CN106588577B - The synthetic method of Pentafluorophenol - Google Patents
The synthetic method of Pentafluorophenol Download PDFInfo
- Publication number
- CN106588577B CN106588577B CN201510677256.0A CN201510677256A CN106588577B CN 106588577 B CN106588577 B CN 106588577B CN 201510677256 A CN201510677256 A CN 201510677256A CN 106588577 B CN106588577 B CN 106588577B
- Authority
- CN
- China
- Prior art keywords
- pentafluoride
- phenyl
- pentafluorophenol
- temperature
- mcm
- 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
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002808 molecular sieve Substances 0.000 claims description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 6
- 229940079864 sodium stannate Drugs 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000706 filtrate Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical class FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- -1 Cetyl trimethyl bromine Chemical compound 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 150000002978 peroxides Chemical class 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
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to medicinal chemistry arts, more particularly to a kind of synthetic method of Pentafluorophenol.The present invention be directed to current synthetic routes in industrialized production, process flow is complicated, the higher problem of production cost, a kind of preparation method of completely new Pentafluorophenol is provided, using phenyl-pentafluoride as raw material, under the action of catalyst, it is aoxidized through one step of hydrogen peroxide, synthesis cost is low, simple process, is suitble to industrial mass production.
Description
Technical field
The present invention relates to the field of chemical synthesis, more particularly relate to a kind of synthetic method of Pentafluorophenol.
Background technique
Pentafluorophenol, the entitled Pentafluorophenol of English.Pentafluorophenol is a kind of important medicine intermediate,
It can be used to prepare pentafluorophenyl group active ester, which can promote the formation of peptide bond, and almost without any side effect.In addition, five
Fluorophenol or a kind of liquid crystal material intermediate, especially suitable for the preparation of polyfluoro class monomeric liquid crystal material, which glues with low
Degree and high dielectric anisotropy nematic liquid crystalline material are used in mixed way, and can increase the dipole moment of molecule, are reduced the response time, are changed
The display performance of kind liquid crystal material, improves clarity, has great importance to production high-performance liquid crystal material.
Currently, the method for preparing Pentafluorophenol have it is following several:
1, patent CN1847210 is disclosed using five bromofluorobenzenes as raw material, is initially formed Grignard Reagent, then anti-with peroxide
It answers, finally passes through HCl treatment, obtain Pentafluorophenol.The method starting material is expensive, and is related to grignard reaction, is unfavorable for work
Industry metaplasia produces.
2, patent CN102718635 is raw material using five bromofluorobenzenes, through lithiumation, esterification, hydrolysis, oxidation four-step reaction, is obtained
To Pentafluorophenol.The same method starting material is expensive, and first step reaction uses n-BuLi, and there are security risks, is not suitable for
Industrialized production.
3, document Journal of Organic Chemistry.1991,56 (26), 7350-7354. are using phenyl-hexafluoride
Raw material generates phenyl-pentafluoride phenates, then through acidic hydrolysis, obtain Pentafluorophenol under alkaline condition.The starting material price is more
Valuableness is also not suitable for industrialized production.
Summary of the invention
The purpose of the present invention is provide a kind of preparation method of completely new Pentafluorophenol in view of the above technical problems.
The purpose of the present invention can be achieved through the following technical solutions:
The synthetic method of the first Pentafluorophenol disclosed by the invention, this method is using phenyl-pentafluoride as raw material, with high-copper MCM-
41 molecular sieves are catalyst, and using hydrogen peroxide as oxidant, raw material phenyl-pentafluoride is under the action of the catalyst and oxidant, instead
Pentafluorophenol should be generated；
The high-copper MCM-41 molecular sieve the preparation method comprises the following steps: cetyl trimethylammonium bromide is added to deionization
Template solution is obtained in water, it is alkalescent that alkaline reagent to template solution, which is added, and it is molten that ethyl orthosilicate is slowly added into template
It in liquid and stirs evenly, obtains colorless and transparent substance；It is slowly added to copper nitrate in colorless and transparent substance and stirs evenly, rises
Temperature keeps the temperature 5~48h, obtains product to 100~180 DEG C；Product is adopted and is washed with deionized to neutrality, is centrifugated
To white solid, which is put into Muffle furnace and is calcined to get high-copper MCM-41 molecular sieve is arrived.
