JP3966929B2 - Substituted pyrazole derivatives, process for producing the same, and agricultural and horticultural fungicides containing the same as active ingredients - Google Patents

Description

［式中、Ｒ¹は水素原子、ハロゲン原子、低級アルキル基、シクロアルキル基、アルケニル基、シアノ基、アルコキシカルボニル基、ニトロ基、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基、または

（式中、Ｒ⁵およびＲ⁶はそれぞれ独立して、水素原子、低級アルキル基を表わす。）で示される基を表わし、
Ｒ²は水素原子、アルキル基、フェニル基、シクロアルキル基、ハロアルキル基、ハロゲン原子、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基を表わし、
Ｒ³は水素原子または低級アルキル基を表わし、
Ｒ⁴は低級アルキル基を表わし、
Ａｒはフェニル基または置換フェニル基を表わす。］
で示される置換ピラゾール誘導体、
２）一般式（II）

（式中、Ｒ¹、Ｒ²、Ｒ⁴およびＡｒは前記と同じ意味を表わす。）で示される化合物を塩基の存在下、アルキル化剤と反応させる一般式（Ｉ）で示される置換ピラゾール誘導体の製造方法、および
３）前記１記載の一般式（Ｉ）で示される置換ピラゾール誘導体の１種または２種以上を有効成分として含有する農園芸用殺菌剤に関するものである。
【０００５】
前記一般式（Ｉ）中、Ｒ¹ およびＲ² が表わすハロゲン原子は弗素、塩素、臭素、ヨウ素原子であり、塩素原子、臭素原子、ヨウ素原子が好ましい。
【０００６】
一般式（Ｉ）中、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ が表わすアルキル基は、炭素数１〜６のものであり、直鎖状でも分枝状でも良い。具体例としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシルおよびその異性体基が挙げられる。
【０００７】
一般式（Ｉ）中、Ｒ¹ およびＲ² が表わすシクロアルキル基は、炭素数３〜６のものであり、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシルが挙げられ、中でもシクロプロピルが好ましい。
【０００８】
一般式（Ｉ）中、Ｒ¹ が表わすアルケニル基は、炭素数２〜４のものであり、直鎖状でも分枝状でも良い。例えばビニル、プロペニル、ブテニルが挙げられ、中でもプロペニルが好ましい。
【０００９】
一般式（Ｉ）中、Ｒ¹ が表わすアルコキシカルボニル基は、炭素数２〜５のものであり、アルコキシ基中のアルキル基部分は直鎖状でも分枝状でも良い。例としてはメトキシカルボニル、エトキシカルボニルが挙げられ、中でもメトキシカルボニル基が好ましい。
【００１０】
一般式（Ｉ）中、Ｒ¹ およびＲ² が表わすアルキルチオ基、アルキルスルフィニル基、およびアルキルスルホニル基は、アルキル部分の炭素数１〜４のものであり、基中のアルキル基部分は直鎖状でも分枝状でも良い。
アルキルチオ基の例としては、メチルチオ、エチルチオが挙げられ、中でもメチルチオが好ましい。
アルキルスルフィニル基の例としてはメチルスルフィニル、エチルスルフィニルが挙げられ、中でもメチルスルフィニルが好ましい。
アルキルスルホニル基の例としては、メチルスルホニル、エチルスルホニルが挙げられ、中でもメチルスルホニルが好ましい。
【００１１】
一般式（Ｉ）中、Ｒ² が表わすハロアルキル基は、前記アルキル基中の水素原子が１〜３個のハロゲン原子で置換されたものに相当し、例えばトリフルオロメチルが挙げられる。
【００１２】
一般式（Ｉ）中、Ａｒが表わす置換フェニル基の置換基としては、例えば、低級（炭素数１〜４程度、以下同じ。）アルキル、低級ハロアルキル、低級アルコキシ、低級ハロアルコキシ、ハロゲン（弗素、塩素、臭素など）、フェニル、ジ低級アルキルアミノ、シアノ等が挙げられる。上記置換基は、同一または異なるものが複数存在していてもよい。
【００１３】
次に、一般式（Ｉ）で表される本発明化合物の代表例、およびその物性を第１表に示す。但し、本発明化合物はこれらのみに限定されるものではない（化合物番号は、後の記載においても参照される。）。なお、表中のＭｅはメチル基、Ｐｒはプロピル基を表わす。
【００１４】

【００１５】

【００１６】

【００１７】
また、第２表に油状物、樹脂状物のＮＭＲデータを示す。

【００１８】
次に本発明化合物の製造法について説明する。
一般式（Ｉ）で示される本発明化合物は、下記反応工程式（ａ）に示すように、例えば一般式（II）で示される化合物を塩基の存在下、アルキル化剤と反応させることにより製造することができる。
【００１９】

