CN115124476A - 一种除草剂中间体的制备方法 - Google Patents
一种除草剂中间体的制备方法 Download PDFInfo
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- CN115124476A CN115124476A CN202210804705.3A CN202210804705A CN115124476A CN 115124476 A CN115124476 A CN 115124476A CN 202210804705 A CN202210804705 A CN 202210804705A CN 115124476 A CN115124476 A CN 115124476A
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- potassium
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- sodium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 18
- 239000004009 herbicide Substances 0.000 title claims abstract description 17
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 14
- FTWJRPLRTPYTJN-UHFFFAOYSA-N 4-chloro-2-fluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(Cl)C=C1F FTWJRPLRTPYTJN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 4
- 239000012022 methylating agents Substances 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- NXVKRKUGIINGHD-ARJAWSKDSA-N ethyl (z)-3-amino-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)\C=C(/N)C(F)(F)F NXVKRKUGIINGHD-ARJAWSKDSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 230000011987 methylation Effects 0.000 claims description 3
- 238000007069 methylation reaction Methods 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UKFPAGCSDWQXFT-UHFFFAOYSA-N 3-phenyl-4,5-dihydro-1,2-oxazole Chemical class O1CCC(C=2C=CC=CC=2)=N1 UKFPAGCSDWQXFT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- GRPWQLDSGNZEQE-UHFFFAOYSA-N 2-chloro-4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1Cl GRPWQLDSGNZEQE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- KENAMMSVUHVEOL-UHFFFAOYSA-N 4-chloro-2-fluoro-5-methylaniline Chemical compound CC1=CC(N)=C(F)C=C1Cl KENAMMSVUHVEOL-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- FBXGQDUVJBKEAJ-UHFFFAOYSA-N 4h-oxazin-3-one Chemical compound O=C1CC=CON1 FBXGQDUVJBKEAJ-UHFFFAOYSA-N 0.000 description 1
