CN104744219A - Preparation method of thymol - Google Patents
Preparation method of thymol Download PDFInfo
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- CN104744219A CN104744219A CN201510192742.3A CN201510192742A CN104744219A CN 104744219 A CN104744219 A CN 104744219A CN 201510192742 A CN201510192742 A CN 201510192742A CN 104744219 A CN104744219 A CN 104744219A
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- thymol
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- cresol
- preparation
- catalyzer
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- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000005844 Thymol Substances 0.000 title claims abstract description 49
- 229960000790 thymol Drugs 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229940100630 metacresol Drugs 0.000 claims description 28
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 26
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 26
- 229910018182 Al—Cu Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 description 8
- 244000025254 Cannabis sativa Species 0.000 description 3
- 241000402754 Erythranthe moschata Species 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 241000134874 Geraniales Species 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 240000007673 Origanum vulgare Species 0.000 description 1
- 235000004383 Origanum vulgare subsp. vulgare Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010619 basil oil Substances 0.000 description 1
- 229940018006 basil oil Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010678 thyme oil Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing thymol, wherein m-cresol and isopropanol are used as reaction raw materials, and the preparation process comprises the following steps: uniformly stirring m-cresol and isopropanol, adding a catalyst into a mixture of the m-cresol and the isopropanol, and uniformly stirring again to obtain a reaction material; reacting the reaction materials for 0.1-60 min under microwave radiation with the power of 200-1000W and at the reaction temperature of 100-200 ℃ to obtain a target product thymol; wherein the mass ratio of the m-cresol to the isopropanol is 1: 0.01-10; the dosage of the catalyst is 1-30% of the mass sum of m-cresol and isopropanol. The reaction temperature of the preparation method of thymol is 100-200 ℃, which is greatly lower than the temperature of thymol prepared by the existing Friedel-crafts alkylation reaction; the reaction time is short and only needs 0.1-60 min.
Description
Technical field
The present invention relates to the preparation method of thymol.
Background technology
Thymol (also known as thymol, thymol), chemical name is 5-thymol, is white crystal or semi-transparent clear crystal at normal temperatures.Thymol purposes is very extensive, is a kind of conventional edible flavouring spices, sanitas, sterilant and antioxidant, is also the primary raw materials synthesizing many chemical, such as thymol hydrogenation synthesis menthol simultaneously.
The source of thymol mainly contains two kinds: one extracts from natural product (thyme oil, wild marjoram oil, basil oil), and another is that synthetic obtains.Due to the limited and extraction cost of natural resource and environmental stress higher, at present mainly based on synthetic musk grass phenol.
The method of synthetic musk grass phenol mainly contains following several: (1) is that catalyst meta-cresol and Virahol prepare thymol through oversulfonate and alkylation with oleum.But strong acid sulfuric acid corrosion resistance of being fuming is too strong, the inadequate environmental protection of this technique.(2) be solvent with perhydronaphthalene, prepare thymol through catalytic pyrolysis again by after alpha-pinene catalytic oxidation.This technological reaction step is many, and productive rate is low.(3) by after geraniol catalysis closed loop, thymol is prepared through catalytic dehydrogenation.This technological reaction step is many, and the catalytic dehydrogenation catalyst life-span is short, and upstream raw material geranial source is few simultaneously.(4) focus of at present research mainly concentrates on meta-cresol and Virahol as raw material carries out Friedel-Crafts alkylation to prepare thymol.
In the document and patent of open report, Friedel-Crafts alkylation is prepared thymol and is needed at high temperature to carry out, and long reaction time.Such as: patent documentation DE-OS 2528303 discloses at 360 ~ 365 DEG C, pressure is 48 ~ 50 × 10
5utilize meta-cresol and propylene to prepare thymol under the condition of Pa, the method catalyzer used is activated alumina, carries out alkylated reaction in the liquid phase and obtains thymol.The method needs to carry out under high pressure, high temperature.
Chinese patent literature CN 101402551 A(application number 200810219106.5) also disclose a kind of preparation method of thymol, be at ambient pressure with meta-cresol and isopropylating agent for raw material, react in fixed-bed reactor, temperature of reaction is 200 ~ 300 DEG C, reaction times is 4 ~ 7 h, and rare gas element is carrier gas.Time prepared by aforesaid method, need to use fixed-bed reactor, the loading of the catalyzer of fixed bed and replace more time-consuming, effort, also need rare gas element as carrier, the most important reacts still to need at high temperature to carry out, and long reaction time.
