CN1143637A - 二氢哒嗪酮和哒嗪酮以及它们作为杀真菌剂和杀虫剂的用途 - Google Patents
二氢哒嗪酮和哒嗪酮以及它们作为杀真菌剂和杀虫剂的用途 Download PDFInfo
- Publication number
- CN1143637A CN1143637A CN96104596A CN96104596A CN1143637A CN 1143637 A CN1143637 A CN 1143637A CN 96104596 A CN96104596 A CN 96104596A CN 96104596 A CN96104596 A CN 96104596A CN 1143637 A CN1143637 A CN 1143637A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- compound
- benzyl
- halo
- thiazolinyl
- 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.)
- Granted
Links
- 239000000417 fungicide Substances 0.000 title claims description 4
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical class OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 title description 26
- 239000002917 insecticide Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 43
- -1 pyridazinone compound Chemical class 0.000 claims description 32
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 18
- 241000238631 Hexapoda Species 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 13
- SSDAKJLEKSSAMH-UHFFFAOYSA-N 2,4-dihydro-1h-pyridazin-3-one Chemical compound O=C1CC=CNN1 SSDAKJLEKSSAMH-UHFFFAOYSA-N 0.000 claims description 10
- 229940073608 benzyl chloride Drugs 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 4
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001318 4-trifluoromethylbenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(F)(F)F 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 5
- 241000233866 Fungi Species 0.000 claims 2
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 claims 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 230000000749 insecticidal effect Effects 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 51
- 239000001301 oxygen Substances 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 30
- 239000002585 base Substances 0.000 description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 235000019439 ethyl acetate Nutrition 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 12
- 229910052801 chlorine Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- 241000209140 Triticum Species 0.000 description 9
- 235000021307 Triticum Nutrition 0.000 description 9
- 201000010099 disease Diseases 0.000 description 9
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229940031815 mycocide Drugs 0.000 description 9
- 239000002689 soil Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000004563 wettable powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 240000008067 Cucumis sativus Species 0.000 description 6
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- 238000011081 inoculation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000012312 sodium hydride Substances 0.000 description 6
- ITUVPRZRSCWUPA-UHFFFAOYSA-N 3-(2-hydroxyphenyl)-1H-pyridazin-6-one Chemical compound OC1=CC=CC=C1C1=NNC(=O)C=C1 ITUVPRZRSCWUPA-UHFFFAOYSA-N 0.000 description 5
- 244000046052 Phaseolus vulgaris Species 0.000 description 5
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000233679 Peronosporaceae Species 0.000 description 4
- 235000009754 Vitis X bourquina Nutrition 0.000 description 4
- 235000012333 Vitis X labruscana Nutrition 0.000 description 4
- 240000006365 Vitis vinifera Species 0.000 description 4
- 235000014787 Vitis vinifera Nutrition 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 3
- 241000239290 Araneae Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000221785 Erysiphales Species 0.000 description 3
- 240000005979 Hordeum vulgare Species 0.000 description 3
- 235000007340 Hordeum vulgare Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 241000409991 Mythimna separata Species 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 2
- XKBJVQHMEXMFDZ-UHFFFAOYSA-N 1-octadecylglycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCCCCOCC(O)COP([O-])(=O)OCC[N+](C)(C)C XKBJVQHMEXMFDZ-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- DTLMMDCZLVWYNR-UHFFFAOYSA-N 2-(dimethylamino)ethyl (2-methoxy-3-octadecoxypropyl) hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOCC(OC)COP(O)(=O)OCCN(C)C DTLMMDCZLVWYNR-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 241000371644 Curvularia ravenelii Species 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 240000003768 Solanum lycopersicum Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000002024 ethyl acetate extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012628 flowing agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 230000000361 pesticidal effect Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
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- 238000004809 thin layer chromatography Methods 0.000 description 2
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- YGRFXPCHZBRUKP-WJRQTEJMSA-N (1R,2S)-2-amino-1-(2,5-dimethoxyphenyl)propan-1-ol hydrochloride Chemical compound Cl.COC1=CC=C(OC)C([C@@H](O)[C@H](C)N)=C1 YGRFXPCHZBRUKP-WJRQTEJMSA-N 0.000 description 1
- JTLAIKFGRHDNQM-UHFFFAOYSA-N 1-bromo-2-fluoroethane Chemical compound FCCBr JTLAIKFGRHDNQM-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- OPMFFAOEPFATTG-UHFFFAOYSA-N 2,2,2-trifluoroethylhydrazine Chemical compound NNCC(F)(F)F OPMFFAOEPFATTG-UHFFFAOYSA-N 0.000 description 1
- KUGJWNGMHIMCBN-UHFFFAOYSA-N 2,3-dihydro-1h-pyridazin-4-one Chemical compound O=C1CNNC=C1 KUGJWNGMHIMCBN-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- SKNGHROBOKBHGJ-UHFFFAOYSA-N 2-methoxyiminoacetamide Chemical compound CON=CC(N)=O SKNGHROBOKBHGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- JADVVTZXHQUFLS-UHFFFAOYSA-N 3,4-dichloropyridazine Chemical compound ClC1=CC=NN=C1Cl JADVVTZXHQUFLS-UHFFFAOYSA-N 0.000 description 1
