TWI277391B - Fungicidal mixtures based on oxime ether derivatives - Google Patents
Fungicidal mixtures based on oxime ether derivatives Download PDFInfo
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- TWI277391B TWI277391B TW090131096A TW90131096A TWI277391B TW I277391 B TWI277391 B TW I277391B TW 090131096 A TW090131096 A TW 090131096A TW 90131096 A TW90131096 A TW 90131096A TW I277391 B TWI277391 B TW I277391B
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 230000000855 fungicidal effect Effects 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000002156 mixing Methods 0.000 claims description 6
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 241000233866 Fungi Species 0.000 abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 abstract description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical group 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
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- 125000001188 haloalkyl group Chemical group 0.000 abstract 3
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 125000004774 dichlorofluoromethyl group Chemical group FC(Cl)(Cl)* 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Chemical group 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- UYOVAKKUHLDHMB-UHFFFAOYSA-N phenoxymethanamine Chemical compound NCOC1=CC=CC=C1 UYOVAKKUHLDHMB-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
1277391 A7 B7 五、發明説明(1 ) 基於肟醚衍生物及額外活性化合物之殺菌混合物乃屬已 知,例如,W0 99/4 83 65有關一種包含以協同有效量的 以下組分作為活性成分之殺菌混合物·· a)式(I)之苯基乙酸衍生物及其鹽類,及b)至少一種式 (II)至式(VII)化合物。
W 0 9 9 / 4 6 3 6 8有關一種包含以協同有效量的以下組分 作為活性成分之殺菌混合物: a)式(I)之苯基乙酸衍生物及其鹽類,及b)至少一種式 (II)至式(VII)化合物。 -6 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1277391 A7 B7
m
(VM) WO 9 9/4 83 69有關一種包冬以桫门丄 ^ 彳匕口以協同有效量的以下組分 作為活性成分之殺菌混合物: 及b )至少一種式 a)式(I)之苯基乙酸衍生物及其鹽麵 (II)至式(V)化合物。
W0 99/48370有關一種包含以協同有效量的以下組分 作為活性成分之殺菌混合物: a)式(I)之苯基乙酸衍生物及其鹽類,及b)至少一種式 (II)至式(III)化合物。 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1277391 五、發明説明(3
、Ν ⑴ 0
(III) 本發明之目的係提出一種且 物’尤其是對抗穀類之真菌疾病艮:殺菌活性之殺菌混合 之效果。 (過孩混合物組份本身 吾人發現此目的係根據本發 之混合物達成。 發月精由中請專利範圍第Μ 本發明有關-種殺菌混合物,其包含協合有效量之以下 活性組份 A )具有通式I之肟醚衍生物
其中: X係為NH或氧; R】,R3個別係為氫、氰基、CrCr烷基、環丙基或Ci· • 8 - 本紙張尺度適用中國國家標準(CNS) Α4ί見格(210 X 297公釐) — " 1277391 A7 B7 五、發明説明 C 4 - 1¾乾基, R2,R4個別係為氫、Cl-CV烷基、C3_C6_烯基、C3-c6-炔基、CrCc _烷基、C3_c6- _烯基或鹵炔 基; 及 B)至少一種具有通式II之化合物
其中: R1,R2個別係為<:厂(:6-烷基; R3、R4,R5個別係為氫或Cl_C4_烷基; R6係為鹵素、C〗-C4 -烷基或c ! · c 4 -鹵烷基; η係為2、3或4,其中基團R6可相異。 具有通式I之化合物本身係已知,且係描述於文獻中[比 較 W0 97/15552 ]。 具有通式II之殺菌劑同樣亦已知,且描述於文獻中[比較 ΕΡ-Α 262 393 ]。 因為其C = C及C = N雙鍵,化合物I之製備產生Ε/Ζ異構 物混合物,可依習用方式分離成個別化合物,例如藉結晶 或層析。 然而,若合成產生異構物混合物,則通常並非必要進行 分離’因為在某些情況下,個別異構物可在製備或使用之 -9- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1277391 A7 B7 五、發明説明(5 過程中轉化成另一種異構物(例如在光、酸或鹼之作用 下)。相同之轉化亦可能發生在使用之後,例如在處理植 物時,於經處理之植物身上或在有害之真菌或名欠防治之動 物害蟲體内。 因為其生物活性,故較佳化合物!係其中Rl&R3係為 氫、氰基、環丙基、甲基、乙基、卜甲基乙基或CF3者。 特佳係為其中係為Ci_C4_烷基者。 另一種特佳化合物I係為其中R 1係為甲基者。 此外’其中R 1係為C F 3之化合物I較佳。 此外,較佳化合物I係為其中化2及化4係為氫、環丙基、 甲基、乙基或異丙基者。 而且’其中R 4係為甲基之化合物I較佳。 此外,較佳化合物I中R4係為乙基或異丙基。 相同地,特佳式I肟醚衍生物中X係為nh。 另一種較佳化合物I係列示於W0 97/15552中,以提 明確併入本文中。 ^ 就對抗有害真菌諸如例如pyricularia 〇iyzae之殺菌活性而 言,在苯氧甲醯胺II中,較佳者係具有以下取代基者,各 可單獨或組合使用: 若R1及R2相異,則帶有該基團RiAR2之碳原子以具有 R構型為佳。 ’ 較佳苯氧甲醯胺II中R1係為甲基且R2係為乙基、正丙基 或異丙基;特佳之化合物11中r 1係為甲基且R2係為異丙 基。 -10- 本紙張尺度適用中國國家標準(CNS) A4规格(210X 297公釐)
裝
1277391
/ ―種/父佳者係為式11之苯氧甲酿胺,其中R3係為甲基 或氣。R3以氫為特佳。 較佳係式苯氧甲醯胺,其中R4及R5係為氫或甲基。 亦特佳者係為式Π之苯氧甲醯胺,其中尺4係為氫且以5係 為甲基。 若R4及R5相異, 構型為佳。 則帶有基團R4及R5之碳原子以具有尺 較佳式Π化合物中,不對稱之兩中心的構型係為R,R。 本發明亦有關其他在合成中所得之非鏡像異構物混合物 R ’ S ; R,S與S,R ; s,S與S,S。 另-種較佳者係為式η之苯氧甲醯胺,其中指數η係為 二或三,尤其是二。 R6之較佳意義係為卣素&Ci_C4_烷基,尤其是氟、氯 或甲基。 另一種較佳者係為式Π之苯氧甲醯胺,其中R6=氯。 此外,較佳係式II之苯氧甲醯胺,其中基團R6係位於2 _ 及4-位置。 、 就其用途而言,特佳化合物丨及]^係下表丨及2所收集 者0 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1277391 A7 B7 五、發明説明(7 ) 表1 具有通式I之妨醚衍生物
No. R1 R2 R3 R4 X 1-1 Η H H H NH 1-2 Η ch3 H ch3 NH 1-3 ch3 H ch3 H NH 1-4 ch3 ch3 ch3 ch3 NH 1-5 ch3 cyclo-C3H5 ch3 cyclo-C3H5 NH 1-6 ch3 CH2CH3 ch3 CH2CH3 NH 1-7 ch3 CH (CH3)2 ch3 CH (CH3)2 NH 1-8 ch3 ch2ch=ch2 ch3 ch2ch=ch2 NH 1-9 cf3 H cf3 H NH 1-10 cf3 ch3 cf3 ch3 NH 1-11 cf3 CH(CH3)2 cf3 CH (CH3)2 NH 1-12 CN H ch3 H NH 1-13 CN ch3 ch3 ch3 NH 1-14 H H H H 〇 裝 線 -12-本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1277391 A7 B7 五、發明説明(8 ) 1-15 Η ch3 H ch3 0 1-16 ch3 H ch3 H 0 1-17 ch3 ch3 ch3 ch3 0 1-18 ch3 cyclo-C3H5 ch3 cyclo-C3H5 0 1-19 ch3 CH2CH3 ch3 CH2CH3 0 1-20 ch3 CH (CH3)2 ch3 CH (CH3)2 0 1-21 ch3 ch2ch=ch2 ch3 ch2ch=ch2 0 1-22 cf3 H cf3 H 0 1-23 cf3 ch3 cf3 ch3 0 1-24 CN H ch3 H 0 1-25 CN ch3 ch3 ch3 0
裝 表2 具有通式Π之苯氧甲醯胺,其中R1至R6之組合的意義係 列示於表2中。
II •13- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1277391 A7 B7 五、發明説明(9 )
No. R1 R2 R3 R4 R5 (R6)n II-1 ch3 CH3 H H ch3 2,3,4-Cl3 II-2 ch3 ch2ch3 H H ch3 253, 4-Cl3 II-3 ch3 ch2ch2ch3 H H ch3 25 3?4-Cl3 II-4 ch3 CH (CH3)2 H H ch3 25 3?4-Cl3 II-5 ch3 ch3 ch3 H ch3 2, 3, 4-Cl3 II-6 ch3 CH2CH3 CH3 H ch3 25 3?4-Cl3 II-7 ch3 ch2ch2ch3 ch3 H ch3 25 3?4-Cl3 II-8 ch3 CH(CH3)2 ch3 H ch3 25 3?4-Cl3 II-9 ch3 ch3 H H ch3 2, 4-Cl2 11-10 ch3 CH2CH3 H H ch3 2,4-Cl2 11-11 ch3 ch2ch2ch3 H H ch3 2, 4-Cl2 11-12 ch3 ch(ch3)2 H H ch3 2, 4-Cl2 11-13 ch3 ch3 ch3 H ch3 2, 4-Cl2 11-14 ch3 ch2ch3 ch3 H ch3 2? 4-Cl2 11-15 ch3 ch2ch2ch3 ch3 H ch3 2, 4-Cl2 11-16 ch3 CH (CH3)2 ch3 H ch3 2? 4-Cl2 特佳者係為化合物I - 4與11 - 1 2之混合物(俗名:吩噁札尼 (fenoxanil)) 0 文初所出示之化合物I及11的定義中,使用一般表示以下 基團之總稱: -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1277391
鹵素:氟、氯、溴及碘; 乾基··具有1至4個碳原子乏亩左击 , 男卞<直鏈或分枝鏈烷基,例如Cr C 4 -烷基,諸如甲基、乙基、 丙基、1-甲基乙基、丁基、 1-甲基丙基、2-甲基丙基及Lb二甲基乙基· 函燒基:具有1至4個碳原子之直鏈i分枝鏈燒基,其中 此寺基團中之邵分或所有氫原子皆由前述㈣子所置換, 例如C〗-C 2 -鹵烷基,諸如翕甲| - 万如乳甲基、二氯甲基'三氯甲基、 氟甲基、二氟甲基、三氟甲其备 一 基鼠鼠甲基、二氯氟甲基、 鼠一氟甲基、1-氟乙基、2 签 △氟乙基、2,2_二氟乙基、 2,2,2 -三氟乙基、2 -氯-2-翕r其、〇 > 礼/鼠乙基、2-氯二氟乙基、 2,2-二氯-2-氟乙基、2,2,2_二氯乙基及五氟乙基; 環燒基:具有3至6個環員之單環燒基,例如環丙基、環 丁基、環戊基及環己基; 埽基:且有3至6個碳原子及位於任何位置之雙键的直鏈 或分枝鏈婦基,例如烯基,諸如[丙婦基、2_丙婦 基、1 -甲基乙烯基、1 · 丁烯基、2 _ 丁烯基、3 •丁埽基、卜 甲基-1-丙埽基、2·甲基-·丙烯基、丨_甲基_2_丙烯基及 2-甲基-2-丙烯基; 炔基:且有3至6個碳原子及位於任何位置之參鍵的直鏈 或分枝鏈炔基,例如CrCr炔基,諸如2_丙炔基、2_ 丁炔 基、3 -丁炔基及1-甲基·2_丙炔基。 π邵分或完全卣化”之說明意指所述之基團中之部分或所 有氫原子可被相同或相異之前述函原子所置換。 製備該混合物時,較佳係採用純活性化合物I及π,其可 -15- 本紙張尺度適用巾酬家料(CNS) Μ規格(21()χ挪公爱)
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1277391 A7 B7___ 五、發明説明(11 ) 摻合其他對抗有害真菌或其他害蟲諸如昆蟲、蜘蛛或線蟲 之活性化合物,或除草或生長調節活性化合物或肥料。 化合物I與至少一種化合物11之混合物可同時、結合或個 別地使用,且對於廣泛之植物病菌,尤其是子囊菌 (Ascomycetes)、擔子菌(Basidiomycetes)、藻菌(Phycomycetes)及 半知菌(Deuteromycetes)類具有優越之活性。其中部分係整體 作用型,故亦可作為葉上-及土壤-作用型殺菌劑。 本發明殺菌混合物係包含協合有效量之至少一種式I之 肟醚衍生物及至少一種式II之化合物;通常,活性化合物I 及11之混合比例係由2 0 : 1至1 : 3 0。特佳混合比例係由1 : 1 至1 : 3 0。在特定條件下,在此範圍之外,亦可實驗到式I 與11之化合物之間的協合相互作用。 其對於大各式各樣作用中防治許多真菌極為重要,諸如 棉、蔬菜(例如黃瓜、豆子、蕃茄、洋芋及葫藍)、大麥、 青草、燕麥、香蕉、咖啡、玉米、水果、稻子、黑麥、大 豆、葡萄樹、小麥、觀賞植物、甘蔗、及各種種子。 其特別適於防治以下植物病菌:穀類之Blumeria graminis (白 粉病)、葫董之二孢白粉菌(Erysiphe cichoracearum )及單絲殼 (Sphaerotheca fuliginea)、韻果之白叉絲單囊菌(Podosphaera leucotricha)、棉、稻及草地之絲核菌(Rhizoctonia)、穀類及甘 喪之黑粉菌(Ustilago)、韻果之黑星菌(Venturia inaequalis)(斑 點病)、穀類及稻子之長螺孢屬(Helminthosporium )、小麥之 穎枯殼針孢(Septoria nodorum)、草苺、蔬菜、觀賞植物及葡 萄樹之灰葡萄孢(Botrytis cinerea )(灰霉)、落花生之落花生尾 -16- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1277391 A7 B7 五、發明説明(i2 孢(Cercospora arachidicola)、小麥及大麥之假長孢 (Pseudocercosporella herpotrichoides)、稻子及草地之(Pyricularia oryzae )、洋芋及蕃%之致病疫霉(Phytophthora infestans )、葡萄 樹之葡萄生單軸霉(Plasmopara viticola )、啤酒花及黃瓜之假 霜霉(Pseudoperonospora)屬、蔬菜及水果之鏈格孢(Altemaria) 屬、香蕉之球腔菌(Mycosphaerella)屬及鐮孢屬(Fusarium)及 輪枝孢屬(Verticillium)。 本發明混合物尤其可用以防治Pyricularia oryzae。 該化合物I及至少一種化合物11可同時施加--或一起或個 別,或連續地施加,若為個別施加,則順序通常對於防治 結果不具有任何影響。 視所需之效果的類型而言,本發明混合物之施用率一尤 其是在農作物區中一係由〇.〇1至8公斤/公頃,以0.1至5公斤 /公頃為佳,尤其是0.5至3.0公斤/公頃。 化合物I之施用率係由〇.〇1至2.5公斤/公頃,以0.05至2.5 公斤/公頃為佳,尤其是〇·1至1·〇公斤/公頃。 相對地’若為化合物Π,則施用率係由0.001至5公斤/公 頃’以0.005至2公斤/公頃為佳,尤其是0.01至1.0公斤/公 頃。 就種子處理而言,該混合物之施用率通常係由〇.〇〇i至 250克/公斤種子,以0,01至100克/公斤為佳,尤其是0.01至 5 0克/公斤。 若欲防治植物病菌,則可藉著在植物播種之前或之後, 或在植物萌芽之前或之後,於種子、植物或土壤上噴灑或 • 17- 本紙張尺度適用中國國家榡準(CNS) A4規格(21〇x297公釐)
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1277391 A7
賣秦,而個別或結合地施加化合物j及至少一種化合物〗j。 、本發明殺菌協合作用混合物可調配成例如即可噴灑型溶 夜粕末及懸浮液,或高濃縮型水性、油性或其他懸浮 履、分散液、乳液、油分散液、糊劑、粉齊】、撒播用材料 或顆粒形式’且藉噴灑、喷霧、撒粉、播撒或灌溉而施 用使用形式視所需之目的而定;在任何情況下,皆應確 足本發明混合物之分佈儘可能細密且均勻。 忒凋配物係藉已知方式製備,例如使用溶劑及/或載體 稀釋孩活性化合物,若需要.,則使用乳化劑及分散劑,若 使用水作為稀釋劑,則亦可使用其锩有機溶劑以作為輔助 溶劑。適於此種目的之辅劑基本上有:溶劑諸如芳族物(例 =一曱苯)、氯化芳族物(例如氯苯)、石蠟(例如礦油部 分)、醇類(例如曱醇、丁醇)、酮類(例如環己酮)、胺類 (例如乙醇版、二甲基甲醯胺)及水;載體諸如磨碎之天然 廣物(例如同嶺土、黏土、滑石、白堊)及磨碎之合成礦物 (例如細粉狀二氧化矽、矽酸鹽);乳化劑諸如非離子性及 陰離子性乳化劑(例如聚環氧乙烷、脂肪醇醚、磺酸烷酯 及飧酸芳酯)及分散劑諸如木質亞硫酸酯廢液及甲基纖維 素0 適當(界面活性劑有芳族磺酸之鹼金屬鹽、鹼土金屬鹽 ^銨鹽,例如木質_、酚_、莕-及二丁基莕磺酸者,或脂肪 故k基及心基芳基續酸酯、燒基、月桂基_及脂肪醇 或脂肪醇二醇 十七-及十八烷醇 醚者,%化奈及其衍生物與甲醛之縮合物、莕與苯磺酸與 -18- ^張尺度適财關 1277391 A7
酚及甲醛之縮合物、聚環氧 基_、辛A i;工心辛基酚醚、乙氧化異辛 中基-或壬基酚、烷基酚或三丁— , 基芳基聚醚含 S丄一上 土+土水一醇酸、燒 氧化篆二、、十三醇、脂肪醇/氧化乙埽縮合物、乙 乳化昆麻油、聚環氧乙烷烷基 桂醇聚二醇鍵乙酸酿、山梨糖醇;=丙鍵、月 甲基纖維素。 :^搪…木質亞硫酸酿廢液或 私末、供撒播使用之材料及粉劑可藉著混合或結合研磨 化合物Ϊ與至少一種化合物π或化合及至少一種化合物 II與固體載體之混合物而製備。 ,顆粒(例如經塗佈之顆粒'經浸潰之顆粒或均勻顆粒)通 常係藉著黏合該活性化合物或活性化合物等於固體載體上 而製備。 填料或固體載體係為例如礦土,諸如二氧化矽、矽膠、 矽酸鹽、滑石、咼嶺土、石灰石、石灰、白堊、膠塊黏 土、肓土、黏土、白雲石、矽藻土、硫酸鈣、硫酸鎂、氧 化鎂、經研磨之合成材料及肥料諸如硫酸銨、磷酸銨、硝 酸銨、尿素、及植物來源產物諸如穀粉、樹皮粉、木粉及 堅果粉、纖維素粉末或其他固體载體。 遠调配物通常包含由〇·1至9 5重量百分比,以〇·5至9 〇重 量百分比為佳之一種化合物I及至少一種化合物π或該化合 物I與至少一種化合物11之混合物。該活性化合物之使用純 度係由9 0百分比至100百分比,以9 5百分比至1〇〇百分比為 佳(根據NMR光譜或HPLC)。 對應之調配物係藉著使用殺菌活性量之該混合物或(若 -19- 本紙張尺度適用中國國家標準(CNS) Α4規格(210X 297公釐) 1277391 A7 B7 五、發明説明(l5 ) 個別施用時)化合物I及至少一種化合物π處理該有害真 趙、其居處、或欲去除該害菌之植物、種子、土壤、巴 域、材料或空間而施用。 施藥可在該有害真菌感染之前或之後進行。 包含該活性化合物之配製劑的實例有.· I · 9 0重量份數活性化合物與丨〇重量份數之甲基Ρ比咯 烷酮之溶液;此溶液適於在微滴形式下使用; II · 2 0重量份數之該活性化合物、8 〇重量份數之二甲苯、 1 〇重量份數之8至1 0莫耳氧化乙婦相對於i莫耳油酸 N-單乙醇醯胺之加合物、5重量份數之十二苯橫酸的 鈣鹽、5重量份數之4 0莫耳氧化乙婦相對於1莫耳萬麻 油的加合物之混合物,藉著將該溶液極細密地分佈於 水中,而製得分散液; III· 20重量份數之該活性化合物、40重量份數之環己酮、 30重量份數之異丁醇、20重量份數之40莫耳氧化乙 婦與1莫耳篦麻油之加合物之含水分散液; IV · 2 0重量份數之該活性化合物、2 5重量份數之環己醇、 6 5重量份數之沸點為2 1 0至2 8 0 °C的礦油餾分、及i 〇 重量份數之4 0莫耳氧化乙烯相對於1莫耳篦麻油的加 合物之含水分散液; V ·在錘磨機中研磨之8 0重量份數該活性化合物、3重量 份數之二異丁基茶-1-續酸的麵鹽、10重量份數來自 亞硫酸廢液之木質磺酸的鈉鹽及7重量份數之粉狀石夕 膠的混合物;噴灑用混合物係藉著將該混合物細密地 -20- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1277391 A7 B7 五、發明説明(16 分佈於水中而製得; VI · 3重量份數該活性化合物與9 7重量份數細粉狀高嶺土 的細密混合物;此粉劑係包含3重量百分比之活性化 合物; VII · 3 0重份數该活性化合物、9 2重量份數粉碎之碎膠及 8重量份數已噴霧於該矽膠表面上之石蠟油的細密混 合物;此碉配物於該活性化合物上賦予良好之黏著 性; VIII · 4 0重量份數該活性化合·物、1 〇重量份數之酚磺酸/尿 素/甲醛縮合物的鈉鹽、2重量份數矽膠及48重量份數 水之安定含水分散液;此分散液可進一步稀釋; IX · 2 0重量份數該活性化合物、2重量份數十二基苯磺酸 的鈣鹽、8重量份數脂肪醇聚二醇醚、2〇重量份數酉分 磺酸/尿素/甲醛縮合物之鈉鹽及8 8重量份數之石蟻礦 油的安定含油分散液。 用途實施例 本發明混合物之協合活性可由以下實驗證明: 該活性化合物…個別或一起一在6 3重量百分比環己酮與 2 7重量百分比乳化劑之混合物中調配成丨〇百分比乳液,使 用水稀釋至所需之濃度。 藉者測足雙感染之葉片面積的百分比而進行評估。此等 百分比換算成效率。該效率(d係如下使用阿布公式 (Abbot’s formula)計算: W == (1 - a / y3 ) X 100 -21 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) * "一一 — 1277391 A7 B7 五、發明説明(Γ7 ) « 對應於經處理植物的真菌感染百分比且 β 對應於未經處理(對照組)植物的真菌感染百分比。 效率0意指經處理之植物的感染程度係對應於未經處理 之對照組植物;效率1〇〇意指經處理植物未被感染。 活性化合物之混合物的預測效率係使用柯比公式(colby,s formula)決定[R.S· Colby,Weeds II,20-22 (1967 )]且與所實驗之效 率比較。 柯比公式:E = x + y- x· y/l〇〇 E使用濃度a及b之活性化合物A及B之混合物時的預測效 率,以未經處理之對照組的百分比表示 X使用濃度a之活性化合物A時的效率,以未經處理之對 照組的百分比表示 y使用ί辰度b之活性化合物b時的效率,以未經處理之對 照組的百分比表示。 用途貫施例1 :對抗由Pyricularia oryzae所致之稻痕病的保護 活性 品種” Tai-N〇ng67 ”已於盆中長成之稻苗的葉子使用活性化 合物之含水配製劑噴藥至滴流點,該含水配製劑係由1 〇百 分比活性化合物、8 5百分比環己酮及5百分比乳化劑所組 成之儲液所製備。次日,植物使用Pyricularia 〇ryzae含水之孢 子懸浮液接種。試驗植物隨之放置於22-24°c&95_99百 分比相對大氣溼度的人工氣候室中歷經6日。之後,目測 葉片上之疾病發展程度。 -22- 本紙張尺度適用中國國豕標準(CMS) A4規格(210X297公爱)
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▲ 1277391 A7 B7 五、發明説明(is ) 表A -個別活性化合物 實施例 活性化合物 噴液中活性化合 物濃度[ppm] 未經處理之對照 組的效率% 1 對照組(未經處理) (96%感染) 0 2 1-4 10 28 5 28 2.5 0 3 吩p惡札尼(fenoxanil) 200 84 (11-12) 100 79 50 69 表B -根據本發明之組合 實施例 活性化合物之混合 物 濃度混合比例 實驗效率 計算效率*) 4 1-4+ 11-12 10 + 200 ppm 1:20 99 89 5 1-4+ 11-12 5 + 100 ppm 1:20 95 85 6 1-4+ 11-12 2.5 + 50 ppm 1:20 90 69 7 1-4+ 11-12 5 + 50 ppm 1:10 90 78 8 1-4+ 11-12 10+ 50 ppm 1:5 97 78 *)使用柯比公式計算 試驗結果顯示,對所有混合比例而言,實驗效果皆高於 預先使用柯比公式計算之值。 -23- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
Claims (1)
1277391 一一 一,as ! Λ L .l!B8 !,一C8 _. . r、 '〆 1 D8
六、申請專利範圍 1. 一種殺菌混合物,其包含協合有效量之以下活性組份 A )具有通式I之肟醚衍生物
其中: X係為NH ;及 R1,R2,R3及R4個另》J係為C^C^-烷基; 及 B )至少一種具有通式11之化合物
其中: R1,R2個別係為匕-匸^烷基; R3、R4個別係為氫; R $ 係 C 1 - C 4 - fe 基, R6係為位於2及4位置之氯;及 η係為2 ^ 2. 如申請專利範圍第1項之殺菌混合物,其中組份Α及Β之 混合比例係由1 : 1至1 : 3 0。 3. 如申請專利範圍第1或2項之殺菌混合物,其係分成兩部 分,一份包含固體或液體之載體,而另一份包含位於固 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
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| KR (1) | KR100805559B1 (zh) |
| CN (1) | CN100345482C (zh) |
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| CA2858914A1 (en) | 2002-03-21 | 2003-11-06 | Basf Aktiengesellschaft | Fungicidal mixtures |
| EP1830647A2 (de) * | 2004-12-20 | 2007-09-12 | Basf Aktiengesellschaft | Verfahren zur bekämpfung von pilzkrankheiten bei leguminosen |
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| EG18578A (en) * | 1986-08-29 | 1993-07-30 | Shell Int Research | Aryloxycarboxylic acid derivatives,the preparation and use thereof |
| DE19539324A1 (de) * | 1995-10-23 | 1997-04-24 | Basf Ag | Phenylessigsäurederivate, Verfahren und Zwischenprodukte zu ihrer Herstellung und sie enthaltende Mittel |
| WO1999048366A1 (de) * | 1998-03-24 | 1999-09-30 | Basf Aktiengesellschaft | Fungizide mischungen auf der basis von tripeloximetherderivaten und insektiziden |
| CA2323598A1 (en) * | 1998-03-24 | 1999-09-30 | Basf Aktiengesellschaft | Fungicide mixtures based on triple oxime ether derivatives and other strobilurins |
| KR100557364B1 (ko) * | 1998-03-24 | 2006-03-10 | 바스프 악티엔게젤샤프트 | 삼옥심에테르 유도체 및 리족토니아 살진균제를 기본으로하는 살진균제 혼합물 |
| CN1294489A (zh) * | 1998-03-24 | 2001-05-09 | 巴斯福股份公司 | 基于三(肟醚)衍生物和稻杀真菌剂的杀真菌混合物 |
| AU3331799A (en) * | 1998-03-24 | 1999-10-18 | Basf Aktiengesellschaft | Fungicide mixtures based on triple oxime ether derivatives and resistance inductors |
| EP1082010A1 (de) * | 1998-03-24 | 2001-03-14 | Basf Aktiengesellschaft | Fungizide mischungen auf der basis von tripeloximetherderivaten und weiteren fungiziden |
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| CN100345482C (zh) | 2007-10-31 |
| KR100805559B1 (ko) | 2008-02-20 |
| JP4307835B2 (ja) | 2009-08-05 |
| KR20030059348A (ko) | 2003-07-07 |
| JP2004520303A (ja) | 2004-07-08 |
| AU2002235781A1 (en) | 2002-07-01 |
| WO2002049434A1 (de) | 2002-06-27 |
| WO2002049434A9 (de) | 2002-09-19 |
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