CN114057687B - 吡啶基吡唑烷酮羧酸酯类化合物的制备方法 - Google Patents
吡啶基吡唑烷酮羧酸酯类化合物的制备方法 Download PDFInfo
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- CN114057687B CN114057687B CN202010777963.8A CN202010777963A CN114057687B CN 114057687 B CN114057687 B CN 114057687B CN 202010777963 A CN202010777963 A CN 202010777963A CN 114057687 B CN114057687 B CN 114057687B
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- China
- Prior art keywords
- sodium
- catalyst
- ester compound
- hexafluoroacetylacetonate
- pyridylpyrazolidone
- Prior art date
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- -1 pyridyl pyrazolone carboxylic ester compound Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 150000005690 diesters Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- NWELCUKYUCBVKK-UHFFFAOYSA-N pyridin-2-ylhydrazine Chemical compound NNC1=CC=CC=N1 NWELCUKYUCBVKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims description 6
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 claims description 5
- CVZIHXRHSDYALS-UHFFFAOYSA-N 1-fluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)CF CVZIHXRHSDYALS-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-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
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- PMXKWEPBGALTJL-UHFFFAOYSA-N [K].CCCO Chemical compound [K].CCCO PMXKWEPBGALTJL-UHFFFAOYSA-N 0.000 claims description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 2
- SPUCFJYSOOULRC-UHFFFAOYSA-N [Na].CC(C)CO Chemical compound [Na].CC(C)CO SPUCFJYSOOULRC-UHFFFAOYSA-N 0.000 claims description 2
- RZBSVYZMOJXQJU-UHFFFAOYSA-N [Na].CCCO Chemical compound [Na].CCCO RZBSVYZMOJXQJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- TWEGKFXBDXYJIU-UHFFFAOYSA-M sodium;2-methylpropanoate Chemical compound [Na+].CC(C)C([O-])=O TWEGKFXBDXYJIU-UHFFFAOYSA-M 0.000 claims description 2
- VSCLJRSWEGZJNY-UHFFFAOYSA-N sodium;butan-2-olate Chemical compound [Na+].CCC(C)[O-] VSCLJRSWEGZJNY-UHFFFAOYSA-N 0.000 claims description 2
- WVROFDYCUUILSJ-UHFFFAOYSA-N sodium;pentan-1-olate Chemical compound [Na+].CCCCC[O-] WVROFDYCUUILSJ-UHFFFAOYSA-N 0.000 claims description 2
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 claims description 2