- GANBUJGJERTPPV-UHFFFAOYSA-N 5-amino-2-chloro-4-fluorobenzoic acid Chemical compound NC1=CC(C(O)=O)=C(Cl)C=C1F GANBUJGJERTPPV-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
- 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
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 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 group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- GNHDVXLWBQYPJE-UHFFFAOYSA-N saflufenacil Chemical compound C1=C(Cl)C(C(=O)NS(=O)(=O)N(C)C(C)C)=CC(N2C(N(C)C(=CC2=O)C(F)(F)F)=O)=C1F GNHDVXLWBQYPJE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种除草剂中间体的制备方法,以2‑氟‑4‑氯‑5‑三氟甲基苯胺为原料,经过多步反应合成2‑氯‑4‑氟‑5‑(3‑甲基‑2,6‑二酮‑4‑三氟甲基‑2,3‑二氢嘧啶基‑1(6H)‑基)苯甲醛,产品的总收率达到53%以上,纯度则在94%以上,反应操作简单,产生的三废少,具有良好的工业化前景,提供了适合工业化大生产的新思路。
Description
技术领域
本发明涉及有机化学合成技术领域,具体涉及一种除草剂中间体的制备方法。
背景技术
全世界广泛分布的杂草有30000多种,每年约1800种对作物造成不同程度的危害.每年因杂草危害造成的农作物减产高达9.7%。杂草的防治成为现代农业生产的重要一环。随着全球环境意识的提高和农业可持续发展的需要.研究开发高效、环保的除草剂显示出重要的社会意义和经济价值。
专利WO2016095768报道了苯基异噁唑啉类化合物可有效控制多种杂草,低剂量下表现出除草效果好,对作物安全等优点。专利WO2016095768、CN108570041、CN113105405和CN113880774公开了一系列苯基异噁唑啉类化合物的制备。2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛是该类化合物的重要母体之一。
文献报道2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛及通过简单反应即可用于合成2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛的类似物的制备主要有以下几种方法:
一、专利CN113880774公开了以2-氟-4-氯-5-甲基苯胺为原料,依次经过酰化、环合、甲基化、溴代、水解制成目标化合物的方法。该方法使用的原料不易得,价格高,三废多,不利于工业化生产,其反应路线如下:
二、专利US2002045550公开了以2-氯-4-氟苯甲酸为原料,依次经过硝化、还原制得2-氯-4-氟-5-氨基苯甲酸再与噁嗪酮中间体环合,再经甲基化制得2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲酸,该方法使用硫酸、硝酸、氢化钠、五氯化磷、三氯氧磷等危险、剧毒、不易保存的试剂,后处理产生大量酸性废水,对设备要求高,操作繁琐,安全性差。其反应路线如下:
三、文献:苯嘧磺草胺的合成和生物活性测定[J],农药,2012,51(8):565-568,报道了以2-氯-4-氟-5-氨基苯甲酸甲酯为原料,先制成异氰酸酯中间体,再与3-氨基-4,4,4-三氟丁烯酸乙酯环合得到2-氯-5-(2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)-4-氟苯甲酸甲酯。该方法在制备异氰酸酯过程中需使用剧毒试剂光气,且该异氰酸酯稳定性差,易变质,导致反应收率较低,其路线如下:
发明内容
因此,本发明要解决的技术问题在于现有的除草剂中间体的制备过程使用危害性大的有毒试剂原料,操作繁琐以及收率不高的问题,本发明提供一种反应过程安全、收率高、纯度高的除草剂中间体的制备方法。