In the synthetic method of the first Pentafluorophenol: reaction dissolvent is selected from least one of acetonitrile, acetone, water, reaction
Temperature is 0~100 DEG C, and preferable reaction temperature is 50~70 DEG C；It is preferred that the molal weight of phenyl-pentafluoride and high-copper MCM-41 molecular sieve
Than for 1mol:1~10g, the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is 1mol:0.1~1L；Cetyl trimethyl bromine
Change ammonium: ethyl orthosilicate: the molar ratio of copper nitrate is 1~3:2~6:0.5~2.
In the synthetic method of the first Pentafluorophenol: white solid is put into calcining manners in Muffle furnace are as follows: the first stage is
From room temperature to 300 DEG C, 1~3h is kept the temperature, the heating rate in the stage is 5~8 DEG C/min；Second stage heats up from 300 DEG C
To 550 DEG C, 3~8h is kept the temperature, the heating rate in the stage is 10~12 DEG C/min.
The synthetic method of second of Pentafluorophenol disclosed by the invention, this method is using phenyl-pentafluoride as raw material, with the double gold of tin zinc
Category MCM-41 molecular sieve be catalyst, using hydrogen peroxide as oxidant, phenyl-pentafluoride under the action of the catalyst and oxidant,
Reaction generates Pentafluorophenol；
The tin zinc bimetallic MCM-41 molecular sieve the preparation method comprises the following steps: cetyl trimethylammonium bromide is added to
Template solution is obtained in deionized water, it is alkalescent that alkaline reagent to template solution, which is added, and ethyl orthosilicate is slowly added into
It in template solution and stirs evenly, obtains colorless and transparent substance；Be slowly added in colorless and transparent substance molar ratio be 1:2~
5 sodium stannate and zinc sulfate mixed solution simultaneously stir evenly, and are warming up to 100~180 DEG C, keep the temperature 5~48h, obtain product；It will produce
Object, which is adopted, to be washed with deionized to neutrality, and white solid is centrifugally separating to obtain, which is put into Muffle furnace and is calcined,
Obtain tin zinc bimetallic MCM-41 molecular sieve.
In the synthetic method of second of Pentafluorophenol: reaction dissolvent is selected from least one of acetonitrile, acetone, water, reaction
Temperature is 0~100 DEG C, and preferable reaction temperature is 50~70 DEG C；It is preferred that phenyl-pentafluoride and tin zinc bimetallic MCM-41 molecular sieve rub
Your mass ratio is 1mol:1~10g, and the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is 1mol:0.1~1L；Cetyl three
Methyl bromide ammonium: ethyl orthosilicate: the molar ratio of sodium stannate is 1~3:2~6:0.05~0.1.
In the synthetic method of second of Pentafluorophenol: white solid is put into calcining manners in Muffle furnace are as follows: the first stage is
From room temperature to 300 DEG C, 1~3h is kept the temperature, the heating rate in the stage is 5~8 DEG C/min；Second stage heats up from 300 DEG C
To 550 DEG C, 3~8h is kept the temperature, the heating rate in the stage is 10~12 DEG C/min.
The synthetic method of the third Pentafluorophenol, this method is using phenyl-pentafluoride as raw material, using TS-1 molecular sieve as catalyst, with
Hydrogen peroxide is oxidant, and for phenyl-pentafluoride under the action of the catalyst and oxidant, reaction generates Pentafluorophenol；Wherein five fluorine
The molal weight ratio of benzene and TS-1 molecular sieve is 1mol:1~10g, and the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is 1mol:
0.1~1L；Reaction dissolvent is selected from least one of acetonitrile, acetone, water, and reaction temperature is 0~100 DEG C, preferable reaction temperature
It is 50~70 DEG C.
Alkalescent described in technical solution of the present invention refers to that pH value is 9~10.
