CN102093225A - Method for preparing acifluorfen by catalyzing and nitrifying with solid super acid - Google Patents
Method for preparing acifluorfen by catalyzing and nitrifying with solid super acid Download PDFInfo
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- CN102093225A CN102093225A CN2010105703842A CN201010570384A CN102093225A CN 102093225 A CN102093225 A CN 102093225A CN 2010105703842 A CN2010105703842 A CN 2010105703842A CN 201010570384 A CN201010570384 A CN 201010570384A CN 102093225 A CN102093225 A CN 102093225A
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- acid
- acifluorfen
- catalyst
- trifluoromethyl
- solid super
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- 239000007787 solid Substances 0.000 title claims abstract description 76
- 239000003930 superacid Substances 0.000 title claims abstract description 64
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000001546 nitrifying effect Effects 0.000 title abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 63
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 238000001914 filtration Methods 0.000 claims abstract description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 61
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 40
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000004821 distillation Methods 0.000 claims description 18
- 239000000284 extract Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 1
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 abstract 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 238000006396 nitration reaction Methods 0.000 description 19
- 230000009466 transformation Effects 0.000 description 19
- 230000032683 aging Effects 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 17
- 238000011084 recovery Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 6
- 238000006424 Flood reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing acifluorfen by catalyzing and nitrifying with solid super acid and relates to a preparation method of a nitro compound. The method comprises the following steps of: reacting 3-[2-chlorine-4-(trifluoromethyl) phenoxyl] benzoic acid and fuming nitric acid under the catalysis of solid super acid for 1-20 hours at 20-80 DEG C in the presence of acetic anhydride in dichloroethane; filtering and recovering a solid super acid catalyst; and layering, drying and evaporating the solution to obtain an acifluorfen product. In the invention, the used solid super acid is a load type super acid using metallic oxides as carriers, wherein the carriers comprise iron sesquioxide, titanium dioxide and zirconium dioxide. Compared with the traditional mixed acid nitrification, the method has the advantages of high yield, good selectivity, easiness of product separation, catalyst recycling capability and low environmental pollution and has industrial application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of nitro-compound, be specifically related to a kind of with solid super-strong acid as catalyzer, catalytic nitration 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid prepares the method for acifluorfen.
Technical background
Acifluorfen is the widely used weedicide efficiently of a class, also is the intermediate of synthetic other agricultural chemicals.At present, the nitrated technology of industrial widely-used nitric-sulfuric acid is to 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid carries out nitrated making (WO9710199), mainly there is the problem of two aspects in this technology: the one, and no nitrated selectivity, the production cost of reaction mixture and isomer separation is very high; The 2nd, spent acid recycling difficulty in reaction back produces a large amount of acid-bearing wastewaters during aftertreatment, etching apparatus not only, and cause serious environmental to pollute.
