CN111205187A - Preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride - Google Patents
Preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride Download PDFInfo
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- HFHAVERNVFNSHL-UHFFFAOYSA-N 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC([N+]([O-])=O)=C1Cl HFHAVERNVFNSHL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006396 nitration reaction Methods 0.000 claims abstract description 61
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 22
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000012044 organic layer Substances 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005191 phase separation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000011964 heteropoly acid Substances 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- -1 choline quaternary ammonium salt Chemical class 0.000 abstract description 4
- 238000006065 biodegradation reaction Methods 0.000 abstract description 3
- 229960001231 choline Drugs 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- QLYAKTFRIKHOFC-UHFFFAOYSA-N ClC1=C(C=C(C=C1[N+](=O)[O-])C(F)(F)F)[N+](=O)[O-].ClC1=CC=C(C=C1)C(F)(F)F Chemical compound ClC1=C(C=C(C=C1[N+](=O)[O-])C(F)(F)F)[N+](=O)[O-].ClC1=CC=C(C=C1)C(F)(F)F QLYAKTFRIKHOFC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FPWVDXSTQKFZEI-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[SH4+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[SH4+2] FPWVDXSTQKFZEI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/06—Hydrogenosulfates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride, which adopts strongly acidic and highly active heteropoly acid phosphotungstate as anion and easily biodegradable choline quaternary ammonium salt as cationic N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate as catalyst, organically combines the catalytic activities of strongly acidic, oxidizing and phase transfer with biodegradation, and has high activity and no pollution; in addition, the mixed solution of the dinitrogen pentoxide and the concentrated nitric acid is a nitration reagent, so that the activity of nitration reaction is improved, the dinitrogen pentoxide can absorb water generated in the primary nitration reaction process and convert the water into the nitric acid, and the concentration of the nitric acid in the whole reaction system is maintained in a range capable of carrying out secondary nitration, so that a primary nitration product can be directly heated to carry out secondary nitration reaction without separation and purification, the whole primary nitration process and the secondary nitration process are carried out in one reaction device, and the traditional process is simplified.
Description
Technical Field
The invention relates to a preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride, belonging to the technical field of chemical material preparation.
Background
Nitration is an important organic synthesis unit reaction, substituted aromatic hydrocarbon nitrated compounds are a very important chemical product, and research on nitration methods and processes of aromatic compounds is conducted in both academia and industry. Energy conservation and emission reduction are important subjects facing human beings, and clean nitration of aromatic compounds becomes one of the hot spots of research of people.
The nitration product of 4-chloro-benzotrifluoride 4-chloro-3, 5-dinitro-benzotrifluoride is widely applied to the industrial fields of medicine, pesticide, fine chemical intermediates and the like. The prior art adopts a nitrate-sulfur mixed acid nitration method which is used up to now for one hundred years, takes 4-chloro-benzotrifluoride as a raw material and fuming nitric acid as a nitration reagent to carry out nitration reaction, and the method has the defects of serious corrosion, more byproducts, separation and purification, respective proportioning and step-by-step implementation of the first-stage nitration reaction and the second-stage nitration reaction, complex treatment procedures after the reaction, incapability of separating, purifying, recycling and reusing after the nitric acid is mixed with sulfuric acid, serious three-waste pollution and the like.
Heteropolyacid anions are bulky, highly symmetrical and have a low charge density and are therefore strong protonic acids, whether in the solid or liquid state, and have a much stronger acid strength than inorganic acids consisting of the corresponding central or coordinating atoms. These characteristics make heteropolyacids exhibit good catalytic activity in many organic reactions, and in recent years, they have been regarded as important in the field of catalytic research.
The method disclosed and reported generally uses quaternary ammonium salt, rare earth salt, transition metal salt, lanthanide salt, etc. as catalyst, and acetic anhydride or trifluoroacetic anhydride is often used as cocatalyst in the nitration process. The catalytic and cocatalyst materials have potential harm to the environment, and the use of acetic anhydride and trifluoroacetic anhydride has high cost, is difficult to separate and purify from the product and is difficult to recycle, so that the difficulty of post-treatment and product separation is increased, and the dual benefits of environment and economy cannot be met.
Disclosure of Invention
The invention aims to provide a method for synthesizing 4-chloro-3, 5-dinitrobenzotrifluoride by replacing concentrated sulfuric acid which is commonly used at present with a recyclable heteropoly acid type quaternary ammonium salt catalyst, wherein the product and the catalyst are easy to separate, the product purity is high, and the first-stage nitration and the second-stage nitration can be carried out by a one-pot method.