Beneficial effects of the present invention:
The present invention is using compound ii phenyl-pentafluoride as starting material, I Pentafluorophenol of prepare compound, raw materials used production cost
It is low, and production procedure is simple, it is easy to industrialized production.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Embodiment 1-1
Cetyl trimethylammonium bromide (1mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (2mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；It is slowly added to copper nitrate (0.6mmol) in colorless and transparent substance and stirs evenly, is warming up to 100
~180 DEG C, 30h is kept the temperature, product is obtained；Product is adopted and is washed with deionized to neutrality, white solid is centrifugally separating to obtain
The white solid is put into Muffle furnace and is calcined, the first stage is to keep the temperature 2h, the heating in the stage from room temperature to 300 DEG C
Speed is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 6h, and the heating rate in the stage is 10~12
DEG C/min, obtain high-copper MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetonitrile (20ml), above-mentioned high-copper MCM-41 molecular sieve (0.05g) is added, to system
Middle dropwise addition 30%H2O2(6ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slowly dropped to
Room temperature filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, is extracted, is associated with toluene (20ml*3)
Machine phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains Pentafluorophenol
9.6mmol, yield 96%.
Embodiment 1-2
Cetyl trimethylammonium bromide (2mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (4mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；It is slowly added to copper nitrate (1mmol) in colorless and transparent substance and stirs evenly, it is warming up to 100~
180 DEG C, 30h is kept the temperature, product is obtained；Product is adopted and is washed with deionized to neutrality, white solid is centrifugally separating to obtain.It will
The white solid, which is put into Muffle furnace, to be calcined, and the first stage is to keep the temperature 2h, the heating speed in the stage from room temperature to 300 DEG C
Degree is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 6h, and the heating rate in the stage is 10~12 DEG C/
Min obtains high-copper MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetone (20ml), above-mentioned high-copper MCM-41 molecular sieve (0.03g) is added, to system
Middle dropwise addition 30%H2O2(10ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slowly dropped to
Room temperature filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, is extracted, is associated with toluene (20ml*3)
Machine phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains Pentafluorophenol
9.5mmol, yield 95%.
Embodiment 1-3
Cetyl trimethylammonium bromide (3mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (6mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；It is slowly added to copper nitrate (2mmol) in colorless and transparent substance and stirs evenly, it is warming up to 100~
180 DEG C, 30h is kept the temperature, product is obtained；Product is adopted and is washed with deionized to neutrality, white solid is centrifugally separating to obtain.It will
The white solid, which is put into Muffle furnace, to be calcined, and the first stage is to keep the temperature 2h, the heating speed in the stage from room temperature to 300 DEG C
Degree is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 6h, and the heating rate in the stage is 10~12 DEG C/
Min obtains high-copper MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetonitrile (20ml), above-mentioned high-copper MCM-41 molecular sieve (0.1g) is added, to system
Middle dropwise addition 30%H2O2(3ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slowly dropped to
Room temperature filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, is extracted, is associated with toluene (20ml*3)
Machine phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains Pentafluorophenol
9.4mmol, yield 94%.
Embodiment 2-1
Cetyl trimethylammonium bromide (2mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (4mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；It is mixed that sodium stannate (0.08mmol) and zinc sulfate (0.16mmol) is slowly added in colorless and transparent substance
It closes object and stirs evenly, be warming up to 100~180 DEG C, keep the temperature 48h, obtain product；Product is adopted and is washed with deionized to neutrality
Afterwards, it is centrifugally separating to obtain white solid.The white solid is put into Muffle furnace and is calcined, the first stage be from room temperature to
300 DEG C, 3h is kept the temperature, the heating rate in the stage is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 8h,
The heating rate in the stage is 10~12 DEG C/min, obtains tin zinc bimetallic MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetone (20ml), above-mentioned tin zinc bimetallic MCM-41 molecular sieve (0.06g) is added,
30%H is added dropwise into system2O2(8ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slow
Slowly it is down to room temperature, filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, extracted with toluene (20ml*3),
Merge organic phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains phenyl-pentafluoride
Phenol 9.3mmol, yield 93%.
