CN117924087A - Safe and environment-friendly preparation method of dinitroaromatic hydrocarbon - Google Patents
Safe and environment-friendly preparation method of dinitroaromatic hydrocarbon Download PDFInfo
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- CN117924087A CN117924087A CN202311662422.0A CN202311662422A CN117924087A CN 117924087 A CN117924087 A CN 117924087A CN 202311662422 A CN202311662422 A CN 202311662422A CN 117924087 A CN117924087 A CN 117924087A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000006396 nitration reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 25
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- 230000001546 nitrifying effect Effects 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000004323 potassium nitrate Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 235000010333 potassium nitrate Nutrition 0.000 claims description 21
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 16
- 238000010791 quenching Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- DVFVNJHIVAPTMS-UHFFFAOYSA-N 1-methyl-2-(trifluoromethyl)benzene Chemical compound CC1=CC=CC=C1C(F)(F)F DVFVNJHIVAPTMS-UHFFFAOYSA-N 0.000 claims description 14
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 claims description 12
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 8
- LRLRAYMYEXQKID-UHFFFAOYSA-N 1-methyl-4-(trifluoromethyl)benzene Chemical compound CC1=CC=C(C(F)(F)F)C=C1 LRLRAYMYEXQKID-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940073735 4-hydroxy acetophenone Drugs 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 17
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 238000007867 post-reaction treatment Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 33
- 239000012295 chemical reaction liquid Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 230000000171 quenching effect Effects 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 238000001514 detection method Methods 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- LXOMTLHUSOHRMK-UHFFFAOYSA-N 2-methyl-1,5-dinitro-3-(trifluoromethyl)benzene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1C(F)(F)F LXOMTLHUSOHRMK-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 5
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 5
- CVYZVNVPQRKDLW-UHFFFAOYSA-N 2,4-dinitroanisole Chemical compound COC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CVYZVNVPQRKDLW-UHFFFAOYSA-N 0.000 description 5
- YKEVTSMJXUJEMX-UHFFFAOYSA-N 2-methyl-1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound CC1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O YKEVTSMJXUJEMX-UHFFFAOYSA-N 0.000 description 5
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- PBOPJYORIDJAFE-UHFFFAOYSA-N 2,4-dinitrobromobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C([N+]([O-])=O)=C1 PBOPJYORIDJAFE-UHFFFAOYSA-N 0.000 description 4
- DYWSJJHARHAYDC-UHFFFAOYSA-N 4-methoxy-3,5-dinitrobenzaldehyde Chemical compound COC1=C([N+]([O-])=O)C=C(C=O)C=C1[N+]([O-])=O DYWSJJHARHAYDC-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LWTJGYMKYXJXBH-UHFFFAOYSA-N potassium acetic acid nitrate Chemical compound [N+](=O)([O-])[O-].[K+].C(C)(=O)O LWTJGYMKYXJXBH-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- -1 dinitro aromatic hydrocarbon Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 description 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- JDKJQRXKQXPFMO-UHFFFAOYSA-N C1=CC=CC=C1.[N+](=O)(O)[O-].[N+](=O)(O)[O-] Chemical compound C1=CC=CC=C1.[N+](=O)(O)[O-].[N+](=O)(O)[O-] JDKJQRXKQXPFMO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- 229960004236 pefloxacin Drugs 0.000 description 1
- FHFYDNQZQSQIAI-UHFFFAOYSA-N pefloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCN(C)CC1 FHFYDNQZQSQIAI-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of chemical intermediate preparation, in particular to a safe and environment-friendly preparation method of dinitroaromatic hydrocarbon. The invention adopts a nitration method of a liquid acid/nitrate system, which starts from aromatic hydrocarbon, takes nitrate as a nitration reagent, takes polyphosphoric acid (PPA) as a reaction solvent, and carries out nitration reaction at room temperature to prepare dinitroaromatic hydrocarbon. The dinitration synthesis method provided by the invention adopts nitrate/polyphosphoric acid as a nitrifying reagent to replace a traditional aromatic hydrocarbon dinitration mixed acid system, solves the problems of environmental pollution, equipment corrosion and the like caused by adopting the traditional mixed acid system, and has the advantages of simple synthesis method and post-reaction treatment, mild and safe reaction conditions, high dinitration product yield and the like. From the perspective of green synthesis angle, the method accords with the development concept of green chemistry, and provides a new idea and method for large-scale industrialized preparation of dinitroaromatic hydrocarbon.
