TW200522863A

TW200522863A - Fungicidal mixtures for controlling rice pathogens

Info

Publication number: TW200522863A
Application number: TW093130639A
Authority: TW
Inventors: Jordi Tormo I Blasco; Thomas Grote; Maria Scherer; Reinhard Stierl; Siegfried Strathmann; Ulrich Schoefl
Original assignee: Basf Ag
Priority date: 2003-10-09
Filing date: 2004-10-08
Publication date: 2005-07-16
Also published as: JP2007508258A; EA200600658A1; IL174439A0; BRPI0415077A; EP1672980A1; MXPA06003408A; ZA200603577B; KR20060088120A; UA79217C2; WO2005034629A1; CN1859849A; CA2540292A1; NO20061386L; EA009086B1; CO5670336A2; KR100760746B1; AR046098A1

Abstract

Fungicidal mixtures for controlling rice pathogens, which mixtures comprise, as active components, (1) the triazolopyrimidine derivative of the formula I, and (2) fenhexamid of the formula II, in a synergistically effective amount, methods for controlling rice pathogens using mixtures of the compound I with the compound II, the use of the compound I with the compound II for preparing such mixtures and compositions comprising these mixtures are described.

Description

200522863 九、發明說明：【發明所屬之技術領域】混合物，此本i月係關於用以控制稻米病原體之殺真菌混合物包含協同作用有效量之活性成分··、 1)式I之三哇幷。密σ定衍生物200522863 IX. Description of the invention: [Technical field to which the invention belongs] Mixtures, which are related to fungicidal agents used to control rice pathogens. The mixtures contain synergistically effective amounts of the active ingredients ... 1) The three wows of formula I. Dense sigma derivative

F 及 2)式II之環醯菌胺F and 2) Cyclosporin of Formula II

Η 此外，本發明係關於一種使用化合物I與化合物„之混合物來控制稻米病原體的方法，且係關於化合物消化合物Η 用於製備該等混合物及包含該等混合物之組合物的用途。【先前技術】 ' 化合物I，即5-氯-7-(4-甲基六氫吡啶基）_6_(2,4,6_三& 苯基）-[1，2,4]三㈣[l，5-a]t定，其製備方法及其對抗有= 真菌之作用自文獻（W〇98M66〇7)中為吾人所知。几害化合物Π，即則2,3-二氯_4_經苯基）]_甲基環己烷甲胺’其製備方法及其對抗有害真菌之仙自文嘴 \ ^· Br 96430.doc 200522863Η In addition, the present invention relates to a method for controlling rice pathogens using a mixture of Compound I and Compound „, and relates to the use of compound sterilizing compound 制备 for the preparation of such mixtures and compositions containing the same. [Previous technology ] 'Compound I, which is 5-chloro-7- (4-methylhexahydropyridyl) _6_ (2,4,6_tri & phenyl)-[1,2,4] triamidine [l, 5 -a] t, its preparation method and its anti-fungal effect are known to us from the literature (WO98M66〇7). Several harmful compounds Π, that is, 2,3-dichloro_4_ via benzene Group)] _ Methylcyclohexanemethylamine ', its preparation method and its anti-harmful fungus, Zhizizui \ ^ · Br 96430.doc 200522863