Summary of the invention
The preparation method of the thymol that technical problem to be solved by this invention is carried out under being to provide short, normal pressure, low temperature of a kind of reaction times.The technical scheme realizing the object of the invention is a kind of preparation method of thymol, reaction raw materials is meta-cresol and Virahol, and preparation process is as follows: after meta-cresol and Virahol being stirred, in the mixture of meta-cresol and Virahol, add catalyzer, again stir, obtain reaction mass; Be obtain target product thymol after reacting 0.1 ~ 60min under the microwave radiation of 200 ~ 1000W, under the temperature of reaction of 100 ~ 200 DEG C at power by reaction mass; Wherein the ratio of the amount of substance of meta-cresol and Virahol is 1: 0.01 ~ 10; The consumption of catalyzer is 1 ~ 30% of meta-cresol and Virahol quality sum.
Described catalyzer is Al-Cu/HAP catalyzer, and HAP is hydroxyapatite, and aluminium atom and copper atom load are on hydroxyapatite; In catalyzer, the mol ratio of Al and Cu is 1: 0.001 ~ 3; In catalyzer, the charge capacity of Al-Cu is 1 ~ 50wt%.
The preparation method of above-mentioned Al-Cu/HAP is as follows: be dissolved in dilute hydrochloric acid by Al salt, Cu salt, obtain mixing solutions; Be that 100 ~ 200 object hydroxyapatite powders add above-mentioned mixing solutions using the particle diameter as carrier, obtain mixture; In mixture obtained above, add the NaOH solution as precipitation agent, after stirring, by above-mentioned material filtering, after the filter residue deionized water wash obtained, drying, after calcining, obtain catalyst A l-Cu/HAP.
Wherein Al salt is AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3in one or more mixture, mantoquita is CuCl
2, CuSO
4, Cu (NO
3)
2in one or more mixture.
Time prepared by above-mentioned catalyst A l-Cu/HAP, calcining temperature is 450 ~ 550 DEG C, and calcination time is 0.5 ~ 6h.
As preferably, reaction mass obtains target product thymol react 5 ~ 15min under power is the microwave radiation of 400 ~ 800W, under the temperature of reaction of 150 ~ 200 DEG C after.
The present invention has positive effect: the temperature of reaction of the preparation method of (1) thymol of the present invention is 100 ~ 200 DEG C, is significantly less than the temperature that existing Friedel-Crafts alkylation prepares thymol; Reaction times is shorter, only needs 0.1 ~ 60min.
(2) preparation method of the present invention can carry out under normal pressure and low temperature, and the transformation efficiency of meta-cresol is high, and the selection rate of reaction is high, and side reaction is few; Production technique is simple, and energy consumption of reaction is low, and catalyzer can be reused, and has good economic benefit and social benefit.
Embodiment
The reaction formula of synthetic musk grass phenol of the present invention is as follows:
In above-mentioned reaction formula, microwave is microwave.Al-Cu/HAP is catalyzer, and the preparation method of Al-Cu/HAP is as follows:
Al salt, Cu salt are dissolved in dilute hydrochloric acid, obtain mixing solutions; Be that 100 ~ 200 object hydroxyapatite (HAP) powder add above-mentioned mixing solutions using the particle diameter as carrier, obtain mixture; In mixture obtained above, add the NaOH solution as precipitation agent, after stirring, by above-mentioned material filtering, after the filter residue deionized water wash obtained, drying, calcine 0.5 ~ 6h at 450 ~ 550 DEG C after, obtain catalyst A l-Cu/HAP.Wherein Al salt is AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3in one or more mixture, mantoquita is CuCl
2, CuSO
4, Cu (NO
3)
2in one or more mixture; In catalyzer, the mol ratio of Al and Cu is 1: 0.001 ~ 3; In catalyzer, the charge capacity (mass percentage) of Al-Cu is 1 ~ 50wt%.
(embodiment 1)
The preparation method of the thymol of the present embodiment is as follows:
In 50mL round-bottomed flask, add 0.1 mol meta-cresol and 0.1 mol Virahol, after stirring, in the mixture of meta-cresol and Virahol, add Al-Cu/HAP catalyzer 1g, again stir, obtain reaction mass.Be under the microwave radiation of 400 W at power by reaction mass, under the temperature of reaction of 150 DEG C, react 5 min, obtain target product thymol 7.38g.Wherein the transformation efficiency of meta-cresol is 50.36%, and the selection rate of reaction is 97.57%.
