CN101225016A - Method for preparing entafluorobenzene by non-catalytic decarboxylation of entafluorobenzoic acid in high-temperature liquid water - Google Patents
Method for preparing entafluorobenzene by non-catalytic decarboxylation of entafluorobenzoic acid in high-temperature liquid water Download PDFInfo
- Publication number
- CN101225016A CN101225016A CNA2008100591133A CN200810059113A CN101225016A CN 101225016 A CN101225016 A CN 101225016A CN A2008100591133 A CNA2008100591133 A CN A2008100591133A CN 200810059113 A CN200810059113 A CN 200810059113A CN 101225016 A CN101225016 A CN 101225016A
- Authority
- CN
- China
- Prior art keywords
- pentafluorobenzoic acid
- organic phase
- warming
- fluoro benzene
- penta fluoro
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 238000006114 decarboxylation reaction Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title 1
- 230000003197 catalytic effect Effects 0.000 title 1
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims abstract description 60
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012074 organic phase Substances 0.000 claims abstract description 40
- 238000010792 warming Methods 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 230000000911 decarboxylating effect Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000003556 assay Methods 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- JDUOVEUODZOXPH-UHFFFAOYSA-N C#N.FC=1C(=C(C(=C(C1)F)F)F)F Chemical compound C#N.FC=1C(=C(C(=C(C1)F)F)F)F JDUOVEUODZOXPH-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000005446 dissolved organic matter Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YZERDTREOUSUHF-UHFFFAOYSA-N pentafluorobenzoic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1F YZERDTREOUSUHF-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YATDSXRLIUJOQN-SVRRBLITSA-N (2,3,4,5,6-pentafluorophenyl)methyl (1r,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=C(F)C(F)=C1F YATDSXRLIUJOQN-SVRRBLITSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229950006668 fenfluthrin Drugs 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 pentachlorobenzene formonitrile Chemical compound 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method using pentafluorobenzoic acid for non-catalysis decarboxylation in high temperature liquid water to prepare pentafluorobenzene, which is characterized in that: 1). Deionized water and pentafluorobenzoic acid are added in high-pressure reactor for stirring and warming up to boiling at atmospheric pressure; mass ratio for the deionized water and the pentafluorobenzoic acid is 2:1 to 8:1; exhaust valve is opened for 2 to 5 minutes; 2). The exhaust valve is closed and temperature continues to warmed up to 150 to 250 DEG C and decarboxylation is made for 5 to 45 minutes; 3). Decarboxylated products are cooled; residue pentafluorobenzoic acid is filtered from recovery reaction; the filtrate is kept still for liquid-liquid equilibrium to get organic phase; water phase can be used after circulation; 4). Distillation and active carbon decoloration are made upon organic phase to get pentafluorobenzene. The preparation method for pentafluorobenzene has the advantages of no need to add catalysts, simple process, environmental protection and high yield and purity, and solves the problem of pollution during synthesizing pentafluorobenzene process.
Description
Technical field
The present invention relates to the method that pentafluorobenzoic acid catalyst-free decarboxylating in a kind of high temperature liquid water prepares penta fluoro benzene.
Background technology
Penta fluoro benzene (1,2,3,4,5-pentafluorobenzene, CAS No.363-72-4), colourless liquid, density 1.514, fusing point-48 ℃, 85 ℃ of boiling points, specific refractory power 1.39～1.392,10 ℃ of flash-points can be miscible with ethanol, ether, acetone, benzene, tetracol phenixin, is insoluble in water (solubleness 0.2g/L).Structural formula is as follows:
Penta fluoro benzene is important organic fluoride, is basic aromatic series organic fluorine raw material.Penta fluoro benzene can synthesize multiple medicine, agricultural chemicals, dyestuff, polymer fluoroplastics intermediate through nitrated, chlorination, bromination, hydrocarbonylation, acidylate, reduction etc., as Norxin, fenfluthrin, penta fluoro benzene L-Ala etc.In recent years, along with developing rapidly of medicine, agricultural chemicals, dyestuff, fluorocarbon surfactant and fluoroplastics industry, penta fluoro benzene is as the basic raw material of organic fluorine, and the market requirement increases year by year.
Pentafluorobenzoic acid (2,3,4,5,6-pentafluorobenzoic acid, CAS No.602-94-8) is important medicine, pesticide intermediate.Normal temperature is down for solid-state, and fusing point 100-104 ℃, 220 ℃ of boiling points can be miscible with ethanol, ether, acetone, benzene, tetracol phenixin, is slightly soluble in water (solubleness 4.2g/L).