Embodiment 2-2
Cetyl trimethylammonium bromide (3mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (6mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；Sodium stannate (0.1mmol) is slowly added in colorless and transparent substance to mix with zinc sulfate (0.3mmol)
Object simultaneously stirs evenly, and is warming up to 100~180 DEG C, keeps the temperature 48h, obtains product；Product is adopted and is washed with deionized to neutrality
Afterwards, it is centrifugally separating to obtain white solid.The white solid is put into Muffle furnace and is calcined, the first stage be from room temperature to
300 DEG C, 3h is kept the temperature, the heating rate in the stage is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 8h,
The heating rate in the stage is 10~12 DEG C/min, obtains tin zinc bimetallic MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetonitrile (20ml), above-mentioned tin zinc bimetallic MCM-41 molecular sieve (0.03g) is added,
30%H is added dropwise into system2O2(5ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slow
Slowly it is down to room temperature, filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, extracted with toluene (20ml*3),
Merge organic phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains phenyl-pentafluoride
Phenol 9.4mmol, yield 94%.
Embodiment 2-3
Cetyl trimethylammonium bromide (1mmol) is add to deionized water to obtain template solution, alkalinity examination is added
Ethyl orthosilicate (3mmol) is slowly added into template solution and is stirred evenly, obtained to pH=9~10 of template solution by agent
To colorless and transparent substance；It is mixed that sodium stannate (0.06mmol) and zinc sulfate (0.3mmol) is slowly added in colorless and transparent substance
It closes object and stirs evenly, be warming up to 100~180 DEG C, keep the temperature 48h, obtain product；Product is adopted and is washed with deionized to neutrality
Afterwards, it is centrifugally separating to obtain white solid.The white solid is put into Muffle furnace and is calcined, the first stage be from room temperature to
300 DEG C, 3h is kept the temperature, the heating rate in the stage is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 8h,
The heating rate in the stage is 10~12 DEG C/min, obtains tin zinc bimetallic MCM-41 molecular sieve.
Phenyl-pentafluoride (10mmol) is dissolved in acetone (20ml), above-mentioned tin zinc bimetallic MCM-41 molecular sieve (0.1g) is added,
30%H is added dropwise into system2O2(10ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material react completely.It is slow
Slowly it is down to room temperature, filters, 20% solution of sodium bisulfite (10ml) is slowly added dropwise into filtrate, extracted with toluene (20ml*3),
Merge organic phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains phenyl-pentafluoride
Phenol 9.5mmol, yield 95%.
Embodiment 3-1
Phenyl-pentafluoride (10mmol) is dissolved in the mixed solution of acetonitrile (15ml) and water (5ml), TS-1 molecular sieve is added
(0.1g), 30%H is added dropwise into system2O2(3ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material are complete
Reaction.It is slowly dropped to room temperature, filters, 20% solution of sodium bisulfite (12ml) is slowly added dropwise into filtrate, with toluene (20ml*
3) it extracts, merges organic phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains
To Pentafluorophenol 8.8mmol, yield 88%.
Embodiment 3-2
Phenyl-pentafluoride (10mmol) is dissolved in the mixed solution of acetonitrile (15ml) and water (5ml), TS-1 molecular sieve is added
(0.05g), 30%H is added dropwise into system2O2(8ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material are complete
Reaction.It is slowly dropped to room temperature, filters, 20% solution of sodium bisulfite (12ml) is slowly added dropwise into filtrate, with toluene (20ml*
3) it extracts, merges organic phase, it is dry with anhydrous sodium sulfate, it filters, filtrate decompression distillation, the fraction of 110~115 DEG C of recycling obtains
To Pentafluorophenol 8.6mmol, yield 86%.
