CN108689855A - A kind of method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene - Google Patents
A kind of method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene Download PDFInfo
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- CN108689855A CN108689855A CN201810606237.2A CN201810606237A CN108689855A CN 108689855 A CN108689855 A CN 108689855A CN 201810606237 A CN201810606237 A CN 201810606237A CN 108689855 A CN108689855 A CN 108689855A
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- chlorotolu
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- perfluorinated sulfonic
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- 238000000034 method Methods 0.000 title claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 18
- 239000010457 zeolite Substances 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 230000005855 radiation Effects 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006396 nitration reaction Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 21
- 238000013019 agitation Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000004587 chromatography analysis Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 11
- 150000004075 acetic anhydrides Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000003460 sulfonic acids Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that microwave radiation technology zeolite catalysis nitrifies ortho-chlorotolu'ene, step is:Solvent is added into container, sequentially adds ortho-chlorotolu'ene, acetic anhydride, fuming nitric aicd, modified zeolite molecular sieve catalyst and silicon dioxide carried perfluorinated sulfonic resin;Microwave 4~12min of heating, keeps the temperature stopped reaction after 8~10min.Microwave technology is applied to nitrification ortho-chlorotolu'ene process by the present invention, greatly accelerates reaction process, while using silicon dioxide carried perfluorinated sulfonic resin, perfluorinated sulfonic resin is dispersed in SiO2In network or duct, since effective surface area greatly increases, the fully acidic site of exposure perfluorinated sulfonic resin, the potentiality of the resin catalyst are made to be played, improve conversion ratio and yield, and modified zeolite molecular sieve catalyst Bi β provide acid site and pore passage structure, Studies On The Shape-selective Catalysis is provided, improve reaction selectivity, yield is up to 80.9%, for the high selectivity of the chloro- 4- nitrotoleunes of 2- up to 84.1%, this method is easy to operate, energy-efficient, easily controllable, is a kind of environmentally protective ortho-chlorotolu'ene nitration method.
Description
Technical field
The invention belongs to organic matters to nitrify field, and in particular to a kind of side of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene
Method.
Background technology
Nitro ortho-chlorotolu'ene is important pesticide, dyestuff, medicine intermediate, is mainly produced by ortho-chlorotolu'ene nitrification process.
The nitrating agent used in nitrification process mainly has nitric acid, nitric acid-sulfuric acid, nitric acid anhydride system and Nitrates, traditional industrialization
Production uses nitric acid-sulfuric acid mixed acid nitrifying, and still, length, poor selectivity, sour corrosion are set the time required to this method has nitrification
Standby, spent acid pollutes the problems such as environment.
Currently used mode of heating is all first to be heated from body surface, and heat passes to interior of articles by surface again.Microwave
Heating can directly heat interior of articles.Microwave can greatly speed up organic synthesis rate, shorten the reaction time.Microwave
The reaction rate of organic synthesis can be traditional fast several times to thousands of times of heating, and this method with easy to operate, yield is high,
The features such as easy purification of products.The principle of microwave heating is under the action of electromagnetic field, and polar molecule becomes from original random distribution
To be orientated according to the polar alignment of electric field, under the action of high Electromagnetic Field, these orientations are constantly become by the frequency of alternating electromagnetism
Change, it is to cause mutual movement and the friction of molecule to generate a large amount of heat, i.e., so-called " interior heating ".This " interior heating "
With heating speed, fast, homogeneous heating makes microwave not only can effectively improve reaction without temperature gradient, without characteristics such as hysteresis effects
Selectivity, dramatically speed up reaction speed, may also help in startup some be difficult to the reaction carried out, be a kind of very promising
Reaction promote means.Currently, the organic reaction of types of applications microwave radiation technology is extensively studied.However so far, to the greatest extent
There are many method that pipe nitrifies ortho-chlorotolu'ene, but the method for related microwave radiation nitrification ortho-chlorotolu'ene is rarely reported.