At present, the method for synthetic penta fluoro benzene has following three kinds, 1) be raw material with the phenyl-hexafluoride, generate penta fluoro benzene with ethylmagnesium bromide reaction posthydrolysis; 2) phenyl-hexafluoride and NaSH reaction obtains 1-and dredges basic penta fluoro benzene, is catalyzer again with the Raney's nickel, and hydrogenating reduction is a penta fluoro benzene; 3) industrial extensive employing at present is to be the raw material production penta fluoro benzene with the cyanobenzene, process is as follows: cyanobenzene generates the pentachlorobenzene formonitrile HCN by chlorination, adding KF makes fluorine-based replacement chloro produce the penta fluoro benzene formonitrile HCN, the penta fluoro benzene formonitrile HCN obtains pentafluorobenzoic acid through sulphuric acid hydrolysis, last pentafluorobenzoic acid is with N, accelerine is as reaction medium and catalyzer, and 120 ℃ of following decarboxylations obtain penta fluoro benzene.Though this technology is ripe, and productive rate height, but the pentafluorobenzoic acid decarboxylation obtains using N in this step of penta fluoro benzene, and accelerine is a catalyzer, N, accelerine toxicity is very big, unfavorable to environment, also there is technology to attempt with replacement N such as trolamine, accelerine, but produce little effect, use organism still very big to the pollution of environment as catalyzer.The route map that with the cyanobenzene is the synthetic penta fluoro benzene of raw material is as follows:
High temperature liquid water, typically referring to the compressed liquid water of temperature between 150～350 ℃. it not only self has the function of acid catalysis and base catalysis, and has a characteristic of dissolved organic matter and inorganics simultaneously, simultaneously, physicochemical property such as the specific inductivity of high temperature liquid water, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, the rerum natura that is high temperature liquid water has controllability, therefore as reaction medium, high temperature liquid water has different solvent properties and reactivity worth at different states.In recent years, as a kind of environmental friendliness medium, the applied research of high temperature liquid water in organic synthesis obtained concern, and the organic synthesis in the high temperature liquid water has become one of method of green organic synthesis.
Summary of the invention
The purpose of this invention is to provide the method that pentafluorobenzoic acid catalyst-free decarboxylating in a kind of high temperature liquid water prepares penta fluoro benzene.
The step of method is as follows:
1) add deionized water and pentafluorobenzoic acid in autoclave, deionized water and pentafluorobenzoic acid mass ratio are 2: 1～8: 1, open stirring, are warming up to boiling under the normal pressure, open vent valve 2-5 minute;
2) close vent valve, continue to be warming up to 150～250 ℃ of decarboxylation 5～45min;
3) decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, and water can be recycled;
4) organic phase obtains the product penta fluoro benzene behind rectifying, activated carbon decolorizing.
The mass ratio of deionized water described in the step 1) and pentafluorobenzoic acid is preferably 4: 1～and 6: 1; Step 2) decarboxylation temperature described in is preferably 170～220 ℃.
The purpose that " is warming up to boiling under the normal pressure, opened vent valve 2-5 minute " in the step 1) of the present invention is to utilize water vapour to take away the interior oxygen of still, to reduce the generation of side reaction, improves the yield of product.
The present invention need not add any catalyzer in reaction process, self acid-base catalysis characteristic of utilizing high temperature liquid water makes pentafluorobenzoic acid generate penta fluoro benzene with characteristic that can dissolved organic matter, solved a chemical synthesis process pollution on the environment difficult problem, reaction and sepn process are simple, the product yield height, and realized the greenization of production process.
Description of drawings
Accompanying drawing is the process flow diagram that the pentafluorobenzoic acid catalyst-free decarboxylating prepares penta fluoro benzene in the high temperature liquid water.
Embodiment
The present invention utilizes the character of high temperature liquid water uniqueness, replace N, accelerine is applied in the decarboxylation of pentafluorobenzoic acid, need not any catalyzer in its reaction process, can not produce pollution with water as solvent to environment, and, separates easyly, quick because penta fluoro benzene is water insoluble, utilize the characteristic of high temperature liquid water to invent and do not have catalysis, efficient, method that green prepares penta fluoro benzene by pentafluorobenzoic acid.Its reaction formula is as follows:
The analysis condition of high effective liquid chromatography for measuring penta fluoro benzene purity is as follows among the present invention:
Diamonsil
TMC
18Chromatographic column (250 * 4.6mm, 5 μ m), mobile phase methanol-0.05mol/LNaH
2PO
4(H
3PO
4Transfer pH3.5) (70: 30), flow velocity 1mLmin
-1, 30 ℃ of column temperatures, ultraviolet detection wavelength 215nm.