The technical solution for realizing the purpose of the invention is as follows:
a preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride is characterized in that N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate is used as a catalyst, 4-chlorotrifluoromethane is used as a raw material, a nitric acid solution of dinitrogen pentoxide is used as a nitration reagent, the raw material and the nitric acid solution are stirred and mixed at normal temperature and normal pressure to realize the mononitration reaction of 4-chlorotrifluoromethyl, the prepared mononitration product is directly and slowly heated without separation and purification to carry out the dinitration reaction, the 4-chloro-3, 5-dinitrobenzotrifluoride is synthesized, and the whole nitration reaction is carried out in a system;
the structure of the N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate catalyst used in the invention is shown as the formula (1):
the preparation of the N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate catalyst used in the invention is shown as the formula (2):
the molar ratio of the materials used in the invention is n (p-chlorotrifluoromethylene): n (nitric acid): n (dinitrogen pentoxide) ═ 1: 1: 0.3-0.4, the using amount of the catalyst is 1-10% of the mole number of the 4-chlorotrifluoromethane, and the materials and the catalyst are fed, mixed and stirred according to the proportion.
Further, the reaction temperature is divided into two sections, wherein the primary nitration is normal temperature, and the secondary nitration is 85-90 ℃.
Further, the total time of the primary nitration and the secondary nitration is 3-10 hours.
Further, the concentration of the nitric acid is 90-100%.
The preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride is characterized in that after the reaction is finished, the reaction system is kept stand, and is divided into an organic layer and a water layer, wherein the upper organic layer is a crude product of the 4-chloro-3, 5-dinitrobenzotrifluoride, and the lower water layer is a mixture containing N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate catalyst, nitric acid and a small amount of water; removing the upper organic layer product by phase separation, and obtaining a refined product after washing, neutralizing and vacuum dewatering; filtering the catalyst in the water layer, dehydrating and drying under 4kPa under negative pressure, recycling, feeding according to the material proportion of the previous batch to perform the next batch of synthetic reaction, wherein the filtrate is nitric acid containing a small amount of water, and can be recycled after concentration. The disclosed concentration technology of nitric acid is more, such as: magnesium nitrate can be added to absorb moisture to improve the concentration, or the concentration can be carried out by adopting a concentration device special for nitric acid sold in the market.
The chemical reaction principle on which the invention is based is as shown in formula (3):
according to the preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride provided by the invention, the technical key is that N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate which takes a strongly acidic and high-activity heteropoly acid phosphotungstic acid root structure as an anion and a choline type quaternary ammonium salt structure which is easy to biodegrade as a cation is taken as a catalyst, and the strongly acidic, oxidative and phase-transfer catalytic activities and biodegradation are organically combined together, so that the preparation method is high in activity and free of pollution; in addition, the mixed solution of the dinitrogen pentoxide and the concentrated nitric acid is a nitration reagent, which not only improves the activity of nitration reaction, and the dinitrogen pentoxide can absorb water generated in the course of primary nitration reaction and convert it into nitric acid, so that the nitric acid concentration in the whole reaction system can be maintained in the range capable of making secondary nitration, therefore, the primary nitration product can be directly heated to carry out the dinitration reaction without separation and purification, the whole primary nitration process and the dinitration process are carried out in one reaction device, namely, the organic reaction is commonly called as a 'one-pot method', two operation steps of separating, drying and purifying the primary nitration product before the dinitration in the traditional process are simplified, the method does not use other inorganic acids except the catalyst in the whole process flow of the secondary nitration reaction, the nitric acid in the post-treatment process only contains a small amount of water, and the nitric acid is convenient to recover and regenerate by the conventional concentration method.
Compared with the prior art, the invention has the advantages that:
(1) the catalyst with heteropoly acid anion structure is adopted, the raw material source is wide, and the preparation is convenient; the catalyst is stable to water, does not deactivate, and has good recycling effect;
(2) the heteropoly acid forming the anion has stronger strength than the corresponding inorganic acid, and simultaneously has good oxidability, high catalytic activity, less dosage and environmental protection;
(3) the cation is a choline type structure which is easy to biodegrade, the biodegradation performance is good, and the secondary pollution caused by the loss of the catalyst in the production process is effectively avoided;
(4) the dinitrogen pentoxide/concentrated nitric acid nitration reagent has high nitration activity, and primary nitration and secondary nitration are combined into a system, so that the operation process flow is simplified;
(5) the method uses N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate to replace concentrated sulfuric acid, solves the technical problems that a mixed system of nitric acid and sulfuric acid cannot be separated and is difficult to recycle during aftertreatment in a nitric-sulfuric mixed acid process, is convenient for concentrating nitric acid containing a small amount of water, is an environment-friendly nitration process, and has industrial application prospects.
