CN105503533B - The method that carvacrol is prepared with L carveols - Google Patents
The method that carvacrol is prepared with L carveols Download PDFInfo
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- CN105503533B CN105503533B CN201510876719.6A CN201510876719A CN105503533B CN 105503533 B CN105503533 B CN 105503533B CN 201510876719 A CN201510876719 A CN 201510876719A CN 105503533 B CN105503533 B CN 105503533B
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- carveols
- carvacrol
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- palladium carbon
- catalyst
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- 235000007746 carvacrol Nutrition 0.000 title claims abstract description 26
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 150000001752 carveol derivatives Chemical class 0.000 title abstract 5
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000006837 decompression Effects 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract description 8
- 238000013019 agitation Methods 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 240000007087 Apium graveolens Species 0.000 claims description 2
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 claims description 2
- 235000010591 Appio Nutrition 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006462 rearrangement reaction Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 240000009164 Petroselinum crispum Species 0.000 description 3
- 235000002770 Petroselinum crispum Nutrition 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 235000011203 Origanum Nutrition 0.000 description 2
- 241001529744 Origanum Species 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000007822 carvacrol derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the method that carvacrol is prepared with L carveols, in the container provided with agitating device, palladium carbon, L carveols are separately added into, 115 140 DEG C, insulation reaction 13 hours are heated under agitation（Air can be blasted simultaneously）Afterwards, room temperature is cooled to, is filtered, filtrate decompression distills to obtain carvacrol.Catalyst palladium carbon is 1: 10 50 with L carveols mass ratio.The present invention is using L carveols as raw material, and one-step synthesis method carvacrol, the reaction time is short, and technique is simple, and catalyst is easily reclaimed and reusable multiple, and product yield is high, solvent-free, and no sewage generation, safety and environmental protection is adapted to industrialized production.
Description
Technical field
The present invention relates to chemical field, and in particular to the method that carvacrol is prepared with L- carveols.
Technical background
Carvacrol is to be used for food additives, spices, antioxidant, pest repellant, sanitary disinfecting agent, preservative, deodorization agent, doctor
The staple product in the fields such as medicine intermediate, market prospects are very wide, in addition, the chief active of carvacrol or natural origanum oil
Component.Origanum oil is the feed addictive that the Ministry of Agriculture of China has been approved by using, with it is safe efficient, green, without incompatibility
Chinese medicine additive.
Carvacrol is also known as Carvacrol, is a kind of colourless to faint yellow stiff for having a thymol smell
Oily liquids, structural formula is：
The synthetic method of current carvacrol mainly has two kinds.Described in U.S. patent Nos US Patent 2064885
Using orthoresol as raw material, aluminum trichloride (anhydrous) is catalyst, and the method that condensation reaction prepares carvacrol is carried out with 2 cbloropropane isopropyl chloride, though
Right the method can obtain the carvacrol of higher yields, but the solvent used is dichloroethanes, and the toxicity of dichloroethanes is non-
Chang Gao, is deadly poisonous compound, while being also carcinogen, not only brings harm to working environment, and bring certain to product
Toxic residue, synthesis, which has to pass through, strictly to be refined, and could be used reluctantly.The A of Chinese invention patent CN 101475448 are described
Using L- carvols as raw material, organic acid or inorganic acid are used for major catalyst, using PEG-400 or PEG-600 as cocatalyst, instead
High-content carvacrol should be made.Method acid is as major catalyst, and addition is larger, and this is high to equipment requirement, and post processing is also
Need alkali lye to neutralize, this will necessarily produce substantial amounts of waste water, very big difficulty is brought to wastewater treatment.
The content of the invention
The purpose of the present invention：In view of the shortcomings of the prior art there is provided a kind of method that carvacrol is prepared with L- carveols, no
Non-toxic residual thing in the carvacrol only obtained, and to working environment non-hazardous in building-up process, also not producing need to be to be processed
Waste water.
The present invention is achieved through the following technical solutions：
The method that carvacrol is prepared with L- carveols, after catalyst palladium carbon is mixed with L- carveols, through dehydrogenation and molecule
Interior rearrangement reaction, its filtrate obtains through distillation, and catalyst palladium carbon is 1: 10-50 with L- carveols mass ratio.
Specific preparation process is as follows：
In the container provided with agitating device, 1 part of palladium carbon, 10-50 parts of L- carveols are separately added into, are heated under agitation
115-140 DEG C, insulation reaction 1-3 hours（Air can be blasted simultaneously）Afterwards, it is cooled to room temperature（20-30℃）, filtering, filtrate decompression
Distill to obtain carvacrol.
Palladium content in the palladium carbon is 5-10%.
The pressure of vacuum distillation is 1-5mmHg.
Reaction equation is as follows：
The present invention is using L- carveols as raw material, and one-step synthesis method carvacrol, the reaction time is short, and technique is simple, and catalyst is easy
Reclaim and reusable multiple, product yield is high, solvent-free, no sewage generation, safety and environmental protection is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is hydrogen mass spectrogram of the invention
Fig. 2 is carbonaceous spectrogram of the invention
Embodiment
Embodiment 1：
20.0 grams of L- carveols, 1.0 grams of palladium carbons are separately added into 50mL there-necked flask（Containing 10%Pd）, use magnetic agitation
Device is stirred, and oil bath heating is to 135 DEG C, and insulation reaction 1 hour after TLC detection L- carveols all disappear, is cooled to room temperature, mistake
Filter, filtrate decompression distills to obtain 18.2 grams of flaxen carvacrols, and yield is 91%.Obtained palladium-carbon catalyst may be reused.
