CN104744219B - The preparation method of thymol - Google Patents
The preparation method of thymol Download PDFInfo
- Publication number
- CN104744219B CN104744219B CN201510192742.3A CN201510192742A CN104744219B CN 104744219 B CN104744219 B CN 104744219B CN 201510192742 A CN201510192742 A CN 201510192742A CN 104744219 B CN104744219 B CN 104744219B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- thymol
- metacresol
- reaction
- isopropanol
- 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
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000005844 Thymol Substances 0.000 title claims abstract description 44
- 229960000790 thymol Drugs 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940100630 metacresol Drugs 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910018182 Al—Cu Inorganic materials 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- 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 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 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
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 241000402754 Erythranthe moschata Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 240000002657 Thymus vulgaris Species 0.000 description 2
- 235000007303 Thymus vulgaris Nutrition 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 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
- 239000011261 inert gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001585 thymus vulgaris Substances 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- 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
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical group CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 1
- AVBKOZVDMFKBCC-UHFFFAOYSA-N 5-methyl-2-propan-2-ylphenol propan-2-ol Chemical compound CC(C)O.CC(C)C1=CC=C(C)C=C1O AVBKOZVDMFKBCC-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 240000004784 Cymbopogon citratus Species 0.000 description 1
- 235000017897 Cymbopogon citratus Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 235000010676 Ocimum basilicum Nutrition 0.000 description 1
- 240000007926 Ocimum gratissimum Species 0.000 description 1
- 241001529744 Origanum Species 0.000 description 1
- 235000011203 Origanum 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
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000003899 bactericide agent Substances 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
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 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
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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 kind of preparation method of thymol, reaction raw materials are metacresol and isopropanol, and preparation process is as follows：After metacresol and isopropanol are stirred, catalyst is added into the mixture of metacresol and isopropanol, is again stirring for uniformly, obtaining reaction mass；Reaction mass is obtained into target product thymol in the case where power is 200~1000W microwave radiation, after 0.1~60min is reacted under 100~200 DEG C of reaction temperature；Wherein the ratio between amount of material of metacresol and isopropanol is 1: 0.01~10；The consumption of catalyst is the 1~30% of metacresol and isopropanol quality sum.The reaction temperature of the preparation method of thymol of the present invention is 100~200 DEG C, is significantly less than the temperature that existing Friedel-Crafts reaction prepares thymol；Reaction time is shorter, it is only necessary to 0.1~60min.
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- isopropyl phenols, at normal temperatures
For white crystal or semi-transparent clear crystal.Thymol purposes is quite varied, is a kind of conventional edible flavouring spices, anti-corrosion
Agent, bactericide and antioxidant, while being also the primary raw materials for synthesizing many chemicals, such as thymol hydrogenation synthesis peppermint
Alcohol.
The source of thymol mainly has two kinds：One kind is from natural products（Thyme linaloe oil, origanum oil, basil）In carry
Take, another is artificial synthesized acquisition.Because natural resources are limited and extraction cost and environmental pressure are higher, it is presently mainly
Based on the careless phenol of synthetic musk.
The method of synthetic musk grass phenol mainly has following several：（1）Using oleum as catalyst metacresol
With isopropanol thymol is prepared by sulfonation and alkylation.But smoke strong acid sulfuric acid corrosion resistance is too strong, the inadequate ring of the technique
Protect.（2）Using decahydronaphthalene as solvent, thymol will be prepared through catalytic pyrolysis again after alpha-pinene catalytic oxidation.The technological reaction is walked
It is rapid many, and low yield.（3）After lemongrass alcohol catalysis closed loop, thymol is prepared through catalytic dehydrogenation.The technological reaction step
It is many, catalytic dehydrogenation catalyst short life, while upstream raw material citronellal source is few.（4）The focus studied at present is concentrated mainly on
Carry out Friedel-Crafts alkylation to prepare thymol using metacresol and isopropanol as raw material.