【００２０】
一般式（II）で示される化合物とアルキル化剤との反応において、アルキル化剤としてはヨウ化メチル等のアルキルハロゲン化物、ジメチル硫酸等の硫酸エステル類が使用される。
塩基としては、炭酸カリウム、炭酸ナトリウム等の炭酸塩類、水素化ナトリウム、水酸化ナトリウム等のナトリウム塩等が用いられる。
反応に供せられる試剤の量は、一般式（II）で示される化合物１当量に対してアルキル化剤は通常約１〜１０当量、塩基は約１〜２当量である。
上記反応において反応温度および反応時間は通常約０℃〜１００℃、１０分〜２４時間である。
上記反応は通常溶媒が用いられる。使用しうる溶媒としてはジエチルエーテル、テトラヒドロフラン、１，２−ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、アセトン、メチルエチルケトン等のケトン類等があげられる。
反応終了後は通常の後処理を行い、必要に応じてクロマトグラフィー、再結晶等の操作によって精製することにより、目的とする一般式（Ｉ）で示される本発明化合物を得ることができる。
【００２１】
上記反応において出発原料として用いた一般式（II）で示される化合物は、例えば下記反応工程式（ｂ）で示されるように、一般式(III) で示されるピラゾール誘導体と一般式（IV）で示されるヒドロキシイミノ酢酸エステル誘導体（例えば、２−クロロ−２−ヒドロキシイミノ酢酸アルキルエステル、２−ブロモ−２−ヒドロキシイミノ酢酸アルキルエステルなど）とを塩基の存在下反応させることにより製造することができる。
【００２２】

【００２３】
この反応において使用し得る塩基としては、例えばピリジン、トリエチルアミン、４−Ｎ，Ｎ−ジメチルアミノピリジン等の三級アミン、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基等が挙げられる。
反応に供せられる試剤の量は、一般式(III) で示されるピラゾール誘導体１当量に対して、一般式(IV)で示されるヒドロキシイミノ酢酸エステル誘導体を約１〜２当量、塩基は約１〜２当量である。
上記反応において、反応温度および反応時間は、通常約１０℃〜１５０℃、約１０分〜２４時間の範囲である。
また、反応溶媒は必ずしも必要とはしないが、使用する場合、ジエチルエーテル、テトラヒドロフラン、１，２−ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類等、アセトン、メチルエチルケトン等のケトン類、アセトニトリル、Ｎ−メチルピロリドン等が使用される。
【００２４】
なお、上記工程（ｂ）で出発原料として用いた一般式(III) で示されるピラゾール誘導体は、例えば下記反応工程式に従って製造することができる。式中Ｂは塩基を表わし、他の記号は前記と同じ意味を表わす。
【００２５】