Invention content
The present invention will provide a kind of method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene, to overcome prior art neighbour's chlorine
The problem of methylbenzene nitration method nitrifies poor selectivity, time-consuming.
To realize above-mentioned technical problem, the technical solution used in the present invention is:
A kind of method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene, includes the following steps:
(1) under magnetic agitation, solvent is added into container, sequentially adds ortho-chlorotolu'ene, acetic anhydride, fuming nitric aicd, change
Property zeolite molecular sieve catalyst and silicon dioxide carried perfluorinated sulfonic resin;
(2) 4~12min of microwave heating, keeps the temperature stopped reaction after 8~10min;
(3) Filtration of catalyst, gas chromatographic analysis after liquid phase washing water removal is dry.
Preferably, in step (1), the molar ratio of ortho-chlorotolu'ene, acetic anhydride and fuming nitric aicd three is 1:1~3:1~4.
It is furthermore preferred that in step (1), the molar ratio of the ortho-chlorotolu'ene and fuming nitric aicd is 3:4.5~9.0.
It is furthermore preferred that in step (1), the molar ratio of the ortho-chlorotolu'ene and acetic anhydride is 3:4~8.
Preferably, in step (1), the adding proportion of modified zeolite molecular sieve catalyst and ortho-chlorotolu'ene is 0.05~
1.00g:3mmol.
Preferably, in step (1), the ratio of silicon dioxide carried perfluorinated sulfonic resin and ortho-chlorotolu'ene is 0.1g:3mmol.
Preferably, in step (1), the modified zeolite molecular sieve catalyst is one in Ag β, Bi β, Zn β, H β or Ce β
Kind, more preferable Bi β.
It is furthermore preferred that the adding proportion of the modified zeolite molecular sieve catalyst Bi β and ortho-chlorotolu'ene is 0.05~0.2g:
3mmol。
Preferably, in step (2), 8~12min of the microwave heating-up time keeps the temperature 10min.
Compared with prior art, obtained by the present invention to have the beneficial effect that:(1) microwave technology is applied to nitrification by the present invention
Ortho-chlorotolu'ene process, compared with traditional heating flows back nitrification ortho-chlorotolu'ene, the reaction time is short.(2) present invention uses silica
Perfluorinated sulfonic resin is loaded, perfluorinated sulfonic resin is dispersed in SiO2In network or duct, since effective surface area greatly increases, fill
The acidic site for dividing exposure perfluorinated sulfonic resin, makes the potentiality of the resin catalyst be played, and improves conversion ratio and yield, together
When, modified zeolite molecular sieve catalyst Bi β provide acid site and pore passage structure, provide Studies On The Shape-selective Catalysis, improve selecting response
Property, yield are up to the high selectivities of the chloro- 4- nitrotoleunes of 80.9%, 2- up to 84.1%.(3) simultaneously, microwave heating speed it is fast and
Uniformly, reaction process is greatly accelerated, production efficiency is improved, a large amount of time can be saved.(4) in addition, this method is easily grasped
Make, is energy-efficient, easily controllable, being a kind of environmentally protective ortho-chlorotolu'ene nitration method.
Specific implementation mode
Technical scheme of the present invention is further described in detail with reference to specific embodiment.
The method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene of the present invention, includes the following steps:
(1) under magnetic agitation, solvent 10mL is added into round-bottomed flask, sequentially adds ortho-chlorotolu'ene 3.0mmol, acetic acid
3.0~9.0mmol of acid anhydride, 3.0~12.0mmol of fuming nitric aicd, 0.05~1.00g of modified zeolite molecular sieve catalyst and titanium dioxide
Silicon loads perfluorinated sulfonic resin 0.1g;
(2) 4~12min of microwave heating-up time keeps the temperature stopped reaction after 10min;
(3) Filtration of catalyst, gas chromatographic analysis after liquid phase washing water removal is dry.
Embodiment 1
It is adjacent that 10mL1,2- dichloroethanes, 3.0mmol are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Chlorotoluene, 3.0mmol acetic anhydrides, 12mmol fuming nitric aicds, Ag beta-zeolite molecular sieve catalysts 0.20g and silicon dioxide carried complete
After perfluorosulfonic acid resin 0.1g, microwave heating 8min (outlet temperature is set as the boiling temperature of 1,2- dichloroethanes) keep the temperature 10min
Into reaction mixture plus 5mL water stopped reactions, after Filtration of catalyst, organic phase uses 10mL water, 10mL mass point successively
The NaHCO that number is 5%3With 10mL water washings, standing separation goes out organic phase.Gas phase color is carried out using para-nitrotoluene as internal standard compound
Spectrum analysis.The result shows that yield 78.3%, the chloro- 4- nitrotoleunes of 2- selective 80.5%.
Embodiment 2
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 9mmol fuming nitric aicds, H beta-zeolite molecular sieve catalysts 0.30g and silicon dioxide carried perfluorinated sulfonic acid
Resin 0.1g, microwave heating 10min (outlet temperature is set as the boiling temperature of dichloromethane) are mixed after keeping the temperature 10min to reaction
In object plus 5mL water stopped reactions, after Filtration of catalyst, it is 5% that organic phase uses 10mL water, 10mL mass fractions successively
NaHCO3With 10mL water washings, standing separation goes out organic phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.Knot
Fruit shows that yield is the chloro- 4- nitrotoleunes of 75.4%, 2- selective 80.2%.
Embodiment 3
10mL ethyl acetate, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 9.0mmol acetic anhydrides, 6mmol fuming nitric aicds, Bi beta-zeolite molecular sieve catalysts 0.05g and silicon dioxide carried perfluorinated sulfonic acid
Resin 0.1g, microwave heating 12min (outlet temperature is set as the boiling temperature of ethyl acetate) are mixed after keeping the temperature 10min to reaction
In object plus 5mL water stopped reactions, after Filtration of catalyst, it is 5% that organic phase uses 10mL water, 10mL mass fractions successively
NaHCO3With 10mL water washings, standing separation goes out organic phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.Knot
Fruit shows that yield is the chloro- 4- nitrotoleunes of 74.6%, 2- selective 83.7%.
Embodiment 4
Sequentially added under the conditions of magnetic agitation into the round-bottomed flask of 25mL 10mL n-hexanes, 3.0mmol ortho-chlorotolu'enes,
3.0mmol acetic anhydrides, 4.5mmol fuming nitric aicds, Zn beta-zeolite molecular sieve catalysts 0.40g and silicon dioxide carried perfluorinated sulfonic acid
To reaction mixture after resin 0.1g, microwave heating 6min (outlet temperature is set as the boiling temperature of n-hexane) heat preservation 10min
In plus 5mL water stopped reactions, after Filtration of catalyst, it is 5% that organic phase uses 10mL water, 10mL mass fractions successively
NaHCO3With 10mL water washings, standing separation goes out organic phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.Knot
Fruit shows that yield is the chloro- 4- nitrotoleunes of 68.2%, 2- selective 80.3%.
Embodiment 5
10mL carbon tetrachloride, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 3mmol fuming nitric aicds, H beta-zeolite molecular sieve catalysts 0.50g and silicon dioxide carried perfluorinated sulfonic acid
Resin 0.1g, microwave heating 4min (outlet temperature is set as the boiling temperature of carbon tetrachloride) are mixed after keeping the temperature 10min to reaction
In object plus 5mL water stopped reactions, after Filtration of catalyst, it is 5% that organic phase uses 10mL water, 10mL mass fractions successively
NaHCO3With 10mL water washings, standing separation goes out organic phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.Knot
Fruit shows that yield is the chloro- 4- nitrotoleunes of 65.3%, 2- selective 79.8%.
Embodiment 6
It is adjacent that 10mL1,2- dichloroethanes, 3.0mmol are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Chlorotoluene, 6.0mmol acetic anhydrides, 6mmol fuming nitric aicds, Ce beta-zeolite molecular sieve catalysts 1.00g and silicon dioxide carried perfluor
Add 5mL water stopped reactions into reaction mixture after sulfonate resin 0.1g, microwave heating 8min heat preservations 10min, is filtered to remove and urges
After agent, organic phase is successively with 10mL water, the NaHCO that 10mL mass fractions are 5%3With 10mL water washings, standing separation goes out to have
Machine phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.The result shows that yield 72.6%, the chloro- 4- nitros of 2-
Methylbenzene selective 82.5%.
Embodiment 7
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 6mmol fuming nitric aicds, Bi beta-zeolite molecular sieve catalysts 0.10g and silicon dioxide carried perfluorinated sulfonic acid
Add 5mL water stopped reactions, Filtration of catalyst into reaction mixture after resin 0.1g, microwave heating 10min heat preservations 10min
Afterwards, the NaHCO that organic phase uses 10mL water successively, 10mL mass fractions are 5%3With 10mL water washings, standing separation goes out organic phase.
Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.The result shows that yield 80.9%, the chloro- 4- nitrotoleunes of 2-
Selectivity 84.1%.
Embodiment 8
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 6mmol fuming nitric aicds, Bi beta-zeolite molecular sieve catalysts 0.10g and silicon dioxide carried perfluorinated sulfonic acid
Add 5mL water stopped reactions, Filtration of catalyst into reaction mixture after resin 0.1g, microwave heating 10min heat preservations 10min
Afterwards, the NaHCO that organic phase uses 10mL water successively, 10mL mass fractions are 5%3With 10mL water washings, standing separation goes out organic phase.
Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.The result shows that yield 80.9%, the chloro- 4- nitrotoleunes of 2-
Selectivity 84.1%.
Comparative example 1
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 6mmol fuming nitric aicds and silicon dioxide carried perfluorinated sulfonic resin 0.1g, microwave heating 10min are protected
After warm 10min into reaction mixture plus 5mL water stopped reactions, after Filtration of catalyst, organic phase use successively 10mL water,
The NaHCO that 10mL mass fractions are 5%3With 10mL water washings, standing separation goes out organic phase.Using para-nitrotoluene as internal standard compound
Carry out gas chromatographic analysis.The result shows that yield 79.8%, the chloro- 4- nitrotoleunes of 2- selective 72.5%.
Comparative example 2
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides, 6mmol fuming nitric aicds and Bi beta-zeolite molecular sieve catalyst 0.10g, microwave heating 10min heat preservations
After 10min into reaction mixture plus 5mL water stopped reactions, after Filtration of catalyst, organic phase uses 10mL water, 10mL successively
The NaHCO that mass fraction is 5%3With 10mL water washings, standing separation goes out organic phase.It is carried out using para-nitrotoluene as internal standard compound
Gas chromatographic analysis.The result shows that yield 65.6%, the chloro- 4- nitrotoleunes of 2- selective 83.4%.
Comparative example 3
10mL dichloromethane, 3.0mmol neighbour's chloromethane are sequentially added into the round-bottomed flask of 25mL under the conditions of magnetic agitation
Benzene, 6.0mmol acetic anhydrides and 6mmol fuming nitric aicds, microwave heating 10min add 5mL water into reaction mixture after keeping the temperature 10min
Stopped reaction, after Filtration of catalyst, organic phase uses 10mL water successively, 10mL mass fractions are 5% NaHCO3And 10mL
Water washing, standing separation go out organic phase.Gas chromatographic analysis is carried out using para-nitrotoluene as internal standard compound.The result shows that yield
For the chloro- 4- nitrotoleunes of 64.7%, 2- selective 70.8%.
The nitrification ortho-chlorotolu'ene of the above various embodiments method is easy to operate, energy conservation and environmental protection, production efficiency are high, production cost
It is low, it is a kind of nitration method being worthy to be popularized.
It should be noted last that the above specific implementation mode is merely illustrative of the technical solution of the present invention and unrestricted,
Although being described the invention in detail with reference to preferred embodiment, it will be understood by those of ordinary skill in the art that, it can be right
Technical scheme of the present invention is modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range,
It is intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of method of microwave radiation technology zeolite catalysis nitrification ortho-chlorotolu'ene, which is characterized in that include the following steps:
(1) under stirring, solvent is added into container, sequentially adds ortho-chlorotolu'ene, acetic anhydride, fuming nitric aicd, modified zeolite point
Sub- sieve catalyst and silicon dioxide carried perfluorinated sulfonic resin;
(2) 4~12min of microwave heating, keeps the temperature stopped reaction after 8~10min, obtains the target product.
2. the method as described in claim 1, which is characterized in that in step (1), ortho-chlorotolu'ene, acetic anhydride and fuming nitric aicd three
The molar ratio of person is 1:1~3:1~4.
3. the method as described in claim 1, which is characterized in that in step (1), the molar ratio of ortho-chlorotolu'ene and fuming nitric aicd is
3:4.5~9.0.
4. the method as described in claim 1, which is characterized in that in step (1), the molar ratio of ortho-chlorotolu'ene and acetic anhydride is 3:
4~8.
5. the method as described in claim 1, which is characterized in that in step (1), modified zeolite molecular sieve catalyst and adjacent chloromethane
The adding proportion of benzene is 0.05~1.00g:3mmol.
6. the method as described in claim 1, which is characterized in that in step (1), silicon dioxide carried perfluorinated sulfonic resin and neighbour
The ratio of chlorotoluene is 0.1g:3mmol.
7. the method as described in claim 1, which is characterized in that in step (1), modified zeolite molecular sieve catalyst is Ag β, Bi
One kind in β, Zn β, H β or Ce β.
8. the method as described in claim 1, which is characterized in that in step (1), modified zeolite molecular sieve catalyst is Bi β.
9. method as claimed in claim 8, which is characterized in that modified zeolite molecular sieve catalyst Bi β and ortho-chlorotolu'ene add
It is 0.05~0.2g to add ratio:3mmol.
10. the method as described in claim 1, which is characterized in that in step (2), 8~12min of microwave heating-up time, heat preservation
10min。
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| CN110577470A (en) * | 2019-10-09 | 2019-12-17 | 蚌埠学院 | method for catalyzing selective nitration of 2-naphthyl methyl ether by zeolite molecular sieve |
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|---|---|---|---|---|
| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification method |
| CN103086892A (en) * | 2012-11-22 | 2013-05-08 | 安徽淮化股份有限公司 | Method for preparing p-nitrochlorobenzene by nitrifying chlorobenzene by using nitrogen dioxide |
| CN105037163A (en) * | 2015-08-10 | 2015-11-11 | 合肥师范学院 | Method for fast and selectively nitrifying meta-xylene through microwave radiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification method |
| CN103086892A (en) * | 2012-11-22 | 2013-05-08 | 安徽淮化股份有限公司 | Method for preparing p-nitrochlorobenzene by nitrifying chlorobenzene by using nitrogen dioxide |
| CN105037163A (en) * | 2015-08-10 | 2015-11-11 | 合肥师范学院 | Method for fast and selectively nitrifying meta-xylene through microwave radiation |
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| CN110577470A (en) * | 2019-10-09 | 2019-12-17 | 蚌埠学院 | method for catalyzing selective nitration of 2-naphthyl methyl ether by zeolite molecular sieve |
| CN110577470B (en) * | 2019-10-09 | 2022-12-27 | 蚌埠学院 | Method for catalyzing selective nitration of 2-naphthyl methyl ether by using zeolite molecular sieve |
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