CN105693474B - The method for synthesizing carvacrol with * enediols - Google Patents
The method for synthesizing carvacrol with * enediols Download PDFInfo
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- CN105693474B CN105693474B CN201610042499.1A CN201610042499A CN105693474B CN 105693474 B CN105693474 B CN 105693474B CN 201610042499 A CN201610042499 A CN 201610042499A CN 105693474 B CN105693474 B CN 105693474B
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- enediol
- catalyst
- carvacrol
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- carvenone
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/06—Alkylated phenols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses the methods for synthesizing carvacrol with enediol, include the following steps：Step 1, enediol are dissolved in solvent with catalyst A, and heating makes enediol that dehydration and open loop rearrangement reaction occur, Carvenone is generated, after reaction, in aqueous slkali and pH to 7~8, stratification, organic phase rectification under vacuum obtain Carvenone finished product；Carvenone made from step 1 and catalyst B are dissolved in solvent by step 2, and heating occurs dehydrogenation oxidation reaction, generates carvacrol, be separated by filtration catalyst B, filtrate decompression rectifying obtains carvacrol finished product.The raw material sources of the present invention are convenient, cheap and easy to get；Synthesis technology is environmentally protective；Post-processing purification is simple for process only by rectifying；Catalyst can be recycled, and be suitble to industrialized production.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of chemical synthesis process, and in particular to are synthesized with enediol
The method of carvacrol.
Technical background
Carvacrol is colourless to the faint yellow stiff oily liquids for having thymol smell, as a kind of common food additive
Add agent and aromatic, it has the characteristics that hypotoxicity, natural sex, and safe food additives are approved in US and European.
Natural carvacrol is primarily present in a variety of lip class plants, such as thyme, wild marjoram.Carvacrol has extensive function
And application value.It is by destroying and changing the membrane structure of pathogenic bacteria or mycelial structure or effectively inhibit mitogenetic spore
The activity of son, good growth inhibition effect is all had to bacterium, saccharomycete, fungi, insect and mite class, has suppression well
Bacterium, insecticidal effect.It is thyme active ingredient promoting blood circulation and removing blood stasis, passes through the R for mediating antithromboxin to join through G13 albumen lotus roots
The signal transduction pathway of hoA/Rho- kinases realizes platelet activation.These effects make it widely be used as natural bacteriostatic anti-corrosion
Agent is applied in the products such as food, drug, cosmetics.
Currently, there are mainly two types of the synthetic methods of carvacrol：First, using carvol as raw material, in strong acid or metal catalytic
Aromatization is carried out under the action of agent is combined to carvacrol.As CN101475448A is reported using organic acid or inorganic acid as main catalytic
Agent, PEG-400 or PEG-600 are the example that cocatalyst promotes carvol intramolecular rearrangement synthesis carvacrol；In addition,
Linstead, R. P. report the reaction that catalyzing by metal palladium carvol dehydroisomerization is combined to carvacrol（Journal of the Chemical Society, 1940, 1139-1147）.The advantages of such methods is good reaction selectivity, and yield is high, but
It is its raw material carvol itself as a kind of fragrance product, higher price so that the big heavy discount of cost advantage of the technique.Second is that
Using ortho-methyl phenol as raw material, by synthesizing carvacrol with the Friedel-Crafts reaction of isopropanol or 2- halogenopropanes.Such as patent CN
It is reported in 1488615 and promotes ortho-methyl phenol to react synthesis carvacrol with 2 cbloropropane isopropyl chloride with alchlor or ferric trichloride
Method, but this method has a large amount of aluminium salt and molysite solid waste and generates, and causes environmental pollution, limit its in production into
One step application.
Invention content
In view of the drawbacks of the prior art, the present invention provides the methods for synthesizing carvacrol with enediol, to enediol
It efficiently uses, a kind of completely new carvacrol synthetic method is provided while turning waste into wealth.
