CN116693453A - Novel process for preparing quinclorac by catalytic oxidation - Google Patents
Novel process for preparing quinclorac by catalytic oxidation Download PDFInfo
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- CN116693453A CN116693453A CN202310552397.4A CN202310552397A CN116693453A CN 116693453 A CN116693453 A CN 116693453A CN 202310552397 A CN202310552397 A CN 202310552397A CN 116693453 A CN116693453 A CN 116693453A
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- Prior art keywords
- quinclorac
- dichloro
- reaction
- chloride
- catalyst
- Prior art date
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- FFSSWMQPCJRCRV-UHFFFAOYSA-N quinclorac Chemical compound ClC1=CN=C2C(C(=O)O)=C(Cl)C=CC2=C1 FFSSWMQPCJRCRV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 52
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- RTSCXWFBJWJHNJ-UHFFFAOYSA-N CC1=C2N=CC=CC2=CC=C1Cl.Cl Chemical compound CC1=C2N=CC=CC2=CC=C1Cl.Cl RTSCXWFBJWJHNJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 12
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Chemical group 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 239000003570 air Chemical group 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 13
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 6
- KWVNKWCJDAWNAE-UHFFFAOYSA-N 2,3-dichloroquinoline Chemical compound C1=CC=C2N=C(Cl)C(Cl)=CC2=C1 KWVNKWCJDAWNAE-UHFFFAOYSA-N 0.000 claims 1
- 108010009736 Protein Hydrolysates Proteins 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 9
- KZCUOIQIIRVGRF-UHFFFAOYSA-N 3,7-dichloroquinoline-8-carbaldehyde Chemical compound O=CC1=C(Cl)C=CC2=CC(Cl)=CN=C21 KZCUOIQIIRVGRF-UHFFFAOYSA-N 0.000 abstract description 8
- -1 3, 7-dichloro-8, 8-dichloromethylquinoline Chemical compound 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- SQQMOCHTAKMTGJ-UHFFFAOYSA-N 3,7-dichloro-8-(chloromethyl)quinoline Chemical compound ClC1=CN=C2C(CCl)=C(Cl)C=CC2=C1 SQQMOCHTAKMTGJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000003541 multi-stage reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical group CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- NKWDCLXGUJHNHS-UHFFFAOYSA-N 7-chloro-8-methylquinoline Chemical compound C1=CN=C2C(C)=C(Cl)C=CC2=C1 NKWDCLXGUJHNHS-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- ZKAIPXMHVYCWND-UHFFFAOYSA-N 3,7-dichloroquinoline-8-carbonitrile Chemical compound N#CC1=C(Cl)C=CC2=CC(Cl)=CN=C21 ZKAIPXMHVYCWND-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 241000192043 Echinochloa Species 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 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 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 229940041260 vanadyl sulfate Drugs 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WRTYWQVFBXCVBE-UHFFFAOYSA-N 8-(trichloromethyl)quinoline Chemical compound C1=CN=C2C(C(Cl)(Cl)Cl)=CC=CC2=C1 WRTYWQVFBXCVBE-UHFFFAOYSA-N 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- BCEOEOBICHVYDJ-UHFFFAOYSA-M sodium;formic acid;formate Chemical compound [Na+].OC=O.[O-]C=O BCEOEOBICHVYDJ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a novel process for preparing quinclorac by catalytic oxidation of 7-chloro-8-methylquinoline chloride, which adopts stepwise reaction to prepare quinclorac through a first-step hydrolysis reaction and a second-step oxidation reaction, has the advantages of simple operation, high yield and environmental protection, and is suitable for industrial production. The first hydrolysis reaction is to react 7-chloro-8-methylquinoline chloride (the main component is a mixture of 3, 7-dichloro-8-chloromethylquinoline and 3, 7-dichloro-8, 8-dichloromethylquinoline) as a raw material, one or more mixtures of acetic acid, acetonitrile, methanol, acetone and propionic acid as a solvent, one or more mixtures of oxides of ruthenium, copper, zinc, manganese and cobalt or salts thereof as a catalyst with water at 10-100 ℃ for 5-72 hours, and separating to obtain corresponding hydrolysis products of 3, 7-dichloro-8-quinolinecarbonol and 3, 7-dichloro-8-quinolinecarboxaldehyde, wherein the chloride conversion rate is 10-95%. The second oxidation reaction takes hydrolysis products of the first step, namely 3, 7-dichloro-8-quinolinecarboxyl alcohol and 3, 7-dichloro-8-quinolinecarboxaldehyde as raw materials, takes one or more than one mixture of hydrogen peroxide, tertiary butyl hydrogen peroxide, oxygen or air as an oxidant, takes one or more than one mixture of oxides of metallic ruthenium, copper, zinc, manganese, cobalt, iron and vanadium or salts thereof as a catalyst, takes one or more than one mixture of acetic acid, acetonitrile, methanol, acetone, water and propionic acid as a solvent, and reacts for 1-72 hours at 20-130 ℃ to obtain 3, 7-dichloro-8-quinolinecarboxylic acid, namely quinclorac, and the yield range is 5-92%.
