CN115057843A - Preparation method of chlorantraniliprole insecticide - Google Patents
Preparation method of chlorantraniliprole insecticide Download PDFInfo
- Publication number
- CN115057843A CN115057843A CN202210676153.2A CN202210676153A CN115057843A CN 115057843 A CN115057843 A CN 115057843A CN 202210676153 A CN202210676153 A CN 202210676153A CN 115057843 A CN115057843 A CN 115057843A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound shown
- phosgene
- reaction
- chlorantraniliprole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005886 Chlorantraniliprole Substances 0.000 title claims abstract description 43
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002917 insecticide Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000007112 amidation reaction Methods 0.000 claims abstract description 18
- -1 alkylamine hydrochloride Chemical class 0.000 claims abstract description 17
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002252 acyl group Chemical group 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OVZVWDITHBBFCO-UHFFFAOYSA-N 2-pyridin-2-ylpyrazole-3-carboxylic acid Chemical class OC(=O)C1=CC=NN1C1=CC=CC=N1 OVZVWDITHBBFCO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical group [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 5
- GFYHSKONPJXCDE-UHFFFAOYSA-N 2,3,5-trimethylpyridine Chemical compound CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 4
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- IXCXVGWKYIDNOS-UHFFFAOYSA-N 1-cyclopropylethanamine Chemical compound CC(N)C1CC1 IXCXVGWKYIDNOS-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WZWFMMNJURDPFP-UHFFFAOYSA-N 1-cyclopropylethylazanium;chloride Chemical compound Cl.CC(N)C1CC1 WZWFMMNJURDPFP-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- ISYORFGKSZLPNW-UHFFFAOYSA-N propan-2-ylazanium;chloride Chemical compound [Cl-].CC(C)[NH3+] ISYORFGKSZLPNW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 9
- 239000005889 Cyantraniliprole Substances 0.000 description 7
- DVBUIBGJRQBEDP-UHFFFAOYSA-N cyantraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl DVBUIBGJRQBEDP-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 4
- FSVBRVFURKUWIP-UHFFFAOYSA-N 5-bromo-2-(3,5-dichloropyridin-2-yl)pyrazole-3-carbonyl chloride Chemical compound ClC(=O)C1=CC(Br)=NN1C1=NC=C(Cl)C=C1Cl FSVBRVFURKUWIP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- KTHTXLUIEAIGCD-UHFFFAOYSA-N 2-amino-3,5-dichlorobenzoic acid Chemical compound NC1=C(Cl)C=C(Cl)C=C1C(O)=O KTHTXLUIEAIGCD-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KOPXCQUAFDWYOE-UHFFFAOYSA-N 2-amino-5-chloro-3-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC(C(O)=O)=C1N KOPXCQUAFDWYOE-UHFFFAOYSA-N 0.000 description 2
- HBGLZGRTSLJJQL-UHFFFAOYSA-N 5-bromo-2-(3,5-dichloropyridin-2-yl)pyrazole-3-carboxylic acid Chemical compound OC(=O)C1=CC(Br)=NN1C1=NC=C(Cl)C=C1Cl HBGLZGRTSLJJQL-UHFFFAOYSA-N 0.000 description 2
- ONILAONOGQYBHW-UHFFFAOYSA-N 5-bromo-n-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloropyridin-2-yl)pyrazole-3-carboxamide Chemical compound CNC(=O)C1=CC(Cl)=CC(Cl)=C1NC(=O)C1=CC(Br)=NN1C1=NC=C(Cl)C=C1Cl ONILAONOGQYBHW-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 239000005758 Cyprodinil Substances 0.000 description 2
- HAORKNGNJCEJBX-UHFFFAOYSA-N cyprodinil Chemical compound N=1C(C)=CC(C2CC2)=NC=1NC1=CC=CC=C1 HAORKNGNJCEJBX-UHFFFAOYSA-N 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SBNFWQZLDJGRLK-RTWAWAEBSA-N (1R)-trans-phenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-RTWAWAEBSA-N 0.000 description 1
- PWXLBVZWVKCFHR-UHFFFAOYSA-N 2-amino-3-bromo-5-chlorobenzoic acid Chemical compound NC1=C(Br)C=C(Cl)C=C1C(O)=O PWXLBVZWVKCFHR-UHFFFAOYSA-N 0.000 description 1
- FYPIIMYXBCWBPQ-UHFFFAOYSA-N 2-amino-5-cyano-3-methylbenzoic acid Chemical compound CC1=CC(C#N)=CC(C(O)=O)=C1N FYPIIMYXBCWBPQ-UHFFFAOYSA-N 0.000 description 1
- RAMUASXTSSXCMB-UHFFFAOYSA-N 3-bromo-N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide Chemical compound C1CC1C(C)NC(=O)C1=CC(Cl)=CC(Br)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl RAMUASXTSSXCMB-UHFFFAOYSA-N 0.000 description 1
- YHOYYHYBFSYOSQ-UHFFFAOYSA-N 3-methylbenzoyl chloride Chemical compound CC1=CC=CC(C(Cl)=O)=C1 YHOYYHYBFSYOSQ-UHFFFAOYSA-N 0.000 description 1
- XUPBMMROJMAMOB-UHFFFAOYSA-N 5-bromo-2-(3-chloropyridin-2-yl)-n-[2,4-dichloro-6-(ethylcarbamoyl)phenyl]pyrazole-3-carboxamide Chemical compound CCNC(=O)C1=CC(Cl)=CC(Cl)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl XUPBMMROJMAMOB-UHFFFAOYSA-N 0.000 description 1