- XZJJVTCGDNXMHT-UHFFFAOYSA-N 3-(3-hydroxyphenyl)-1h-pyridazin-6-one Chemical class OC1=CC=CC(C2=NNC(=O)C=C2)=C1 XZJJVTCGDNXMHT-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- QOAMWZMAXNNNDC-UHFFFAOYSA-N 4-(1,2-thiazol-3-yl)oxadiazole Chemical compound S1C=CC(C=2N=NOC=2)=N1 QOAMWZMAXNNNDC-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KKUDXOKHDMURBM-UHFFFAOYSA-N 6-(3-hydroxyphenyl)-2-(2,2,2-trifluoroethyl)pyridazin-3-one Chemical class OC1=CC=CC(C2=NN(CC(F)(F)F)C(=O)C=C2)=C1 KKUDXOKHDMURBM-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
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- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- AEXITZJSLGALNH-UHFFFAOYSA-N n'-hydroxyethanimidamide Chemical compound CC(N)=NO AEXITZJSLGALNH-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 239000005645 nematicide Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GUIXQLOVLAOCCT-UHFFFAOYSA-N oxaldehydic acid;sodium;hydrate Chemical compound O.[Na].OC(=O)C=O GUIXQLOVLAOCCT-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- TVPRCLHSULCNLV-UHFFFAOYSA-N pyridazin-3-one Chemical compound O=C1C=CC=N[N]1 TVPRCLHSULCNLV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
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- 230000001131 transforming effect Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000003828 vacuum filtration Methods 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
- C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
- C07D237/14—Oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
- C07D237/14—Oxygen atoms
- C07D237/16—Two oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
具有杀真菌和杀虫性质的下式化合物,其中W是CH3-O-A=C-CO(V)CH3;n是0或1;A是N或CH;V是O或NH;其中Y是O,S,NR1,或R6,含有R4和R5的环键是单键或双键,且R4和R5分别选自氢和取代的或未取代的烷基和芳基。
Description
本发明涉及二氢哒嗪酮,哒嗪酮及相关化合物,含有这些化合物的组合物以及通过使用毒杀霉菌和杀虫量的这些化合物来控制霉菌和昆虫的方法。
公开于1991年9月13日,标题为“二氢哒嗪酮,哒嗪酮和相关化合物以及它们作为杀真菌剂的用途”的专利申请No.91-308,404.2公开了作为有效杀真菌剂的哒嗪酮化合物。这些哒嗪酮没有苯基取代环,而且该环是被β-甲氧基丙烯酸甲酯,甲氧基亚氨基乙酸酯或甲氧基亚氨基乙酰胺取代的。本发明是新的组合物,具有杀真菌和杀虫性质。
本发明二氢哒嗪酮和哒嗪酮用式(I)表示,其中:
W是CH3-O-A=C-CO(V)CH3;
A是N或CH;
V是O或NH;
n是0或1;
Y是O,S,NR1,或R6,含有R4和R5的环键是单键或双键;
X独立地选自氢,卤素,(C1-C4)烷基,(C1-C4)烷氧基以及与-HC=CH-CH=CH-形成的萘环;
R2独立地选自氢,(C1-C12)烷基,(C1-C12)烷氧基,卤代(C1-C12)烷基,卤代(C1-C12)烷氧基,羟基(C1-C12)烷基,(C1-C12)烷氧基(C1-C12)烷基,(C1-C12)烷氧基羰基(C1-C12)烷基,(C2-C8)烯基,卤代(C2-C8)烯基,(C3-C10)炔基,卤代(C3-C10)炔基,(C3-C7)环烷基,(C3-C7)环烷基(C1-C4)烷基,环氧(C1-C12)烷基,PO(OR1)2(C1-C12)烷基,R1S(O)2(C1-C12)烷基,(R1)3Si(C1-C12)烷基,芳基,芳氧基(C1-C12)烷基,芳基羰基(C1-C12)烷基,芳烷基,芳烯基,杂环基,杂环基(C1-C12)烷基,N-吗啉基(C1-C12)烷基,N-哌啶基(C1-C12)烷基;
R1独立地选自(C1-C12)烷基,(C2-C8)烯基和芳基;
R4和R5分别选自氢,卤素,(C1-C8)烷基,(C1-C8)烷氧基,氰基,卤代(C1-C12)烷基,(C2-C8)烯基,(C3-C10)炔基,芳基和芳烷基;
R6是(C1-C12)亚烷基和(C2-C12)亚烯基。
上述(C1-C12)烷基,(C1-C12)烷氧基,(C2-C8)烯基,(C3-C10)炔基和(C3-C7)环烷基,可以任意被至多3个选自氢,硝基,三卤甲基和氰基的取代基所取代。
术语“烷基”包括含有1-12个碳原子的支链和直链烷基。典型的烷基有甲基,乙基,正丙基,异丙基,正丁基,第二丁基,异丁基,叔丁基,正戊基,异戊基,正己基,正庚基,异辛基,壬基,癸基,十一烷基,十二烷基等等。术语“卤代烷基”指被1-3个卤素取代的烷基。
术语“烯基”指基直链或支链,具有2-12个碳原子链长和1或2个烯键的烯不饱和烃基。术语“卤代烯基”指被1-3个卤原子取代的烯基。术语“炔基”指直链或支链,具有2-12个碳原子链长和1或2个炔键的不饱和烃基。
术语“亚烷基”指二价烷基,其中两个游离键在相同或不同的碳原子上。术语“亚烯基”指二价烯基,其中两个游离键在相同或不同的碳原子上,烯基也可被1-3个卤原子取代。
术语“环烷基”指有3-7个碳原子的饱和环系。
术语“芳基”包括苯基或萘基,它们可以任意被至多3个选自氢,氰基,硝基,三卤甲基,苯基,苯氧基,(C1-C4)烷基,(C1-C4)烷硫基,(C1-C4)烷基亚磺酰基,(C1-C6)烷氧基和卤代(C1-C4)烷基的取代基所取代。
典型的芳基取代基包括但不限于4-氯苯基,4-氟苯基,4-溴苯基,2-甲氧基苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2,4-二溴苯基,3,5-二氟苯基,2,4,6-三氯苯基,4-甲氧基苯基,2-氯萘基,2,4-二甲氧基苯基,4-(三氟甲基)苯基和2-碘-4-甲基苯基。
术语“杂环基”指任意取代的5或6元不饱和环,含有1,2或3个杂原子,优选含有1或2个选自氧,氮和硫的杂原子,或是二环不饱和环系,该环系含有至多10个原子,其中一个是选自氧,氮和硫的杂原子。杂环基的实例包括但不限于2-,3-或4-吡啶基,吡嗪基,2-,4-或5-嘧啶基,哒嗪基,三唑基,咪唑基,2-或3-噻吩基,2-或3-呋喃基,吡咯基,噁唑基,异噁唑基,噻唑基,异噻唑基,噁二唑基,噻二唑基,喹啉基和异喹啉基。该杂环可以任意被至多2个分别选自(C1-C2)烷基,卤素,氰基,硝基和三卤代甲基的取代基取代。
术语“芳烷基”用来描述其中烷基链是1-10个碳原子并且可以是支链或直链,优选直链,并有上述芳基部分的基团。典型的芳烷基取代基包括但不限于2-氯苄基,3-氯苄基,4-氯苄基,4-氟苄基,4-三氟甲基苄基,2,4-二氯苄基,2,4-二溴苄基,4-氯苯乙基,4-氟苯乙基,4-三氟甲基苯乙基,3-甲基苯乙基,4-甲基苯乙基,2,4-二氯苯乙基,3,5-二甲氧基苯乙基,4-氯苯丙基,2,4,5-三甲基苯丁基,2,4-二氯苯丁基等等。术语“芳烷基”还包括CH2-(2-W)芳基,其中W定义如上。
卤素或卤代指碘,氟,溴和氯部分。
由于C=C或C=N双键,通式I的新化合物可以制备成E/Z异构体混合物。这些异构体可以用常规方法分离成单一成分。单一异构体化合物及其混合物构成本发明主题并可用作杀真菌剂。
本发明优选实施方案是式(I)的化合物,对映体,盐和复合物,其中R4和R5是氢及R2是(C1-C12)烷基,(C2-C8)烯基,优选被2个选自卤素,三卤甲基,氰基,(C1-C4)烷基,(C1-C4)烷硫基,(C1-C4)烷氧基或苯基的取代基取代的苯基或苄基,含有R4和R5的键是双键,Y是直接碳键且其中OCH2(2-W-芳基)连接在Y的间位。
本发明更优选实施方案是式(I)的化合物,对映体,盐和复合物,其中R4和R5是氢及R2是甲基,乙基,烯丙基或正丙基,A是CH,V是O。优选几何形状是当A为CH或N时,它为E异构体。
本发明式II,III和IV概括的典型化合物包括表1,2和3中所列的那些化合物。
表1化合物 R2 R4 R5 X A V Y n1 CH3 H H H CH O - 02 C2H5 H H H CH O - 03 CH2CH2CH3 H H H CH O - 04 CH(CH3)2 H H H CH O - 05 CH2CH(CH3)2 H H H CH O - 06 CH2(CH2)3CH3 H H H CH O - 07 Ar(4Cl) H H H CH O - 08 CH2Ar(4Cl) H H H CH O - 09 CH2CH2Ar H H H CH O - 010 CH2CF3 H H H CH O - 011 CH3 H H H CH O O 112 CH2CH3 H H H CH O O 113 CH2环丙基 H H H CH O O 114 CH2CH2CH3 H H H CH O O 115 CH2CH3 H H H N O - 016 CH2CH2CH3 H H H N O - 017 CH2CH=CH2 H H H N O - 018 CH2CO2CH3 H H H N O - 019 CH2CH2CH3 H H H N O O 020 CH2CH=CH2 H H H N O O 021 CH2CH2CH=CH2 H H H N O O 022 CH2CH3 H H H N NH - 023 CH2CH2F H H H N NH - 024 CH2-环-C3H7 H H H N NH - 025 CH2-1H-1,2,4-三唑 H H H N NH - 026 (CH2)3Ar H H H N NH O 127 CH2-(3-吡啶基) H H H N NH O 1
表2化合物 R2 R4 R5 X A V Y n28 CH(CH3)2 H H H CH O - 029 CH2CH(CH3)2 H H H CH O - 030 C(CH3)3 H H H CH O - 031 CH2(CH2)3CH3 H H H CH O - 032 C(CH3)CH2CH2CH3 H H H CH O - 033 CH2C(CH3)3 H H H CH O - 034 CH2CH2OCH2CH3 H H H CH O - 035 CH2CH(CH3)OH H H H CH O - 036 CH2CH2OCOCH3 H H H CH O - 037 CH2OCOAr H H H CH O - 038 CH2CH2OCOAr H H H CH O - 039 CH2CH2Br H H H CH O - 040 (CH2)2Ar(4Cl) H H H CH O - 041 (CH2)2Ar(4Cl) H H 3'Cl CH O - 042 (CH2)3Ar(4Cl) H H H CH O 043 (CH2)4Ar H H H CH O - 044 (CH2)2OAr H H H CH O - 045 CH2C(Cl)=CH2 H H H CH O - 046 CH2CCH H H H CH O - 047 CH2CH2OAr H H 3'-OMe CH O - 048 CH2OCH2Ar H H H CH O - 049 CH2CH2OCH2Ar H H H CH O - 050 CH2CH=CHAr H H H CH O - 051 2-吡啶基 H H H CH O - 052 4-吡啶基 H H H CH O - 053 2-嘧啶基 H H H CH O - 054 4-嘧啶基 H H H CH O - 0