Description
Technical Field
The invention belongs to the field of pesticide chemical industry, relates to a preparation method of aromatic acid, and in particular relates to a method for preparing quinclorac through two steps of catalytic hydrolysis-oxidation of 7-chloro-8-methylquinoline chloride.
Background
Quinclorac (Quinclorac), also known as 3, 7-dichloro-8-quinolinecarboxylic acid, having the formula C 10 H 5 Cl 2 NO 2 The molecular weight was 242.1. The quinclorac is a specific selective herbicide for preventing and removing barnyard grass in rice fields, belongs to hormone type quinoline carboxylic acid herbicides, has similar weed poisoning symptoms as auxins, is mainly used for preventing and treating barnyard grass, has longer pot life, is effective in 1-7 leaf periods, and has good safety to rice. In recent years, quinclorac is favored by the market due to the excellent weeding performance, and the price of the raw medicine is high, so that the quinclorac has great development value and good popularization and use prospect.
The prior quinclorac production process comprises the following steps: 3-chloro-2-methylaniline and glycerin are used as main raw materials, and the reaction equations are as follows through three synthetic process routes of condensation, chlorination, oxidation and the like (Chen Zhang, quinclorac oxidation process discussion, pesticide 35 (6): 17-18, 1996):
the general steps are as follows: firstly, in sulfuric acid medium, potassium iodide catalyzes 3-chloro-2-methylaniline to react with glycerin in a condensation way to obtain 7-chloro-8-methylquinoline; and then, in dichlorobenzene solution, the 7-chloro-8-methylquinoline and the introduced chlorine gas undergo free radical chlorination reaction under the catalysis of azodiisobutyronitrile to obtain 7-chloro-8-methylquinoline chloride (the chlorination depth is controlled to obtain a mixture of 3, 7-dichloro-8-chloromethylquinoline and 3, 7-dichloro-8, 8-dichloromethylquinoline, which is called chloride for short). Finally, the mixed acid oxidation of the chloride by using concentrated nitric acid and concentrated sulfuric acid is carried out to obtain the target compound 3, 7-dichloro-8-quinolinecarboxylic acid (quinclorac), and the mixed acid oxidation of the chloride is a key step of the whole quinclorac synthesis process, so that the research of the key step has important theoretical significance and practical value.
U.S. Pat. No. 3,3779 and U.S. Pat. No. 3, 4497651 disclose a method for preparing quinclorac from a quinclorac derivative, wherein 7-chloro-8-methylquinoline is used as a raw material, azobisisobutyronitrile is used as a catalyst, p-dichlorobenzene is used as a solvent, chlorine is introduced for chlorination, and reaction conditions are controlled to obtain 3, 7-dichloro-8-chloromethylquinoline, 3, 7-dichloro-8, 8-dichloromethylquinoline and 3, 7-dichloro-8, 8-trichloromethylquinoline, respectively. Wherein 3, 7-dichloro-8-chloromethyl quinoline firstly reacts with hydroxylamine hydrochloride in a formic acid-sodium formate system to obtain 3, 7-dichloro-8-cyano quinoline, and then the 3, 7-dichloro-8-cyano quinoline is hydrolyzed in 65% concentrated sulfuric acid solution at 140 ℃ for 20 hours to obtain quinclorac, the process route has more steps, the total yield is only 55-60%, the types of used reagents are more, and a large amount of acid-containing wastewater is generated at the same time, so that the environmental pollution is serious.