- ALGLHCFROQVWRL-UHFFFAOYSA-N 5-bromo-2-(3-chloropyridin-2-yl)pyrazole-3-carboxamide Chemical compound NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl ALGLHCFROQVWRL-UHFFFAOYSA-N 0.000 description 1
- IBSREHMXUMOFBB-JFUDTMANSA-N 5u8924t11h Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O3)C=C[C@H](C)[C@@H](C(C)C)O4)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 IBSREHMXUMOFBB-JFUDTMANSA-N 0.000 description 1
- 239000005660 Abamectin Substances 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 241000098289 Cnaphalocrocis medinalis Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- ONAJTUFTOLSKOU-UHFFFAOYSA-N NC(C1=CC(Br)=NN1C(C(Cl)=C1)=NC=C1Cl)=O Chemical compound NC(C1=CC(Br)=NN1C(C(Cl)=C1)=NC=C1Cl)=O ONAJTUFTOLSKOU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000346285 Ostrinia furnacalis Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229950008167 abamectin Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AIMMVWOEOZMVMS-UHFFFAOYSA-N cyclopropanecarboxamide Chemical compound NC(=O)C1CC1 AIMMVWOEOZMVMS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Insects & Arthropods (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a preparation method of chlorantraniliprole insecticide, which takes substituted 1- (pyridine-2-yl) -1H-pyrazole-5-carboxylic acid as a raw material, adds an organic amine catalyst, and sequentially performs an acyl chlorination reaction with phosgene, an amidation reaction with substituted anthranilic acid, an acyl chlorination reaction with phosgene and an amidation reaction with alkylamine or alkylamine hydrochloride in an organic solvent to obtain a target product, wherein the yield reaches 91.5-93.7%. The method realizes that the same solvent is used for completing multi-step reaction in one pot, avoids the complex operations of material transfer, solvent replacement and the like, and has the advantages of low cost, easy operation, less pollution, suitability for large-scale industrial production requirements and the like.
Description
Technical Field
The invention relates to the technical field of organic compound preparation, in particular to a preparation method of chlorantraniliprole insecticide.
Background
The 1-pyridyl pyrazole amide compound has broad spectrum activity and is an important component of bisamide insecticides (such as chlorantraniliprole, cyantraniliprole, tetrachloro-cyantraniliprole, cyclopropane carboxamide and the like). The bisamide insecticide is an insecticide product which is most concerned by the market after the neonicotinoid insecticide, and is also the insecticide product which is the fastest growing in recent years. The outstanding bisamide insecticide represents chlorantraniliprole, not only is one of four milestones (phenothrin, imidacloprid, abamectin and chlorantraniliprole) in the field of insecticide research and development, but also is a leaderboard champion for insecticide sale since 2014, wherein the annual sale amount of the chlorantraniliprole 2014 reaches 14.7 billion dollars, and the annual sale amount of the chlorantraniliprole 2019 reaches 17.5 billion dollars. Cyantraniliprole, test code: DPX-HGW86, also known as Cyazypyr. The o-formamido benzamide pesticide which is discovered and developed by DuPont in 2007 and first marketed in Argentina in 2012. Cyantraniliprole is a sister product of chlorantraniliprole, and has wider application range and wider insecticidal range compared with the chlorantraniliprole. The sales of cyantraniliprole is continuously increasing, and the sales of cyantraniliprole reaches $ 1.20 billion in 2019. Tetrachloro worm amide, test code: SYP-9080, discovered and developed by Shenyang chemical research institute in 2008, temporarily registered in China in 2013, and formally registered anthranilamide insecticides in China in 2017. The tetrachlorantraniliprole is the most economic bisamide insecticide and can be used for crops such as cabbage, rice, corn and the like to prevent and control pests with chewing mouthparts such as cnaphalocrocis medinalis, corn borers and the like. The sales of the tetrachlorantraniliprole are continuously increased and reach $ 0.30 hundred million in 2019. Cyprodinil, test code: IKI-3106, a anthranilamide insecticide which was first marketed in Korea in 2017, was discovered and developed by Shiyuan corporation in 2005. The sales of cyprodinil continue to increase, reaching $ 0.22 million in 2019.