Description
Technical Field
The invention relates to a safe and environment-friendly preparation method of dinitroaromatic hydrocarbon, in particular to a method for dinitrating aromatic hydrocarbon compounds under the conditions of polyphosphoric acid and potassium nitrate, belonging to the field of fine chemical industry.
Background
The nitration reaction of aromatic compounds is an important electrophilic substitution reaction in chemical production, and the nitration products of aromatic compounds are also important fine chemical intermediates, and are widely used in the fields of dyes, medicines, pesticides, explosives and the like. For example, 2, 4-dinitrofluorobenzene is an important basic raw material of organic fluorine fine chemicals, is a main raw material for manufacturing quinolone medicines such as ciprofloxacin, pefloxacin, difluoro-floxacin and the like, and is also used as a raw material of fluorine-containing pesticides, insecticides and fluorine-containing herbicides; 2, 4-dinitrochlorobenzene is a common molecular polymerization inhibitor in industry, and can be used for preparing high-added value downstream products such as sulfur black dye, o-benzoyl sulfimide, 2, 4-dinitroaniline, 2,4, 6-trinitrophenol and the like; 2, 4-dinitroanisole is mainly used as a dye intermediate and an insecticidal egg agent; 2, 4-dinitrotoluene and 2,4, 6-trinitrotoluene are widely used for making explosives. However, due to the special properties of dinitrated aromatic compounds, the national production process of dinitrated aromatic compounds is strictly regulated, and the demand for dinitrated products is high in China at present, so that the state of short supply is often caused.
The preparation process of dinitroaromatic hydrocarbon mostly adopts a concentrated nitric acid system or a mixed acid system. For a concentrated nitric acid system, russian patent RU2572516C1 reports that the dinitration of phenol at 80℃using a concentrated nitric acid system produces 2, 4-dinitrophenol in excellent yields. For a mixed acid system, a common system is a concentrated nitric acid-concentrated sulfuric acid system, and China patent CN103936559A reports that 1, 3-dinitrobenzene is generated by dinitration of benzene at 120 ℃ by using the concentrated nitric acid-concentrated sulfuric acid system, and the yield is excellent; foreign patent WO2020175671A1 reports that 4-methyl-3, 5-dinitrobenzotrifluoride is produced by dinitration of 4-methyltrifluorotoluene at 50℃using a concentrated nitric acid-concentrated sulfuric acid system; in addition, wuYanxuan and the like innovatively use a mixed acid system of trifluoromethanesulfonic acid and concentrated nitric acid to dinitrate benzene at room temperature to generate 1, 3-dinitrobenzene, and the yield is good (Journal ofOrganic Chemistry,2023,88 (15), 11322-11327). However, the two traditional dinitration systems have high requirements on reaction environment, high purification cost on reaction products, difficult recycling of waste acid, and large amount of volatile nitric acid or nitrogen dioxide gas overflows in the production process, so that equipment is easy to corrode, serious environmental pollution is caused, and the health of production workers is threatened. Based on the ideas of protecting environment and safe production, the research on nitration reaction should be transferred to the research on green nitration technology in order to radically reduce or eliminate the pollution of chemical industry to the environment. In contrast, the invention adopts a liquid acid/nitrate nitration system of polyphosphoric acid-potassium nitrate which has little environmental pollution, uses less acid than sulfuric acid and nitric acid, has no oxidizing capability, provides acidic conditions for nitration reaction, has high reaction efficiency and excellent yield, is simple to post-treat, extracts products after water is added dropwise for hydrolysis, has excellent production environment safety, and can carry out nitration reaction at room temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior nitration technology and provides a safe and environment-friendly preparation method of dinitroaromatic hydrocarbon.