Detailed Description
The following examples further illustrate the invention in order to provide a better understanding of the invention. The examples do not limit the scope of the invention in any way. Modifications and adaptations of the present invention within the scope of the claims may occur to those skilled in the art and are intended to be within the scope and spirit of the present invention.
A preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride comprises the steps of firstly preparing a catalyst N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate, sequentially adding 0.1mol (14g) of choline chloride and 30mL of cyclohexane into a 1000mL round-bottom flask, slowly dropwise adding 0.1mol (11.6g) of chlorosulfonic acid under normal temperature and pressure stirring, continuously stirring for 0.5 hour after dropwise adding, evaporating the solvent, slowly adding a prepared phosphotungstic acid aqueous solution (0.1mol, 288g of phosphotungstic acid is dissolved in 300mL of deionized water), stirring for 1 hour at normal temperature and pressure, filtering and separating, washing with diethyl ether, and drying in vacuum to obtain the target catalyst, wherein the yield can reach over 90%.
Example 1
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.1mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 20mmol (1.26g) of 100% nitric acid and 3mmol (0.32g) of dinitrogen pentoxide, mixing and stirring for 2 hours at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 85 ℃ for 2 hours, then keeping the temperature for 6 hours, standing, dividing a reaction system into an organic layer and an aqueous layer, wherein the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower aqueous layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 93%; filtering the catalyst, dehydrating and drying for 2 hours at the temperature of 60 ℃ under the negative pressure of 4kPa for recycling, feeding the materials according to the proportion of the materials of the previous batch for carrying out the synthesis reaction of the next batch, wherein the nitric acid in the water layer contains a small amount of water and can be recycled after concentration. Magnesium nitrate can be added to absorb water during the concentration of the nitric acid, or a concentration device special for the nitric acid on the market is adopted for concentration.
Example 2
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.5mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 20mmol (1.26g) of 100% nitric acid and 0.33g of dinitrogen pentoxide, mixing and stirring for 1 hour at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 90 ℃ for 1 hour, then keeping the temperature for 1 hour, standing, wherein the reaction system is divided into an organic layer and a water layer, the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower water layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 91%; the catalyst is filtered, dehydrated and dried for 1 hour under the negative pressure of 4kPa at the temperature of 80 ℃ and then recycled, and the materials are fed according to the proportion of the materials in the previous batch to carry out the next batch of synthesis reaction.
Example 3
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.5mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 10mmol (0.63g) of 100% nitric acid and 0.33g of dinitrogen pentoxide, mixing and stirring for 1 hour at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 90 ℃ for 2 hours, then keeping the temperature for 2 hours, standing, wherein the reaction system is divided into an organic layer and a water layer, the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower water layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 92%; the catalyst and nitric acid were recovered and regenerated by the post-treatment process of reference example 1.
Example 4
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 1mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 20mmol (1.4g) of 90% nitric acid and 4mmol (0.43g) of dinitrogen pentoxide, mixing and stirring for 2 hours at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 90 ℃ for 1 hour, then keeping the temperature for 1 hour, standing, dividing a reaction system into an organic layer and an aqueous layer, wherein the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower aqueous layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 95%; the catalyst and nitric acid were recovered and regenerated by the post-treatment process of reference example 1.
Example 5
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.5mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 20mmol (1.33g) of 95% nitric acid and 0.38g of dinitrogen pentoxide, mixing and stirring for 1.5 hours at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 90 ℃ for 2 hours, then keeping the temperature for 2 hours, standing, dividing a reaction system into an organic layer and an aqueous layer, wherein the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower aqueous layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 92%; the catalyst and nitric acid were recovered and regenerated by the post-treatment process of reference example 1.
Example 6
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.5mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 30mmol (1.89g) of 100% nitric acid and 0.33g of dinitrogen pentoxide, mixing and stirring for 1 hour at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 85 ℃ for 1 hour, then keeping the temperature for 1 hour, standing, wherein the reaction system is divided into an organic layer and a water layer, the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower water layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 95%; the catalyst and nitric acid were recovered and regenerated by the post-treatment process of reference example 1.