The synthesis methods of chlorantraniliprole insecticides are reported more, for example, the synthesis method of chlorantraniliprole is as follows: wangyanjun et al [ pesticide 2010, 49(3): 170-5-propanoic acid 173] use 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carboxylic acid as raw material, add 5-chloro-3-methyl-2-aminobenzoic acid and acetonitrile, then cool down and drop 3-methylpyridine and acetonitrile solution of methylsulfonyl chloride in turn, add right amount of water after reaction, filter by suction to obtain yellow solid 6-chloro-2- (3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazol-5-yl) -8-methyl-4H-3, 1-benzoxazine-4-one. The compound is dissolved in acetonitrile, and 25% methylamine water solution is dripped to obtain white solid chlorantraniliprole with the total yield of 76.1%. The method is a common synthesis method of chlorantraniliprole, but has the disadvantages of low total yield, complex operation, large amount of three wastes and high production cost. For example, the synthesis method of the tetrachloro insect amide: plum bin and the like (modern pesticides 2014 (3): 17-20) take acetonitrile as a solvent, and 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carboxylic acid and 3, 5-dichloro-2-aminobenzoic acid are reacted under the action of methylsulfonyl chloride and triethylamine to obtain 2- [ 3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H-5-pyrazolyl ] -6, 8-dichloro-4H-benzo [ d ] [1,3] oxazin-4-one; the compound was then reacted with 30% aqueous methylamine in tetrahydrofuran to give the tetrachloro-worm-amide in 19.4% overall yield. The method has the advantages of low total yield, complex operation, large amount of three wastes and high production cost.
Related patents of the chlorantraniliprole insecticide will expire successively, and in order to break monopoly, reduce the use cost of the product and fully utilize the advantage of phosgene resources of enterprises, research on the synthesis process of the chlorantraniliprole insecticide is necessary, so that the product yield is improved, the production cost is reduced, the environmental pollution is reduced, and the enterprise competitiveness is enhanced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of the chlorantraniliprole insecticide, which has the advantages of low cost, easy operation, less pollution and suitability for large-scale industrial production requirements.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of chlorantraniliprole insecticide comprises the following steps:
the method comprises the steps of taking 1- (pyridine-2-yl) -1H-pyrazole-5-carboxylic acid substituted by a compound shown as a formula (VI) as a raw material, adding an organic amine catalyst, carrying out acyl chlorination reaction with phosgene in an organic solvent in sequence to obtain 1- (pyridine-2-yl) -1H-pyrazole-5-formyl chloride substituted by the compound shown as the formula (V), carrying out amidation reaction on the compound shown as the formula (V) and substituted anthranilic acid shown as the formula (IV) to obtain a compound shown as the formula (III), carrying out acyl chlorination reaction on the compound shown as the formula (III) and phosgene to obtain a compound shown as the formula (II), carrying out amidation reaction on the compound shown as the formula (II) and alkylamine or alkylamine hydrochloride to obtain a target product chlorantraniliprole insecticide shown as the formula (I), the reaction process is shown as the formula (1):
wherein: r 1 Is hydrogen or chlorine, R 2 Is methyl, chlorine or bromine, R 3 Is chlorine or cyano, R 4 Is hydrogen or chlorine, R is methyl, ethyl, propyl, isopropyl or 1-cyclopropylethyl.
In the above method for preparing chlorantraniliprole insecticide, preferably, the organic amine catalyst is one or more of N, N-dimethylformamide, N-dimethylacetamide, triethylamine, tri-N-butylamine, N-dimethylaniline, N-diethylaniline, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4, 6-trimethylpyridine and 2,3, 5-trimethylpyridine, and the mass of the organic amine catalyst is 0.1-1% of that of the compound represented by formula (VI).
Preferably, the organic solvent is one of toluene, chlorobenzene, xylene, o-dichlorobenzene, acetonitrile, tetrahydrofuran, 1, 4-dioxane, methyl isobutyl ketone and ethylene glycol dimethyl ether, and the mass of the organic solvent is 3-10 times that of the compound shown in the formula (VI).
In the preparation method of the chlorantraniliprole insecticide, preferably, the specific preparation process of the compound shown as the formula (V) is as follows: mixing the compound shown in the formula (VI), an organic amine catalyst and an organic solvent, heating to reflux, introducing phosgene until the compound shown in the formula (VI) completely reacts, stopping introducing the phosgene, preserving heat, then cooling, introducing nitrogen to blow away the residual phosgene and hydrogen chloride in the reaction solution, and obtaining the organic solution containing the compound shown in the formula (V).
Preferably, in the specific preparation process of the compound shown in the formula (V), the molar ratio of the compound shown in the formula (VI) to phosgene is 1: 1.05-1.5, the temperature of the acyl chlorination reaction is 66-179 ℃, and the time for introducing phosgene is 1-8 h.