Crop Prot. Conf. > PP〇fc τλ·Crop Prot. Conf. &Gt; PP〇fc τλ ·

Dls·，1998, Bd. 2, S· 327 ;通用名：環fe]胺）中同樣為吾人 ^ ^ ^ 八所知。商業上，已知環醯菌胺主要用於&制葡甸樹及特種作物中之貴腐黴菌（〜州叫感染。一坐幷’疋何生物與環醯菌胺形成之混合物以概括方式自EP-A 988 790中兔五人&匕心马口人所知。該化合物！係涵蓋於此公開案之概述揭示内交φ，/ 土 Ί 仁未明確提及。因此，化合物I與環醯菌胺之組合是新穎的。 ^ ，自A 98 8 790已知之協同作用混合物係描述為對穀類水果及‘菜之各種疾病、例如小麥及大麥之徽病或顧果之灰黴具有殺真菌有效性。歸因於稻米植物之特殊栽培條件，稻綠真菌劑必須滿足之要求相當大之程度上不同於歸榖類友戈水果種植之殺真菌劑所必須滿足之彼等要求。在施用方法上存在差異：在現代稻来栽培中’除了許多地方所使用之葉敷方法外，殺真菌劑係於播種期間或播種後不久直接施用至土壤。殺真菌劑係經由根而吸收進入植物且在植物之汁液中傳輸至待保護之植物部分。相反，在穀類或水果種植中，通常將殺真菌劑施用於葉片或水果上；因此，在該等農作物中活性化合物之系統性作用在相當程度上顯得很不重要。此外，稻米病原體通常不同於穀類或水果中之彼等病原體。稻米植物中最流行疾病之病原體有稽，樂病崴 (Pyricularia oryzae)、稻米旋孢腔菌（c〇chu〇b〇ius miyabeanus) I 紋枯病菌（Corticium sasakii)m 立枯絲核菌 ⑽Μ〜/㈣㈧。卫# ·絲游磨係來自亞綱蘑菇亞綱 96430.doc 200522863 一病原體。與大多數染而不是經由孢子來 (Agaricomycetidae)之有農業意義之唯其匕真囷相比，此真菌經由菌絲體感侵襲植物。出於此原因，在穀類或水果栽培中 τ v汉杈具囷劑活性之發現不能轉移至稻米作物上。農業實務經驗已顯示，重複性及獨_性施用個別活性化合物在控制有害真菌中有許多情況會導致快速篩選出已產生對抗有疑慮活性化合物之天然或適應性抗藥性之該等真菌品系’故以有疑慮活性化合物有效控制該等真菌：不再可能。為了減小篩選出具抗性真菌品系之風險，現今通常係採用不同活性化合物之混合物來控财害真菌。藉由組合具有不同作用機制之活性化合物，可確保在相對長之時間内能成功地控制有害真菌。【發明内容】、，以在儘可能低之施藥率下有效管理抗藥性及有效控制稻米病原體為目的，本發明之一目標係提供於降低所施用之活性化合物總量下，具有抵抗有害真菌之改良作用之混合物0 吾人已發現可藉由開始所定義之混合物達成此目標。此外，吾人已發現，化合物1及化合物II之同時（組合方式或個別方式）¼用或化合物j及化合物13[之連續施用允許比施用單獨之化合物更好地控制稻米病原體。在製備該等混合物時，較佳使用純淨活性化合物I及II， 96430.doc 200522863 可視需要向其中添加對抗有害真菌或對抗其它害蟲（如昆蟲、蜘蛛類或線蟲類）之其它活性化合物，或者除草或調節生長之活性化合物或肥料。就上述意義而言，其它適合之活性化合物尤其為選自以下各群組之殺真菌劑：Dls ·, 1998, Bd. 2, S · 327; Common name: Cyclo] amine) is also known to me ^ ^ ^ eight. Commercially, it is known that cyclosporam is mainly used for the production of noble Pythium in amphibians and specialty crops (~ state is called infection. A mixture formed by the organisms and cyclosporam is summarized in a general way. It is known from EP-A 988 790 by the rabbits and daggers. This compound! The summary covered in this publication reveals the introgression φ, and the earthworm kernel is not explicitly mentioned. Therefore, compound I and The combination of cyclosporine is novel. ^, Synergistic mixtures known from A 98 8 790 are described as having a killing effect on cereal fruits and various diseases of vegetables, such as wheat and barley emblem disease, or gray mold of fruit. Fungal effectiveness. Due to the special cultivation conditions of the rice plant, the requirements that the rice green fungicide must meet are quite different from those that must be met by the fungicides that are cultivated by the guiyou fruits. There are differences in methods: In modern rice cultivation, 'in addition to the leaf application method used in many places, fungicides are applied directly to the soil during or shortly after sowing. Fungicides are absorbed into the plant through the root and Transported in the plant sap to the plant part to be protected. In contrast, in cereal or fruit cultivation, fungicides are usually applied to leaves or fruits; therefore, the systemic effects of active compounds in these crops are considerable It doesn't seem to matter much. In addition, rice pathogens are usually different from other pathogens in cereals or fruits. The pathogens of the most prevalent diseases in rice plants are well documented, Pyricularia oryzae, cochleae 〇b〇ius miyabeanus) I Corticium sasakii m. Rhizoctonia solani ⑽M ~ / ㈣㈧. ## · The silkworm mill is a pathogen from the subclass Mushroom Subclass 96430.doc 200522863. It is associated with most In contrast to the agriculturally significant spores of Agaricomycetidae, this fungus invades plants through mycelium sensation. For this reason, the τ v Chinese branch has tincture activity in cereal or fruit cultivation. The findings can not be transferred to rice crops. Agricultural practice has shown that repeated and independent application of individual active compounds in many cases in the control of harmful fungi will This led to the rapid screening of these fungal strains that have developed natural or adaptive resistance to the suspected active compound, so effective control of the fungi with the suspected active compound: no longer possible. In order to reduce the selection of resistant fungal strains Risk, currently, a mixture of different active compounds is usually used to control financially harmful fungi. By combining active compounds with different mechanisms of action, it can ensure that harmful fungi can be successfully controlled in a relatively long period of time. [Summary of the Invention] For the purpose of effectively managing drug resistance and effectively controlling rice pathogens at the lowest possible application rate, one of the objectives of the present invention is to provide a mixture having an improvement effect against harmful fungi at a reduced total amount of active compounds to be applied. It has been found that this can be achieved by the mixture defined at the outset. In addition, we have found that simultaneous application of Compound 1 and Compound II (combined or separate) or the continuous application of Compound j and Compound 13 [allows better control of rice pathogens than the application of compounds alone. In preparing these mixtures, it is preferred to use pure active compounds I and II, 96430.doc 200522863, if necessary, to add other active compounds against harmful fungi or other pests (such as insects, spiders or nematodes), or weeding Or an active compound or fertilizer that regulates growth. In the above sense, other suitable active compounds are especially fungicides selected from the following groups:

• 驢基丙胺酸（acylalanine)類，諸如本達樂（benalaxyl)、滅達樂（metalaxyl)、吱醯胺（ofurace)、歐殺斯（oxadixyl)， •胺衍生物，諸如4-十二烧基-2,6-二甲基嗎啡（&1(5丨111(^0]1) 、嗎菌靈（dodemorph)、苯鏽口定（fenpropidin)、克熱淨 (guazatine)、雙脈辛胺（iminoctadine)或三得芬 (tridemorph)， •抗菌素類，諸如環己醢亞胺（cycloheximid)、灰黃黴素 (griseofulvin)、嘉賜黴素（kasugamycin)、遊黴素（natamycin) 、保粒菌素（polyoxin)或鏈黴素（streptomycin)， • °坐類，諸如比多農（bitertanol)、漠克座（bromoconazole)• acylalanine, such as benalaxyl, metalaxyl, ofurace, oxadixyl, • amine derivatives, such as 4-dodecyl -2,6-dimethylmorphine (& 1 (5 丨 111 (^ 0] 1), dodemorph, fenpropidin, guazatine) Iminoctadine or tridemorph, • antibiotics such as cycloheximid, greoeofulvin, kasugamycin, natamycin, Polyoxin or streptomycin, ° ° Sitting classes, such as bitertanol, bromoconazole

、環克座（cyproconazole)、待凱利（difenoconazole)、二石肖克座（dinitroconazole)、恩康嗤（enilconazole)、芬克座（fenbuconazole)、氟噎克唾（fluquinconazole)、護石夕得（flusilazole)、護汰芬（flutriafol)、菲克利（hexaconazole) 、依滅列（imazalil)、依普克吐（ipconazole)、邁克尼 (myclobutanil)、平克座（penconazole)、普克利 (propiconazole)、撲克拉（prochloraz)、丙硫醇並克峻 (prothioconazole)、石夕氟口坐（simeconazole)、四凯利 (tetraconazole)、三泰芬（triadimefon)、三泰隆（triadimenol) 96430.doc 200522863 、賽福座（1：1^11111112〇16)或環菌。坐（1：14衍。01182〇16)， •二魏甲酷亞胺（dicarboximide)，諸如米克淋（myclozolin) 或撲滅寧（procymidone)， •二硫代胺基甲酸鹽類，諸如富爾邦（ferbam)、鈉乃浦 (nabam)、威百故（metam)、曱基辞乃浦（propineb)、聚胺基曱酸鹽、福美辞（ziram)或鋅乃浦（zineb)， •雜環化合物，諸如敵菌靈（anilazine)、博克利（boscalid) 、貝芬替（carbendazim)、萎鏽靈（carboxin)、嘉保信 (oxycarboxin)、賽座滅（cyazofamid)、邁隆（dazomet)、凡殺同（famoxadon)、苯胺吐_ (fenamidon)、麥穗靈 (fuberidazole)、福多寧（flutolanil)、福拉比（furametpyr) 、亞賜圃（isoprothiolan)、滅普寧（mepronil)、尼瑞莫 (nuarimol)、撲殺熱（probenazole)、百快隆（pyroquilon) 、石夕硫芬（silthiofam)、腐絕（thiabendazol)、赛氟滅 (thifluzamide)、汰敵寧（tiadinil)、三賽唾（tricyclazole) 或賽福寧（triforine)， •琐基苯基衍生物，諸如百蜗克（binapacryl)、白粉克 (dinocap)、大脫瞒（dinobuton)或石肖基鄰苯二曱酸異丙基（nitrophthalisopropyl)， •苯基°比洛，諸如拌種洛（fenpiclonil)或護汰寧 (fludioxonil)， •硫， •其它殺真菌劑，諸如酸化苯幷噻二唑-S-甲酯 (acibenzolar-S-methyl)、力口普胺（carpropamid)、四氯異 96430.doc -10· 200522863, Cyproconazole, difenoconazole, dinitroconazole, enilconazole, fenbuconazole, fluquinconazole, and stone protector ( flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, myclobutanil, penconazole, propiconazole, Prochloraz, prothioconazole, simeconazole, tetraconazole, triadimefon, triadimenol 96430.doc 200522863, Saifu (1: 11: 111111112〇16) or ring bacteria. Seated (1:14. 01182〇16), • dicarboximide, such as myclozolin or procymidone, • dithiocarbamates, such as Ful Ferbam, nabam, metam, propineb, polyurethane, ziram or zineb, Cyclic compounds such as anilazine, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, Famoxadon, fenamidon, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, neryl Nuarimol, probenazole, pyroquilon, silthiofam, thiabendazol, thifluzamide, tiadinil, sansaisal ( tricyclazole) or triforine, • Triphenyl derivatives, such as bi napacryl), dinocap, dinobuton or nitrophthalisopropyl, phenyl ° bilo, such as fenpiclonil or fludioxonil , • sulfur, • other fungicides, such as acibenzolar-S-methyl acid, carpropamid, tetrachloroiso 96430.doc -10 · 200522863

苯腈（chlorothalonil)、σ塞芬胺（cyflufenamid)、克絕 (cymoxanil)、°達菌清（diclomezin)、二氯西莫（diclocymet) 、乙黴威（diethofencarb)、護粒松（edifenphos)、乙嗟博胺（ethaboxam)、三苯醋錫（fentin-acetate)、禾草靈 (fenoxanil)、口密菌腙（ferimzone)、扶吉胺（fluazinam)、福賽得（fosetyl)、六氯苯（hexachlorobenzene)、美曲芬諾（metrafenone)、賓克隆（pencycuron)、普拔克 (propamocarb)、熱必斯（phthalide)、甲基-脫克松 (toloclofos-methyl)、五氯石肖基苯（quintozene)，或氯苯醯胺（zoxamide)， •菌胺（strobilurin)，諸如氟氧菌胺（fluoxastrobin)、苯氧菌胺（metominostrobin)、奥瑞菌胺（orysastrobin)或百克敏（pyraclostrobin)， •次續酸衍生物，諸如四氣丹（captafol)， •肉桂醯胺及類似化合物，諸如氟美醯胺（flumetover)。在根據本發明混合物之一個實施例中’可將另一殺真菌劑III或兩種殺真菌劑III及IV添加至化合物I及II中。較佳為帶有成分III之化合物I及化合物Π之混合物。尤佳者為化合物I及化合物II之混合物。同時（即組合方式或個別方式）使用化合物I及化合物π之混合物、或化合物I及化合物II顯示出具有抵抗源自子囊菌綱、半知菌綱及擔子菌綱事娜之稻米病原體之顯者作用。其可用於處理種子及作為作用於葉片及土壤之殺真菌劑之用。施用 96430.doc 11 200522863 化合物i及化合物π較佳係喷灑於葉片。施用化合物亦可以施用顆粒或灑粉於土壤上進行。該等化合物對於控制稻米植物及其種子之有害真菌（諸如平臍Η抱（Bipolaris)及內臍蠕抱（Drechs丨era)種，以及稻熱病菌）而言是非常重要的。其尤其適合於控制由稻米旋孢腔菌所引起之稻米褐斑病。此外’根據本發明化合物I及Η之組合亦適用於控制其它病原體，諸如（例如）縠類中之殼針孢菌及柄鏽菌種及蔬菜、水果及葡萄樹中之交鏈孢菌及貴腐黴菌種。【實施方式】可同時（亦即組合方式或個別方式）或連續施用化合物工及化合物II，在個別方式施用之情況下，該順序通常不會對控制措施之結果有任何影響。化合物I及化合物II通常係以重量比1〇〇:1至1 ]〇〇施用，較佳為20:1至1:50,尤其為1〇:1至1:10。若需要，可將成分III及（若適當）成分IV& 2〇:1至ι:2〇之比率添加至化合物I中。視化合物之類型及所要之效果而定，根據本發明之混合物之施藥率為5公克/公頃至2000公克/公頃，較佳為5〇至 15〇〇公克/公頃，尤其為50至750公克/公頃。相應地，化合物I之施藥率通常為}至1000公克/公頃，較佳為10至750公克/公頃，尤其為20至500公克/公頃。相應地，化合物II之施藥率通常為1至1〇〇〇公克/公頃，較佳為10至750公克/公頃，尤其為20至500公克/公頃。 96430.doc -12- 200522863 在種子處理中，混合物之施藥率通常為每100公斤種子1 至1000公克，較佳為每100公斤種子1至750公克，尤其為每 100公斤種子5至500公克。在控制稻米植物病原性有害真菌中，在植物播種之前或之後或在植物種子發芽之前或之後，藉由向種子、秧苗、植物或土壤噴霧或撒粉來進行化合物I及化合物II或化合物 I與化合物II之混合物之個別方式或組合方式施用。根據本發明之混合物或化合物I及化合物Η可轉化為慣用調配物，例如溶液、乳液、懸浮液、粉劑、散劑、糊劑及顆粒劑。該施用形式係視特定之目的而定；在每一狀況下，應確保根據本發明之化合物精細及均勻分佈。該等調配物係以已知方式、例如藉由用溶劑及/或載劑（若需要可使用乳化劑及分散劑）來增量該活性化合物而製備。適合於此目的之溶劑/助劑基本上為： -水、芳族溶劑（例如Solvesso產物、二曱苯）、石蝶（例如礦物餾份）、醇類（例如甲醇、丁醇、戊醇、节醇）、酮（例如環己酮、γ-丁内酯）、吡咯烷酮（NMp、N〇p)、乙酸酯（二醇二乙酸酯）、二醇、脂肪酸二甲醯胺、脂肪酸及脂肪酸酯。原則上，亦可使用溶劑混合物。 -載劑，諸如粉狀天然礦物（例如高嶺土（ka〇lin)、黏土、滑石、白堊）及粉狀合成礦物（例如高度分散之二氧化矽、矽酸鹽乳化劑，諸如非離子型及陰離子型乳化劑（例如聚環氧乙：)：完脂肪醇趟、烧基續酸鹽及芳基綠酸鹽）及分散劑，諸如木質素亞硫酸鹽（lignin_sulfhe)廢液 96430.doc -13- 200522863 及甲基纖維素。合適界面活性劑為木質素績酸、萘確酸、苯酚續酸、二丁基萘磺酸之鹼金屬、鹼土金屬及銨鹽、烷基芳基磺酸鹽、烧基硫酸鹽、烷基磺酸鹽、脂肪醇硫酸鹽、脂肪酸及硫酸化脂肪醇二醇i|(sulfated fatty alcohol glycol ether)類，此外有磺酸化萘及萘衍生物與甲醛之濃縮物、萘或萘磺酸與苯酚及甲醛之濃縮物、聚環氧乙烷辛基苯基醚、乙氧基化異辛基苯酚、辛基苯酚、壬基苯酚、烷基苯基聚乙二醇醚、三丁基苯基聚乙二醇醚、三硬酯醯基苯基聚乙二醇醚、烷芳基聚醚醇類、醇及脂肪醇/環氧乙烷濃縮物，乙氧基化蓖麻油、聚氧化乙烯烷基醚類、乙氧基化聚氧化丙烯、月桂醇聚乙二醇醚乙縮盤（lauryl alc〇h〇i p〇lygiyc()i acetal)、山梨糖醇酯、木質素亞硫酸鹽（lignin_sulfite)廢液及甲基纖維素。適合於製備可直接噴灑之溶液、乳液、糊劑或油狀分散液之物質為中至咼沸點之礦物油餾份，諸如煤油或柴油，此外還有煤焦油及植物原或動物原油，脂族烴、環烴及芳族經，例如甲苯、二甲苯、石壤、四氫化萘、烧基化蔡或其衍生物，乙醇、丙醇、丁醇、環己醇、環己酮、異佛爾酮（isophorone)、強極性溶劑（例如二甲基亞砜、n 甲基吡咯烧酮及水）。可藉由使活性物質與固體載劑混合或相伴性研磨來製備散劑、散佈之材料及可粉塵化之產物。、顆粒劑（例如經塗覆之顆粒、經浸潰貝心稍粒及均質顆粒） 96430.doc 200522863 可藉由使該等活性化合物結合至固體載劑而製備。固體載劑之貫例為：礦物土，諸如二氧化石夕凝膠、石夕酸鹽、滑石、 N嶺土、美國活性白土（attaclay)、石灰石、石灰、白堊、紅玄武土（bole)、黃土、黏土、白雲石、矽藻土、硫酸鈣、硫酸鎮、氧化鎂；粉狀合成材料；肥料，諸如（例如）硫酸銨、碗酸銨、硝酸銨、尿素；及植物原產物，諸如穀粉、樹皮粉、木粉及堅果殼粉、纖維素散劑及其它固體載劑。一般而言，該等調配物包含0 01至95重量％、較佳為〇」至90重量％之活性化合物。採用9〇%至ι〇〇%、較佳為％%至 1〇〇%之純度（根據NMR光譜）之該等活性化合物。以下為调配物之實例：1 ·以水稀釋之產品 A) 水溶性濃縮物（water-soluble concentrates ; SL) 將重量比10份之活性化合物溶解於水中或水溶性溶劑中。另一選擇為添加濕潤劑或其它助劑。該活性化合物在以水稀釋時溶解。 B) 分散性濃縮物（dispersible concentrates ; DC) 將重量比20份之活性化合物溶解於添加有例如聚乙烯吡咯烷酮之分散劑之環己酮中。以水稀釋產生分散液。 c)可乳化之濃縮物（emulsifiable c〇ncent]rates ; EC) 將重量比15份之活性化合物溶解於添加有十二烷基苯磺酸鈣及蓖麻油乙氧基化物（在每一狀況下5%濃度）之二甲苯中。以水稀釋產生乳液。 D)乳液（EW、E0) 將重量比40份之活性化合物溶解於添加有十二烧基苯績 96430.doc -15- 200522863 酸#5及蓖麻油乙氧基化物（在每一狀況下5 %濃度）之二甲苯中。將該混合物藉由乳化機（Ultraturrax)引入水中且製成均質乳液。以水稀釋產生乳液。 E) 懸浮液（SC、OD) 在攪拌型球磨機中，將重量比20份之活性化合物添加分散劑、濕潤劑及水或有機溶劑進行粉碎以得到精細之活性化合物懸浮液。以水稀釋產生該活性化合物之穩定懸浮液。 F) 水分散性顆粒劑及水溶性顆粒劑（wg、SG) 將重量比50份之該等活性化合物添加分散劑及濕潤劑一起精細研磨且藉助於技術設備（例如擠壓、喷霧塔、流體化床）製成水分散性或水溶性顆粒劑。以水稀釋產生該活性化合物之穩定之分散液或溶液。 G) 水分散性散劑及水溶性散劑（WP、SP) 將重量比75份之該等活性化合物添加分散劑、濕潤劑及二氧化矽凝膠在一台轉子-定子研磨機中進行研磨。以水稀釋產生該活性化合物之穩定之分散液或溶液。 2.不經稀釋施用之產品 H) 可粉塵化散劑（dustable powders ; DP) 將重1比5份該等化合物精細研磨，且與95%經精細切分之咼嶺土完全混合。以此方式產生可粉塵化之產物。 I) 顆粒劑（GR、FG、GG、MG) 將重ΐ比0.5份之該等化合物精細研磨，且與95·5%載劑結合。目前方法為擠壓、喷霧乾燥或流體化床。以此方式產生不經稀釋施用之顆粒。 96430.doc -16- 200522863 J)ULV 溶液（UL) 將重量比10份之該等化合物溶解 T本之有機溶劑中。以此方式產生不經稀釋施用之產物。該等活性化合物可藉助於噴灑、霧化作用、粉塵化作用、散佈或傾倒而以其調配物形式或從中所製備之使用形式 (例如可直接錢之溶液、散劑、料液或分散液、乳液^ 油狀分散液、糊劑、可粉塵化之產物、散佈材料或顆粒劑之形式）來使用。該等使用形式完全視期望之目的而定·所期望之目的係在所有狀況下確保根據本發明之該等活性化合物最佳之可能分佈。將乳液濃縮物、糊劑或可濕性散劑（可喷灑性散劑、油狀分散液）藉由添加水可製傷含水之制形式。為製備乳液、糊劑或油狀分散液’可藉助於濕潤劑、增黏劑、分散劑或乳化劑將該等或溶解於油或溶劑中之物f在水中均質化。另-種方式是，亦可製備由活性物質、濕潤劑、增黏劑、分散劑或乳化劑及（若適當）溶劑或油所組成4濃縮物，並將該等濃縮物以水適當稀釋。在即時使用（ready-t0_use)製劑中，該等活性化合物濃度可在相對廣泛範圍内變化。一般而言，該等濃度為〇〇〇〇1 至10%，較佳為〇.〇丨至1%。該等活性化合物亦可成功地用於超低容量（uhra_1〇w_ volume)方法（ULV)中，有可能施用包含超過％重量％之活性化合物之調配物，或甚至施用不含添加劑之活性化合物。若適當在立即使用之前（桶混劑）可將各種類型之油、濕 96430.doc 200522863 潤劑、佐劑、料劑、殺真菌劑、其它殺蟲劑或殺菌劑添力至活（'生化合物。通常可以丨：丨0至丨〇:丨之重量比率將該等藥劑與根據本發明之藥劑相混合。以殺真菌有效量之化合物！及Η之混合物或（在個別方式施用之狀況下）化合物〗及„藉由處理有害真菌或處理欲保持避免真菌之害之植物、種子、土壤、地區、材料或空間來施用化合物I及Π或其混合物或其對應調配物。可在由有害真菌引起感染之前或之後進行施用。化合物及混合物之殺真菌作用可藉由以下實驗加以說明：將活性化合物單獨地或結合地製備為丙酮或DMS0中具有0.25重i %活性化合物之儲備溶液。向此溶液中添加i重量％之乳化劑Uniperol® EL(具有基於乙氧基化烷基苯酚之礼化及分散作用之濕潤劑），且該溶液以水稀釋至所要濃度。使用實例-對抗由稽次漩癌屋彦引起之稻米褐斑病之活性’保護性施用栽培品種”Tai-Nong 67”盆栽稻米秧苗之葉片以具有下述活性化合物濃度之含水懸浮液喷灑至溢流點（run〇ff point)。第二天，將該等稻米秧苗以禮米漩癌避磨水孢子懸浮液進行接種。然後將測試植物於22-24。(：下及空氣相對濕度為95-99%之空氣調節室（ciimatized chamber)内置放6 天。然後可視覺測定葉片上受感染之發展程度。藉由測定受感染植物之百分比來實施評估。該等百分比 96430.doc •18- 200522863 轉換為效力。使用如下Abbot公式來計算效力⑦）： Ε=(1-α/β)· 1〇〇 α對應於按％計之經處理植物之真菌感染，且 β對應於按％計之未經處理（對照組）之植物之真菌感染效力為〇意謂經處理之植物之感染水平與未經處理之對照植物之感染水平—致；效力為1()()意謂經處理之植物未為感染。又使用 c〇lby公式（Colby，R s，Weeds，15, 2〇_22, 196⑽定了活性化合物之混合物之預期效力且與所觀察之比較。Chlorothalonil, σflufenamid, cymoxanil, diclomezin, dilocymet, diethofencarb, edifenphos, Ethaboxam, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, hexachlorobenzene (Hexachlorobenzene), metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene ), Or zoxamide, • strobilurin, such as fluoxastrobin, metominostrobin, orysastrobin, or pyraclostrobin, • Hyaluronic acid derivatives, such as captafol, cinnamamide and similar compounds, such as flumetover. In one embodiment of the mixture according to the invention ' another fungicide III or two fungicides III and IV may be added to compounds I and II. Mixtures of compound I and compound II with component III are preferred. Especially preferred is a mixture of compound I and compound II. Simultaneous (ie, combined or individual) use of a mixture of compound I and compound π, or compound I and compound II has shown resistance to rice pathogens derived from Ascomycetes, Deuteromycetes and Basidiomycetes effect. It can be used to treat seeds and as a fungicide on leaves and soil. Application 96430.doc 11 200522863 Compound i and compound π are preferably sprayed on the leaves. Application of the compounds can also be carried out by applying granules or dusting the soil. These compounds are important for controlling harmful fungi of rice plants and their seeds, such as Bipolaris and Drechsera species, and rice fever bacteria. It is particularly suitable for controlling brown spot disease of rice caused by H. oryzae. In addition, the combination of compounds I and Η according to the invention is also suitable for controlling other pathogens, such as, for example, C. spp. And Puccinia spp. And spp. In vegetables, fruits and grapevines Pythium species. [Embodiment] The compound method and the compound II can be applied simultaneously (that is, in a combined manner or in an individual manner) or continuously. In the case of individual application, the order usually does not have any effect on the results of the control measures. Compound I and compound II are usually applied in a weight ratio of 100: 1 to 1], preferably 20: 1 to 1:50, and especially 10: 1 to 1:10. If necessary, component III and (if appropriate) component IV & 20: 1 to ι: 20 can be added to compound I at a ratio. Depending on the type of compound and the desired effect, the application rate of the mixture according to the invention is 5 g / ha to 2000 g / ha, preferably 50 to 150,000 g / ha, especially 50 to 750 g / Ha. Accordingly, the application rate of Compound I is usually from} to 1,000 g / ha, preferably from 10 to 750 g / ha, especially from 20 to 500 g / ha. Accordingly, the application rate of Compound II is usually 1 to 1,000 g / ha, more preferably 10 to 750 g / ha, especially 20 to 500 g / ha. 96430.doc -12- 200522863 In seed treatment, the application rate of the mixture is usually 1 to 1000 g per 100 kg of seed, preferably 1 to 750 g per 100 kg of seed, especially 5 to 500 g per 100 kg of seed . In controlling phytopathogenic harmful fungi of rice, Compound I and Compound II or Compounds I and II are sprayed or dusted on seeds, seedlings, plants or soil before or after planting or before or after germination of plant seeds. The mixture of compounds II is applied individually or in combination. The mixtures or compounds I and VII according to the invention can be converted into customary formulations such as solutions, emulsions, suspensions, powders, powders, pastes and granules. The application form depends on the particular purpose; in each case, a fine and uniform distribution of the compound according to the invention should be ensured. These formulations are prepared in a known manner, for example, by extending the active compound with a solvent and / or carrier (emulsifiers and dispersants if necessary). The solvents / auxiliaries suitable for this purpose are basically:-water, aromatic solvents (eg Solvesso products, dibenzobenzene), stone butterflies (eg mineral fractions), alcohols (eg methanol, butanol, pentanol, Benzyl alcohol), ketones (such as cyclohexanone, γ-butyrolactone), pyrrolidone (NMp, Nop), acetate (diol diacetate), glycols, fatty acid dimethylformamide, fatty acids and Fatty acid esters. In principle, solvent mixtures can also be used. -Vehicles such as powdered natural minerals (such as kaolin, clay, talc, chalk) and powdered synthetic minerals (such as highly dispersed silica, silicate emulsifiers, such as nonionic and anionic Type emulsifiers (such as polyethylene oxide :): finished fatty alcohols, burned acid salts and aryl chlorates) and dispersants, such as lignin_sulfhe waste liquid 96430.doc -13- 200522863 and methyl cellulose. Suitable surfactants are lignin, naphthoic acid, phenolic acid, alkali metals, alkaline earth metals and ammonium salts of dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonic acids Acid salts, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, in addition to sulfonated naphthalene and naphthalene derivatives and formaldehyde concentrates, naphthalene or naphthalenesulfonic acid with phenol and Formaldehyde concentrate, polyethylene oxide octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyethylene glycol ether, tributylphenyl polyethylene Glycol ethers, tristearyl fluorenyl phenyl polyethylene glycol ethers, alkaryl polyether alcohols, alcohols and fatty alcohol / ethylene oxide concentrates, ethoxylated castor oil, polyoxyethylene alkyl ethers Type, ethoxylated polyoxypropylene, lauryl alc0h〇ip〇lygiyc () i acetal, sorbitol ester, lignin_sulfite waste liquid And methyl cellulose. Suitable for the preparation of solutions, emulsions, pastes or oily dispersions that can be sprayed directly are medium to boiling point mineral oil fractions, such as kerosene or diesel, in addition to coal tar and vegetable or animal crude oils, aliphatic Hydrocarbons, cyclic hydrocarbons, and aromatics, such as toluene, xylene, rocky soil, tetralin, calcined Chai or its derivatives, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophor Isophorone, strong polar solvents (such as dimethyl sulfoxide, n-methylpyrrolidone and water). Powders, dispersing materials and dustable products can be prepared by mixing the active substance with a solid carrier or concomitantly grinding. Granules (such as coated granules, impregnated shells, and homogeneous granules) 96430.doc 200522863 can be prepared by combining these active compounds with a solid carrier. Common examples of solid carriers are: mineral soils, such as sulphur dioxide gel, oxalate, talc, N ridge clay, American active clay (attaclay), limestone, lime, chalk, red basalt (bole), Loess, clay, dolomite, diatomaceous earth, calcium sulfate, sulphate, magnesium oxide; powdery synthetic materials; fertilizers such as, for example, ammonium sulfate, ammonium bowl, ammonium nitrate, urea; and raw plant products such as cereal flour , Bark powder, wood powder and nut shell powder, cellulose powder and other solid carriers. In general, these formulations contain from 0.01 to 95% by weight, preferably from 0 "to 90% by weight, of the active compound. These active compounds are used in a purity (from NMR spectrum) of 90% to 100%, preferably %% to 100%. The following are examples of formulations: 1. Products diluted with water A) Water-soluble concentrates (SL) Dissolve 10 parts by weight of the active compound in water or a water-soluble solvent. Another option is to add humectants or other auxiliaries. The active compound is dissolved when diluted with water. B) Dispersible concentrates (DC) Dissolve 20 parts by weight of the active compound in cyclohexanone to which a dispersant such as polyvinylpyrrolidone is added. Dilution with water produces a dispersion. c) Emulsifiable concentrates; EC) Dissolve 15 parts by weight of active compound in calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% concentration) in xylene. Dilution with water produces an emulsion. D) Emulsion (EW, E0) Dissolve 40 parts by weight of the active compound in dodecylbenzene. 96430.doc -15- 200522863 Acid # 5 and castor oil ethoxylate (5 in each case) % Concentration) in xylene. This mixture was introduced into water by an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water produces an emulsion. E) Suspension (SC, OD) In a stirred ball mill, 20 parts by weight of the active compound is added with a dispersant, a wetting agent, and water or an organic solvent to pulverize to obtain a fine active compound suspension. Dilution with water produces a stable suspension of the active compound. F) Water-dispersible granules and water-soluble granules (wg, SG) 50 parts by weight of these active compounds are added with a dispersant and a wetting agent to finely grind them together with the aid of technical equipment (such as extrusion, spray tower, Fluidized bed) into water-dispersible or water-soluble granules. Dilution with water produces a stable dispersion or solution of the active compound. G) Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of these active compounds are added with a dispersant, a wetting agent, and a silica gel for grinding in a rotor-stator mill. Diluting with water produces a stable dispersion or solution of the active compound. 2. Products to be applied without dilution H) dustable powders (DP) Will finely grind 1 to 5 parts of these compounds, and completely mix with 95% of finely divided molybdenum clay. In this way a dustable product is produced. I) Granules (GR, FG, GG, MG) These compounds are finely ground to a weight ratio of 0.5 parts and combined with a 95.5% carrier. Current methods are extrusion, spray drying or fluidized beds. In this way, granules are applied without dilution. 96430.doc -16- 200522863 J) ULV solution (UL) Dissolve 10 parts by weight of these compounds in organic solvents. In this way the product is applied without dilution. The active compounds can be sprayed, atomized, dusted, dispersed or poured in the form of their formulations or the use forms prepared therefrom (e.g., solutions, powders, feeds or dispersions, emulsions, which can be used directly) ^ In the form of oily dispersions, pastes, dustable products, dispersing materials or granules). The use forms depend entirely on the intended purpose. The desired purpose is to ensure in all cases the best possible distribution of the active compounds according to the invention. Emulsion concentrates, pastes or wettable powders (sprayable powders, oily dispersions) can be made into water-containing forms by adding water. To prepare an emulsion, paste or oily dispersion ', the substance f or a substance dissolved in an oil or a solvent f may be homogenized in water by means of a wetting agent, a thickener, a dispersant or an emulsifier. Alternatively, 4 concentrates consisting of an active substance, a humectant, a thickener, a dispersant or an emulsifier, and (if appropriate) a solvent or oil may be prepared, and these concentrates may be appropriately diluted with water. In ready-to-use formulations, the concentrations of these active compounds can vary over a relatively wide range. Generally, these concentrations are from 0.001 to 10%, preferably from 0.001 to 1%. These active compounds can also be successfully used in the ultra low volume (uhra_10w_volume) method (ULV), it is possible to apply formulations containing more than% by weight of active compound, or even to apply active compounds without additives. If appropriate, you can add various types of oils, wet 96430.doc 200522863 emollients, adjuvants, ingredients, fungicides, other pesticides or fungicides to live ('Bio Compounds. These agents can usually be mixed with the agents according to the invention in a weight ratio of 丨: 丨 0 to 丨 0: 丨. A fungicidal effective amount of the compound! And a mixture of tadpoles or (in the case of individual application) ) Compounds and „Apply compounds I and Π or their mixtures or their corresponding formulations by treating harmful fungi or plants, seeds, soil, areas, materials, or spaces that are to be protected from fungal damage. The application is performed before or after the infection is caused. The fungicidal action of the compounds and mixtures can be illustrated by the following experiments: The active compounds are prepared individually or in combination as acetone or DMS0 stock solutions with 0.25 wt% active compound. To this Add iwt% of emulsifier Uniperol® EL (wetting agent with etiquette and dispersion based on ethoxylated alkylphenol) to the solution, and the solvent Dilute with water to the desired concentration. Example of use-activity against rice brown spot disease caused by Kojima Kazuya "protective application of cultivar" Tai-Nong 67 "potted rice seedlings with the following active compound concentration The aqueous suspension was sprayed to the runoff point. The next day, the rice seedlings were inoculated with a rice spore cancer avoiding water spore suspension. The test plants were then placed at 22-24. : Built-in air-conditioning chamber (ciimatized chamber) with relative air humidity of 95-99% for 6 days. Then the degree of infection development on the leaves can be visually measured. Evaluation is performed by measuring the percentage of infected plants. These The percentage 96430.doc • 18- 200522863 is converted to potency. The potency is calculated using the following Abbot formula ⑦): E = (1-α / β) · 100α corresponds to the fungal infection of the treated plants in%, and β corresponds to the fungal infection efficacy of the untreated (control) plant in%, which means that the infection level of the treated plant and the infection level of the untreated control plant are the same; the efficacy is 1 () ( ) Means The treated plants were not infected. The expected efficacy of a mixture of active compounds was determined using the Colby formula (Colby, R s, Weeds, 15, 20-22, 196) and compared with the observed.

Colby公式： E=x+y—x.y/1〇〇 E當使用濃度咖之活性化合物八糾之混合物時，以未經處理之對照組之％表示之預期效力 X當使用濃度a之活性化合物A卑〜八吋’ U未經處理之對照組之 °/〇表示之效力 y當使用濃度b之活性化合物b時，以未經處理之對照組之 °/〇表示之效力使用自EP_A 988 790中所描沭夕供於社〜人” ^ 田处之裱醯菌胺混合物已知之化合物A與B作為對比性化合物： 96430.doc > 19- 200522863Colby's formula: E = x + y—xy / 1〇〇E when using a mixture of the active compound of the concentration of eight, the expected efficacy expressed as% of the untreated control group X when the active compound A of the concentration a is used U ~~ 8 inches' U Efficacy expressed in ° / 〇 of untreated control group y When using active compound b at a concentration of b, Efficacy expressed in ° / 〇 of untreated control group is used from EP_A 988 790 The description is given to the society ~ people "^ The compound A and B known as the comparative compound of the bacteriocin mixture in the field: 96430.doc > 19- 200522863

表A-單獨活性化合物實例活性化合物喷灑溶液中之活性化合物濃度 [ppm] 以未經處理之對照組之％表示之效力 1 對照組(未處理） - (85%感染） 2 I 16 4 17 5 3 11(環醯菌胺） 16 4 0 0 4 對比性化合物A 16 4 53 29 5 對比性化合物B 16 4 41 5 表B-根據本發明之混合物實例活性化合物之混合物濃度混合比觀察效力計算效力*) 6 I+II 16+4 ppm 4:1 76 17 7 I+II 16+16 ppm 1:1 88 17 8 I+II 4+16 ppm 1:4 70 5 *)使用Colby公式所計算之效力 96430.doc -20- 200522863 表c-對比測試實例活性化合物之混合物濃度混合比觀察效力計算效力1) 9 A+II 16+4 ppm 4:1 29 53 10 A+II 16+16 ppm 1:1 17 53 11 A+II 4+16 ppm 1:4 17 29 12 B+II 16+4 ppm 4:1 53 41 13 B+II 16+16 ppm 1:1 53 41 14 B+II 4+16 ppm 1:4 41 5Table A-Examples of active compounds alone Active compound concentration in active compound spray solution [ppm] Efficacy expressed as% of untreated control group 1 Control group (untreated)-(85% infection) 2 I 16 4 17 5 3 11 (Cyclosporine) 16 4 0 0 4 Comparative compound A 16 4 53 29 5 Comparative compound B 16 4 41 5 Table B-Mixture examples according to the invention Mixture concentration of active compounds Mixture ratio Observation of efficacy calculation Potency *) 6 I + II 16 + 4 ppm 4: 1 76 17 7 I + II 16 + 16 ppm 1: 1 88 17 8 I + II 4 + 16 ppm 1: 4 70 5 *) Calculated using Colby's formula Efficacy 96430.doc -20- 200522863 Table c- Comparative test example Active compound mixture concentration Mix ratio Observation of efficacy Calculate efficacy 1) 9 A + II 16 + 4 ppm 4: 1 29 53 10 A + II 16 + 16 ppm 1: 1 17 53 11 A + II 4 + 16 ppm 1: 4 17 29 12 B + II 16 + 4 ppm 4: 1 53 41 13 B + II 16 + 16 ppm 1: 1 53 41 14 B + II 4 + 16 ppm 1: 4 41 5

96430.doc -21 - 1 使用Colby公式所計算之效力測試結果展示：儘管對比性化合物作為獨立化合物、在相同之施用率下比化合物I更加有效，但是根據本發明之混合物歸因於強大之協同作用而比自EP-A 988 790已知之環醯菌胺混合物顯著地更加有效。96430.doc -21-1 The potency test results calculated using the Colby formula show that although the comparative compound is more effective than the compound I as an independent compound at the same application rate, the mixture according to the invention is attributed to the strong synergy It is significantly more effective than the cyclosporine mixture known from EP-A 988 790.

Claims

200522863 X. Scope of patent application: L A fungicidal mixture for controlling rice pathogens, the mixture contains synergistically effective amounts of: 1) Triazole pyrimidine derivatives of formula I

And 2) fenhexamid of formula 11

2. The fungicidal mixture according to claim 1, comprising a weight ratio of the formula terrestrial compound to the formula trioxide compound of 100 ·· 1 to 1: 100. σ 3 ·-a fungicidal composition 'which comprises a liquid or solid carrier and a compound as claimed or 2 of the above. 4. A method for controlling rice pathogenic harmful fungi, comprising treating the orthobacteria, bean living environment or protecting seeds, soil or plants from fungi with an effective amount of a compound such as the item 丨 and combining them . 〃 5. The method according to claim 4, wherein the combination of the compounds and the combination of the compounds are applied simultaneously in a combination or individually, or continuously. 6. 4 μ Method of finding item 4 'wherein the application amount of the mixture of item j or 2 is 96430.doc 200522863 from 5 g / ha to 2000 g / ha. The method as claimed in item 4 or 5, wherein the amount of the mixture of eight Tn clothing items 1 or 2 is from 1 to 1000 g per 100 kg of seeds, such as φ Λ Λ human ". A compound as claimed is suitable for H control, and it is a composition used for the preparation of a king hundred harmful fungi. 96430.doc 200522863 VII. Designated representative map: (1) The designated representative map of this case is: (none) (II) The component symbols of this representative map are briefly explained: 8. If there is a chemical formula in this case, please disclose the one that can best show the characteristics of the invention. Chemical formula:

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