【００２６】
本発明による化合物（Ｉ）の適用は植物に対して、有効成分を、噴霧、散布、塗布等して処理するか、または植物の種子、または植物の周囲の土壌あるいは種子を播種する土壌、水田、水耕栽培の水を有効成分で処理することにより行うことができる。適用は植物が病原菌に感染する前または感染後に行うことができる。
【００２７】
本化合物は通常の製剤の様態、例えば液剤，水和剤、乳化剤、懸濁剤、液状濃縮剤、錠剤、顆粒剤、エアロゾル、ペースト剤、粉末剤、燻煙剤などのような農薬用殺菌剤に適する薬剤として使用することができる。このような態様は、少なくとも一種の本発明化合物と適当な固体または液体の担体類、及び所望により、有効成分の分散性や、他の性質の改善のために適当な補助剤（例えば、界面活性剤、展着剤、分散剤、安定剤）とともに混合する通常の方法によって得ることができる。
【００２８】
固体の担体、または希釈剤の例としては、植物性物質、繊維状物質、人工の可塑性粉末、粘土（例えば、カオリン、ベントナイト、白土）、タルク及び無機物（軽石、硫黄粉末）、化学肥料などがある。液体の担体類および希釈剤としては、水、アルコール類、ケトン類、エーテル類、芳香族炭化水素、脂肪族炭化水素、エステル類、ニトリル類、アミド類（Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド）、ハロゲン化炭化水素などがある。
【００２９】
界面活性剤の例としては、アルキル硫酸エステル、スルホン酸アルキル、ポリエチレングリコールエーテル、多価アルコールエステル類などがある。展着剤または分散剤の例は、カゼイン、ゼラチン、デンプン粉、カルボキシメチルセルロース、アラビアゴム、アルギン酸、リグニン、ベントナイト、ポリビニルアルコール、パイン油、糖蜜及び寒天などが挙げられる。
【００３０】
安定剤としては、イソプロピルリン酸塩混合物、燐酸トリクレジル、トルー油、エポキシ油、界面活性剤類、脂肪酸類およびそのエステル類が挙げられる。上記の成分に加えて、本発明の製剤は他の殺菌剤、殺虫剤、除草剤、または肥料と混合して使用することができる。
【００３１】
一般に、上記製剤は、少なくとも一種の本発明化合物（Ｉ）を、１〜９５重量％、好ましくは１〜５０重量％含む。これらの製剤は単独でまたは希釈して使用することができ、本発明の化合物を約１ｇ〜５ｋｇ／ヘクタール、好ましくは約２ｇ〜１００ｇ／ヘクタールを、通常約１〜 50000ｐｐｍ，好ましくは約５０〜1000ｐｐｍの濃度で使用する。
【００３２】
本発明化合物が優れた防除効果を示す植物病害としては、イネのいもち病(Pyricularia oryzae)、ごま葉枯病(Cochliobolus miyabeanus) 、紋枯病(Rhizoctonia solani)、馬鹿苗病(Gibberella fujikuroi)、ムギ類のうどんこ病(Erysiphe graminis f.sp. hordei, Erysiphe graminis f.sp. tritici) 、さび病(Puccinia striiformis, Puccinia graminis, Puccinia recondita f.sp. tritici, Puccinia hordei)、赤かび病(Gibberella zeae) 、網斑病(Pyrenophora teres) 、雪腐病(Typhula incarnata, Typhula ishikariensis, Sclerotinia borealis, Micronectriell a nivalis)、裸黒穂病(Ustilago nuda) 、なまぐさ黒穂病(Tilletia caries, Tilletia toetida) 、眼紋病(Tapesia yallundea) 、雲形病(Phynchosporium secalis f.sp. hordei) 、葉枯病(Septoria tritici)、ふ枯病(Lentosphaeria nodorum) 、カンキツの黒点病(Diaporthe citri) 、そうか病(Elsinoe fawcettii) 、褐色腐敗病(Phytophthora citrophthora) 、緑かび病(Penicillium digitatum) 、青かび病(Penicillium italicum)、リンゴのモニリア病(Monilinia mali)、腐らん病(Valsa ceratosperma)、うどんこ病(Podosphaera leucotricha) 、斑点落葉病(Alternaria alternata apple pathotype)、黒星病(Venturia inaequalis) 、赤星病(Gymnosporangium yamadae) 、輪紋病(Botriophaeria berengeriana f.sp. piricola) 、すす点病(Zygophiala jamaicensis)、すす斑病(Gloeodes pomigena) 、黒点病(Mycosphaerella pomi) 、炭そ病(Glomerella cingulata)、褐斑病(Diplocarpon mali)、ナシの黒星病(Venturia nashicola)、黒斑病(Alternaria alternata japanese pear pathotype)、輪紋病(Physalospora piricola) 、赤星病(Gymnosporangium asiaticum) 、モモの灰星病(Monilinia fructicola)、黒星病(Cladosporium carpophilum)、フォモプシス腐敗病(Phomopsis sp.) 、ブドウのべと病(Plasmopara viticola) 、褐斑病(Pseudocercospora vitis)、輪紋病(Marssonina viticola) 、黒とう病(Elsinoe ampelina)、晩腐病(Glomerella cingulata)、うどんこ病(Uncinula necator)、さび病(Phakopsora ampelopsidis) 、枝膨病(Phomopsis sp.) 、カキのうどんこ病(Phyllactinia kakicola) 、炭そ病(Colletotrichum gloeosporioides)、角斑落葉病(Cercospora kaki,)、丸星落葉病(Mycosphaerella n awae) 、ウメの黒星病(Cladosporium carpophilum)、オウトウの灰星病(Monilinia fructicola)、ウリ類のうどんこ病(Sphaerotheca fuliginea)、べと病(Pseudoperonospora cubensis)、つる枯病(Didymella bryoniae)、炭そ病(Colletotorichum legenarium)、苗立枯病(Pythium cucurbitacearum, Pythium debaryanum, Rhizoctonia solani) 、トマト輪紋病(Alternaria solani) 、葉かび病(Cladosporium fulvum) 、疫病(Phytophthora infestans)、ナスの褐紋病(Phomopsis vexans)、うどんこ病(Erysiphe cichoracearum)、アブラナ科野菜の黒斑病(Alternaria ja ponica, Alternaria bracicae, Alternaria brassicicola)、白斑病(Cercosporella brassicae) 、ホウレンソウのべと病(Peronospora spinaciae) 、疫病(Phytophthora sp.)