The invention is realized by the following technical scheme：
The method for synthesizing carvacrol with enediol, includes the following steps：
Step 1, enediol are dissolved in solvent with catalyst A, and heating makes the active ingredient enediol of enediol occur
Dehydration and open loop rearrangement reaction generate Carvenone, are monitored by gas-chromatography in reaction process, and raw material disappears, reaction
Terminate.After reaction, with 5~10 wt% NaHCO3In aqueous solution and pH to 7~8, stratification, organic phase decompression are smart
It evaporates to obtain Carvenone finished product；
Carvenone made from step 1 and catalyst B are dissolved in solvent by step 2, and it is anti-that dehydrogenation oxidation occurs for heating
It answers, generates carvacrol, monitored by gas-chromatography in reaction process, terminated when Carvenone content is left 30%-40%
Reaction, is separated by filtration catalyst B, responseless Carvenone, solvent, further rectifying are recycled in filtrate decompression rectifying
Obtain carvacrol finished product.
Chemical equation is as follows：
Further improvement of the present invention scheme is：
In the step 1, solvent be can azeotrope with water inert substance, including toluene, fluorobenzene, methyl phenyl ethers anisole, dimethylbenzene,
Catalyst A is organic or inorganic acid, including trifluoroacetic acid, sulfonic acid, sulfuric acid, hydrochloric acid；The quality of enediol and catalyst A
Than being 1000：5~30；Reaction temperature is 110~160 DEG C, and the reaction time is 3~7h；.
In the step 2, solvent be can azeotrope with water inert substance, including toluene, fluorobenzene, methyl phenyl ethers anisole, dimethylbenzene,
Its dosage is adjusted according to reaction required temperature.；Catalyst B is Cu-C composite catalysts；Carvenone and catalyst B
Mass ratio be 500：100~500；Reaction temperature is 190~230 DEG C, and the time is 4~10h；The catalyst B being obtained by filtration is followed
Ring uses at least once, and catalytic activity does not weaken.
The present invention further improvement project be：
The step 2, dehydrogenation oxidation reaction later stage slow and by-product increases, thus surplus stock close to 30~
It is selectively best when 40%, it can stop reacting at this time；Constantly dehydrogenation is produced to drum air under reaction liquid level with pump in reaction process
Raw water constantly steams, to promote the conversion of reaction, air or oxygen atmosphere to the progress of reaction advantageously.
Beneficial effects of the present invention are：
The raw material sources of the present invention are convenient, cheap and easy to get；Synthesis technology is environmentally protective；Post-processing purification only by rectifying,
It is simple for process；Catalyst can be recycled, and be suitble to industrialized production.
Specific implementation mode
Embodiment one：
600g enediols, 300g toluene and 18g p-methyl benzenesulfonic acid is added in step 1 in 1000 mL reaction kettles, then
It is reacted about 3~4 hours at 120~150 DEG C, GC is shown after reaction, and kettle temperature is down to 40 DEG C hereinafter, 300g 5wt% are added
NaHCO3Aqueous solution is washed to PH=7~8, and the organic phase that liquid separation obtains obtains the different dihydro that content is more than 90% by rectification under vacuum
Carvol 510g, yield 85%.
Step 2 puts into 510g Carvenones obtained above and 40g dimethylbenzene in 1000 mL there-necked flasks, later
400g catalyst B are added, are reacted under 190~220 DEG C of reflux states, constantly uses and is pumped under reaction liquid level in reaction process
Drum air, about 4~5 hours, GC showed Carvenone residue 30%, stopped reaction, filtering removal catalyst, and filtrate carries out
Rectification under vacuum, recycling design 37g and responseless raw material 151g, further rectifying obtain content more than 98% carvacrol at
Product 254g, effective yield 71%.The repeatable utilizations of catalyst B being obtained by filtration.
Note：" effective yield " is based on participation reaction in step 2（Deduct recycling）Carvenone amount counted
It calculates.
Embodiment two：
600g enediols, 300g toluene and 15g p-methyl benzenesulfonic acid is added in step 1 in 1000 mL reaction kettles, so
It is reacted about 4~5 hours at 120~150 DEG C afterwards, GC is shown after reaction, and kettle temperature is down to 40 DEG C hereinafter, 250g is added
5wt% NaHCO3Aqueous solution is washed to PH=7~8, and the organic phase that liquid separation obtains obtains content by rectification under vacuum and is more than 90%
Carvenone 504g, yield 84%.
