CN102574810B - 制备4-亚磺酰基吡唑衍生物的方法 - Google Patents
制备4-亚磺酰基吡唑衍生物的方法 Download PDFInfo
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- CN102574810B CN102574810B CN201080048020.6A CN201080048020A CN102574810B CN 102574810 B CN102574810 B CN 102574810B CN 201080048020 A CN201080048020 A CN 201080048020A CN 102574810 B CN102574810 B CN 102574810B
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- barium
- catalyzer
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- HGAMRMFMRCGNAR-UHFFFAOYSA-N 4-sulfinylpyrazole Chemical class O=S=C1C=NN=C1 HGAMRMFMRCGNAR-UHFFFAOYSA-N 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011575 calcium Substances 0.000 claims abstract description 25
- -1 oxides Chemical class 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- 229910052788 barium Inorganic materials 0.000 claims abstract description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims abstract description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 9
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 230000000994 depressogenic effect Effects 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 abstract 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- DRTNVNKYVPOWCY-UHFFFAOYSA-N 2,2,2-trichloroethaneperoxoic acid Chemical compound OOC(=O)C(Cl)(Cl)Cl DRTNVNKYVPOWCY-UHFFFAOYSA-N 0.000 abstract 1
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- FNELVJVBIYMIMC-UHFFFAOYSA-N Ethiprole Chemical compound N1=C(C#N)C(S(=O)CC)=C(N)N1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl FNELVJVBIYMIMC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910052740 iodine Chemical group 0.000 description 3
- 239000011630 iodine Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000006012 2-chloroethoxy group Chemical group 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
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- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- 125000004797 2,2,2-trichloroethoxy group Chemical group ClC(CO*)(Cl)Cl 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- NNKADNNVPMGMRX-UHFFFAOYSA-N 2,2,2-trifluoroacetic acid;zinc Chemical compound [Zn].OC(=O)C(F)(F)F NNKADNNVPMGMRX-UHFFFAOYSA-N 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical group CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