Embodiment 3-3
Phenyl-pentafluoride (10mmol) is dissolved in the mixed solution of acetonitrile (15ml) and water (5ml), TS-1 molecular sieve is added
(0.03g), 30%H is added dropwise into system2O2(10ml), is added dropwise, and controls 65 DEG C of reaction 3h of temperature.TLC contact plate, raw material are complete
Full response.It is slowly dropped to room temperature, filters, 20% solution of sodium bisulfite (12ml) is slowly added dropwise into filtrate, uses toluene
(20ml*3) extraction, merges organic phase, dry with anhydrous sodium sulfate, filters, and filtrate decompression distillation, 110~115 DEG C of recycling evaporates
Point, obtain Pentafluorophenol 8.5mmol, yield 85%.
Claims (6)
1. a kind of synthetic method of Pentafluorophenol, it is characterised in that: this method is using phenyl-pentafluoride as raw material, with high-copper MCM-41 molecule
Sieve is catalyst, and using hydrogen peroxide as oxidant, under the action of the catalyst and oxidant, reaction generates raw material phenyl-pentafluoride
Pentafluorophenol；
The high-copper MCM-41 molecular sieve preparation method are as follows: be add to deionized water to obtain by cetyl trimethylammonium bromide
Template solution, it is alkalescent that alkaline reagent to template solution, which is added, and ethyl orthosilicate is slowly added into template solution and is stirred
It mixes uniformly, obtains colorless and transparent substance；It is slowly added to copper nitrate in colorless and transparent substance and stirs evenly, is warming up to 100
~180 DEG C, 5~48h is kept the temperature, product is obtained；Product is adopted and is washed with deionized to neutrality, it is solid to be centrifugally separating to obtain white
The white solid is put into Muffle furnace and calcines to get high-copper MCM-41 molecular sieve is arrived by body；
Wherein: reaction dissolvent is selected from least one of acetonitrile, acetone, water, and reaction temperature is 0~100 DEG C；Phenyl-pentafluoride and high-copper
The molal weight ratio of MCM-41 molecular sieve is 1mol:1~10g, and the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is 1mol:
0.1~1L；
White solid is put into calcining manners in Muffle furnace are as follows: the first stage is to keep the temperature 1~3h, the rank from room temperature to 300 DEG C
The heating rate of section is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 3~8h, the heating speed in the stage
Degree is 10~12 DEG C/min.
2. the synthetic method of Pentafluorophenol according to claim 1, it is characterised in that: cetyl trimethylammonium bromide:
Ethyl orthosilicate: the molar ratio of copper nitrate is 1~3:2~6:0.5~2.
3. a kind of synthetic method of Pentafluorophenol, it is characterised in that: this method is using phenyl-pentafluoride as raw material, with tin zinc bimetallic MCM-
41 molecular sieves are catalyst, and using hydrogen peroxide as oxidant, phenyl-pentafluoride is under the action of the catalyst and oxidant, reaction life
At Pentafluorophenol；
The tin zinc bimetallic MCM-41 molecular sieve preparation method are as follows: cetyl trimethylammonium bromide is added to deionized water
In obtain template solution, it is alkalescent that alkaline reagent to template solution, which is added, and ethyl orthosilicate is slowly added into template solution
In and stir evenly, obtain colorless and transparent substance；The stannic acid that molar ratio is 1:2~5 is slowly added in colorless and transparent substance
Sodium and zinc sulfate mixed solution simultaneously stir evenly, and are warming up to 100~180 DEG C, keep the temperature 5~48h, obtain product；Product is used
Deionized water is washed to neutrality, and white solid is centrifugally separating to obtain, which is put into Muffle furnace and is calcined to get arriving
Tin zinc bimetallic MCM-41 molecular sieve；
Reaction dissolvent is selected from least one of acetonitrile, acetone, water, and reaction temperature is 0~100 DEG C；Phenyl-pentafluoride and the double gold of tin zinc
Belong to the molal weight ratio of MCM-41 molecular sieve for 1mol:1~10g, the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is 1mol:
0.1~1L；
White solid is put into calcining manners in Muffle furnace are as follows: the first stage is to keep the temperature 1~3h, the rank from room temperature to 300 DEG C
The heating rate of section is 5~8 DEG C/min；Second stage is warming up to 550 DEG C from 300 DEG C, keeps the temperature 3~8h, the heating speed in the stage
Degree is 10~12 DEG C/min.
