US20020115865A1 - 2-methoxyimino-2- (pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring - Google Patents
2-methoxyimino-2- (pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring Download PDFInfo
- Publication number
- US20020115865A1 US20020115865A1 US10/060,882 US6088202A US2002115865A1 US 20020115865 A1 US20020115865 A1 US 20020115865A1 US 6088202 A US6088202 A US 6088202A US 2002115865 A1 US2002115865 A1 US 2002115865A1
- Authority
- US
- United States
- Prior art keywords
- halo
- alkyl
- compounds
- alkoxy
- compound
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 3
- 229920000570 polyether Polymers 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 14
- -1 halo-C1-6 alkoxy Chemical group 0.000 claims description 31
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims 6
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical class NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004480 active ingredient Substances 0.000 abstract description 4
- 241000196324 Embryophyta Species 0.000 description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 22
- 0 *C.C*C1=CC=CC=C1/C(C(=O)NC)=[Cm-](/[Fm])N=O.C1=CC=NC=C1.CC.C[W].C[Y].[2*]B[1*]*C Chemical compound *C.C*C1=CC=CC=C1/C(C(=O)NC)=[Cm-](/[Fm])N=O.C1=CC=NC=C1.CC.C[W].C[Y].[2*]B[1*]*C 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 235000019439 ethyl acetate Nutrition 0.000 description 16
- 229910000104 sodium hydride Inorganic materials 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 201000010099 disease Diseases 0.000 description 15
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 239000012267 brine Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000004533 oil dispersion Substances 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 241000233866 Fungi Species 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 241000209140 Triticum Species 0.000 description 8
- 235000021307 Triticum Nutrition 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000004495 emulsifiable concentrate Substances 0.000 description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 6
- XJIRPXWWLNGHSS-UHFFFAOYSA-N 2-[2-(hydroxymethyl)phenyl]-2-methoxyimino-n-methylacetamide Chemical compound CNC(=O)C(=NOC)C1=CC=CC=C1CO XJIRPXWWLNGHSS-UHFFFAOYSA-N 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N CC1=CC=C(C)C=C1 Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003415 peat Substances 0.000 description 5
- 238000004382 potting Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MKZHJJQCUIZEDE-UHFFFAOYSA-N 1-[(2-hydroxy-3-naphthalen-1-yloxypropyl)-propan-2-ylamino]-3-naphthalen-1-yloxypropan-2-ol Chemical compound C1=CC=C2C(OCC(O)CN(CC(O)COC=3C4=CC=CC=C4C=CC=3)C(C)C)=CC=CC2=C1 MKZHJJQCUIZEDE-UHFFFAOYSA-N 0.000 description 4
- MBTGBRYMJKYYOE-UHFFFAOYSA-N 2,6-difluoropyridine Chemical compound FC1=CC=CC(F)=N1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 4
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 4
- 241001533598 Septoria Species 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- 239000002024 ethyl acetate extract Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 230000002538 fungal effect Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000000361 pesticidal effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 4
- 229910000105 potassium hydride Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- PNDQPXQWJMZJCK-UHFFFAOYSA-N 2-[2-[(6-fluoropyridin-2-yl)oxymethyl]phenyl]-2-methoxyimino-n-methylacetamide Chemical compound CNC(=O)C(=NOC)C1=CC=CC=C1COC1=CC=CC(F)=N1 PNDQPXQWJMZJCK-UHFFFAOYSA-N 0.000 description 3
- VPROCFCAMZUTGC-UHFFFAOYSA-N 2-fluoro-6-(2-propoxyethoxy)pyridine Chemical compound CCCOCCOC1=CC=CC(F)=N1 VPROCFCAMZUTGC-UHFFFAOYSA-N 0.000 description 3
- VKJLDXGFBJBTRQ-UHFFFAOYSA-N CC1CC1C Chemical compound CC1CC1C VKJLDXGFBJBTRQ-UHFFFAOYSA-N 0.000 description 3
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N CCC1=CC=C(C)C=C1 Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 3
- 208000031888 Mycoses Diseases 0.000 description 3
- 241000736122 Parastagonospora nodorum Species 0.000 description 3
- 241000221300 Puccinia Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 240000006365 Vitis vinifera Species 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012259 ether extract Substances 0.000 description 3
- 238000003359 percent control normalization Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 231100000167 toxic agent Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- MHCMMWMTYCHJFZ-UHFFFAOYSA-N 3,6-dichloro-2-(2-ethoxyethyl)pyridine Chemical compound CCOCCC1=NC(Cl)=CC=C1Cl MHCMMWMTYCHJFZ-UHFFFAOYSA-N 0.000 description 2
- JHXLXHOLJYFMOP-UHFFFAOYSA-N 3-chloro-2-(2-ethoxyethyl)-6-methylsulfanylpyridine Chemical compound CCOCCC1=NC(SC)=CC=C1Cl JHXLXHOLJYFMOP-UHFFFAOYSA-N 0.000 description 2
- VJUCLSIJOMEZLJ-UHFFFAOYSA-N 3-chloro-2-(2-ethoxyethyl)-6-methylsulfonylpyridine Chemical compound CCOCCC1=NC(S(C)(=O)=O)=CC=C1Cl VJUCLSIJOMEZLJ-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N CC1=CC=CC(C)=C1 Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 241001157813 Cercospora Species 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 206010061217 Infestation Diseases 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 241000233679 Peronosporaceae Species 0.000 description 2
- 241000233626 Plasmopara Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000008135 aqueous vehicle Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- CNLIIAKAAMFCJG-UHFFFAOYSA-N 2,3,5-trichloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1 CNLIIAKAAMFCJG-UHFFFAOYSA-N 0.000 description 1
- QZZBZHKKTYBQDC-UHFFFAOYSA-N 2,3-dichloro-6-(2-ethoxyethoxy)pyridine Chemical compound CCOCCOC1=CC=C(Cl)C(Cl)=N1 QZZBZHKKTYBQDC-UHFFFAOYSA-N 0.000 description 1
- DXNJCKCAAMIRFB-UHFFFAOYSA-N 2,3-dichloro-6-(2-ethoxyethyl)pyridine Chemical compound CCOCCC1=CC=C(Cl)C(Cl)=N1 DXNJCKCAAMIRFB-UHFFFAOYSA-N 0.000 description 1
- WZAXXVLZMJYRJI-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]-6-fluoropyridine Chemical compound CCOCCOCCOC1=CC=CC(F)=N1 WZAXXVLZMJYRJI-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- GLQLUDOQALFWAK-UHFFFAOYSA-N 3-chloro-2-(2-ethoxyethoxy)-6-methylsulfanylpyridine Chemical compound CCOCCOC1=NC(SC)=CC=C1Cl GLQLUDOQALFWAK-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 241001480061 Blumeria graminis Species 0.000 description 1
- PQRHXMQCQLHRCU-UHFFFAOYSA-N C.CCOCCO.CCOCCOC1=NC(Cl)=C(Cl)C=C1.CCOCCOC1=NC(Cl)=CC=C1Cl.ClC1=NC(Cl)=C(Cl)C=C1 Chemical compound C.CCOCCO.CCOCCOC1=NC(Cl)=C(Cl)C=C1.CCOCCOC1=NC(Cl)=CC=C1Cl.ClC1=NC(Cl)=C(Cl)C=C1 PQRHXMQCQLHRCU-UHFFFAOYSA-N 0.000 description 1
- DLSWYBDDWQPPJH-FHNICHEJSA-N CC(C)OCCO.CNC(=O)/C(=N/OC)C1=C(COC2=NC(F)=CC=C2)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=NC(OCCOC(C)C)=CC=C2)C=CC=C1 Chemical compound CC(C)OCCO.CNC(=O)/C(=N/OC)C1=C(COC2=NC(F)=CC=C2)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=NC(OCCOC(C)C)=CC=C2)C=CC=C1 DLSWYBDDWQPPJH-FHNICHEJSA-N 0.000 description 1