、タマネギのべと病(Peronospora destructor)、疫病(Phytophthora nicotiana)、灰色腐敗病(Botrytis allii)、ネギのさび病(Puccinia allii)、ショウガの根茎腐敗病(Pyrhium ultimum, Pythium zigiberis)、イチゴのうどんこ病(Sphaerotheca humuli) 、炭そ病(Glomerella cingulata)、ダイズの紫斑病(Cercospora kikuchii) 、べと病(Peronospora manshurica)、黒とう病(Elsinoe glycines)、黒点病(Diaporthe phaseolorum var. sojae)、アズキの褐斑病(Cercospora canescens)、さび病(Uromyces phaseoli var. azukicola)、インゲンの炭そ病(Colletotrichum lindemuthianum) 、ラッカセイの黒渋病(Cercosporidium personatum) 、褐斑病(Cercospora arachidicola) 、そうか病(Shaceloma arachidis) 、エンドウのうどんこ病(Erysiphe pisi) 、ジャガイモの夏疫病(Alternaria solani) 、疫病(Phytophthora infestans)、チャの網もち病(Exobasidium reticulatum) 、白星病(Elsinoe leucospila)、輪斑病(Pestalotiopsis theae, Pestalotiopsis longiseta)、タバコの赤星病(Alternaria longipes) 、うどんこ病(Erysiphe cichoracearum)、炭そ病(Colletotrichum gloeosporioides)、テンサイの褐斑病(Cercospora beticola) 、シバのカーブラリア葉枯病(Curvularia geniculata) 、葉枯病(Rhizoctonia solani)、疑似葉枯病(Ceratobasidium spp.) 、ピシウム病(Pythium periplocum, Pythium graminicola, Pythium vanterpoolii) 、バラの黒星病(Diplocarpon rosae) 、うどんこ病(Shaerotheca pannosa) 、キクの褐斑病(Septoria obesa)、白さび病(Puccinia horiana)、種々の作物の灰色かび病(Botrytis cinerea)、菌核病(Sclerotinia sclerotiorum)等が挙げられる。
【００３３】
【実施例】
次に、本発明化合物の製造例、参考例、本発明化合物の農園芸用殺菌剤としての試験例を具体的に説明する。
【００３４】
製造例１：メチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート（化合物Ｎｏ．２０）の合成
メチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−ヒドロキシイミノアセテート 3.6ｇ（12.3ｍｍｏｌ）を乾燥Ｎ，Ｎ−ジメチルホルムアミド２０ｍｌに溶解し、これに炭酸カリウム 2.5ｇ（18.4ｍｍｍｏｌ）を室温で加えた。この溶液にジメチル硫酸 2.3ｇ（18.4ｍｍｏｌ）を室温下に滴下し、同温で１６時間撹拌した。反応混合物を６０ｍｌの水にあけ、酢酸エチル５０ｍｌで３回抽出した。集めた有機層を飽和食塩水５０ｍｌで洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を留去し残渣をシリカゲルクロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：９）にて精製し、メチル２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 3.1ｇを淡黄色油状物として得た（収率８２％）。
【００３５】
製造例２：メチル ２−（４−クロロ−３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート（化合物Ｎｏ．２１）の合成
製造例１で合成したメチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 0.7ｇ（ 2.3ｍｍｏｌ）をアセトン１０ｍｌに溶解し、１，３−ジクロロ−５，５−ジメチルヒダントイン 0.5ｇ（ 2.3ｍｍｏｌ）を室温で加え同温で１６時間撹拌した。その後溶媒を留去し、残渣をシリカゲルクロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：９）にて精製し、メチル ２−（４−クロロ−３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 1.7ｇを無色油状物として得た（収率８９％）。
【００３６】
製造例３：メチル ２−（４−ブロモ−３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート（化合物Ｎｏ．２２）の合成
製造例１で合成したメチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 1.1ｇ（ 3.6ｍｍｏｌ）をアセトン１０ｍｌに溶解し、１，３−ジクロロ−５，５−ジメチルヒダントイン 0.7ｇ（ 2.5ｍｍｏｌ）を室温で加え同温で１６時間撹拌した。その後溶媒を留去し、残渣をシリカゲルクロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：９）にて精製し、メチル ２−（４−ブロモ−３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 1.2ｇを無色油状物として得た（収率８９％）。
【００３７】
製造例４：メチル ２−（４−ヨード−５−メチル−３−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート（化合物Ｎｏ．２３）の合成
製造例１で合成したメチル ２−（５−メチル−３−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 1.0ｇ（ 3.2ｍｍｏｌ）を塩化メチレン１５ｍｌに溶解し、ヨウ素 0.8ｇ（ 3.2ｍｍｏｌ）を加え、次いで７０％硝酸 0.3ｇ（ 3.2ｍｍｏｌ）を室温で滴下し、同温で１６時間撹拌した。反応混合物を６０ｍｌの水にあけ、塩化メチレン層を分離し、水槽を５０ｍｌの塩化メチレンで３回抽出した。集めた有機層を飽和食塩水５０ｍｌで洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を留去し残渣をシリカゲルクロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：４）にて精製し、メチル ２−（４−ヨード−３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−メトキシイミノアセテート 2.1ｇを油状物として得た（収率９７％）。
【００３８】
参考例：メチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−ヒドロキシイミノアセテートの合成
５−メチル−３−（４−クロロフェニル）ピラゾール10.0ｇ（51.9ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド６０ｍｌに溶解し、炭酸水素ナトリウム 6.5ｇ（78.0ｍｍｏｌ）を室温下に加えた。この溶液に２−クロロ−２−ヒドロキシイミノ酢酸メチル10.7ｇ（78.0ｍｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド１０ｍｌの溶液を室温下に速やかに滴下した。その後溶液を１００℃に加熱し、同温で１時間加熱した。室温まで冷却した溶液を１００ｍｌの水にあけ、５０ｍｌの酢酸エチルで３回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウム上で乾燥した。溶媒を留去後残渣をシリカゲルクロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：２）にて精製し、メチル ２−（３−メチル−５−（４−クロロフェニル）ピラゾール−１−イル）−２−ヒドロキシイミノアセテート 3.6ｇ（12.3ｍｍｏｌ：収率２４％）およびその位置異性体であるメチル ２−（５−メチル−３−（４−クロロフェニル）ピラゾール−１−イル）−２−ヒドロキシイミノアセテート 5.4ｇ（18.4ｍｍｏｌ：収率３５％）をそれぞれ得た。
【００３９】
試験例
次に本発明化合物の農園芸用殺菌剤としての試験例を記載する。
防除効果は、調査時の発病面積率、発病長、病斑数を肉眼観察し、防除指数を下記の５段階で示した。評価基準は特記した場合を除き、本評価基準に従った。
指数５：病斑が認められない、
指数４：発病面積率、発病長、病斑数が無処理区の１〜１０％未満、
指数３：発病面積率、発病長、病斑数が無処理区の１０〜３０％未満、
指数２：発病面積率、発病長、病斑数が無処理区の３０〜５０％未満、
指数１：発病面積率、発病長、病斑数が無処理区の５０〜１００％未満、
指数０：発病面積率、発病長、病斑数が無処理区と同等。
【００４０】
試験例１：ウリ類うどんこ病防除試験