In the Chinese patent ZL 201010193644.9 and CN 201210194619.1, a method for obtaining quinclorac by oxidizing 3, 7-dichloro-8-chloromethyl quinoline is disclosed, concentrated sulfuric acid and nitric acid are adopted as oxidizing agents in the oxidation process, alkylsulfonic acid and the like are adopted as auxiliary oxidizing agents to obtain a quinclorac crude product, and the quinclorac crude product is refined by a one-step pressure kettle method to obtain a product with the content of more than or equal to 98 percent, wherein the yield of the step is 65 percent, and the method has the characteristics of simplicity and convenience in operation and low production cost. Although the method has higher yield of quinclorac, a large amount of sulfuric acid and nitric acid are used in the reaction, serious corrosion is caused to equipment in production, a large amount of acid-containing wastewater and nitrogen oxides generated after the reaction is finished cause serious pollution to the environment, and a small amount of polynitro compounds are generated to influence the quality of the product, so that the method is unfavorable for the marketing of the product.
In order to overcome the harm caused by concentrated nitric acid as an oxidant, the Chinese patent ZL 20081012369. X discloses a method for preparing a catalyst by using 7-chloro-8-methylThe method for preparing quinclorac by using the quinclorac chloride as raw material, water and sulfuric acid as solvents, oxy-acid of chlorine, bromine and iodine and salts thereof as well as hydrogen peroxide as oxidizing agents has the product content of more than 80 percent. The oxidant of the method is oxygen acid of chlorine, bromine and iodine, alkali metal salt and hydrogen peroxide, which is superior to concentrated nitric acid, and compared with the prior art, the method saves the production cost and improves the product quality, but still uses a large amount of sulfuric acid as a solvent to generate a large amount of acid wastewater, which has serious corrosion to equipment. The Chinese patent ZL201210151638.6 and CN202011201236.3 disclose a method for preparing quinclorac by catalytic oxidation of 7-chloro-8-methylquinoline chloride with oxygen as oxidant and cobalt-manganese-bromine ternary complex as catalyst and aliphatic carboxylic acid such as acetic acid as solvent. The method adopts green oxygen as an oxidant, improves the problem that a large amount of waste acid generated in the prior quinclorac preparation process is not easy to treat, and obtains high-content quinclorac (more than or equal to 97%). However, the method has the defects of high reaction temperature, high pressure and the like, and the catalyst is difficult to recover. Chinese patent CN 201610871748.8 reports that air, oxygen, hydrogen peroxide or tert-butyl hydroperoxide is used as oxidant, transition metal salt is used as main catalyst, quaternary ammonium salt andthe molecular sieve is taken as a cocatalyst, a composite catalytic system is constructed, a process route for preparing quinclorac by catalytic oxidation of 7-chloro-8-methylquinoline chloride is carried out, the yield range is 26-84%, the method has the advantages of mild operation condition and simple reaction, but the recycling and application problems of the catalyst molecular sieve, metal salt and quaternary ammonium salt exist.
In summary, in the quinclorac production process, the current industrial production process is a mixed acid oxidation system of concentrated nitric acid and concentrated sulfuric acid, and the method has the defects of large environmental pollution, serious equipment corrosion and toxic polynitro compound contained in the product. The oxidation process using air, oxygen, hydrogen peroxide or tert-butyl hydroperoxide as the green oxidant has not been industrialized yet due to the difficulties of difficult recovery and application of the catalyst, unstable process and the like, and the development of a new catalytic oxidation process is necessary.