- CWACJFNSYQAFHW-UHFFFAOYSA-N CC1(C)OCC(CO)O1.CC1(C)OCC(COC2=NC(F)=CC=C2)O1.FC1=CC=CC(F)=N1 Chemical compound CC1(C)OCC(CO)O1.CC1(C)OCC(COC2=NC(F)=CC=C2)O1.FC1=CC=CC(F)=N1 CWACJFNSYQAFHW-UHFFFAOYSA-N 0.000 description 1
- SKRKMZPRYYIOLN-IJOOXKJBSA-N CC1(C)OCC(CO)O1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(OCC3COC(C)(C)O3)=N2)C=CC=C1 Chemical compound CC1(C)OCC(CO)O1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(OCC3COC(C)(C)O3)=N2)C=CC=C1 SKRKMZPRYYIOLN-IJOOXKJBSA-N 0.000 description 1
- LWHUGSHVTGDUEX-WLXFHBHLSA-N CC1(C)OCC(COC2=NC(F)=CC=C2)O1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(OCC3COC(C)(C)O3)=N2)C=CC=C1 Chemical compound CC1(C)OCC(COC2=NC(F)=CC=C2)O1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(OCC3COC(C)(C)O3)=N2)C=CC=C1 LWHUGSHVTGDUEX-WLXFHBHLSA-N 0.000 description 1
- QOGHRLGTXVMRLM-UHFFFAOYSA-N CC1=CC=C(Br)C=C1C Chemical compound CC1=CC=C(Br)C=C1C QOGHRLGTXVMRLM-UHFFFAOYSA-N 0.000 description 1
- RVZTXPNWMVCLCT-UHFFFAOYSA-N CCC1=C(C)C=C(OC)C=C1 Chemical compound CCC1=C(C)C=C(OC)C=C1 RVZTXPNWMVCLCT-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N CCC1=C(C)C=CC=C1 Chemical compound CCC1=C(C)C=CC=C1 HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- CWGZSTNMSBXQLZ-UHFFFAOYSA-N CCC1=CC(C)=C(OC)C=C1 Chemical compound CCC1=CC(C)=C(OC)C=C1 CWGZSTNMSBXQLZ-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N CCC1CO1 Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- XSOHESJSTICKQC-YSCFGMSNSA-N CCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CCCOC1=NC(F)=CC=C1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 Chemical compound CCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CCCOC1=NC(F)=CC=C1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 XSOHESJSTICKQC-YSCFGMSNSA-N 0.000 description 1
- UYJJGOLUZRGUPD-UHFFFAOYSA-N CCCOCCO.CCCOCCOC1=NC(F)=CC=C1.FC1=CC=CC(F)=N1 Chemical compound CCCOCCO.CCCOCCOC1=NC(F)=CC=C1.FC1=CC=CC(F)=N1 UYJJGOLUZRGUPD-UHFFFAOYSA-N 0.000 description 1
- GGMMKXTVDOUWJR-CAHCMBQESA-N CCCOCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1 Chemical compound CCCOCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1 GGMMKXTVDOUWJR-CAHCMBQESA-N 0.000 description 1
- BPCGIYJTLRSIRO-WVRMSDGUSA-N CCOCCOC1=C(Cl)C=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CCOCCOC1=NC(C)=CC=C1Cl.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 Chemical compound CCOCCOC1=C(Cl)C=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CCOCCOC1=NC(C)=CC=C1Cl.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 BPCGIYJTLRSIRO-WVRMSDGUSA-N 0.000 description 1
- BMRHKWFMGYWPFW-UHFFFAOYSA-N CCOCCOC1=NC(C)=CC=C1Cl.CCOCCOC1=NC(SC)=CC=C1Cl.ClCCl Chemical compound CCOCCOC1=NC(C)=CC=C1Cl.CCOCCOC1=NC(SC)=CC=C1Cl.ClCCl BMRHKWFMGYWPFW-UHFFFAOYSA-N 0.000 description 1
- YDXWVGKQABYSRS-JCJDDGPNSA-M CCOCCOC1=NC(Cl)=CC=C1Cl.CCOCCOC1=NC(SC)=CC=C1Cl.CS[Na].[2H]C[SH]=O Chemical compound CCOCCOC1=NC(Cl)=CC=C1Cl.CCOCCOC1=NC(SC)=CC=C1Cl.CS[Na].[2H]C[SH]=O YDXWVGKQABYSRS-JCJDDGPNSA-M 0.000 description 1
- ZXMLUWICLPQDBO-ZAJNFPKVSA-N CCOCCOCCOC1=CC=CC(F)=N1.CCOCCOCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 Chemical compound CCOCCOCCOC1=CC=CC(F)=N1.CCOCCOCCOC1=CC=CC(OCC2=C(/C(=N\OC)C(=O)NC)C=CC=C2)=N1.CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1 ZXMLUWICLPQDBO-ZAJNFPKVSA-N 0.000 description 1
- GYIHIEFZSRCSRX-JJQCNIIASA-N CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1.FC1=CC=CC(F)=N1 Chemical compound CNC(=O)/C(=N/OC)C1=C(CO)C=CC=C1.CNC(=O)/C(=N/OC)C1=C(COC2=CC=CC(F)=N2)C=CC=C1.FC1=CC=CC(F)=N1 GYIHIEFZSRCSRX-JJQCNIIASA-N 0.000 description 1
- SJZAUIVYZWPNAS-UHFFFAOYSA-N COC1=CC(C)=CC=C1C Chemical compound COC1=CC(C)=CC=C1C SJZAUIVYZWPNAS-UHFFFAOYSA-N 0.000 description 1
- LVUBSVWMOWKPDJ-UHFFFAOYSA-N COC1=CC=C(C)C(C)=C1 Chemical compound COC1=CC=C(C)C(C)=C1 LVUBSVWMOWKPDJ-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N COC1=CC=C(C)C=C1 Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 241000221787 Erysiphe Species 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 241000228456 Leptosphaeria Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241001518729 Monilinia Species 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 241001281803 Plasmopara viticola Species 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000682843 Pseudocercosporella Species 0.000 description 1
- 241000540505 Puccinia dispersa f. sp. tritici Species 0.000 description 1
- 241001123569 Puccinia recondita Species 0.000 description 1
- 241001123583 Puccinia striiformis Species 0.000 description 1
- 241000231139 Pyricularia Species 0.000 description 1
- 241001361634 Rhizoctonia Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 241001617088 Thanatephorus sasakii Species 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 1
- 241001360088 Zymoseptoria tritici Species 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229940060367 inert ingredients Drugs 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 239000003350 kerosene Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- C07D409/12—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 chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Definitions
- the present invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds with polyether substituents on the pyridine ring, their use as fungicidal compounds, and their use in fungicidal compositions comprising at least one of the 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds as the active ingredient.
- This invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds of formula (1), below
- m is an integer 0-3;
- L is —O—, —CH 2 —, —SO—, —CH 2 O—, —OCH 2 —, —CH 2 S—, —SCH 2 —, —CH ⁇ CH—, —C ⁇ C—, or
- n is an integer 0-2;
- X, Y, and Z are each independently H, C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkyl, halo-C 1-6 alkoxy, halo, nitro, carbo-C 1-6 alkoxy, cyano, C 1-6 alkylthio, or halo-C 1-6 alkylthio;
- W is H, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo-C 1-4 alkyl, or C 1-4 alkylthio;
- A is O, S, NR, OCH 2 , SCH 2 ;
- B is O or S
- R 1 is a C 1 -C 4 alkyl group (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, arylalkyl, cyano, cyanoalkyl, halo, or haloalkyl), optionally substituted phenyl, or an optionally substituted aryl or heteroaryl ring;
- R 2 is a C 1 -C 8 alkyl, (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, arylalkyl, cyano, cyanoalkyl, halo, or haloalkyl), optionally substituted phenyl, or an optionally substituted aryl or heteroaryl ring;
- R 1 —B—R 2 can be an optionally substituted 4-6 membered saturated or unsaturated heterocyclic ring
- R 3 is H or C 1-6 alkyl.
- the present invention also provides compositions comprising one or more compounds of Formula (1) in combination with phytologically-acceptable carriers and/or diluents. Methods for the use of compounds of formula (1) and compositions comprising one or more compounds of formula (1) are also provided.
- halogen or “halo” refers to F, Cl, I, or Br.
- alkyl refers to a straight chain or branched chain carbon radical containing the designated number of carbon atoms.
- alkoxy refers to a straight or branched chain alkoxy group.