直径６ｃｍのプラスチックポットにて育成した３葉期のキュウリ（品種：光３号Ｐ型）に、キュウリうどんこ病菌（Sphaerotheca fuliginea）の分生胞子を振りかけ接種した。３日後、有効成分化合物をTween 20を含む水で希釈して５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。その後、ポットを温室内に保持し、接種１２日後に第１、２本葉に形成された病斑面積を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：３，４，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２４，２５，２６，２８，２９，３０，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４１】
試験例２：イネいもち病防除試験
直径９ｃｍのプラスチックポットして育成した３葉期のイネ（品種：コシヒカリ）に有効成分化合物をTween 20を含む水で希釈して５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。翌日イネいもち病（Pyricularia oryzae）の分生胞子懸濁液を噴霧接種した。ポットを２３℃湿室下に２４時間保持した後、次いで温室内に７日間保った後、接種葉の病斑数を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：３，４，１０，１１，１２，１５，１６，１７，１８，２４，２５，２６，２８，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４２】
試験例３：ウリ類べと病防除試験
直径６ｃｍのプラスチックポットにて育成した３葉期のキュウリ（品種：光３号Ｐ型）に有効成分化合物をTween 20を含む水で希釈して５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。５００ｐｐｍに調整した薬液２０ｍｌをスプレーガンを用いて散布した。翌日キュウリべと病（Pseudoperonospora cubensis）遊走子懸濁液を噴霧接種した。ポットを２２℃湿室下に１８時間保持した後、次いで温室内に５日間保って病斑長を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：２，３，４，６，１０，１１，１２，１３，１５，１６，１７，１８，２０，２１，２４，２５，２６，２８，２９，３０，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４３】
試験例４：イネ紋枯病防除試験
直径９ｃｍのプラスチックポットして育成した３葉期のイネ（品種：コシヒカリ）に有効成分化合物をTween 20を含む水で希釈して５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。５００ｐｐｍに調製した薬液２０ｍｌをスプレーガンを用いて散布した。翌日ＰＤＡ培地上に生育したイネ紋枯病病（Rhizoctonia solani）の菌そうをコルクボーラーで打ち抜き、葉鞘に張り付けることにより接種した。ポットを２８℃湿室下に２４時間保持した後、次いで温室内に３日間保った後、病斑長を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：１１，１２，１３，１５，１６，１７，１８，２１，２４，２５，２６，２８，２９，３０，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４４】
試験例５：ハクサイ黒斑病防除試験
直径６ｃｍのプラスチックポットにて育成した５葉期のハクサイ（品種：野崎２号）に有効成分化合物をTween 20を含む水で希釈して５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。翌日ハクサイ黒斑病（Alternaria brassicae）分生子懸濁液を噴霧接種した。ポットを２４℃湿室下に３日間保持した後、次いで温室内に１日間保った後、接種葉の発病面積率を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：３，４，５，１０，１１，１２，１３，１５，１６，１７，１８，２４，２５，２６，２８，２９，３０，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４５】
試験例６：キュウリ灰色かび病防除試験
直径９ｃｍのプラスチックポットして育成した子葉期のキュウリ（品種：光３号Ｐ型）に有効成分化合物をTween 20を含む水で希釈し、５００ｐｐｍに調製した薬液２００リットル／１０ａ相当量をスプレーガンを用いて散布した。翌日キュウリ灰色かび病（Botrytis cinerea）の分生胞子懸濁液を噴霧接種した。ポットを２２℃湿室下に２４時間保持した後、次いで温室内に２日間保った後、接種葉の病斑数を調査し、前述評価基準に従い防除指数を求めた。その結果、以下の化合物が５００ｐｐｍにて指数５を示した。
指数５を示した本発明化合物番号：２，３，４，１０，１１，１２，１３，１５，１６，１７，１８，２４，２５，２６，２８，２９，３０，３２，３３，３４，４０，４１，４４，４５，４６，６４，６５。
【００４６】
【発明の効果】
本発明の新規な置換ピラゾール誘導体は、広範な植物病害に対して予防、治療、浸透移行性に関して優れた防除効果を示す一方、作物に対しては安全性を示し優れた殺菌効果を示す農園芸用の殺菌剤として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel pyrazole derivative, a process for producing the same, and an agricultural and horticultural fungicide containing the derivative as an active ingredient.
[0002]
[Prior art and problems]
Various bactericides have been developed so far, but they are not necessarily satisfactory due to their efficacy and the emergence of resistant bacteria.
JP-A-61-291565 describes that certain pyrazole derivatives have bactericidal activity. Even in the compounds described therein, efficacy, residual efficacy, phytotoxicity, etc. This is not satisfactory in terms of the point, and there is a demand for the development of a more useful agricultural and horticultural fungicide against plant diseases.
[0003]
[Means for solving problems]
In view of such circumstances, the present inventors have made various studies in order to develop a compound having excellent bactericidal activity. As a result, an N-alkoxyiminoacetate group is bonded to the nitrogen atom at the 1-position of the pyrazole ring and an aromatic ring is bonded to the 5-position. The present inventors have found that a novel substituted pyrazole derivative has an excellent bactericidal activity and have completed the present invention.
[0004]
That is, the present invention
1) General formula (I)