The preparation method of the chlorantraniliprole pesticide is preferably characterized in that the compound shown in the formula (III) is prepared by the following specific steps: mixing the substituted anthranilic acid shown in the formula (IV) with an organic solution containing the compound shown in the formula (V), heating and refluxing to perform amidation reaction, and obtaining an organic solution containing the compound shown in the formula (III) after the reaction is finished.
Preferably, in the specific preparation process of the compound shown in the formula (III), the molar ratio of the substituted anthranilic acid shown in the formula (IV) to the compound shown in the formula (V) is 1: 1, the temperature of the amidation reaction is 66-179 ℃, and the time of the amidation reaction is 0.5-4 h.
In the preparation method of the chlorantraniliprole insecticide, preferably, the specific preparation process of the compound shown in the formula (II) is as follows: keeping the organic solution containing the compound shown in the formula (III) to reflux, introducing phosgene until the compound shown in the formula (III) completely reacts, stopping introducing the phosgene, preserving heat, cooling, introducing nitrogen to blow away the phosgene and hydrogen chloride remained in the reaction solution, and obtaining the organic solution containing the compound shown in the formula (II).
Preferably, in the specific preparation process of the compound shown in the formula (II), the molar ratio of the compound shown in the formula (III) to phosgene is 1: 1.05-1.5, the temperature of the acyl chlorination reaction is 66-179 ℃, and the time for introducing phosgene is 1-8 h.
In the preparation method of the chlorantraniliprole insecticide, preferably, the specific preparation process of the target product shown in the formula (I) is as follows: mixing an organic solution containing the compound shown in the formula (II) with alkylamine or alkylamine hydrochloride, heating and refluxing for amidation reaction, removing 65-85% of solvent after the reaction is finished, cooling, adding water, continuously stirring, filtering and drying to obtain the target product shown in the formula (I).
Preferably, the alkylamine is methylamine, ethylamine, propylamine, isopropylamine or 1-cyclopropylethylamine, the alkylamine hydrochloride is methylamine hydrochloride, ethylamine hydrochloride, propylamine hydrochloride, isopropylamine hydrochloride or 1-cyclopropylethylamine hydrochloride, the molar ratio of the compound shown in the formula (II) to the alkylamine or alkylamine hydrochloride is 1: 1-1.5, the temperature of the amidation reaction is 66-179 ℃, the time of the amidation reaction is 0.5-4 h, and the mass of water is 0.2-0.5 times of the mass of the compound shown in the formula (VI).
In the invention, the phosgene is stopped and then the temperature is maintained, the temperature is usually maintained for 0.5h, but the temperature is not limited to the above, on one hand, the temperature can be maintained for the time of sampling and analyzing the reaction progress, and on the other hand, part of excessive phosgene and generated hydrogen chloride gas can be driven away.
Compared with the prior art, the invention has the advantages that:
the invention provides a brand new preparation route of the chlorantraniliprole insecticide, realizes that the same solvent is used for completing multi-step reaction by a one-pot method, obviously reduces the quantity of raw materials, effectively avoids complicated operations such as complex post-treatment, material transfer and the like, has good single-step reaction selectivity and simple operation, has less three wastes and is beneficial to industrial production. The preparation method of the invention has high product yield, and the total yield reaches 91.5-93.7%.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
the preparation method of the chlorantraniliprole insecticide comprises the following steps:
(1) synthesis of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride
308.7g (98 percent, 1mol) of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 3.08g N, N-dimethylacetamide and 3087g of tetrahydrofuran are mixed and heated to 66 ℃ for reflux, 115.5g (90 percent, 1.05mol) of phosgene is introduced within 8H, the phosgene is stopped, the reaction is kept at a constant temperature for 0.5H, the temperature is reduced, nitrogen is introduced to blow away the phosgene and hydrogen chloride remained in the reaction solution, and the tetrahydrofuran solution of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride is obtained, wherein the amount of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carbonyl chloride is 1 mol.
(2) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-methylbenzoic acid
189.4g (98%, 1mol) of 2-amino-5-chloro-3-methylbenzoic acid was mixed with the above tetrahydrofuran solution of 3-bromo-1- (3-chloropyridin-2-pyridyl) -1H-pyrazole-5-carbonyl chloride, and then heated to 66 ℃ for reflux for 4 hours to give a tetrahydrofuran solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-methylbenzoic acid, wherein the amount of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-carboxamide) -5-chloro-3-methylbenzoic acid is 1 mol.
(3) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-methylbenzoyl chloride
Keeping the tetrahydrofuran solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-chloro-3-methylbenzoic acid at a reflux temperature of 66 ℃, introducing 115.5g (90 percent and 1.05mol) of phosgene within 8H, stopping introducing the phosgene, then carrying out heat preservation reaction for 0.5H, reducing the temperature, introducing nitrogen to blow off residual phosgene and hydrogen chloride in the reaction solution, and obtaining the tetrahydrofuran solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-chloro-3-methylbenzoyl chloride, wherein 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-chloro-3-methylbenzoyl chloride The amount of 3-methylbenzoyl chloride is 1 mol.