The invention adopts the following technical scheme:
A process for preparing the safe and environment-friendly dinitro aromatic hydrocarbon includes such steps as proportionally mixing aromatic hydrocarbon with nitrate as nitrifying agent in polyphosphoric acid, stirring at room temp for 1-15 hr until reaction is finished. Finally, adding water to quench the reaction, extracting the product by an organic solvent, washing, drying, filtering, concentrating and purifying to obtain the dinitroaromatic compound.
Further, the nitrifying salt in the nitrifying reagent is any one of sodium nitrate, potassium nitrate, zinc nitrate and ferric nitrate, and more preferably potassium nitrate.
Further, polyphosphoric acid (PPA) is a nitrating solvent.
Further, the addition amount of the nitrifying agent is 2.2 to 2.4 equivalents, more preferably 2.3 equivalents.
Further, the aromatic hydrocarbon is a compound containing an electron donating group or both an electron donating group and an electron withdrawing group.
Further, the aromatic hydrocarbon includes, but is not limited to, benzene, chlorobenzene, fluorobenzene, anisole, bromobenzene, 4-methoxybenzaldehyde, 2-methyltrifluorotoluene, 4-methoxyacetophenone, 4-methyltrifluorotoluene, 4-hydroxyacetophenone and the like.
The organic solvent is dichloromethane or dichloroethane, more preferably dichloroethane.
As can be seen from the above description of the present invention, compared with the prior art of nitration, the present invention has the following beneficial effects:
First, the innovation of the invention is mainly realized by abandoning the traditional mixed acid dinitration system, and selecting a liquid acid/nitrate system with higher safety coefficient and more thorough reaction. The mechanism of nitrate nitration is the process by which the aromatic radical cation traps NO 2 + to form wheland intermediate. The process has the advantages of less waste acid emission, low corrosiveness, easy separation of products and the like. The selected nitrifying reagent, namely potassium nitrate, has low price, is harmless to human bodies and is easy to store; the selected protonic acid solvent-polyphosphoric acid can dissolve low-molecular and high-molecular compounds; the acidity of the polyphosphoric acid is weaker than that of nitric acid and sulfuric acid, and stronger than that of acetic acid, and the polyphosphoric acid has no oxidizing ability and small toxicity to human bodies;
Secondly, the traditional concentrated nitric acid system or the mixed acid system of concentrated nitric acid and concentrated sulfuric acid causes serious acid water environmental pollution because of the strong acid used by the system, and the severe reaction process and the strong corrosion to equipment are affected by most processes. The application has the advantages of little environmental pollution, less acid than sulfuric acid, nitric acid, no oxidizing ability, more stable and safe polyphosphoric acid for nitration reaction, high reaction efficiency, excellent yield, simple post-treatment, extraction of products after water is added dropwise for hydrolysis, safe production environment and capability of carrying out nitration reaction at room temperature. From the perspective of green synthesis angle, the method accords with the concepts of green chemistry and safe production, and provides a new idea and method for large-scale industrialized preparation of dinitroaromatic hydrocarbon.