Embodiment 1
In 500mL intermittent type autoclave, add 300g deionized water and 37.5g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 150 ℃ of decarboxylation 45min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 25.7g behind rectifying, activated carbon decolorizing, product is 90.1% through the HPLC purity assay, and mass yield is 61.7%.
Embodiment 2
In 500mL intermittent type autoclave, add 300g deionized water and 42.9g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 160 ℃ of decarboxylation 40min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 31.1g behind rectifying, activated carbon decolorizing, product is 93.2% through the HPLC purity assay, and mass yield is 67.5%.
Embodiment 3
In 500mL intermittent type autoclave, add 300g deionized water and 50g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 170 ℃ of decarboxylation 35min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 37.3g behind rectifying, activated carbon decolorizing, product is 97.5% through the HPLC purity assay, and mass yield is 72.7%.
Embodiment 4
In 500mL intermittent type autoclave, add 300g deionized water and 60g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 180 ℃ of decarboxylation 30min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 45.5g behind rectifying, activated carbon decolorizing, product is 98.7% through the HPLC purity assay, and mass yield is 74.9%.
Embodiment 5
In 500mL intermittent type autoclave, add 300g deionized water and 75g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 190 ℃ of decarboxylation 28min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 56.4g behind rectifying, activated carbon decolorizing, product is 99% through the HPLC purity assay, and mass yield is 74.5%.
Embodiment 6
In 500mL intermittent type autoclave, add 300g deionized water and 100g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 200 ℃ of decarboxylation 25min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 76.8g behind rectifying, activated carbon decolorizing, product is 96.2% through the HPLC purity assay, and mass yield is 73.9%.
Embodiment 7
In 500mL intermittent type autoclave, add 300g deionized water and 150g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 210 ℃ of decarboxylation 20min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 112.9g behind rectifying, activated carbon decolorizing, product is 95.3% through the HPLC purity assay, and mass yield is 71.7%.
Embodiment 8
In 500mL intermittent type autoclave, add 300g deionized water and 75g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 220 ℃ of decarboxylation 18min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 55.6g behind rectifying, activated carbon decolorizing, product is 97.5% through the HPLC purity assay, and mass yield is 72.3%.
Embodiment 9
In 500mL intermittent type autoclave, add 300g deionized water and 50g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 230 ℃ of decarboxylation 40min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 37.5g behind rectifying, activated carbon decolorizing, product is 94.7% through the HPLC purity assay, and mass yield is 71%.
Embodiment 10
In 500mL intermittent type autoclave, add 300g deionized water and 60g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 240 ℃ of decarboxylation 8min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 45.4g behind rectifying, activated carbon decolorizing, product is 94% through the HPLC purity assay, and mass yield is 71.2%.
Embodiment 11
In 500mL intermittent type autoclave, add 300g deionized water and 37.5g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 250 ℃ of decarboxylation 5min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 26.4g behind rectifying, activated carbon decolorizing, product is 92% through the HPLC purity assay, and mass yield is 64.7%.
Embodiment 12
In 500mL intermittent type autoclave, add 300g deionized water and 100g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 170 ℃ of decarboxylation 37min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 73.1g behind rectifying, activated carbon decolorizing, product is 95.6% through the HPLC purity assay, and mass yield is 69.9%.
Embodiment 13
In 500mL intermittent type autoclave, add 300g deionized water and 150g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 180 ℃ of decarboxylation 32min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 108.1g behind rectifying, activated carbon decolorizing, product is 96.2% through the HPLC purity assay, and mass yield is 69.3%.
Embodiment 14
In 500mL intermittent type autoclave, add 300g deionized water and 42.9g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 3 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 220 ℃ of decarboxylation 15min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 30.6g behind rectifying, activated carbon decolorizing, product is 93.1% through the HPLC purity assay, and mass yield is 66.3%.
Embodiment 15
In 500mL intermittent type autoclave, add 300g deionized water and 50g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 5 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 200 ℃ of decarboxylation 18min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 36.6g behind rectifying, activated carbon decolorizing, product is 98.5% through the HPLC purity assay, and mass yield is 72.1%.