表2(续)化合物 R2 R4 R5 X A V Y n55 CH2-(2-吡啶基) H H H CH O - 056 CH2-(3-吡啶基) H H H CH O - 057 CH2-吡嗪基 H H H CH O - 058 CH2-(2-噻吩基) H H H CH O - 059 CH2-(3-噻吩基) H H H CH O - 060 CH2-(1-吗啉基) H H H CH O - 061 CH2-(1-哌啶基) H H H CH O - 062 CH2-(2-呋喃基) H H H CH O - 063 CH2-环氧化物 H H H CH O - 064 CH2-Si(CH3)3 H H H CH O - 065 CH2-Si(CH3)2-叔丁基 H H H CH O - 066 CH2-Si(CH3)2Ar H H H CH O - 067 CH2-PO(OCH3)2 H H H CH O - 068 CH2-PO(OC2H5)2 H H H CH O - 069 CH2OSO2CH3 H H H CH O - 070 CH2OSO2Ar H H H CH O - 071 CH2-(4-CF3-吡啶-2-基 H H H CH O - 072 CH2-(1-萘基) H H H CH O - 073 CH2(2-萘基基) H H H CH O - 074 CH2-CO2C2H5 H H H CH O - 075 CH2-CH=CH-CO2CH3 H H H CH O - 076 CH2CH2CH2CN H H H CH O - 077 CH2-CH=C(CH3)2 H H H CH O - 078 CH2-C(CH3)=CHCH3 H H H CH O - 079 CH2-C(CH3)=C(CH3)2H H H CH O - 080 C2H5 CH3 CH3 H CH O - 081 CH2CH2CH3 CH3 CH3 H CH O - 082 CH2CF3 CH3 CH3 H CH O - 083 CH2CH(CH3)2 CH3 CH3 H CH O - 084 C(CH3)3 CH3 CH3 H CH O - 085 CH2(CH2)3CH3 CH3 CH3 H CH O - 086 CH(CH3)(CH2)2CH3 CH3 CH3 H CH O - 087 (CH2)2C(CH3)2 CH3 CH3 H CH O - 088 CH2C(CH3)3 CH3 CH3 H CH O - 089 C2H5 H H 3′Cl CH O - 090 CH2CH2CH3 H H 3′OCH3 CH O - 091 CH(CH3)2 H H 3′Cl CH O - 092 CH2CH(CH3)2 H H 3′OCH3 CH O - 093 C(CH3)3 H H 3′Cl CH O - 094 CH2(CH2)3CH3 H H 3′OCH3 CH O - 095 C(CH3)CH2CH2CH3 H H 3′Cl CH O - 096 (CH2)2CH(CH3)2 H H 3′OCH3 CH O - 097 CH2C(CH3)3 H H 3′Cl CH O - 098 CH2CCH H H 3′OCH3 CH O - 0
表2(续)化合物 R2 R4 R5 X A V Y n99 CH(CH3)2 H H H CH O O 1100 CH2CH(CH3)2 H H H CH O O 1101 CH2CF3 H H H CH O O 1102 CH2(CH2)3CH3 H H H CH O O 1103 CH(CH3)CH2CH2CH3 H H H CH O O 1104 (CH2)2CH(CH3)2 H H H CH O O 1105 CH2C(CH3)3 H H H CH O O 1106 CH2CH2OH H H H CH O O 1107 CH2CH(CH3)OH H H H CH O O 1108 CH2CH2F H H H CH O O 1109 CH2CH2Cl H H H CH O O 1110 CH2CH2Br H H H CH O O 1111 (CH2)2Ar H H H CH O O 1112 (CH2)2Ar(4Cl) H H H CH O O 1113 (CH2)3Ar H H H CH O O 1114 (CH2)2OAr H H H CH O O 1115 CH2-(2-吡啶基) H H H CH O O 1116 CH2-(3-吡啶基) H H H CH O O 1117 CH2-吡嗪基 H H H CH O O 1118 CH2-(2-噻吩基) H H H CH O O 1119 CH2-(3-噻吩基) H H H CH O O 1120 CH2-(1-吗啉基) H H H CH O O 1121 CH2(1-哌啶基) H H H CH O O 1122 CH2-(3-嘧啶基) H H H CH O O 1123 CH2C(Cl)=CH2 H H H CH O O 1124 CH2CCH H H H CH O O 1125 CH2-环-C5H9 H H H CH O O 1126 CH2CH2OCH2Ar H H H CH O O 1127 CH2CH=CHAr H H H CH O O 1128 CH2-1H-1,2,4三唑 H H H CH O O 1129 CH2-(3-吡啶基) H H H CH O O 1130 CH2-(1-吗啉基) H H H CH O O 1131 CH3 H H H CH O CH2 1132 CH2CH3 H H H CH O CH2 1133 CH2CH2CH3 H H H CH O CH2 1134 CH3 H H H CH O NCH3 1135 CH2CH3 H H H CH O NCH3 1136 CH2CH2CH3 H H H CH O NCH3 1137 CH2CH3 H H H CH O S 1138 CH2CH2F H H H CH O S 1139 CH2CH=CH2 H H H CH O S 1140 CH2-1H-1,2,4-三唑 H H H CH O S 1141 CH2-(3-吡啶基) H H H CH O S 1142 CH2-(1-吗啉基) H H H CH O S 1
表2(续)EX# R2 R4 R5 X A V Y n143 CH2CH3 H H H N O - 0144 CH2CF3 H H H N O - 0145 CH2CH2CH3 H H H N O - 0146 CH2CH-(CH3)2 H H H N O - 0147 C(CH3)3 H H H N O - 0148 CH2(CH2)3CH3 H H H N O - 0149 CH2CH2F H H H N O - 0150 CH2CH2Cl H H H N O - 0151 (CH2)2Ar H H H N O - 0152 (CH2)2Ar(4Cl) H H H N O - 0153 (CH2)3Ar H H H N O - 0154 (CH2)2OAr H H H N O - 0155 CH2CCH H H H N O - 0156 CH2-1H-1,2,4-三唑 H H H N O - 0157 CH2-(3-吡啶基) CH3 CH3 H N O - 0158 CH(CH3)2 H H H N O O 1159 CH2CH(CH3)2 H H H N O O 1160 C(CH3)3 H H H N O O 1161 CH2(CH2)3CH3 H H H N O O 1162 CH2CH3 H H H N O S 1163 CH2CH3 H H H N O CH2 1164 CH2CH3 H H H N O NCH3 1165 CH2CH3 H H H N NH - 0166 CH2CH=CH2 H H H N NH - 0167 CH2CH2CH3 H H H N NH - 0168 CH2CH(CH3)2 H H H N NH - 0169 C(CH3)3 H H H N NH - 0170 CH2(CH2)3CH3 H H H N NH - 0171 CH2CCH H H H N NH - 0172 CH2-cyclo-C5H9 H H H N NH - 0173 CH2CH2O)CH2Ar H H H N NH - 0174 CH2CH=CHAr H H H N NH - 0175 CH2-1H- 1,2,4-三唑 H H H N NH - 0176 CH2-(3吡啶基) H H H N NH - 0177 CH2-(1-吗啉基) H H H N NH - 0178 CH3 H H H N NH O 1179 CH2CH3 H H H N NH O 1180 CH2CH2CH3 H H H N NH O 1181 CH(CH3)2 H H H N NH O 1182 CH2CH(CH3)2 H H H N NH O 1183 CH2CH2F H H H N NH O 1184 CH2CH2Cl H H H N NH O 1185 CH3 H H H N NH S 1
表3化合物 R2 R4 R5 X A V Y n186 CH3 H H H CH O - 0187 CH2CH3 H H H CH O - 0188 CH2CH2CH3 H H H CH O - 0189 CH(CH3)2 H H H CH O - 0190 CH2CH(CH3)2 H H H CH O - 0191 CH2CH2F H H H CH O - 0192 CH2CH2Cl H H H CH O - 0193 CH3 H H H CH O - 0194 CH2CH3 H H H CH O - 0195 CH2CH2CH3 H H H CH O - 0196 CH3 H H H CH O O 1197 CH2CH3 H H H CH O O 1198 CH2CH2CH3 H H H CH O O 1199 CH2(CH2)2CH3 H H H CH O O 1200 CH2CH2F H H H CH O O 1201 CH3 H H H CH O S 1202 CH2CH3 H H H CH O S 1203 CH2CH2=CH2 H H H CH O S 1204 CH3 H H H N O - 0205 CH2CH3 H H H N O O 1206 CH2CH2CH3 H H H N O - 0207 CH2(CH2)2CH3 H H H N O O 1208 CH2CH2F H H H N O - 0209 CH2CH2=CH2 H H H N O O 1210 CH2CH2OCOCH3 H H H N O - 0211 CH2-(2-吡啶基) H H H N O 0 1212 CH3 H H H N NH - 0213 CH2CH3 H H H N NH O 1214 CH2CH2CH3 H H H N NH - 0215 CH2(CH2)2CH3 H H H N NH O 1216 CH2CH2F H H H N NH - 0217 CH2CH2=CH2 H H H N NH - 1218 CH2CH2OCOCH3 H H H N NH - 0
表1,2和3中的Ar代表苯基。表1,2和3中的Ar代表苯基。
本发明哒嗪酮和二氢哒嗪酮可以用常规合成方法制备。例如,当式(V)中的n为0及A和V同式(I)中的定义时,式(I)哒嗪酮是按路线A所示,通过6-(羟基)苯基-2,4,5-三取代-哒嗪-3-酮(VI)的烷基化制备的。
4,5,6-三取代-3(2H)-哒嗪酮(VI)和4,5-二氢哒嗪酮可以按EP308404所述方法制备。特别是6-(羟基苯基)-2-取代哒嗪-3-酮(VI,其中R4=R5=H)可按路线B所示制备。
或者,如路线C所示,可用肼处理羟基乙酰苯和乙醛酸,得到6-(羟基苯基)-3(2H)-哒嗪酮(VII)。2-,3-或4-羟基乙酰苯可用于缩合,它提供异构的6-(羟基苯基)哒嗪酮(VI和VII)。
哒嗪酮(VII)在碱性条件下如在含NaH的DMF中,含氢氧化钾的DMSO中或含碳酸钾的DMF或丙酮中烷基化,得到路线D所示的N和O烷基化产物的混合物。氮单烷基化产物(VI)可用常规色谱技术分离和用2-W-苄基溴处理得到(V),或(VI)和(VIII)的混合物可用苄基溴化物当场((VI)或(VII)不分离)烷基化,之后通过色谱法将(V)从未反应的(VIII)中分离。
哒嗪酮(VI)与E-α-(2-溴甲基苯基)-β-甲氧基丙烯酸甲酯的反应是在碱如金属氢化物,优选NaH存在下,在非质子传递溶剂如N,N-二甲基-甲酰胺中进行,得到其中A是CH和V是氧的式(V)化合物。E-α-(2-溴甲基苯基)-β-甲氧基丙烯酸甲酯作为单个E异构体,可按照前面美国专利4,914,128所述分两步从2-甲基苯基乙酸酯制备。或者,按照EP348766,EP178826和DE3705389所述,哒嗪酮(VI)可与2-(溴甲基)苯基乙醛酸甲酯反应,接着与甲氧基甲基三苯膦进行Wittig缩合。
其中A是N和V是氧的式(V)化合物是在碱如金属氢化物,优选NaH存在下,在非质子传递溶剂如N,N-二甲基甲酰胺中,通过哒嗪酮(VI)与E-2-(溴甲基)苯基乙醛酸甲酯O-甲肟反应制备的。2-(溴甲基)苯基乙醛酸甲酯O-甲肟可以按美国专利4,999,042和5,157,144所述制备。在碱性条件下,2-甲基苯基乙酸甲酯用亚硝酸烷基酯处理,甲基化之后得到2-(溴甲基)苯基乙醛酸甲酯O-甲肟,它还可以通过用2-羟基胺盐酸化物处理2-甲基苯基乙醛酸甲酯,并甲基化或用甲氧胺盐酸化物处理来制备。或者,当A是N和V是氧时,哒嗪酮(VI)可与2-(溴甲基)苯基乙醛酸甲酯反应,接着与甲氧胺HCl反应,或先与羟基胺HCl反应,接着进行甲基化。
肟基乙酸酯到肟基乙酰胺的氨解反应在美国专利5,185,342,5,221,691和5,194,662中已有所描述。其中A是N和V是O的式(V)化合物是用40%甲胺的甲醇水溶液处理,得到其中V是NH(CH3)的式(V)化合物。或者,在碱如金属氢化物,优选NaH存在下,在非质子传递溶剂如二甲基甲酰胺(DMF)中,哒嗪酮(VI)与N-甲基E-2-甲氧基亚氨基-2-[2-(溴甲基)苯基]乙酰胺反应。N-甲基E-2-甲氧基亚氨基-2-[2-(溴甲基)苯基]乙酰胺如WO9419331所述。
其中n=1且更特别地是Y是氧的式(I)化合物是按流程E制备的。
路线E