为此,本发明提供了一种除草剂中间体的制备方法,本发明所述的除草剂中间体的制备方法即为2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛的制备方法,包括如下步骤:
a)将2-氟-4-氯-5-三氟甲基苯胺溶解于第一溶剂中,加入第一碱性催化剂、卤代甲酸酯,反应后得到中间体(1),将中间体(1)溶解于第二溶剂中,加入卤化物,反应后得到中间体(3);
或者,将2-氟-4-氯-5-三氟甲基苯胺溶解于第二溶剂中,加入卤化物,反应后得到中间体(2),将中间体(2)溶解于第一溶剂中,加入第一碱性催化剂、卤代甲酸酯,反应后得到中间体(3);
b)将中间体(3)溶解于第三溶剂中,加入第二碱性催化剂、3-氨基-4,4,4-三氟丁烯酸酯,反应后得到中间体(4);
c)将中间体(4)溶解于第四溶剂中,加入第三碱性催化剂、甲基化试剂,反应后得到中间体(5);
d)将中间体(5)溶解于第五溶剂中,加入第四碱性催化剂、亚磷酸二乙酯,反应后得到中间体(6);
e)将中间体(6)与水解试剂混合,反应后得到2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛,即本发明的除草剂中间体。
反应路线如下:
R、R1为烷基、烯烃或者芳香烃,R、R1各自独立地选自甲基、乙基、正丙基、异丙基、乙烯基、丙烯基、2-丁烯基、3-丁烯基、苯基、苄基、对甲苯基、对甲氧基苯基、对硝基苯基、2,4-二氯苯基等的一种或两种;
X取代基为卤素,如氟、氯、溴、碘等的任意一种。
优选地,所述第一溶剂为甲苯、二甲苯、氯苯、二氯甲烷、二氯乙烷、氯仿、四氯化碳、乙酸乙酯、四氢呋喃、甲基四氢呋喃、二氧六环、N,N-二甲基甲酰胺、乙腈或二甲亚砜中的至少一种;
所述第一碱性催化剂为氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、磷酸钾、磷酸氢钾、磷酸二氢钾、甲醇钠、乙醇钠、叔丁醇钠、三乙胺、二异丙基乙胺或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)中的至少一种;
所述第二溶剂为甲苯、二甲苯、氯苯、二氯甲烷、二氯乙烷、氯仿或四氯化碳中的至少一种。
优选地,所述卤化物为三氯化铁、三氯化铝、氯化钙、氯化锌、三溴化铁、三溴化铝、溴化钙、溴化锌、三碘化铁、三碘化铝、碘化钙或碘化锌中的至少一种。
优选地,步骤a)中,所述反应的温度为室温,所述2-氟-4-氯-5-三氟甲基苯胺、卤代甲酸酯、卤化物的摩尔比为1:(1~1.2):(1.5~2)。
优选地,所述第三溶剂、第四溶剂、第五溶剂各自独立地选自乙腈、乙酸乙酯、四氢呋喃、甲基四氢呋喃、N,N-二甲基甲酰胺、二甲亚砜、二甲苯、邻二氯苯、二氯乙烷或间二氯苯中的至少一种;
所述第二碱性催化剂、第三碱性催化剂、第四催化剂各自独立地选自氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、磷酸钾、磷酸氢钾、磷酸二氢钾、甲醇钠、乙醇钠、叔丁醇钠、三乙胺、二异丙基乙胺或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)中的至少一种。
优选地,步骤b)中,所述反应的温度为20~30℃,所述3-氨基-4,4,4-三氟丁烯酸乙酯与中间体(3)的摩尔比为1:1~1:1.2。
优选地,所述甲基化试剂为碘甲烷或硫酸二甲酯中的至少一种。
优选地,步骤c)中,所述反应的温度为40~50℃,所述甲基化试剂与中间体(4)的摩尔比为1:0.8~1:1.2。
优选地,步骤d)中,所述反应的温度为80~120℃,所述亚磷酸二乙酯与中间体(5)的摩尔比为1:0.8~1:1.2。
优选地,所述水解试剂为甲酸、乙酸、丙酸、硫酸、磷酸或盐酸中的至少一种;
步骤e)中,所述反应的温度为80~100℃,所述水解试剂与中间体(6)的摩尔比为1:8~1:20。
本发明技术方案,具有如下优点:
1、本发明的一种2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛的制备方法,以2-氟-4-氯-5-三氟甲基苯胺为原料,经过多步反应合成2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛,产品的总收率达到53%以上,纯度则在94%以上;
2、本发明的一种2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛的制备方法,反应操作简单,产生的三废少,各反应步骤中并未使用现有合成方法中常用的易燃易爆、剧毒或不易保存的试剂,避免对环境以及操作人员的危害,具有良好的工业化前景,提供了适合工业化大生产的新思路。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