In the mixed acid oxidation process of nitric acid and sulfuric acid, according to U.S. Pat. No. 3, 4632696, 4497651 and German patent DE3108873, in combination with corresponding literature reports (Chen's commercial, quinclorac oxidation process discussion, pesticides, 35 (6): 17-18, 1996), we consider that the last step of the in-situ mixed acid process is carried out stepwise, firstly 7-chloro-8-methylquinoline chloride is first hydrolyzed in sulfuric acid to form the corresponding 3, 7-dichloro-8-quinolinecarbonol and 3, 7-dichloro-8-quinolinecarboxaldehyde, which are further oxidized by nitric acid to give quinclorac, while sulfuric acid of a suitable concentration can reduce or avoid hydrolysis of the 3-chlorine on the quinoline ring, reducing by-products. According to the idea, the process is split into two steps of hydrolysis and oxidation, and a specific reaction equation is as follows:
the difficulty and innovation of the stepwise reaction are as follows: firstly, how to select proper catalyst and reaction condition in the hydrolysis process, inhibit the hydrolysis of 3-chlorine on quinoline ring, and hydrolyze raw materials as much as possible to completely generate intermediate 3, 7-dichloro-8-quinoline methanol and 3, 7-dichloro-8-quinoline formaldehyde, thereby reducing byproducts. Second, how to select proper conditions to control the oxidation rate of 3, 7-dichloro-8-quinolinecarboxaldehyde and 3, 7-dichloro-8-quinolinecarboxaldehyde in the oxidation step. Third is how the product, hydrolysis reaction intermediates and starting materials are separated.
The invention provides a method for preparing quinclorac. Firstly, raw material 7-chloro-8-methylquinoline chloride reacts with water under the action of a catalyst to obtain corresponding hydrolysate (3, 7-dichloro-8-quinolinecarboxyl alcohol and 3, 7-dichloro-8-quinolinecarboxaldehyde), and then the hydrolysate is oxidized by an oxidant under the action of an oxidation catalyst to obtain quinclorac. The invention adopts a stepwise reaction and prepares the quinclorac by a hydrolysis-oxidation method, has the advantages of simple operation, high yield and environmental protection, and is suitable for industrial production.
Disclosure of Invention
The invention provides a novel process for preparing quinclorac by catalytic oxidation of 7-chloro-8-methylquinoline chloride, which adopts stepwise reaction to prepare quinclorac through a first-step hydrolysis reaction and a second-step oxidation reaction. Has the advantages of simple operation, high yield and environmental protection, and is suitable for industrial production.
The first hydrolysis reaction is to react 7-chloro-8-methylquinoline chloride (the main component is a mixture of 3, 7-dichloro-8-chloromethylquinoline and 3, 7-dichloro-8, 8-dichloromethylquinoline) as a raw material, one or more than one mixture of acetic acid, acetonitrile, methanol, acetone and propionic acid as a solvent, and one or more than one mixture of oxides of ruthenium, copper, zinc, manganese and cobalt or salts thereof as a catalyst with water at 10-100 ℃ for 5-72 hours, and then to separate the catalyst and wash the catalyst with the solvent to obtain hydrolysis products (the mixture of 3, 7-dichloro-8-quinolinecarbonol and 3, 7-dichloro-8-quinolinecarboxaldehyde).
The second step of oxidation reaction is to take the hydrolysate of the previous step as raw material, take one or more than one mixture of hydrogen peroxide, tertiary butyl hydrogen peroxide, oxygen or air as oxidant, take one or more than one mixture of oxides of metallic ruthenium, copper, zinc, manganese, cobalt, iron and vanadium or salts thereof as catalyst, take one or more than one mixture of acetic acid, acetonitrile, methanol, acetone, water and propionic acid as solvent, react for 1-72 hours at 20-130 ℃, separate the catalyst and wash with solvent to obtain the quinclorac (3, 7-quinclorac-8-carboxylic acid).
Detailed Description
Example 1
The first step of hydrolysis reaction: into a 1000 ml four-neck round bottom flask, 50 g of 7-chloro-8-methylquinoline chloride, 50ml of water, 450 ml of solvent acetonitrile and 1.0 g of catalyst copper oxide are added in sequence, and the mixture is reacted for 5 hours at 80 ℃ under rapid stirring. The reaction solution was cooled to room temperature, discharged, the catalyst was separated, and washed with a solvent to obtain a hydrolysate containing 20% of 3, 7-dichloro-8-quinolinecarbonol and 50% of 3, 7-dichloro-8-quinolinecarboxaldehyde, and the conversion rate of the chloride was 65% by HPLC analysis.