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- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- 239000005899 Fipronil Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005108 alkenylthio group Chemical group 0.000 description 1
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- 125000004414 alkyl thio group Chemical group 0.000 description 1
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- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 239000003849 aromatic solvent Substances 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 239000003610 charcoal Substances 0.000 description 1
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
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- 239000012043 crude product Substances 0.000 description 1
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- OJOZHRCRUJKPIJ-UHFFFAOYSA-N magnesium;2,2,2-trifluoroacetic acid Chemical compound [Mg].OC(=O)C(F)(F)F OJOZHRCRUJKPIJ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XGMOTIJYDDLHCK-UHFFFAOYSA-N manganese;2,2,2-trifluoroacetic acid Chemical compound [Mn].OC(=O)C(F)(F)F XGMOTIJYDDLHCK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 150000008048 phenylpyrazoles Chemical class 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- SJVXIGYYHRAHDR-UHFFFAOYSA-N strontium;2,2,2-trifluoroacetic acid Chemical compound [Sr].OC(=O)C(F)(F)F SJVXIGYYHRAHDR-UHFFFAOYSA-N 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 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
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
Abstract
本发明涉及一种通过在选自锂、镁、钙、锶、钡、钛(IV)、锌(II)和锰(II)的氢氧化物、氧化物、硫酸盐、乙酸盐或三氟乙酸盐的催化剂存在下用选自三氟过乙酸和三氯过乙酸的氧化剂氧化式(II)化合物而制备式(I)化合物的新方法,其中R1、R2、R3、R4和R5各自独立地选自氢、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、硝基、氰基和五氟硫基,R6为C1-C4烷基或C1-C4卤代烷基。
Description
本发明涉及一种通过在选自锂、镁、钙、锶、钡、钛(IV)、锌(II)和锰(II)的氢氧化物、氧化物、硫酸盐、乙酸盐或三氟乙酸盐的催化剂存在下用选自三氟过乙酸和三氯过乙酸的氧化剂氧化式(II)化合物而制备式(I)化合物的新方法:
其中
R1、R2、R3、R4和R5各自独立地选自氢、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、硝基、氰基和五氟硫基;和R6为C1-C4烷基或C1-C4卤代烷基;
其中R1、R2、R3、R4、R5和R6如对式(I)化合物所定义。
式(I)的4-亚磺酰基吡唑衍生物是重要的农药。尤其重要的4-亚磺酰基吡唑衍生物是锐劲特(fipronil)和乙虫清(ethiprole)。