- halo alkyl refers to a straight or branched alkyl group substituted with one or more halo atoms.
- halo alkoxy refers to an alkoxy group substituted with one or more halo atoms.
- aryl or “Ph” refers to a phenyl group.
- substituted aryl refers to a phenyl group substituted with C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, halo, nitro, carbo-C 1 -C 6 alkoxy, or cyano.
- heteroaryl refers to pyridyl, pyridinyl, pyrazinyl, pyridazinyl or thiophene.
- Me refers to a methyl group.
- Et refers to an ethyl group.
- Pr refers to a propyl group.
- Bu refers to a butyl group.
- EtOAc refers to ethyl acetate
- ppm refers to parts per million.
- psi refers to pounds per square inch.
- M.P. refers to melting point.
- bp refers to boiling point.
- a preferred class includes those compounds of Formula (2), below
- a more preferred class includes those compounds of Formula (3), below
- L is either —O—, —CH 2 O—, or —OCH 2 —, and the other substituents are as defined in Formula (1), above.
- a next more preferred class includes those compounds of Formula (4), below
- a next more preferred class includes those compounds of Formula (5), below
- a next more preferred class includes those compounds of Formula (5-1), below
- a compound of formula (7) is reacted with an appropriately substituted pyridine derivative of formula (6) in the presence of a base in an aprotic solvent.
- a solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone.
- Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium t-butoxide, potassium carbonate, or a tertiary amine derivative such as triethylamine.
- the intermediate so formed is then reacted with a compound of formula (9) in the presence of a base in an aprotic solvent.
- a solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone.
- Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- a compound of formula (9) is reacted with an appropriately substituted pyridine derivative of formula (6) in the presence of a base in an aprotic solvent.
- a solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone.
- Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- the intermediate so formed is then reacted with a compound of formula (7) in the presence of a base in an aprotic solvent.
- a solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone.
- Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- the compounds of formula (1) thus produced are usually obtained as a mixture of the E and Z forms, which can then be separated, via standard means known in the art, into each of those forms, if desired.
- the compounds of the present invention have been found to control fungi, particularly plant pathogens.
- the compounds When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount.
- Application may be performed before and/or after the infection with fungi on plants.
- Application may also be made through treatment of seeds of plants, soil where plants grow, paddy fields for seedlings, or water for perfusion.
- the term “disease inhibiting and phytologically acceptable amount”, refers to an amount of a compound of the present invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/Acre.
- the compounds of the present invention have significant activity for agricultural use, such as, for example, for use with agricultural crops, many of the compounds are effective for use with horticultural plants, stored grain and other non-plant loci, such as, for example, wood, paint, leather or carpet, to protect such materials from fungal infestation.
- Compound Formulation Compound formulation was accomplished by dissolving technical materials in acetone, with serial dilutions then made in acetone to obtain desired rates. Final treatment volumes were obtained by adding nine volumes 0.05% aqueous Tween-20 or Triton X-100, depending upon the pathogen.
- Vines (cultivar Carignane) were grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 10-20 cm tall. These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 96 hours the test plants were inoculated by spraying with an aqueous sporangia suspension of Plasmopara viticola . The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Wheat (cultivar Monon) was grown in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then inoculated with Erysiphe graminis by dusting spores from stock plants onto the test plants. After 48 hours the plants were sprayed to run off with the test compound at a rate of 25 ppm and then kept in the greenhouse until disease developed on the untreated control plants.
- Glume blotch of wheat ( Leptosphaeria nodorum —LEPTNO):
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum . The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Brown rust Puccinia recondite —PUCCRT
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension of Puccinia recondita . The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Septoria leaf spot Septoria tritici —SEPTTR
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension of Septoria tritici . The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- the compounds of this invention are preferably applied in the form of a composition comprising one or more of the compounds of formula (1) with a phytologically-acceptable carrier.
- the compositions are either concentrated formulations which are dispersed in water or another liquid for application, or are dust or granular formulations which are applied without further treatment.
- the compositions are prepared according to procedures which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions is given to assure that agricultural chemists can readily prepare desired compositions.
- the dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds.
- Such water-soluble, water suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or liquids, usually known as emulsifiable concentrates or aqueous suspensions.
- the present invention contemplates all vehicles by which the compounds of this invention can be formulated for delivery for use as a fungicide. AS will be readily appreciated, any material to which these compounds can be added may be used, provided they yield the desired utility without significant interference with activity of the compounds of this invention as antifungal agents.
- Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants.
- concentration of the active compound is usually from about 10% to about 90% w/w, more preferably about 25% to about 75% w/w.
- the toxicant products can be compounded with any of the finely divided solids, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like.
- the finely divided carrier is ground or mixed with the toxicant in a volatile organic solvent.
- Effective surfactants comprising from about 0.5% to about 10% of the wettable powder, include sulfonated lignins, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants, such as ethylene oxide adducts of alkyl phenols.
- Emulsifiable concentrates of the compounds of this invention comprise a convenient concentration, such as from about 10% to about 50% w/w, in a suitable liquid.
- the compounds are dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
- the concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions.
- Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.
- Emulsifiers which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers.
- nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene.
- Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts.
- Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil soluble salts or sulphated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
- Representative organic liquids which can be employed in preparing the emulsifiable concentrates of the present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, and the methyl ether of triethylene glycol.
- Mixtures of two or more organic liquids are also often suitably employed in the preparation of the emulsifiable concentrate.
- the preferred organic liquids are xylene, and propyl benzene fractions, with xylene being most preferred.
- the surface active dispersing agents are usually employed in liquid compositions and in the amount of from 0.1 to 20 percent by weight of the combined weight of the dispersing agent and active compound.
- the active compositions can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
- Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% w/w.
- Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types above discussed.
- Inert ingredients such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
- the compounds may also be applied as granular compositions, which are particularly useful for applications to the soil.
- Granular compositions usually contain from about 0.5% to about 10% w/w of the compound, dispersed in an inert carrier which consists entirely or in large part of coarsely divided attapulgite, bentonite, diatomite, clay or a similar inexpensive substance.
- Such compositions are usually prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm.
- Such compositions may also be formulated by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle.
- Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% w/w of the compound.
- a suitable dusty agricultural carrier such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% w/w of the compound.
- the active compositions may contain adjuvant surfactants to enhance deposition, wetting and penetration of the compositions onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will vary from 0.01 percent to 1.0 percent v/v based on a spray-volume of water, preferably 0.05 to 0.5%. Suitable adjuvant surfactants include ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines and blends of surfactants with mineral or vegetable oils.
- the composition may optionally include fungicidal combinations which comprise at least 1% of one or more of the compounds of this invention with another pesticidal compound.
- additional pesticidal compounds may be fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds.
- the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use.
- the compounds in combination can generally be present in a ratio of from 1:100 to 100:1.
- the present invention includes within its scope methods for the control or prevention of fungal attack. These methods comprise applying to the locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidal amount of one or more of the compounds of this invention or compositions.
- the compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity.
- the compounds are useful in a protectant or eradicant fashion.
- the compounds of this invention are applied by any of a variety of known techniques, either as the compounds or as compositions including the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants.
- the materials are applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates. These materials are conveniently applied in various known fashions.
- the compounds of this invention have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants, or with wood, paint, leather or carpet backing.
- the compounds effectively control a variety of undesirable fungi which infect useful plant crops.
- Activity has been demonstrated for a variety of fungi, including for example the following representative fungi species: Downy Mildew of Grape ( Plasmopara viticola —PLASVI), Late Blight of Tomato (Phytophthora infestans—PHYTIN), Apple Scab ( Venturia inaejualis —VENTIN), Brown Rust of Wheat ( Puccinia recondita —PUCCRT), Stripe Rust of Wheat ( Puccinia striiformis —PUCCST), Rice Blast ( Pyricularia oryzae —PYRIOR), Cercospora Leaf Spot of Beet ( Cercospora beticola —CERCBE), Powdery Mildew of Wheat ( Ezysiphe graminis —ERYSGT), Leaf Blotch of Wheat ( Septoria tritici —SEPTTR), Sheath Blight of Rice ( Rhizoc
- the compounds of this invention have broad ranges of efficacy as fungicides.