(4) Synthesis of chlorantraniliprole
103.34g (98%, 1.5mol) methylamine hydrochloride is mixed with the tetrahydrofuran solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-carboxamide) -5-chloro-3-methylbenzoyl chloride, heated to 66 ℃ for refluxing for 4H, 2623.95g tetrahydrofuran is extracted and cooled, 154.35g water is added, and stirring, filtering and drying are carried out to obtain 452.03g white solid with the content of 97.8% and the yield of 91.5%. Melting point 209.1 deg.C-210.2 deg.C. LC-MS (M/z) 484.2(M + H) + )； 1 H NMR(CDCl 3 ，300MHz)δ:2.18(s，3H，Ph-CH 3 )，2.95(s，3H，NH-CH 3 )，6.17(br，1H，NH)，6.84(s，1H，Pyrazole H)，7.24(dd，J＝8.1Hz，J＝4.5Hz，1H，Py H)，7.33(d，J＝1.8Hz，1H，Ph H)，7.37(d，J＝1.8Hz，1H，Ph H)，7.86(d，J＝8.1Hz，1H，Py H)，8.45(d，J＝4.5Hz，1H，Py H)，10.04(br，1H，NH)。
Example 2:
the preparation method of the chlorantraniliprole insecticide comprises the following steps:
(1) synthesis of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride
308.7g (98 percent, 1mol) of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 1g of triethylamine and 1852.2g of xylene are mixed and heated to 140 ℃ for reflux, 165g (90 percent, 1.5mol) of phosgene is introduced within 2H, the reaction is kept at the temperature for 0.5H after the phosgene introduction is stopped, the temperature is reduced, nitrogen is introduced to blow off the phosgene and hydrogen chloride remained in the reaction liquid, and the xylene solution of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride is obtained, wherein the amount of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carbonyl chloride is 1 mol.
(2) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-cyano-3-methylbenzoic acid
179.78g (98%, 1mol) of 2-amino-5-cyano-3-methylbenzoic acid was mixed with the xylene solution of the above-mentioned 3-bromo-1- (3-chloropyridin-2-pyridyl) -1H-pyrazole-5-carbonyl chloride, and then heated to 140 ℃ for reflux for 1H to give a xylene solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-cyano-3-methylbenzoic acid, wherein the amount of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-carboxamide) -5-cyano-3-methylbenzoic acid is 1 mol.
(3) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-cyano-3-methylbenzoyl chloride
Keeping the xylene solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-cyano-3-methylbenzoic acid at 140 ℃ for reflux, introducing 115.5g (90 percent and 1.05mol) of phosgene within 2H, keeping the temperature for reaction for 0.5H after stopping introducing the phosgene, reducing the temperature, introducing nitrogen to blow off residual phosgene and hydrogen chloride in the reaction solution, and obtaining the xylene solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-cyano-3-methylbenzoyl chloride, wherein 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-cyano-3-methylbenzoyl chloride The amount of the (E) -3-methylbenzoyl chloride was 1 mol.
(4) Synthesis of cyantraniliprole
103.34g (98%, 1.5mol) methylamine hydrochloride is mixed with the xylene solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-carboxamide) -5-cyano-3-methylbenzoyl chloride, heated to 140 ℃ for refluxing for 1H, 1500g xylene is extracted and cooled, 154.35g water is added, stirring is carried out, filtering is carried out, and a filter cake is dried to obtain 432.64g white solid with the content of 98.6% and the yield of 92.6%. Melting point 170.3 deg.C-171.6 deg.C. LC-MS (M/z):475(M + H) + )； 1 H NMR(CDCl 3 ，300MHz)δ:2.16(s，3H，Ph-CH 3 )，2.95(s，3H，NH-CH 3 )，6.27(br，1H，NH)，7.14(s，1H，Pyrazole H)，7.24(dd，J＝8.1Hz，J＝4.5Hz，1H，Py H)，7.33(d，J＝1.8Hz，1H，Ph H)，7.37(d，J＝1.8Hz，1H，Ph H)，7.88(d，J＝8.1Hz，1H，Py H)，8.46(d，J＝4.5Hz，1H，Py H)，10.08(br，1H，NH)。
Example 3:
the preparation method of the chlorantraniliprole insecticide comprises the following steps:
(1) synthesis of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride
308.7g (98 percent, 1mol) of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 1g of pyridine and 1852.2g of methyl isobutyl ketone are mixed and heated to 116 ℃ for reflux, 165g (90 percent, 1.5mol) of phosgene is introduced within 2H, the reaction is kept at the temperature for 0.5H after the phosgene introduction is stopped, the temperature is reduced, nitrogen is introduced to blow off the residual phosgene and hydrogen chloride in the reaction solution, so that the methyl isobutyl ketone solution of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride is obtained, wherein the amount of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carbonyl chloride is 1 mol.