The preparation method of above-mentioned Al-Cu/HAP catalyzer is as follows: by 0.1 molAl (NO
3)
39H
2o, 0.01 mol CuSO
45H
2o is dissolved in the dilute hydrochloric acid of 0.05 mol/L of 100mL, obtains mixing solutions; The 5 g hydroxyapatites (HAP) as carrier are added above-mentioned mixing solutions, obtains solidliquid mixture; In solidliquid mixture obtained above, add the NaOH solution 400mL of 1 mol/L, after stirring, by above-mentioned material filtering, after the filter residue deionized water wash obtained, drying, calcine 2 h at 500 DEG C after, obtain catalyst A l-Cu/HAP.
(embodiment 2)
The preparation method of the thymol of the present embodiment is as follows:
In 50mL round-bottomed flask, add 0.1 mol meta-cresol and 0.3 mol Virahol, after stirring, in the mixture of meta-cresol and Virahol, add Al-Cu/HAP catalyzer 1g, again stir, obtain reaction mass.Be under the microwave radiation of 400 W at power by reaction mass, under the temperature of reaction of 150 DEG C, react 5 min, obtain target product thymol 13.34g.Wherein the transformation efficiency of meta-cresol is 91.48%, and the selection rate of reaction is 97.12%.
Identical with embodiment 1 of the present embodiment catalyzer used.
(embodiment 3)
All the other are identical with embodiment 1 for the preparation method of the thymol of the present embodiment, and difference is: reaction mass reacts 10 min under power is the microwave radiation of 400 W, under the temperature of reaction of 150 DEG C, obtains target product thymol 9.51g.Wherein the transformation efficiency of meta-cresol is 65.34%, and the selection rate of reaction is 96.98%.
(embodiment 4)
All the other are identical with embodiment 1 for the preparation method of the thymol of the present embodiment, and difference is: reaction mass reacts 5min under power is the microwave radiation of 600 W, under the temperature of reaction of 150 DEG C, obtains target product thymol 10.90g.Wherein the transformation efficiency of meta-cresol is 75.16%, and the selection rate of reaction is 96.57%.
(embodiment 5)
All the other are identical with embodiment 1 for the preparation method of the thymol of the present embodiment, and difference is: the add-on of Al-Cu/HAP catalyzer is 2g; Reaction end obtains target product thymol 8.51g.Wherein the transformation efficiency of meta-cresol is 57.19%, and the selection rate of reaction is 98.98%.
(embodiment 6)
The preparation method of the thymol of the present embodiment is as follows:
In 50mL round-bottomed flask, add 0.1 mol meta-cresol and 0.3 mol Virahol, after stirring, in the mixture of meta-cresol and Virahol, add Al-Cu/HAP catalyzer 2g, again stir, obtain reaction mass.Be under the microwave radiation of 600 W at power by reaction mass, under the temperature of reaction of 180 DEG C, react 5 min, obtain target product thymol 14.30g.Wherein the transformation efficiency of meta-cresol is 98.34%, and the selection rate of reaction is 96.82%.
(embodiment 7)
All the other are identical with embodiment 1 for the preparation method of the thymol of the present embodiment, and difference is that the preparation method of Al-Cu/HAP catalyzer used is as follows: by 0.05mol Al
2(SO
4)
316H
2o, 0.01mol CuCl
22H
2o is dissolved in the dilute hydrochloric acid of 0.05 mol/L of 100mL, obtains mixing solutions; The 5 g hydroxyapatites (HAP) as carrier are added above-mentioned mixing solutions, obtains solidliquid mixture; In solidliquid mixture obtained above, add the NaOH solution 400mL of 1mol/L, after stirring, by above-mentioned material filtering, after the filter residue deionized water wash obtained, drying, calcine 2 h at 500 DEG C after, obtain catalyst A l-Cu/HAP.
Thymol 7.21g is obtained after reaction terminates; The transformation efficiency of meta-cresol is 49.53%, and the selection rate of reaction is 96.85%.
Each embodiment and application examples are the explanations to the specific embodiment of the present invention above; but not limitation of the present invention; person skilled in the relevant technique without departing from the spirit and scope of the present invention; can also make various conversion and change and obtain corresponding equivalent technical scheme, therefore all equivalent technical schemes all should be included into scope of patent protection of the present invention.