In the document and patent of open report, Friedel-Crafts alkylation, which prepares thymol, to be needed to carry out at high temperature,
And the reaction time is long.For example：Patent document DE-OS 2528303 is disclosed at 360~365 DEG C, pressure be 48~50 ×
105Thymol is prepared using metacresol and propylene under conditions of Pa, the catalyst used by this method is activated alumina, in liquid
Reaction is alkylated in phase thymol is made.This method needs to carry out under high pressure, high temperature.
The A of Chinese patent literature CN 101402551（Application number 200810219106.5）Also disclose that a kind of thymol
Preparation method, be at ambient pressure, using metacresol and isopropylating agent as raw material, to be reacted in fixed bed reactors, instead
It is 200~300 DEG C to answer temperature, and the reaction time is 4~7 h, and inert gas is carrier gas., it is necessary to using solid when prepared by the above method
Fixed bed reactor, the loading of the catalyst of fixed bed and is replaced relatively time-consuming, laborious, in addition it is also necessary to which inert gas is as carrier, most
It is important that reaction stills need to carry out at high temperature, and the reaction time is long.
The content of the invention
The technical problems to be solved by the invention are to provide the thyme carried out under a kind of short reaction time, normal pressure, low temperature
The preparation method of phenol.The technical scheme for realizing the object of the invention is a kind of preparation method of thymol, reaction raw materials be between first
Phenol and isopropanol, preparation process are as follows：After metacresol and isopropanol are stirred, into the mixture of metacresol and isopropanol
Catalyst is added, is again stirring for uniformly, obtaining reaction mass；By reaction mass in the microwave radiation that power is 200~1000W
Under, under 100~200 DEG C of reaction temperature react 0.1~60min after obtain target product thymol；Wherein metacresol and
The ratio between amount of material of isopropanol is 1: 0.01~10；The consumption of catalyst be metacresol and isopropanol quality sum 1~
30%。
The catalyst is Al-Cu/HAP catalyst, and HAP is hydroxyapatite, and aluminium atom and copper atom are supported on hydroxyl
On apatite；Al and Cu mol ratio is 1: 0.001~3 in catalyst；Al-Cu load capacity is 1~50wt% in catalyst.
Above-mentioned Al-Cu/HAP preparation method is as follows：Al salt, Cu salt are dissolved in watery hydrochloric acid, mixed solution is obtained；Will
Above-mentioned mixed solution is added for the hydroxyapatite powder of 100~200 mesh as the particle diameter of carrier, mixture is obtained；To above-mentioned
The NaOH solution as precipitating reagent is added in obtained mixture, after stirring, by above-mentioned material filtering, obtained filter residue is used
After deionized water washing, drying, catalyst Al-Cu/HAP is obtained after calcining.
Wherein Al salt is AlCl3、Al2(SO4)3、Al(NO3)3In one or more kinds of mixtures, mantoquita is
CuCl2、CuSO4、Cu(NO3)2In one or more kinds of mixtures.
When prepared by above-mentioned catalyst Al-Cu/HAP, calcining heat is 450~550 DEG C, and calcination time is 0.5~6h.
As preferred, reaction mass is in power under 400~800W microwave radiation, in 150~200 DEG C of reaction temperature
Target product thymol is obtained after 5~15min of the lower reaction of degree.
The present invention has positive effect：（1）The reaction temperature of the preparation method of thymol of the present invention is 100~200
DEG C, it is significantly less than the temperature that existing Friedel-Crafts alkylation prepares thymol；Reaction time is shorter, it is only necessary to 0.1~60min.
（2）The preparation method of the present invention can be carried out under normal pressure and low temperature, the high conversion rate of metacresol, and the choosing reacted
Select rate high, side reaction is few；Simple production process, energy consumption of reaction is low, and catalyst may be reused, with preferable economic benefit
And social benefit.