实施例1
一种2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛的制备方法,包括如下步骤:
a)中间体(3)的制备
将10.7g 2-氟-4-氯-5-三氟甲基苯胺与10.1g三乙胺溶于200ml二氯乙烷中,降温至0℃,搅拌下滴加7.9g氯甲酸苯酯,室温反应2h后,加入碳酸钠溶液洗涤、分液、干燥浓缩得到16.3g中间体(1),收率98.2%,HPLC纯度>93%;
将16.3g中间体(1)溶于150ml二氯乙烷中,室温搅拌下分批加入10g无水三氯化铝,加完室温反应2h后,慢慢倾倒在100mL冰水中,分液,有机相用水洗涤、干燥浓缩得到18.9g中间体(3),收率98.7%,HPLC纯度>93%;
b)中间体(4)的制备
将9.0g 3-氨基-4,4,4-三氟丁烯酸乙酯与30g乙腈混合,搅拌并降温至0℃,缓慢加入9.6g叔丁醇钠后于20~30℃保温反应0.5h,然后缓慢滴加由18g中间体(3)与30g乙腈组成的溶液。滴完保温1h,加入1mol/L稀盐酸调至pH为4左右,加入二氯乙烷萃取、分液、干燥浓缩得到18.6g中间体(4),收率92.5%,HPLC纯度>97%;
c)中间体(5)的制备
将18.0g中间体(4)、8.3g无水碳酸钾与30gN,N-二甲基甲酰胺混合,升温至40~50℃保温反应0.5h,然后滴加7.5g碘甲烷,滴完保温反应1h,降至室温,过滤,滤液减压浓缩,无水乙醇重结晶,得15.8g中间体(5),收率84.6%,HPLC纯度>97%。
d)中间体(6)的制备
将15g中间体(5)、6.8g三乙胺与100g二氯乙烷混合,加热至回流,向其滴加4.7g亚磷酸二乙酯,滴完继续回流2h。然后降温至10~20℃,加水稀释,分液,干燥浓缩,粗品用无水乙醇重结晶,得11.8g中间体(6),收率85%,HPLC含量>96%。
e)2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-3,6-二氢嘧啶-1(2H)-基)苯甲醛的制备
将10g中间体(6)与50g 70%硫酸混合,搅拌升温至80℃反应2h,降温至0~10℃,析出固体,过滤得7.2g产品,收率83.4%,HPLC纯度>99%。
反应总收率为53.8%。
实施例2
一种2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-3,6-二氢嘧啶-1(2H)-基)苯甲醛的制备方法,包括如下步骤:
a)中间体(3)的制备
将10.7g 2-氟-4-氯-5-三氟甲基苯胺溶于100ml二氯乙烷中,室温搅拌下分批加入13g无水三氯化铝,加完室温反应2h后,慢慢倾倒在100mL冰水中,分液,有机相用水洗涤、干燥浓缩得到13.3g中间体(3),收率100%,HPLC纯度>95%;
将13.2g中间体(2)与10.1g三乙胺溶于200ml甲苯中,降温至0℃,搅拌下滴加8.0g氯甲酸苯酯,室温反应2h后,加入饱和碳酸氢钠溶液洗涤、分液、干燥浓缩得到18.5g中间体(3),收率96.6%,HPLC纯度>95%;
b)中间体(4)的制备
将9.0g 3-氨基-4,4,4-三氟丁烯酸乙酯与30g N,N-二甲基甲酰胺混合,搅拌并降温至0℃,缓慢加入9.6g叔丁醇钠后于20~30℃保温反应0.5h,然后缓慢滴加由18g中间体(3)与30g N,N-二甲基甲酰胺组成的溶液。滴完保温1h,加入1mol/L稀盐酸调至pH为4左右,加入二氯乙烷萃取、分液、干燥浓缩得到18.1g中间体(4),收率90%,HPLC纯度>96%;
c)中间体(5)的制备
将18.0g中间体(4)、8.3g无水碳酸钾与30gN,N-二甲基甲酰胺混合,升温至40~50℃保温反应0.5h,然后滴加9.0g硫酸二甲酯,滴完保温反应1h,降至室温,过滤,滤液减压浓缩,无水乙醇重结晶,得16.8g中间体(5),收率90%,HPLC纯度>95%。
d)中间体(6)的制备
将15g中间体(5)、6.8g三乙胺与100g二氯乙烷混合,加热至回流,向其滴加4.7g亚磷酸二乙酯,滴完继续回流2h。然后降温至10~20℃,加水稀释,分液,干燥浓缩,粗品用无水乙醇重结晶,得11.8g中间体(6),收率85%,HPLC含量>96%。