Step 2 puts into 504g Carvenones obtained above and 35g dimethylbenzene in 1000 mL there-necked flasks, later
300g catalyst B are added, are reacted under 190~220 DEG C of reflux states, constantly uses and is pumped under reaction liquid level in reaction process
Drum air, about 5~6 hours, GC showed Carvenone residue 38%, stopped reaction, filtering removal catalyst, and filtrate carries out
Rectification under vacuum, recycling design 30g and responseless raw material 190g, further rectifying obtain content more than 98% carvacrol at
Product 234g, effective yield 74.5%.
Embodiment three：
600g enediols, 300g toluene and 7g p-methyl benzenesulfonic acid is added in step 1 in 1000 mL reaction kettles, then
It is reacted 6~7 hours at 120~150 DEG C, GC is shown after reaction, and kettle temperature is down to 40 DEG C hereinafter, 200g 5wt% are added
NaHCO3Aqueous solution is washed to PH=7~8, and the organic phase that liquid separation obtains obtains the different dihydro that content is more than 90% by rectification under vacuum
Carvol 486g, yield 81%.
Step 2 puts into 486g Carvenones obtained above and 30g dimethylbenzene in 1000 mL there-necked flasks, later
150g catalyst B are added, are reacted under 190~220 DEG C of reflux states, constantly uses and is pumped under reaction liquid level in reaction process
Drum air, about 9~10 hours, GC showed Carvenone residue 34%, stopped reaction, filtering removal catalyst, and filtrate carries out
Rectification under vacuum, recycling design 28g and responseless raw material 164g, further rectifying obtain content more than 98% carvacrol at
Product 251g, effective yield 78%.
Example IV：
600g enediols, 300g toluene and 10g sulfuric acid is added in step 1 in 1000 mL reaction kettles（60wt%）, so
It is reacted about 4~5 hours at 120~150 DEG C afterwards, GC is shown after reaction, and kettle temperature is down to 40 DEG C hereinafter, 380g is added
10wt% NaHCO3Aqueous solution is washed to PH=7~8, and the organic phase that liquid separation obtains obtains content by rectification under vacuum and is more than 90%
Carvenone 472g, yield 78.8%.
Step 2 puts into 472g Carvenones obtained above and 36g chlorobenzenes in 1000 mL there-necked flasks, Zhi Houjia
Enter 200g catalyst B, reacted under 190~220 DEG C of reflux states, constantly uses and pumped under reaction liquid level in reaction process
Drum air, about 7~8 hours, GC showed Carvenone residue 35%, stopped reaction, filtering removal catalyst, and filtrate carries out
Rectification under vacuum, recycling design 35g and responseless raw material 165g, further rectifying obtain content more than 98% carvacrol at
Product 232g, effective yield 75.7%.
Embodiment five：
600g enediols, 300g toluene and 16g sulfuric acid is added in step 1 in 1000 mL reaction kettles（60wt%）, so
It is reacted about 3~4 hours at 120~150 DEG C afterwards, GC is shown after reaction, and kettle temperature is down to 40 DEG C hereinafter, 600g is added
10wt% NaHCO3Aqueous solution is washed to PH=7~8, and the organic phase that liquid separation obtains obtains content by rectification under vacuum and is more than 90%
Carvenone 477g, yield 79.5%.
Step 2 puts into 477g Carvenones obtained above and 39g chlorobenzenes in 1000 mL there-necked flasks, Zhi Houjia
Enter 160g catalyst B, reacted under 190~220 DEG C of reflux states, constantly uses pump to drum under reaction liquid level in reaction process
Air, about 7~8 hours, GC showed Carvenone residue 30%, stopped reaction, filtering removal catalyst, and filtrate is subtracted
Rectifying, recycling design 35g and responseless raw material 143g, further rectifying is pressed to obtain the carvacrol finished product that content is more than 98%
240g, effective yield 72%.