Drawings
FIG. 1 is a scheme for the synthesis of 1, 3-dinitrobenzene;
FIG. 2 is a GC spectrum of benzene;
FIG. 3 is a GC spectrum of benzene nitration reaction liquid;
FIG. 4 is a GC spectrum of a1, 3-dinitrobenzene standard sample;
FIG. 5 is a synthetic route diagram of 2, 4-dinitrochlorobenzene;
FIG. 6 is a GC spectrum of chlorobenzene;
FIG. 7 is a GC spectrum of chlorobenzene nitration reaction liquid;
FIG. 8 is a GC spectrum of a standard sample of 2, 4-dinitrochlorobenzene;
FIG. 9 is a synthetic route diagram of 2, 4-dinitrofluorobenzene;
FIG. 10 is a GC spectrum of fluorobenzene;
FIG. 11 is a GC spectrum of fluorobenzene nitration reaction liquid;
FIG. 12 is a GC spectrum of a standard sample of 2, 4-dinitrofluorobenzene;
FIG. 13 is a synthetic route diagram of 2, 4-dinitroanisole;
FIG. 14 is a GC spectrum of anisole;
FIG. 15 is a GC spectrum of anisole nitration reaction liquid;
FIG. 16 is a GC spectrum of a standard sample of 2, 4-dinitroanisole;
FIG. 17 is a synthetic route diagram of 2, 4-dinitrobromobenzene;
FIG. 18 is a GC spectrum of bromobenzene;
FIG. 19 is a GC spectrum of bromobenzene nitration reaction liquid;
FIG. 20 is a GC spectrum of a standard sample of 2, 4-dinitrobromobenzene;
FIG. 21 is a synthetic route diagram of 4-methoxy-3, 5-dinitrobenzaldehyde;
FIG. 22 is a GC spectrum of 4-methoxybenzaldehyde;
FIG. 23 is a GC spectrum of a 4-methoxybenzaldehyde nitration reaction liquid;
FIG. 24 is a GC spectrum of a standard sample of 4-methoxy-3, 5-dinitrobenzaldehyde;
FIG. 25 is a synthetic route diagram of 2-methyl-3, 5-dinitrobenzotrifluoride;
FIG. 26 is a GC spectrum of 2-methyltrifluorotoluene;
FIG. 27 is a GC spectrum of a 2-methyltrifluorotoluene nitration reaction solution;
FIG. 28 is a GC spectrum of a standard sample of 2-methyl-3, 5-dinitrobenzotrifluoride;
FIG. 29 is a synthetic route diagram of 4-methoxy-3, 5-dinitroacetophenone;
FIG. 30 is a GC spectrum of 4-methoxyacetophenone;
FIG. 31 is a GC spectrum of a 4-methoxyacetophenone nitration reaction liquid;
FIG. 32 is a GC spectrum of a standard sample of 4-methoxy-3, 5-dinitroacetophenone;
FIG. 33 is a synthetic route diagram of 4-methyl-3, 5-dinitrobenzotrifluoride;
FIG. 34 is a GC spectrum of 4-methyltrifluorotoluene;
FIG. 35 is a GC spectrum of the 4-methyltrifluorotoluene nitration reaction liquid;
FIG. 36 is a GC spectrum of a standard sample of 4-methyl-3, 5-dinitrobenzotrifluoride;
FIG. 37 is a synthetic route diagram of 4-hydroxy-3, 5-dinitroacetophenone;
FIG. 38 is a GC spectrum of 4-hydroxyacetophenone;
FIG. 39 is a GC spectrum of a 4-hydroxyacetophenone nitration reaction liquid;
FIG. 40 is a GC spectrum of a standard sample of 4-hydroxy-3, 5-dinitroacetophenone;
FIG. 41 is a GC diagram of a reaction solution of 2-methyltrifluorotoluene dinitration (potassium nitrate-acetic acid nitration system);
FIG. 42 is a GC spectrum of a 2-methyltrifluorotoluene dinitration (potassium nitrate-concentrated sulfuric acid nitration system) reaction solution;
FIG. 43 is a GC spectrum of a 2-methyltrifluorotoluene dinitration (concentrated nitric acid-concentrated sulfuric acid nitration system) reaction solution;
Detailed Description
The invention is further described below by means of specific embodiments.
A preparation method of safe and environment-friendly dinitroaromatic hydrocarbon comprises the steps of stirring a reaction system consisting of aromatic hydrocarbon serving as a raw material and nitrate serving as a nitrifying reagent in polyphosphoric acid for 1-15 hours at room temperature until the reaction is completed; and finally, adding a proper amount of water for quenching reaction, and extracting a product by an organic solvent, washing, drying, filtering, concentrating and purifying to obtain the dinitroaromatic compound.