Embodiment 16
In 500mL intermittent type autoclave, add 300g deionized water and 60g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 210 ℃ of decarboxylation 22min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 45.3g behind rectifying, activated carbon decolorizing, product is 97.8% through the HPLC purity assay, and mass yield is 73.9%.
Embodiment 17
In 500mL intermittent type autoclave, add 300g deionized water and 75g pentafluorobenzoic acid, open stirring, be warming up to boiling under the normal pressure, opened vent valve 4 minutes, utilize water vapour to get rid of the interior air of still; Close vent valve, continue to be warming up to 190 ℃ of decarboxylation 25min, after the decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, organic phase obtains penta fluoro benzene 57.1g behind rectifying, activated carbon decolorizing, product is 99.2% through the HPLC purity assay, and mass yield is 75.5%.
Claims (3)
1. the pentafluorobenzoic acid catalyst-free decarboxylating prepares the method for penta fluoro benzene in the high temperature liquid water, it is characterized in that the step of method is as follows:
1) add deionized water and pentafluorobenzoic acid in autoclave, deionized water and pentafluorobenzoic acid mass ratio are 2: 1～8: 1, open stirring, are warming up to boiling under the normal pressure, open vent valve 2-5 minute;
2) close vent valve, continue to be warming up to 150～250 ℃ of decarboxylation 5～45min;
3) decarboxylate cooling, the pentafluorobenzoic acid that the filtered and recycled reaction is residual, filtrate is left standstill back liquid-liquid layering and is obtained organic phase, and water can be recycled;
4) organic phase obtains the product penta fluoro benzene behind rectifying, activated carbon decolorizing.
2. the pentafluorobenzoic acid catalyst-free decarboxylating prepares the method for penta fluoro benzene in a kind of high temperature liquid water according to claim 1, and the mass ratio that it is characterized in that deionized water described in the step 1) and pentafluorobenzoic acid is 4: 1～6: 1;
3. the pentafluorobenzoic acid catalyst-free decarboxylating prepares the method for penta fluoro benzene in a kind of high temperature liquid water according to claim 1, it is characterized in that step 2) described in decarboxylation temperature be 170～220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810059113A CN100586911C (en) | 2008-01-14 | 2008-01-14 | Method for preparing pentafluorobenzene by non-catalytic decarboxylation of pentafluorobenzoic acid in high-temperature liquid water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810059113A CN100586911C (en) | 2008-01-14 | 2008-01-14 | Method for preparing pentafluorobenzene by non-catalytic decarboxylation of pentafluorobenzoic acid in high-temperature liquid water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101225016A true CN101225016A (en) | 2008-07-23 |
| CN100586911C CN100586911C (en) | 2010-02-03 |
Family
ID=39857256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810059113A Expired - Fee Related CN100586911C (en) | 2008-01-14 | 2008-01-14 | Method for preparing pentafluorobenzene by non-catalytic decarboxylation of pentafluorobenzoic acid in high-temperature liquid water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100586911C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718649A (en) * | 2012-06-21 | 2012-10-10 | 浙江工业大学 | Chemical synthesis method of 2, 3, 4, 5-tetrafluoro-benzoic acid |
| CN105330509A (en) * | 2014-08-11 | 2016-02-17 | 浙江化工院科技有限公司 | Preparation method of 1,2,3,4-tetrafluorobenzene from 2,3,4,5-tetrafluorobenzoic acid |
| CN105418359A (en) * | 2014-08-11 | 2016-03-23 | 浙江化工院科技有限公司 | Method for preparing 2,3,4,5-tetrafluoro benzoic acid and 1,2,3,4-tetrafluorobenzene |
| CN105732302A (en) * | 2014-12-08 | 2016-07-06 | 浙江化工院科技有限公司 | Method for preparing polyfluorobenzene through polyfluorobenzoic acid decarboxylation |
| CN114163296A (en) * | 2021-12-20 | 2022-03-11 | 阜新睿光氟化学有限公司 | Preparation method of 1, 3-dichloro-2, 4, 6-trifluorobenzene |