碱性条件下用R2X对(X)的烷基化方法类似于对(VII)的烷基化方法。6-((2′-(W)苄氧基)苯氧基)-4,5-二取代-3(2H)-哒嗪酮(X)是通过6-((2′-(W)苄氧基)苯氧基)-4,5-二取代-3-氯哒嗪酮(IX)酸性水解来制备的,后者是按照路线F所示,在与(VI)到(V)转化类似的条件下,通过用各种苄基溴烷基化酚中间体来制备(XII)。当A是CH或N和V是氧和NH时,提供各种烷基化试剂。如路线F所示,6-(羟基苯氧基)-4,5-二取代-3-氯哒嗪(XII)是通过二氯哒嗪与二羟基苯如间苯二酚与邻苯二酚的反应来制备。
其中Y是S或N-R6的式(I)化合物可用路线F所述相似方法制备。如果Y是S,可用取代的巯基酚;类似地,如果Y是N-R6,可用氨基酚。
下列表4中实例用以说明本发明。
表4化合物 结构式 R2 R4 R5 X A V Y n219 II CH2CCCH2CH3 H H H CH O - 0220 II C2H5 H H H CH O - 0221 II CH2CCCH2CH3 H H 3′-OCH3 CH O - 0222 II CH2CCCH2CH3 H H 3′-Cl CH O - 0223 III CH2CCCH2CH3 H H H CH O - 0224 III CH2CO2CH3 H H H CH O - 0225 II CH2Ar H H 3′-OCH3 CH O - 0226 II CH2Ar H H H CH O - 0227 III CH3 H H H CH O - 0228 III CH2Ar H H H CH O - 0229 IV CH2CCCH2CH3 H H H CH O - 0230 III CH2CH=CH2 H H H CH O - 0231 III C2H5 H H H CH O - 0232 III n-C3H7 H H H CH O - 0233 III CH2CH2CN H H H CH O - 0234 III CH2CH2CH=CH2 H H H CH O - 0235 III CH2CH2OCH3 H H H CH O - 0236 III Ar H H H CH O - 0237 III CH3 H H H CH O O 1238 III CH2CH2F H H H CH O - 0239 III CH3 H H H N O - 0240 III CH2COAr H H H CH O - 0241 III CH3 H H H N NH - 0
表4(续)化合物 结构式 R2 R4 R5 X A V Y n242 III CH2环丙基 H H H CH O - 0243 III CH2(2-萘基) H H H CH O - 0244 III CH2CF3 H H H CH O - 0245 III Ar(3Cl) H H H CH O - 0246 III Ar(2Cl) H H H CH O - 0247 III CH3 H H 3′-OCH3 CH O - 0248 III CH2Ar H H H CH O O 1249 III CH2CH=CH2 H H H CH O O 1250 III CH2CCCH2CH3 H H H CH O O 1251 III n-C3H7 H H H CH O O 1252 III H H H H CH O O 1253 III n-C4H9 H H H CH O - 0254 III sec-C4H9 H H H CH O - 0255 III CH2-(5′-Cl-2-噻吩基) H H H CH O - 0256 III (CH2)2-(1-吗啉基) H H H CH O - 0257 III (CH2)3-Ar H H H CH O - 0258 III CH2-Ar(2Cl) H H H CH O - 0259 III CH2-Ar(3Cl) H H H CH O - 0260 III CH2-Ar(4Cl) H H H CH O - 0261 III CH2-环己基 H H H CH O - 0262 III H H H H CH N O 1263 III CH2Ar H H H CH N O 1264 III CH2CCCH2CH3 H H H CH N O 1265 III CH2CH=CH2 H H H CH N O 1266 III CH2CH2CH3 H H H CH N O 1267 III CH2CO2CH2Ar H H H CH O - 0268 III (CH2)3OAr H H H CH O - 0269 III CH2CH(CH2CH3)2 H H H CH O - 0270 III CH2-1H-1,2,4-三唑 H H H CH O - 0271 III CH2CH2Ar H H H CH O - 0272 III CH2CH2OH H H H CH O - 0273 III CH2CH2CI H H H CH O - 0274 III CH=CH2 H H H CH O - 0275 III CH2CH2CH(CH3)2 H H H CH O - 0276 III CH2CH=CHCH3 H H H CH O - 0277 III CH2CH=C(CH3)2 H H H CH O - 0278 II H H H H CH O O 1279 II CH2CH=CH2 H H H CH O O 1280 II CH2CCCH2CH3 H H H CH O O 1Ex.281 Ex.282表4中Ar代表苯基。
本发明化合物可根据下面所述方法制备。
实施例1α-[2-(3-(2′-(2″,2″,2″-三氟乙基)哒嗪-3′-酮-6′-基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(表4;化合物244)
在装有磁搅拌器的500ml圆底烧瓶中加入0.95g(3.51mmol)6-(3-羟基苯基)-2-(2′,2′,2′-三氟乙基)-3(2H)-哒嗪酮和20ml二甲基甲酰胺(DNF)。在该溶液中加入0.23g(3.51mmol)粉末87%氢氧化钾,接着加入1.0gα-(2-溴甲基苯基)-β-甲氧基丙烯酸甲酯。在室温下搅拌18小时,然后倒入100ml水中并用乙酸乙酯(3×100ml)萃取。乙酸乙酯萃取液用100ml水和100ml饱和氯化钠溶液洗涤,无水硫酸镁干燥并过滤。减压蒸发浓缩滤液,得到1.4g黄色液体,然后在中性氧化铝和硅胶的混合柱上进行色谱分离,用100%乙酸乙酯洗脱。合并纯馏分部分,得到1.1gα-[2-(3-(2′-(2″,2″,2-三氟乙基)哒嗪-3′-酮-6′-基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯为深黄色油。
实施例2α-[2-(3-(2′-(2″-氟乙基)哒嗪-3′-酮-6′-基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(表4;化合物238)
在装有磁搅拌器的500ml圆底烧瓶中加入1.0g(5.32mmol)6-(3-羟基苯基)-3(2H)-哒嗪酮,0.74g(5.32mmol)碳酸钾和20mlDNF。在该混合物中加入0.67g(5.32mmol)1-溴-2-氟乙烷。在室温下搅拌20小时,接着加入0.35g(5.32mmol)粉状87%KOH和1.5g(5.32mmol)α-(2-溴甲基苯基)-β-甲氧基丙烯酸甲酯。再将反应混合物在室温搅拌18小时,然后倒入100ml水中并用乙酸乙酯(3×100ml)萃取。乙酸乙酯萃取液用100ml水和100ml饱和氯化钠溶液洗涤,无水硫酸镁干燥并过滤。减压蒸发浓缩滤液,得到1.2g红色液体,然后在中性氧化铝和硅胶的混合柱上进行色谱分离,用100%乙酸乙酯洗脱。合并纯物质部分,得到0.4gα-[2-(3-(2′-(2″-氟乙基)哒嗪-3′-酮-6′-基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯为深黄色油。
实施例36-(3-羟基苯基)-3(2H)-哒嗪酮的制备(用于制备实施例2化合物)
在装有磁搅拌器,温度计,加料漏斗和pH电极的500ml圆底烧瓶中加入18.4g(0.2mol)二羟乙酸一水合物和75ml水。将溶液冷至10℃并加入20%氢氧化钾水溶液使pH升至8。将部分3′-羟基乙酰苯(27.2g,0.2mol)的KOH(20g,0.36mol)溶液立即全部加到冷二羟乙酸钠溶液中,并在室温下搅拌2小时。所得深棕色溶液重新冷却至10℃,并加入乙酸使pH至8。将反应物倒入分液漏斗,用4×100ml二氯甲烷萃取水溶液以除去未反应的3′-羟基乙酰苯。将溶水部分再倒入反应烧瓶,冷却至10℃,用乙酸进一步处理至pH4.5,然后用浓氢氧化铵调至pH8。将溶液与肼一水合物(10ml,0.2mol)一起加热回流2小时,冷却得到黄色固体,真空过滤收集并用水洗涤。产物在40℃真空中干燥过夜,得到25.2g6-(3-羟基苯基)-3(2H)-哒嗪酮(产率:90.6%)。NMR(200MHz,d6-DMSO):6.9(m,1H),7.4(m,3H),8.0(d,1H),9.8(brs,1H),和13.2(brs,1H)
实施例46-(3-羟基苯基)-2-(2′,2′,2′-三氟乙基)-3(2H)-哒嗪酮的制备(用于制备实施例1化合物)
除了使用70%2,2,2-三氟乙基肼外,与实施例3相同。NMR(200MHz,d6-DMSO):5.0(q,2H),6.9(m,1H),7.1(d,1H),7.3(m,3H),和8.0(d,1H)。
实施例5α-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(表4;化合物252)
在500ml三颈圆底烧瓶中加入9.3gα-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(1.0当量,0.022mol),5.4g乙酸钠(3当量,0.065mol)以及200ml冰醋酸,并在115℃加热16小时。薄层色谱显示相对于起始原料的强产物点和弱强度点。将反应溶液倒入300ml水中淬灭,并另加900ml水和500ml乙酸乙酯处理。分离有机相,用250ml水洗涤,用纯净碳酸氢钠碱化至pH8,再用2×250ml水洗涤,无水硫酸镁干燥。在旋转蒸发器中(40℃)减压除去溶剂,得到7.4g粗产品为褐色粘性玻璃状固体。
1.3g粗产品用快速色谱法纯化,9∶1乙酸乙酯/甲醇作洗脱剂,得到1.07gα-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯为褐色固体产物(m.p.59-63℃,外推产率:67.8%)。
实施例6α-[2-(3-(2′-苄基哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(表4;化合物248)
在氮气氛下,在250ml三颈圆底烧瓶中加入0.117g氢化钠(1.2当量,2.93mmol,分散在矿物油中的比例为60%),用己烷和5ml DMF洗涤。通过移液吸管在上述碱中加入1.0gα-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(1.0当量,2.44mmol)的8ml DMF。将反应混合物搅拌几分钟,然后通过移液吸管加入0.42g苄基溴(1.0当量,2.44mmol)的3mlDMF溶液。2小时后的薄层色谱显示主要产物点和无起始试剂点。2.5小时添加75ml水和75ml乙酸乙酯将反应淬灭。另加入125ml水和乙酸乙酯到反应产物中。用3×200ml水洗涤分离有机相,无水硫酸镁干燥,在旋转蒸发器中(40℃)减压除去溶剂,得到1.4g橙/棕色粗产品。
粗产品用快速色谱法纯化,9∶1乙酸乙酯/己烷作洗脱剂,得到0.92gα-[2-(3-(2′-苄基哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯为黄色油(产率:75.7%)。
实施例73-(3-氯哒嗪-6-基氧基)酚的制备(用于制备实施例8和9化合物)
在氮气氛下,在1L三颈圆底烧瓶中加入10.0g氢化钠(1.1当量,0.25mol,分散在矿物油中的比例为60%),用30ml己烷洗涤,然后加入100ml DMF。用冰浴保持温度<30℃的情况下通过加料漏斗加入25.0g间苯二酚的100mlDMF溶液。在室温下搅拌反应混合物45分钟,均匀快速地加入3,6-二氯哒嗪(33.9g,1.0当量,0.23mol)的50mlDMF溶液,使之在添加漏斗放热至31℃。3g一批地加入6.0g氢化钠(0.65当量,0.15mol)的同时在室温搅拌反应混合物26小时。气相色谱分析显示有两个主产物,其中单烷基化物质和双烷基化物质的比例为1.5∶1。在反应进行26小时时添加150ml乙酸乙酯和150ml水淬灭反应。
恢复到室温后,形成双烷基化产物的沉淀,过滤得到8.9g褐色固体。为改善分配在淬灭的反应产物中加入水使总体积达到800ml(pH9),然后用2×300ml乙酸乙酯萃取并合并。用2×250ml碱水(25g 50%氢氧化钠)萃取合并的600ml乙酸乙酯并合并。产物在碱性水溶液中沉淀过夜,然后过滤,用水洗涤,干燥,得到11.8g褐色固体。在600ml合并的乙酸乙酯产物(减少体积后)进行第二次碱萃取之后将之酸化,再用乙酸乙酯萃取,用水和乙醚洗涤之后得到0.53g产物。在第一次水洗液(800ml,pH9)中过夜沉淀该产物。滤除沉淀并用2×100ml水和50ml乙醚洗涤,得到7.9g棕色固体。从800ml水洗液(pH9),通过调节使其中性化(pH6),用乙酸乙酯萃取,除去溶剂,得到的2.38g另一个产物,为棕色固体,再用2×50ml水和50ml乙醚洗涤该固体。分离出全部22.61g(产率:44.1%)单烷基化产物,3-(3-氯哒嗪-6-基氧基)酚为白色固体(m.p.185-187℃)。NMR(200MHz,CDCL3):6.6-7.9(m,6H),和8.7(s,1H).