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000575 pesticide Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- XAYCTBDPZIKHCW-UHFFFAOYSA-N (3-chloropyridin-2-yl)hydrazine Chemical compound NNC1=NC=CC=C1Cl XAYCTBDPZIKHCW-UHFFFAOYSA-N 0.000 description 5
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 5
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- GWGIBEMOOVJUPI-UHFFFAOYSA-N ethyl 2-(3-chloropyridin-2-yl)-5-oxopyrazolidine-3-carboxylate Chemical compound CCOC(=O)C1CC(=O)NN1C1=NC=CC=C1Cl GWGIBEMOOVJUPI-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000749 insecticidal effect Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 2
- 239000005889 Cyantraniliprole Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical group [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- JHHUAXCALQXWPV-UHFFFAOYSA-N 2-amino-1-(2-amino-5-chloro-3-methylphenyl)ethanone Chemical compound NC1=C(C(=O)CN)C=C(C=C1C)Cl JHHUAXCALQXWPV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 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
- YANGEQGVCHDGGT-UHFFFAOYSA-N 5-bromo-2-pyridin-2-ylpyrazole-3-carboxylic acid Chemical compound N1=C(C=CC=C1)N1N=C(C=C1C(=O)O)Br YANGEQGVCHDGGT-UHFFFAOYSA-N 0.000 description 1
- OIIUJYQDYUAOJU-UHFFFAOYSA-N 5-bromo-n-(2-carbamoyl-4,6-dichlorophenyl)-2-(3,5-dichloropyridin-2-yl)pyrazole-3-carboxamide Chemical compound NC(=O)C1=CC(Cl)=CC(Cl)=C1NC(=O)C1=CC(Br)=NN1C1=NC=C(Cl)C=C1Cl OIIUJYQDYUAOJU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005886 Chlorantraniliprole Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229940045799 anthracyclines and related substance Drugs 0.000 description 1
- 150000003936 benzamides Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 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 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- ZLPMCQAPSAWTMK-UHFFFAOYSA-L copper;triphenylphosphane;diiodide Chemical compound [Cu+2].[I-].[I-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZLPMCQAPSAWTMK-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000006450 cyclopropyl cyclopropyl group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
Abstract
本发明属于有机合成领域,具体地涉及一种吡啶基吡唑烷酮羧酸酯类化合物的制备方法。反应式如下,
Description
技术领域
本发明属于有机合成领域,具体地涉及一种吡啶基吡唑烷酮羧酸酯类化合物的制备方法。
