JP4526385B2 - 4,6−ジクロロ−5−フルオロピリミジンの調製方法 - Google Patents
4,6−ジクロロ−5−フルオロピリミジンの調製方法 Download PDFInfo
- Publication number
- JP4526385B2 JP4526385B2 JP2004513265A JP2004513265A JP4526385B2 JP 4526385 B2 JP4526385 B2 JP 4526385B2 JP 2004513265 A JP2004513265 A JP 2004513265A JP 2004513265 A JP2004513265 A JP 2004513265A JP 4526385 B2 JP4526385 B2 JP 4526385B2
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- JP
- Japan
- Prior art keywords
- fluoropyrimidine
- formula
- phosgene
- preparation
- catalyst
- 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.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title claims description 24
- DGMIGAHDDPJOPN-UHFFFAOYSA-N 4,6-dichloro-5-fluoropyrimidine Chemical compound FC1=C(Cl)N=CN=C1Cl DGMIGAHDDPJOPN-UHFFFAOYSA-N 0.000 title description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 24
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 22
- -1 alkali metal salt Chemical class 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- XGSFAIWGUAFXSG-UHFFFAOYSA-N 5-fluoro-4-hydroxy-1h-pyrimidin-6-one Chemical compound OC=1N=CNC(=O)C=1F XGSFAIWGUAFXSG-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003444 phase transfer catalyst Substances 0.000 description 6
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical class OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 150000003230 pyrimidines Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- XJPZKYIHCLDXST-UHFFFAOYSA-N 4,6-dichloropyrimidine Chemical compound ClC1=CC(Cl)=NC=N1 XJPZKYIHCLDXST-UHFFFAOYSA-N 0.000 description 2
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical compound OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YCBRTSYWJMECAH-UHFFFAOYSA-N tributyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC YCBRTSYWJMECAH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FZOUAEDABZNHJD-UHFFFAOYSA-L 1-(2-ethylhexyl)-N,N-dimethylpyridin-1-ium-4-amine sulfate Chemical compound CCCCC(CC)C[N+]1=CC=C(C=C1)N(C)C.CCCCC(CC)C[N+]1=CC=C(C=C1)N(C)C.[O-]S(=O)(=O)[O-] FZOUAEDABZNHJD-UHFFFAOYSA-L 0.000 description 1
- DIFDOPSLBYNPKJ-UHFFFAOYSA-M 1-(2-ethylhexyl)-n,n-dimethylpyridin-1-ium-4-amine;bromide Chemical compound [Br-].CCCCC(CC)C[N+]1=CC=C(N(C)C)C=C1 DIFDOPSLBYNPKJ-UHFFFAOYSA-M 0.000 description 1
- VENGGGZJFDLMED-UHFFFAOYSA-M 1-(2-ethylhexyl)-n,n-dimethylpyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCC(CC)C[N+]1=CC=C(N(C)C)C=C1 VENGGGZJFDLMED-UHFFFAOYSA-M 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- DNCYBUMDUBHIJZ-UHFFFAOYSA-N 1h-pyrimidin-6-one Chemical compound O=C1C=CN=CN1 DNCYBUMDUBHIJZ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- NYEOKRVTIYIBGF-UHFFFAOYSA-N 4,6-dichloro-5-phenylpyrimidine Chemical compound ClC1=NC=NC(Cl)=C1C1=CC=CC=C1 NYEOKRVTIYIBGF-UHFFFAOYSA-N 0.000 description 1
- DBPKMSBWOKAKLA-UHFFFAOYSA-N 4-chloropyrimidine Chemical compound ClC1=CC=NC=N1 DBPKMSBWOKAKLA-UHFFFAOYSA-N 0.000 description 1
- IRGAQJPJIPBZCT-UHFFFAOYSA-N 4-hydroxy-5-phenyl-1h-pyrimidin-6-one Chemical compound N1=CNC(=O)C(C=2C=CC=CC=2)=C1O IRGAQJPJIPBZCT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- MWSPFHZPVVWJCO-UHFFFAOYSA-M hydron;methyl(trioctyl)azanium;sulfate Chemical compound OS([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC MWSPFHZPVVWJCO-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002955 isolation Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- QYQXCUGHLJZLMP-UHFFFAOYSA-L methyl(trioctyl)azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QYQXCUGHLJZLMP-UHFFFAOYSA-L 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 239000011814 protection agent Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000010626 work up procedure 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
- C07D239/30—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
R1、R2、R3及びR4は、各々独立して、分枝鎖若しくは直鎖のC1−C16−アルキルであるか、又は、ベンジル、カプリル、フェニル若しくはトリチルであり、その際、これらの各々は、場合により、ニトロ、メチル、エチル、n−プロピル、i−プロピル、n−ブチル、i−ブチル、s−ブチル、t−ブチル、メトキシ、エトキシ、ジフルオロメチル、トリフルオロメチル、アリル又はプロパルギルで置換されており;
Mは、P又はNであり;
及び、
X2は、ハロゲン化物イオン、硫酸水素イオン、テトラフルオロホウ酸イオン、トリフルオロメタンスルホン酸イオン、酢酸イオン、過塩素酸イオン、リン酸二水素イオン又は硝酸イオンである]
で表される化合物などがある。
4,6−ジヒドロキシ−5−フルオロピリミジンから4,6−ジクロロ−5−フルオロピリミジンを調製するための一般的な手順(1)
Claims (7)
- 使用する前記触媒が4−ジメチルアミノピリジンであることを特徴とする、請求項1に記載の方法。
- 使用する前記触媒がトリアルキルホスフィンオキシドであることを特徴とする、請求項1に記載の方法。
- 使用する前記触媒がトリフェニルホスフィンオキシドであることを特徴とする、請求項1に記載の方法。
- 前記方法を、40℃から反応混合物の還流温度までの温度で実施することを特徴とする、請求項1〜4のいずれか1項に記載の調製方法。
- 式(I)の化合物を調製するために、式(II)の化合物1モル当たり2〜20モルのホスゲンを使用することを特徴とする、請求項1〜5のいずれか1項に記載の方法。
- 式(I)の化合物を調製するために、式(II)の化合物1モル当たり0を越え、30モル%までの触媒を使用することを特徴とする、請求項1〜6のいずれか1項に記載の方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10226220A DE10226220A1 (de) | 2002-06-13 | 2002-06-13 | Verfahren zur Herstellung von 4,6-Dichlor-5-fluorpyrimidin |
PCT/EP2003/005778 WO2003106432A1 (de) | 2002-06-13 | 2003-06-03 | Verfahren zur herstellung von 4,6-dichlor-5-fluorpyrimidin |
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JP2005529184A JP2005529184A (ja) | 2005-09-29 |
JP2005529184A5 JP2005529184A5 (ja) | 2010-02-04 |
JP4526385B2 true JP4526385B2 (ja) | 2010-08-18 |
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JP2004513265A Expired - Lifetime JP4526385B2 (ja) | 2002-06-13 | 2003-06-03 | 4,6−ジクロロ−5−フルオロピリミジンの調製方法 |
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US (1) | US7129353B2 (ja) |
EP (1) | EP1515954B1 (ja) |
JP (1) | JP4526385B2 (ja) |
KR (1) | KR101020656B1 (ja) |
CN (1) | CN1659149B (ja) |
AT (1) | ATE458723T1 (ja) |
AU (1) | AU2003238198A1 (ja) |
BR (1) | BR0311761B1 (ja) |
DE (2) | DE10226220A1 (ja) |
IL (1) | IL165718A (ja) |
MX (1) | MXPA04012361A (ja) |
TW (1) | TW200407314A (ja) |
WO (1) | WO2003106432A1 (ja) |
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JP2008266316A (ja) * | 2007-03-28 | 2008-11-06 | Sumitomo Chemical Co Ltd | 4,5,6−トリクロロピリミジン類の製造方法 |
AR100015A1 (es) | 2013-07-08 | 2016-09-07 | Arysta Lifescience Corp | Procedimiento para preparar fluoxastrobin |
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DE1164418B (de) * | 1960-11-26 | 1964-03-05 | Basf Ag | Verfahren zur Herstellung heterocyclischer Chlorverbindungen |
US4739057A (en) * | 1986-06-30 | 1988-04-19 | Stauffer Chemical Co. | Process for converting organo-hydroxyl compounds to halides |
JPS6422858A (en) * | 1987-07-16 | 1989-01-25 | Mitsui Toatsu Chemicals | Fluorine-containing pyrimidine derivative and its preparation |
US4977264A (en) * | 1988-11-21 | 1990-12-11 | Lonza Ltd. | Process for the production of 4,5-dichloro-6-ethylpyrimidine |
GB9408270D0 (en) * | 1994-04-26 | 1994-06-15 | Zeneca Ltd | Chemical process |
AT402818B (de) * | 1995-06-02 | 1997-09-25 | Chemie Linz Gmbh | Verfahren zur herstellung von reinem 4,6-dichlorpyrimidin |
DE19642533A1 (de) | 1996-10-15 | 1998-04-16 | Bayer Ag | Verfahren zur Herstellung von 4,6-Dichlorpyrimidin |
DE19710609A1 (de) * | 1997-03-14 | 1998-09-17 | Bayer Ag | Substituierte Aminosalicylsäureamide |
WO2000046212A1 (en) * | 1999-02-05 | 2000-08-10 | Syngenta Participations Ag | Method of producing substituted pyrimidine derivatives |
KR100676222B1 (ko) * | 1999-08-18 | 2007-01-30 | 바이엘 악티엔게젤샤프트 | 4,6-디클로로-5-플루오로피리미딘의 제조방법 |
US20020042514A1 (en) * | 2000-06-26 | 2002-04-11 | Doyle Timothy John | Synthesis of chlorinated pyrimidines |
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Publication number | Publication date |
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KR101020656B1 (ko) | 2011-03-09 |
DE50312447D1 (de) | 2010-04-08 |
CN1659149B (zh) | 2011-06-22 |
US7129353B2 (en) | 2006-10-31 |
JP2005529184A (ja) | 2005-09-29 |
EP1515954A1 (de) | 2005-03-23 |
CN1659149A (zh) | 2005-08-24 |
DE10226220A1 (de) | 2003-12-24 |
BR0311761B1 (pt) | 2014-09-16 |
IL165718A (en) | 2011-10-31 |
TW200407314A (en) | 2004-05-16 |
WO2003106432A1 (de) | 2003-12-24 |
EP1515954B1 (de) | 2010-02-24 |
MXPA04012361A (es) | 2005-02-25 |
WO2003106432A8 (de) | 2004-03-18 |
BR0311761A (pt) | 2005-03-08 |
ATE458723T1 (de) | 2010-03-15 |
AU2003238198A1 (en) | 2003-12-31 |
IL165718A0 (en) | 2006-01-15 |
AU2003238198A8 (en) | 2003-12-31 |
US20060014952A1 (en) | 2006-01-19 |
KR20050019113A (ko) | 2005-02-28 |
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