CN106928183B - 吡啶基吡唑烷酮羧酸类化合物的制备方法 - Google Patents
吡啶基吡唑烷酮羧酸类化合物的制备方法 Download PDFInfo
- Publication number
- CN106928183B CN106928183B CN201511009005.1A CN201511009005A CN106928183B CN 106928183 B CN106928183 B CN 106928183B CN 201511009005 A CN201511009005 A CN 201511009005A CN 106928183 B CN106928183 B CN 106928183B
- Authority
- CN
- China
- Prior art keywords
- sodium
- carboxylic acid
- catalyst
- ester compound
- acid ester
- 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.)
- Active
Links
- -1 pyridyl pyrazoles Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000002585 base Substances 0.000 claims description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 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 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- NWELCUKYUCBVKK-UHFFFAOYSA-N pyridin-2-ylhydrazine Chemical class NNC1=CC=CC=N1 NWELCUKYUCBVKK-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 4
- NSHQEUFMYDDCJR-UHFFFAOYSA-N pentan-1-ol;sodium Chemical compound [Na].CCCCCO NSHQEUFMYDDCJR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims description 4
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 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
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-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
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 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 6
- 238000000034 method Methods 0.000 abstract description 6
- 239000002917 insecticide Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 7
- 125000004494 ethyl ester group Chemical group 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 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
- 239000000460 chlorine Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 238000010812 external standard method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZDCGBGBQRTYDFC-UHFFFAOYSA-N (pyridin-2-ylamino)azanium;chloride Chemical compound Cl.NNC1=CC=CC=N1 ZDCGBGBQRTYDFC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000005886 Chlorantraniliprole Substances 0.000 description 2
- 239000005889 Cyantraniliprole Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 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
- 150000005690 diesters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- WPGHPGAUFIJVJF-UHFFFAOYSA-N 3,5-dichloropyridine Chemical compound ClC1=CN=CC(Cl)=C1 WPGHPGAUFIJVJF-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
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 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
- 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
- XLOMEDHGELECDS-UHFFFAOYSA-L dibromonickel;triphenylphosphane Chemical compound Br[Ni]Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XLOMEDHGELECDS-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 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
- 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
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(通用名为cyantraniliprole)具有高的杀虫活性，杜邦公司已开发为杀虫剂。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(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，也已经开发为杀虫剂，通用名为四氯虫酰胺。