通过氧化硫原子由相应的烷硫基、链烯硫基或炔硫基化合物制备某些带有亚磺酰基或磺酰基的苯基吡唑类通常给于EP-A1 295177中。作为可能的氧化剂提到过氧化氢、由三氟乙酸酐和过氧化氢就地形成的三氟过乙酸、三氟过乙酸酐或优选在溶剂如二氯甲烷、氯仿、三氟乙酸中的3-氯过苯甲酸。或者将在溶剂如甲醇或水中的过硫酸氢钾或过一硫酸钾盐作为氧化剂给出。
许多文献涉及氧化式(II)化合物以制备式(I)化合物,尤其是锐劲特。
在IPCOM000156770D中描述了在作为溶剂的二氯甲烷中在三氟乙酸存在下用过氧化氢氧化式(II)化合物。CN 101250158A提到在惰性溶剂(一氯苯、氯仿)中用过氧化氢和硫酸催化氧化式(II)化合物,但没有描述催化剂的结构。类似地,在Shanghai Chemical Industry 2007,7(32),17中提到了在二氯甲烷中用过氧化氢催化氧化式(II)化合物,但没有给出催化剂的结构详情。
CN 101168529A教导了在离子液体和乙腈的溶剂混合物中在三氯化钌作为催化剂存在下用三氯异氰酸氧化式(II)化合物。类似地,在Journal ofFluorine Chemistry 2006,127,948中提到在作为溶剂的二氯甲烷中用三氯异氰酸氧化式(II)化合物。
WO 2007/122440教导了在二氯乙酸或二氯甲烷中用三氯乙酸/过氧化氢氧化式(II)化合物。
WO 2009/077853列出了许多用于氧化式(II)化合物的试剂:三氟乙酸和过硫酸氢钾制剂;在乙醇中的三氟甲磺酸酐和过氧化氢;在乙腈中的亚环己基双氢过氧化物(cyclohexylidenebishydroperoxide)、碘化钠和过氧化氢;在二氯甲烷中的鲸蜡基溴化铵(cerammoniumbromide)、溴酸钠和硅胶;以及在甲醇中的过氧化氢加上催化量的HAuCl4。
氧化式(II)化合物而得到式(I)化合物的上述方法并不完全令人满意。合适的大规模氧化方法的标准如下:(1)高度选择性氧化成式(I)的亚砜产物(即得到少量砜副产物,其中式(I)化合物中的S(=O)R6-基团过度氧化成S(=O)2R6-基团);(2)高收率的式(I)化合物;(3)由于氟化氢在氧化过程中就地形成而抑制腐蚀;(4)氧化反应速率高(决定了生产率)。迄今为止,解决问题(1)、(2)和(3)的最合适组合由WO01/30760讨论,其描述了在腐蚀抑制化合物存在下用三氟过乙酸氧化式(II)化合物。然而,对该方法而言决定生产率的反应速率仍不能高到大规模工业方法所需速率。
因此,本发明的目的是提供一种将化合物(II)氧化成化合物(I)的新型且改进方法。具体而言,目的是提供一种以改进(更高)反应速率将化合物(II)氧化成化合物(I)的新型且改进方法。在优选实施方案中,目的是提供一种将化合物(II)催化氧化成化合物(I)的新型且改进方法,其中可以将催化剂容易地从反应产物中除去(例如通过用水洗涤)。
因此,发现了开头所定义的本发明方法。惊人的是加入选自锂、镁、钙、锶、钡、钛、锌和锰的氢氧化物、氧化物、硫酸盐、乙酸盐或三氟乙酸盐的化合物显著提高了反应速率,从而提高生产率(每单位时间生产的产物)。
本发明可以用于制备作为制备丁烯锐劲特(化合物III)的中间体化合物的锐劲特。丁烯锐劲特如CN 3198515所述通过锐劲特的烷基化得到。
各取代基具有下列含义:
术语卤素在每种情况下表示氟、溴、氯或碘,尤其是氟、氯或溴,优选氯或氟。
本文所用术语“C1-C4烷基”指具有1-4个碳原子的饱和直链或支化烃基,例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基和1,1-二甲基乙基。
本文所用术语“C1-C4卤代烷基”指具有1-4个碳原子的直链或支化饱和烷基(如上所述),其中这些基团中的部分或全部氢原子被上述卤原子替换,如氯甲基、溴甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、氯氟甲基、二氯一氟甲基、一氯二氟甲基、1-氯乙基、1-溴乙基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、2-氯-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、五氟乙基等。
本文所用术语“C1-C4烷氧基”指经由氧原子连接的具有1-4个碳原子的直链或支化饱和烷基(如上所述)。实例包括甲氧基、乙氧基、OCH2-C2H5、OCH(CH3)2、正丁氧基、OCH(CH3)-C2H5、OCH2-CH(CH3)2和OC(CH3)3。
本文所用术语“C1-C4卤代烷氧基”指上述C1-C4烷氧基,其中氢原子部分或完全被氟、氯、溴和/或碘替代,即例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、二氯一氟甲氧基、一氯二氟甲氧基、2-氟乙氧基、2-氯乙氧基、2-溴乙氧基、2-碘乙氧基、2,2-二氟乙氧基、2,2,2-三氟乙氧基、2-氯-2-氟乙氧基、2-氯-2,2-二氟乙氧基、2,2-二氯-2-氟乙氧基、2,2,2-三氯乙氧基、五氟乙氧基、2-氟丙氧基、3-氟丙氧基、2,2-二氟丙氧基、2,3-二氟丙氧基、2-氯丙氧基、3-氯丙氧基、2,3-二氯丙氧基、2-溴丙氧基、3-溴丙氧基、3,3,3-三氟丙氧基、3,3,3-三氯丙氧基、2,2,3,3,3-五氟丙氧基、七氟丙氧基、1-(氟甲基)-2-氟乙氧基、1-(氯甲基)-2-氯乙氧基、1-(溴甲基)-2-溴乙氧基、4-氟丁氧基、4-氯丁氧基、4-溴丁氧基、九氟丁氧基,尤其是氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、2-氟乙氧基、2-氯乙氧基或2,2,2-三氟乙氧基。
对于本发明方法,式(I)和(II)化合物的取代基优选具有下列含义:
R1和R5优选选自卤素和C1-C4卤代烷基,甚至更优选选自氯、氟和三氟甲基,最优选选自氯。
R2和R4优选为氢。
R3优选为C1-C4烷基、C1-C4卤代烷基或五氟硫基,甚至更优选C1-C4卤代烷基,最优选三氟甲基。
R6优选为乙基或三氟甲基。
R6优选为乙基。
R6最优选为三氟甲基。
最优选式(I)和(II)化合物的取代基具有如下含义:
R1和R5为氯;
R2和R4为氢;
R3为三氟甲基;和
R6为乙基或三氟甲基,优选三氟甲基。
在尤其优选的实施方案中,本发明方法用于制备方案I的化合物I-1或I-2。
方案I
最优选本发明方法用于制备锐劲特。
式(II)化合物可以根据文献如WO 01/30760,WO 05/44806和EP-A1 295117中所述程序得到。
合适的氧化剂是三氟过乙酸(例如由三氟乙酸和过氧化氢就地形成)或三氯过乙酸(例如由三氯乙酸和过氧化氢就地形成)。优选三氟过乙酸。最优选使用由三氟乙酸和过氧化氢就地形成的三氟过乙酸。过氧化氢通常作为50重量%水溶液使用且相对于式(II)化合物通常为约1.0-2.0当量,优选约1.2-1.6当量,更优选约1.30-1.45当量,甚至更优选约1.35-1.40当量。
本发明方法优选在选自三氟乙酸,三氟乙酸和一氯苯或三氟乙酸和二氯甲烷的混合物以及三氯乙酸与熔点降低剂如一氯苯、一氯乙酸、二氯乙酸、二氯乙烷和二氯甲烷的混合物的溶剂中进行。
若使用三氯乙酸和熔点降低剂的混合物,则该熔点降低剂通常以三氯乙酸的20-30重量%使用。优选每摩尔式(II)化合物使用1.0-2.0升三氯乙酸。
优选的溶剂是三氟乙酸。优选相对于化合物(II)的所用摩尔量使用约10-20mol三氟乙酸,更优选约14-16摩尔当量,最优选约15.2-15.8摩尔当量。
在本发明的优选方面,将三氟乙酸用作溶剂且在反应完成时将一氯苯加入反应混合物中,然后通过共沸蒸馏除去三氟乙酸。
该催化剂选自锂、镁、钙、锶、钡、钛(IV)、锌(II)和锰(II)的氢氧化物、氧化物、硫酸盐、乙酸盐或三氟乙酸盐。
实例是LiOH(氢氧化锂),Mg(OH)2(氢氧化镁),Ca(OH)2(氢氧化钙),Sr(OH)2(氢氧化锶),Ba(OH)2(氢氧化钡),Mn(OH)2(氢氧化锰(II)),MgOH(氧化镁),CaO(氧化钙),BaO(氧化钡),TiO2(二氧化钛),ZnO(氧化锌(II)),MnO(氧化锰(II)),三氟乙酸镁,三氟乙酸钙,三氟乙酸钡,三氟乙酸锶,三氟乙酸锌,三氟乙酸锰,乙酸镁,乙酸钙,乙酸钡,乙酸锶,乙酸锌,乙酸锰,硫酸镁,硫酸钙,硫酸钡,硫酸锶,硫酸锌,硫酸锰。
优选可以市购的上面所列催化剂。
金属阳离子优选选自锂、镁、钙、锶、钡、钛(IV)、锌(II)和锰(II)的阳离子,最优选选自钙、钡、锶和锌(II)的阳离子。尤其优选的阳离子是锌(II)。
优选的催化剂选自锂、镁、钙、锶和钡的氢氧化物以及钙、钡、钛(IV)、锌(II)和锰(II)的氧化物。
优选锂、镁、钙、锶和钡,尤其是钙、锶和钡的氢氧化物。
优选钙、钡、钛(IV)、锌(II)和锰(II)的氧化物。最优选的催化剂是ZnO和CaO。尤其优选ZnO。还尤其优选CaO。
优选钙和锌(II),尤其是钙的三氟乙酸盐。
还优选钙和锌(II),尤其是钙的乙酸盐。
优选镁、钙、锶、钡和锌(II),尤其是钙、锶和钡的硫酸盐。
本发明方法可以在选自硼酸、碱金属硼酸盐和二氧化硅,优选硼酸的氟化物腐蚀抑制剂存在下进行。在将三氟乙酸用作溶剂的情况下,有利的是在氟化物腐蚀抑制剂存在下进行该方法。腐蚀抑制化合物的用量相对于式(II)化合物通常为约0.01-0.99摩尔当量,优选约0.01-0.2摩尔当量,更优选约0.03-0.15摩尔当量,最优选约0.06-0.1摩尔当量。
本发明方法优选在-40℃至80℃,更优选0-60℃,甚至更优选10-30℃,甚至更优选10-20℃的温度下进行。本发明方法最优选在10-15℃,有利的是在12℃下进行。
反应速率取决于温度并且提高反应速率的有利效果可以在整个温度范围内观察到。当根据本发明方法,即在催化剂存在下进行时,反应速率高于在相同温度下但不加入催化剂下进行的反应的速率。
若判断氧化反应完全,则优选用二氧化硫、亚硫酸钠或等价试剂终止该反应。在将三氟乙酸用作溶剂的情况下,优选通过加入一氯苯并随后在减压下共沸蒸馏而将其除去。在优选实施方案中,将醇如乙醇、甲醇或异丙醇加入残余物中并温热至约80℃,直到形成溶液,然后冷却至约40℃,此时式(I)化合物结晶。
必要的话,分离的式(I)化合物可以通过诸如层析、再结晶等的技术提纯。粗产物的提纯还可以经由在木炭或二氧化硅上过滤或用水洗涤而实现。