实施例8α-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯(用于制备实施例5化合物)
在氮气氛下,在250ml三颈圆底烧瓶中加入0.1 48g氢化钠(1.1当量,3.7mmol,分散在矿物油中的比例为60%),用己烷和5ml DMF洗涤。通过移液吸管加入0.75g 3-(3-氯哒嗪-6′-基氧基)酚(1.0当量,3.4mmol)的8ml DMF至该碱中,引起放热从23℃升至26℃。搅拌30分钟后通过移液吸管加入0.96gα-(2-溴甲基苯基)-β-甲氧基丙烯酸甲酯(1.0当量,3.4mmol)的10ml DMF,引起轻微放热和2℃的变化。2.5小时后的气相色谱显示90%产率,再搅拌1小时后添加50ml水和50ml乙酸乙酯将反应淬灭。加入150ml以上的水和乙酸乙酯到反应产物中,分离有机相,并用3×200ml水洗涤,无水硫酸镁干燥,在旋转蒸发器中(40℃)减压除去溶剂,得到1.5g粗产品为黄色油。
粗产品用快速色谱法纯化,2∶3乙酸乙酯/己烷作洗脱剂,得到0.82g(产率:56.6%)α-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-β-甲氧基丙烯酸甲酯,为黄色粘性油。NMR(200MHz,CDCL3):3.7(s,3H),3.8(s,3H),4.95(s,2H),6.7-7.6(m,11H).
实施例92-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯(用于制备实施例10化合物)
在氮气氛下,在500ml三颈圆底烧瓶中加入2.0g氢化钠(1.1当量,49.5mmol,分散在矿物油中的比例为60%),用己烷和35ml DMF洗涤。通过移液吸管加入10.0g 3-(3-氯哒嗪-6′-基氧基)酚(1.0当量,45.0mmol 70%纯度)的35ml DMF至反应物中,用冰浴控制放热<30℃。搅拌30分钟后通过移液吸管加入18.4g 2-(2-甲基苯基)-2-甲氧基亚氨基乙酸甲酯(1.0当量,45.0mmol)的35ml DMF,引起放热从24℃到31℃。1小时后的气相色谱显示80%产率,再搅拌1小时后添加100ml水和100ml乙酸乙酯将反应淬灭。加入200ml以上乙酸乙酯和300ml以上水到反应中,用HCl酸化该溶液,分离有机相,并用3×250ml水洗涤,无水硫酸镁干燥,在旋转蒸发器中(40℃)减压除去溶剂,得到23.9g粗产品为棕色粘性油。
通过快速色谱法纯化上述反应得到的3.7g粗产品的合并物和0.9g类似产品,1∶1乙酸乙酯/己烷作洗脱剂,得到2.72g 2-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯为黄色粘性油(外推产率:72.1%)。NMR(200MHz,CDCL3):3.8(s,3H),4.0(s,3H),4.95(s,2H),6.7-7.6(m,10H).
实施例102-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯(表4,化合物262)
在1L三颈圆底烧瓶中加入20.0g 2-[2-(3-(3′-氯哒嗪-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯(1.0当量,0.047mol),11.5g乙酸钠(3当量,0.14mol)和250ml冰醋酸。将反应混合物在117℃加热5小时,之后薄层色谱分析显示相对于起始原料的强产物点和弱强度点。
用500ml水和250ml乙酸乙酯淬灭反应。有机相被分离,并用2×250ml乙酸乙酯从水相中萃取,同时每次加250ml以上的水至水相。合并乙酸乙酯萃取液750ml,用750ml水洗涤,再用500ml水洗涤,用纯碳酸氢钠碱化至pH8,用2×400ml水洗涤,无水硫酸镁干燥,在旋转蒸发器中减压除去溶剂,得到19.3g粗产品为棕色粘性油。
用20ml甲醇滴定6g粗产品并过滤所得固体,用10ml甲醇洗涤并于真空箱干燥,得到2.6g 2-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯为褐色固体(m.p.115-117℃,外推产率:41.7%)。
实施例112-[2-(3-(2′-正丙基哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯(表4,化合物266)
在氮气氛下,在250ml三颈圆底烧瓶中加入0.35g氢化钠(1.2当量,8.8mmol,分散在矿物油中的比例为60%),用己烷和15ml DMF洗涤。加入3.0g粗2-[2-(3-(3(2H)-哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯(1.0当量,7.3mmol)的15ml DMF。搅拌该混合物30分钟,然后通过移液吸管将0.90g丙基溴(1.0当量,7.3mmol)加到反应混合物中。5小时后的薄层色谱分析显示主产物点和无起始试剂点。5小时后添加75ml水和75ml乙酸乙酯淬灭反应。
加入125ml以上水和乙酸乙酯以增加反应。分离有机相,并用3×200ml水洗涤,无水硫酸镁干燥,在旋转蒸发器中(40℃)减压除去溶剂,得到3.2g粗产品为橙/棕色油。
粗产品通过快速色谱纯化,乙酸乙酯洗脱,得到1.3g 2-[2-(3-(2′-正丙基哒嗪-3′-酮-6′-基氧基)苯基)氧甲基苯基]-2-甲氧基亚氨基乙酸甲酯为黄色胶状油(产率:39.5%)。
实施例12
质子NMR数据(200MHz)用来提供给表4所列化合物EX# H-nmr(TMS=0ppm)219 1.1(t,3H);2.2(m,2H);3.6(s,3H);3.8(s,3H);4.9(m,2H);5.0(s,2H);6.9(m,2H);
7.1(t,1H);7.2(m,1H);7.3-7.5(m,4H)7.6(s,1H);7.7(m,1H);7.8(d,1H)220 1.4(t,3H);3.6(s,3H);3.8(s,3H);4.3(q,2H);5.0(s,2H);6.9(m,2H);7.1(t,1H);
7.2(m,1H);7.3-7.5(m,4H)7.6(s,1H);7.7(m,1H);7.8(d,1H)221 1.1(t,3H);2.2(m,2H);3.6(s,3H);3.75(s,3H);3.8(s,3H);4.9(m,2H);5.0(s,2H);6.5(d,1H);6.6(m,1H);6.8(d,1H);7.2(m,1H);7.3(m,2H);7.4(m,1H)7.6(m,2H);
7.8(d,1H)222 1.1(t,H);2.2(m,2H);3.6(s,3H);3.8(s,3H);4.9(m,2H);5.0(s,2H);6.9-7.5(m,8H);
7.6(s,1H);7.8(d,1H)223 1.1(t,3H);2.2(m,2H);3.7(s,3H);3.9(s,3H);4.9(s,2H);5.0(s,2H);6.9(m,1H);
7.0(d,1H);7.2(d,1H);7.25-7.4(m,5H);7.5(m,1H);7.6(s,1H);7.7(d,1H)224 3.6(s,3H);3.75(s,3H);3.8(s,3H);4.9(s,2H); 5.0(s,2H);6.9(m,1H);7.0(d,1H);
7.2(m,1H);7.3-7.5(m,5H);7.55(m,1H);7.6(s,1H);7.7(d,1H)225 3.6(s,3H);3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);6.9(d,1H);7.0(m,1H);
7.15(m,1H);7.2-7.65(m,10H);7.8(d,1H)226 3.6(s,3H);3.7(s,3H);5.0(s,2H);5.4(s,2H);6.5(s,1H);6.6(m,1H);6.9(d,1H);
7.2(m,1H);7.3-7.6(m,8H);7.8(d,1H)227 3.7(s,3H);3.8(s,3H);3.9(s,3H);5.0(s,2H);6.9(m,2H);7.2(m,1H);7.25-
7.4(m,5H);75-7.8(m,3H)228 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);7.0(m,2H);7.2(m,1H);7.3-7.5(m,6H);
7.5-7.7(m,5H)229 1.1(t,3H);2.2(m,2H);3.7(s,3H);3.8(s,3H);4.9(s,2H);5.0(s,2H);6.9(m,1H);
7.0(m,3H);7.2(m,1H);7.3(m,3H);7.5(m,1H);7.6(m,3H)230 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);7.0(m,2H);7.2(m,1H);7.3-7.5(m,6H);
7.5-7.7(m,5H)231 1.4(t,3H);3.7(s,3H);3.8(s,3H);4.3(q,2H);5.0(s,2H);7.0(m,2H);7.2(m,1H);7.3-
7.5(m,5H);7.6(m,3H)232 1.0(t,3H);1.9(q,2H);3.7(s,3H);3.8(s,3H);4.2(t,2H);5.0(s,2H);7.0(m,2H);
7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)EX# nmr(TMS=0ppm)233 3.0(t,2H);3.7(s,3H);3.8(s,3H);4.5(t,2H);5.0(s,2H);7.0(m,2H);7.2(m,1H);7.3-
7.5(m,5H);7.6(m,1H);7.65(s,1H);7.7(d,1H)234 2.6(q,2H);3.7(s,3H);3.8(s,3H);4.3(t,2H);5.0(m,4H);5.9(m,1H);7.0(m,2H);
7.2(m,1H);7.3-7.5(m,5H);7.65(m,3H)235 3.4(s,3H);3.6(s,3H);3.8(s,3H);3.85(m,2H);4.4(t,2H);5.0(s,2H);7.0(m,2H);
7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)236 3.6(s,3H);3.8(s,3H);5.0(s,2H);6.9(m,1H);7.1(d,1H);7.2(m,1H);7.3-
7.6(m,11H);7.7(m,2H)237 3.6(s,3H);3.7(s,3H);3.8(s,3H);5.0(s,2H);6.6-6.8(m,3H);6.9-7.4(m,6H);
7.5(m,1H);7.6(s,1H)238 3.7(s,3H);3.8(s,3H);4.4(m,1H);4.6(m,1H);4.8(m,1H);4.95(m,1H);5.0(s,2H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);7.5-7.7(m,3H)239 3.7(s,3H);3.8(s,3H);4.0(s,3H);5.0(s,2H);7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);