(2) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-bromobenzoic acid
255.59g (98%, 1mol) of 2-amino-3-bromo-5-chlorobenzoic acid was mixed with a methyl isobutyl ketone solution of the above-mentioned 3-bromo-1- (3-chloropyridin-2-pyridyl) -1H-pyrazole-5-carbonyl chloride and heated to 116 ℃ for refluxing for 1 hour to give a methyl isobutyl ketone solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-bromobenzoic acid, wherein the amount of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-carboxamide) -5-chloro-3-bromobenzoic acid is 1 mol.
(3) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-bromobenzoyl chloride
Keeping the methyl isobutyl ketone solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-chloro-3-bromobenzoic acid to reflux at 116 ℃, introducing 115.5g (90 percent and 1.05mol) of phosgene within 2H, stopping introducing the phosgene, then carrying out heat preservation reaction for 0.5H, reducing the temperature, introducing nitrogen to blow off residual phosgene and hydrogen chloride in the reaction solution, and obtaining the methyl isobutyl ketone solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-chloro-3-bromobenzoic acid chloride, wherein the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H pyrazole-5-formamide) -5-bromobenzoic acid The amount of-chloro-3-bromobenzoyl chloride is 1 mol.
(4) Synthesis of cyclic bromoantraniliprole
86.89g (98%, 1mol) of 1-cyclopropylethylamine was mixed with the methyl isobutyl ketone solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -5-chloro-3-bromobenzoyl chloride and heated to 116 ℃ for reflux for 1H, 1500g of methyl isobutyl ketone was taken and cooled, 61.74g of water was added, stirring was carried out,Filtration and drying to obtain 572g of white solid with the content of 98 percent and the yield of 93.1 percent. Melting point 235.6-236.8 deg.C. LC-MS (M/z):603.9(M + H) + )； 1 H NMR(CDCl 3 ，300MHz)δ:0.25～0.75(m，4H)，1.16～1.35(m，4H)，3.37～3.39(m，1H)，7.12(s，1H，Pyrazole H)，7.27(d，J＝4.5Hz，1H，Py H)，7.33(d，J＝1.8Hz，1H，Ph H)，7.37(d，J＝1.8Hz，1H，Ph H)，8.47(d，J＝4.5Hz，1H，Py H)，8.441(br，1H，NH)，10.10(br，1H，NH)。
Example 4:
the preparation method of the chlorantraniliprole insecticide comprises the following steps:
(1) synthesis of 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carbonyl chloride
343.83g (98%, 1mol) of 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carboxylic acid, 1g N, N-dimethylaniline and 1852.2g of o-dichlorobenzene are mixed, heated to 179 ℃ for reflux, 165g (90%, 1.5mol) of phosgene is introduced within 1H, the reaction is kept at the temperature for 0.5H after the phosgene introduction is stopped, the temperature is reduced, nitrogen is introduced to blow off the phosgene and hydrogen chloride which remain in the reaction solution, and the o-dichlorobenzene solution of 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carbonyl chloride is obtained, wherein the amount of 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carbonyl chloride is 1 mol.
(2) Synthesis of 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoic acid
210.22g (98%, 1mol) of 3, 5-dichloro-2-aminobenzoic acid was mixed with the o-dichlorobenzene solution of the above-mentioned 1- (3, 5-dichloropyridin-2-yl) -3-bromo-1H-pyrazole-5-carbonyl chloride, and then heated to 179 ℃ for refluxing for 0.5H to obtain an o-dichlorobenzene solution of 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoic acid, wherein the amount of 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoic acid is 1 mol.
(3) Synthesis of 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoyl chloride
Keeping the o-dichlorobenzene solution of the 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H pyrazole-5-formamide) -3, 5-dichlorobenzoic acid at 179 ℃ for reflux, introducing 165g (90 percent, 1.5mol) of phosgene within 1H, stopping introducing the phosgene, then carrying out heat preservation reaction for 0.5H, reducing the temperature, introducing nitrogen to blow off the residual phosgene and hydrogen chloride in the reaction solution, thus obtaining the o-dichlorobenzene solution of 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H pyrazole-5-formamide) -3, 5-dichlorobenzoyl chloride, wherein 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H pyrazole-5-formamide) -3, the amount of 5-dichlorobenzoyl chloride was 1 mol.