[Wherein R ¹ Is a hydrogen atom, halogen atom, lower alkyl group, cycloalkyl group, alkenyl group, cyano group, alkoxycarbonyl group, nitro group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, or

(Wherein R ^Five And R ⁶ Each independently represents a hydrogen atom or a lower alkyl group. ) Represents a group represented by
R ² Represents a hydrogen atom, an alkyl group, a phenyl group, a cycloalkyl group, a haloalkyl group, a halogen atom, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group,
R ^Three Represents a hydrogen atom or a lower alkyl group;
R ^Four Represents a lower alkyl group,
Ar represents a phenyl group or a substituted phenyl group. ]
Substituted pyrazole derivatives represented by
2) General formula (II)

(Wherein R ¹ , R ² , R ^Four And Ar have the same meaning as described above. And a method for producing a substituted pyrazole derivative represented by the general formula (I), wherein the compound represented by formula (I) is reacted with an alkylating agent in the presence of a base, and
3) It relates to an agricultural and horticultural fungicide containing as an active ingredient one or more of the substituted pyrazole derivatives represented by the general formula (I) described in 1 above.
[0005]
In the general formula (I), R ¹ And R ² The halogen atom represented by is a fluorine, chlorine, bromine or iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom.
[0006]
In general formula (I), R ¹ , R ² , R ^Three , R ^Four , R ^Five And R ⁶ The alkyl group represented by is one having 1 to 6 carbon atoms and may be linear or branched. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl and isomer groups thereof.
[0007]
In general formula (I), R ¹ And R ² The cycloalkyl group represented by is one having 3 to 6 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and among these, cyclopropyl is preferable.
[0008]
In general formula (I), R ¹ The alkenyl group represented by is one having 2 to 4 carbon atoms and may be linear or branched. For example, vinyl, propenyl, and butenyl are exemplified, and propenyl is preferable.
[0009]
In general formula (I), R ¹ Represents an alkoxycarbonyl group having 2 to 5 carbon atoms, and the alkyl group in the alkoxy group may be linear or branched. Examples include methoxycarbonyl and ethoxycarbonyl, with a methoxycarbonyl group being preferred.
[0010]
In general formula (I), R ¹ And R ² The alkylthio group, the alkylsulfinyl group, and the alkylsulfonyl group represented by are those having 1 to 4 carbon atoms in the alkyl moiety, and the alkyl group moiety in the group may be linear or branched.
Examples of the alkylthio group include methylthio and ethylthio. Among them, methylthio is preferable.
Examples of the alkylsulfinyl group include methylsulfinyl and ethylsulfinyl. Among them, methylsulfinyl is preferable.
Examples of the alkylsulfonyl group include methylsulfonyl and ethylsulfonyl. Among them, methylsulfonyl is preferable.
[0011]
In general formula (I), R ² The haloalkyl group represented by represents a group in which a hydrogen atom in the alkyl group is substituted with 1 to 3 halogen atoms, and examples thereof include trifluoromethyl.
[0012]
In the general formula (I), examples of the substituent of the substituted phenyl group represented by Ar include, for example, lower (about 1 to 4 carbon atoms, the same shall apply hereinafter) alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, halogen (fluorine, Chlorine, bromine, etc.), phenyl, di-lower alkylamino, cyano and the like. A plurality of the same or different substituents may be present.
[0013]
Next, typical examples of the compounds of the present invention represented by formula (I) and their physical properties are shown in Table 1. However, this invention compound is not limited only to these (a compound number is referred also in subsequent description). In the table, Me represents a methyl group, and Pr represents a propyl group.
[0014]

[0015]

[0016]

[0017]
Table 2 shows the NMR data of the oily substance and the resinous substance.