7.6(m,1H);7.7(d,1H)240 3.6(s,3H);3.8(s,3H);5.0(s,2H);5.7(s,2H);6.9(m,1H);7.0(d,2H);7.2(m,1H);7.3-
7.45(m,4H);7.5-7.8(m,7H);8.0(m,2H)241 2.9(d,3H);3.9(s,3H);4.0(s,3H);5.0(s,2H);6.8(m,1H);7.0(m,2H);7.2(m,1H);7.3-
7.5(m,5H);7.6(m,1H);7.7(d,1H)242 0.3-0.8(m,4H);1.4(m,1H);3.7(s,3H);3.85(s,3H);4.1(d,2H);5.0(s,2H);
7.0(m,2H);7.1-7.5(m,6H);7.6(m,3H)243 3.6(s,3H);3.7(s,3H);5.0(s,2H);5.5(s,2H);6.9(m,2H);7.2(m,1H);7.3-7.5(m,7H);
7.5-7.7(m,4H);7.8(m,3H);7.9(s,1H)244 3.7(s,3H);3.85(s,3H);4.9(q,2H);5.0(s,2H);7.0(m,2H);7.2(m,2H);7.4(m,4H);
7.6(m,1H);7.7(s,1H);7.8(d,1H)245 3.6(s,3H);3.7(s,3H);5.0(s,2H);7.0(m,2H);7.2(m,2H);7.3-7.5(m,6H);7.5-
7.7(m,4H);7.8(s,1H)246 3.6(s,3H);3.7(s,3H);5.0(s,2H);7.0(m,2H);7.2(m,2H);7.3-7.4(m,6H);7.5-
7.7(m,4H);7.8(d,1H)247 3.7(s,3H);3.8(s,3H);3.85(s,3H);3.9(s,3H);5.1(s,2H);6.5(m,2H);6.9(m,4H);
7.3(m,2H);7.6(m,2H)248 3.7(s,3H);3.78(s,3H);4.95(s,2H);5.1(s,2H);6.7-7.6(m,16H)249 3.65(s,3H);3.8(s,3H);4.6(d,2H);4.95(s,2H);5.15-5.25(m,2H);5.8-6.05(m,1H);
6.65-7.6(9m,11H)250 1.0-1.1(t,3H);2.1-2.25(m,2H);3.65(s,3H);3.8(s,3H); 4.7(s,2H);4.95(s,2H);6.7-
7.6(m,11H)EX# nmr(TMS=0ppm)251 0.85-0.95(t,3H);1.65-1.8(m,2H);3.65(s,3H);3.8(s,3H);3.9-4.0(t,2H);4.95(s,2H);
6.6-7.6(m,11H)252 2.7(s,3H);2.8(s,3H);4.9(s,2H);6.65-7.6(m,11H);10.6(s,1H)253 1.0(t,3H);1.4(m,2H);1.8(m,4H);3.7(s,3H);3.8(s,3H);4.2(t,2H);5.0(s,2H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)254 0.9(t,3H);1.4(d,3H);1.9(m,2H);3.7(s,3H);3.8(s,3H);5.0(s,2H);5.2(q,1H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)255 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);6.8(d,1H);7.0(m,3H);7.2(m,1H);7.3-
7.5(m,5H);7.6(m,3H)256 2.6(m,4H);2.9(m,2H);3.7(m,7H);3.9(s,3H);4.4(t,2H);5.0(s,2H);7.0(m,2H);
7.2-7.5(m,6H);7.6(m,3H)257 2.2(m,2H);2.7(t,2H);3.7(s,3H);3.8(s,3H);4.3(t,2H);5.0(s,2H);7.0(m,2H);7.1-
7.5(m,11H);7.6(m,3H)258 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.6(s,2H);6.9(m,1H);7.1(d,1H);7.15-
7.5(m,10H);7.6(m,1H);7.65(s,1H);7.7(d,1H)259 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);7.0(m,2H);7.2-7.5(m,10H);7.6(m,3H)260 3.7(s,3H);3.8(s,3H);5.0(s,2H);5.4(s,2H);7.0(m,2H);7.2-7.5(m,10H);7.6(m,3H)261 10-1.4(m,5H);1.6-2.0(m,6H);3.7(s,3H);3.8(s,3H);4.1(d,2H);5.0(s,2H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)262 3.8(s,3H),4.0(s,3H),5.0(s,2H),(s,2H),6.7-7.6(m,10H),10.7(s,1H)263 3.8(s,3H),4.0(s,3H),4.95(s,2H),5.1(s,2H),6.65-7.6(m,15H)264 1.05-1.15(t,3H),2.1-2.25(m,2H),3.8(s,3H),4.0(s,3H),4.7(m,2H),4.95(s,2H),
6.7-7.6(m,10H)265 3.8(s,3H),4.0(s,3H),4.55-4.65(m,2H),4.95(s,2H),5.1-5.2(m,2H),5.8-6(m,1H),
6.65-7.6(m,10H).266 0.85-0.95(t,3H),1.6-1.8(m,2H),3.8(s,3H),3.9-4.0(t,2H),4.0(s,3H),4.95(s,2H),
6.6-7.6(m,10H)267 3.7(s,3H);3.8(s,3H);4.6(s,2H);5.0(s,2H);5.3(s,2H);6.9(m,1H);7.0(d,1H);7.2-
7.4(m,11H);7.5(m,1H);7.6(s,1H);7.7(d,1H)268 2.4(t,2H);3.7(s,3H);3.8(s,3H);4.1(m,2H);4.5(t,2H);5.0(s,2H);6.9(m,5H);7.1-
7.4(m,7H);7.5(m,1H);7.6(s,1H);7.7(d,1H)269 1.0(m,6H);1.5(m,4H);2.0(m,1H);3.7(s,3H);3.8(s,3H);4.2(d,2H);5.0(s,2H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H);7.6(m,3H)EX# nmr(TMS=0ppm)270 3.7(s,3H);3.8(s,3H);5.0(s,2H);6.4(s,2H);7.0(m,2H);7.2(m,1H);7.3-7.4(m,4H);
7.5(m,1H);7.6(s,1H);7.9(s,1H);8.5(s,1H)271 3.2(t,2H);3.7(s,3H);3.8(s,3H);4.5(t,2H);5.0(s,2H);70(m,2H);7.2-7.5(m,11H);
7.6(m,3H)272 3.7(s,3H);3.8(s,3H);4.1(t,2H);4.4(t,2H);5.0(s,2H);7.0(m,2H);7.2(m,1H);7.3-
7.4(m,5H);7.6(m,3H)273 3.7(s,3H);3.8(s,3H);4.0(t,2H);4.6(t,2H);5.0(s,2H);7.0(m,2H);7.2(m,1H);7.3-
7.5(m,5H);7.7(m,3H)274 3.7(s,3H);3.8(s,3H);5.0(m,3H);5.9(d,1H);7.0(m,2H);7.2(m,1H);7.3-
7.5(m,5H);7.6(m,3H);7.8(dd,1H)275 1.0(d,6H);1.7(m,3H);3.7(s,3H);3.8(s,3H);4.3(m,2H);5.0(s,2H);7.0(m,2H);
7.2(m,1H);7.3-7.5(m,5H);7.7(m,3H)276 1.7(d,3H);3.7(s,3H);3.8(s,3H);4.8(d,2H);5.0(s,2H);5.8(m,2H);7.0(m,2H);
7.2(m,1H);7.3-7.5(m,5H);7.7(m,3H)277 1.7(s,3H);1.9(s,3H);3.7(s,3H);3.8(s,3H);4.8(d,2H);5.0(s,2H);5.5(m,1H);
7.0(m,2H);7.2(m,1H);7.3-7.5(m,5H); 7.6(m,3H)278 3.7(s,3H),3.8(m,3H),5.0(s,2H),6.9-7.6(m,11H),10.4(m,1H)279 3.75(s,3H),3.85(s,3H),4.5-4.6(d,2H),5.0(s,2H),5.1-5.2(m,2H),5.8-6.0(m,1H),
6.9-7.65(m,11H)280 1.0-1.1(t,3H),2.0-2.2(m,2H),3.7(s,3H),3.8(s,3H),4.65(s,2H),5.0(s,2H),6.9-
7.65(m,11H)281 1.1(t,3H);2.2(m,2H),3.6(s,3H),3.7(s,3H),4.8(s,2H),5.0(s,2H),6.8(d,1H),
7.2(m,1H),7.4(m,2H),7.5(m,3H),7.6(m,1H),7.7-7.85(m,3H),7.9(d,1H),
8.15(m,1H)282 3.6(s,3H);3.7(s,3H);3.8(d,6H);5.0(s,2H);5.3(bs,2H);6.9(m,2H);7.2(m,2H);
7.25-7.5(m,7H);7.6(m,4H)
实施例13
下面将描述本发明大量化合物抵御病害所进行的自然条件下的杀真菌活性试验。将这些化合物溶解在2∶1∶1(体积)水∶丙酮∶甲醇的混合物中,然后喷洒在植物上,让其干燥(1-2小时),然后给这些植物接种霉菌。给每个试验所用的对照植物喷洒水,丙酮和甲醇混合物,然后接种霉菌。每个试验剩下的技术将在下面给出,表4中由实施例号代表的各化合物使用每公顷300g的剂量对各种霉菌试验结果。结果用相对于对照组杀真菌效果的百分比表示,100%表示控制住全部病害,0表示对病害没有控制作用。给试验植物接种的霉菌如下:
小麦叶锈病(WLR)
将puccinia recondita(f.sp.tritici)在暖房中的7日龄小麦(cultivar Fielder)上培养1 4天。用铝箔收集叶子上的孢子,通过250μm开口筛对孢子筛选,储存或使用新鲜的。储存是将孢子放入密封包并置于超低温冷冻箱。制备孢子悬浮液是在干uredia中添加Soltrol油,每mL油含20mg(9.5百万)孢子。将该悬浮液分装到连接油喷雾器的明胶胶囊中(每粒含0.7mL)。每块有20个植有7日龄Fielder小麦的2平方英寸窝的地用一个胶囊。至少等15分钟,等油从小麦叶上蒸发后将作物置入暗湿箱(18-20℃,相对湿度100%)中24小时。再将作物放回暖房,渡过潜伏期,10天后评判病害程度。对于防护试验,用杀真菌化合物喷洒作物后将作物接种1天。
黄瓜霜霉病(CDM)
在潮湿的18-22℃恒温室内,将pseudoperonosporacubensis保持在生长的Bush Champion黄瓜作物叶上用中等强度的光照射7-8天。用从患病叶子上收集的孢子制成水悬浮液,浓度调节到每mL水约1×105个孢子。用De Viilbiss喷雾器在叶子背面喷洒直到叶子上出现小水珠,从而给Bush Champion黄瓜幼苗接种。接种的作物在约70°F的潮湿箱中培养24小时,接着在潮湿的65-75°F恒温室内培养6-7天。接种7天后测定控制病害的百分比。
葡萄霜霉病(GDM)
在有潮湿空气的20℃恒温箱内,将Plasmopara vticola保持在生长的cv.Delaware葡萄作物叶上用中等强度的光照射7-8天。用从患病叶子上收集的孢子制成水悬浮液,浓度调节到每mL水约3×105个孢子。用De Viilbiss喷雾器在叶子背面喷洒直到叶子上出现小水珠,从而给Delaware葡萄作物接种。接种的作物在20℃的潮湿箱中培养24小时。接种7天后以控制的百分比记录控制病害值。
对于黄瓜霜霉病试验,如果使用剂量为每公顷300g,实施例233-242表现为85%或更好的控制效果。对于小麦叶锈病试验,以每公顷300g的剂量施用,实施例227-236和238-251表现为75%或更好的控制效果。对葡萄霜霉病,实施例242-261,264-269和271-277以每公顷300g表现75%或更好的控制效果。
因此,二氢哒嗪酮和哒嗪酮及其对映体,酸加成盐和金属盐复合物可用作农业杀真菌剂并可用于各种场合如施用于种子,土壤或叶片。
二氢哒嗪酮和哒嗪酮及其对映体,盐和复合物可用作杀真菌喷洒剂,通过常规使用方法如常规高—加仑(大容量)水压喷洒,低—加仑喷洒,气喷喷洒,飞机喷洒和播撒。使用的稀释度和比例取决于所用设备的类型,使用方法,需要处理的作物种类和需要控制的病害。总之,本发明化合物的用量为每公顷约0.005-50kg,优选约0.025-25kg活性组分。
作为种子保护剂,种子毒性包衣的剂量比例通常为每100kg种子上有约0.05-20g活性物质,优选约0.05-4g,更优选约0.1-1g。作为土壤杀真菌剂,该化学组分可以混入土壤或施用于土壤表面,使用的比例通常为每公顷土地约0.02-20kg,优选约0.05-10kg,更优选约0.1-5kg。作为叶片杀真菌剂,对生长作物施用该毒剂的比例通常为每公顷约0.01-10kg,优选约0.02-5kg,更优选约0.25-1kg。
由于二氢哒嗪酮和哒嗪酮及其对映体,盐和复合物显示出杀真菌活性,因此这些化合物可与其它已知杀真菌剂结合使用以取得广谱杀菌活性。适宜的这类杀真菌剂包括但不限于美国专利5,252,594(尤其见14和15栏)所列的那些化合物。
二氢哒嗪酮和哒嗪酮及其对映体,酸加成盐和金属盐复合物更可以各种方式使用。由于这些化合物具有广谱杀菌活性,因此它们可用于谷物颗粒的贮存方面。这些复合物可用作谷物如小麦,大麦和黑麦,大米,花生,豆类和葡萄的杀真菌剂,用于草坪,水果,干果和蔬菜种植园以及高尔夫球场。
本发明化合物所抵御的病害实例包括玉米和大麦胡麻斑病(helminthosporium),小麦和大麦白粉病,小麦叶和茎锈病,番茄早期枯萎病,番茄晚期枯萎病,花生早期叶斑病,葡萄白粉病,葡萄黑腐病,苹果黑星病,苹果白粉病,黄瓜白粉病,水果褐腐病,甘薯灰霉僵腐病,豆白粉病,黄瓜炭疽病,小麦斑结病(septoria nodorum),稻纹枯病和稻瘟病。
实施例14
下面将描述本发明大量化合物防治虫害所进行的活体杀虫活性试验。下列试验方法用于评价本发明化合物的杀虫活性。将要测定的化合物溶解于适当溶剂,通常为丙酮,甲醇和水的混合物,用平板扇叶喷嘴(flat fan nozzle)喷洒到整个三片切开的叶片表面。喷洒后可将叶片干燥。将其中两片染上食叶昆虫(南方粘虫和墨西哥豆甲),第三片在喷洒前已经染上两点黄蜘蛛,即试验的昆虫种类有:
AW 南方粘虫 Spodoptera eridamia
BB 墨西哥豆甲 Epilachna varivestis
MTA 两点黄蜘蛛 Teranychus uricate喷洒后24-48小时通过观察确定控制效果的百分比。
实施例234,242-245,253,255,258-260,269-270和273-277为防治南方粘虫的试验,用量为600g/公顷,获得90%或更好的控制效果。实施例230,232,234,243,244,253,255-257,268,269和275-277为防治墨西哥豆甲和两点黄蜘蛛的试验,用量为300g/公顷,获得90%或更好的控制效果。
本发明组合物和化合物可直接用于需要防护的区域(例如,被虫害侵蚀的经济作物或其周围地区)或需要阻止虫害蔓延的植物。具体害虫的实例属于下列科目:鳞翅目,鞘翅目,双翅目,缨翅目,膜翅目,异翅亚目,同翅目和蜱螨目。所说组合物和化合物既可用作接触式农药又可作为内吸性农药。本发明化合物对害虫生长有作用的用量为每公顷0.0005-10kg,优选约0.05-5kg,最优选的是0.1-1kg。
在本发明方法的实际应用中,活性化合物可以用于土壤或叶片,由此被植物吸收,然后传送到植物的其它部分,通过害虫或昆虫对植物部分的摄取而摄取最终对其产生作用。这种使用方法称为“内吸”应用。或者,将活性化合物用于土壤并直接接触到那里的昆虫和其它需要控制的害虫。这种使用方法称为“土壤”应用。再者,将活性化合物施在植物叶片上,使食用叶片的昆虫和其它害虫吃到它们。本发明组合物和制剂也可以包含已知杀虫化合物。这就拓宽了本制剂的广谱活性,并产生最佳协同效应。现有技术中已知的适宜杀虫剂包括美国专利5,074,471所列的那些,尤其见14和15栏。
本发明化合物可以组合物或制剂形式使用。组合物和制剂的具体制备实例可以在下列文献中查到:美国化学协会出版物“Pesticidal Formulation Research″,(1969),Advancesin Chemistry Series No.86,Wade Van Valkenburg著和MarcelDekker,Inc.出版物″Pesticide Formulation″,(1973),由WadeVan Valkenburg编辑。在这些组合物和制剂中,活性物质与常规惰性农业上可接受的(即植物相容和/或杀虫惰性的)杀虫稀释剂或填充剂如固体或液体载体材料,即常规用于杀虫组合物或制剂中的那些混合使用。所谓“农业上可接受的载体”是指可使活性组分溶解或分散到组合物中又不削弱活性组分功效,而其本身对土壤,设备,植物对象或农业环境没有重大影响的任何物质。如果需要,还可以加入辅剂如表面活性剂,稳定剂,消泡剂和阻移剂(antidrift agent)一起使用。
本发明组合物和制剂的实例有水溶液和分散剂,油性溶液和油性分散剂,糊剂,灰粉剂,可湿性粉剂,乳化浓缩液流动剂,颗粒,诱饵,可转化乳液,烟雾剂和熏烛。可湿性粉剂,糊剂,流动剂和乳化浓缩液是通过浓缩制成的,它们可以在使用前或使用中用水稀释。在这些制剂中,化合物用液体或固体载体填充,如果需要,可以混入适当的表面活性剂。诱饵通常含有食物或其它吸引昆虫的物质,但至少含有一种本发明化合物。
通常要求含有辅剂,特别是对叶片喷洒制剂时,如根据农业实际需要添加润湿剂,展开剂,分散剂,增稠剂,粘结剂等等。这些辅剂一般是现有技术中使用的,关于辅剂的讨论可以在许多文献中查到,如John W.McCutcheon,Inc.出版物″Detergents和Emulsifiers,Annual″。
本发明活性化合物可单独使用或与其它固体和/或液体可分散载体,和/或其它已知可容性活性剂混合使用,尤其是植物保护剂,例如其它杀虫剂,arthropodicides,杀线虫剂,杀真菌剂,杀菌剂,杀噬齿动物剂,除草剂,肥料,生长调节剂,增效剂。
在本发明组合物中,活性化合物的含量一般约为混合物重量的0.0001-99%。为使组合物便于贮存或运输,活性组分的含量优选约0.5-90%wt,更优选约1-75%wt。适于直接或田间使用的组合物一般含有活性化合物的量约占混合物为0.0001-95%wt,优选约0.0005-90%wt,更优选约0.001-75%wt。组合物也可以用化合物对载体的比例表述。在本发明中,这些物质的重量比(活性化合物/载体)可以从99∶1到1∶4变化,优选10∶1到1∶3。
通常,本发明化合物可以溶解于某些溶剂如丙酮,甲醇,乙醇,二甲基甲酰胺,吡啶或二甲亚砜,并用水稀释溶液。溶液的浓度可以从约1%到90%变化,优选约5-50%。
为制备乳化浓缩液,可将本发明化合物与乳化剂一起溶解于适当的有机溶剂或溶剂的混合物,以提高化合物在水中的分散性。乳化浓缩液中活性组分的浓度通常约为10-90%,在可流动乳化浓缩液中的浓度可高达约75%。
适于喷洒的可湿性粉剂可以通过化合物与精细的固体混合来制备,如粘土,无机硅酸盐和碳酸盐及硅胶,而且,湿润剂,增稠剂和/或分散剂也以这种方式混合。这些制剂中活性组分的浓度一般约为20-99%,优选约40-75%。典型的可湿性粉剂是混合50份哒嗪酮,45份合成的沉淀水合二氧化硅如以Hi-SilR商标出售的,和5份木质素磺酸钠。在另一种上述可湿性粉剂的制备中用高岭土型(Barden)粘土代替Hi-SilR,另一种制备方法中是用以ZeolexR7出售的合成硅铝酸钠代替25%Hi-SilR。
粉剂是通过哒嗪酮或其对映体,盐和复合物与精细的惰性固体(可以是天然有机物或无机物)混合制备的。用于这一目的的材料有植物粉,硅胶,硅酸盐,碳酸盐和粘土。制备粉剂的一种常规方法是用精细分离的载体稀释可湿性粉剂。粉剂中活性组分的含量通常约为20-80%,然后稀释成约1-10%的使用浓度。
活性化合物可作为通常使用的喷洒方法的杀虫剂,如常规的高—加仑式喷洒,低—加仑喷洒,超低体积喷洒,气吹喷洒,飞机喷洒和尘洒。
本发明还涉及杀死,抵御或控制害虫的方法,它考虑到用抵御或毒死害虫量(即有效杀虫量)的至少一种本发明活性化合物单独或与载体制成上述混合制剂(如组合物或制剂)接触害虫使用。本说明书和权利要求书中所用术语“接触”意指用于至少下面一种情况:(a)这些害虫和(b)它们的生长(即要保护的场所如生长的作物或作物生长的区域),本发明化合物单独使用或作为组合物或制剂的组分使用。
除上述组分外,本发明的制剂还可以含有常用于这类制剂的其它物质。例如,润滑剂如硬脂酸钙或硬脂酸镁,或加入可湿性粉剂或混合制成颗粒。而且,例如可以添加“粘结剂”如聚乙烯醇—纤维素衍生物或其它胶状物质,如酪素,以改善杀虫剂对被保护物体表面的粘性。
Claims (20)
其中
W是CH3-O-A=C-CO(V)CH3;
A是N或CH;
V是O或NH;
其中Y是O,S,NR1,或R6,含有R4和R5的环键是单键或双键;
n是0或1;
X独立选自氢,卤素,(C1-C4)烷基,(C1-C4)烷氧基以及与-HC=CH-CH=CH-形成的萘环;
R2独立选自氢,(C1-C12)烷基,(C1-C12)烷氧基,卤代(C1-C12)烷基,卤代(C1-C12)烷氧基,羟基(C1-C12)烷基,(C1-C12)烷氧基(C1-C12)烷基,(C1-C12)烷氧基羰基(C1-C12)烷基,(C2-C8)烯基,卤代(C2-C8)烯基,(C3-C10)炔基,卤代(C3-C10)炔基,(C3-C7)环烷基,(C3-C7)环烷基(C1-C4)烷基,环氧(C1-C12)烷基,PO(OR1)2(C1-C12)烷基,R1S(O)2(C1-C12)烷基,(R1)3Si(C1-C12)烷基,芳基,芳氧基(C1-C12)烷基,芳基羰基(C1-C12)烷基,芳烷基,芳烯基,杂环基,杂环基(C1-C12)烷基,N-吗啉基(C1-C12)烷基,N-哌啶基(C1-C12)烷基;