(4) Synthesis of tetrachloro worm amide
103.34g (98%, 1.5mol) of methylamine hydrochloride is mixed with the o-dichlorobenzene solution of the 2- (3-bromo-1- (3, 5-dichloropyridin-2-yl) -1H pyrazole-5-formamide) -3, 5-dichlorobenzoyl chloride, the mixture is heated to 179 ℃ for refluxing for 0.5H, 1500g of o-dichlorobenzene is taken out and cooled, 103.15g of water is added, stirring, filtering and drying are carried out, 512.62g of white solid with the content of 97.5% is obtained, and the yield of 92.9%. Melting point 176.6 deg.C-177.8 deg.C. LC-MS (M/z):539(M + H) + )； 1 H NMR(CDCl 3 ，300MHz)δ:2.89(s，3H，NH-CH 3 )，6.37(br，1H，NH)，6.98(s，1H，Pyrazole H)，7.24(d，J＝4.5Hz，1H，Py H)，7.33(d，J＝1.8Hz，1H，Ph H)，7.37(d，J＝1.8Hz，1H，Ph H)，8.41(d，J＝4.5Hz，1H，Py H)，10.01(br，1H，NH)。
Example 5:
the preparation method of the chlorantraniliprole insecticide comprises the following steps:
(1) synthesis of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride
308.7g (98 percent, 1mol) of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 0.31g N, N-dimethylformamide and 926.1g of toluene are mixed and heated to 110 ℃ for reflux, 115.5g (90 percent, 1.05mol) of phosgene is introduced within 2H, the reaction is kept at the temperature for 0.5H after the phosgene introduction is stopped, the temperature is reduced, nitrogen is introduced to blow away the phosgene and hydrogen chloride remained in the reaction solution, and the toluene solution of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride is obtained, wherein the amount of 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-carbonyl chloride is 1 mol.
(2) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoic acid
220.22g (98%, 1mol) of 3, 5-dichloro-2-aminobenzoic acid and the toluene solution of the 3-bromo-1- (3-chloropyridine-2-pyridyl) -1H-pyrazole-5-formyl chloride are mixed and heated to 110 ℃ for reaction for 1H to obtain the toluene solution of 2- (3-bromo-1- (3-chloropyridine-2-yl) -1H-pyrazole-5-formamide) -3, 5-dichlorobenzoic acid, wherein the amount of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoic acid is 1 mol.
(3) Synthesis of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoyl chloride
Keeping the toluene solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide) -3, 5-dichlorobenzoic acid at a reflux temperature of 110 ℃, introducing 115.5g (90 percent and 1.05mol) of phosgene within 2H, stopping introducing the phosgene, then carrying out heat preservation reaction for 0.5H, reducing the temperature, introducing nitrogen to blow off the residual phosgene and hydrogen chloride in the reaction solution, obtaining the toluene solution of 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide) -3, 5-dichlorobenzoyl chloride, wherein 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide) -3, the amount of 5-dichlorobenzoyl chloride was 1 mol.
(4) Synthesis of 3-bromo-1- (3-chloropyridin-2-yl) -N- (2, 4-dichloro-6- (ethylcarbamoyl) phenyl) -1H-pyrazole-5-carboxamide
83.2g (98%, 1mol) of ethylamine hydrochloride and the toluene solution of the 2- (3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide) -3, 5-dichlorobenzoyl chloride are mixed, heated to 110 ℃ and refluxed for 1H, 602g of toluene is extracted and cooled, 62g of water is added, and 494.37g of white solid with the content of 98.1% and the yield of 93.7% is obtained after stirring, filtering and drying. Melting point 227.1 ℃ to 228.2 ℃. LC-MS (M/z) 518.6(M + H) + )； 1 H NMR(CDCl 3 ，300MHz)δ:1.23(t，J＝7.2Hz，3H，CH 3 ),3.28～3.34(m，2H，CH 2 )，6.17(br，1H，NH)，6.84(s，1H，Pyrazole H)，7.34(dd，J＝8.1Hz，J＝4.5Hz，1H，Py H)，7.36(d，J＝1.8Hz，1H，Ph H)，7.54(d，J＝1.8Hz，1H，Ph H)，7.87(d，J＝8.1Hz，1H，Py H)，8.42(d，J＝4.5Hz，1H，Py H)，10.06(br，1H，NH)。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. A preparation method of chlorantraniliprole insecticide is characterized by comprising the following steps:
the method comprises the steps of taking 1- (pyridine-2-yl) -1H-pyrazole-5-carboxylic acid substituted by a compound shown as a formula (VI) as a raw material, adding an organic amine catalyst, carrying out acyl chlorination reaction with phosgene in an organic solvent in sequence to obtain 1- (pyridine-2-yl) -1H-pyrazole-5-formyl chloride substituted by the compound shown as the formula (V), carrying out amidation reaction on the compound shown as the formula (V) and substituted anthranilic acid shown as the formula (IV) to obtain a compound shown as the formula (III), carrying out acyl chlorination reaction on the compound shown as the formula (III) and phosgene to obtain a compound shown as the formula (II), carrying out amidation reaction on the compound shown as the formula (II) and alkylamine or alkylamine hydrochloride to obtain a target product chlorantraniliprole insecticide shown as the formula (I), the reaction process is shown as formula (1):
wherein: r is 1 Is hydrogen or chlorine, R 2 Is methyl, chlorine or bromine, R 3 Is chlorine or cyano, R 4 Is hydrogen or chlorine, R is methyl, ethyl, propyl, isopropyl or 1-cyclopropylethyl.