Claims (9)
1. the method for synthesizing carvacrol with enediol, it is characterised in that include the following steps：
Step 1, enediol are dissolved in solvent with catalyst A, and heating makes enediol that dehydration and open loop rearrangement reaction occur, raw
At Carvenone, after reaction, with, with pH to 7~8, stratification, organic phase rectification under vacuum obtains different in aqueous slkali
Dihydro carvone finished product；
Carvenone made from step 1 and catalyst B are dissolved in solvent by step 2, and dehydrogenation oxidation reaction occurs for heating,
Carvacrol is generated, is separated by filtration catalyst B, filtrate decompression rectifying obtains carvacrol finished product；
The catalyst A is organic or inorganic acid, and in the step 2, catalyst B is that copper is supported on carbon dielectric material
Catalyst, the wherein content of copper are 3wt%;
It is described Step 1: in step 2, solvent be can azeotrope with water inert substance, including toluene, fluorobenzene, methyl phenyl ethers anisole, diformazan
Benzene.
2. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that chemical equation
As follows：
。
3. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：In the step 1,
Catalyst A is trifluoroacetic acid, sulfonic acid, sulfuric acid or hydrochloric acid.
4. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：The step 1 and step
In rapid two, solvent is the mixing of one or both of toluene, fluorobenzene, methyl phenyl ethers anisole or dimethylbenzene.
5. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：In the step 1,
Reaction temperature is 110~160 DEG C；In the step 2, reaction temperature is 190~230 DEG C.
6. the method for synthesizing carvacrol with enediol according to claim 1 or 5, it is characterised in that：The step 1
Terminated by GC display reactions；It is monitored by gas-chromatography in the step 2 reaction process, when Carvenone content is surplus
Reaction is terminated when lower 30%-40%, the reaction was continued can cause selectivity to be remarkably decreased.
7. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：In the step 1,
The mass ratio of enediol and catalyst A are 1000：5~30；In the step 2, the matter of Carvenone and catalyst B
Amount is than being 500：100~500.
8. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：In the step 2,
The catalyst B being obtained by filtration is recycled at least once.
9. the method according to claim 1 for synthesizing carvacrol with enediol, it is characterised in that：Alkali described in step 1
Solution is 5~10 wt% NaHCO, 3 aqueous solutions.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610042499.1A CN105693474B (en) | 2016-01-22 | 2016-01-22 | The method for synthesizing carvacrol with * enediols |
| PCT/CN2016/084008 WO2017124675A1 (en) | 2016-01-22 | 2016-05-31 | Method for using menthene diol to synthesise carvacrol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610042499.1A CN105693474B (en) | 2016-01-22 | 2016-01-22 | The method for synthesizing carvacrol with * enediols |
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| Publication Number | Publication Date |
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| CN105693474A CN105693474A (en) | 2016-06-22 |
| CN105693474B true CN105693474B (en) | 2018-10-26 |
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| WO (1) | WO2017124675A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112441899B (en) * | 2021-01-07 | 2023-03-28 | 江苏宏邦化工科技有限公司 | Method for synthesizing chiral carvone by using chiral 8-hydroxy carvone |
| CN115448819B (en) * | 2022-09-22 | 2023-07-25 | 南平青华科技有限公司 | Method for preparing carvacrol from p-cymene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1523471A (en) * | 1967-03-24 | 1968-05-03 | Centre Nat Rech Scient | Process for the manufacture of methylisopropylphenols and in particular of carvacrol |
| US3538164A (en) * | 1968-02-08 | 1970-11-03 | Reynolds Tobacco Co R | Synthesis of dihydrocarvone |
| CN1244530C (en) * | 2003-09-08 | 2006-03-08 | 中国农业科学院饲料研究所 | Green synthesis process for carvacrol for fodder antibacterial agent |
| CN101475448B (en) * | 2009-01-21 | 2011-08-24 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| 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 |
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- 2016-01-22 CN CN201610042499.1A patent/CN105693474B/en active Active
- 2016-05-31 WO PCT/CN2016/084008 patent/WO2017124675A1/en active Application Filing
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| WO2017124675A1 (en) | 2017-07-27 |
| CN105693474A (en) | 2016-06-22 |
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