背景技术
苯甲酰胺类化合物是一类高效、安全的新型杀虫剂。其中3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(通用名为国际chlorantraniliprole)、3-溴-N-(2-甲基-4-氰基-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(国际通用名为cyantraniliprole)具有高的杀虫活性,杜邦公司已将其开发为杀虫剂。石原产业株式会社正在开发的双酰胺类化合物3-溴-N-(2-氯-4-溴-6-((1-环丙基乙基)酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺的(国际通用名为cyclaniliprole),具有广谱的杀虫活性。沈阳化工研究院发现了具有高杀虫活性的3-溴-N-(2,4-二氯-6-(甲氨酰基)苯基)-1-(3,5-二氯-2-吡啶基)-1H-吡唑-5-甲酰胺(国际通用名为tetrachlorantraniliprole),也已经开发为杀虫剂。
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸酯是合成chlorantraniliprole、cyantraniliprole、cyclaniliprole的共用关键中间体,WO2004011453中公开了1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸酯的合成,由肼基吡啶与马来酸二酯在回流温度下反应制得,反应收率仅为55%。专利CN106928183中,公开了有机膦配体和金属酮、镍的盐形成配合物催化合成吡啶基吡唑烷酮羧酸酯类化合物,收率达到79%。
南开大学徐凤波等报道了使用结构复杂的含蒽环的双胺配合物A作为催化剂合成1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的方法(参考文献:农药研究与应用.14(2),14-15,2009),收率为70%。催化剂具体结构如下:
但随着实际需求技术人员不断研究开发新的、更为先进合理的吡啶基吡唑烷酮羧酸酯类化合物制备方法,以期获得质量更优、价格更低的苯甲酰胺类杀虫剂。
发明内容
本发明的目的在于提供一种更为简便、更加高效地吡啶基吡唑烷酮羧酸酯类化合物的制备方法。
为实现上述目的,本发明采用的技术方案为:
一种吡啶基吡唑烷酮羧酸酯类化合物的制备方法,反应式如下:
式中:R1选自H或Cl;R2选自C1-C6烷基、C3-C6环烷基、苄基、卤素取代的苄基或C1-C4烷基取代的苄基;
肼基吡啶(II)在碱性条件下、在适宜的溶剂中,通过催化剂的作用与马来酸二酯(III),在0℃至所用溶剂的沸点范围内反应制得吡啶基吡唑烷酮羧酸酯类化合物(I);其中,催化剂为乙酰丙酮或氟代乙酰丙酮与铜、钴或镍形成的配合物。
所述催化剂为乙酰丙酮铜,三氟乙酰丙酮铜,六氟乙酰丙酮铜,乙酰丙酮钴,三氟乙酰丙酮钴,六氟乙酰丙酮钴,乙酰丙酮镍,三氟乙酰丙酮镍或六氟乙酰丙酮镍。
所述肼基吡啶、碱、马来酸二酯和催化剂的摩尔配比为1:1-2:1-5:0.00001-0.01。
所述适宜的溶剂选自甲苯,氯苯,羧酸酯类,烷基醇类,醚类或极性非质子性溶剂;
所述碱选自碱金属的氢化物、碱金属的氨化物或烷基醇化物。
所述碱金属的氢化物为氢化锂、氢化钠或氢化钾;碱金属的氨化物为氨基锂、氨基钠或氨基钾;烷基醇化物为甲醇钠,乙醇钠,丙醇钠,丁醇钠,戊醇钠,异丙醇钠,异丁醇钠,仲丁醇钠,叔丁醇钠,甲醇钾、乙醇钾,丙醇钾或叔丁醇钾;碱金属选自锂,钠或钾;
所述羧酸酯类为乙酸酯,富马酸二酯;烷基醇类为甲醇,乙醇,丙醇,丁醇,戊醇,异丙醇,异丁醇,仲丁醇或叔丁醇;醚类为四氢呋喃,2-甲基四氢呋喃,二氧六环;极性非质子性溶剂为乙腈,N,N-二甲基甲酰胺,N,N-二甲基乙酰胺或二甲基亚砜。
所述肼基吡啶(II)在碱性条件下、在适宜的溶剂中,通过催化剂的作用与马来酸二酯(III),在20-50℃下反应制得吡啶基吡唑烷酮羧酸酯类化合物(I),
其中,肼基吡啶、碱、马来酸二酯和催化剂的摩尔配比为1:1.2-1.5:1.5-2:0.0001-0.001;催化剂选自三氟乙酰丙酮铜,六氟乙酰丙酮铜,三氟乙酰丙酮钴,六氟乙酰丙酮钴,三氟乙酰丙酮镍或六氟乙酰丙酮镍。
所述催化剂选自六氟乙酰丙酮铜或六氟乙酰丙酮钴。
所述碱选自甲醇钠,乙醇钠,丙醇钠,丁醇钠,戊醇钠,异丙醇钠,异丁醇钠,另丁醇钠或叔丁醇钠;所述适宜的溶剂选自甲醇,乙醇,丙醇,丁醇,戊醇,异丙醇,异丁醇,另丁醇或叔丁醇。
更进一步的说,所述碱选自乙醇钠;所述适宜的溶剂选自乙醇。
上面给出的合成方法及各通式化合物中基团的定义中,汇集所用术语一般定义如下:
烷基是指直链或支链形式,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基等基团。环烷基是指包括环状链形式,例如环丙基、环丁基、环戊基、环己基、甲基环丙基、环丙基环丙基等基团。烯基是指直链或支链烯基,如1-丙烯基、2-丙烯基和不同的丁烯基等。炔基是指直链或支链炔烃,如1-丙炔基、2-丙炔基和不同的丁炔基等。卤素是指氟、氯、溴、碘。
本发明所具有特点:
本发明采用结构简单的乙酰丙酮或氟代乙酰丙酮与金属铜、钴、镍形成的配合物,如乙酰丙酮铜、乙酰丙酮镍,作为合成吡啶基吡唑烷酮羧酸酯的高效催化剂。该类催化剂可以高效催化吡啶基肼和马来酸二酯的加成反应,提高了反应的选择性,有效抑制了未合环副产通式(IV)类化合物,进而明显提高了制备吡啶基吡唑烷酮羧酸酯的收率,从而完成了本发明,并且本发明制备过程后处理简单;此外,本发明的催化剂结构更加简单,合成更容易,价格更低廉,因此,本发明的催化剂更易于在工业化生产中的应用。
具体实施方式
下面通过列举实施例来对本发明进行更详细的说明吡啶基吡唑烷酮羧酸酯类化合物制备方法,但并不意味着限制本发明。
实施例1
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
在1000毫升反应瓶内加入500毫升无水乙醇和乙醇钠(32.9克,0.483摩尔),3-氯-2-肼基吡啶(51.3克,98%,0.35摩尔),再加入催化剂三氟乙酰丙酮铜(0.05克)混合物加热至35℃,滴加马来酸二乙酯(67.5克,0.385摩尔)。保持此温度4h,而后将反应混合物用冰乙酸(30克)中和。混合物用500毫升水稀释,冷至室温,有固体析出。过滤收集固体,用2×50毫升40%的乙醇水溶液洗涤。干燥后得1-(3-氯-2-吡啶基)-3-吡唑烷酮-5-甲酸乙酯橙色固体80.8克,外标法定量分析其含量为98%,收率84%。1H NMR(300MHz,DMSO):8.289-8.269(q,1H),7.956-7.190(q,1H),7.231-7.190(q,1H),4.862-4.816(q,1H),4.236-4.165(q,2H),2.967-2.879(q,1H),2.396-2.336(q,1H),1.250-1.202(t,3H)。
实施例2
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
在1000毫升反应瓶内加入500毫升无水乙醇和乙醇钠(32.9克,0.483摩尔),3-氯-2-肼基吡啶(51.3克,98%,0.35摩尔),再加入催化剂三氟乙酰丙酮钴(0.05克)混合物加热至40℃,滴加马来酸二乙酯(67.5克,0.385摩尔)。保持此温度4h,而后将反应混合物用冰乙酸(30克)中和。混合物用500毫升水稀释,冷至室温,有固体析出。过滤收集固体,用2×50毫升40%的乙醇水溶液洗涤。干燥后得1-(3-氯-2-吡啶基)-3-吡唑烷酮-5-甲酸乙酯橙色固体81.8克,外标法定量分析其含量为98%,收率85%。1H NMR(300MHz,DMSO):8.289-8.269(q,1H),7.956-7.190(q,1H),7.231-7.190(q,1H),4.862-4.816(q,1H),4.236-4.165(q,2H),2.967-2.879(q,1H),2.396-2.336(q,1H),1.250-1.202(t,3H)。
实施例3
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
在1000毫升反应瓶内加入500毫升无水异丙醇和异丙醇钠(40.4克,0.483摩尔),3-氯-2-肼基吡啶(51,。36克,98%,0.35摩尔),再加入催化剂六氟乙酰丙酮铜(0.07克)混合物加热至45℃,滴加马来酸二乙酯(67.5克,0.385摩尔)。保持此温度3h,而后将反应混合物用冰乙酸(30克)中和。混合物用500毫升水稀释,冷至室温,有固体析出。过滤收集固体,用2×50毫升40%的乙醇水溶液洗涤。干燥后得1-(3-氯-2-吡啶基)-3-吡唑烷酮-5-甲酸乙酯橙色固体83.7克,外标法定量分析其含量为98%,收率87%。1H NMR(300MHz,DMSO):8.289-8.269(q,1H),7.956-7.190(q,1H),7.231-7.190(q,1H),4.862-4.816(q,1H),4.236-4.165(q,2H),2.967-2.879(q,1H),2.396-2.336(q,1H),1.250-1.202(t,3H)。
实施例4
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
在1000毫升反应瓶内加入500毫升无水乙醇和乙醇钠(32.9克,0.483摩尔),3-氯-2-肼基吡啶(50.6克,98%,0.35摩尔),再加入催化剂六氟乙酰丙酮镍(0.07克)混合物加热至40℃,滴加马来酸二乙酯(67.5克,0.385摩尔)。保持此温度4h,而后将反应混合物用冰乙酸(30克)中和。混合物用500毫升水稀释,冷至室温,有固体析出。过滤收集固体,用2×50毫升40%的乙醇水溶液洗涤。干燥后得1-(3-氯-2-吡啶基)-3-吡唑烷酮-5-甲酸乙酯橙色固体86.6克,外标法定量分析其含量为98%,收率90%。1H NMR(300MHz,DMSO):8.289-8.269(q,1H),7.956-7.190(q,1H),7.231-7.190(q,1H),4.862-4.816(q,1H),4.236-4.165(q,2H),2.967-2.879(q,1H),2.396-2.336(q,1H),1.250-1.202(t,3H)。
实施例5