e)2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-3,6-二氢嘧啶-1(2H)-基)苯甲醛的制备
将10g中间体(6)、30g甲酸混合,搅拌升温回流反应2h,反应降温至0-10℃,析出固体,过滤得6.9g产品,收率80%,HPLC纯度>99%。
反应总收率为53.2%。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种除草剂中间体的制备方法,其特征在于,包括如下步骤:
a)将2-氟-4-氯-5-三氟甲基苯胺溶解于第一溶剂中,加入第一碱性催化剂、卤代甲酸酯,反应后得到中间体(1),将中间体(1)溶解于第二溶剂中,加入卤化物,反应后得到中间体(3);
或者,将2-氟-4-氯-5-三氟甲基苯胺溶解于第二溶剂中,加入卤化物,反应后得到中间体(2),将中间体(2)溶解于第一溶剂中,加入第一碱性催化剂、卤代甲酸酯,反应后得到中间体(3);
b)将中间体(3)溶解于第三溶剂中,加入第二碱性催化剂、3-氨基-4,4,4-三氟丁烯酸酯,反应后得到中间体(4);
c)将中间体(4)溶解于第四溶剂中,加入第三碱性催化剂、甲基化试剂,反应后得到中间体(5);
d)将中间体(5)溶解于第五溶剂中,加入第四碱性催化剂、亚磷酸二乙酯,反应后得到中间体(6);
e)将中间体(6)与水解试剂混合,反应后得到除草剂中间体2-氯-4-氟-5-(3-甲基-2,6-二酮-4-三氟甲基-2,3-二氢嘧啶基-1(6H)-基)苯甲醛。
2.根据权利要求1所述的除草剂中间体的制备方法,其特征在于,所述第一溶剂为甲苯、二甲苯、氯苯、二氯甲烷、二氯乙烷、氯仿、四氯化碳、乙酸乙酯、四氢呋喃、甲基四氢呋喃、二氧六环、N,N-二甲基甲酰胺、乙腈或二甲亚砜中的至少一种;
所述第一碱性催化剂为氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、磷酸钾、磷酸氢钾、磷酸二氢钾、甲醇钠、乙醇钠、叔丁醇钠、三乙胺、二异丙基乙胺或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)中的至少一种;
所述第二溶剂为甲苯、二甲苯、氯苯、二氯甲烷、二氯乙烷、氯仿或四氯化碳中的至少一种。
3.根据权利要求1所述的除草剂中间体的制备方法,其特征在于,所述卤化物为三氯化铁、三氯化铝、氯化钙、氯化锌、三溴化铁、三溴化铝、溴化钙、溴化锌、三碘化铁、三碘化铝、碘化钙或碘化锌中的至少一种。
4.根据权利要求1~3任一项所述的除草剂中间体的制备方法,其特征在于,步骤a)中,所述反应的温度为室温,所述2-氟-4-氯-5-三氟甲基苯胺、卤代甲酸酯、卤化物的摩尔比为1:(1~1.2):(1.5~2)。
5.根据权利要求1所述的除草剂中间体的制备方法,其特征在于,所述第三溶剂、第四溶剂、第五溶剂各自独立地选自乙腈、乙酸乙酯、四氢呋喃、甲基四氢呋喃、N,N-二甲基甲酰胺、二甲亚砜、二甲苯、邻二氯苯、二氯乙烷或间二氯苯中的至少一种;
所述第二碱性催化剂、第三碱性催化剂、第四催化剂各自独立地选自氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、磷酸钾、磷酸氢钾、磷酸二氢钾、甲醇钠、乙醇钠、叔丁醇钠、三乙胺、二异丙基乙胺或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)中的至少一种。
6.根据权利要求1或5所述的除草剂中间体的制备方法,其特征在于,步骤b)中,所述反应的温度为20~30℃,所述3-氨基-4,4,4-三氟丁烯酸乙酯与中间体(3)的摩尔比为1:1~1:1.2。
7.根据权利要求1或5所述的除草剂中间体的制备方法,其特征在于,所述甲基化试剂为碘甲烷或硫酸二甲酯中的至少一种。
8.根据权利要求7所述的除草剂中间体的制备方法,其特征在于,步骤c)中,所述反应的温度为40~50℃,所述甲基化试剂与中间体(4)的摩尔比为1:0.8~1:1.2。
9.根据权利要求1或5所述的除草剂中间体的制备方法,其特征在于,步骤d)中,所述反应的温度为80~120℃,所述亚磷酸二乙酯与中间体(5)的摩尔比为1:0.8~1:1.2。
10.根据权利要求1所述的除草剂中间体的制备方法,其特征在于,所述水解试剂为甲酸、乙酸、丙酸、硫酸、磷酸或盐酸中的至少一种;
步骤e)中,所述反应的温度为80~100℃,所述水解试剂与中间体(6)的摩尔比为1:8~1:20。
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