R1独立选自(C1-C12)烷基,(C2-C8)烯基和芳基;
R4和R5分别选自氢,卤素,(C1-C8)烷基,(C1-C8)烷氧基,氰基,卤代(C1-C12)烷基,(C2-C8)烯基,(C3-C10)炔基,芳基和芳烷基;
R6是(C1-C12)亚烷基和(C2-C12)亚烯基。
2.权利要求1的化合物,其中键连R4和R5之间碳的环键是双键。
3.权利要求2的化合物,其中A是CH。
4.权利要求2的化合物,其中A是N。
5.权利要求3的化合物,其中V是O。
6.权利要求4的化合物,其中V是O。
8.权利要求7的化合物,其中n=0,X是氢,R2选自乙基,丙基,丁基,乙烯基,烯丙基,氯乙基,氟乙基和取代的苄基。
9.权利要求8的化合物,其中R2}选自卤素取代的苄基,(C1-C4)烷基取代的苄基,三卤代苄基和氰基取代的苄基。
10.权利要求9的化合物,其中R2选自2-氯苄基,3-氯苄基,4-氯苄基,2-氟苄基,3-氟苄基,4-氟苄基,2-氰基苄基,3-氰基苄基,4-氰基苄基和4-三氟甲基苄基。
12.权利要求11的化合物,其中n=0,X是氢,R2选自乙基,丙基,丁基,乙烯基,烯丙基,氯乙基,氟乙基和取代的苄基。
13.权利要求12的化合物,其中R2选自卤代的苄基,(C1-C4)烷基取代的苄基,三卤代苄基和氰基取代的苄基。
14.权利要求13的化合物,其中R2选自2-氯苄基,3-氯苄基,4-氯苄基,2-氟苄基,3-氟苄基,4-氟苄基,2-氰基苄基,3-氰基苄基,4-氰基苄基和4-三氟甲基苄基。
15.一种用于控制植物学真菌的杀真菌组合物,包括农业上可接受的载体和权利要求1的化合物,其中载体与化合物的比例为99∶1至1∶4。
16.权利要求15的组合物,其中农业上可接受的载体与化合物的比例为10∶1至1∶3。
17.一种控制植物学真菌的方法,包括将权利要求1化合物以每公顷0.005-50kg的比例施用到需要控制的场所。
18.权利要求17的方法,其中所用权利要求1化合物的比例为每公顷0.025-10kg。
19.一种控制昆虫的方法,包括给昆虫活动区域以每公顷0.005-10kg的比例施用权利要求1化合物。
20.权利要求19的方法,其中所用化合物的比例为每公顷0.01-1kg。
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JPS5826802A (ja) * | 1981-08-10 | 1983-02-17 | Sankyo Co Ltd | 農園芸用殺菌剤 |
NZ213630A (en) * | 1984-10-19 | 1990-02-26 | Ici Plc | Acrylic acid derivatives and fungicidal compositions |
DE3545319A1 (de) * | 1985-12-20 | 1987-06-25 | Basf Ag | Acrylsaeureester und fungizide, die diese verbindungen enthalten |
GB8617648D0 (en) * | 1986-07-18 | 1986-08-28 | Ici Plc | Fungicides |
DE3705389A1 (de) * | 1987-02-20 | 1988-09-01 | Basf Ag | Substituierte crotonsaeureester und diese enthaltende fungizide |
EP0283271A3 (en) * | 1987-03-17 | 1990-04-25 | Ube Industries, Ltd. | Pyridazinone derivative, process for producing thereof and insecticide, acaricide and fungicide containing said derivative as active ingredient |
DE3821503A1 (de) * | 1988-06-25 | 1989-12-28 | Basf Ag | (alpha)-aryl-acrylsaeureester und diese enthaltende fungizide |
ATE169616T1 (de) * | 1988-11-21 | 1998-08-15 | Zeneca Ltd | Zwischenverbindungen zur herstellung von fungiziden |
DK0629609T3 (da) * | 1989-05-17 | 1996-12-23 | Shionogi & Co | Fremgangsmåde til fremstilling af alkoxyiminoacetamidderivater og et mellemprodukt dertil |
ES2110421T5 (es) * | 1990-06-27 | 2004-12-01 | Basf Aktiengesellschaft | O-bencil-oximeteres y los agentes protectores de las plantas que contienen estos compuestos. |
ATE180475T1 (de) * | 1990-09-21 | 1999-06-15 | Rohm & Haas | Dihydropyridazinone und pyridazinone als fungizide |
JPH06504538A (ja) * | 1991-01-30 | 1994-05-26 | ゼネカ・リミテッド | 殺菌剤 |
DE4142191A1 (de) * | 1991-12-20 | 1993-06-24 | Bayer Ag | Verfahren zur herstellung von 3-alkoxy-acrylestern |
DE4305502A1 (de) * | 1993-02-23 | 1994-08-25 | Basf Ag | Ortho-substituierte 2-Methoxyiminophenylessigsäuremethylamide |
-
1995
- 1995-04-21 US US08/426,514 patent/US5635494A/en not_active Expired - Fee Related
-
1996
- 1996-04-09 EP EP96302488A patent/EP0738716A3/en not_active Withdrawn
- 1996-04-09 IL IL11786596A patent/IL117865A0/xx unknown
- 1996-04-09 AU AU50550/96A patent/AU713334B2/en not_active Ceased
- 1996-04-10 NZ NZ286342A patent/NZ286342A/en unknown
- 1996-04-16 CA CA002174296A patent/CA2174296A1/en not_active Abandoned
- 1996-04-17 CZ CZ961106A patent/CZ110696A3/cs unknown
- 1996-04-17 TW TW085104563A patent/TW499294B/zh not_active IP Right Cessation
- 1996-04-18 AR AR33621296A patent/AR001656A1/es unknown
- 1996-04-19 KR KR1019960011980A patent/KR100430695B1/ko not_active IP Right Cessation
- 1996-04-19 CO CO96019024A patent/CO4650121A1/es unknown
- 1996-04-19 BR BR9602004A patent/BR9602004A/pt not_active Application Discontinuation
- 1996-04-19 JP JP8120852A patent/JPH08291147A/ja active Pending
- 1996-04-19 HU HU9601035A patent/HUP9601035A3/hu unknown
- 1996-04-19 TR TR96/00328A patent/TR199600328A2/xx unknown
- 1996-04-19 AR AR33622896A patent/AR001667A1/es unknown
- 1996-04-19 ZA ZA963140A patent/ZA963140B/xx unknown
- 1996-04-19 CN CN96104596A patent/CN1124267C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9918525B2 (en) | 2013-02-22 | 2018-03-20 | Velcro BVBA | Touch fastener structures |
WO2024104345A1 (zh) * | 2022-11-17 | 2024-05-23 | 沈阳中化农药化工研发有限公司 | 一种哒嗪酮衍生物及其用途 |
Also Published As
Publication number | Publication date |
---|---|
HUP9601035A2 (en) | 1997-04-28 |
CO4650121A1 (es) | 1998-09-03 |
AR001656A1 (es) | 1997-11-26 |
AU5055096A (en) | 1996-10-31 |
IL117865A0 (en) | 1996-08-04 |
AR001667A1 (es) | 1997-11-26 |
EP0738716A2 (en) | 1996-10-23 |
BR9602004A (pt) | 1998-04-07 |
KR960037663A (ko) | 1996-11-19 |
CA2174296A1 (en) | 1996-10-22 |
CN1124267C (zh) | 2003-10-15 |
KR100430695B1 (ko) | 2004-07-30 |
TR199600328A2 (tr) | 1996-11-21 |
TW499294B (en) | 2002-08-21 |
HU9601035D0 (en) | 1996-06-28 |
NZ286342A (en) | 1998-04-27 |
CZ110696A3 (en) | 1996-11-13 |
HUP9601035A3 (en) | 1999-04-28 |
EP0738716A3 (en) | 1998-12-30 |
JPH08291147A (ja) | 1996-11-05 |
AU713334B2 (en) | 1999-12-02 |
US5635494A (en) | 1997-06-03 |
ZA963140B (en) | 1996-10-21 |
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