Palladium-carbon catalyst is commercially available in Aladdin.1H NMR (400mHz, CDCl3): δ1.26（D, 6H, J=6.8Hz）, 2.27 (s,
3H), 2.83-2.90 (m, 1H), 5.33 (s, 1H), 6.71（D, 1H, J=1.7Hz）, 6.77 (dd, 1H, J=7.6Hz, 1.7Hz),
7.08 (d, 1H, J=7.6Hz) (such as Fig. 1).13C-NMR(100mHz, CDCl3):δ 15.4,24.0,33.7,113.1,118.7,
121.0,130.8,148.4,153.7（Such as Fig. 2）.
Embodiment 2：
20.0 grams of L- carveols, 2.0 grams of palladium carbons are separately added into 50mL there-necked flask（Containing 10%Pd）, use magnetic agitation
Device is stirred, and oil bath heating is to 125 DEG C, and insulation reaction 1 hour is cooled to room temperature, and filtering, filtrate decompression distills to obtain 18.4 grams of Sheep's-parsleys
Phenol, yield is 92%.Remaining implements such as embodiment 1.
Embodiment 3：
20.0 grams of L- carveols, 2.0 grams of palladium carbons are separately added into 50mL there-necked flask（Containing 5%Pd）, use magnetic stirring apparatus
Stirring, oil bath heating is to 125 DEG C, and insulation reaction 1 hour is cooled to room temperature, and filtering, filtrate decompression distills to obtain 17.6 grams of Sheep's-parsleys
Phenol, yield is 88%.Remaining implements such as embodiment 1.
Embodiment 4：
20.0 grams of L- carveols, 1.0 grams of palladium carbons are separately added into 50mL there-necked flask（Containing 5%Pd）, use magnetic stirring apparatus
Stirring, oil bath heating is to 125 DEG C, and insulation reaction 1.5 hours is cooled to room temperature, and filtering, filtrate decompression distills to obtain 17.8 grams of Sheep's-parsleys
Phenol, yield is 89%.Remaining implements such as embodiment 1.
Embodiment 5：
20.0 grams of L- carveols, 2.0 grams of palladium carbons are separately added into 50mL there-necked flask（Containing 10%Pd）, use magnetic agitation
Device is stirred, and oil bath heating is to 115 DEG C, and insulation reaction 1.5 hours is cooled to room temperature, and filtering, filtrate decompression distills to obtain 18.2 grams of perfume (or spice)
Celery phenol, yield is 91%.Remaining implements such as embodiment 1.
Claims (5)
1. the method for carvacrol is prepared with L- carveols, it is characterised in that：After catalyst palladium carbon is mixed with L- carveols, through de-
Hydrogen and intramolecular rearrangement reaction, its filtrate obtain through distillation.
2. the method as claimed in claim 1 that carvacrol is prepared with L- carveols, it is characterised in that：Catalyst palladium carbon is fragrant with L-
Celery alcohol mass ratio is 1: 10-50.
3. the method as claimed in claim 1 or 2 that carvacrol is prepared with L- carveols, it is characterised in that specific preparation process is such as
Under：
In the container provided with agitating device, palladium carbon, L- carveols are separately added into, 115-140 DEG C, insulation are heated under agitation
After reaction 1-3 hours, room temperature is cooled to, is filtered, filtrate decompression distills to obtain carvacrol.
4. the method as claimed in claim 1 or 2 that carvacrol is prepared with L- carveols, it is characterised in that：In the palladium carbon
Palladium content is 5-10%.
5. the method as claimed in claim 3 that carvacrol is prepared with L- carveols, it is characterised in that：The pressure of vacuum distillation is
1-5mmHg。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510876719.6A CN105503533B (en) | 2015-12-03 | 2015-12-03 | The method that carvacrol is prepared with L carveols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510876719.6A CN105503533B (en) | 2015-12-03 | 2015-12-03 | The method that carvacrol is prepared with L carveols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105503533A CN105503533A (en) | 2016-04-20 |
| CN105503533B true CN105503533B (en) | 2017-10-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN113185383B (en) * | 2021-04-28 | 2022-07-12 | 福州大学 | Preparation method of carvacrol by using limonene epoxide as hydrogenation receptor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171896A (en) * | 1992-03-05 | 1992-12-15 | Texaco Chemical Company | Alkylphenol synthesis using acid-modified inorganic clay catalysts |
| CN101372445B (en) * | 2007-08-24 | 2013-01-30 | 深圳泛胜塑胶助剂有限公司 | Resorcin synthetic process |
| 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 |
| CN101538191B (en) * | 2009-05-06 | 2012-01-18 | 西安力邦制药有限公司 | Synthetic method of high-purity propofol |
| CN101891602A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Method for synthesizing carvone |
| CN103044205A (en) * | 2012-12-08 | 2013-04-17 | 浙江鼎龙科技有限公司 | Preparation method of 3-methyl-4-isopropylphenol |
| CN103691431B (en) * | 2013-12-24 | 2016-07-06 | 湘潭大学 | A kind of palladium-carbon catalyst and preparation method and application |
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Address after: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Patentee after: Wanxiang Technology Group Co.,Ltd. Country or region after: China Address before: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Patentee before: Wanxiang Technology Co.,Ltd. Country or region before: China |