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％。
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做为催化剂合成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：
一直以来，技术人员致力于不断研究开发新的、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选自甲C1-C6烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、卤素或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，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；催化剂选自：Cu(L1)Cl，Cu(L1)Br，Cu(L1)I，Cu(L2)2Cl，Cu(L2)2Br，Cu(L2)2I；Ni(L1)Cl2，Ni(L1)Br2，Ni(L1)I2，Ni(L2)2Cl2，Ni(L2)2Br2，Ni(L2)2I2，其中L1选自：
L2选自：
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、氢化钾，碱金属的氨化物为氨基锂、氨基钠、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，另丁醇钠，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，富马酸二酯或马来酸二酯；烷基醇类为甲醇，乙醇，丙醇，丁醇，戊醇，异丙醇，异丁醇，另丁醇或叔丁醇；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。
优选,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Cu(L1)Br，Cu(L1)I，Cu(L2)2Br或Cu(L2)2I；其中
L1选自：
L2选自：
进一步优选，所述催化剂选自Cu(L1)I或Cu(L2)2I，其中
L1选自：
L2选自：
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。
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。
本发明所具有有点：本发明采用结构简单的不含氮的苯基膦化合物作为催化吡啶基吡唑烷酮羧酸酯的合成的催化剂，可以大大提高反应的收率，从而完成了本发明。同时，本发明反应可在较低温度下进行，使反应的安全性大大提高。另外，本发明的催化剂还存在合成简单易行、价格低廉的优势，只需金属盐和苯基膦在乙醇中反应即可制得。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-A European 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％。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)。
催化剂的合成方法如下：
在2000毫升反应瓶内依次加入1000毫升无水乙醇、三苯基膦(500克,1,9mol)、CuI(181克,0.95mol)，升温至80℃反应1h后，自然降温至室温，过滤，干燥，得产品644.9克，收率95％。
下述其它催化剂选择适宜的原料可按照此方式制备获得。
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300毫升无水乙醇和乙醇钠(16.97克，0.249摩尔)，3-氯-2-肼基吡啶(30.75克，98％，0.21摩尔)，再加入催化剂Cu(binap)I(0.017克，0.000021摩尔)(2,2'-双-(二苯膦基)-1,1'-联萘简称binap，合成方法参加：Chemistry-A EuropeanJournal,16(39),11822-11826,2010)混合物加热至30℃，滴加马来酸二乙酯(44.23克，0.252摩尔)。保持此温度4h，而后将反应混合物用冰乙酸(15克，)中和。混合物用300毫升水稀释，冷至室温，有固体析出。过滤收集固体，用3×50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47.06克，外标法定量分析其含量为95％，收率79％。
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300毫升无水乙醇和乙醇钠(16.97克，0.249摩尔)，3-氯-2-肼基吡啶(30.75克，98％，0.21摩尔)，再加入催化剂Cu(PPh3)2Br(0.042克，0.000063摩尔)(双三苯基膦溴化亚铜，合成方法参加：Chemistry-A European Journal,16(39),11822-11826,2010)，混合物加热至35℃，滴加马来酸二乙酯(44.23克，0.252摩尔)。保持此温度4h，而后将反应混合物用冰乙酸(15克)中和。混合物用300毫升水稀释，冷至室温，有固体析出。过滤收集固体，用3×50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45.98克，外标法定量分析其含量为96％，收率78％。
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300毫升无水乙醇和乙醇钠(16.97克，0.249摩尔)，3-氯-2-肼基吡啶(30.75克，98％，0.21摩尔)，再加入催化剂Ni(PPh3)2Br2(0.047克，0.000063摩尔)(双三苯基膦二溴化镍合成方法参加：Appl.Organometal.Chem.,23,455-459,2009)，混合物加热至45℃，滴加马来酸二乙酯(44.23克，0.252摩尔)。保持此温度4h，而后将反应混合物用冰乙酸(15克)中和。混合物用300毫升水稀释，冷至室温，有固体析出。过滤收集固体，用3×50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45.98克，外标法定量分析其含量为96％，收率78％。
按照实施例1中的方法，使用催化剂Cu(PPh3)2I(双三苯基膦碘化亚铜)可以高收率的制得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
按照南开大学公开方法(参考文献：农药研究与应用.14(2),14-15,2009)合成了1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯。