1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
按照实施例1中的方法,使用催化剂六氟乙酰丙酮镍,可以制得1-(3,5-二氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯。1H NMR(300MHz,CDCl3):8.146(q,1H),7.658(q,1H),5.073(dd,1H),4.241(q,2H),3.029(dd,1H),2.721(dd,1H),1.258(t,3H)。
对照实施例
按照专利CN106928183中公开方法合成了1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯。
在2000毫升反应瓶内加入1000毫升无水乙醇和乙醇钠(65.7克,0.966摩尔),3-氯-2-肼基吡啶(101.04克,98%,0.69摩尔),再加入催化剂Cu(PPh3)2I(0.15克,0.00021摩尔)(双三苯基膦碘化亚铜,合成方法参加:Chemistry-AEuropean Journal,16(39),11822-11826,2010)混合物加热至40℃,滴加马来酸二乙酯(145.7克,0.83摩尔)。保持此温度4h,而后将反应混合物用冰乙酸(60克)中和。混合物用1000毫升水稀释,冷至室温,有固体析出。过滤收集固体,用3×150毫升40%的乙醇水溶液洗涤。干燥后得1-(3-氯-2-吡啶基)-3-吡唑烷酮-5-甲酸乙酯橙色固体149.91克,外标法定量分析其含量为98%,收率79%。
应用实例
按照上述反应式,将上述实施例制备所得3-氯吡啶基吡唑烷酮羧酸乙酯经溴化、水解得到3-溴代-1-吡啶基吡唑-5-羧酸。水解所得吡唑羧酸再经过酰化、氧化,制得吡唑酰氯,再与2-氨基-3-甲基-5-氯苯甲酰甲胺反应制得商品化品种chlorantraniliprole,反应的总收率为56.7%(以3-氯吡啶基吡唑烷酮羧酸乙酯计)。
从上述各实施例以及对比例可见,本发明采用结构简单、廉价易得的乙酰丙酮或氟代乙酰丙酮与金属铜、钴、镍形成的配合物作为催化剂,本发明所采用的催化剂与现的有机膦配合物相比结构更简单,同时还避免了制备吡啶基吡唑烷酮羧酸酯类化合物过程中含膦有机废物的产生,另外本发明的催化剂还提高了反应的选择性,有效控制了未合环副产通式(IV)类化合物的生成,进而实现在本行业中认可的更高的收率,并得到了工业放大应用。
Claims (8)
1.一种吡啶基吡唑烷酮羧酸酯类化合物的制备方法,其特征在于:
反应式如下:
式中:R1选自H或Cl;R2选自C1-C6烷基、C3-C6环烷基、苄基、卤素取代的苄基或C1-C4烷基取代的苄基;
肼基吡啶(II)在碱性条件下、在适宜的溶剂中,通过催化剂的作用与马来酸二酯(III),在0℃至所用溶剂的沸点范围内反应制得吡啶基吡唑烷酮羧酸酯类化合物(I);其中,催化剂为氟代乙酰丙酮与铜、钴或镍形成的配合物。
2.按权利要求1所述的制备方法,其特征在于:所述催化剂为三氟乙酰丙酮铜,六氟乙酰丙酮铜,三氟乙酰丙酮钴,六氟乙酰丙酮钴,三氟乙酰丙酮镍或六氟乙酰丙酮镍。
3.按权利要求1所述的制备方法,其特征在于:所述肼基吡啶、碱、马来酸二酯和催化剂的摩尔配比为1:1-2:1-5:0.00001-0.01。
4.按权利要求1所述的制备方法,其特征在于:所述适宜的溶剂选自烷基醇类或极性非质子性溶剂;
所述碱选自碱金属的氢化物、碱金属的氨化物或碱金属的烷基醇化物。
5.按权利要求4所述的吡啶基吡唑烷酮羧酸酯类化合物的制备方法,其特征在于:所述碱金属的氢化物为氢化锂、氢化钠或氢化钾;碱金属的氨化物为氨基锂、氨基钠或氨基钾;碱金属的烷基醇化物为甲醇钠,乙醇钠,丙醇钠,丁醇钠,戊醇钠,异丙醇钠,异丁醇钠,仲丁醇钠,叔丁醇钠,甲醇钾、乙醇钾,丙醇钾或叔丁醇钾;碱金属选自锂,钠或钾;
所述烷基醇类为甲醇,乙醇,丙醇,丁醇,戊醇,异丙醇,异丁醇,仲丁醇或叔丁醇;极性非质子性溶剂为甲苯、氯苯、乙腈,N,N-二甲基甲酰胺,N,N-二甲基乙酰胺、二甲基亚砜、羧酸酯类或醚类;
所述羧酸酯类为乙酸酯,富马酸二酯;醚类为四氢呋喃,2-甲基四氢呋喃,二氧六环。
6.按权利要求1-5任意一项所述的吡啶基吡唑烷酮羧酸酯类化合物的制备方法,其特征在于:所述肼基吡啶(II)在碱性条件下、在适宜的溶剂中,通过催化剂的作用与马来酸二酯(III),在20-50℃下反应制得吡啶基吡唑烷酮羧酸酯类化合物(I),
其中,肼基吡啶、碱、马来酸二酯和催化剂的摩尔配比为1:1.2-1.5:1.5-2:0.0001-0.001;催化剂选自三氟乙酰丙酮铜,六氟乙酰丙酮铜,三氟乙酰丙酮钴,六氟乙酰丙酮钴,三氟乙酰丙酮镍或六氟乙酰丙酮镍。
7.按权利要求6所述的吡啶基吡唑烷酮羧酸酯类化合物的制备方法,其特征在于:所述催化剂选自六氟乙酰丙酮铜或六氟乙酰丙酮钴。
8.按权利要求6所述的吡啶基吡唑烷酮羧酸酯类化合物的制备方法,其特征在于:所述碱选自甲醇钠,乙醇钠,丙醇钠,丁醇钠,戊醇钠,异丙醇钠,异丁醇钠,另丁醇钠或叔丁醇钠;所述适宜的溶剂选自甲醇,乙醇,丙醇,丁醇,戊醇,异丙醇,异丁醇,另丁醇或叔丁醇。
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