Example 7
Sequentially adding 10mmol (1.81g) of 4-chlorotrifluoromethylene and 0.5mmol of the catalyst into a 50mL round-bottom flask, slowly dropping a mixture of 20mmol (1.26g) of 100% nitric acid and 0.33g of dinitrogen pentoxide, mixing and stirring for 1 hour at normal temperature and normal pressure, monitoring the completion of a primary nitration reaction by gas chromatography, slowly heating to 90 ℃ for 1 hour, then keeping the temperature for 1 hour, standing, wherein the reaction system is divided into an organic layer and a water layer, the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower water layer is a mixture of the catalyst, the nitric acid and a small amount of water; removing an upper organic layer product through phase separation, and obtaining a refined product 4-chloro-3, 5-dinitrobenzotrifluoride after washing, neutralization and vacuum dehydration, wherein the yield is 92%; the catalyst and nitric acid were recovered and regenerated by the post-treatment process of reference example 1.
Example 8
After the crude product at the upper layer is separated, the catalyst contained in the lower layer is filtered, dehydrated and dried, then added into a 50mL round-bottom flask for recycling, 10mmol (1.81g) of 4-chlorotrifluoromethane is sequentially added, a mixture of 20mmol (1.26g) of 100% nitric acid and 0.33g of dinitrogen pentoxide is slowly dropped, the mixture is mixed and stirred for 1 hour at normal temperature and normal pressure, then the temperature is slowly raised to 90 ℃ for 1 hour, then the mixture is kept for 1 hour and then kept stand, the reaction system is divided into an organic layer and a water layer, the organic layer at the upper layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the water layer at the lower layer is a mixture of the catalyst, nitric acid and; the upper organic layer product is removed by phase separation, and the refined product 4-chloro-3, 5-dinitrobenzotrifluoride is obtained after washing, neutralization and vacuum dehydration, with the yield of 92 percent. The catalyst and nitric acid were recovered and regenerated in the same manner as in example 1.
Claims (5)
1. A preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride is characterized by comprising the following steps: the method comprises the following steps of taking N, N, N-trimethyl-N-sulfonic acid ethyl ammonium phosphotungstate as a catalyst, 4-chlorotrifluoromethane as a raw material and a nitric acid solution of dinitrogen pentoxide as a nitration reagent, stirring and mixing at normal temperature and normal pressure to realize a mononitration reaction of the 4-chlorotrifluoromethane, directly and slowly heating a prepared mononitration product without separation and purification to perform a dinitration reaction, synthesizing the 4-chloro-3, 5-dinitrobenzotrifluoride, and performing the whole nitration reaction in a system; standing after the reaction is finished, wherein the reaction system is divided into an organic layer and a water layer, the upper organic layer is a nitration product of 4-chlorotrifluoromethylbenzene, and the lower water layer is a mixture of a catalyst, nitric acid and water; removing the upper organic layer product by phase separation, and obtaining a refined product after washing, neutralizing and vacuum dewatering; filtering the catalyst containing water at normal pressure, dehydrating and drying under the negative pressure of 4kPa, recycling, and feeding according to the proportion of the material of the previous batch to perform the next batch of synthetic reaction; the catalyst has the following structure:
2. the process according to claim 1 for the preparation of 4-chloro-3, 5-dinitrobenzotrifluoride, wherein: the molar ratio of the used materials of 4-chlorotrifluoromethane, nitric acid and dinitrogen pentoxide is 1: 1: 0.3-0.4, wherein the using amount of the catalyst is 1-10% of the mole number of the 4-chlorotrifluoromethane, and the materials and the catalyst are fed, mixed and stirred according to the proportion.
3. The process according to claim 1 for the preparation of 4-chloro-3, 5-dinitrobenzotrifluoride, wherein: the reaction temperature is divided into two stages, wherein the primary nitration is carried out at normal temperature, and the secondary nitration is carried out at 85-90 ℃.
4. The process according to claim 1 for the preparation of 4-chloro-3, 5-dinitrobenzotrifluoride, wherein: the total time of the primary nitration and the secondary nitration is 3-10 hours.
5. The process according to claim 1 for the preparation of 4-chloro-3, 5-dinitrobenzotrifluoride, wherein: the mass percentage concentration of the nitric acid is 90-100%.
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