在1000毫升反应瓶内加入300毫升无水乙醇和钠(5.22克，0.227摩尔)，搅拌至无气泡产生，加入3-氯-2-肼基吡啶(30.00克，0.205摩尔)，混合物加热至回流5min，再加入催化剂A 0.003克，滴加马来酸二乙酯(36.00克，0.209摩尔)。保持回流30min，而后将反应混合物冷却至65℃用冰乙酸(25.2克)中和。混合物用300毫升水稀释，冷至室温，有固体析出。过滤收集固体，用3×50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45.2克，归一含量96％，外标法定量分析其含量为85.4％，收率70％。
本发明得到的吡啶基吡唑烷酮羧酸酯进一步经卤化、水解得到3-卤代-1-吡啶基吡唑-5-羧酸。吡唑羧酸和取代苯胺反应制得通式Ⅳ所示的苯甲酰胺类化合物。表1列出部分通式(Ⅳ)化合物的结构。
表1.部分通式(Ⅳ)化合物的结构
Claims (5)
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选自甲C1-C6烷基、C2-C4烯基、C2-C4炔基、C3-C6环烷基、卤素或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，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；催化剂选自：Cu(L1)Cl，Cu(L1)Br，Cu(L1)I，Cu(L2)2Cl，Cu(L2)2Br，Cu(L2)2I；Ni(L1)Cl2，Ni(L1)Br2，Ni(L1)I2，Ni(L2)2Cl2，Ni(L2)2Br2，Ni(L2)2I2，其中L1选自：
L2选自：
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、氢化钾，碱金属的氨化物为氨基锂、氨基钠、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，另丁醇钠，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，富马酸二酯或马来酸二酯；烷基醇类为甲醇，乙醇，丙醇，丁醇，戊醇，异丙醇，异丁醇，另丁醇或叔丁醇；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。
2.按权利要求1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：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Cu(L1)Br，Cu(L1)I，Cu(L2)2Br或Cu(L2)2I；其中
L1选自：
L2选自：
3.按权利要求2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Cu(L1)I或Cu(L2)2I，其中
L1选自：
L2选自：
4.按权利要求1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。
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：所述碱选自乙醇钠， 所述适宜的溶剂选自乙醇。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511009005.1A CN106928183B (zh) | 2015-12-29 | 2015-12-29 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
| BR112018013249-7A BR112018013249B1 (pt) | 2015-12-29 | 2016-12-08 | Método de preparação de compostos de carboxilato depiridil pirazolidinona |
| PCT/CN2016/108984 WO2017114121A1 (zh) | 2015-12-29 | 2016-12-08 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
| CN201680060148.1A CN108137535B (zh) | 2015-12-29 | 2016-12-08 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511009005.1A CN106928183B (zh) | 2015-12-29 | 2015-12-29 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106928183A CN106928183A (zh) | 2017-07-07 |
| CN106928183B true CN106928183B (zh) | 2019-09-24 |
Family
ID=59224566
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511009005.1A Active CN106928183B (zh) | 2015-12-29 | 2015-12-29 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
| CN201680060148.1A Active CN108137535B (zh) | 2015-12-29 | 2016-12-08 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680060148.1A Active CN108137535B (zh) | 2015-12-29 | 2016-12-08 | 吡啶基吡唑烷酮羧酸类化合物的制备方法 |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN106928183B (zh) |
| BR (1) | BR112018013249B1 (zh) |
| WO (1) | WO2017114121A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317016A (zh) * | 2016-08-24 | 2017-01-11 | 河北艾林国际贸易有限公司 | 一种环丙虫酰胺化合物及其制备方法和应用 |
| CN109988150B (zh) * | 2017-12-29 | 2022-04-12 | 江苏中旗科技股份有限公司 | N-烷基-n-氰基烷基苯甲酰胺类化合物及其应用 |
| CN108484572A (zh) * | 2018-04-29 | 2018-09-04 | 江苏省农用激素工程技术研究中心有限公司 | 新型双酰胺类化合物及其制备方法和应用 |
| CN110330455B (zh) * | 2019-05-31 | 2023-04-28 | 湖北省生物农药工程研究中心 | 酰胺衍生物及其制备方法和用途 |
| WO2021033165A1 (en) * | 2019-08-21 | 2021-02-25 | Gharda Chemicals Limited | Process for synthesis of pyrazolidinone compounds |