In recent years with SO
4 2-/M
xO
yUse at catalytic field for the solid super-strong acid of feature and to have obtained extensive studies (Hino M, Arata K.Catalysis letters, 1995,30 (1): 25-30.), because solid super-strong acid has the acidity stronger than 100% sulfuric acid, and have the catalytic activity height, high temperature resistant, preparation is easy, be easy to separate and reusable, advantage such as environmental pollution is little, and the nitrated acid catalyzed reaction that waits is shown good catalytic activity, has obtained people's extensive concern.1979, reported first such as Japanese scholar M.Hino SO
4 2-/ M
xO
yThe preparation method of type solid super-strong acid, and use it for catalysis isomerization of paraffins reaction, demonstrate very high catalytic activity (Hino M, et al.J Am Chem Soc, 1979,101:6439.).Xi Limin etc. are with SO
4 2-/ ZrO
2The nitrated preparation oil of mirbane that is used for catalysis benzene, the result shows, and when catalyst activation temperature is 650 ℃, nitric acid and benzene mole are than 2.0, and yield reaches 78.3% and (uses chemical industry, 2005,34 (10): 603-605).SO such as Pan Shengcheng
4 2-/ TiO
2The solid superacid as catalyst nitration of toluene prepares nitrotoluene, shows catalytic activity and selectivity preferably, and the transformation efficiency of toluene reaches 81%, and catalyzer can be by roasting regeneration (Speciality Petrochemicals progress, 2003,4 (6): 17-19).Xi Limin etc. find to use solid super-strong acid SO
4 2-/ Fe
2O
3Catalytic nitration benzene prepares oil of mirbane, has catalytic activity preferably, and nitrated yield reaches 83.9% (Industrial Catalysis, 2006,14 (2): 31-34).Wang Tao etc. synthesize polynite, molecular sieve, silicon oxide, aluminum oxide a kind of super acids of loading type as carrier, the green nitration that is used for diphenyl ether derivative, demonstrate catalytic activity preferably, yield is 74.3%, product content is 81.1% (CN101165043), but this invention still fails to solve the low problem of nitrated preparation acifluorfen selectivity.The present invention has extensively screened various super acids on the basis of forefathers' research, finding to adopt with ferric oxide, zirconium dioxide and titanium dioxide is the solid super-strong acid of carrier, catalysis 3-[2-chloro-4-(trifluoromethyl) phenoxy group] the nitrated preparation acifluorfen of phenylformic acid, has higher selectivity, selectivity can be increased to 92%, yield is 88%, and bibliographical information is not seen in relevant research, and possesses good industrial prospect.
Summary of the invention
The objective of the invention is to be that the solid super acid catalyst of carrier is applied in the technology of nitrated preparation acifluorfen with ferric oxide, zirconium dioxide and titanium dioxide, substitute traditional sulfuric acid, be bordering on sulfuric acid even be higher than vitriolic transformation efficiency and selectivity in the hope of obtaining, reduce environmental pollution simultaneously.
In the preparation process of the used solid super-strong acid of the present invention, a certain amount of metal oxide carrier is immersed in the certain density sulfuric acid, behind the dipping certain hour, gets through filtration, drying, grinding, roasting.In the preparation process of acifluorfen, in the reaction vessel of placing ethylene dichloride, add 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid, add a certain amount of solid super acid catalyst and a certain amount of acetic anhydride again, stir 10-30min, in 5-10min, temperature is-drip a certain amount of nitrosonitric acid under the 10-10 ℃ condition, be warming up to 20-80 ℃ of stirring reaction 1-20h again, the filtered and recycled solid super acid catalyst, tell organic phase, water layer extracts with ethylene dichloride, merges organic layer, drying, distillation removes solvent and obtains the product acifluorfen.
In the above-mentioned solid super strong acid preparation process, metal oxide carrier is TiO
2, Fe
2O
3Or ZrO
2Carrier is immersed in the sulphuric acid soln that concentration is 0.25-0.75mol/L with the amount of 2-30g/mL; Dipping time is 1-8h; Be ground to the 100-500 order; Maturing temperature is 400-700 ℃.
The consumption of above-mentioned solid super acid catalyst is 3-[2-chloro-4-(trifluoromethyl) phenoxy group] 10-80% of phenylformic acid weight; Acetic anhydride and 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic mol ratio is 1.2-2.5: 1; Nitrosonitric acid and 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic mol ratio is 1.0-1.6: 1.
The present invention is 3-[2-chloro-4-(trifluoromethyl) phenoxy group in reaction process] benzoic transformation efficiency is 90-100%, and product yield is 80-90%, and HPLC detects purity greater than 90%.
In the method for the present invention, reaction formula is as follows:
Method of the present invention has the advantage that catalytic activity height, simple to operate, product are easy to separate, catalyzer is reusable and environmental pollution is little, is suitable for suitability for industrialized production.
Embodiment
Below by concrete example the present invention is described in detail.
Embodiment 1-9 is the method for preparing the solid super-strong acid of using as catalyzer in the acifluorfen.