Wherein the nitrifying salt is sodium nitrate, potassium nitrate, zinc nitrate or ferric nitrate, more preferably potassium nitrate; specifically, the addition amount of the nitrifying agent is 2.2 to 2.4 equivalents, more preferably 2.3 equivalents.
Aromatic hydrocarbons are compounds containing an electron donating group or both an electron donating group and an electron withdrawing group; specifically, the aromatic hydrocarbon is benzene, chlorobenzene, fluorobenzene, anisole, bromobenzene, 4-methoxybenzaldehyde, 2-methyltrifluorotoluene, 4-methoxyacetophenone, 4-methyltrifluorotoluene, 4-hydroxyacetophenone.
Example 1
Process for the preparation of 1, 3-dinitrobenzene, the synthetic route of which is shown in FIG. 1
The specific method comprises the following steps:
500mg benzene is taken in a 100ml three-mouth bottle, 1.491g potassium nitrate is added, 10ml PPA is added, the reaction is carried out for 1 hour under stirring at room temperature, the reaction is finished, 80ml water quenching reaction is added dropwise, dichloroethane is added for extracting the reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled off soon to obtain the product, and the yield is 98.6% as determined by GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 60 ℃ and the temperature-rising step is 30 ℃/min until the temperature-rising time is finished.
Example 2
Process for the preparation of 2, 4-dinitrochlorobenzene, the synthetic route of which is shown in FIG. 5
The specific method comprises the following steps:
500mg of chlorobenzene is taken in a 100ml three-mouth bottle, 1.033g of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 2 hours under stirring at room temperature, the reaction is finished, 80ml of water quenching reaction is added dropwise, dichloroethane is added for extracting reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled off soon to obtain the product, and the yield is 100.0% of 2, 4-dinitrochlorobenzene through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Example 3
Preparation method of 2, 4-dinitrofluorobenzene, synthetic route thereof is shown in FIG. 9
The specific method comprises the following steps:
500mg of fluorobenzene is taken in a 100ml three-mouth bottle, 1.210g of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 3 hours under stirring at room temperature, the reaction is finished, 80ml of water quenching reaction is added dropwise, dichloroethane is added for extracting reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled soon to obtain a product, and the yield is 100.0% of 2, 4-dinitrofluorobenzene through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 50 ℃ and the temperature-rising step is 30 ℃/min until the temperature-rising time is finished.
Example 4
Process for the preparation of 2, 4-dinitroanisole, the synthetic route of which is shown in FIG. 13
The specific method comprises the following steps:
500mg anisole is taken in a 100ml three-mouth bottle, 1.075g potassium nitrate is added, 10ml PPA is added, the reaction is carried out for 2 hours under stirring at room temperature, the reaction is finished, 80ml water quenching reaction is dripped, dichloroethane is added for extracting reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled soon to obtain the product, and the yield is 100.0 percent of 2, 4-dinitroanisole through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 120 ℃ and the temperature-rising step is 20 ℃/min until the temperature-rising time is finished.
Example 5
Preparation method of 2, 4-dinitrobromobenzene, and synthetic route thereof is shown in FIG. 17
The specific method comprises the following steps:
500mg bromobenzene is taken in a 100ml three-mouth bottle, 740mg potassium nitrate is added, 10ml PPA is added, the reaction is carried out for 15 hours under stirring at room temperature, the reaction is finished, 80ml water quenching reaction is dripped, dichloroethane is added for extracting the reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried, filtration is carried out, the filtrate is distilled off soon to obtain the product, and the yield is 100.0% of 2, 4-dinitrobromobenzene through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 120 ℃ and the temperature-rising step is 20 ℃/min until the temperature-rising time is finished.
Example 6
Preparation method of 4-methoxy-3, 5-dinitrobenzaldehyde, and synthetic route thereof is shown in FIG. 21
The specific method comprises the following steps:
500mg of 4-methoxybenzaldehyde is taken in a 100ml three-necked flask, 854mg of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 8 hours at room temperature under stirring, the reaction is finished, 80ml of water quenching reaction is added dropwise, dichloroethane is added for extracting the reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled soon to obtain the product, and the yield is 74.3% of 4-methoxy-3, 5-dinitrobenzaldehyde through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 180 ℃ and the temperature-rising step is 15 ℃/min until the temperature-rising time is finished.
