthesis process of antibacterial agent fragrance carvacrol |
| CN112920022A (en) * | 2021-01-11 | 2021-06-08 | 吴樟强 | Method for efficiently preparing carvacrol from o-cresol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475448A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| CN101475449A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Method for preparing carvacrol by recycling carvone synthesis by-product |
| US20120021959A1 (en) * | 2004-02-27 | 2012-01-26 | Morgan Iii George Kavin | Muttiple Use Fabric Conditioning Composition With Blooming Perfume |
-
2015
- 2015-12-30 CN CN201511011195.0A patent/CN105523897A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120021959A1 (en) * | 2004-02-27 | 2012-01-26 | Morgan Iii George Kavin | Muttiple Use Fabric Conditioning Composition With Blooming Perfume |
| CN101475448A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| CN101475449A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Method for preparing carvacrol by recycling carvone synthesis by-product |
Non-Patent Citations (2)
| Title |
|---|
| CHRISTEL GOZZI等: "Heterogeneous acid-catalysed isomerization of carvone to carvacrol", 《REACT KINET CATAL LETT》 * |
| 李立等: "关于蒙脱土K-10 催化的烯丙醇脱水重排和二烯-酮-酚重排机理探讨", 《河北科技大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851479A (en) * | 2019-01-17 | 2019-06-07 | 亿如科技(北京)有限公司 | A kind of chemical synthesis process of antibacterial agent fragrance carvacrol |
| CN109851479B (en) * | 2019-01-17 | 2022-07-05 | 亿如科技(北京)有限公司 | Chemical synthesis process of antibacterial agent spice carvacrol |
| CN112920022A (en) * | 2021-01-11 | 2021-06-08 | 吴樟强 | Method for efficiently preparing carvacrol from o-cresol |
| CN112920022B (en) * | 2021-01-11 | 2023-09-01 | 福建中农牧生物科技有限公司 | Method for preparing carvacrol from o-cresol |
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Application publication date: 20160427 |