[0018]
Next, the manufacturing method of this invention compound is demonstrated.
The compound of the present invention represented by the general formula (I) is produced, for example, by reacting the compound represented by the general formula (II) with an alkylating agent in the presence of a base, as shown in the following reaction process formula (a). can do.
[0019]

[0020]
In the reaction between the compound represented by the general formula (II) and the alkylating agent, alkyl halides such as methyl iodide and sulfates such as dimethyl sulfate are used as the alkylating agent.
Examples of the base include carbonates such as potassium carbonate and sodium carbonate, sodium salts such as sodium hydride and sodium hydroxide, and the like.
The amount of the reagent used for the reaction is usually about 1 to 10 equivalents for the alkylating agent and about 1 to 2 equivalents for the base with respect to 1 equivalent of the compound represented by the general formula (II).
In the above reaction, the reaction temperature and reaction time are usually about 0 ° C. to 100 ° C. and 10 minutes to 24 hours.
In the above reaction, a solvent is usually used. Solvents that can be used include ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, acid amides such as N, N-dimethylformamide, and ketones such as acetone and methyl ethyl ketone.
After completion of the reaction, normal post-treatment is performed, and purification by an operation such as chromatography, recrystallization or the like can obtain the target compound of the present invention represented by the general formula (I) as necessary.
[0021]
The compound represented by the general formula (II) used as a starting material in the above reaction is, for example, a pyrazole derivative represented by the general formula (III) and a general formula (IV) as represented by the following reaction process formula (b). It can be produced by reacting the hydroxyiminoacetic acid ester derivative shown (for example, 2-chloro-2-hydroxyiminoacetic acid alkyl ester, 2-bromo-2-hydroxyiminoacetic acid alkyl ester, etc.) in the presence of a base. .
[0022]

[0023]
Examples of the base that can be used in this reaction include tertiary amines such as pyridine, triethylamine, 4-N, N-dimethylaminopyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, hydrogenation. Examples thereof include inorganic bases such as sodium.
The amount of the reagent used for the reaction is about 1 to 2 equivalents of the hydroxyiminoacetic acid ester derivative represented by the general formula (IV) and about 1 equivalent of the base to 1 equivalent of the pyrazole derivative represented by the general formula (III). ~ 2 equivalents.
In the above reaction, the reaction temperature and reaction time are usually in the range of about 10 ° C. to 150 ° C. and about 10 minutes to 24 hours.
A reaction solvent is not necessarily required. However, when used, ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, acid amides such as N, N-dimethylformamide, acetone, methyl ethyl ketone and the like Ketones, acetonitrile, N-methylpyrrolidone and the like are used.
[0024]
The pyrazole derivative represented by the general formula (III) used as the starting material in the above step (b) can be produced, for example, according to the following reaction process formula. In the formula, B represents a base, and other symbols have the same meaning as described above.
[0025]