| CN114436762A (en) * | 2021-12-23 | 2022-05-06 | 宁夏忠同生物科技有限公司 | Safe and green production method of pentafluorobenzene |
-
2008
- 2008-01-14 CN CN200810059113A patent/CN100586911C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718649A (en) * | 2012-06-21 | 2012-10-10 | 浙江工业大学 | Chemical synthesis method of 2, 3, 4, 5-tetrafluoro-benzoic acid |
| CN102718649B (en) * | 2012-06-21 | 2014-12-10 | 浙江工业大学 | Chemical synthesis method of 2, 3, 4, 5-tetrafluoro-benzoic acid |
| CN105330509A (en) * | 2014-08-11 | 2016-02-17 | 浙江化工院科技有限公司 | Preparation method of 1,2,3,4-tetrafluorobenzene from 2,3,4,5-tetrafluorobenzoic acid |
| CN105418359A (en) * | 2014-08-11 | 2016-03-23 | 浙江化工院科技有限公司 | Method for preparing 2,3,4,5-tetrafluoro benzoic acid and 1,2,3,4-tetrafluorobenzene |
| CN105330509B (en) * | 2014-08-11 | 2017-11-10 | 浙江化工院科技有限公司 | A kind of method that 1,2,3,4 phenyl tetrafluorides are prepared by 2,3,4,5 tetrafluorobenzoic aids |
| CN105418359B (en) * | 2014-08-11 | 2018-04-17 | 浙江化工院科技有限公司 | A kind of method for preparing 2,3,4,5 tetrafluorobenzoic aids and 1,2,3,4 phenyl tetrafluorides |
| CN105732302A (en) * | 2014-12-08 | 2016-07-06 | 浙江化工院科技有限公司 | Method for preparing polyfluorobenzene through polyfluorobenzoic acid decarboxylation |
| CN114163296A (en) * | 2021-12-20 | 2022-03-11 | 阜新睿光氟化学有限公司 | Preparation method of 1, 3-dichloro-2, 4, 6-trifluorobenzene |
| CN114163296B (en) * | 2021-12-20 | 2023-10-13 | 阜新睿光氟化学有限公司 | Preparation method of 1, 3-dichloro-2, 4, 6-trifluorobenzene |
| CN114436762A (en) * | 2021-12-23 | 2022-05-06 | 宁夏忠同生物科技有限公司 | Safe and green production method of pentafluorobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100586911C (en) | 2010-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100586911C (en) | Method for preparing pentafluorobenzene by non-catalytic decarboxylation of pentafluorobenzoic acid in high-temperature liquid water | |
| CN112851493B (en) | Preparation method of 2,4, 5-trifluoro phenylacetic acid | |
| CN109180501B (en) | Synthetic method of 4, 4' -diaminodiphenyl ether | |
| CN103497162B (en) | The synthetic method of 2-(4,6-dimethyl pyrimidine-2-base carbamoylamino alkylsulfonyl) methyl benzoate | |
| WO2016125185A2 (en) | Process for the preparation of 4-substituted-1-(trifluoromethoxy)benzene compounds | |
| JP2007001888A (en) | Method for producing 1, 4-dihydro-1, 4-methanoanthracene | |
| CN103787960A (en) | Synthetic method of 2-chloro-5-trichloromethyl pyridine | |
| CN104292113A (en) | Preparation method of 3-chloro-4-fluoroaniline | |
| EP0460639B1 (en) | Process for producing 3,5-difluoroaniline and derivative thereof | |
| CN111039802A (en) | Process for preparing aromatic diether diamine | |
| TW200837053A (en) | Preparation of organic compounds bearing a trifluoromethyl group on a quaternary carbon | |
| CN104402737A (en) | New method for preparing bromhexine hydrochloride | |
| CN105418359B (en) | A kind of method for preparing 2,3,4,5 tetrafluorobenzoic aids and 1,2,3,4 phenyl tetrafluorides | |
| CN108314624B (en) | Preparation method of polyfluoroaniline | |
| CN112209814B (en) | Novel method for synthesizing vitamin K2 | |
| CN104119238B (en) | A kind of preparation method of 4-(a chlorine difluoro-methoxy) aniline | |
| CN108752218A (en) | A kind of variation route prepared by Du Lutewei key intermediates 2,4- difluorobenzylamines | |
| CN102977012B (en) | Synthesis method of methyl 4-bromopyridyl-2-formate | |
| CN113416139B (en) | 4-fluorine substituted aryl amine compound and synthetic method thereof | |
| CN111302930B (en) | Preparation method of p-phenylbutoxy benzoic acid | |
| CN114702408B (en) | Preparation method and application of clenbuterol impurity | |
| CN111763193B (en) | Synthesis method of 1, 4-cyclohexanedione monoethylene glycol ketal | |
| CN102675033A (en) | Synthesis method of brominated fluoroalkane | |
| JP5766053B2 (en) | Method for producing biaryl compound | |
| CN108191903B (en) | Method for synthesizing coronadimide and derivative thereof based on perylene diimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20140114 |