Embodiment
The reaction equation of the careless phenol of musk ambrette of the present invention is as follows：
In above-mentioned reaction equation, microwave is microwave.Al-Cu/HAP is catalyst, and Al-Cu/HAP preparation method is as follows：
Al salt, Cu salt are dissolved in watery hydrochloric acid, mixed solution is obtained；Using as the particle diameter of carrier be 100~200 purposes
Hydroxyapatite（HAP）Powder adds above-mentioned mixed solution, obtains mixture；Added into mixture obtained above as heavy
The NaOH solution of shallow lake agent, after stirring, by above-mentioned material filtering, obtained filter residue is washed with deionized, dry after,
Catalyst Al-Cu/HAP is obtained after calcining 0.5~6h at 450~550 DEG C.Wherein Al salt is AlCl3、Al2(SO4)3、Al
(NO3)3In one or more kinds of mixtures, mantoquita is CuCl2、CuSO4、Cu(NO3)2In it is one or more kinds of
Mixture；Al and Cu mol ratio is 1: 0.001~3 in catalyst；Al-Cu load capacity in catalyst（Weight/mass percentage composition）
For 1~50wt%.
（Embodiment 1）
The preparation method of the thymol of the present embodiment is as follows：
0.1 mol metacresols and 0.1 mol isopropanols are added into 50mL round-bottomed flasks, after stirring, to a first
Al-Cu/HAP catalyst 1g are added in the mixture of phenol and isopropanol, are again stirring for uniformly, obtaining reaction mass.By reactant
Expect in the case where power is 400 W microwave radiation, in reacting 5 min under 150 DEG C of reaction temperature, obtain target product thymol
7.38g.Wherein the conversion ratio of metacresol is 50.36%, and the selection rate of reaction is 97.57%.
The preparation method of above-mentioned Al-Cu/HAP catalyst is as follows：By 0.1 molAl (NO3)3·9H2O、0.01 mol
CuSO4·5H2O is dissolved in 100mL 0.05 mol/L watery hydrochloric acid, obtains mixed solution；5 g hydroxyl phosphorus of carrier will be used as
Lime stone（HAP）Above-mentioned mixed solution is added, solidliquid mixture is obtained；1 mol/L is added into solidliquid mixture obtained above
NaOH solution 400mL, after stirring, by above-mentioned material filtering, obtained filter residue is washed with deionized, dry after,
Calcined at 500 DEG C and catalyst Al-Cu/HAP is obtained after 2 h.
（Embodiment 2）
The preparation method of the thymol of the present embodiment is as follows：
0.1 mol metacresols and 0.3 mol isopropanols are added into 50mL round-bottomed flasks, after stirring, to a first
Al-Cu/HAP catalyst 1g are added in the mixture of phenol and isopropanol, are again stirring for uniformly, obtaining reaction mass.By reactant
Expect in the case where power is 400 W microwave radiation, in reacting 5 min under 150 DEG C of reaction temperature, obtain target product thymol
13.34g.Wherein the conversion ratio of metacresol is 91.48%, and the selection rate of reaction is 97.12%.
Catalyst used by the present embodiment is identical with embodiment 1.
（Embodiment 3）
Remaining is same as Example 1 for the preparation method of the thymol of the present embodiment, and difference is：Reaction mass exists
Under the microwave radiation that power is 400 W, in reacting 10 min under 150 DEG C of reaction temperature, target product thymol is obtained
9.51g.Wherein the conversion ratio of metacresol is 65.34%, and the selection rate of reaction is 96.98%.
（Embodiment 4）
Remaining is same as Example 1 for the preparation method of the thymol of the present embodiment, and difference is：Reaction mass exists
Under the microwave radiation that power is 600 W, in reacting 5min under 150 DEG C of reaction temperature, target product thymol is obtained
10.90g.Wherein the conversion ratio of metacresol is 75.16%, and the selection rate of reaction is 96.57%.
（Embodiment 5）
Remaining is same as Example 1 for the preparation method of the thymol of the present embodiment, and difference is：Al-Cu/HAP
The addition of catalyst is 2g；Reaction end obtains target product thymol 8.51g.The conversion ratio of wherein metacresol is
57.19%, the selection rate of reaction is 98.98%.
（Embodiment 6）
The preparation method of the thymol of the present embodiment is as follows：
0.1 mol metacresols and 0.3 mol isopropanols are added into 50mL round-bottomed flasks, after stirring, to a first
Al-Cu/HAP catalyst 2g are added in the mixture of phenol and isopropanol, are again stirring for uniformly, obtaining reaction mass.By reactant
Expect in the case where power is 600 W microwave radiation, in reacting 5 min under 180 DEG C of reaction temperature, obtain target product thymol
14.30g.Wherein the conversion ratio of metacresol is 98.34%, and the selection rate of reaction is 96.82%.