| WO2021033166A1 (en) | 2019-08-21 | 2021-02-25 | Gharda Chemicals Limited | Process for synthesis of pyrazolidinone compounds |
| CN114057687B (zh) * | 2020-08-05 | 2023-11-14 | 沈阳中化农药化工研发有限公司 | 吡啶基吡唑烷酮羧酸酯类化合物的制备方法 |
| CN113072472A (zh) * | 2021-04-07 | 2021-07-06 | 湖南科技学院 | 一种2-甲硫基马来酸二酯化合物的合成方法 |
| US20240308988A1 (en) | 2021-08-05 | 2024-09-19 | Syngenta Crop Protection Ag | Method For Controlling Diamide Resistant Pests and Compounds Therefor |
| CN114478365A (zh) * | 2022-02-11 | 2022-05-13 | 大连九信作物科学有限公司 | 一种2-氨甲基-3-氯-5-三氟甲基吡啶醋酸盐的纯化方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA79799C2 (uk) * | 2002-07-31 | 2007-07-25 | Е.І. Дю Пон Де Немур Енд Компані | Спосіб одержання 3-гало-4,5-дигідро-1h-піразолів |
| US7211270B2 (en) * | 2002-10-04 | 2007-05-01 | E. I. Du Pont De Nemours And Company | Anthranilamide insecticides |
| TWI367882B (en) * | 2003-03-26 | 2012-07-11 | Du Pont | Preparation and use of 2-substituted-5-oxo-3-pyrazolidinecarboxylates |
-
2015
- 2015-12-29 CN CN201511009005.1A patent/CN106928183B/zh active Active
-
2016
- 2016-12-08 WO PCT/CN2016/108984 patent/WO2017114121A1/zh not_active Ceased
- 2016-12-08 CN CN201680060148.1A patent/CN108137535B/zh active Active
- 2016-12-08 BR BR112018013249-7A patent/BR112018013249B1/pt active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| BR112018013249A2 (pt) | 2019-02-12 |
| CN108137535B (zh) | 2021-02-19 |
| BR112018013249B1 (pt) | 2022-03-22 |
| WO2017114121A1 (zh) | 2017-07-06 |
| CN108137535A (zh) | 2018-06-08 |
| CN106928183A (zh) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108137535A (zh) | 吡啶基吡唑烷酮羧酸类化合物的制备方法 | |
| DE60217126T2 (de) | Herstellung von aminopyrimidinverbindungen | |
| CN110028489B (zh) | 一种减压法制备苯甲酰胺类化合物的方法 | |
| US20100280257A1 (en) | Process for the synthesis of organic compounds | |
| CA2935594A1 (en) | 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation | |
| CN102020647B (zh) | 1-(2,2-二氟乙氧基)-6-三氟甲基-n-([1,2,4]三氮唑[1,5-c]嘧啶-2-)苯磺酰胺的制备方法 | |
| CN102020633A (zh) | 一种1-(3，5-二氯吡啶-2-基)-吡唑甲酰胺类化合物的制备方法 | |
| EP2501682A1 (de) | Verfahren zum herstellen von 5-fluor-1-alkyl-3-fluoralkyl-1h-pyrazol-4-carbonsäurechloriden | |
| ES2480278T3 (es) | Procedimiento para la preparación de 1-bencil-3-hidroximetil-1H-indazol y sus derivados y productos intermedios de magnesio requeridos | |
| WO2022028258A1 (zh) | 一种溴代吡唑羧酸酯类化合物的制备方法 | |
| KR100720220B1 (ko) | 치환 아닐린 화합물의 제조방법 | |
| CN102001979A (zh) | 2-(2’,2’-二氟乙氧基)-6-三氟甲基苯基丙基硫醚的制备方法 | |
| KR20160120009A (ko) | 4,4-디플루오로-((2-디알킬아미노)메틸렌)-3-옥소부탄산 알킬에스테르의 새로운 제조방법 | |
| CN114057687B (zh) | 吡啶基吡唑烷酮羧酸酯类化合物的制备方法 | |
| CN104496909B (zh) | 一种双核苯并咪唑离子盐及其制备方法和应用 | |
| CN110396079A (zh) | 一种氯虫苯甲酰胺中间体的制备方法及其应用 | |
| CN115141180B (zh) | 一种鲁索替尼中间体的制备方法 | |
| CN102304014B (zh) | 一种氟环唑中间体的制备方法 | |
| CN106234385B (zh) | 一种含苯并吡嗪结构的1,2,4-三唑衍生物作为杀菌剂的应用 | |
| CN115974729B (zh) | 2-(2,2-二氟乙氧基)-6-三氟甲基苯磺酰氯的制备方法 | |
| CN108503590A (zh) | 一种哒嗪酮类化合物及其合成方法 | |
| CN106220554B (zh) | 一种芳基吡啶及其衍生物的制备方法 | |
| CN115894518B (zh) | 一种唑啉草酯代谢物m3的合成方法 | |
| CN104003944B (zh) | 一种嘧菌胺的制备方法 | |
| CN110272389B (zh) | 一种合成4-多氟烷基-3,5-二羰基吡唑化合物的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |