CN101284815B - 吡唑氧乙酸类化合物、制备方法及用途 - Google Patents
吡唑氧乙酸类化合物、制备方法及用途 Download PDFInfo
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- CN101284815B CN101284815B CN2008100248660A CN200810024866A CN101284815B CN 101284815 B CN101284815 B CN 101284815B CN 2008100248660 A CN2008100248660 A CN 2008100248660A CN 200810024866 A CN200810024866 A CN 200810024866A CN 101284815 B CN101284815 B CN 101284815B
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- Prior art keywords
- fluorophenyl
- reacting
- acid
- hours
- compound
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WWQSCJXWLLECRO-UHFFFAOYSA-N 2-(1h-pyrazol-5-yloxy)acetic acid Chemical class OC(=O)COC=1C=CNN=1 WWQSCJXWLLECRO-UHFFFAOYSA-N 0.000 title description 4
- -1 pyrazolyloxyacetic acid compound Chemical class 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 239000003899 bactericide agent Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 71
- 238000001914 filtration Methods 0.000 claims description 60
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 49
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 48
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 11
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- 241000221696 Sclerotinia sclerotiorum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 241001330975 Magnaporthe oryzae Species 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 239000000417 fungicide Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 claims description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CBNLNXLAIMQSTR-UHFFFAOYSA-N 5-ethyl-1h-pyrazole Chemical compound CCC1=CC=NN1 CBNLNXLAIMQSTR-UHFFFAOYSA-N 0.000 claims 3
- MZFBFIIJQKAWCQ-UHFFFAOYSA-N (2-methoxyphenyl) hypofluorite Chemical compound COC1=CC=CC=C1OF MZFBFIIJQKAWCQ-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 241000209140 Triticum Species 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 125000000532 dioxanyl group Chemical group 0.000 claims 1
- MSPOSRHJXMILNK-UHFFFAOYSA-N ethyl 1h-pyrazole-5-carboxylate Chemical compound CCOC(=O)C1=CC=NN1 MSPOSRHJXMILNK-UHFFFAOYSA-N 0.000 claims 1
- 230000000855 fungicidal effect Effects 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 123
- 239000000243 solution Substances 0.000 description 50
- 238000010992 reflux Methods 0.000 description 43
- 238000003756 stirring Methods 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 21
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000007664 blowing Methods 0.000 description 20
- 238000004821 distillation Methods 0.000 description 20
- 238000000605 extraction Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000003814 drug Substances 0.000 description 11
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229940067157 phenylhydrazine Drugs 0.000 description 9
- 240000008067 Cucumis sativus Species 0.000 description 8
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 8
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 8
- 201000010099 disease Diseases 0.000 description 8
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 8
- MDXDLWCTQWPZLI-UHFFFAOYSA-N acetic acid;1h-pyrazole Chemical compound CC(O)=O.C=1C=NNC=1 MDXDLWCTQWPZLI-UHFFFAOYSA-N 0.000 description 6
- IIBXQGYKZKOORG-QPJJXVBHSA-N methyl (e)-3-(4-chlorophenyl)prop-2-enoate Chemical compound COC(=O)\C=C\C1=CC=C(Cl)C=C1 IIBXQGYKZKOORG-QPJJXVBHSA-N 0.000 description 6
- VEZIKIAGFYZTCI-VMPITWQZSA-N methyl 4-methoxycinnamate Chemical compound COC(=O)\C=C\C1=CC=C(OC)C=C1 VEZIKIAGFYZTCI-VMPITWQZSA-N 0.000 description 6
- VEZIKIAGFYZTCI-UHFFFAOYSA-N methyl ester of p-methoxycinnamic acid Natural products COC(=O)C=CC1=CC=C(OC)C=C1 VEZIKIAGFYZTCI-UHFFFAOYSA-N 0.000 description 6
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 5
- 229940106681 chloroacetic acid Drugs 0.000 description 5
- 229930016911 cinnamic acid Natural products 0.000 description 5
- 235000013985 cinnamic acid Nutrition 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 5
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 5
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZTPAUBJZUBGGEY-UHFFFAOYSA-N (2,4-dichlorophenyl)hydrazine Chemical compound NNC1=CC=C(Cl)C=C1Cl ZTPAUBJZUBGGEY-UHFFFAOYSA-N 0.000 description 4
- CUBAAXZFAYBIAI-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-yloxy)propanehydrazide Chemical compound NNC(=O)C(C)OC1=CC=C2OCOC2=C1 CUBAAXZFAYBIAI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 229940114081 cinnamate Drugs 0.000 description 4
- YOOKYIPLSLPRTC-VMPITWQZSA-N ethyl (e)-3-(4-bromophenyl)prop-2-enoate Chemical compound CCOC(=O)\C=C\C1=CC=C(Br)C=C1 YOOKYIPLSLPRTC-VMPITWQZSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- HSNCAEKOZRUMTB-QPJJXVBHSA-N methyl (e)-3-(4-fluorophenyl)prop-2-enoate Chemical compound COC(=O)\C=C\C1=CC=C(F)C=C1 HSNCAEKOZRUMTB-QPJJXVBHSA-N 0.000 description 4
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 3
- QPKCNTDHLKSHGT-UHFFFAOYSA-N (4-tert-butylphenyl)hydrazine Chemical compound CC(C)(C)C1=CC=C(NN)C=C1 QPKCNTDHLKSHGT-UHFFFAOYSA-N 0.000 description 3
- GXLIFJYFGMHYDY-ZZXKWVIFSA-N 4-chlorocinnamic acid Chemical compound OC(=O)\C=C\C1=CC=C(Cl)C=C1 GXLIFJYFGMHYDY-ZZXKWVIFSA-N 0.000 description 3
- 244000098338 Triticum aestivum Species 0.000 description 3
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000006540 mitochondrial respiration Effects 0.000 description 3
- 150000004031 phenylhydrazines Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 2
- RYTBBLWPDBZDHT-MDZDMXLPSA-N (e)-3-(3-phenoxyphenyl)prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=CC(OC=2C=CC=CC=2)=C1 RYTBBLWPDBZDHT-MDZDMXLPSA-N 0.000 description 2
- CPDDDTNAMBSPRN-ZZXKWVIFSA-N (e)-3-(4-bromophenyl)prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=C(Br)C=C1 CPDDDTNAMBSPRN-ZZXKWVIFSA-N 0.000 description 2
- YTFVRYKNXDADBI-SNAWJCMRSA-N 3,4,5-trimethoxycinnamic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1OC YTFVRYKNXDADBI-SNAWJCMRSA-N 0.000 description 2
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- JXRYDOZRPYFBKO-UHFFFAOYSA-N 3,4-dimethoxy-cinnamic acidmethyl ester Natural products COC(=O)C=CC1=CC=C(OC)C(OC)=C1 JXRYDOZRPYFBKO-UHFFFAOYSA-N 0.000 description 2
- HJBWJAPEBGSQPR-GQCTYLIASA-N 3,4-dimethoxycinnamic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1OC HJBWJAPEBGSQPR-GQCTYLIASA-N 0.000 description 2
- VFQOFJQVKVEXIY-UHFFFAOYSA-N 3-(phenylmethoxycarbonylamino)-3-piperidin-3-ylpropanoic acid Chemical compound C1CCNCC1C(CC(=O)O)NC(=O)OCC1=CC=CC=C1 VFQOFJQVKVEXIY-UHFFFAOYSA-N 0.000 description 2
- RURHILYUWQEGOS-VOTSOKGWSA-N 4-Methylcinnamic acid Chemical compound CC1=CC=C(\C=C\C(O)=O)C=C1 RURHILYUWQEGOS-VOTSOKGWSA-N 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- HJBWJAPEBGSQPR-UHFFFAOYSA-N DMCA Natural products COC1=CC=C(C=CC(O)=O)C=C1OC HJBWJAPEBGSQPR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YTFVRYKNXDADBI-UHFFFAOYSA-N O-Methylsinapic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1OC YTFVRYKNXDADBI-UHFFFAOYSA-N 0.000 description 2
- 241000233654 Oomycetes Species 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 241000233679 Peronosporaceae Species 0.000 description 2
- 241000813090 Rhizoctonia solani Species 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000006013 carbendazim Substances 0.000 description 2
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AUMBJIRASKDNSF-UHFFFAOYSA-N ethyl 3-[4-(trifluoromethyl)phenyl]prop-2-enoate Chemical compound CCOC(=O)C=CC1=CC=C(C(F)(F)F)C=C1 AUMBJIRASKDNSF-UHFFFAOYSA-N 0.000 description 2
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- GPKUSCCWJPPDPE-UHFFFAOYSA-N methyl 3-(3-phenoxyphenyl)prop-2-enoate Chemical compound COC(=O)C=CC1=CC=CC(OC=2C=CC=CC=2)=C1 GPKUSCCWJPPDPE-UHFFFAOYSA-N 0.000 description 2
- IKUJXQVPFHNUET-UHFFFAOYSA-N methyl 3-(4-phenoxyphenyl)prop-2-enoate Chemical compound C1=CC(C=CC(=O)OC)=CC=C1OC1=CC=CC=C1 IKUJXQVPFHNUET-UHFFFAOYSA-N 0.000 description 2
- JXRYDOZRPYFBKO-FNORWQNLSA-N methyl-3,4-dimethoxycinnamate Chemical compound COC(=O)\C=C\C1=CC=C(OC)C(OC)=C1 JXRYDOZRPYFBKO-FNORWQNLSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 description 2
- 239000005648 plant growth regulator Substances 0.000 description 2
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- ANRMAUMHJREENI-ZZXKWVIFSA-N (E)-4-(trifluoromethyl)cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=C(C(F)(F)F)C=C1 ANRMAUMHJREENI-ZZXKWVIFSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DXVGPNIYWFSYOB-UHFFFAOYSA-N 1,5-bis(4-fluorophenyl)pyrazolidin-3-one Chemical compound C1C(N(NC1=O)C2=CC=C(C=C2)F)C3=CC=C(C=C3)F DXVGPNIYWFSYOB-UHFFFAOYSA-N 0.000 description 1
- QZUHOTWAEKOWAE-UHFFFAOYSA-N 1-(4-fluorophenyl)-5-(3-phenoxyphenyl)pyrazolidin-3-one Chemical compound C1C(N(NC1=O)C2=CC=C(C=C2)F)C3=CC(=CC=C3)OC4=CC=CC=C4 QZUHOTWAEKOWAE-UHFFFAOYSA-N 0.000 description 1
- UEYXUGKLZBPNML-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-5-phenylpyrazolidin-3-one Chemical compound CC(C)(C)C1=CC=C(C=C1)N2C(CC(=O)N2)C3=CC=CC=C3 UEYXUGKLZBPNML-UHFFFAOYSA-N 0.000 description 1
- KECVDIRJXLPJAD-UHFFFAOYSA-N 2,3-bis(4-fluorophenyl)-1H-pyrazol-5-one Chemical compound C1=CC(=CC=C1C2=CC(=O)NN2C3=CC=C(C=C3)F)F KECVDIRJXLPJAD-UHFFFAOYSA-N 0.000 description 1
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- WUIMREVKIJCBHL-UHFFFAOYSA-N 2-(4-fluorophenyl)-3-(3-phenoxyphenyl)-1H-pyrazol-5-one Chemical compound C1=CC=C(C=C1)OC2=CC=CC(=C2)C3=CC(=O)NN3C4=CC=C(C=C4)F WUIMREVKIJCBHL-UHFFFAOYSA-N 0.000 description 1
- OXAVXMZJZYADSY-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-3-phenyl-1H-pyrazol-5-one Chemical compound C(C)(C)(C)C1=CC=C(C=C1)N1N=C(C=C1C1=CC=CC=C1)O OXAVXMZJZYADSY-UHFFFAOYSA-N 0.000 description 1
- PAGMIENLSYUQLX-UHFFFAOYSA-N 2-phenyl-3-(3,4,5-trimethoxyphenyl)-1h-pyrazol-5-one Chemical compound COC1=C(OC)C(OC)=CC(C=2N(NC(=O)C=2)C=2C=CC=CC=2)=C1 PAGMIENLSYUQLX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种吡唑氧乙酸类化合物、制备方法及用途,该结构通式(I)的化合物,其中,X或Y分别为氢、C1~4烷基、C1~4烷氧基、取代或无取代苯氧基、卤素、硝基或三氟甲基;R为氢或C1~4烷基。本发明还公开了一种这类化合物的制备方法以及其在制备杀菌剂方面的应用。
Description
技术领域
本发明属于有机化学领域,具体涉及一种吡唑氧乙酸类化合物、制备方法,以及这类化合物在杀菌剂方面的应用。
背景技术
含氮杂环是一类具有重要应用价值和良好的生物活性的化合物,已有许多杂环被开发成新的医药和农药品种,在人类健康和农业生产中发挥着重要作用。目前国内外许多课题组在从事这一领域的研究与开发。随着我国加入WTO,实行知识产权保护,迫切需要加强杂环领域的研究,发出具有自己知识产权的新药。目前关于新型杂环的研究十分活跃,吡唑类杂环由于具有广泛的生物活性而备受重视,已发现许多吡唑类杀菌剂、杀虫剂、除草剂、植物生长调节剂和医药等。
Yoshioka Koichi报道,一些吡唑烷酮类化合物具有杀菌性能[Koichi Y,Norikazu T.Preparation of 2-(3-oxo-2-pyrazolidinyl)-5-oxo-2-tetrahydrofurancarboxylic acid derivatives antibaceterial agents[P].JP 6221558,1987,09]。该类化合物表现出良好的杀菌活性,在田间试验中具有触杀、内吸活性,表现出良好的保护和治疗活性,尤其对卵菌引起的霜霉病、疫病等具有很好的活性。而由卵菌引起的植物病害大多难以控制,尤其是霜霉病和疫病潜育期短,再浸染次数多,在植物的一个生长季节内可迅速发展造成病害流行。对其杀菌作用机制的研究显示出:它是一种新型线粒体呼吸抑制剂,线粒体呼吸抑制剂由于作用方式独特、杀菌谱广、尤其对抗性菌株有效而备受关注。菌体所需的能量来自体内的糖类、脂肪、蛋白质等营养物质的氧化分解,最终生成二氧化碳和水,其中伴随着脱氢过程和电子传递的一系列氧化还原反应,即生物呼吸。而通过抑制菌体线粒体呼吸进而抑制能量生成而起到杀菌作用,正是线粒体呼吸抑制剂独特的作用机制。赵雁来等也报道了一些具有杀菌性能的吡唑类化合物[赵雁来,何林泉.杂环化学导论[M].北京.高等教育出版社.1992:229]。同时苯氧乙酸的衍生物也具有较强的抗菌活性,通常应用于除草剂,也可以作为植物生长调节剂,在医药领域多作为降血脂类的药物使用。
发明内容
本发明的目的是提供一种具有药效活性的吡唑氧乙酸类化合物。
本发明的另一目的是提供一种上述化合物的制备方法。
本发明还有一个目的是提供一种上述化合物的用途。
本发明的目的可以通过以下措施达到:
一种结构通式(I)的化合物或其盐,
其中,
X或Y分别为氢、C1~4烷基、C1~4烷氧基、取代或无取代苯氧基、卤素、硝基或三氟甲基,优选为氢、C1~4烷基、甲氧基、苯氧基、氟、氯、溴、硝基或三氟甲基;
R为氢或C1~4烷基,优选为氢或乙基。
本发明所述的取代或无取代苯氧基,其中的取代基为C1~4烷基、硝基或卤素,优选为无取代的苯氧基。
一种结构通式(I)的化合物的制备方法,其合成路线如下:
取代的肉桂酸在对甲苯磺酸的存在下与甲醇或乙醇反应,生成取代的肉桂酸酯;向甲醇钠溶液中加入正丁醇和取代的肉桂酸酯,在0~100℃下反应1~24h,再加入苯肼或取代苯肼,反应0~24h,得到1,5-二芳基-3-吡唑烷酮;将1,5-二芳基-3-吡唑烷酮于N,N-二甲基甲酰胺溶液中,鼓入空气,在0~100℃下反应,冷却后过滤得到1,5-二芳基-3-羟基吡唑;然后与卤代烷酸或卤代烷酸酯反应,生成化合物(I)。其中取代的肉桂酸中的取代基X的概念如上所述,取代苯肼中的取代基Y的概念如上所述。
在搅拌下,向无水乙醇、无水甲醇中加入取代的肉桂酸,对甲苯磺酸,回流反应0~24h,生成取代的肉桂酸酯;在搅拌下向新制的甲醇钠溶液中加入正丁醇,再加入取代的肉桂酸酯,回流反应0~24h,再加入适量的苯肼或取代苯肼,继续加热回流反应0~24h,冷却后,过滤,得到1,5-二芳基-3-吡唑烷酮。将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在10~100℃下反应0~24h后,冷却至室温,倒入盛有水的烧杯中,冷却后过滤得到1,5-二芳基-3-羟基吡唑;然后在二氧六环、乙睛、N,N-二甲基甲酰胺、丙酮、二氯甲烷、三氯甲烷等溶剂或水溶液中,在三乙胺、碳酸钾、碳酸钠,氢氧化钠,氢氧化钾碱性条件下与溴乙酸、氯乙酸、氯乙酸钠、溴乙酸乙酯、氯乙酸乙酯反应后成权利1所述结构的(I)型1,5-二芳基-3-氧乙酸乙酯吡唑;然后在氢氧化钠水溶液中水解生成1,5-二芳基-3-氧乙酸吡唑。。
本发明的化合物可以制备杀菌剂,可以应用在油菜菌核病敏株Sclerotiniasclerotiorum、蔬菜灰霉病敏感菌株Botryris cinerea Pers.、赤霉病敏感菌株Gibbrellazeae(Schw.)Petch、小麦纹枯病敏感菌株Rhizoctorua solani或稻瘟病菌Pyricularia oryzaeCav等菌引起的多种病害。
本发明的新型吡唑氧乙酸类杀菌剂可以用多种作物的病害防治,包括人参、西洋参、三七、白术、贝母、砂仁、菊花、枸杞或百合的药用植物;小麦、玉米、水稻、马铃薯、甜菜、花生或棉花的大田植物;白菜、番茄、黄瓜、辣椒或扁豆的蔬菜作物;桃、梨、葡萄或草莓的园艺作物;君子兰或芦荟的花卉。
具体实施方式
实施例1
在搅拌下,向4-甲氧基肉桂酸(0.05mol)中加入无水甲醇50ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏除去甲醇得到4-甲氧基肉桂酸甲酯8.82g;在搅拌下向新制的28%甲醇钠溶液中加入4-甲氧基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入8ml苯肼,继续加热回流反应24h后,冷却,过滤,得到1-苯基-5-(4-甲氧基苯基)-3-吡唑烷酮10.11g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-苯基-5-(4-甲氧基苯基)-3-羟基吡唑8.92g,收率66.9%;取其中4.42g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-苯基-5-(4-甲氧基苯基)-3-氧乙酸乙酯基吡唑4.91g,收率83.4%。1H NMRδ:1.30(t,3H),3.79(s,3H),4.27(q,2H),4.86(s,2H),5.98(s,1H),6.80(d,2H),7.13~7.29(m,7H)。
实施例2
在搅拌下,向3,4,5-三甲氧基肉桂酸(0.1mol)中加入无水甲醇100ml,对甲苯磺酸0.5g,回流反应2h后,减压蒸馏得4-甲氧基肉桂酸甲酯19.68g;在搅拌下向新制的28%甲醇钠溶液中加入3,4,5-三甲氧基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入10ml苯肼,继续加热回流反应24h后,冷却,过滤,得到1-苯基-5-(3,4,5-三甲氧基苯基)-3-吡唑烷酮24.96g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-苯基-5-(3,4,5-三甲氧基苯基)-3-羟基吡唑22.61g,收率69.3%;取其中11.31g羟基吡唑加到100ml水中,滴加等量的溴乙酸,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-苯基-5-(3,4,5-三甲氧基苯基)-3-氧乙酸基吡唑10.50g,收率79.0%。1H NMRδ:3.57(s,6H),3.65(s,3H),4.83(s,2H),6.26(s,1H),6.48(s,2H),7.22~7.39(m,5H),8.0(s,1H)。
实施例3
在搅拌下,向4-溴肉桂酸(0.05mol)中加入无水乙醇20ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-溴肉桂酸乙酯11.29g;在搅拌下向新制的28%甲醇钠溶液中加入4-溴肉桂酸乙酯和50ml正丁醇,在100℃下反应4h后,再加入6.55g对氟苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-氟苯基)-5-(4-溴苯基)-3-吡唑烷酮12.1g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-氟苯基)-5-(4-溴苯基)-3-羟基吡唑10.92g,收率65.3%;取其中5.32g羟基吡唑加到100ml水中,滴加等量的氯乙酸,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-氟苯基)-5-(4-溴苯基)-3-氧乙酸基吡唑4.98g,收率80.0%。1H NMRδ:4.88(s,2H),6.26(s,1H),6.88(d,2H),7.02(d,2H),7.22(d,2H)7.43(d,2H),8.5(s,1H)。
实施例4
在搅拌下,向4-三氟甲基肉桂酸(0.05mol)中加入无水乙醇20ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-三氟甲基肉桂酸乙酯9.77g;在搅拌下向新制的28%甲醇钠溶液中加入4-三氟甲基肉桂酸乙酯和50ml正丁醇,在100℃下反应4h后,再加入8ml苯肼,继续加热回流反应24h后,冷却,过滤,得到1-苯基-5-(4-三氟甲基苯基)-3-吡唑烷酮,10.15g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-苯基-5-(4-三氟甲基苯基)-3-羟基吡唑,9.40g,收率70.2%;取其中5.40g羟基吡唑加到100ml水中,滴加等量的氯乙酸钠,在100℃下反应2h后,乙酸乙酯提取,水层用1N盐酸溶液中和,再用乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-苯基-5-(4-三氟甲基苯基)-3-氧乙酸基吡唑5.40g,收率82.1%。1H NMRδ:4.83(s,2H),6.16(s,1H),7.10~7.31(m,9H),8.5(s,1H)。
实施例5
在搅拌下,向4-氟肉桂酸(0.05mol)中加入无水甲醇20ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-氟肉桂酸甲酯8.28g;在搅拌下向新制的28%甲醇钠溶液中加入4-氟肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入9.4g对甲基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-甲基苯基)-5-(4-氟苯基)-3-吡唑烷酮10.45g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-甲基苯基)-5-(4-氟苯基)-3-羟基吡唑8.20g,收率61.2%;取其中4.00g羟基吡唑加到100ml水中,滴加等量的氯乙酸钠,在100℃下反应2h后,用1N盐酸溶液中和,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-甲基苯基)-5-(4-氟苯基)-3-氧乙酸基吡唑4.10g,收率84.2%。1H NMRδ:2.49(s,3H),4.83(s,2H),6.16(s,1H),7.10~7.21(m,4H),7.280~7.41(m,4H),8.5(s,1H)。
实施例6
在搅拌下,向3,4-二甲氧基肉桂酸(0.03mol)中加入无水甲醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得3,4-二甲氧基肉桂酸甲酯5.95g和50ml正丁醇;在搅拌下向新制的28%甲醇钠溶液中加入3,4-二甲氧基肉桂酸甲酯,在100℃下反应4h后,再加入3.75g对氟苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-氟苯基)-5-(3,4-二甲氧基苯基)-3-吡唑烷酮7.28g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-氟苯基)-5-(3,4-二甲氧基苯基)-3-羟基吡唑6.50g,收率72.8%;取其中3.50g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-氟苯基)-5-(3,4-二甲氧基苯基)-3-氧乙酸乙酯基吡唑3.40g,收率74.8%。1H NMRδ:1.30(t,3H),3.73(s,6H),4.27(q,2H),4.83(s,2H),6.09(s,1H),6.80~7.08(m,5H),7.20~7.29(d,2H)
实施例7
在搅拌下,向肉桂酸(0.05mol)中加入无水甲醇50ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得肉桂酸甲酯7.85g;在搅拌下向新制的28%甲醇钠溶液中加入肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入9.8g对叔丁基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-叔丁基苯基)-5-苯基-3-吡唑烷酮14.55g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-叔丁基苯基)-5-苯基-3-羟基吡唑,14.65g,收率89.9%;取其中7.65g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-叔丁基苯基)-5-苯基-3-氧乙酸乙酯基吡唑9.1g,收率94.0%。1H NMRδ:1.32(s,9H),4.25(q,2H),4.80(s,2H),6.12(s,1H),7.26~7.49(m,9H)。
实施例8
在搅拌下,向4-甲基肉桂酸(0.05mol)中加入无水甲醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-甲基肉桂酸甲酯8.00g;在搅拌下向新制的28%甲醇钠溶液中加入4-甲基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入2,4-二氯苯肼9.8g,继续加热回流反应24h后,冷却,过滤,得到1-(2,4-二氯苯基)-5-(4-甲基苯基)-3-吡唑烷酮10.95g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应2h后,冷却至室温,过滤,得到1-(2,4-二氯苯基)-5-(4-甲基苯基)-3-羟基吡唑,8.90g,收率55.2%;取其中4.90g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(2,4-二氯苯基)-5-(4-甲基苯基)-3-氧乙酸乙酯吡唑5.20g,收率83.2%。1H NMRδ:1.30(t,3H),2.35(s,3H),4.12(q,2H),4.90(s,2H),6.12(s,1H),7.12~7.36(m,7H)。
实施例9
在搅拌下,向3-苯氧基肉桂酸(0.05mol)中加入无水甲醇80ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-苯氧基肉桂酸甲酯10.50g;在搅拌下向新制的28%甲醇钠溶液中加入3-苯氧基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入2,4-二氯苯肼9.8g,继续加热回流反应24h后,冷却,过滤,得到1-(2,4-二氯苯基)-5-(3-苯氧基苯基)-3-吡唑烷酮15.60g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应3h后,冷却至室温,过滤,得到1-(2,4-二氯苯基)-5-(3-苯氧基苯基)-3-羟基吡唑11.90g,收率59.3%;取其中6.90g羟基吡唑加到100ml四口烧瓶中,加入3.0g碳酸钾和100ml丙酮,慢慢滴加等量的溴乙酸乙酯,回流反应2h后,除去丙酮,加入水100ml,用乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(2,4-二氯苯基)-5-(4-苯氧基苯基)-3-氧乙酸乙酯吡唑6.10g,收率72.5%。1H NMRδ:1.32(t,3H),4.25(q,2H),4.80(s,2H),6.12(s,1H),6.86~7.20(m,10H),7.40~7.47(d,2H)。
实施例10
在搅拌下,向4-氯肉桂酸(0.05mol)中加入无水甲醇50ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-氯肉桂酸甲酯8.85g;在搅拌下向新制的28%甲醇钠溶液中加入4-氯肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入2,4-二硝基苯肼11.0g,继续加热回流反应24h后,冷却,过滤,得到1-(2,4-二硝基苯基)-5-(4-氯苯基)-3-吡唑烷酮12.0g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应4h后,冷却至室温,过滤,得到1-(2,4-二硝基苯基)-5-(4-氯苯基)-3-羟基吡唑9.70g,收率53.5%;取其中6.70g羟基吡唑加到100ml四口烧瓶中,加入0.8g氢氧化钠和100ml无水甲醇,慢慢滴加等量的溴乙酸乙酯,回流反应2h后,除去甲醇,加入水100ml,用乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(2,4-二硝基苯基)-5-(4-氯苯基)-3-氧乙酸乙酯基吡唑6.10g,收率73.1%。1H NMRδ:1.32(t,3H),4.25(q,2H),4.80(s,2H),6.12(s,1H),7.30~7.33(d,2H),7.42~7.47(d,2H),7.80(d,1H),8.62(d,1H),8.99(s,1H)。
实施例11
搅拌下,向4-氯肉桂酸(0.03mol)中加入无水甲醇20ml,对甲苯磺酸0.2g,回流反应2h后,减压蒸馏除去甲醇得到4-氯肉桂酸甲酯5.55g;在搅拌下向新制的28%甲醇钠溶液中加入4-氯肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入4.9g对叔丁基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-叔丁基苯基)-5-(4-氯苯基)-3-吡唑烷酮8.10g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-叔丁基苯基)-5-(4-氯苯基)-3-羟基吡唑6.18g,收率62.3%;取其中4.00g羟基吡唑加到100ml水中,滴加等量的氯乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-叔丁基苯基)-5-(4-氯苯基)-3-氧乙酸乙酯吡唑3.84g,收率75.8%。1H NMRδ:1.29(t,3H),1.32(s,9H),4.23(q,2H),4.89(s,2H),6.02(s,1H),7.16~7.33(m,8H)。
实施例12
在搅拌下,向4-甲基肉桂酸(0.05mol)中加入无水甲醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-甲基肉桂酸甲酯8.10g;在搅拌下向新制的28%甲醇钠溶液中加入4-甲基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入对氟苯肼6.5g,继续加热回流反应24h后,冷却,过滤,得到1-(对氟苯基)-5-(4-甲基苯基)-3-吡唑烷酮10.65g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应2h后,冷却至室温,过滤,得到1-(对氟苯基)-5-(4-甲基苯基)-3-羟基吡唑,9.50g,收率70.4%;取其中5.50g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(对氟苯基)-5-(4-甲基苯基)-3-氧乙酸乙酯吡唑5.53g,收率75.6%。1H NMRδ:1.29(t,3H),2.45(s,3H),4.26(q,2H),4.83(s,2H),6.12(s,1H),7.16~7.33(m,8H)。
实施例13
在搅拌下,向肉桂酸(0.05mol)中加入无水甲醇50ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得肉桂酸甲酯7.55g;在搅拌下向新制的28%甲醇钠溶液中加入肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入2,4-二氯苯肼8.9g,继续加热回流反应24h后,冷却,过滤,得到1-(2,4-二氯苯基)-5-苯基-3-吡唑烷酮12.78g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应2h后,冷却至室温,过滤,得到1-(2,4-二氯苯基)-5-苯基-3-羟基吡唑,10.85g,收率70.2%;取其中5.85g羟基吡唑加到100ml水中,滴加等量的氯乙酸,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(2,4-二氯苯基)-5-苯基-3-氧乙酸吡唑4.12g,收率60.0%。1H NMRδ:4.69(s,2H),6.22(s,1H),7.26~7.43(m,8H),10.0(s,1H)。
实施例14
在搅拌下,向4-甲氧基肉桂酸(0.05mol)中加入无水甲醇20ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏除去甲醇得到4-甲氧基肉桂酸甲酯8.90g;在搅拌下向新制的28%甲醇钠溶液中加入4-甲氧基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入6.5g对氟苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-氟苯基)-5-(4-甲氧基苯基)-3-吡唑烷酮11.38g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-氟苯基)-5-(4-甲氧基苯基)-3-羟基吡唑9.42g,收率65.9%;取其中5.00g羟基吡唑加到100ml水中,滴加等量的氯乙酸,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-氟苯基)-5-(4-甲氧基苯基)-3-氧乙酸基吡唑4.81g,收率80.1%。1H NMRδ:3.89(s,3H),4.89(s,2H),6.12(s,1H),7.22~7.43(m,8H),8.0(s,1H)。
实施例15
在搅拌下,向3,4-二甲氧基肉桂酸(0.03mol)中加入无水甲醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得3,4-二甲氧基肉桂酸甲酯6.00g和50ml正丁醇;在搅拌下向新制的28%甲醇钠溶液中加入3,4-二甲氧基肉桂酸甲酯,在100℃下反应4h后,再加入4.9g对叔丁基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-叔丁基苯基)-5-(3,4-二甲氧基苯基)-3-吡唑烷酮8.55g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-叔丁基苯基)-5-(3,4-二甲氧基苯基)-3-羟基吡唑7.70g,收率72.3%;取其中4.70g羟基吡唑加到100ml水中,滴加等量的氯乙酸,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-叔丁基苯基)-5-(4-三氟甲基苯基)-3-氧乙酸吡唑4.30g,收率78.9%。1H NMRδ:1.32(s,9H),4.89(s,2H),6.12(s,1H),7.02~7.23(m,4H),7.32~7.48(m,4H),8.0(s,1H)。
实施例16
在搅拌下,向3,4,5-三甲氧基肉桂酸(0.05mol)中加入无水甲醇40ml,对甲苯磺酸0.5g,回流反应2h后,减压蒸馏得4-甲氧基肉桂酸甲酯10.90g;在搅拌下向新制的28%甲醇钠溶液中加入3,4,5-三甲氧基肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入6.5g对甲基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-甲基苯基)-5-(3,4,5-三甲氧基苯基)-3-吡唑烷酮13.80g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-甲基苯基)-5-(3,4,5-三甲氧基苯基)-3-羟基吡唑10.75g,收率63.3%;取其中6.45g羟基吡唑加到100ml水中,滴加等量的溴乙酸乙酯,在100℃下反应2h后,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-甲基苯基)-5-(3,4,5-三甲氧基苯基)-3-氧乙酸乙酯基吡唑6.63g,收率81.5%。1H NMRδ:1.30(t,3H),2.32(s,3H),3.56(s,6H),3.65(s,3H),4.26(q,2H),4.89(s,2H),6.11(s,1H),7.12~7.23(m,4H),7.48(d,2H)。
实施例17
在搅拌下,向4-溴肉桂酸(0.05mol)中加入无水乙醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-溴肉桂酸乙酯11.10g;在搅拌下向新制的28%甲醇钠溶液中加入4-溴肉桂酸乙酯和50ml正丁醇,在100℃下反应4h后,再加入6.5g对甲基苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-甲基苯基)-5-(4-溴苯基)-3-吡唑烷酮12.10g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-甲基苯基)-5-(4-溴苯基)-3-羟基吡唑10.87g,收率65.9%;取其中5.87g羟基吡唑加到100ml无水丙酮溶液中,滴加等量的溴乙酸乙酯,回流反应2h后,除去丙酮,加水,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-甲基苯基)-5-(4-溴苯基)-3-氧乙酸乙酯吡唑5.87g,收率78.8%。1H NMRδ:1.30(t,3H),2.32(s,3H),4.26(t,2H),4.89(s,2H),6.08(s,1H),6.82~7.03(d,2H),7.08~7.23(m,4H),7.32~7.43(d,2H)。
实施例18
搅拌下,向4-氯肉桂酸(0.05mol)中加入无水甲醇50ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏除去甲醇得到4-氯肉桂酸甲酯8.90g;在搅拌下向新制的28%甲醇钠溶液中加入4-氯肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入2,4-二氯苯肼8.9g,继续加热回流反应24h后,冷却,过滤,得到1-(4-2,4-二氯苯基)-5-(4-氯苯基)-3-吡唑烷酮13.30g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应5h后,冷却至室温,过滤,得到1-(4-2,4-二氯苯基)-5-(4-氯苯基)-3-羟基吡唑12.49g,收率72.7%;取其中6.00g羟基吡唑加到100ml水中,滴加等量的氯乙酸钠,在100℃下反应2h后,6N盐酸溶液中和,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-2,4-二氯苯基)-5-(4-氯苯基)-3-氧乙酸基吡唑5.76g,收率82.2%。1H NMRδ:,4.86(s,2H),6.18(s,1H),6.89~7.23(m,4H),7.38~7.43(m,2H),7.52~7.53(s,1H)。
实施例19
在搅拌下,向4-氟肉桂酸(0.05mol)中加入无水甲醇40ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-氟肉桂酸甲酯8.38g;在搅拌下向新制的28%甲醇钠溶液中加入4-氟肉桂酸甲酯和50ml正丁醇,在100℃下反应4h后,再加入6.5g对氟苯肼,继续加热回流反应24h后,冷却,过滤,得到1-(4-氟苯基)-5-(4-氟苯基)-3-吡唑烷酮11.25g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应1h后,冷却至室温,过滤,得到1-(4-氟苯基)-5-(4-氟苯基)-3-羟基吡唑9.91g,收率72.3%;取其中5.91g羟基吡唑加到100ml水中,滴加等量的氯乙酸钠,在100℃下反应2h后,6N盐酸溶液中和,乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-氟苯基)-5-(4-氟苯基)-3-氧乙酸基吡唑5.01g,收率70.0%。1H NMRδ:4.69(s,2H),5.98(s,1H),6.82(d,2H),7.15~7.23(m,4H),7.43(m,2H)。
实施例20
在搅拌下,向3-苯氧基肉桂酸(0.05mol)中加入无水甲醇80ml,对甲苯磺酸0.3g,回流反应2h后,减压蒸馏得4-苯氧基肉桂酸甲酯9.50g和50ml正丁醇;在搅拌下向新制的28%甲醇钠溶液中加入3-苯氧基肉桂酸甲酯,在100℃下反应4h后,再加入对氟苯肼6.5g,继续加热回流反应24h后,冷却,过滤,得到1-(4-氟苯基)-5-(3-苯氧基苯基)-3-吡唑烷酮13.60g;将该化合物溶于N,N-二甲基甲酰胺溶液中,鼓入空气,在100℃下反应3h后,冷却至室温,过滤,得到1-(4-氟苯基)-5-(3-苯氧基苯基)-3-羟基吡唑10.84g,收率62.1%;取其中5.84g羟基吡唑加到100ml四口烧瓶中,加入0.7g氢氧化钠和100ml丙酮,慢慢滴加等量的溴乙酸乙酯,回流反应2h后,除去丙酮,加入水100ml,用乙酸乙酯提取,无水硫酸镁干燥,过滤,除去乙酸乙酯后得到1-(4-氟苯基)-5-(4-苯氧基苯基)-3-氧乙酸乙酯基吡唑5.76g,收率78.6%。1H NMRδ:1.30(t,3H),4.26(q,2H),4.79(s,2H),6.08(s,1H),6.98~7.22(m,11H),7.44(d,2H)。
实施21吡唑氧乙酸类杀菌剂的杀菌实验
以实施例1制得的最终产物进行杀菌效果评定,同时选取多菌灵、腐霉利作为对比。以油菜菌核病敏株Sclerotinia sclerotiorum、蔬菜灰霉病敏感菌株Botryris cinerea Pers.、赤霉病敏感菌株Gibbrella zeae(Schw.)Petch、小麦纹枯病敏感菌株Rhizoctorua solani、稻瘟病菌Pyricularia oryzae Cav作为靶标,以盆栽子叶期黄瓜苗为试验作物,处理药剂量:离体:10ug/ml活体:1000ug/ml,以清水对照进行杀菌活性试验。
1离体试验方法:
1.1含药培养基制备:处理药剂用丙酮溶解配制成母液;对照药剂多菌灵用0.02mol/L的稀HCl配制成母液。按照一定的浓度梯度,将测试药剂及对照药剂分别加入经灭菌并冷却至45℃左右的培养基中混匀,倒入平皿,制成含药平板。
1.2毒力测定:采用菌落直径法。在含药平板中央接一菌碟,菌丝朝下。25℃培养至空白对照菌落布满培养皿2/3以上时,测量各处理的菌落直径。每个菌落按十字交叉法测量2次,以其平均数代表菌落的大小。计算药剂对菌体生长率的抑制。
2活体试验方法:
2.1作物培养:黄瓜催芽后,点播于d=6cm的塑料盆中,吸足水份,置于网室中培养至子叶期备用。
2.2施药方法:室内通风橱内,用喉头喷雾器均匀施于黄瓜苗全株。
2.3接种方法:预先转接油菜菌核病菌、蔬菜灰霉病菌,长至四分之三皿备用。施药24小时后,用d=5mm的打孔器在菌落边缘打菌饼,将菌饼菌丝向下接于叶片正面。
2.4培养:接好菌的黄瓜置于保湿箱中恒温保湿培养,培养温度25℃,湿度100%,光/暗=16/8:
离体试验在菌落长至2/3平皿以上时测量菌落直径;活体试验保湿培养3天后调查结果,具体结果见下表1,表2
表1离体杀菌活性结果表
表2活体杀菌活性表
分级标准:A级:抑制率≥90%;B级:90%>抑制率≥70%;C级:70%>抑制率≥50%;D级:50%>抑制率。
Claims (5)
1.如下所述的化合物或其盐,选自:
1-苯基-5-(4-甲氧基苯基)-3-氧乙酸乙酯基吡唑
1-苯基-5-(3,4,5-三甲氧基苯基)-3-氧乙酸基吡唑
1-(4-氟苯基)-5-(4-溴苯基)-3-氧乙酸基吡唑
1-苯基-5-(4-三氟甲基苯基)-3-氧乙酸基吡唑
1-(4-甲基苯基)-5-(4-氟苯基)-3-氧乙酸基吡唑
1-(4-氟苯基)-5-(3,4-二甲氧基苯基)-3-氧乙酸乙酯基吡唑
1-(4-叔丁基苯基)-5-苯基-3-氧乙酸乙酯基吡唑
1-(2,4-二氯苯基)-5-(4-甲基苯基)-3-氧乙酸乙酯吡唑
1-(2,4-二硝基苯基)-5-(4-氯苯基)-3-氧乙酸乙酯基吡唑
1-(4-叔丁基苯基)-5-(4-氯苯基)-3-氧乙酸乙酯吡唑
1-(对氟苯基)-5-(4-甲基苯基)-3-氧乙酸乙酯吡唑
1-(2,4-二氯苯基)-5-苯基-3-氧乙酸吡唑
1-(4-氟苯基)-5-(4-甲氧基苯基)-3-氧乙酸基吡唑
1-(4-甲基苯基)-5-(3,4,5-三甲氧基苯基)-3-氧乙酸乙酯基吡唑
1-(4-甲基苯基)-5-(4-溴苯基)-3-氧乙酸乙酯吡唑
1-(2,4-二氯苯基)-5-(4-氯苯基)-3-氧乙酸基吡唑
1-(4-氟苯基)-5-(4-氟苯基)-3-氧乙酸基吡唑。
3.根据权利要求2所述的结构通式(I)的化合物的制备方法,其特征在于:当制备杀菌剂(I)时,E与卤代烷酸或卤代烷酸酯,所用的有机溶剂为二氧六环、乙腈、N,N-二甲基甲酰胺、丙酮、二氯甲烷或三氯甲烷,所用的碱性催化剂为三乙胺、碳酸钾、碳酸钠、氢氧化钠或氢氧化钾。
4.权利要求1所述的化合物在制备杀菌剂方面的应用。
5.权利要求4所述的应用,其中所述的菌为油菜菌核病敏株、蔬菜灰霉病敏感菌株、赤霉病敏感菌株、小麦纹枯病敏感菌株或稻瘟病菌。
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