式(I)化合物如乙虫清或锐劲特,优选锐劲特的结晶通常由在具有非反应性取代基如氯、氟、氰基、硝基、C1-C8烷基或C1-C8卤代烷基的非极性、惰性、优选芳族溶剂中的溶液进行,特别优选由在如下溶剂中的溶液进行:苯、乙苯、一氯苯、一氟苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、苯乙烯、异丙基苯、正丙基苯、2-氯甲苯、3-氯甲苯、4-氯甲苯、叔丁基苯、仲丁基苯、异丁基苯、正丁基苯、1,3-二异丙基苯、1,4-二异丙基苯、2-硝基甲苯、3-硝基甲苯、4-硝基甲苯、硝基苯、苄腈、三氟甲基苯、1,2-二氯乙烷、乙腈、二甲亚砜、四氢呋喃、丙酮,醇如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、2-丁醇或叔丁醇,或其混合物,优选由在一氯苯、二氯苯、乙苯或甲苯中的溶液进行。
优选由一氯苯进行结晶。
优选由二氯苯进行结晶。
优选由乙苯进行结晶。
优选由甲苯进行结晶。
可能有利的是加入约1-30%极性溶剂如酮类、酰胺、醇类、酯类或醚类,优选酯类、酮类或醚类,如丙酮、甲基乙基酮、戊-2-酮、二乙基酮、4-甲基-2-戊酮、3-甲基-2-丁酮、叔丁基甲基酮、环己酮、乙酸甲酯、乙酸乙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、碳酸二乙酯、乙酸2-丁氧基乙酯、二甲基甲酰胺、二甲基乙酰胺、二甲亚砜、硝基甲烷、硝基乙烷、水、乙醇、甲醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、叔丁醇、2-甲基-1-丙醇、2-甲基-2-丙醇、3-戊醇、2-甲基-1-丁醇、3-甲基-1-丁醇、1,2-乙二醇、1,3-丙二醇、1,2-丙二醇、环己醇、二烷、四氢呋喃、乙醚、甲基叔丁基醚、2-甲基四氢呋喃、乙腈、丙腈或其混合物。
实施例
反应根据下面在实施例1、2和对比例中所给程序进行。反应速率在所有情况下由HPLC测量以监测原料到所需亚砜的转化率。一旦由HPLC检测到硫化物量>97%且砜量>2%就确定反应结束。
HPLC在装有Chromolith RP18e,100×3mm柱(Merck)的HewlettPackard HP 1050,Chemstation上读取,洗脱剂:450mL水+330mL乙腈+220mL MeOH+1mL磷酸,流速:1.0ml/min,检测:220nm。
各试验进行两次。通过相应改变,使用实施例1和2中所述程序以不同催化剂和/或不同的催化剂摩尔当量进行其他制备试验。试验结果列于下表1中。
实施例1:在ZnO作为催化剂存在下制备锐劲特
锐劲特通过用50重量%过氧化氢水溶液(23.6g,0.35mol)在三氟乙酸(443.4g,3.89mol)中在ZnO(4.9g,0.06mol)存在下于10-12℃氧化5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-4-三氟甲硫基吡唑(105.3g,0.25mol)而得到。4小时后反应完全(转化率根据HPLC分析>97%),然后用SO2终止该反应,然后加入一氯苯并通过在减压下共沸蒸馏而除去三氟乙酸。残余物由一氯苯/乙醇结晶。通过减压蒸馏除去乙醇并将悬浮液在10℃下过滤。用一氯苯、乙醇/水和水洗涤,然后真空干燥,以无色固体得到锐劲特(96-97g,纯度根据HPLC>95重量%)。
实施例2:在ZnO作为催化剂存在下并在加入腐蚀抑制剂下制备锐劲特
锐劲特通过用50重量%过氧化氢水溶液(23.6g,0.35mol)在三氟乙酸(443.4g,3.89mol)中在硼酸(1.3g,0.02mol)和ZnO(4.9g,0.06mol)存在下于10-12℃氧化5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-4-三氟甲硫基吡唑(105.3g,0.25mol)而得到。4小时后反应完全(转化率根据HPLC分析>97%),然后用SO2终止该反应,然后加入一氯苯并通过在减压下共沸蒸馏而除去三氟乙酸。残余物由一氯苯/乙醇结晶。通过减压蒸馏除去乙醇并将悬浮液在10℃下过滤。用一氯苯、乙醇/水和水洗涤,然后真空干燥,以无色固体得到锐劲特(94-96g,纯度根据HPLC>95重量%)。
对比例:在不加入催化剂下制备锐劲特
该反应如上面对实施例2所述进行,但不加入催化剂。该反应在6.5小时内完成(转化率根据HPLC分析大于97%)。锐劲特以无色固体得到(96-97g,纯度根据HPLC>95重量%)。
表1:制备锐劲特
实施例号 | 催化剂 | mol | B(OH)3加料[mol] | 温度[℃] | 反应完成时间[小时]# |
1 | ZnO | 0.06 | - | 10-12℃ | 4 |
2 | ZnO | 0.06 | 0.02 | 10-12℃ | 4 |
3 | ZnO | 0.12 | - | 10-12℃ | 3.5 |
4 | ZnO | 0.03 | - | 10-12℃ | 4.5 |
5 | ZnO | 0.06 | - | 5-7℃ | 6 |
6 | ZnO | 0.06 | - | 15-17℃ | 3.5 |
7 | CaO | 0.06 | - | 10-12℃ | 3-4 |
8 | CaO | 0.06 | 0.02 | 10-12℃ | 3-4 |
9 | CaO | 0.12 | - | 10-12℃ | 3 |
10 | CaO | 0.03 | - | 10-12℃ | 4 |
11 | CaO | 0.06 | - | 5-7℃ | 5 |
12 | CaO | 0.06 | - | 15-17℃ | 3 |
13 | BaO | 0.06 | - | 10-12℃ | 4.5 |
14 | MnO | 0.06 | - | 10-12℃ | 6 |
15 | TiO2 | 0.06 | - | 10-12℃ | 6.25 |
16 | Ca(OH)2 | 0.06 | - | 10-12℃ | 4 |
17 | Ca(OH)2 | 0.03 | - | 10-12℃ | 5 |
18 | Mg(OH)2 | 0.06 | - | 10-12℃ | 6 |
19 | LiOH | 0.12 | - | 10-12℃ | 6 |
20 | Ba(OH)2 | 0.06 | - | 10-12℃ | 4.5 |
21 | Sr(OH)2 | 0.06 | - | 10-12℃ | 4 |
22 | CaSO4 | 0.06 | - | 10-12℃ | 6 |
23 | 乙酸钙 | 0.06 | - | 10-12℃ | 3.5 |
对比例 | 无 | - | 0.02 | 10-12℃ | 6.5 |
#转化率根据HPLC分析大于97%
Claims (17)
1.通过在选自锂、镁、钙、锶、钡、钛(IV)、锌(II)和锰(II)的氢氧化物、氧化物、硫酸盐、乙酸盐或三氟乙酸盐的催化剂存在下用选自三氟过乙酸和三氯过乙酸的氧化剂氧化式(II)化合物而制备式(I)化合物的方法:
其中
R1、R2、R3、R4和R5各自独立地选自氢、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、硝基、氰基和五氟硫基;和
R6为C1-C4烷基或C1-C4卤代烷基;
其中R1、R2、R3、R4、R5和R6如对式(I)化合物所定义。
2.根据权利要求1的方法,其中
R1和R5为氯;
R2和R4为氢;和
R3为三氟甲基。
3.根据权利要求1的方法,其中R6为三氟甲基或乙基。
4.根据权利要求2的方法,其中R6为三氟甲基或乙基。
5.根据权利要求2的方法,其中R6为三氟甲基。
6.根据权利要求1-5中任一项的方法,其中所述方法在选自如下的溶剂中进行:三氟乙酸,三氟乙酸和一氯苯或三氟乙酸和二氯甲烷的混合物,以及三氯乙酸与熔点降低剂的混合物。
7.根据权利要求6的方法,其中所述熔点降低剂选自一氯苯、一氯乙酸、二氯乙酸、二氯乙烷和二氯甲烷。
8.根据权利要求1-5中任一项的方法,其中所述方法在作为溶剂的三氟乙酸中进行。
9.根据权利要求6的方法,其中所述方法在作为溶剂的三氟乙酸中进行。
10.根据权利要求1-5中任一项的方法,其中所述催化剂选自锂、镁、钙、锶和钡的氢氧化物以及钙、钡、钛(IV)、锌(II)和锰(II)的氧化物。
11.根据权利要求8的方法,其中所述催化剂选自锂、镁、钙、锶和钡的氢氧化物以及钙、钡、钛(IV)、锌(II)和锰(II)的氧化物。
12.根据权利要求1-5中任一项的方法,其中所述催化剂为ZnO或CaO。
13.根据权利要求10的方法,其中所述催化剂为ZnO或CaO。
14.根据权利要求1-5中任一项的方法,其中所述方法在选自硼酸、碱金属硼酸盐和二氧化硅的氟化物腐蚀抑制剂存在下进行。
15.根据权利要求12的方法,其中所述方法在选自硼酸、碱金属硼酸盐和二氧化硅的氟化物腐蚀抑制剂存在下进行。
16.根据权利要求1-5中任一项的方法,其中所述方法在0-40℃的温度下进行。
17.根据权利要求14的方法,其中所述方法在0-40℃的温度下进行。
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BRPI1104747B1 (pt) * | 2011-09-14 | 2017-11-28 | Rotam Agrochem International Company Limited | Process for the preparation of n-substituted pyrazole compounds |
JP5822349B2 (ja) * | 2011-12-02 | 2015-11-24 | 公立大学法人首都大学東京 | 有機硫黄化合物の酸化触媒 |
CN102633722B (zh) * | 2012-03-20 | 2015-05-06 | 金坛市凌云动物保健品有限公司 | 一种非泼罗尼的制备方法 |
JP6086622B2 (ja) * | 2015-06-16 | 2017-03-01 | 公立大学法人首都大学東京 | 有機硫黄化合物の酸化触媒、有機硫黄化合物の酸化触媒の製造方法、有機硫黄化合物を選択的に酸化する方法 |
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