Claims (5)
1. the preparation method of a thymol, reaction raw materials is meta-cresol and Virahol, it is characterized in that preparation process is as follows: after meta-cresol and Virahol being stirred, in the mixture of meta-cresol and Virahol, add catalyzer, again stir, obtain reaction mass; Be obtain target product thymol after reacting 0.1 ~ 60min under the microwave radiation of 200 ~ 1000W, under the temperature of reaction of 100 ~ 200 DEG C at power by reaction mass; Wherein the ratio of the amount of substance of meta-cresol and Virahol is 1: 0.01 ~ 10; The consumption of catalyzer is 1 ~ 30% of meta-cresol and Virahol quality sum.
2. the preparation method of thymol according to claim 1, is characterized in that: described catalyzer is Al-Cu/HAP catalyzer, and HAP is hydroxyapatite, and aluminium atom and copper atom load are on hydroxyapatite; In catalyzer, the mol ratio of Al and Cu is 1: 0.001 ~ 3; In catalyzer, the charge capacity of Al-Cu is 1 ~ 50wt%.
3. the preparation method of thymol according to claim 2, is characterized in that the preparation method of Al-Cu/HAP is as follows:
Al salt, Cu salt are dissolved in dilute hydrochloric acid, obtain mixing solutions; Be that 100 ~ 200 object hydroxyapatite powders add above-mentioned mixing solutions using the particle diameter as carrier, obtain mixture; In mixture obtained above, add the NaOH solution as precipitation agent, after stirring, by above-mentioned material filtering, after the filter residue deionized water wash obtained, drying, after calcining, obtain catalyst A l-Cu/HAP;
Wherein Al salt is AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3in one or more mixture, mantoquita is CuCl
2, CuSO
4, Cu (NO
3)
2in one or more mixture.
4. the preparation method of thymol according to claim 3, is characterized in that: calcining temperature is 450 ~ 550 DEG C, and calcination time is 0.5 ~ 6h.
5. the preparation method of thymol according to claim 1, is characterized in that: reaction mass obtains target product thymol react 5 ~ 15min under power is the microwave radiation of 400 ~ 800W, under the temperature of reaction of 150 ~ 200 DEG C after.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510192742.3A CN104744219B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
| CN201710481004.XA CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
| CN201710481003.5A CN107398290B (en) | 2015-04-22 | 2015-04-22 | Catalyst for synthesizing thymol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510192742.3A CN104744219B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
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| CN105693471A (en) * | 2016-01-21 | 2016-06-22 | 上海延安药业（湖北）有限公司 | Preparation method of thymol crystals |
| CN112939739A (en) * | 2021-01-11 | 2021-06-11 | 吴樟强 | Acid catalysis preparation method of thymol |
| CN114849769A (en) * | 2022-04-25 | 2022-08-05 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
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| CN108911951B (en) * | 2018-08-15 | 2021-05-14 | 漳州水仙药业股份有限公司 | Thymol and preparation method and pharmaceutical composition thereof |
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| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of hydroxyapatite-supported aluminum trichloride catalyst |
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| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of hydroxyapatite-supported aluminum trichloride catalyst |
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| ASRAF A. ALI ET AL.: "Microwave-Assisted Process Intensification of Synthesis of Thymol Using Carbonized Sulfonic Acidic Resin(CSA) Catalyst", 《IND. ENG. CHEM. RES.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693471A (en) * | 2016-01-21 | 2016-06-22 | 上海延安药业（湖北）有限公司 | Preparation method of thymol crystals |
| CN105693471B (en) * | 2016-01-21 | 2019-01-15 | 上海延安药业（湖北）有限公司 | The preparation method of thymol |
| CN112939739A (en) * | 2021-01-11 | 2021-06-11 | 吴樟强 | Acid catalysis preparation method of thymol |
| CN114849769A (en) * | 2022-04-25 | 2022-08-05 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
| CN114849769B (en) * | 2022-04-25 | 2023-06-13 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
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| CN107398290A (en) | 2017-11-28 |
| CN107382670A (en) | 2017-11-24 |
| CN104744219B (en) | 2017-07-11 |
| CN107398290B (en) | 2020-01-10 |
| CN107382670B (en) | 2020-12-08 |
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