2. The preparation method of the chlorantraniliprole insecticide according to claim 1, wherein the organic amine catalyst is one or more of N, N-dimethylformamide, N-dimethylacetamide, triethylamine, tri-N-butylamine, N-dimethylaniline, N-diethylaniline, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4, 6-trimethylpyridine and 2,3, 5-trimethylpyridine, and the mass of the organic amine catalyst is 0.1-1% of that of the compound shown in formula (VI).
3. The preparation method of the chlorantraniliprole insecticide according to claim 1, wherein the organic solvent is one of toluene, chlorobenzene, xylene, o-dichlorobenzene, acetonitrile, tetrahydrofuran, 1, 4-dioxane, methyl isobutyl ketone and ethylene glycol dimethyl ether, and the mass of the organic solvent is 3-10 times that of the compound shown in the formula (VI).
4. The preparation method of the chlorantraniliprole insecticide according to any one of claims 1 to 3, wherein the compound represented by the formula (V) is prepared by the following specific steps: mixing a compound shown in a formula (VI), an organic amine catalyst and an organic solvent, heating until reflux, introducing phosgene until the compound shown in the formula (VI) completely reacts, stopping introducing the phosgene, preserving heat, cooling, introducing nitrogen to blow away phosgene and hydrogen chloride remained in a reaction solution, and obtaining an organic solution containing the compound shown in the formula (V).
5. The preparation method of the chlorantraniliprole insecticide according to claim 4, wherein in the specific preparation process of the compound shown in the formula (V), the molar ratio of the compound shown in the formula (VI) to phosgene is 1: 1.05-1.5, the temperature of the acyl chlorination reaction is 66-179 ℃, and the time for introducing phosgene is 1-8 h.
6. The preparation method of the chlorantraniliprole insecticide according to any one of claims 1 to 3, wherein the compound represented by the formula (III) is prepared by the following specific steps: mixing the substituted anthranilic acid shown in the formula (IV) with an organic solution containing the compound shown in the formula (V), heating and refluxing to perform amidation reaction, and obtaining an organic solution containing the compound shown in the formula (III) after the reaction is finished.
7. The preparation method of the chlorantraniliprole insecticide as claimed in claim 6, wherein in the specific preparation process of the compound shown in formula (III), the molar ratio of the substituted anthranilic acid shown in formula (IV) to the compound shown in formula (V) is 1: 1, the temperature of the amidation reaction is 66-179 ℃, and the time of the amidation reaction is 0.5-4 h.
8. The preparation method of the chlorantraniliprole insecticide according to any one of claims 1 to 3, wherein the compound represented by the formula (II) is prepared by the following specific steps: keeping the organic solution containing the compound shown in the formula (III) to reflux, introducing phosgene until the compound shown in the formula (III) completely reacts, stopping introducing the phosgene, preserving heat, cooling, introducing nitrogen to blow away the phosgene and hydrogen chloride remained in the reaction solution, and obtaining the organic solution containing the compound shown in the formula (II).
9. The preparation method of the chlorantraniliprole insecticide according to claim 8, wherein in the specific preparation process of the compound shown in the formula (II), the molar ratio of the compound shown in the formula (III) to phosgene is 1: 1.05-1.5, the temperature of the acyl chlorination reaction is 66-179 ℃, and the time for introducing phosgene is 1-8 h.
10. The preparation method of the chlorantraniliprole insecticide according to any one of claims 1 to 3, wherein the target product shown in the formula (I) is prepared by the following specific steps: mixing an organic solution containing a compound shown in a formula (II) with alkylamine or alkylamine hydrochloride, heating and refluxing for amidation reaction, removing 65-85% of solvent after the reaction is finished, cooling, adding water, continuously stirring, filtering and drying to obtain a target product shown in a formula (I);
the alkylamine is methylamine, ethylamine, propylamine, isopropylamine or 1-cyclopropylethylamine, the alkylamine hydrochloride is methylamine hydrochloride, ethylamine hydrochloride, propylamine hydrochloride, isopropylamine hydrochloride or 1-cyclopropylethylamine hydrochloride, the molar ratio of the compound shown in the formula (II) to the alkylamine or alkylamine hydrochloride is 1: 1-1.5, the temperature of the amidation reaction is 66-179 ℃, the time of the amidation reaction is 0.5-4 h, and the mass of water is 0.2-0.5 times of the mass of the compound shown in the formula (VI).
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