And a second step of oxidation reaction: in a 500 mL three-neck round bottom flask, 20.0g of the hydrolysate of the first step, 250mL of solvent acetic acid and 0.2g of cobalt oxide serving as an oxidation catalyst are sequentially added, the temperature is raised to 100 ℃ for reaction for 1 hour, then 8.2mL of 30% hydrogen peroxide is dropwise added into a reaction bottle, and the stirring reaction is continued for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, the catalyst was separated, and the product was washed with a solvent, and analyzed by HPLC, and the yield of quinclorac was 72%.
Example 2
The reaction conditions of example 1 were followed except that the catalyst in the first oxidation was changed to cobalt acetate, the solvent was changed to methanol, and the reaction was carried out at 60℃for 8 hours, the catalyst in the second oxidation was changed to ruthenium chloride, the solvent was changed to propionic acid, and the reaction was carried out at 130℃for 5 hours, and the conversion of chloride was 75% and the yield of quinclorac was 92% by HPLC analysis.
Example 3
The reaction conditions of example 1 were followed except that the catalyst for the first oxidation reaction was changed to ruthenium chloride, the solvent was changed to propionic acid, the reaction was carried out at 130℃for 10 hours, the solvent for the second oxidation reaction was changed to water, the catalyst was changed to ruthenium chloride, the reaction was carried out at 75℃for 3 hours, and the conversion of the chloride was 75% and the yield of quinclorac was 29% as analyzed by HPLC.
Example 4
The reaction conditions of example 1 were followed except that the catalyst for the first oxidation was changed to zinc sulfate, the reaction was carried out at 50℃for 48 hours, the solvent for the second oxidation was changed to methanol, the oxidation catalyst was changed to copper chloride, and the reaction was carried out at 60℃for 24 hours, whereby the conversion of the chloride was 75% and the yield of quinclorac was 63% as determined by HPLC.
Example 5
The reaction conditions of example 1 were followed except that the catalyst of the first oxidation was changed to manganese sulfate, the solvent was changed to acetic acid, the reaction was carried out at 110℃for 12 hours, the solvent of the second oxidation was changed to acetone, the reaction was carried out at 50℃for 48 hours, the catalyst was changed to ferric chloride, and the conversion of the chloride was 55% and the yield of quinclorac was 40% by HPLC analysis.
Example 6
The reaction conditions of example 1 were followed except that the catalyst for the first oxidation was changed to cobalt chloride, the solvent was changed to acetone, the reaction was carried out at 50℃for 18 hours, the solvent for the second oxidation was changed to propionic acid, the oxidation catalyst was changed to ferric chloride, and the reaction was carried out at 130℃for 1 hour, and the conversion of the chloride was 25% and the yield of quinclorac was 18% by HPLC analysis.
Example 7
The reaction conditions of example 1 were followed except that the first oxidation reaction solvent was changed to acetone, the reaction was carried out at 30℃for 64 hours, the second oxidation reaction solvent was changed to methanol, the oxidation catalyst was changed to copper acetate, and the reaction was carried out at 60℃for 6 hours, whereby the conversion of chloride was 20% and the yield of quinclorac was 35% as analyzed by HPLC.
Example 8
The reaction conditions of example 1 were followed except that the first oxidation reaction solvent was changed to methanol, the reaction was carried out at 20℃for 12 hours, the second oxidation reaction solvent was changed to acetonitrile, the oxidation catalyst was changed to a mixture of 0.5 g of vanadyl sulfate and 0.5 g of ruthenium chloride, and the reaction was carried out at 80℃for 48 hours, whereby the conversion of chloride was 45% and the yield of quinclorac was 63%.
Example 9
The reaction conditions of example 1 were followed except that the first oxidation reaction solvent was changed to a mixture of 200 ml of acetone and 250ml of acetonitrile, the reaction was carried out at 35℃for 64 hours, the second oxidation reaction solvent was changed to propionic acid, the catalyst was changed to cobalt acetate, the oxidant was changed to oxygen, the reaction was carried out at 80℃for 3 hours, the conversion of chloride was 50%, and the yield of quinclorac was 33%.