4. the synthetic method of Pentafluorophenol according to claim 3, it is characterised in that: cetyl trimethylammonium bromide:
Ethyl orthosilicate: the molar ratio of sodium stannate is 1~3:2~6:0.05~0.1.
5. a kind of synthetic method of Pentafluorophenol, it is characterised in that: this method is to urge with TS-1 molecular sieve using phenyl-pentafluoride as raw material
Agent, using hydrogen peroxide as oxidant, for phenyl-pentafluoride under the action of the catalyst and oxidant, reaction generates Pentafluorophenol；
The molal weight ratio of phenyl-pentafluoride and TS-1 molecular sieve is 1mol:1~10g, and the mass volume ratio of phenyl-pentafluoride and 30% hydrogen peroxide is
1mol:0.1~1L.
6. the synthetic method of Pentafluorophenol according to claim 5, it is characterised in that: reaction dissolvent be selected from acetonitrile, acetone,
At least one of water, reaction temperature are 0~100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510677256.0A CN106588577B (en) | 2015-10-19 | 2015-10-19 | The synthetic method of Pentafluorophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510677256.0A CN106588577B (en) | 2015-10-19 | 2015-10-19 | The synthetic method of Pentafluorophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106588577A CN106588577A (en) | 2017-04-26 |
| CN106588577B true CN106588577B (en) | 2019-08-06 |
Family
ID=58554478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510677256.0A Active CN106588577B (en) | 2015-10-19 | 2015-10-19 | The synthetic method of Pentafluorophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588577B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180316A (en) * | 2019-06-10 | 2019-08-30 | 哈尔滨理工大学 | Zinc modified molecular sieve type deodorant preparation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143540A (en) * | 1996-07-18 | 1997-02-26 | 吉林大学 | Process for preparing aromatic hydrocarbon oxidation catalyst |
| CN1148844A (en) * | 1994-04-12 | 1997-04-30 | 波列斯科夫催化学会 | Method for production of phenol and its derivatives |
| CN1847210A (en) * | 2005-04-11 | 2006-10-18 | 临海市永太化工有限公司 | Process of producing pentafluorophenol |
| CN103373902A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Method for hydroxylating aromatic hydrocarbon to prepare corresponding phenol or diphenol through |
| CN103801393A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for phenol preparation by benzene hydroxylation |
| CN104801330A (en) * | 2015-03-25 | 2015-07-29 | 嘉兴学院 | Supported type mesoporous molecular sieve catalyst and application thereof |
| CN104909993A (en) * | 2015-06-15 | 2015-09-16 | 江苏蓝丰生物化工股份有限公司 | Industrial synthesis method of dicamba key intermediate 2,5-dichlorophenol |
-
2015
- 2015-10-19 CN CN201510677256.0A patent/CN106588577B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148844A (en) * | 1994-04-12 | 1997-04-30 | 波列斯科夫催化学会 | Method for production of phenol and its derivatives |
| CN1143540A (en) * | 1996-07-18 | 1997-02-26 | 吉林大学 | Process for preparing aromatic hydrocarbon oxidation catalyst |
| CN1847210A (en) * | 2005-04-11 | 2006-10-18 | 临海市永太化工有限公司 | Process of producing pentafluorophenol |
| CN103373902A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Method for hydroxylating aromatic hydrocarbon to prepare corresponding phenol or diphenol through |
| CN103801393A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for phenol preparation by benzene hydroxylation |
| CN104801330A (en) * | 2015-03-25 | 2015-07-29 | 嘉兴学院 | Supported type mesoporous molecular sieve catalyst and application thereof |
| CN104909993A (en) * | 2015-06-15 | 2015-09-16 | 江苏蓝丰生物化工股份有限公司 | Industrial synthesis method of dicamba key intermediate 2,5-dichlorophenol |
Non-Patent Citations (2)
| Title |