Example 7
Preparation method of 2-methyl-3, 5-dinitrobenzotrifluoride, synthetic route thereof is shown in FIG. 25
The specific method comprises the following steps:
500mg of 2-methyltrifluorotoluene is taken in a 100ml three-mouth bottle, 726mg of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 5 hours at room temperature under stirring, 80ml of water quenching reaction is added dropwise after the reaction, dichloroethane is added for extracting the reaction liquid, water washing, anhydrous sodium sulfate drying and filtration are carried out, the filtrate is distilled soon to obtain the product, and the yield is 100.0% of 2-methyl-3, 5-dinitrobenzotrifluoride through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Example 8
Preparation method of 4-methoxy-3, 5-dinitroacetophenone, and synthetic route thereof is shown in FIG. 29
The specific method comprises the following steps:
500mg of 4-methoxyacetophenone is taken in a 100ml three-mouth bottle, 774mg of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 5 hours under stirring at room temperature, the reaction is finished, 80ml of water quenching reaction is added dropwise, dichloroethane is added for extracting reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled soon to obtain the product, and the product is determined to be 4-methoxyl-3, 5-dinitroacetophenone through GC detection, and the yield is 66.1%. The GC temperature-rising program is kept for 2min at the initial temperature of 180 ℃ and the temperature-rising step is 15 ℃/min until the temperature-rising time is finished.
Example 9
Preparation method of 4-methyl-3, 5-dinitrobenzotrifluoride, synthetic route thereof is shown in FIG. 33
The specific method comprises the following steps:
500mg of 4-methyltrifluorotoluene is taken in a 100ml three-mouth bottle, 726mg of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 12 hours at room temperature under stirring, 80ml of water quenching reaction is added dropwise after the reaction, dichloroethane is added for extracting the reaction liquid, water washing, anhydrous sodium sulfate drying and filtration are carried out, the filtrate is distilled soon to obtain the product, and the yield is 100.0% of the 4-methyl-3, 5-dinitrobenzotrifluoride through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Example 10
Preparation method of 4-hydroxy-3, 5-dinitroacetophenone, synthetic route thereof is shown in FIG. 37
The specific method comprises the following steps:
500mg of 4-hydroxyacetophenone is taken in a 100ml three-mouth bottle, 854mg of potassium nitrate is added, 10ml of PPA is added, the reaction is carried out for 8 hours at room temperature under stirring, the reaction is finished, 80ml of water quenching reaction is added dropwise, dichloroethane is added for extracting reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried and filtered, the filtrate is distilled soon to obtain the product, and the product is determined to be 4-hydroxy-3, 5-dinitroacetophenone through GC detection, and the yield is 100.0%. The GC temperature-rising program is kept for 2min at the initial temperature of 180 ℃ and the temperature-rising step is 30 ℃/min until the temperature-rising time is finished.
Comparative example
In order to examine the superiority of the technology of the invention, experiments also try to carry out dinitration reaction of 2-methyltrifluorotoluene in example 7 by a potassium nitrate-acetic acid nitration system, a potassium nitrate-concentrated sulfuric acid nitration system and a concentrated nitric acid-concentrated sulfuric acid nitration system in sequence, and the reaction steps and results are as follows:
Comparative example 1
500Mg of 2-methyltrifluorotoluene is taken in a 100ml three-mouth bottle, 726mg of potassium nitrate is added, 10ml of acetic acid is added, the reaction is carried out for 5 hours at room temperature under stirring, 80ml of water is added dropwise for quenching reaction after the reaction is finished, dichloroethane is added for extracting the reaction liquid, water washing is carried out, anhydrous sodium sulfate is dried, and the filtrate is filtered and distilled. The reaction was found not to proceed by GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Comparative example 2
500Mg of 2-methyltrifluorotoluene is taken in a 100ml three-port bottle, 726mg of potassium nitrate is added, 10ml of concentrated sulfuric acid is added, the reaction is carried out at room temperature under stirring for 5 hours, 80ml of water quenching reaction is added dropwise after the reaction, dichloroethane is added for extracting the reaction liquid, water washing, anhydrous sodium sulfate drying and filtration are carried out, the filtrate is distilled off soon to obtain the product, and the yield is 83.3% of 2-methyl-3, 5-dinitrobenzotrifluoride through GC detection. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Comparative example 3
500Mg of 2-methyltrifluorotoluene is taken in a 100ml three-port bottle, 5.327g of concentrated nitric acid (68%) is added, 10ml of concentrated sulfuric acid is added, the reaction is stirred for 5 hours at room temperature, 80ml of water is added dropwise for quenching reaction after the reaction is finished, dichloroethane is added for extracting reaction liquid, water washing, drying is carried out by anhydrous sodium sulfate, filtration is carried out, and the filtrate is distilled off soon to obtain the product, and the yield is determined to be 2-methyl-3, 5-dinitrobenzotrifluoride by GC detection, and is 100.0%. The GC temperature-rising program is kept for 2min at the initial temperature of 100 ℃ and the temperature-rising step is 25 ℃/min until the temperature-rising time is finished.
Wherein, fig. 41, 42 and 43 are respectively GC spectra of the potassium nitrate-acetic acid nitration system, the potassium nitrate-concentrated sulfuric acid nitration system and the dinitration reaction of the nitric acid-concentrated sulfuric acid nitration system to 2-methyltrifluorotoluene, the yields are respectively 0%,83.3% and 100%, thus the potassium nitrate-acetic acid nitration system and the potassium nitrate-concentrated sulfuric acid nitration system are far inferior to the potassium nitrate-polyphosphoric acid system of the invention. Although the concentrated nitric acid-concentrated sulfuric acid nitration system is consistent with the potassium nitrate-polyphosphoric acid system of the present invention, it is based on the results exhibited by an excess of nitric acid. As can be seen, the concentrated nitric acid-concentrated sulfuric acid nitration system is far less than the results demonstrated in the present invention using 2.3 equivalents of the nitrating agent, potassium nitrate. This is sufficient to show the advantages of the process for the preparation of dinitroaromatic hydrocarbons according to the invention.
Claims (8)
1. A safe and environment-friendly preparation method of dinitroaromatic hydrocarbon is characterized in that: in a nitrifying solvent, stirring a reaction system consisting of aromatic hydrocarbon serving as a raw material and nitrate serving as a nitrifying reagent for 1-15 hours at room temperature until the reaction is completed; finally, adding water to quench the reaction, extracting the product by an organic solvent, washing, drying, filtering, concentrating and purifying to obtain the dinitroaromatic compound.
2. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 1, wherein: the nitrate is any one of sodium nitrate, potassium nitrate, zinc nitrate or ferric nitrate.
3. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 2, wherein: the nitrate used is potassium nitrate.
4. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 1, wherein: the addition amount of the selected nitrate is 2.2-2.4 equivalents.
5. The process for producing safe and environment-friendly dinitroaromatic hydrocarbon according to claim 4, which is characterized in that: the amount of nitrate selected was 2.3 equivalents.
6. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 1, wherein: the selected nitration solvent is polyphosphoric acid PPA.
7. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 1, wherein: the aromatic hydrocarbon comprises any one of benzene, chlorobenzene, fluorobenzene, anisole, bromobenzene, 4-methoxybenzaldehyde, 2-methyltrifluorotoluene, 4-methoxyacetophenone, 4-methyltrifluorotoluene and 4-hydroxyacetophenone.
8. The process for the preparation of safe and environmentally friendly dinitroaromatic hydrocarbons according to claim 1, wherein: the organic solvent is dichloromethane or dichloroethane.
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