Example 10
The reaction conditions of example 1 were followed except that the catalyst of the first step was changed to a mixture of 0.5 g of cobalt acetate and 0.5 g of copper acetate, the catalyst of the second oxidation reaction was changed to manganese chloride, the solvent was changed to methanol, the oxidant was changed to t-butyl hydroperoxide, and the reaction was carried out at 50℃for 12 hours, and the conversion of chloride was 68% and the yield of quinclorac was 41% by HPLC analysis.
Example 11
The reaction conditions of example 1 were followed except that the first catalyst was changed to a mixture of 0.5 g of ruthenium chloride and 0.5 g of cobalt acetate, the second oxidant was changed to t-butyl hydroperoxide, the catalyst was changed to vanadyl sulfate, and the conversion of chloride was 63% and the yield of quinclorac was 90% by HPLC analysis.
Example 12
The reaction conditions of example 1 were followed except that the first reaction time was prolonged to 72 hours, the second oxidant was changed to oxygen, the catalyst was changed to a mixture of copper sulfate and ruthenium chloride, and the conversion of chloride was 75% and the yield of quinclorac was 38% by HPLC analysis.
Example 13
The reaction conditions of example 1 were followed except that the first oxidation reaction solvent was changed to a mixture of 200 ml of acetic acid and 250ml of propionic acid, the second oxidation reaction solvent was changed to air, the solvent was changed to propionic acid, the catalyst was changed to ferric nitrate, and the reaction was carried out at 120℃for 15 hours, and the conversion of chloride was 65% and the yield of quinclorac was 28% by HPLC analysis.
Example 14
The reaction conditions of example 1 were followed except that the second step of oxidizing agent was changed to oxygen, the catalyst was changed to copper nitrate, the solvent was changed to acetonitrile, and the reaction was carried out at 75℃for 15 hours, and the conversion of chloride was 65% and the yield of quinclorac was 53% by HPLC analysis.
Example 15
The reaction conditions of example 1 were followed except that the second-step oxidizing agent was changed to t-butyl hydroperoxide, the catalyst was changed to cobalt chloride, the solvent was changed to acetonitrile, and the reaction was carried out at 20℃for 15 hours, and the conversion of the chloride was 60% and the yield of quinclorac was 23% by HPLC analysis.
Example 16
The reaction conditions of example 1 were followed except that the first step was reacted at 10℃for 72 hours, the second step was changed to a mixture of 100 ml of methanol and 100 ml of acetonitrile, and the reaction was carried out at 25℃for 72 hours, and the conversion of chloride was 10% and the yield of quinclorac was 5% by HPLC analysis.
The above description is only of the preferred embodiments of the present invention, and the present invention is not limited thereto, but various changes, equivalents, improvements and modifications can be made by those skilled in the art, and the present invention is intended to be included in the scope of the present invention.
Claims (3)
1. A method for preparing quinclorac is characterized in that a certain amount of 7-chloro-8-methylquinoline chloride, water, a solvent and a catalyst are reacted for 5-72 hours at the temperature of 10-130 ℃ in the first hydrolysis reaction to obtain a hydrolysate of 7-chloro-8-methylquinoline chloride, wherein the chloride conversion rate is 10-95%; and in the second step, the hydrolysate, the oxidant, the catalyst and the solvent are reacted for 1 to 72 hours at the temperature of 20 to 130 ℃ and post-treated to obtain the dichloroquinoline acid with the yield of 5 to 92 percent.
2. The method according to claim 1, wherein the first hydrolysis reaction solvent is one or more of acetic acid, acetonitrile, methanol, acetone and propionic acid, and the catalyst is one or more of oxides of ruthenium, copper, zinc, manganese and cobalt or salts thereof.
3. The method according to claim 1, wherein the second oxidation catalyst is one or more of oxides of ruthenium, copper, zinc, manganese, cobalt, iron, vanadium or salts thereof, the solvent is one or more of acetic acid, acetonitrile, methanol, acetone, water, propionic acid, and the oxidant is one or more of hydrogen peroxide, tert-butyl hydrogen peroxide, oxygen or air.
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| CN116969887B (en) * | 2023-09-25 | 2023-12-22 | 启农生物科技(北京)有限公司 | Preparation process of intermediate 7-chloro-8-quinolinic acid and synthesis process of quinclorac |
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