（Embodiment 7）
Remaining is same as Example 1 for the preparation method of the thymol of the present embodiment, and difference is Al- used
The preparation method of Cu/HAP catalyst is as follows：By 0.05mol Al2(SO4)3·16H2O、0.01mol CuCl2·2H2O is dissolved in
In 100mL 0.05 mol/L watery hydrochloric acid, mixed solution is obtained；5 g hydroxyapatites of carrier will be used as（HAP）In addition
Mixed solution is stated, solidliquid mixture is obtained；1mol/L NaOH solution 400mL is added into solidliquid mixture obtained above,
After stirring, by above-mentioned material filtering, obtained filter residue is washed with deionized, dry after, calcined at 500 DEG C after 2 h
Obtain catalyst Al-Cu/HAP.
Reaction obtains thymol 7.21g after terminating；The conversion ratio of metacresol is 49.53%, and the selection rate of reaction is
96.85%。
Various embodiments above and application examples are the explanations of the embodiment to the present invention, rather than to the limit of the present invention
System, person skilled in the relevant technique without departing from the spirit and scope of the present invention, can also make various changes
Change and change and obtain corresponding equivalent technical scheme, therefore all equivalent technical schemes should be included into the present invention's
Scope of patent protection.
Claims (3)
1. a kind of preparation method of thymol, reaction raw materials are metacresol and isopropanol, it is characterised in that preparation process is as follows：
After metacresol and isopropanol are stirred, catalyst is added into the mixture of metacresol and isopropanol, is again stirring for uniformly,
Obtain reaction mass；By reaction mass in power under 200~1000W microwave radiation, in 100~200 DEG C of reaction temperature
Target product thymol is obtained after 0.1~60min of lower reaction；Wherein the ratio between amount of material of metacresol and isopropanol is 1:
0.01~10；The consumption of catalyst is the 1~30% of metacresol and isopropanol quality sum；
The catalyst is Al-Cu/HAP catalyst, and HAP is hydroxyapatite, and aluminium atom and copper atom are supported on hydroxy-apatite
Shi Shang；Al and Cu mol ratio is 1: 0.001~3 in catalyst；Al-Cu load capacity is 1~50wt% in catalyst；
Above-mentioned Al-Cu/HAP preparation method is as follows：Al salt, Cu salt are dissolved in watery hydrochloric acid, mixed solution is obtained；Using as
The particle diameter of carrier adds above-mentioned mixed solution for the hydroxyapatite powder of 100~200 mesh, obtains mixture；Obtained to above-mentioned
Mixture in add the NaOH solution as precipitating reagent, after stirring, by above-mentioned material filtering, obtained filter residue spend from
After sub- water washing, drying, catalyst Al-Cu/HAP is obtained after calcining；
Wherein Al salt is AlCl3、Al2(SO4)3、Al(NO3)3In one or more kinds of mixtures, mantoquita is CuCl2、
CuSO4、Cu(NO3)2In one or more kinds of mixtures.
2. the preparation method of thymol according to claim 1, it is characterised in that：When preparing Al-Cu/HAP catalyst,
Calcining heat is 450~550 DEG C, and calcination time is 0.5~6h.