- the exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the toxic active ingredient.
- all the active ingredients of the compounds of this invention, and compositions containing the same may not be equally effective at similar concentrations or against the same fungal species.
- the compounds of this invention and compositions are effective in use with plants in a disease inhibiting and phytologically acceptable amount.
- disease inhibiting and phytologically acceptable amount refers to an amount of a compound which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to about 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds with polyether substituents on the pyridine ring, their use as fungicidal compounds, and their use in fungicidal compositions comprising at least one of the 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds as the active ingredient.
Description
- This application claims a priority from U.S. non-provisional application Ser. No. 09/397,565 which was filed on Sep. 16, 1999. Application Ser. No. 09/397,565 claims a priority based on provisional application 60/100,493 which was filed in the U.S. Patent and Trademark Office on Sep. 16, 1998.
- The present invention provides novel 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds with polyether substituents on the pyridine ring, their use as fungicidal compounds, and their use in fungicidal compositions comprising at least one of the 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamide compounds as the active ingredient.
-
- wherein
- m is an integer 0-3;
-
- wherein n is an integer 0-2;
- X, Y, and Z are each independently H, C1-6 alkyl, C1-6 alkoxy, halo-C1-6 alkyl, halo-C1-6 alkoxy, halo, nitro, carbo-C1-6 alkoxy, cyano, C1-6 alkylthio, or halo-C1-6 alkylthio;
- W is H, halogen, C1-4 alkyl, C1-4 alkoxy, halo-C1-4alkyl, or C1-4 alkylthio;
- A is O, S, NR, OCH2, SCH2;
- B is O or S;
- R1 is a C1-C4 alkyl group (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, arylalkyl, cyano, cyanoalkyl, halo, or haloalkyl), optionally substituted phenyl, or an optionally substituted aryl or heteroaryl ring;
- R2 is a C1-C8 alkyl, (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, arylalkyl, cyano, cyanoalkyl, halo, or haloalkyl), optionally substituted phenyl, or an optionally substituted aryl or heteroaryl ring;
- or the group R1—B—R2 can be an optionally substituted 4-6 membered saturated or unsaturated heterocyclic ring;
- or the group —A—R1—B—R2 can be an optionally substituted 4-6 membered saturated or unsaturated heterocyclic ring containing 2 or more heteroatoms; and
- R3 is H or C1-6 alkyl.
- The present invention also provides compositions comprising one or more compounds of Formula (1) in combination with phytologically-acceptable carriers and/or diluents. Methods for the use of compounds of formula (1) and compositions comprising one or more compounds of formula (1) are also provided.
- Throughout this document, all temperatures are given in degrees Celsius and all percentages are weight percentages, unless otherwise stated.
- The term “halogen” or “halo” refers to F, Cl, I, or Br.
- The term “alkyl”, “alkenyl”, or “alkynyl” refers to a straight chain or branched chain carbon radical containing the designated number of carbon atoms.
- The term “alkoxy” refers to a straight or branched chain alkoxy group.
- The term “halo alkyl” refers to a straight or branched alkyl group substituted with one or more halo atoms. The term “halo alkoxy” refers to an alkoxy group substituted with one or more halo atoms.
- The term “aryl” or “Ph” refers to a phenyl group. The term “substituted aryl” refers to a phenyl group substituted with C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkyl, halo-C1-C6 alkoxy, halo, nitro, carbo-C1-C6 alkoxy, or cyano. The term “heteroaryl” refers to pyridyl, pyridinyl, pyrazinyl, pyridazinyl or thiophene.
- The term “Me” refers to a methyl group. The term “Et” refers to an ethyl group. The term “Pr” refers to a propyl group. The term “Bu” refers to a butyl group.
- The term “EtOAc” refers to ethyl acetate.
- The term “ppm” refers to parts per million. The term “psi” refers to pounds per square inch.
- The term “M.P.” refers to melting point. The term “bp” refers to boiling point.
- While all the compounds of this invention have fungicidal activity, certain classes of compounds may be preferred for reasons such as, for example, greater efficacy or ease of synthesis.
-
- wherein the substituents are as defined in Formula (1), above.
-
- wherein L is either —O—, —CH2O—, or —OCH2—, and the other substituents are as defined in Formula (1), above.
-
- wherein the substituents are as defined in Formula (1), above.
-
- wherein the substituents are as defined in Formula (1), above.
-
- wherein the substituents are as defined in Formula (1), above.
- Compounds of the present invention may be prepared by routes commonly known in the art using commercially available or readily synthesized starting materials. Such general procedures are described in Scheme 1 and Scheme 2, below, wherein the substituents are as described in formula (1), above, and V is a leaving group, such as, for example, F, Cl, or SO2CH3.
- A compound of formula (7) is reacted with an appropriately substituted pyridine derivative of formula (6) in the presence of a base in an aprotic solvent. Examples of an appropriate solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone. Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium t-butoxide, potassium carbonate, or a tertiary amine derivative such as triethylamine.
- The intermediate so formed is then reacted with a compound of formula (9) in the presence of a base in an aprotic solvent. Examples of an appropriate solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone. Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- A compound of formula (9) is reacted with an appropriately substituted pyridine derivative of formula (6) in the presence of a base in an aprotic solvent. Examples of an appropriate solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone. Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- The intermediate so formed is then reacted with a compound of formula (7) in the presence of a base in an aprotic solvent. Examples of an appropriate solvent for this reaction would include, but are not restricted to, tetrahydrofuran, dimethyl sulphoxide, acetone, acetonitrile, dimethyl formamide, N-methylpyrrolidinone. Examples of an appropriate base for this reaction would include, but are not restricted to, sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, or a tertiary amine derivative such as triethylamine.
- The following examples further illustrate this invention. The examples should not be construed as limiting the invention in any manner.
-
- Potassium tert-butoxide (2.14 g, 19.1 mmol) was added to a solution of 2,2-dimethyl-1,3-dioxolane-4-methanol (2.40 g, 18.2 mmol) in 50 mL THF. The resulting mixture was added slowly to a solution of 2,6-difluoropyridine (2.08 g, 18.2 mmol) in THF (50 mL) which was stirred while cooling in an ice bath. After returning the mixture slowly to room temperature and stirring overnight, the mixture was quenched with brine and extracted with EtOAc. Combined extracts were dried with Na2SO4, then concentrated to dryness. Silica gel column chromatography (10-20% EtOAc in hexane) yielded 2-fluoro-6-((2,2-dimethyl-1,3-dioxolanyl)-4-methoxy)pyridine (2.75 g, 67%)as a clear oil.
-
- 2-(Hydroxymethyl)-α-(methoxyimino)-N-methyl-benzeneacetamide (1.00 g, 4.50 mmol) was dissolved in 10 mL THF, then treated slowly with NaH (0.36 g, 60% oil dispersion, 9.0 mmol) while cooling in an ice bath. Then, 2-fluoro-6-((2,2-dimethyl-1,3-dioxolanyl)-4-methoxy)pyridine (1.23 g, 5.40 mmol) in 10 mL THF was added dropwise, and the bath was allowed to return to room temperature overnight. The mixture was stripped to dryness in vacuo, resuspended in 20 mL DMSO, and stirred at room temperature overnight, then it was heated to 50° C. for one hour, followed by stirring at room temperature overnight. Another portion of NaH (0.36 g, 60% oil dispersion, 9.0 mmol) was added, and the mixture was stirred at room temperature overnight. After workup as above with brine and EtOAc, the concentrated extract was purified by silica gel column chromatography (10-50% EtOAc in hexane) to yield the product (0.76 g, 39%) as an oil.
-
- NaH (7.0 g, 60% oil dispersion, 0.176 mol) was added portionwise over five minutes to a stirred slurry of 2-(hydroxymethyl)-α-(methoxyimino)-N-methyl-benzeneacetamide (35.8 g, 0.161 mol) in 700 mL THF. After the resulting mixture was stirred for 3.25 hours, 2,6-difluoropyridine (15.4 g, 0.134 mol) was added neat over a 20 minute period, and the mixture was stirred -2overnight at room temperature. Water (250 mL) was added, THF was removed in vacuo, and the aqueous residue was extracted three times with 250 mL CH2Cl2. The combined extracts were washed with brine (250 mL), filtered through Na2SO4, and concentrated in vacuo. The residue was purified by silica gel chromatography (5% CH3CN in CH2Cl2) to yield 2-[[[6-fluoro-2-pyridinyl]oxy]methyl]-α-(methoxyimino)-N-methyl-benzeneacetamide (33.2 g, 78%).
-
- Two portions of NaH (total 4.1 g, 60% oil dispersion, 0.102 mol) were added to a stirred solution of 2,2-dimethyl-1,3-dioxolane-4-methanol (13.3 g, 0.102 mol) in 400 mL THF. The mixture was stirred two hours at room temperature, becoming gelatinous. 2-[[[6-Fluoro-2-pyridinyl]oxy]methyl]-(-(methoxyimino)-N-methyl-benzeneacetamide (27.0 g, 0.0851 mol) was added neat in one portion, then the resulting cloudy gold solution was stirred at room temperature one hour, heated to 55° C. for 3 hours, and stirred at room temperature overnight. Water (250 mL) was added, the layers were separated, and THF was removed from the organic layer in vacuo. The residue was taken up in CH2Cl2, then partitioned against the original aqueous phase. The aqueous phase was then extracted four times with 125 mL CH2Cl2. All CH2Cl2 fractions were combined, washed with brine (250 mL), filtered through Na2SO4, and concentrated in vacuo to crude product. The crude product was purified through silica gel chromatography (3-8% CH3CN in CH2Cl2) to yield the product (22.7 g, 60%) as an oil.
-
- 2-Propoxyethanol (1.89 g, 18.1 mmol) was dissolved in 50 mL THF, treated with potassium tert-butoxide (3.05 g, 27.2 mmol), stirred to uniform solution, placed in an addition funnel, and added dropwise to a solution of 2,6-difluoropyridine in 50 mL THF. After stirring overnight at room temperature, the solution was diluted with brine and extracted with ether. The ether extracts were combined and dried over Na2SO4, then concentrated in vacuo to yield 2-fluoro-6-(2-propoxyethoxy)-pyridine (3.33 g, 93%) as a yellow oil.
-
- 2-(Hydroxymethyl)-α-(methoxyimino)-N-methyl-benzeneacetamide (1.11 g, 5.00 mmol) was dissolved in 100 mL DMSO, then treated portionwise with NaH (0.40 g, 60% oil dispersion, 10 mmol) while stirring to a cloudy solution. 2-Fluoro-6-(2-propoxyethoxy)pyridine (1.20 g, 6.00 mmol) was added, and the mixture was stirred overnight at room temperature. The mixture was diluted with brine and extracted with EtOAc. The combined EtOAc extracts were dried over Na2SO4 and concentrated in vacuo and the residue was purified by silica gel chromatography (0-50% EtOAc in hexane) to yield the product (0.90 g, 43%) as an oil.
-
- 2-Propoxyethanol (12.5 g, 0.12 mol) was dissolved in 500 mL THF, treated with NaH (4.8 g, 60% oil dispersion, 0.12 mol) portionwise over 5 minutes, and stirred at room temperature for two hours. 2-[[[6-Fluoro-2-pyridinyl]oxy]methyl]-α-(methoxyimino)-N-methyl-benzeneacetamide (31.7 g, 0.1 mol) was added portionwise over 10 minutes, then the mixture was stirred at room temperature for one hour, heated to 55° C. for one hour, and stirred to room temperature overnight. The reaction was quenched with 400 mL water, stripped of THF in vacuo, and extracted 3 times with 300 mL CH2Cl2. The combined extracts were dried over Na2SO4, filtered, and concentrated in vacuo to yield an oil. This residue was purified via silica gel chromatography (pentane:EtOAc, 2:1) to yield an oil which was dried in vacuo, then triturated with a small amount of ether to yield the product (22.2 g, 55%) as a white powder after drying. M.P. 53-54° C.
-
- 2-(Hydroxymethyl)-α-(methoxyimino)-N-methyl-benzeneacetamide (0.62 g, 2.8 mmol) in 10 mL THF was treated portionwise with NaH (0.22 g, 60% oil dispersion, 5.6 mmol) while cooling in an ice bath. 2-Fluoro-6-(2-(2-ethoxyethoxy)ethoxy)pyridine (1.00 g, 3.35 mmol) was added, and the mixture was allowed to return to room temperature. After 3 hours, the mixture was diluted with brine, treated with sufficient dilute HCl to render it weakly acidic, and extracted with EtOAc. The combined EtOAc extracts were dried over Na2SO4, then concentrated in vacuo. The residue was purified via silica gel chromatography (0-50% EtOAc in hexane) to yield the product (0.65 g, 54%) as an oil.
-
- Sodium hydride (0.29 g, 60% oil dispersion, 7.2 mmol) was washed with hexane, then suspended in 20 mL DMF. 2-(l-Methylethoxy)ethanol (0.75 g, 7.2 mmol), dissolved in 5 mL DMF, was added to the NaH suspension over 5 minutes, then the mixture was stirred at room temperature for 40 minutes. This mixture, with the aid of 20 mL additional DMF, was added to a stirred solution of 2-[[[6-fluoro-2-pyridinyl]oxy]methyl]-α-(methoxyimino)-N-methyl-benzeneacetamide (2.28 g, 7.2 mmol) in 30 mL DMF. The reaction was stirred at room temperature one hour, then heated to 60° C. for 19 hours. Additional 2-(1-methylethoxy)ethanol (2.50 g, 24.0 mmol) was dissolved in 30 mL DMF, treated with NaH (0.96 g, 60% oil dispersion), stirred for 5-10 minutes, and transferred to the above reaction mixture. The new mixture was heated to 60° C. for one hour, then diluted with 800 mL water. The aqueous suspension was extracted twice with 100 mL ether, then twice with 60 mL ether. The combined ether extracts were washed twice with 100 mL water, diluted with 150 mL hexane, filtered through phase-separating paper, concentrated in vacuo, and concentrated twice more with 100 mL toluene. The residue was purified over silica gel (step gradient: 4, 5, 8, and 10% CH3CN in CH2Cl2) to yield the product (1.04 g, 36%) as an oil.
-
- 2,3,5-Trichloropyridine (9.12g, 0.050 mol) and 2-ethoxyethanol (5.40 g, 0.060 mol) were dissolved in 50 mL DMSO, followed by portionwise addition of NaH (2.4 g, 60% dispersion in oil, 0.060 mol). The mixture was heated to 80° C. for 3 hours, stirred at room temperature overnight, then heated to 120° C. for 5 hours. The reaction mixture was then diluted to 900 mL with brine, and extracted three times with 100 mL ether. The ether extracts were combined, washed twice with 100 mL water, diluted with 300 mL hexane, filtered through phase-separating paper, and concentrated in vacuo. The residue was purified via silica gel chromatography (first column with 10-50% EtOAc in hexane; second column with 0-10% EtOAc in hexane). Concentration of pure fractions gave 3,6-dichloro-2-(2-ethoxyethyl)pyridine as the major isomer (5.78 g white solid, M.P. 33-34° C.) and 2,3-dichloro-6-(2-ethoxyethyl)pyridine as the minor isomer (1.43 g white solid, M.P. 47-48° C.).
-
- 3,6-Dichloro-2-(2-ethoxyethyl)-pyridine (1.18 g, 5.00 mmol) was dissolved in 25 mL DMSO, treated with NaSCH3 (0.53 g, 7.5 mmol), and stirred at room temperature overnight. The mixture was diluted with brine, then extracted with EtOAc. The combined EtOAc extracts were combined, dried over Na2SO4, and concentrated in vacuo to yield 3-chloro-2-(ethoxyethyl)-6-(methylthio)pyridine (0.91 g, 76%) as a yellow oil, used without further purification.
-
- 3-Chloro-2-(ethoxyethyl)-6-(methylthio)pyridine (0.91 g, 3.7 mmol) was dissolved in 25 mL CH2Cl2, cooled in an ice bath, and was treated with m-chloroperoxybenzoic acid (MCPBA; 2.53 g of reagent estimated to be 50-55% pure, ca. 7.3-8.0 mmol) added dropwise in 25 mL CH2Cl2. The reaction was allowed to return to room temperature and stirred overnight. After dilution with more CH2Cl2, the mixture was washed with saturated Na2CO3, then water, and was concentrated to yield 3-chloro-2-(ethoxyethyl)-6-(methylsulphonyl)pyridine (0.60 g, 58%) as a clear oil, used without further purification.
-
- 2-(Hydroxymethyl)-α-(methoxyimino)-N-methyl-benzeneacetamide (0.60 g, 2.1 mmol) was dissolved in 20 mL DMSO, treated portionwise with NaH (0.14 g, 60% oil dispersion, 3.6 mmol), and stirred. 3-Chloro-2-(ethoxyethyl)-6-(methylsulphonyl)pyridine was dissolved in 25 mL DMSO, then added dropwise to the above mixture. After stirring at room temperature overnight, the reaction was quenched with brine and extracted with EtOAc. The EtOAc extracts were combined, dried over Na2SO4, and concentrated in vacuo. The residue was purified via silica gel chromatography (25-60% EtOAc in hexane) to yield the product (0.27 g, 30%), M.P. 94-96° C.
- The following tables identify various compounds of the illustrated general formulas prepared analogous to the procedures illustrated in the preceding examples:
Compound number W X Y Z A R1—B—R2 1 H Cl H Cl OCH2 2,2-dimethyl-1,3- dioxolan-4-yl 2 H H H H OCH2 2,2-dimethyl-1,3- dioxalan-4-yl 3 H Cl H Cl OCH2 2-furyl (E-isomer) 4 H Cl H Cl OCH2 2-furyl (Z-isomer) 5 H H H H OCH2 2-furyl 6 H H H H OCH2 2-methyl-2- trifluoromethyl-1,3- dioxolan-4-yl 7 H H H H OCH2 3-methyloxetan-3-yl 8 H H H H OCH2 2-furyl 9 H H H H OCH2 2-tetrahydropyranyl 10 H H H H OCH2 2-tetrahydrofuranyl 11 H H H H OCH2 2,2-di(trifluoro- methyl)-1,3-dioxolan- 4-yl 12 H H H H S 5-methylthio-1,3,4- thiadiazol-2-yl 13 H H H H S 7-ethoxybenzo- thiazol-2-yl 14 H H H H O 2-tetrahydropyranyl 15 H H H H S 2-thienyl -
Compound Number W X Y Z A R1 B R2 16 —H —Cl —H —Cl O —CH2CH2— O C2H5OC2H4— 17 —H —H —H —H O —CH2CH2— O C2H5— 18 —H —Cl —H —Cl O —CH2CH2— O C2H5— 19 —H —Cl —H —Cl O —CH2CH2— O C3H7OCH2CH2— 20 —H —Cl —H —Cl O —CH(OME)CH2— O CH3— 21 —H —H —H —H O —CH2CH2— O C2H5OC2H4— 22 —H —H —H —H O —CH(OME)CH2— O CH3— 23 —H —Cl —H —Cl NH —CH2CH2— O C2H5— 24 —H —H —H —Cl O —CH2CH2— O C2H5— 25 —H —H —H —H O —CH2CH2— O CH3— 26 —H —Cl —H —Cl O —CH2CH(CH3)— O nC3H7— 28 —H —Cl —H —Cl O —CH2CH(CH3)— O CH3— 29 —H —Cl —H —Cl O —CH2CH2— O nC3H7— 30 —H —H —H —H O —CH2CH(CH3)— O CH3— 31 —H —H —H —H O —CH2CH2— O nC3H7— 32 —H —H —H —H O —CH2CH(CH3)— O nC3H7— 33 —H —Cl —H —Cl O —CH2CH2— O CH3— 34 —H —H —H —H S O CH3— 35 —H —H —H —H S O CH3— 36 —H —H —H —H O —CH2CH2— O nC3H7— 38 —H —H —H —H O O CH3— 39 —H —H —H —H S O CH3— 40 —H —H —H —H S O CH3— 41 —H —H —H —H S O CF3— 42 —H —H —H —H S O CH3— 43 —H —H —H —H S S CH3— 44 —H —H —H —H S O CF3— 45 —H —H —H —H O —CH2CH2— S C2H5— 46 —H —H —H —H O —CH2CH2— O nC4H9— 47 —H —H —H —H O —CH2CH2— S nC4H9— 48 —H —H —H —H O —CH2CH2— S nC4H9— 49 —H —H —H —H O —CH2CH2— O Ph— 50 —H —H —H —H S —CH2CH2— S C2H5— 51 —H —H —H —H O —CH2CH2— O PhCH2— 52 —H —H —H —H S —CH2CH2— S tC4H9— 53 —H —H —H —H O —CH2CH2— O iC3H7— 54 —H —H —H —H O —CH2CH2CH2— O iC3H7— 55 —H —H —H —H O —CH2CH2CH2— O C2H5— 56 —H —H —H —H O —CH2CH2— O 2- Ethylhexyl- 57 —H —H —H —H S O CH3— 58 —H —H —H —H O —CH2CH2— O Cyclobutyl- 59 —F —H —H —H O —CH2CH2— O nC3H7— 60 —Cl —H —H —H O —CH2CH2— O nC3H7— 61 —H —H —H —H O —CH2CH2— O nC5H11— 62 —H —H —H —H O —CH2CH2— O Cyclohexyl- 63 —Cl —H —H —H O —CH2CH2— O C2H5— 64 —H —H —H —H O O C2H5— 65 —H —H —H —H O —(CH2)4— O C2H5— 66 —H —H —H —H O —(CH2)5— O PhCH2— 67 —H —H —H —H O O C2H5— 68 —H —H —H —H O O C2H5— 70 —H —H —H —H O —CH2CH2— O nC6H11— 71 —H —H —H —H O —CH2CH2CH2— O CH3O(CH2)3— 72 —H —H —H —H O —CH(CH═CH2)CH2— O CH3— 73 —H —H —H —H O —CH2CH2— O NCCH2CH2CH(OM e)— 74 —H —H —H —H O —CH2CH2— O 75 —F —H —H —H O —CH2CH2— O nC5H11— 76 —Cl —H —H —H O —CH2CH2— O nC5H11— 77 —F —H —H —H O —CH2CH2CH2— O C2H5— 78 —Cl —H —H —H O —CH2CH2CH2— O C2H5— 79 —F —H —H —H O —CH2CH2CH2— O iC3H7— 80 —Cl —H —H —H O —CH2CH2CH2— O iC3H7— 81 —H —H —H —H O O CH3— 82 —H —H —H —H O O CH3— 83 —H —H —H —H O O CH3— 84 —H —H —H —H O O CH3— 85 —H —H —H —H S O C2H5— 87 —H —H —H —H S O nC3H7— 88 —H —H —H —H O O CH3— 89 —H —H —H —H O —CH2CH2CH2— O nC3H7— -
- The compounds of formula (1) thus produced are usually obtained as a mixture of the E and Z forms, which can then be separated, via standard means known in the art, into each of those forms, if desired.
- The compounds of the present invention have been found to control fungi, particularly plant pathogens. When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount. Application may be performed before and/or after the infection with fungi on plants. Application may also be made through treatment of seeds of plants, soil where plants grow, paddy fields for seedlings, or water for perfusion.
- As used herein, the term “disease inhibiting and phytologically acceptable amount”, refers to an amount of a compound of the present invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/Acre.
- While the compounds of the present invention have significant activity for agricultural use, such as, for example, for use with agricultural crops, many of the compounds are effective for use with horticultural plants, stored grain and other non-plant loci, such as, for example, wood, paint, leather or carpet, to protect such materials from fungal infestation.
- The following experiments were performed in the laboratory to determine the fungicidal efficacy of the compounds of the invention.
- Compound Formulation: Compound formulation was accomplished by dissolving technical materials in acetone, with serial dilutions then made in acetone to obtain desired rates. Final treatment volumes were obtained by adding nine volumes 0.05% aqueous Tween-20 or Triton X-100, depending upon the pathogen.
- Downy Mildew of Grape (Plasmopara viticola-PLASVI) (96 Hour Protectant):
- Vines (cultivar Carignane) were grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 10-20 cm tall. These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 96 hours the test plants were inoculated by spraying with an aqueous sporangia suspension ofPlasmopara viticola. The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Powdery Mildew of Wheat (Erysiphe graminis-ERYSGT):
- Wheat (cultivar Monon) was grown in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then inoculated withErysiphe graminis by dusting spores from stock plants onto the test plants. After 48 hours the plants were sprayed to run off with the test compound at a rate of 25 ppm and then kept in the greenhouse until disease developed on the untreated control plants.
- Glume blotch of wheat (Leptosphaeria nodorum—LEPTNO):
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension ofLeptosphaeria nodorum. The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Brown rust (Puccinia recondite—PUCCRT):
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension ofPuccinia recondita. The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- Septoria leaf spot (Septoria tritici—SEPTTR):
- Wheat (cultivar Monon) was grown from seed in a soilless peat-based potting mixture (Metromix) until the seedlings were 1-2 leaf (BBCH 12). These plants were then sprayed to run off with the test compound at a rate of 100 ppm. After 24 hours the test plants were inoculated with an aqueous spore suspension ofSeptoria tritici. The plants were then transferred to the greenhouse until disease developed on the untreated control plants.
- The following table presents the activity of typical compounds of the present invention when evaluated in these experiments. The effectiveness of the test compounds in controlling disease was rated using the following scale:
- blank space=not tested
- −=0-24% control of plant disease
- +=25-74% control of plant disease
- ++=75-100% control of plant disease
Compound Number PLASVI ERYSGT LEPTNO PUCCRT SEPTTR 1 ++ + ++ ++ 2 ++ + ++ ++ 3 ++ + 4 − − 5 ++ − 6 ++ 7 + ++ 8 ++ − 9 ++ + 10 + ++ 11 ++ 12 − − 13 + − + 14 15 ++ ++ 16 ++ ++ + 17 ++ + ++ 18 ++ + ++ 19 + + ++ 20 + + + 21 ++ + 22 + ++ + 23 ++ ++ 24 ++ ++ + 25 ++ ++ 26 + ++ 27 + + 28 ++ ++ 29 ++ + 30 ++ ++ 31 ++ ++ 32 ++ 33 ++ + 34 ++ ++ 35 ++ 36 ++ + 37 ++ ++ 38 ++ 39 ++ 40 ++ + 41 ++ + 42 ++ ++ 43 ++ − 44 ++ ++ 45 ++ + 46 ++ + 47 ++ ++ 48 + − 49 ++ ++ 50 ++ − 51 ++ ++ 52 ++ ++ + 53 ++ ++ − 54 ++ ++ ++ 55 + + 56 ++ ++ 57 ++ ++ 58 ++ ++ 59 ++ 60 ++ ++ 61 ++ ++ 62 ++ + 63 ++ 64 ++ ++ 65 ++ ++ 66 ++ ++ 67 ++ 68 ++ + 69 ++ 70 + + 71 − 72 − 73 − 74 ++ 75 ++ 76 ++ 77 ++ 78 ++ 79 ++ 80 ++ 81 + 82 ++ 83 ++ 84 ++ 85 − 86 ++ + 87 ++ 88 ++ + ++ + 89 − + − - The compounds of this invention are preferably applied in the form of a composition comprising one or more of the compounds of formula (1) with a phytologically-acceptable carrier. The compositions are either concentrated formulations which are dispersed in water or another liquid for application, or are dust or granular formulations which are applied without further treatment. The compositions are prepared according to procedures which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions is given to assure that agricultural chemists can readily prepare desired compositions.
- The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such water-soluble, water suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or liquids, usually known as emulsifiable concentrates or aqueous suspensions. The present invention contemplates all vehicles by which the compounds of this invention can be formulated for delivery for use as a fungicide. AS will be readily appreciated, any material to which these compounds can be added may be used, provided they yield the desired utility without significant interference with activity of the compounds of this invention as antifungal agents.
- Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually from about 10% to about 90% w/w, more preferably about 25% to about 75% w/w. In the preparation of wettable powder compositions, the toxicant products can be compounded with any of the finely divided solids, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier is ground or mixed with the toxicant in a volatile organic solvent. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, include sulfonated lignins, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants, such as ethylene oxide adducts of alkyl phenols.
- Emulsifiable concentrates of the compounds of this invention comprise a convenient concentration, such as from about 10% to about 50% w/w, in a suitable liquid. The compounds are dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.
- Emulsifiers which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil soluble salts or sulphated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
- Representative organic liquids which can be employed in preparing the emulsifiable concentrates of the present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, and the methyl ether of triethylene glycol. Mixtures of two or more organic liquids are also often suitably employed in the preparation of the emulsifiable concentrate. The preferred organic liquids are xylene, and propyl benzene fractions, with xylene being most preferred. The surface active dispersing agents are usually employed in liquid compositions and in the amount of from 0.1 to 20 percent by weight of the combined weight of the dispersing agent and active compound. The active compositions can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
- Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% w/w. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types above discussed. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
- The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% w/w of the compound, dispersed in an inert carrier which consists entirely or in large part of coarsely divided attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle.
- Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% w/w of the compound.
- The active compositions may contain adjuvant surfactants to enhance deposition, wetting and penetration of the compositions onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will vary from 0.01 percent to 1.0 percent v/v based on a spray-volume of water, preferably 0.05 to 0.5%. Suitable adjuvant surfactants include ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines and blends of surfactants with mineral or vegetable oils.
- The composition may optionally include fungicidal combinations which comprise at least 1% of one or more of the compounds of this invention with another pesticidal compound. Such additional pesticidal compounds may be fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds in combination can generally be present in a ratio of from 1:100 to 100:1.
- The present invention includes within its scope methods for the control or prevention of fungal attack. These methods comprise applying to the locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidal amount of one or more of the compounds of this invention or compositions. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds are useful in a protectant or eradicant fashion. The compounds of this invention are applied by any of a variety of known techniques, either as the compounds or as compositions including the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials are applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates. These materials are conveniently applied in various known fashions.
- The compounds of this invention have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants, or with wood, paint, leather or carpet backing.
- In particular, the compounds effectively control a variety of undesirable fungi which infect useful plant crops. Activity has been demonstrated for a variety of fungi, including for example the following representative fungi species: Downy Mildew of Grape (Plasmopara viticola—PLASVI), Late Blight of Tomato (Phytophthora infestans—PHYTIN), Apple Scab (Venturia inaejualis—VENTIN), Brown Rust of Wheat (Puccinia recondita—PUCCRT), Stripe Rust of Wheat (Puccinia striiformis—PUCCST), Rice Blast (Pyricularia oryzae—PYRIOR), Cercospora Leaf Spot of Beet (Cercospora beticola—CERCBE), Powdery Mildew of Wheat (Ezysiphe graminis—ERYSGT), Leaf Blotch of Wheat (Septoria tritici—SEPTTR), Sheath Blight of Rice (Rhizoctonia solani—RHIZSO), Eyespot of Wheat (Pseudocercosporella herpotrichoides—PSDCHE), Brown Rot of Peach (Monilinia fructicola—MONIFC), Glume Blotch of Wheat (Septoria nodorum—LEPTNO). It will be understood by those in the art that the efficacy of the compounds of this invention for the foregoing fungi establishes the general utility of the compounds as fungicides.
- The compounds of this invention have broad ranges of efficacy as fungicides. The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the toxic active ingredient. Thus, all the active ingredients of the compounds of this invention, and compositions containing the same, may not be equally effective at similar concentrations or against the same fungal species. The compounds of this invention and compositions are effective in use with plants in a disease inhibiting and phytologically acceptable amount. The term “disease inhibiting and phytologically acceptable amount” refers to an amount of a compound which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to about 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre.
Claims (6)
1. A compound of Formula (1)
wherein
m is an integer 0-3;
L is —O—, —CH2—, —SQn, —OCH2—, —SCH2—, —CH═CH—, —C═C—, or
wherein n is an integer 0-2;
X, Y, and Z are each independently H, C1-6 alkyl, C1-6 alkoxy, halo-C1-6 alkyl, halo-C1-6 alkoxy, halo, nitro, carbo-C1-6 alkoxy, cyano, C1-6 alkylthio, or halo-C1-6 alkylthio;
W is H, halogen, C1-4 alkyl, C1-4 alkoxy, halo-C1-4 alkyl, or C1-4 alkylthio;
A is O, S, NR3, OCH2, SCH2;
B is O or S;
R1 is a C1-C4 alkyl group (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, aralkyl, cyano, cyanoalkyl, halo, or haloalkyl), or an optionally substituted aryl or heteroaryl ring;
R2 is a C1-C8 alkyl (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, aralkyl, cyano, cyanoalkyl, halo, or haloalkyl), or an optionally substituted aryl or heteroaryl ring; and
R3 is H or C1-6 alkyl.
3. A compound of claim 2 wherein R1—B—R2 is —CH2CH2—O—nC3H7.
5. A fungicidal composition comprising the compound of claim 1 and a phytologically acceptable carrier.
6. A fungicidal method which comprises applying to the locus to be treated a fungicidally-effective amount of a compound of formula (1)
wherein
m is an integer 0-3;
L is —O—, —CH, —SO—, —OCH2—, —SCH2—, —CH═CH—, —C═C—, or
wherein n is an integer 0-2;
X, Y, and Z are each independently H, C1-6 alkyl, C1-6 alkoxy, halo-C1-6 alkyl, halo-C1-6 alkoxy, halo, nitro, carbo-C1-6 alkoxy, cyano, C1-6 alkylthio, or halo-C1-6alkylthio;
W is H, halogen, C1-4 alkyl, C1-4 alkoxy, halo-C1-4 alkyl, or C1-4 alkylthio;
A is O, S, NR3, OCH21 SCH2;
B is O or S;
R1 is a C1-C4 alkyl, (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, aralkyl, cyano, cyanoalkyl, halo, or haloalkyl), or an optionally substituted aryl or heteroaryl ring;
R, is a C1-C8 alkyl (optionally substituted by alkenyl, cycloalkyl, alkoxy, alkoxycarbonyl, aralkyl, cyano, cyanoalkyl, halo, or haloalkyl), or an optionally substituted aryl or heteroaryl ring; and
R3 is H or C1-6alkyl.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/060,882 US6432990B1 (en) | 1998-09-16 | 2002-01-30 | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10049398P | 1998-09-16 | 1998-09-16 | |
US09/397,565 US6369083B1 (en) | 1998-09-16 | 1999-09-16 | 2-methoxyimino-2 (pyrinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
US10/060,882 US6432990B1 (en) | 1998-09-16 | 2002-01-30 | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/397,565 Division US6369083B1 (en) | 1998-09-16 | 1999-09-16 | 2-methoxyimino-2 (pyrinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
Publications (2)
Publication Number | Publication Date |
---|---|
US6432990B1 US6432990B1 (en) | 2002-08-13 |
US20020115865A1 true US20020115865A1 (en) | 2002-08-22 |
Family
ID=22280046
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/397,565 Expired - Fee Related US6369083B1 (en) | 1998-09-16 | 1999-09-16 | 2-methoxyimino-2 (pyrinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
US10/060,882 Expired - Fee Related US6432990B1 (en) | 1998-09-16 | 2002-01-30 | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/397,565 Expired - Fee Related US6369083B1 (en) | 1998-09-16 | 1999-09-16 | 2-methoxyimino-2 (pyrinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring |
Country Status (3)
Country | Link |
---|---|
US (2) | US6369083B1 (en) |
AU (1) | AU6251799A (en) |
WO (1) | WO2000015635A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003516968A (en) * | 1999-12-15 | 2003-05-20 | ダウ・アグロサイエンス・エル・エル・シー | Pyridine derivatives having fungicidal activity and their production and use |
TW200409629A (en) | 2002-06-27 | 2004-06-16 | Bristol Myers Squibb Co | 2,4-disubstituted-pyridine N-oxides useful as HIV reverse transcriptase inhibitors |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0278595B2 (en) | 1987-02-09 | 2000-01-12 | Zeneca Limited | Fungicides |
DE3823991A1 (en) | 1988-07-15 | 1990-02-15 | Basf Ag | HETEROCYCLICALLY SUBSTITUTED (ALPHA) -ARYL-ACRYLIC ACID ESTERS AND FUNGICIDES THAT CONTAIN THESE COMPOUNDS |
DE3835028A1 (en) | 1988-10-14 | 1990-04-19 | Basf Ag | OXIMETHER DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
GB8828543D0 (en) | 1988-12-07 | 1989-01-11 | Ici Plc | Insecticides |
EP0629609B1 (en) | 1989-05-17 | 1996-12-04 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Process for the preparation of Alkoxyiminoacetamide derivatives and an intermediate therefor |
GB9016783D0 (en) | 1989-09-01 | 1990-09-12 | Ici Plc | Agrochemical compositions |
GB9218541D0 (en) | 1991-09-30 | 1992-10-14 | Ici Plc | Fungicides |
CA2102078A1 (en) | 1992-11-02 | 1994-05-03 | Akira Takase | A process for producing (e)-alkoxyimino or hydroxyiminoacetamide compounds and intermediates therefor |
TW305836B (en) * | 1994-05-20 | 1997-05-21 | Shionogi & Co | |
DK0781764T3 (en) | 1994-09-06 | 2000-07-10 | Shionogi & Co | Process for the preparation of alkoxyiminoacetamide derivatives |
WO1996020164A1 (en) | 1994-12-26 | 1996-07-04 | Shionogi & Co., Ltd. | Process for producing 2-(2-hydroxymethylphenyl)acetamide derivative and intermediate for the production thereof |
PT840726E (en) | 1995-06-28 | 2002-02-28 | Syngenta Ltd | METHOD FOR PREPARING 2- (PYRID-2-YLOXIMETHYL SUBSTITUTED IN POSITION 6) PHENYLATE |
GB9602623D0 (en) | 1996-02-09 | 1996-04-10 | Zeneca Ltd | Fungicides |
GB9624615D0 (en) | 1996-11-26 | 1997-01-15 | Zeneca Ltd | Chrystallisation process |
KR100514941B1 (en) | 1997-02-03 | 2005-09-15 | 다우 아그로사이언시즈 엘엘씨 | 2-Methoxyimino-2-(pyridinyloxymethyl)phenyl acetamides with carboxylic acid derivatives on the pyridine ring as fungicides |
WO1999025713A1 (en) | 1997-11-14 | 1999-05-27 | Dow Agrosciences Llc | 2-methoxyimino-2-phenyl acetamides containing a ketal- or dialkoxy substituted pyridine moiety, their preparation and their use as fungicides |
-
1999
- 1999-09-16 US US09/397,565 patent/US6369083B1/en not_active Expired - Fee Related
- 1999-09-16 AU AU62517/99A patent/AU6251799A/en not_active Abandoned
- 1999-09-16 WO PCT/US1999/021350 patent/WO2000015635A1/en active Application Filing
-
2002
- 2002-01-30 US US10/060,882 patent/US6432990B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2000015635A1 (en) | 2000-03-23 |
US6369083B1 (en) | 2002-04-09 |
US6432990B1 (en) | 2002-08-13 |
AU6251799A (en) | 2000-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3106461B1 (en) | Derivatives of uk-2a | |
US6133294A (en) | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with 5 membered heterocyclic rings on the pyridine ring | |
EP2432767B1 (en) | Compounds and methods for controlling fungi | |
US6432990B1 (en) | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with polyether derivatives on the pyridine ring | |
US6211202B1 (en) | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with substituted ketal derivatives on the pyridine ring | |
US6436963B1 (en) | 2-methoxyimino-2-(pyridinyloxymethyl) phenyl acetamides with (derivatised) hydroxyalkyl derivatives on the pyridine ring | |
US20040002545A1 (en) | Thiazole derivatives of 2-methoxyimino-2-(pyridinyloxymethyl)-phenyl-acetamides useful as fungicides | |
US20050130968A1 (en) | Fungicidal 4-(2-aminopyridin-4-yl)-N-phenyl-1,3,5-triazin-2-amine derivatives | |
US6734143B2 (en) | 2-methoxyimino-2(pyridinyloxymethyl)phenyl acetamides useful as fungicides | |
US6559170B1 (en) | Pyridine derivatives having fungicidal activity and processes to produce and use same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20060813 |