|---|
| "Cu/ MCM- 41 对苯羟基化为苯酚的催化作用";邵凤琴等;《抚顺石油学院学报》;200206;第22卷(第2期);18-21页 |
| "铜、锌锡掺杂的MCM-41的合成、表征及催化性能";蒋斯扬;《中国优秀博硕士学位论文全文数据库 (硕士)工程科技Ⅰ辑》;20070515(第 05 期);B014-67，第2.2.2节、第2.2.4.3节、第2.4节、第4.2.2节、第5.2.2节、第5.4节、第15页第4段 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106588577A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448284B (en) | A kind of preparation method of diallyl end capped polyether | |
| CN101613363B (en) | Preparation process for hexamethyldisilazane | |
| CN106588577B (en) | The synthetic method of Pentafluorophenol | |
| CN107416894A (en) | A kind of perovskite-like material C sPb2Br5, preparation method and use | |
| CN102766156B (en) | The preparation method of tetramethyl divinyl disilazane | |
| CN104014338B (en) | Solid base carrier thallium catalyst and preparation method | |
| CN104788340A (en) | Method for preparing n-phenylglycinenitrile | |
| CN106008197A (en) | Preparation method for o-fluorobenzoyl chloride | |
| CN105646334A (en) | Preparation method of 2,6-pyridinedimethanol | |
| CN104926599A (en) | Method for preparing high-purity 4,4'-bis(chloromethyl)-1,1'-biphenyl under novel solvent system | |
| CN113336764A (en) | Bipyridine ligand with axial chirality and synthetic method thereof | |
| CN110845371B (en) | Method for synthesizing o-sulfobenzaldehyde under normal pressure | |
| CN103183599A (en) | Method for preparing 2-valproic acid | |
| CN109096225B (en) | Aryl hydrocarbon activation halogenation reaction method using 2,1, 3-benzothiadiazole as guide group | |
| CN106010502B (en) | A kind of preparation method of the rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance | |
| CN102219825A (en) | Method for synthesizing 3beta-hydroxy-16alpha,17alpha-epoxy-5-pregnene-20-ketone | |
| CN105439927A (en) | Method for enantioselective synthesis of tacalcitol | |
| CN105884724B (en) | A kind of preparation method of benzofuran compounds | |
| CN103304405B (en) | A kind of method of selective chlorination | |
| CN113198530B (en) | Au-Mg/SAPO-11 molecular sieve catalyst, and preparation method and application thereof | |
| CN105330631B (en) | The method that one kettle way prepares n butylphthalide | |
| CN106905135A (en) | A kind of preparation method to bromomethyl phenylacetic acid | |
| CN111039920B (en) | Chiral tetraphenylethylene and synthesis method thereof | |
| CN105481662A (en) | Method for preparing intermediate for producing difluoromethoxy containing liquid crystal compound | |
| CN102093269A (en) | Synthesis method of 4,4'-thiobisbenzenethiol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190605 Address after: 223800 Suqian Eco-chemical Science and Technology Industrial Park, Suqian City, Jiangsu Province Applicant after: Jiangsu Furui Kangtai Pharmaceutical Co.,Ltd. Address before: 210 042 32 blocks, 699-18 Xuanwu Avenue, Nanjing, Jiangsu Province Applicant before: JIANGSU FURUI BIOPHARMACEUTICAL CO.,LTD. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The synthetic method of pentafluorophenol Effective date of registration: 20220805 Granted publication date: 20190806 Pledgee: Bank of Jiangsu Co.,Ltd. Suqian Suyu sub branch Pledgor: Jiangsu Furui Kangtai Pharmaceutical Co.,Ltd. Registration number: Y2022320000439 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address |
Address after: 223800 Suqian Eco-chemical Science and Technology Industrial Park, Suqian City, Jiangsu Province Patentee after: Jiangsu Alpha Group Furui Pharmaceutical (Suqian) Co.,Ltd. Country or region after: China Address before: 223800 Suqian Eco-chemical Science and Technology Industrial Park, Suqian City, Jiangsu Province Patentee before: Jiangsu Furui Kangtai Pharmaceutical Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |