TW201143615A

TW201143615A - Novel pyridazine derivatives

Info

Publication number: TW201143615A
Application number: TW99144718A
Authority: TW
Inventors: Stephan Trah; Clemens Lamberth; Francesca Perruccio
Original assignee: Syngenta Participations Ag
Priority date: 2009-12-22
Filing date: 2010-12-20
Publication date: 2011-12-16
Also published as: GB0922376D0; WO2011076501A1; UY33133A; AR079548A1

Abstract

The present invention relates to novel pyridazine derivatives of formula (I) as active ingredients which have microbiocidal activity, in particular fungicidal activity.

Description

201143615 六、發明說明：【發明所屬之技術領域】本發明係關於作為活性成分之新賴。答口井衍生物，其具有敘微生物活性’尤其是殺真菌活性。本發明亦關於此等活性成分之製備；關於用作製備此等活性成分之中間物的新穎雜衍生物，關於此等新賴中間物之製備；關於包含至少-種該等新穎活性成分的農業化學組成物；關於此等組成物之製備；及關於該等活性成分或組成物在農業或園藝中用於控制或預防植物'收穫之食用作物、種子或非生命物質被植物病原性微生物（較佳是真菌）感染之用途。【先前技術】國際專利申請案 WO 2005/121104、WO 2006/001175、 WO 2007/066601、WO 2007/080720、WO 2008/009405 及 W〇 2__94G6中提出用作殺真®劑之❽井衍生物。需要控制真菌之替代性方法。新化合物較佳可具有改良之殺真菌特性’諸如改良之功效、&良之選擇性、產生抗性之傾向性低或具有針對更廣譜真菌之活性。化合物可經更適宜地調配，或在作用部位提供更有效傳遞及滯留，或可更輕易地生物降解。特定言之，需要具有改良治療作用的殺真菌劑。令人驚言牙的是已發現本發明之嗒畊化合物展現出乎意料的殺真菌活性，包括出乎意料的治療活性，且因此適合在農業中用作作物保護劑來對抗或預防真菌感染。 4 201143615 【發明内容j 本發明提供一種式（1)化合物201143615 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a new one as an active ingredient. A well derivative having a microbial activity, especially a fungicidal activity. The invention also relates to the preparation of such active ingredients; to novel hetero-derivatives useful as intermediates in the preparation of such active ingredients, to the preparation of such novel intermediates; to agriculture comprising at least one such novel active ingredient a chemical composition; for the preparation of such compositions; and for the use of such active ingredients or compositions in agricultural or horticultural use for controlling or preventing plant harvesting of food crops, seeds or non-living substances by phytopathogenic microorganisms (compare Good is the use of fungal infections. [Prior Art] A well derivative which is used as a killer agent is proposed in the international patent applications WO 2005/121104, WO 2006/001175, WO 2007/066601, WO 2007/080720, WO 2008/009405 and W〇 2__94G6. There is a need to control alternative methods of fungi. The novel compound preferably has improved fungicidal properties such as improved efficacy, & good selectivity, low resistance to development, or activity against a broader spectrum of fungi. The compounds may be formulated more suitably, or provide more efficient delivery and retention at the site of action, or may be more readily biodegradable. In particular, there is a need for a fungicide having an improved therapeutic effect. Surprisingly, it has been found that the mashing compounds of the present invention exhibit unexpected fungicidal activity, including unexpected therapeutic activity, and are therefore suitable for use as crop protection agents in agriculture to combat or prevent fungal infections. 4 201143615 [Summary of the Invention] The present invention provides a compound of the formula (1)

RR

R4 其中 R為甲基或乙基； R2為Η、氟或氯； R3為氟或氯； R為氟或曱氧基；及 r5為氯或曱氧基；或其農業化學上可用之鹽形式。本發明包括式⑴化合物之 ,>θ ^ Λ, i Γ犯之異構形式及其牛例而s ’滞轉異構體可由於圍繞單鍵限制性旋轉而產生。在一較佳具體實例中： R1為甲基； R2為Η或氟； R3為氟或氯； r4為氟或甲氧基；且 201143615 R5為氣。較佳個別化合物選自 3-氣-6-曱基-5-(6-三氟曱基0比啶·3_*)·4_(2,4,6-三氟苯基）嗒〇井； 3-氣-5-(6-二氟曱基吡啶_3_基）·6甲基_4_(2,4,6-三氟笨基）嗒口井； 3-氣-4-(2,6-二氟-4-甲氧基苯基）_5_(6_二氟曱基α比啶_3· 基）-6·甲基荅D井； 3-氣-4-(2,6-二氟-4-甲氧基笨基）_6_甲基-5-(6-三氟甲基吼啶 • 3 -基）-塔α井； 3- 甲氧基-6-甲基- 5-(6-三氟曱基咐>咬-3-基）-4-(2,4,6-三氟苯基）°荅畊；及 4- (6-二氟甲基吡啶-3-基）-6-f氧基-3-f基-5-(2,4,6-三說苯基）"荅α井。【實施方式】本發明化合物可根據以下反應流程製備’其中除非另外說明，否則各變數Ri、r2、R3及R4之定義如上文關於式 (1)化合物所定義。式（1.2)化合物可藉由用甲醇及鹼或用曱醇鈉轉化式 (1.1 )化合物而獲得。 6 201143615R4 wherein R is methyl or ethyl; R2 is fluorene, fluoro or chloro; R3 is fluoro or chloro; R is fluoro or decyloxy; and r5 is chloro or decyloxy; or an agrochemically useful salt form thereof . The present invention includes the compound of the formula (1), > θ ^ Λ, i Γ 异构异构异构及其及其及其及其及其及其及其及其及其及其而 ’ ’ ’ 滞滞滞。。。。。。。。。。。。。。。 In a preferred embodiment: R1 is methyl; R2 is deuterium or fluorine; R3 is fluorine or chlorine; r4 is fluorine or methoxy; and 201143615 R5 is gas. Preferably, the individual compound is selected from the group consisting of 3-gas-6-mercapto-5-(6-trifluorodecyl 0-pyridyl·3_*)·4_(2,4,6-trifluorophenyl) anthracene; - gas-5-(6-difluorodecylpyridine_3_yl)·6 methyl_4_(2,4,6-trifluorophenyl) 嗒 well; 3- gas -4-(2,6 -difluoro-4-methoxyphenyl)_5_(6-difluoroindolyl α-pyridyl_3·yl)-6·methylindole D; 3-gas-4-(2,6-difluoro -4-methoxyphenyl)_6-methyl-5-(6-trifluoromethylacridine•3-yl)-tower α well; 3-methoxy-6-methyl-5-(6 -trifluoromethyl hydrazine> -3-yl)-4-(2,4,6-trifluorophenyl) ° arable; and 4-(6-difluoromethylpyridin-3-yl)- 6-foxy-3-f-yl-5-(2,4,6-tri-phenyl) "荅α well. [Embodiment] The compound of the present invention can be produced according to the following reaction scheme' wherein, unless otherwise stated, the definitions of each of the variables Ri, r2, R3 and R4 are as defined above for the compound of the formula (1). The compound of the formula (1.2) can be obtained by converting the compound of the formula (1.1) with methanol and a base or with sodium decylate. 6 201143615

ch3〇h,鹼或 NaOC4Ch3〇h, base or NaOC4

式（1.1)化合物可藉由用氧氣化磷或亞硫醯氯轉化式 (1.3)化合物而獲得。The compound of the formula (1.1) can be obtained by converting a compound of the formula (1.3) with oxygenated phosphorus or sulfinium chloride.

Ρ〇〇3 或 SOC12Ρ〇〇3 or SOC12

式（1.3 )化合物可藉由用肼衍生物（例如水合肼）轉化式（II)化合物而獲得。The compound of the formula (1.3) can be obtained by converting a compound of the formula (II) with an anthracene derivative such as hydrazine hydrate.

(1.3) 式（II)化合物可藉由用氧、空氣或3-氣過苯甲酸氧化轉化式（III)化合物而獲得。 201143615(1.3) The compound of the formula (II) can be obtained by oxidizing a compound of the formula (III) with oxygen, air or 3-air perbenzoic acid. 201143615

異丙基乙胺、1，5-二氮雜雙環[4.3.0]壬-5-烯或1,8-二氮雜雙環[5.4.0]十一-7-烯）轉化式（IV)化合物（其中R1、R2、 R3及R4如關於式（I )所定義）而獲得。Isopropylethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene) (IV) Compounds wherein R1, R2, R3 and R4 are as defined for formula (I) are obtained.

式（IV )化合物可藉由用式（VI)化合物及鹼（例如吡啶、三乙胺、二異丙基乙胺、1,5-二氮雜雙環[4.3.0]壬-5-烯或1，8-二氮雜雙環[5.4.0]十一-7-烯）轉化式（V)化合物 (其中Hal為鹵素，較佳氯或溴）而獲得。The compound of the formula (IV) can be obtained by using a compound of the formula (VI) and a base (for example, pyridine, triethylamine, diisopropylethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-Diazabicyclo[5.4.0]undec-7-ene) is obtained by converting a compound of the formula (V) wherein Hal is a halogen, preferably chlorine or bromine.

8 201143615 式（Ι·3)、（ II)、（ ΠΙ)及（IV)之化合物形成本發明之其他態樣。式（I )化合物可以未修飾形式使用，或較佳與調配技術中通常所用之載劑及佐劑一起使用。因此’本發明另外提供用於控制及防止植物病原性微生物的組成物，其包含式（I)化合物及惰性載劑；及控制或預防有用植物被植物病原性微生物感染之方法，其中向植物、其部分或其所在地施用包含式（1)化合物作為活性成分’及包含惰性載劑的組成物。此外，本發明可用於保護非生命物質（例如木材、牆板及塗料）免受真菌侵襲。為此目的，式（I)化合物及惰性載劑宜以已知方式調配成可軟化濃縮物、可塗佈糊劑、可直接錢或可膨服溶液、稀乳液、可濕潤粉末、可溶性粉末、粉劑、顆粒以及膠囊化物（例如在聚合物質中）。如同組成物之類型一般，可根據所欲目標及主要情形來選擇施用方法（諸如喷灑、霧化、撒佈、散播、塗佈或傾倒）。組成物亦可含有其他佐劑，諸如穩定劑、消泡劑、黏度調節齊卜黏合劑或乳白劑以及肥料、微量營養素施斗、成 π 胥I供應物或獲得特定作用之其他調配物。適合載劑及佐劑可為固體志该舻Bm ~ u避或液體且為適用於調配技術之物質’例如天然或再生礦妝暂、六m v u 订王貭物备、浴劑、分散劑、濕潤劑、增黏劑、增稠劑、黏合劑或肥祖。兮楚# 7 ,8 201143615 Compounds of the formula (Ι·3), (II), (ΠΙ) and (IV) form other aspects of the invention. The compound of formula (I) may be used in unmodified form or preferably together with carriers and adjuvants conventionally employed in the formulation techniques. Accordingly, the present invention further provides a composition for controlling and preventing phytopathogenic microorganisms, comprising a compound of the formula (I) and an inert carrier; and a method for controlling or preventing infection of a useful plant by a plant pathogenic microorganism, wherein the plant, A portion comprising a compound of formula (1) as an active ingredient' and a composition comprising an inert carrier is applied to a portion or a locus thereof. In addition, the present invention can be used to protect non-living substances such as wood, wallboard and paint from fungal attack. For this purpose, the compound of the formula (I) and the inert carrier are preferably formulated in a known manner into a softenable concentrate, a coatable paste, a direct or extendable solution, a dilute emulsion, a wettable powder, a soluble powder, Powders, granules and capsules (for example in polymeric substances). As with the type of the composition, the application method (such as spraying, atomizing, spreading, spreading, coating or pouring) can be selected according to the desired target and the main situation. The composition may also contain other adjuvants such as stabilizers, defoamers, viscosity-adjusting binders or opacifiers, as well as fertilizers, micronutrient fights, π 胥I supplies or other formulations that achieve a particular effect. Suitable carriers and adjuvants can be solids, such as Bm ~ u, or liquids, and are suitable for blending technology. For example, natural or reclaimed minerals, six mvu, kings, baths, dispersants, moisturizing Agent, tackifier, thickener, binder or fat progenitor.兮楚# 7 ,

J ·^巴枓。邊荨载劑例如描述於WO 201143615 97/33890 中。式⑴化合物或包含式⑴化合物作為活性成分及包含情性載劑的組成物可與其他化合物同時或連續施用於欲處理之植物所在地或植物。此等其他化合物可為例如肥：或微量營養素供應物或影響植物生長之其他製劑。其亦可為選擇〖生除草劑、植物生長調節劑以及殺昆蟲劑、殺真菌劑、殺細菌劑、殺線蟲劑、殺軟體動物藥劑或數種此等製劑之混合物’必要時與其他載劑、界面活性劑或調配技術中常用之促施用佐劑一起。施用式（I)化合物或包含式（Z)化合物作為活性成分，及包含惰性載劑之組成物的較佳方法為葉面施用。施用頻率及施用率取決於被相應病原體感染之風險。然而，式（1) 化合物亦可藉由用液體調配物浸潤植物所在地，或藉由向土壤施用固體形式（例如顆粒形式）之化合物（土壌施用）而經由土壤（系統性作用）穿過根滲透植物。在水稻作物中’該等顆粒可施用於水稻田（fl〇〇ded rice field )。亦可藉由用殺真菌劑之液體調配物浸潰種子或塊莖或用固體調配物塗佈種子或塊莖而施用式（I)化合物於種子（塗佈）。調配物（亦即包含式（D化合物及（必要時）固體或液體佐劑之組成物）以已知方式，典型地藉由緊密混合及/ 或研磨該化合物與增量劑（例如溶劑、固體載劑及視情況選用之表面活性化合物（界面活性劑））來製備。農業化學調配物通常含有0.1 Wt%至99 wt%、較佳0J wt%至 95 wt%式（！）化合物，99.9 wt%至 1 wt%、較佳 99 8 201143615 wt%至5 wt%固體或液體佐劑，及〇至25wt%、較佳〇 i 至25 wt%界面活性劑。儘管較佳將商品調配成濃縮物，但最終使用者通常使用稀調配物。適宜之施用率通常為每公頃（ha) 5g至2kg活性成分 (a.i.) ’較佳為10 g至} kg a」/ha，最佳為层至g a.κ/ha。當用作種子浸潤劑時，適宜之施用率為每公斤種子 mg至lg活性物質。獲得所要作用之施用率可藉由實驗測定。舉例而言，其取決於作用類型、有用植物之發育階段及施用（位置、時序、施用方法），且可因此等參數而大幅度變化。本發明係關於一種控制或預防有用植物被植物病原性微生物感染的方法’其中將式⑴化合物作為活性成分施用於植4匆其。卩分或其所在地。本發明之式（I)化合物之特點在於.在低施用率下具有極佳活性，為植物所良好耐又及對壤境安全。其具有極有用之治療、預防及系統性特性且可用於保護多種有用植物。< ⑴化合物可用於抑制或撲滅不同有用植物作物之植物或植物部分（果實、花、葉莖、塊莖、根）上出現的疾病，同時亦保護隨後生長之彼等植物部分免受例如植物病原性微生物影響。亦有可能使用式（I)化合物作為拌種劑來處理植物繁殖材料’尤其種子（果實、塊莖、榖粒）及植物插枝（例如稻）’卩防止真菌感染以及土壤中存在之植物病原性真菌。 ^ 11 201143615 此外，本發明之式（制真菌，㈣護技術材料V:二在相關領域中用於控文術材枓（包括木及木相關之枯淋吝品）、食品儲存或衛生管理。 u 在本發明之範圍内，人保4之有用植物典型地包含下植物之群組：榖類Γ ,丨也 Α 匕s以奴類（小麥、大麥、黑麥、燕麥、稻米、玉蜀黍、高粱及相關物種）；甜菜（糖用甜菜及例料甜仁果、核果及小果（蘋果、梨、术字祧、杏仁、櫻桃、草每、樹每及黑每）；豆科植物（豆、小扁豆、豌豆、大豆）. 油料植物一（油菜、芥菜、馨粟、橄揽、向曰葵、椰子麻、可可旦、化生）；葫蘆科植物（南瓜、黃瓜、甜瓜）； .截維植物（棉、亞麻、大麻、黃麻措橘類水果（撥子、檸檬、葡萄柚、柑橘）；蔬菜（蔽菜 '萬望、產苟、甘藍菜、胡蘿蔔、洋菌、、番祐、馬鈴薯、辣椒）；樟類（鱷梨、肉桂、樟腦广或諸如煙草、堅果、咖啡'说子、甘薦、茶樹、胡椒、藤本植物、蛇麻草、香蔑及天然橡膠植物的植物；以及觀賞植物。術語「有用植物（useful plant)」及/或「目標作物（target crop )」應理解為亦包括已因習知育種或遺傳工程改造方法而耐受以下之有用植物：除草劑，如溴苯腈（bromoxynil); 或各類除草劑（諸如HPPD抑制劑；ALS抑制劑，例如氟嘧磺隆（primisulfuron)、氟磺隆（prosulfur〇n)及三氟啶磺隆（trifl〇xySulfuron) ; EpsPS ( 5-烯醇-丙酮酸 _莽草酸 _3· 礙酸-合成酶（5-enol-pyrovy】-shikimate-3-phosphate-synthase ))抑制劑；GS (麵醯胺酸合成酶）抑制劑或ppo 12 201143615 (原。卜琳原氧化酶（protoporphyrinogen-oxidase ))抑制劑）。已因習知育種法（突變誘發）而耐受咪唑啉酮 (imidazblinone )(例如曱氧口米草煙（imazamox ))之作物的一實例為Clearfield®夏季油菜（卡諾拉（Canola))。已因遺傳工程改造法而耐受除草劑或各類除草劑的作物之實例包括抗草甘膦（glyph〇Sate)與耐受固殺草（glufosinate) 之玉蜀黍變種，可以商標名RoundupReady®、Herculex I® 及 LibertyLink®購得。術語「有用植物」及/或「目標作物」應理解為亦包括已藉由使用重組DNA技術轉型，從而能夠合成一或多種選擇性作用毒素，諸如已知由例如產生毒素之細菌（尤其芽抱桿菌（Bacillus )屬細菌）所產生之毒素的有用植物。術浯「有用植物」及/或「目標作物」應理解為亦包括藉由使用重組DNA技術轉型，從而能夠合成具有選擇性作用之抗病原物質，諸如所謂「病原相關蛋白 (pathogenesis-related protein)」（ prp，參見例如 Ep_A_〇 392 225 ))的有用植物。該等抗病原物質及能夠合成該等抗病原物質之轉殖基因植物的實例由例如Ep_A_〇 392 225、 95/338 1 8 及 ΕΡ-Α-0 353 1 Q1 & p λ· . . ：553 191而已知。產生該等轉殖基因植物之方法-般為|^習此項技術者戶斤已知且描述於例如上述公開案中。如本文所用之術語有用植物之「所在地（)」意欲涵蓋有用植物生長之場所，太兮王長之％所，在s亥場所中播種有用植物之植物繁殖材料，或在該場所中將古田# 寻有用植物之植物繁殖材料置 13 201143615 於土壤中。該所在地之一音办丨_* ^貫例為作物生長之田地。術語「植物繁殖材料（ ^ P]ant propagation material), Μ 理解為表示有生殖能力之植物 &丄你 " 植物部分，諸如種子，其可用於 ^殖植物，及有生長力之分紐 .I. 料，诸如插枝或塊莖（例如馬鈐薯）。可提及例如種子（嚴格意義上）、根、果實、塊莖、球莖、根莖及植物之部分。亦可提及欲在自土壤發芽後或出苗後移植之發芽植物及a苗。政匕等秩苗可在移植之前藉由全部或部分浸潰處理來保護^「植物繁殖材料」較佳應理解為表示種子。式（I )化合物例如有效對抗以下類別之植物病原性真菌：不完全真菌（Fungi imperfecti )(例如交鏈孢菌屬 (J/ierwarz'a spp.));擔子菌（Basidiomycete )(例如膏藥蕈屬（Coriz'czwm spp.)、角擔菌屬（spp. )、Faz.Zea 屣、亡革菌餍（Thanatephorus spp.)、絲、校菌屬（Rhizoctonia spp.)、錢菌屬（Z/ewu7ez.iz spp.)、柄錢菌屬（PMccz'/n.fl spp.)、層銹菌屬（spp·)、黑粉菌屬（tAsh/ago spp.)、腥黑穗病菌屬（spp.));子囊菌（Ascomycete )(例如黑星菌属（Kewiwri’a spp_ )、布氏白粉菌屬（ spp.)、白粉菌屬（五spp.)、叉絲單囊殼屬 (Spp.)、鉤絲殼菌層（Spp.)、鏈核盤菌屬（Μοη!7ι·/η·α spp·)、核盤菌屬（spp.)、炭疽菌屬（CoZ/eioir/c/iMm spp.)、小叢殼屬（SPP·)、嫌抱菌属（尸wsflWwm spp.)、赤徽菌屬（⑺办办SPP_ )、 A/owogriz/7/ie//a屬 '暗球腔菌（户办以似夕六⑼”·“ SPP.)、球腔 14 201143615 菌屬（spp.)、尾孢菌屬（Cercospora spp.)、核腔菌屬（户spp_ )、嗓抱徽屬（ spp.)、大角間座殼屬（MagwaporMe spp.)、頂囊殼屬 (Gaeumannomyces spp. ) 、 Oculimacula 屬、柱隔抱屬 (jRamw/arz_a spp.)、葡萄孢盤菌屬（5οίγ>>οίζ·^π·β spp.))及卵菌（Oomycete )(例如疫黴菌屬（户spp.)、腐黴菌屬（尸ji/n’wm spp.)、單轴黴屬f尸/asmopara spp.)、霜徽菌屬（Perowoaorfl spp.)、假霜黴菌屬（八yeMi/operowoaora spp.)、盤梗徽屬（5remia spp ))。觀察到對抗白粉病（例如葡萄鉤絲殼（C/zic/nM/a «ecaior))、錄病（例如柄錄菌屬）及葉斑病（例如球腔菌屬）之顯著活性、此外，新穎式（I ) 化合物有效對抗植物病原性革蘭氏陰性（gram negative )及革蘭氏陽性（gram positive )細菌（例如黃單胞菌屬 (XawMomowas spp )、假單胞菌屬（Pseudomonas spp )、梨火疫病菌（心wWa amy/ovora )、羅爾斯通氏菌屬（及α/Μ〇„ζ·α spp.))及病毒（例如煙草嵌_蚊病毒（tobacco mosaic virus ))。在本發明之一較佳具體實例中，使用本發明之化合物及組成物對抗真菌生物體禾生球腔菌（ graminicola ) ° 式（I )化合物通常以殺真菌組成物形式用於控制或防止植物病原性微生物，該等殺真菌組成物包含呈自由形式或農業化學上可用之鹽形式的上文所定義之至少一種式（1) 化合物或至少一種較佳個別化合物作為活性成分，及包含至少一種上.述佐劑。 15 201143615 包含呈自由形式或農業化學上可用之鹽形式的上文所定義之至^ 一種式（I)化合物或至少一種較佳個別化合物作為活性成分，及包括至少_種上述佐劑，用於控制或防止植物病原性微生物的該等殺真菌組成物可與其他殺真菌劑混合，在一些情況下產生出乎意料的協同活性。尤佳混合組分為：哇’諸如阿紮康唑（azac〇naz〇le )、BAY 14120、比多農（bitertanol )、糠菌唑（br〇muc〇naz〇le )、環康唑 (cyproconazole )、苯醚甲環唑（difen〇c〇naz〇le )、達克利 (diniconazole )、貌環 η坐（epoxiconazole )、芬克座 (fenbuconazole )、說喹。坐（fiUqUinc〇naz〇ie )、護石夕得 (flusilazole)、護汰分（flutriafole)、己。坐醇（hexaconazole)、依滅列（imazalil )、易胺座（imibenconazole )、依普克嗤 (ipconazole )、葉菌。坐（metconazole )、邁克尼 (myclobutanil )、稻瘂 g旨（pefurazoate )、潘康"坐 (penconazole )、丙硫醇克〇坐（pr〇thioconazole )、比芬諾 (pyrifenox )、撲克拉（prochloraz )、普克利（propiconazole )、石夕氣 °坐（simeconazole )、得克利（tebuconazole )、敗鍵0坐 (tetraconazole )、三泰芬（triadimefon )、三泰隆 (triadimenol )、赛福座（triflumizole )、環菌吐 (triticonazole)； »密。定基甲醇，諸如三環苯〇密醇（ancymidol )、芬瑞莫 (fenarimol )、氟苯喊 °定醇（nuarimol ); 2-胺基啶，諸如績嘧菌靈（bupirimate )、曱菌定 16 201143615 (dimethirimol)、乙菌咬（ethirimol); 嗎琳，諸如嗎菌靈（dodemorph )、苯錄。定 (.fenpropidine )、粉錄琳（fenpropimorph )、螺環菌胺 (spiroxamine )、三得芬(tridemorph )；苯胺基°密咬，諸如西波定（cyprodinil )、米潘尼比林 (mepanipyrim )、比利美沙尼（pyrimethanil ); 0比洛，諸如拌種各（fenpiclonil )、護汰寧（fludioxonil ); 苯基酿胺，諸如苯霜靈（benalaxyl )、吱霜靈 (furalaxyl )、滅達樂（metalaxyl )、R-滅達樂（R-metalaxyl )、吱醯胺（ofurace )、歐殺斯（oxadixyl ); 苯并σ米嗤，諸如免賴得（benomyl )、貝芬替 (carbendazim )、咪菌威（debacarb )、麥穗靈（fuberidazole )、〇塞苯 °米。坐（thiabendazole ); 二曱醯亞胺，諸如乙菌利（chlozolinate )、菌核利 (dichlozoline )、依普同（iprodione )、曱菌利（myclozoline )、撲滅寧（procymidone)、免克寧（vinclozoline); 曱醯胺，諸如博克利（boscalid)、萎銹靈（carboxin)、曱咬醢胺（fenfuram )、氟多寧（flutolanil )、滅銹胺 (mepronil )、氧化萎錄靈（〇XyCarb〇xin )、。比d塞菌胺 (penthiopyrad )、賽敗滅（thifluzamide );胍，諸如雙胍鹽 (guazatine )、多寧（dodine )、雙胍辛胺（iminoctadine ); 嗜毯果傘素，諸如亞托敏（azoxystrobin )、地莫菌胺 (dimoxystrobin )、依尼菌胺（enestr〇burin )、氟氧菌胺 (fluoxastrobin )、克收欣（kresoxim-methyl )、苯氧菌胺 17 201143615 (metominostrobin )、三氟敏（trifloxystrobin )、奥瑞菌胺 (orysastrobin )、啶氧菌胺（picoxystrobin )、百克敏 (pyraclostrobin )；二硫代胺基曱酸酯’諸如福美鐵（ferbam )、猛粉克 (mancozeb )、錳乃浦（maneb )、免得爛（metiram )、曱基鋅乃浦（propineb )、得恩地（thiram )、鋅乃浦（zineb )、益穗（ziram ); Ν·鹵基曱基硫基四氫鄰苯二曱醯亞胺，諸如四氣丹 (captafol)、蓋普丹（captan)、益發靈（dichlofluanid)、氟氯菌核利（fluoromide )、福爾培（f〇lpet )、甲苯氟磺胺 (tolyfluanid )；J ·^巴枓. The side carrier is described, for example, in WO 201143615 97/33890. The compound of the formula (1) or the composition comprising the compound of the formula (1) as an active ingredient and an emotive carrier may be applied simultaneously or continuously with other compounds to the locus or plant of the plant to be treated. Such other compounds may be, for example, fertilizer: or micronutrient supplies or other agents that affect plant growth. It may also be selected as a herbicide, a plant growth regulator and an insecticide, a fungicide, a bactericide, a nematicide, a molluscicide or a mixture of several of these preparations, if necessary with other carriers. Promoting the application of adjuvants, commonly used in surfactants or formulation techniques. A preferred method of applying a compound of formula (I) or a compound comprising formula (Z) as an active ingredient, and a composition comprising an inert carrier is foliar application. The frequency of administration and rate of application will depend on the risk of infection by the corresponding pathogen. However, the compound of the formula (1) may also permeate the root through the soil (systemic action) by infiltrating the plant site with a liquid formulation, or by applying a solid form (for example, a granular form) of the compound (soil application) to the soil. plant. In rice crops, these particles can be applied to the rice field (fl〇〇ded rice field). The compound of formula (I) can also be applied to the seed (coating) by impregnating the seed or tuber with a liquid formulation of the fungicide or by coating the seed or tuber with a solid formulation. Formulations (ie, comprising a composition of the formula (D compound and, if desired) a solid or liquid adjuvant) in a known manner, typically by intimate mixing and/or grinding of the compound with a bulking agent (eg solvent, solid) The carrier and optionally the surface-active compound (surfactant) are used. The agrochemical formulation usually contains 0.1 Wt% to 99 wt%, preferably 0 J wt% to 95 wt% of the compound (!), 99.9 wt. % to 1 wt%, preferably 99 8 201143615 wt% to 5 wt% solid or liquid adjuvant, and 〇 to 25 wt%, preferably 〇i to 25 wt% surfactant. Although it is preferred to formulate the product into a concentrate However, the end user usually uses a dilute formulation. Suitable application rates are usually 5 g to 2 kg active ingredient (ai) per hectare (ha) 'preferably 10 g to } kg a"/ha, preferably layer to g a. κ / ha. When used as a seed sizing agent, a suitable application rate is from mg to lg of active substance per kg of seed. The application rate at which the desired effect is obtained can be determined experimentally. For example, depending on the type of action, Developmental stage and application of useful plants (location, timing, application method) The present invention relates to a method for controlling or preventing infection of a useful plant by a plant pathogenic microorganism, wherein a compound of the formula (1) is administered as an active ingredient to the plant. The compound of the formula (I) of the present invention is characterized in that it has excellent activity at a low application rate, is well tolerated by plants, and is safe for the soil. It has extremely useful therapeutic, prophylactic and systemic properties and can be used for Protects a variety of useful plants. < (1) Compounds can be used to inhibit or extinguish diseases occurring on plants or plant parts (fruits, flowers, stems, tubers, roots) of different useful plant crops, while also protecting the subsequent plant parts Protected from, for example, phytopathogenic microorganisms. It is also possible to use the compounds of formula (I) as seed dressings to treat plant propagation materials 'especially seeds (fruits, tubers, glutinous grains) and plant cuttings (eg rice)' Infection and phytopathogenic fungi present in the soil. ^ 11 201143615 Furthermore, the formula of the invention (fungal, (4) nursing skills Material V: Two for the control of literary materials (including wood and wood related dry dripping), food storage or hygiene management in the related art. u Within the scope of the present invention, the useful plant of PICC 4 typically comprises Groups of plants: 榖 Γ, 丨 Α 匕以 slaves (wheat, barley, rye, oats, rice, maize, sorghum and related species); sugar beet (sugar beet and regular sweet pome fruit, Drupe and small fruit (apple, pear, scorpion, almond, cherry, grass, tree and black); legumes (beans, lentils, peas, soybeans). Oil plant one (canola, mustard, sweet) Millet, olive, hollyhock, coconut hemp, cocoa, metaplasia; cucurbitaceae (pumpkin, cucumber, melon); cut-off plants (cotton, flax, hemp, jute, orange fruit (dial , lemon, grapefruit, citrus); vegetables (bread vegetables, oysters, broccoli, carrots, mushrooms, bananas, potatoes, peppers); oysters (avocado, cinnamon, camphor or tobacco) , nuts, coffee 'speaker, Gan recommended, tea tree, Hu , Vines, hops, fragrant plants contempt and natural rubber plants; and ornamentals. The terms "useful plant" and/or "target crop" are understood to also include the following useful plants that have been tolerated by conventional breeding or genetic engineering methods: herbicides such as bromoxynil ( Bromoxynil); or various herbicides (such as HPPD inhibitors; ALS inhibitors, such as primisulfuron, prosulfur〇n, and trifl〇xySulfuron; EpsPS (5 -enol-pyruvate_shikimate_3·5-enol-pyrovy-shikimate-3-phosphate-synthase) inhibitor; GS (face glutamate synthase) inhibitor or ppo 12 201143615 (original. Protopor phytase-oxidase) inhibitor). An example of a crop that has been rendered tolerant to imidazblinone (e.g., imamzamox) by conventional breeding methods (mutation induced) is Clearfield® Summer Canola (Canola). Examples of crops that have been tolerant to herbicides or herbicides due to genetic engineering methods include glyphosate-resistant (Sate) and glufosinate-resistant maize varieties, which are available under the trade name RoundupReady®, Herculex. I® and LibertyLink® are available. The terms "useful plant" and/or "target crop" are understood to also include transformations that have been made by the use of recombinant DNA technology to enable the synthesis of one or more selective action toxins, such as bacteria known to produce toxins (especially buds). A useful plant of a toxin produced by a bacterium of the genus Bacillus. " useful plants" and/or "target crops" should be understood to include the transformation by using recombinant DNA technology to synthesize selective anti-pathogenic substances, such as the so-called "pathogenesis-related proteins". (prp, see eg Ep_A_〇392 225)) useful plants. Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing the anti-pathogenic substances are, for example, Ep_A_〇392 225, 95/338 18 and ΕΡ-Α-0 353 1 Q1 & p λ· . . :553 191 and known. The method of producing such a transgenic plant is generally known and described, for example, in the above publication. As used herein, the term "location ()" of a useful plant is intended to cover a place where useful plants are grown, a plant of the genus Taiyuan, a plant propagation material for planting useful plants in the s place, or a useful site in the site. The plant propagation material of the plant is placed 13 201143615 in the soil. One of the locations of the local office is the field of crop growth. The term "plant propagation material ("P]ant propagation material", 理解 is understood to mean a plant that has fertility & 丄 you" plant parts, such as seeds, which can be used for planting plants, and for growth. I. Materials, such as cuttings or tubers (such as horse yam). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. It may also be mentioned that it is intended to germinate from the soil. Germinated plants and a seedlings transplanted after emergence or after emergence. Politics and the like can be protected by whole or partial impregnation treatment before transplantation. "Plant propagation material" is preferably understood to mean seeds. The compounds of formula (I) are, for example, effective against phytopathogenic fungi of the following classes: Fungi imperfecti (eg J/ierwarz'a spp.); Basidiomycete (eg plaster 蕈) Genus (Coriz'czwm spp.), Sarc. genus (spp.), Faz. Zea 屣, Thanatephorus spp., genus, Rhizoctonia spp., Z. Ewu7ez.iz spp.), genus PMccz'/n.fl spp., rust genus (spp·), genus genus (tAsh/ago spp.), genus smut (spp) .)); Ascomycete (such as Kewiwri'a spp_), B. baumannii (spp.), powdery mildew (five spp.), singular genus (Spp. ), H. serrata (Spp.), Sclerotinia (Μοη! 7ι·/η·α spp·), Sclerotinia (spp.), Anthrax (CoZ/eioir/c/iMm) Spp.), genus genus (SPP·), genus Bacterium (corpse wsflWwm spp.), genus Echinococcus ((7) SPP_), A/owogriz/7/ie//a genus dark sphere Bacteria (households are equivalent to six (9)" · "SPP.", ball cavity 14 201143615 genus (spp.), genus Cercospora (C Ercospora spp.), genus genus (spp_), genus (spp.), Magwapor Me spp., Gaeumannomyces spp., Oculimacula genus, column occlusion Genus (jRamw/arz_a spp.), Botrytis (5οίγ>>οίζ·^π·β spp.) and Oomycete (eg Phytophthora (spp.), Pythium ( Corpse ji/n'wm spp.), Phytophthora f./Asmopara spp., Perowoaorfl spp., Pseudomonas spp. (Eight yeMi/operowoaora spp.) 5remia spp )). Significant activity against powdery mildew (eg, grape stalk (C/zic/nM/a «ecaior), recorded disease (eg, genus), and leaf spot (eg, genus) was observed, in addition, The novel compounds of formula (I) are effective against phytopathogenic gram negative and gram positive bacteria (eg, XawMomowas spp, Pseudomonas spp) , P. amylovora (heart wWa amy / ovora), Ralstonia (and α / Μ〇 ζ α α spp.) and viruses (such as tobacco mosaic virus (tobacco mosaic virus). In a preferred embodiment of the invention, the compounds and compositions of the invention are used against the fungal organism graminicola. The compound of formula (I) is typically used in the form of a fungicidal composition to control or prevent phytopathogens. a microorganism, the fungicidal composition comprising at least one compound of the formula (1) or at least one preferred individual compound as defined above in free form or in an agrochemically acceptable salt form, and comprising at least one Said 15 201143615 A compound of formula (I) or at least one preferred individual compound as defined above, as defined above, in a free form or agrochemically acceptable salt form, and comprising at least one of the above adjuvants, These fungicidal compositions for controlling or preventing phytopathogenic microorganisms can be combined with other fungicides, in some cases with unexpected synergistic activity. Particularly preferred mixing components are: Wow' such as azaconazole (azac〇naz〇le), BAY 14120, bitertanol, bromomuc〇naz〇le, cyproconazole, difen〇c〇naz〇 Le ), diniconazole, epoxiconazole, fenbuconazole, quinine, sitting (fiUqUinc〇naz〇ie), flusilazole, flutriafole Hexaconazole, imazalil, imibenconazole, ipconazole, leaf fungus, metconazole, myclobutanil, rice blast Pefurazoate ), Pan Kang & q Uot; penconazole, pr〇thioconazole, pyrifenox, prochloraz, propiconazole, simeconazole, texey Tebuconazole ), tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; Stationary methanol, such as ancymidol, fenarimol, fluorophenyl nuarimol; 2-aminopyridine, such as bupirimate, sputum 16 201143615 (dimethirimol), ethirimol; morphine, such as dodemorph (dodemorph), benzene recorded. (.fenpropidine), fenpropimorph, spiroxamine, tridemorph; anilino-based bite, such as cyprodinil, mepanipyrim , pyrimethanil; 0 bilo, such as seed dressing (fenpiclonil), fludioxonil; phenyl stearamine, such as benaxyl (benalaxyl), furaxyl (furalaxyl), annihilation Metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzothymolazole, such as benomyl, carbendazim , debacarb, fuberidazole, bismuth benzene. Sitting on (thiabendazole); diterpene imine, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, and chlorhexidine Vinclozoline); guanamines, such as boscalid, carboxin, fenfuram, fluolanil, mepronil, oxidized sulphate (〇XyCarb) 〇xin ),. Compared with d-cethiopyrad, thifluzamide; 胍, such as guazatine, dodine, iminoctadine; ), dimoxystrobin, enestr〇burin, fluoxastrobin, kresoxim-methyl, phenoxystrobin 17 201143615 (metominostrobin), trifluoro-sensitive (trifloxystrobin), oresastrobin, picoxystrobin, pyraclostrobin; dithioamino phthalate such as ferbam, mancozeb, manganese Maneb, metiram, propineb, thiram, zineb, ziram; Ν·halo sulfhydryl tetrahydrogen O-benzodiazepines, such as captafol, captan, dichlofluanid, fluoromide, folpet, toluene sulfonamide (tolyfluanid );

Cu化合物’諸如波爾多液（Bordeaux mixture )、氣氧化銅、氧氣化銅、硫酸銅、氧化亞銅、代森錳銅（mancopper )、啥琳銅(oxine-copper )；硝基酚衍生物，諸如白粉克（dinocap )、酞菌酯 (nitrothal-isopropyl)；有機填衍生物’例如護粒松（edifenphos )、丙基喜樂松（iprobenphos )、稻瘟靈（isoprothi〇lane )、氯瘟磷 (phosdiphen )、白粉松（pyrazophos )、脫克松 (Tolclofos-methyl); 已知且可藉由 WO 05/121104、WO 06/001 175 及 WO 07/066601中所述之方法製備的β荅卩井衍生物，諸如3 -氣 -5-(4-氣-苯基）-6-曱基-4-(2,4,6-三氟·苯基）-嗒畊（式ρ·ι)、 3-氣-6 -曱基-5-對甲苯基-4-(2，4,6-三氟-苯基）-塔d井（式ρ· 2) 18 201143615Cu compounds such as Bordeaux mixture, copper oxychloride, copper oxychloride, copper sulphate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as Dinocap, nitrothal-isopropyl; organic-filled derivatives such as edifenphos, iprobenphos, isoprothi〇lane, phosdiphen ), pyrazophos, tolclofos-methyl; a known β-well derived from the method described in WO 05/121104, WO 06/001 175 and WO 07/066601 , such as 3-air-5-(4-a-phenyl)-6-mercapto-4-(2,4,6-trifluoro-phenyl)-indole (form ρ·ι), 3- Gas-6-mercapto-5-p-tolyl-4-(2,4,6-trifluoro-phenyl)-tower d (formula ρ· 2) 18 201143615

-°荅D井（式p. 3 );-°荅D well (formula p. 3);

&去°且可藉由WO 98/46607 中所述之方法製備的三唑并嘧啶衍生物，諸如5_氣_7_(4_曱基-哌啶-1·基）-6-(2,4,6·三氟-苯基）-[1，2,4]三唑并[l，5-a]嘧啶（式T.1 )，And a triazolopyrimidine derivative prepared by the method described in WO 98/46607, such as 5-gas-7-(4- mercapto-piperidin-1yl)-6-(2) , 4,6·trifluoro-phenyl)-[1,2,4]triazolo[l,5-a]pyrimidine (formula T.1),

已知且可藉由 WO 04/035589、WO 06/37632、WO 03/074491或WO 03070705中所述之方法製備的甲醯胺衍生物，諸如3-二氟曱基-1-甲基-1H-吡唑-4-曱酸（9-異丙基 -1，2,3,4-四氫-1,4-亞甲基-萘-5-基）-醯胺（式U.1 )、3-二氟甲基-1-甲基-1Η-吡唑-4-曱酸（2-雙環丙基-2-基-苯基）-醯胺 (式 U_2)或 Ν-(3'，4'-二氣-5-氟-1,1、聯笨-2-基）-3-(二氟曱基）-1-曱基-1H-吡唑-4-甲醯胺； 19 201143615A formamide derivative, such as 3-difluorodecyl-1-methyl-1H, which is known and can be prepared by the process described in WO 04/035589, WO 06/37632, WO 03/074491 or WO 03070705 -pyrazole-4-decanoic acid (9-isopropyl-1,2,3,4-tetrahydro-1,4-methylene-naphthalen-5-yl)-decylamine (formula U.1), 3-Difluoromethyl-1-methyl-1Η-pyrazole-4-furic acid (2-biscyclopropyl-2-yl-phenyl)-decylamine (Formula U_2) or Ν-(3',4 '-Digas-5-fluoro-1,1, phenyl-2-yl)-3-(difluoroindolyl)-1-indolyl-1H-pyrazole-4-carboxamide; 19 201143615

N I ch3 U.l ；N I ch3 U.l ;

已知且可藉由WO 2004/016088中所述之方法製備的苯甲醯胺衍生物，諸如N-{-2-[3-氯-5-(三氟曱基）-2-吡啶基] 乙基}-2-三氟曱基苯曱醯胺，其亦以名稱氟吡菌醯胺 (fluopyram)(式 V. 1 )已知；及A benzamide derivative, such as N-{-2-[3-chloro-5-(trifluoromethyl)-2-pyridyl), which is known and can be prepared by the method described in WO 2004/016088 Ethyl}-2-trifluorodecylbenzamide, also known by the name floopyram (formula V. 1);

V.1 20 201143615 各種其他物質，諸如酸化苯并噻二唑-s-曱酯 (acibenzolar-S-methyl )、敵菌靈（anilazine )、苯嗟瓦利 (benthiavalicarb )、殺稻瘟菌素-S ( blasticidin-S )、滅蟎猛 (chinomethionate )、地茂散（chloroneb )、四氣異苯腈 (chlorothalonil )、嘆芬胺（cyflufenamid )、霜脲氰 (cymoxanil )、二氣萘酿（dichlone)、二氯西莫（diclocymet)、嚏菌清（diclomezine )、氯硝胺（dicloran )、乙黴威 (diethofencarb )、達滅芬（dimethomorph )、氟嗎琳 (flumorph )、腈硫醌（dithianon )、乙售博胺（ethaboxam )、依得利（etridiazole )、〇惡口坐菌酮（famoxadone )、0米峻菌 _ (fenamidone )、禾草靈（fenoxanil )、三苯錫（fentin )、。密菌腙（ferimzone )、扶吉胺（fluazinam )、氟°比菌胺 (fluopicolide )、氟硫滅（flusulfamide )、環醯菌胺 (fenhexamid ) ' 乙填銘（fosetyl-aluminium )、惡黴靈 (hymexazol )、绳黴威（iprovalicarb )、賽座滅（cyazofamid )、春曰黴素（kasugamycin )、雙炔醯菌胺（mandipropamid )、石夤菌威（methasulfocarb )、美曲芬諾（metrafenone )、尼可必芬（nicobifen )、賓克隆（pencycuron )、苯醜（phthalide )、多氧菌素（polyoxins )、°塞菌靈（probenazole )、霜黴威 (propamocarb )、普奎那茲（proquinazid )、百快隆 (pyroquilon )、快諾芬（quinoxyfen )、奎脫辛（quintozene )、硫、汰敵寧（tiadinil )、0米"坐α井（triazoxide )、三賽哇 (tricyclazole )、赛福寧（triforine )、維利黴素 (validamycin)、氣苯醯胺（zoxamide)及草甘膦。 21 201143615 本發明之另一態樣係關於如上所定義之式（丨）化合物或較佳個別化合物、包含如上所定義之至少一種式（j)化合物或至少一種較佳個別化合物的組成物、或包含如上所疋義之至少一種式（I)化合物或至少一種較佳個別化合物的殺真菌混合物與上述其他殺真菌劑的混合物用於控制或預防植物、收穫之食用作物、種子或非生命物質被植物病原性微生物、較佳真菌生物體感染的用途。本發明之另一態樣係關於控制或預防作物、收穫之食用作物或非生命物質被可能對人類有害的植物病原性或腐敗性微生物或生物體、尤其真菌生物體感染的方法，其包含向植物、植物之部分或其所在地、種子或非生命物質之任何。P刀施用如上所定義之式（J)化合物或較佳個別化合物作為活性成分。控制或預防意謂使作物或非生命物質被可能對人類有害之植物病原性或腐敗性微生物或生物體、尤其真菌生物體感染減少至展示改良之程度。 / 下表1說明本發明之個別式（1)化合物及中間物（11) 之實例。V.1 20 201143615 Various other substances, such as acidified benzothiadiazole-s-methyl ester, anilazine, benthiavalicarb, blasticidin- S ( blasticidin-S ), chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone ), diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon ), ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, . Ferimzone, fluazinam, fluopicolide, flusulfamide, fenhexamid 'fosetyl-aluminium, carbendazim (hymexazol), iprovalicarb, cyazofamid, kasugamycin, mandipropamid, methasulfocarb, metrafenone , nicofifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, proquinazid ), pyroquilon, quinoxyfen, quintozene, sulphur, tiadinil, 0m"triazoxide, tricyclazole, race Triforine, validamycin, zoxamide, and glyphosate. 21 201143615 Another aspect of the invention relates to a compound of the formula (丨) or a preferred individual compound as defined above, a composition comprising at least one compound of the formula (j) as defined above, or at least one preferred individual compound, or Mixtures of fungicidal mixtures comprising at least one compound of formula (I) or at least one preferred individual compound as defined above with other fungicides described above for controlling or preventing plants, harvested food crops, seeds or non-living matter plants Use of pathogenic microorganisms, preferably fungal organisms. Another aspect of the present invention relates to a method of controlling or preventing infection of a crop, harvested food crop or non-living matter by a phytopathogenic or spoilage microorganism or organism, particularly a fungal organism, which may be harmful to humans, including Any part of a plant, part of a plant or its location, seed or non-living matter. The P knife applies a compound of the formula (J) as defined above or a preferred individual compound as an active ingredient. Control or prevention means that crop or non-living matter is reduced to a level of improvement by phytopathogenic or spoilage microorganisms or organisms, particularly fungal organisms, which may be harmful to humans. / Table 1 below illustrates examples of the individual compound of the formula (1) and the intermediate (11) of the present invention.

化合物編號 ?- 1 (Π) Κ R2 w R5 ----- Rs CHt F F 2 —-- nxi F OH -- F F Cl 22 201143615Compound number ?- 1 (Π) Κ R2 w R5 ----- Rs CHt F F 2 —-- nxi F OH -- F F Cl 22 201143615

~~~—---och3 och3 以卜貫w §兄明不赞明。實施例1 :製備3-氯-4-(2,6-二t 4田e * 虱-4-甲氧基-苯基）-6-甲基 -5-(6-三氟曱基-。比啶-3-基）-嗒0丼（开（化合物編號3) a)製備2-曱基-3-側氧基-3-(6-=患田| 一、—鼠甲基-吡啶_3_基）-丙酸第三丁酯在德下在氮氣氛圍下向二異丙胺（68 g)與7〇 ml 四氫呋喃之混合物中逐滴添加正丁基鋰（ι·6 Μ己烷溶液’ 46 ml )。敁後，向反應混合物中緩慢添加$.7呂丙酸第三丁酉曰且在_7〇(：下繼續攪拌30分鐘。隨後，在_7(rc下向反應此〇物中逐滴添加6_三氟甲基菸鹼酸乙酯（7 4呂）於3〇四氫呋喃中之溶液’且在_7〇。〇下繼續攪拌1小時。添加3〇 ml 第--_ 二丁暴曱基醚及45 ml稀乙酸之後，用乙酸乙酯萃取此s物。用鹽水洗滌有機層，經硫酸鈉脫水且在減壓下浪縮°藉由矽膠層析使用庚烷/乙酸乙酯（9:1 )之混合物作為 '谷離劑純化剩餘部分，獲得呈油狀物之2-曱基-3-側氣基 23 201143615 -3-(6-三氟甲基-。比。定-3-基）-丙酸第三丁醋。 b)製備2-溴-1-(6-三氟曱基-。比啶-3-基）-丙-i_酮在室溫下在氮氣氛圍下向2-甲基-3-側氧基-3-(6-三氟曱基-吡啶-3-基）-丙酸第三丁酯（10.5 g)、〇.5 ml氫溴酸（33% 之乙酸溶液）及30 ml乙酸之混合物中緩慢添加溴（5.0 g )。隨後，緩慢加熱混合物至60°C。在60°C下攪拌反應混合物 30分鐘，隨後進行冷卻。用飽和碳酸氫鈉水溶液中和之後，用乙酸乙酯萃取混合物。用鹽水洗滌有機層，經硫酸鈉脫水且在減壓下濃縮。藉由矽膠層析使用庚烷/乙酸乙酯 (9.1 )隨後曱本/庚烧（2:1 )之混合物作為溶離劑純化剩餘部分，獲得呈油狀物之2_溴d-e·三氟甲基_吡啶_3_基）_丙 -1 -酉同0 c)製備5-羥基·5·曱基_4_(6_ 二氟·笨基）-5Η-呋喃_2_酮向_2_漠-1-(6_三氣甲基“比啶-3-基）-丙小酮（3.0 g)、一氟笨基乙®欠（2.1 g)於50ml乙腈中之溶液中緩慢 : ' 胺（1.2 g 且在室溫下攪拌此混合物1 ό小時。隨後在冷卻下镑，降.天4 t 〇 rnRTT ^ 緩叚添加丨，8-二氮雜雙環[5.4.0]十一烯 L *L) JB U，3 Q λ、 ^ 廊 ·，且繼續攪拌1小時。隨後吹入空氣通過反應混合物歷時1小主且用夺將反應混合物傾入氣化銨水溶液中，且用乙酸乙酯萃取厶經琉酸#。 m纟1合併之有機層，水且在㈣下蒸發1切膠層析使用環己烧/ 24 201143615 乙酸乙醋（3:1 )之混合物作為溶離劑純化剩餘部呈微黃色泡沫狀之5-羥基-5-甲基_4_(6_三氣甲武基）-3-(2,4,6-二氟-苯基）-5H-吱喃-2-g同。 0製備6-曱基-5-(6-三氟甲基-吡咬_3-基）-4-(246-氟“ 基）-2 Η - °荅D井-3 - _ (化合物編號1 ) 向5-羥基-5-曱基-4-(6-三氟曱基-吡啶基4 6 三氟-苯基）-5H-呋喃-2-酮（3.4 g)於20 ml 1-丁醇φ … 峰甲之溶液中添加水合肼（0.5 g )，且加熱此混合物4小時達i 2〇·^。隨後，將混合物傾入20 ml第三丁基曱基醚中。攪拌所得混合物30分鐘，隨後冷卻至0艺且過濾。用第三丁基甲:: 洗滌固體剩餘部分，得到呈棕色固體狀之6_甲基巧_(6_二氟甲基-u比啶-3-基）-4-(2,4,6-三氟-苯基）-2H “荅口井_3__ (化合物編號1 )，熔點2 5 2 - 2 5 3 °C。 e)製備3-氯-6-曱基-5-(6-三氟曱基_D比啶_3_基）·4_(2,4 = 氟-苯基）-嗒D井（化合物編號2 ) 在下加熱6-甲基·5_(6_三氟曱基-吡啶-3_ 基Μ-(2,4,6-三I苯基）_2Η “荅畊小_ (化合物編號丨，12 g)及15 ml氧氯化磷之混合物3〇分鐘。冷卻之後，在減壓下瘵發反應混合物。用乙酸乙酯及水萃取剩餘部分且分離各相用水及鹽水洗滌有機層，經硫酸鈉脫水且在減壓下蒸發。藉由矽膠層析使用庚烷/乙酸乙酯（2:1)之混合物作為心離劑純化殘餘物，獲得呈無色晶體狀之3•氣·6_甲基 25 201143615 •5-(6-三氟甲基-n比。定_3_基）-4-(2,4,6-三氟-苯基）-°荅卩井（化合物編號2 ) ’熔點1 56-1 57°C。 Ο製備4-(2,6-二氟-4-甲氧基-苯基）-3-曱氧基-6-甲基-5-(三氟曱基-吡啶-3-基）-嗒d井（化合物編號4) 加熱3-氣-6-曱基-5-(6-三氟甲基-吡啶-3-基）-4-(2,4,6-三氟-苯基）-嗒畊（化合物編號2，470 mg) '曱醇鈉（30〇/〇之甲醇溶液，770 mg )及5 ml四氫β夫喃之混合物1小時達 5 5°C ‘。隨後，冷卻反應混合物，用水稀釋且用乙酸乙酯萃取。用水及鹽水洗滌經合併之有機層，經硫酸鈉脫水且在減壓下蒸發。藉由矽膠層析使用庚烷/乙酸乙酯（2:1 )之混合物作為溶離劑純化剩餘部分，獲得4-(2,6-二氟-4-曱氧基_苯基）-3 -甲氧基-6-甲基- 5- (三氣曱基-0比。定-3-基）-«>荅口井（化合物編號 4 )，熔點 143-144°C。 g )在110°C下加熱4-(2,6-二氟-4-曱氧基-苯基）-3 -曱氧基曱基-5-(二氟曱基-。比咬_3_基）·》荅u井（化合物編號4，34〇 mg )、4 ml氧氣化磷及80 mg三甲胺鹽酸鹽之混合物分鐘。冷卻之後’在減壓下蒸發反應混合物。藉由矽膠層析使用庚烷/乙酸乙酯（4:1 )之混合物作為溶離劑純化殘餘物’獲得呈無色晶體狀之3-氣-4-(2,6-二氟_4_曱氧基-苯基）-6-曱基-5-(6-三氟曱基-吡啶-3-基嗒畊（化合物編號 3 )，熔點 153-154°C。 26 201143615 生物貫施例番茄早疫病菌（j/iernarz’a so/αΜί· ) /番茄/預防性（對抗番茄上之交鏈孢菌（Alternaria )的作用）在喷霧室中用經調配之測試化合物處理4週齡番茄植物cv. Roter Gnom。施用之後兩天，測試植物藉由用抱子懸浮液噴灑而接種。在溫室中在22/1 8 °C (日/夜）及95% rh 下培育經接種之測試植物’且當未處理對照植物上出現適當程度之疾病時（施用之後5至7天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2、3及4抑制真菌感染達至少80。/。，而在相同條件下，未處理對照植物被植物病原性真菌感染超過80%。虽克葡萄孢盤菌（5〇外0如以⑽）（灰葡萄.孢 (&&少沿Cherei〇) /#茄/預防性（對抗番茄上之葡萄孢菌 (Botrytis)的作用）在噴霧室中用·經調配之測試化合物處理4週齡番茄植 :CV.R〇terGnom。施用之後兩天，測試植物藉由用孢子懸洋液噴漢而接種。在溫室中在奶及95%rh下培育經接種之測試植物’ I當未處理對照植物上出現適當程度之疾病時（施用之後5至6天）収疾病覆蓋之葉面積百分比。在此測試中’200 ppm之本發明化合物2及3抑制真菌物二3::，而在相同條件下，未處理對照植物被植物病原〖生真鹵感染超過80%。 27 201143615 葡萄白粉菌（wecaer )(葡萄鉤絲殼）/葡萄/預防性（對抗葡萄上之白粉病的作用）在喷霧室中用經調配之測試化合物處理5週齡葡萄幼苗cv. Gutedel。藉由在施用之後i天在上方搖動感染有葡萄白粉病之植物而接種測試植物。在24/22。〇(日/夜）及 70% rh下於14/10小時（明/暗）光照方式下培育經接種之測試植物’且當未處理對照植物上出現適當程度之疾病時 (施用之後7至9天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2、3及4抑制真菌感染達至少80%，而在相同條件下，未處理對照植物被植物病原性真菌感染超過80%。稻瘟菌（Magnaporthe grisea)(稻梨孢（pyricularia 〇fyza〇 /稻/預防性（對抗稻熱病之作用）在噴霧室中用經調配之測試化合物處理3週齡稻植物 cv. Koshihikari。施用之後兩天，測試植物藉由用孢子懸浮液喷灑而接種。在25。(：及95% rh下培育經接種之測試植物，且當未處理對照植物上出現適當程度之疾病時（施用之後7至9天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2及3抑制真菌感染達至少' 80〇/〇 ’而在相同條件下，未處理對照植物被植物病原性真菌感染超過80%。 28 201143615 禾生球腔菌（小麥殼針抱（《Sepioria ) /小麥/預防性 (對抗小麥上之殼針孢菌葉斑病（Septoria leaf spot )之作用）在喷霧室中用經調配之測試化合物處理2週齡小麥植物cv. Riband。施用之後一曰，測試植物藉由在其上喷灑孢子懸浮液而接種。在22t/21°C (日/夜）及95%rh下培育丄天之後，將測試植物保持在溫室中22。(：/21。(：（日/夜）及7〇% rh下。當未處理對照植物上出現適當程度之疾病時（施用之後16至19天）評定疾病覆蓋之葉面積百分比。在此測試中’ 200 ppm之本發明化合物2及3抑制真菌感染達至少80%，而在相同條件下，未處理對照植物被植物病原性真菌感染超過80%。禾生球腔菌（小麥殼針孢）/小麥/治療性（對抗小麥上之殼針孢菌葉斑病之作用） 2週齡小麥植物cv_ Riband藉由用孢子懸浮液喷灑而接種。在22。〇/21。(：（日/夜）及95% rh下培育2天之後，將測試植物保持在氣候室中22艺/21。(：（日/夜）及70% rh下》接種之後5天在噴霧室中用經調配之測試化合物處理經接種之測試植物。當未處理對照植物上出現適當程度之疾病時（鈿用之後11至14天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2、3及4抑制真菌感染達至少8〇%，而在相同條件下，未處理對照植物被植物病原性真菌感染超過80%。 29 201143615 隱匿柄銹菌（尸wccz^re__) /小麥/預防性（對抗小麥上之褐錄病（brown rust)的作用）在喷霧室中用經調配之測試化合物處理2週齡小麥植物CV. Arina。施用之後一天，測試植物藉由用抱子懸浮液喷灌而接種。在飢及95%rh下培育i天之後，將測試植物保持在溫室中2(TC/18t (曰/夜）及6〇% rh下。當未處理對照植物上出現適當程度之疾病時（施用之後12至14 天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2、3及4抑制真菌感染達至少80%，而在相同條件下，未處理對照植物被植物病原性真菌感染超過8〇%。圓核腔菌（户声„打）（大麥網斑病菌 (孖kra)) /大麥/預防性（對抗大麥上之網斑病（net blotch)的作用）在喷霧室中用經調配之測試化合物處理丨週齡大麥植物cv· Regina。施用之後2天’測試植物藉由用孢子懸浮液喷濃而接種。纟赃及95%rhT培育經接種之測試植物，且當未處理對照植物上出現適當程度之疾病時（施用之後5 至7天）評定疾病覆蓋之葉面積百分比。在此測試中，200 ppm之本發明化合物2、3及4抑制真菌感染達至）80%’而在相同條件下，未處理對照植物被植物病原性真菌感染超過8〇0/。。 201143615 【圖式簡單說明】無【主要元件符號說明】無 31~~~—---och3 och3 I don’t like it. Example 1: Preparation of 3-chloro-4-(2,6-di-t-tita e* 虱-4-methoxy-phenyl)-6-methyl-5-(6-trifluorodecyl-. Preparation of 2-mercapto-3-oxooxy-3-(6-=field field | I,-mouse methyl-pyridine _ _ pyridine-3-yl)-嗒0丼 (open (compound No. 3) a) 3_yl)-tert-butyl propionate n-butyllithium (1·6 hexane solution) was added dropwise to a mixture of diisopropylamine (68 g) and 7 〇ml of tetrahydrofuran under nitrogen atmosphere. 46 ml ). After the hydrazine, slowly add $.7 butyl tripropionate to the reaction mixture and continue stirring for 30 minutes at _7 〇 (:, then add 6 dropwise to the sputum at _7 (rc) _Trifluoromethyl nicotinic acid ethyl ester (7 4 L) in 3 〇 tetrahydrofuran solution 'and in _7 〇. Continue stirring for 1 hour under the 。. Add 3 〇 ml of the first --- dibutyl thiol ether After 45 ml of dilute acetic acid, the s material was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and evaporated under reduced pressure, using heptane/ethyl acetate (9:1) The mixture was purified as the remainder of the 'particulate agent' to obtain the 2-mercapto-3-yl group in the oil. 23 201143615 -3-(6-trifluoromethyl-. ratio. -3-yl) - propionate tert-butyl vinegar b) preparation of 2-bromo-1-(6-trifluorodecyl-.pyridin-3-yl)-propan-i-one at room temperature under nitrogen atmosphere to 2- Methyl-3-oxo-3-(6-trifluorodecyl-pyridin-3-yl)-propionic acid tert-butyl ester (10.5 g), 〇.5 ml hydrobromic acid (33% acetic acid solution) Bromine (5.0 g) was slowly added to a mixture of 30 ml of acetic acid. Subsequently, the mixture was slowly heated to 60 ° C. at 60 ° C The reaction mixture was stirred for 30 minutes, then cooled. EtOAc m~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Heptane/ethyl acetate (9.1) followed by a mixture of hydrazine/heptane (2:1) as a dissolving agent to purify the residue to afford 2-bromo-de-trifluoromethyl-pyridine-3-yl as an oil. )_丙-1 -酉同0 c)Preparation of 5-hydroxy·5·fluorenyl_4_(6-difluoro·stupyl)-5Η-furan_2-one to _2_漠-1-(6_3 Gas methyl "pyridin-3-yl"-propanone (3.0 g), monofluorophenylethyl amide (2.1 g) in a solution of 50 ml of acetonitrile: 'amine (1.2 g and at room temperature) Stir the mixture for 1 hr. Then, under cooling, pound, drop. Day 4 t 〇rnRTT ^ Add hydrazine, 8-diazabicyclo [5.4.0] undecene L * L) JB U, 3 Q λ , ^ 廊·, and continue to stir for 1 hour. Then, air is blown through the reaction mixture for 1 hour and the reaction mixture is poured into an aqueous solution of ammonium sulfate, and extracted with ethyl acetate. 1 merger Machine layer, water and evaporate under (4) 1 cut gel chromatography using cyclohexane / 24 201143615 ethyl acetate (3:1) mixture as a dissolving agent to purify the remaining part of the yellow-foamed 5-hydroxy-5-A Base_4_(6_Tristromethyl)-3-(2,4,6-difluoro-phenyl)-5H-nonan-2-g is the same. 0 Preparation 6-fluorenyl-5-(6 -trifluoromethyl-pyridyl-3-yl)-4-(246-fluoro"yl)-2 Η - °荅D well-3 - _ (compound number 1) to 5-hydroxy-5-fluorenyl- 4-(6-Trifluorodecyl-pyridyl 4 6 trifluoro-phenyl)-5H-furan-2-one (3.4 g) was added hydrazine hydrate in 20 ml of 1-butanol φ ... peak solution 0.5 g ), and the mixture was heated for 4 hours to reach i 2 〇·^. Subsequently, the mixture was poured into 20 ml of tert-butyl decyl ether. The resulting mixture was stirred for 30 minutes, then cooled to 0 and filtered. The third portion of the solid was washed with a third butyl group:: 6-methyl _(6-difluoromethyl-u-pyridin-3-yl)-4-(2,4,6-tris) as a brown solid. Fluoro-phenyl)-2H "Sakaguchi _3__ (Compound No. 1), melting point 2 5 2 - 2 5 3 ° C. e) Preparation of 3-chloro-6-mercapto-5-(6-trifluoroanthracene Base_D to alkidine_3_yl)·4_(2,4 = fluoro-phenyl)-嗒D well (Compound No. 2) Under heating 6-methyl·5_(6-trifluorodecyl-pyridine-3_ A mixture of Μ-(2,4,6-tri-Iphenyl)_2Η “荅耕小_ (compound number 丨, 12 g) and 15 ml of phosphorus oxychloride for 3 minutes. After cooling, 瘵 under reduced pressure The reaction mixture was extracted with EtOAc EtOAc (EtOAc)EtOAc. 1) The mixture is used as a free radical to purify the residue to obtain 3·gas·6_methyl 25 in the form of colorless crystals. 201143615 •5-(6-trifluoromethyl-n ratio. _3_yl)-4 -(2,4,6-trifluoro-phenyl)-°荅卩井 (Compound No. 2) 'Melting point 1 56-1 57 ° C. Preparation of 4-(2,6-difluoro-4-methoxy Base-phenyl -3-decyloxy-6-methyl-5-(trifluoromethyl-pyridin-3-yl)-indene well (compound No. 4) heated 3-gas-6-mercapto-5-(6- Trifluoromethyl-pyridin-3-yl)-4-(2,4,6-trifluoro-phenyl)-indole (Compound No. 2,470 mg) 'Sodium decyl carbonate (30 〇/〇 methanol solution) , 770 mg ) and a mixture of 5 ml of tetrahydro-β-propanol for 1 hour up to 5 5 ° C. Subsequently, the reaction mixture was cooled, diluted with water and extracted with ethyl acetate. The combined organic layer was washed with water and brine. The sodium was dehydrated and evaporated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of heptane/ethyl acetate (2:1) as solvent to afford 4-(2,6-difluoro-4-oxo -Phenyl)-3-methoxy-6-methyl-5-(trimethyl fluorenyl-0 to -3-yl)-«> 荅井井(化合物编号4), melting point 143- 144 ° C. g) heating 4-(2,6-difluoro-4-indolyl-phenyl)-3-indolyl-5-(difluoroindolyl-) ratio at 110 °C Bite _3_ base) · 荅u well (compound number 4, 34 〇 mg), 4 ml of phosphorus oxychloride and 80 mg of trimethylamine hydrochloride mixture for a minute. After cooling, the reaction mixture was evaporated under reduced pressure. Purification of the residue by gelatin chromatography using a mixture of heptane/ethyl acetate (4:1) as the solvent to afford 3- -4-(2,6-difluoro-4-[ Base-phenyl)-6-mercapto-5-(6-trifluoromethyl-pyridin-3-ylindole (Compound No. 3), melting point 153-154 ° C. 26 201143615 Biologically applied tomato early blight Bacteria (j/iernarz'a so/αΜί· ) / tomato / prophylactic (acting against Alternaria on tomato) 4 weeks old tomato plants cv treated with formulated test compounds in a spray chamber Roter Gnom. Two days after application, the test plants were inoculated by spraying with a suspension of the stalks. The inoculated test plants were incubated at 22/18 ° C (day/night) and 95% rh in the greenhouse. The percentage of leaf area covered by the disease was assessed when an appropriate degree of disease occurred on the untreated control plants (5 to 7 days after administration). In this test, 200 ppm of the inventive compounds 2, 3 and 4 inhibited fungal infections by at least 80. Under the same conditions, untreated control plants were infected with phytopathogenic fungi by more than 80%. 5〇外0如如(10))(灰葡萄. spore (&& less along Cherei〇) /# 茄/prophylaxis (acting against Botrytis on tomato) The formulated test compound was treated with a 4-week-old tomato plant: CV.R〇terGnom. Two days after the application, the test plants were inoculated by spraying with a spore suspension of the ocean. The inoculation was carried out in a greenhouse under milk and 95% rh. Test plant 'I. Percentage of leaf area covered by disease when an appropriate degree of disease occurs on untreated control plants (5 to 6 days after administration). In this test '200 ppm of compounds of the invention 2 and 3 inhibit fungi 2 3::, and under the same conditions, the untreated control plants were infected with more than 80% of the plant pathogens. 27 201143615 Grape white meal (wecaer) (grape croaker) / grape / preventive (against the grape Effect of powdery mildew) 5 weeks old grape seedling cv. Gutedel was treated with the formulated test compound in a spray chamber. The test plants were inoculated by shaking the plants infected with grape powdery mildew on the i day after application. /22.〇(day/night) and 70% rh The inoculated test plants were grown in a 14/10 hour (light/dark) light manner and the percentage of leaf area covered by the disease was assessed when an appropriate degree of disease appeared on the untreated control plants (7 to 9 days after administration). In this test, 200 ppm of the inventive compounds 2, 3 and 4 inhibited fungal infections by at least 80%, while under the same conditions, untreated control plants were infected by phytopathogenic fungi by more than 80%. Magnaporthe grisea (pyricularia 〇fyza〇/rice/prophylactic (acting against rice fever) 3 weeks old rice plant cv. Koshihikari was treated with the formulated test compound in a spray chamber. After application Two days, the test plants were inoculated by spraying with a spore suspension. The inoculated test plants were grown at 25 (and 95% rh) and when the appropriate degree of disease appeared on the untreated control plants (after application 7 Up to 9 days) The percentage of leaf area covered by the disease was assessed. In this test, 200 ppm of the inventive compounds 2 and 3 inhibited fungal infections by at least '80 〇/〇' and under the same conditions, untreated control plants were phytopathogenic Sexual fungal infections over 80%. 28 201143615 Phytophthora sinensis (Sepioria / wheat / prophylactic (acting against the Septoria leaf spot) on the spray The 2 week old wheat plant cv. Riband was treated with the formulated test compound in the chamber. After the application, the test plants were inoculated by spraying a spore suspension thereon. At 22 t / 21 ° C (day / night) and 95%rh After incubation for the next day, the test plants were kept in the greenhouse 22. (: / 21 (: (day/night) and 7〇% rh. When an appropriate degree of disease appeared on the untreated control plants (16 after application) Up to 19 days) Percentage of leaf area covered by disease. In this test '200 ppm of compounds of the invention 2 and 3 inhibited fungal infection by at least 80%, while under the same conditions, untreated control plants were infected with phytopathogenic fungi More than 80%. G. sphaeroides (Saccharomyces cerevisiae) / wheat / therapeutic (acting against the leaf spot of Capsules on wheat) 2 weeks old wheat plant cv_ Riband by spraying with spore suspension Inoculation. After 2 days of incubation at 22. 日 / 21 (: (day / night) and 95% rh, the test plants were kept in the climate chamber 22 / 21 (: (day / night) and 70% rh The inoculated test plants were treated with the formulated test compound in a spray chamber 5 days after inoculation. The disease covered leaf area was assessed when an appropriate degree of disease appeared on the untreated control plants (11 to 14 days after use). Percentage. In this test, 200 ppm of the invention Compounds 2, 3 and 4 inhibit fungal infections by at least 8%, while under the same conditions, untreated control plants are infected by phytopathogenic fungi by more than 80%. 29 201143615 Puccinia serrata (corporate wccz^re__) / wheat /Prophylactic (for the effect of brown rust on wheat) The 2 week old wheat plant CV. Arina was treated with the formulated test compound in a spray chamber. One day after the application, the test plants were inoculated by sprinkling with a suspension of the stalk. After i days of hunger and 95% rh, the test plants were kept in the greenhouse 2 (TC/18t (day/night) and 6〇% rh. When an appropriate degree of disease appeared on the untreated control plants (administration) The percentage of leaf area covered by the disease was assessed 12 to 14 days later. In this test, 200 ppm of the inventive compounds 2, 3 and 4 inhibited fungal infection by at least 80%, while under the same conditions, untreated control plants were treated with plants. More than 8〇% of pathogenic fungal infections. Helicobacter pylori (Huasheng „打) (Barley Phytophthora (孖kra)) / Barley/prophylactic (acting against net blotch on barley) The peri-week-old barley plant cv·Regina was treated with the formulated test compound in a spray chamber. The test plants were inoculated by spraying with a spore suspension 2 days after application. The inoculated test plants were incubated with 95% rhT. , and the percentage of leaf area covered by the disease was assessed when an appropriate degree of disease occurred on the untreated control plants (5 to 7 days after administration). In this test, 200 ppm of the inventive compounds 2, 3 and 4 inhibited fungal infections. To) 80%' and in the same article The untreated control plants are infected with phytopathogenic fungi than 8〇0 / .. 201 143 615 [drawings briefly described the major elements None None REFERENCE SIGNS 31

Claims

201143615 VII. Patent application scope: 1. A compound of formula (I), -.2

Wherein R1 is fluorenyl or ethyl; R2 is hydrazine, fluorine or chlorine; R3 is fluoro or hydrazine; R4 is fluoro or decyloxy; and R5 is a gas or a decyloxy group, or an agrochemically useful salt form thereof. . 2. A compound according to claim 1 wherein R1 is fluorenyl; R2 is hydrazine or fluoro; R3 is fluoro or aryl; R4 is fluoro or decyloxy: and R5 is chloro. 3. A compound according to claim 1 which is selected from the group consisting of 3-gas-6-mercapto-5-(6-trifluoromethylpyridin-3-yl)-4-(2,4,6-tri Fluorophenyl) hydrazine; 3-ox-5-(6-difluoromethyl.pyridin-3-yl)-6-mercapto-4-(2,4,6-trifluorophenyl).荅口井; 32 201143615 bis(,6-fluorononyloxy)-5-(6-difluoromethylpyridine_3_yl)_6_methyl 荅 well; 3_气邻ϋ·4·甲Oxyl stupyl) heptamethyl o. tri-a fluorene bite -3 - base) -.荅p well; base · 6 · fluorenyl trifluoromethyl _ · 3-yl) · 4 · (2,4,6-trifluorophenyl) arable; and 4- (6- bis-methyl). Comparison 唆3·3) _6_methoxy _3-indenyl) Tower D well. V,, a reduction (a fungicidal composition for controlling or preventing phytopathogenic microorganisms) which contains at least one of a free form or an agrochemically usable salt form, as claimed in the third to third patents a compound as an active ingredient, and at least one adjuvant. 5. The composition of claim 4, further comprising at least one other fungicidally active compound preferably selected from the group consisting of: Azole, pyrimidinylmethanol, 2-amino-pyrimidine, morpholine, anilinopyrimidine 'pyrrole, phenylguanamine, benzimidazole, dimethylimine, guanamine, strobilurine, Dithiocarbamate, fluorenyl-halodecylthiotetrazolylphthalide, copper compound, nitrophenol, organophosphorus derivative, hydrazine, oxazolopyrimidine, formamide And benzoguanamine. 6. Use of a compound according to any one of claims 1 to 3 for controlling or preventing plants, harvested food crops, seeds or non-living substances by plant pathogenic microorganisms Infection. 7·—Control or pre- Crops, harvested food crops or non-living substances are phytopathogenic or spoilage microorganisms or organisms that may be harmful to humans 33 201143615 Methods of infection '纟To the plant, parts of the plants or their locus, seeds or The compound of any one of claims 1 to 3 is administered as an active ingredient, as in any one of the non-living substances. 8. The method of claim 7, wherein the control is achieved by therapeutic administration. The method of claim 7, wherein the pathogenic microorganism is a fungal organism. 10. The method of claim 7, wherein the fungal organism is selected from the group consisting of tomato early blight (5〇/α„ ζ·), Botryotinia fuckeliana, Erysiphe necat〇r 'Magnesium bacillus (Mag«叩〇" heart), Phytophthora turf (gamWa/fl), hidden handle Rust (hcchk hill.ie) and Pyrenophora teres. 11. The method of claim 10, wherein the fungal organism is a bacterium of the genus Corydalis. 1.1) of a compound, .2

It comprises reacting a compound of formula (1.3) with oxygenated phosphorus or sulfinium chloride, 34 201143615

Wherein the compound of formula (1.3) is prepared by a solvent reaction; derived from a compound of formula (II) and deuterium.

, the compound of the formula (II) is prepared by reacting a compound of the formula (5)) with oxygen air or 3-air perbenzoic acid; R2

Wherein the hydrazine (III) compound is optionally prepared by reacting a compound of the formula (ιν) 4 with a base;

.R4 R1 W where R, R2, R3 and R4 are as defined in item 1 of the scope of the patent application. Π· A compound selected from the group consisting of (I3), (n), (nl), and (IV) 35 201143615

Wherein R1, R2, R3 and R4 are as defined in item 1 of the scope of the patent application. Eight, schema · None 36