3. the preparation method of thymol according to claim 1, it is characterised in that：Reaction mass power be 400~
Target product thymol is obtained under 800W microwave radiation, after 5~15min is reacted under 150~200 DEG C of reaction temperature.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710481004.XA CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
| CN201510192742.3A CN104744219B (en) | 2015-04-22 | 2015-04-22 | The 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 |
|---|---|---|---|
| CN201510192742.3A CN104744219B (en) | 2015-04-22 | 2015-04-22 | The preparation method of thymol |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710481003.5A Division CN107398290B (en) | 2015-04-22 | 2015-04-22 | Catalyst for synthesizing thymol |
| CN201710481004.XA Division CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104744219A CN104744219A (en) | 2015-07-01 |
| CN104744219B true CN104744219B (en) | 2017-07-11 |
Family
ID=53584580
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510192742.3A Active CN104744219B (en) | 2015-04-22 | 2015-04-22 | The preparation method of thymol |
| CN201710481004.XA Active CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
| CN201710481003.5A Active CN107398290B (en) | 2015-04-22 | 2015-04-22 | Catalyst for synthesizing thymol |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710481004.XA Active CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
| CN201710481003.5A Active CN107398290B (en) | 2015-04-22 | 2015-04-22 | Catalyst for synthesizing thymol |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN104744219B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112939739A (en) * | 2021-01-11 | 2021-06-11 | 吴樟强 | Acid catalysis preparation method of thymol |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
| CN103772154B (en) * | 2014-01-21 | 2016-03-09 | 湘潭大学 | A kind of modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F |
-
2015
- 2015-04-22 CN CN201510192742.3A patent/CN104744219B/en active Active
- 2015-04-22 CN CN201710481004.XA patent/CN107382670B/en active Active
- 2015-04-22 CN CN201710481003.5A patent/CN107398290B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Microwave-Assisted Process Intensification of Synthesis of Thymol Using Carbonized Sulfonic Acidic Resin(CSA) Catalyst;Asraf A. Ali et al.;《Ind. Eng. Chem. Res.》;20110416;第50卷;6543–6555 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107398290B (en) | 2020-01-10 |
| CN107398290A (en) | 2017-11-28 |
| CN104744219A (en) | 2015-07-01 |
| CN107382670B (en) | 2020-12-08 |
| CN107382670A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104744219B (en) | The preparation method of thymol | |
| Singh et al. | Tetragonal Cu 2 Se nanoflakes: synthesis using selenated propylamine as Se source and activation of Suzuki and Sonogashira cross coupling reactions | |
| JP2014503639A5 (en) | ||
| CN105294409B (en) | A kind of eugenol synthetic method | |
| CN105001027A (en) | Fluorne compound preparing method | |
| JP2018524319A (en) | Process for producing aromatic hydrocarbons, p-xylene and terephthalic acid | |
| CN100509721C (en) | Production method of para chlorotoluene | |
| CN101774897B (en) | Method for preparing vanillin and analogue thereof | |
| CN104588089B (en) | A kind of method of the de-olefin of reforming oil catalyst of ammonium fluoride modification preparation | |
| CN102557908A (en) | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone | |
| CN102992982B (en) | Synthesis method of p-hydroxybenzaldehyde | |
| CN104014338B (en) | Solid base carrier thallium catalyst and preparation method | |
| CN100569726C (en) | The synthesis technique of mesitylene carboxylic acid | |
| CN109824613B (en) | Method for producing BTA and co-producing TTA by one-step method | |
| TW200424168A (en) | Process for preparation of hydroxybenzoic acid compounds | |
| CN107353271A (en) | The method for purifying the method for phthalide and phthalide being prepared by phthalic anhydride | |
| CN101857528B (en) | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation | |
| CN106278824B (en) | A method of preparing cresols using modified eutectic solvent alkaline hydrolysis | |
| JP5486491B2 (en) | Propylene glycol production method | |
| CN103240129B (en) | Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol | |
| CN108727172B (en) | Catalytic synthesis method of p-methoxyacetophenone | |
| CN109225349B (en) | Preparation method of catalyst for preparing isobutene by cracking methyl tert-butyl ether | |
| Heravi et al. | Supported Preyssler Nanoparticles in Synthesis of 1, 3‐Diaryl‐5‐Spirohexahydropyrimidines | |
| CN102382272A (en) | Method for preparing polycarboxylic acid water reducer by itaconic acid | |
| CN101139262A (en) | Method for preparing anti-oxidant 2,2'-methano bis(4-methyl-6-tert-butyl phenol) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 1801 Zhong Wu Avenue, Changzhou, Jiangsu Province, Jiangsu Patentee after: Jiangsu University of Technology Address before: 213001 1801 Zhong Wu Avenue, Zhong Lou District, Changzhou, Jiangsu Patentee before: Jiangsu University of Technology |
|
| CP02 | Change in the address of a patent holder |