Embodiment 1:SO
4 2-/ ZrO
2The preparation of solid super acid catalyst
Get 40g zirconium oxychloride solid, be configured to 10% zirconium oxychloride aqueous solution with deionized water.Transfer pH to 9-10 to wherein slowly dripping strong aqua under stirring at room, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till (silver nitrate solution with 0.1mol/L detects) detects.Filter cake is dry 14h under 110 ℃, floods with 0.25mol/L sulfuric acid in the 5mL/g ratio, and dipping time is 1h, filters back oven dry under 110 ℃ and spends the night, and is ground to 100 orders, 550 ℃ of roasting 3h, and taking-up is put into moisture eliminator and is cooled off, and obtains 14g SO
4 2-/ ZrO
2
Embodiment 2:SO
4 2-/ TiO
2The preparation of solid super acid catalyst
Get 30g TiCl
4Add lentamente in 0 ℃ the 0.2mol/L hydrogenchloride deionized water solution, be configured to 20% solution.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.25mol/L sulfuric acid in the 10mL/g ratio, dipping time is 1h, filter back oven dry under 110 ℃ and spend the night, be ground to 200 orders, 500 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 11.7g SO
4 2-/ TiO
2
Embodiment 3:SO
4 2-/ Fe
2O
3The preparation of solid super acid catalyst
Get 100g iron nitrate hydrate, be configured to 10% iron nitrate aqueous solution with deionized water.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.25mol/L sulfuric acid in the 15mL/g ratio, dipping time is 2h, filter back oven dry under 110 ℃ and spend the night, be ground to 300 orders, 500 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 20g SO
4 2-/ Fe
2O
3
Embodiment 4:SO
4 2-/ ZrO
2The preparation of solid super acid catalyst
Get 40g zirconium oxychloride solid, be configured to 10% zirconium oxychloride aqueous solution with deionized water.Transfer pH to 9-10 to wherein slowly dripping strong aqua under stirring at room, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till (silver nitrate solution with 0.1mol/L detects) detects.Filter cake is dry 14h under 110 ℃, floods with 0.25mol/L sulfuric acid in the 20mL/g ratio, and dipping time is 3h, filters back oven dry under 110 ℃ and spends the night, and is ground to 400 orders, 450 ℃ of roasting 3h, and taking-up is put into moisture eliminator and is cooled off, and obtains 14g SO
4 2-/ ZrO
2
Embodiment 5:SO
4 2-/ Fe
2O
3The preparation of solid super acid catalyst
Get 100g iron nitrate hydrate, be configured to 10% iron nitrate aqueous solution with distilled water.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.35mol/L sulfuric acid in the 25mL/g ratio, dipping time is 4h, filter back oven dry under 110 ℃ and spend the night, be ground to 300 orders, 650 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 21g SO
4 2-/ Fe
2O
3
Embodiment 6:SO
4 2-/ TiO
2The preparation of solid super acid catalyst
Get 30g TiCl
4Add lentamente in 0 ℃ the 0.2mol/L hydrogenchloride deionized water solution, be configured to 20% solution.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.45mol/L sulfuric acid in the 30mL/g ratio, dipping time is 5h, filter back oven dry under 110 ℃ and spend the night, be ground to 500 orders, 600 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 11.8g SO
4 2-/ TiO
2
Embodiment 7:SO
4 2-/ ZrO
2The preparation of solid super acid catalyst
Get 40g zirconium oxychloride solid, be configured to 10% zirconium oxychloride aqueous solution with deionized water.Transfer pH to 9-10 to wherein slowly dripping strong aqua under stirring at room, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till (silver nitrate solution with 0.1mol/L detects) detects.Filter cake is dry 14h under 110 ℃, floods with 0.55mol/L sulfuric acid in the 20mL/g ratio, and dipping time is 6h, and the oven dry of spending the night under 110 ℃ after filtering is ground to 400 orders, 700 ℃ of roasting 3h, and taking-up is put into moisture eliminator and is cooled off, and obtains 13g SO
4 2-/ ZrO
2
Embodiment 8:SO
4 2-/ Fe
2O
3The preparation of solid super acid catalyst
Get 100g iron nitrate hydrate, be configured to 10% iron nitrate aqueous solution with deionized water.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.65mol/L sulfuric acid in the 25mL/g ratio, dipping time is 7h, filter back oven dry under 110 ℃ and spend the night, be ground to 300 orders, 650 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 20g SO
4 2-/ Fe
2O
3
Embodiment 9:SO
4 2-/ TiO
2The preparation of solid super acid catalyst
Get 30g TiCl
4Add lentamente in 0 ℃ the 0.2mol/L hydrogenchloride deionized water solution, be configured to 20% solution.Slowly drip strong aqua under the stirring at room and transfer pH to 9-10, separate out a large amount of precipitations, the precipitation of formation is ageing 20h at room temperature.The ageing after-filtration is washed till no Cl with filter cake
-Till detecting (silver nitrate solution with 0.1mol/L detects), filter cake is dry 14h under 110 ℃, flood with 0.75mol/L sulfuric acid in the 10mL/g ratio, dipping time is 8h, filter back oven dry under 110 ℃ and spend the night, be ground to 200 orders, 500 ℃ of roasting 3h, taking-up is put into moisture eliminator and is cooled off, and obtains 11g SO
42-/ TiO
2
Embodiment 10-25 is the example of solid super-strong acid as the nitrated preparation acifluorfen of catalyst.
Embodiment 10:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, (1.24mL 28mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions to temperature again in order to drip nitrosonitric acid under the-10-10 ℃ condition.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.14g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 98%, and product yield is 85%, and purity is 90%.
Embodiment 11:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ Fe
2O
3And acetic anhydride (2.8mL, 30mmol), stirring 20min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.21g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 86%, and purity is 91%.
Embodiment 12:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ TiO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.35g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 88%, and purity is 92%.
Embodiment 13:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 3g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.00g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 95%, and product yield is 83%, and purity is 90%.
Embodiment 14:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 4g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.06g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 99%, and product yield is 84%, and purity is 90%.
Embodiment 15:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 5g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.06g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 98%, and product yield is 84%, and purity is 91%.
Embodiment 16:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 3g solid super acid catalyst SO to phenylformic acid again
4 2-/ TiO
2And acetic anhydride (3.2mL, 34mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.35g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 99%, and product yield is 88%, and purity is 92%.
Embodiment 17:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 3g solid super acid catalyst SO to phenylformic acid again
4 2-/ TiO
2And acetic anhydride (3.6mL, 38mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.06g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 84%, and purity is 91%.
Embodiment 18:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 3g solid super acid catalyst SO to phenylformic acid again
4 2-/ TiO
2And acetic anhydride (4.0mL, 42mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.24mL 28mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.14g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 85%, and purity is 91%.
Embodiment 19:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ Fe
2O
3And acetic anhydride (2.8mL, 30mmol), stirring 20min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.42mL 32mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.21g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 86%, and purity is 91%.
Embodiment 20:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ Fe
2O
3And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.59mL 36mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.14g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 85%, and purity is 90.5%.
Embodiment 21:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.77mL 40mmol), is warming up to stirring reaction 4h under 30 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.14g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 99%, and product yield is 85%, and purity is 91%.
Embodiment 22:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.77mL 40mmol), is warming up to stirring reaction 4h under 40 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.14g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 99%, and product yield is 85%, and purity is 90%.
Embodiment 23:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.77mL 40mmol), is warming up to stirring reaction 8h under 50 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.50g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 90%, and purity is 94%.
Embodiment 24:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ Fe
2O
3And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.77mL 40mmol), is warming up to stirring reaction 12h under 60 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 6.06g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 97%, and product yield is 84%, and purity is 91%.
Embodiment 25:3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic nitration reaction
In the reaction vessel of placing the 15mL ethylene dichloride, adding 3-[2-chloro-4-(trifluoromethyl) phenoxy group] (6.32g 20mmol), adds 2g solid super acid catalyst SO to phenylformic acid again
4 2-/ ZrO
2And acetic anhydride (2.8mL, 30mmol), stirring 10min.In 5-10min, temperature is to drip nitrosonitric acid under the 5-10 ℃ of condition (1.77mL 40mmol), is warming up to stirring reaction 18h under 70 ℃ of conditions again.Stir and finish after-filtration recovery solid super acid catalyst, tell organic phase again, water layer extracts with ethylene dichloride, merges organic layer, drying, and distillation removes solvent and obtains product acifluorfen 5.92g.Learn 3-[2-chloro-4-(trifluoromethyl) phenoxy group by the HPLC analytical results] benzoic transformation efficiency is 100%, and product yield is 82%, and purity is 90%.
Though the present invention has been described in detail in detail, yet it is not to be used to limit the present invention with preferred embodiment.Any those skilled in the art under the situation that does not break away from the spirit and scope of the present invention, should make various modifications and change.Therefore protection scope of the present invention should be considered as appended claims institute restricted portion.
Claims (7)
1. one kind with the nitrated method for preparing acifluorfen of solid superacid as catalyst, it is characterized in that: in the reaction vessel of placing ethylene dichloride, add 3-[2-chloro-4-(trifluoromethyl) phenoxy group] phenylformic acid, add a certain amount of solid super acid catalyst and a certain amount of acetic anhydride again, stir 10-30min, in 5-10min, temperature is-drip a certain amount of nitrosonitric acid under the 10-10 ℃ condition, be warming up to 20-80 ℃ of stirring reaction 1-20h again, the filtered and recycled solid super acid catalyst, tell organic phase, water layer extracts with ethylene dichloride, merges organic layer, drying, distillation removes solvent and obtains the product acifluorfen.
2. a claim 1 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, it is characterized in that: the preparation of used solid super-strong acid is that a certain amount of metal oxide carrier is immersed in the certain density sulfuric acid, behind the dipping certain hour, get through filtration, drying, grinding, roasting.
3. a claim 2 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, and it is characterized in that: used metal oxide carrier is TiO
2, Fe
2O
3Or ZrO
2
4. a claim 2 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, it is characterized in that: carrier is immersed in the sulphuric acid soln that concentration is 0.25-0.75mol/L with the amount of 2-30g/mL, dipping time is 1-8h, be ground to the 100-500 order, maturing temperature is 400-700 ℃.
5. a claim 1 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, and it is characterized in that: the consumption of described solid super-strong acid is 3-[2-chloro-4-(trifluoromethyl) phenoxy group] 10-80% of phenylformic acid weight.
6. a claim 1 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, it is characterized in that: described acetic anhydride and 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic mol ratio is 1.2-2.5: 1.
7. a claim 1 is described a kind of with the nitrated method for preparing acifluorfen of solid superacid as catalyst, it is characterized in that: described nitrosonitric acid and 3-[2-chloro-4-(trifluoromethyl) phenoxy group] benzoic mol ratio is 1.0-1.6: 1.
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| CN113731449A (en) * | 2021-10-09 | 2021-12-03 | 浙江吉泰新材料股份有限公司 | Titanium dioxide immobilized SO42-/ZrO2Catalyst, its preparation and use |
| CN117865811A (en) * | 2024-03-11 | 2024-04-12 | 山东道可化学有限公司 | Method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride |
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| CN1398159A (en) * | 2000-02-11 | 2003-02-19 | 瓦伦特美国公司 | Diphenyl ehter induction of systemic resistance in plants |
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| CN1398159A (en) * | 2000-02-11 | 2003-02-19 | 瓦伦特美国公司 | Diphenyl ehter induction of systemic resistance in plants |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113731449A (en) * | 2021-10-09 | 2021-12-03 | 浙江吉泰新材料股份有限公司 | Titanium dioxide immobilized SO42-/ZrO2Catalyst, its preparation and use |
| CN117865811A (en) * | 2024-03-11 | 2024-04-12 | 山东道可化学有限公司 | Method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride |
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