[0026]
The compound (I) according to the present invention is applied to plants by treating the active ingredients by spraying, spraying, applying, or the like, or plant seeds, soil surrounding plants, or soil seeding seeds, paddy fields It can be performed by treating the water of hydroponics with an active ingredient. Application can be done before or after the plant is infected with the pathogen.
[0027]
This compound is used in the form of normal preparations, for example, liquid chemicals, wettable powders, emulsifiers, suspensions, liquid concentrates, tablets, granules, aerosols, pastes, powders, smoke agents, etc. It can be used as a suitable drug. Such embodiments include at least one compound of the invention and a suitable solid or liquid carrier, and, if desired, suitable adjuvants (eg, surfactants) to improve the dispersibility of the active ingredient and other properties. Agents, spreaders, dispersants, stabilizers).
[0028]
Examples of solid carriers or diluents include plant materials, fibrous materials, artificial plastic powders, clays (eg kaolin, bentonite, white clay), talc and minerals (pumice, sulfur powder), chemical fertilizers, etc. is there. Liquid carriers and diluents include water, alcohols, ketones, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, esters, nitriles, amides (N, N-dimethylformamide, dimethyl sulfoxide) And halogenated hydrocarbons.
[0029]
Examples of the surfactant include alkyl sulfate esters, alkyl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters and the like. Examples of spreading agents or dispersing agents include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, polyvinyl alcohol, pine oil, molasses and agar.
[0030]
Stabilizers include isopropyl phosphate mixtures, tricresyl phosphate, true oil, epoxy oil, surfactants, fatty acids and esters thereof. In addition to the above ingredients, the formulations of the present invention can be used in admixture with other fungicides, insecticides, herbicides, or fertilizers.
[0031]
Generally, the above preparation contains 1 to 95% by weight, preferably 1 to 50% by weight, of at least one compound of the present invention (I). These preparations can be used alone or in a diluted form. The compound of the present invention is used at about 1 to 5 kg / ha, preferably about 2 to 100 g / ha, usually about 1 to 50000 ppm, preferably about 50 to 1000 ppm. Use at a concentration of.
[0032]
Plant diseases for which the compounds of the present invention show excellent control effects include rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiot seedling (Gibberella fujikuroi), wheat Powdery mildew (Erysiphe graminis f.sp.hordei, Erysiphe graminis f.sp.tritici), rust (Puccinia striiformis, Puccinia graminis, Puccinia recondita f.sp. tritici, Puccinia hordei), red mold (Gibberella zeae) ), Net blotch (Pyrenophora teres), snow rot (Typhula incarnata, Typhula ishikariensis, Sclerotinia borealis, Micronectriell a nivalis), naked smut (Ustilago nuda), scab (Tilletia caries, Tilletia toetida) (Tapesia yallundea), cloud disease (Phynchosporium secalis f.sp.hordei), leaf blight (Septoria tritici), blight (Lentosphaeria nodorum), citrus black spot (Diaporthe citri), scab (Elsinoe fawcettii), Brown rot (Phytophthora citrophthora), green mold (Penicillium digitatu) m), blue mold (Penicillium italicum), apple monilia (Monilinia mali), rot (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), spotted leaf (Alternaria alternata apple pathotype), black rot (Venturia inaequalis) , Red star disease (Gymnosporangium yamadae), ring rot disease (Botriophaeria berengeriana f.sp. piricola), soot spot disease (Zygophiala jamaicensis), soot spot disease (Gloeodes pomigena), black spot disease (Mycosphaerella pomi), anthracnose disease (Glomerella cing) ), Brown spot disease (Diplocarpon mali), pear black spot disease (Venturia nashicola), black spot disease (Alternaria alternata japanese pear pathotype), ring rot (Physalospora piricola), red star disease (Gymnosporangium asiaticum), peach ash scab (Monilinia fructicola), black scab (Cladosporium carpophilum), phomopsis sp. (Phomopsis sp.), Grape downy mildew (Plasmopara viticola), brown spot (Pseudocercospora vitis), ring rot (Marssonina viticola), black scab (Elsinoe ampelina), late rot (Glomerella cing) ulata), powdery mildew (Uncinula necator), rust disease (Phakopsora ampelopsidis), branch rot (Phomopsis sp.), oyster powdery mildew (Phyllactinia kakicola), anthracnose (Colletotrichum gloeosporioides), cutlet leaf (Cercospora) kaki,), round star defoliation (Mycosphaerella n awae), ume black scab (Cladosporium carpophilum), sweet scab (Monilinia fructicola), cucurbit (Sphaerotheca fuliginea), downy mildew (Pseudoperonospora cubensis) ), Vine blight (Didymella bryoniae), anthracnose (Colletotorichum legenarium), seedling blight (Pythium cucurbitacearum, Pythium debaryanum, Rhizoctonia solani), tomato ring rot (Alternaria solani), leaf mold (Cladosporium fulvum) Plague (Phytophthora infestans), eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum), cruciferous vegetable black spot (Alternaria ja ponica, Alternaria bracicae, Alternaria brassicicola), vitiligo (Cercosporella brassicae), Spinach downy mildew (Peron ospora spinaciae), plague (Phytophthora sp.), onion downy mildew (Peronospora destructor), plague (Phytophthora nicotiana), gray rot (Botrytis allii), green onion rust (Puccinia allii), ginger rhizome rot ( Pyrhium ultimum, Pythium zigiberis), Strawberry powdery mildew (Sphaerotheca humuli), Anthracnose (Glomerella cingulata), Soybean purpura (Cercospora kikuchii), Downy mildew (Peronospora manshurica), Black mildew (Elsinoe glycines) Black spot disease (Diaporthe phaseolorum var.sojae), brown spot disease of azuki bean (Cercospora canescens), rust disease (Uromyces phaseoli var.azukicola), anthracnose of common bean (Colletotrichum lindemuthianum), black astringency of groundnut (Cercosporidium personatum), Brown spot disease (Cercospora arachidicola), common scab (Shaceloma arachidis), pea powdery mildew (Erysiphe pisi), potato summer plague (Alternaria solani), plague (Phytophthora infestans), tea net rot (Exobasidium reticulatum) , Leprosy (Elsin oe leucospila), ring spot disease (Pestalotiopsis theae, Pestalotiopsis longiseta), tobacco red star disease (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum gloeosporioides), sugar beet brown spot (Cercospora beticola) Curvaularia leaf blight (Curvularia geniculata), leaf blight (Rhizoctonia solani), pseudo-leaf blight (Ceratobasidium spp.), Pythium disease (Pythium periplocum, Pythium graminicola, Pythium vanterpoolii), rose black blight (Diplocarpon ross) , Powdery mildew (Shaerotheca pannosa), brown spot of chrysanthemum (Septoria obesa), white rust (Puccinia horiana), gray mold of various crops (Botrytis cinerea), sclerotia (Sclerotinia sclerotiorum), etc. .
[0033]
【Example】
Next, production examples of the compounds of the present invention, reference examples, and test examples of the compounds of the present invention as agricultural and horticultural fungicides will be specifically described.
[0034]
Production Example 1: Synthesis of methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate (Compound No. 20)
3.6 g (12.3 mmol) of methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-hydroxyiminoacetate was dissolved in 20 ml of dry N, N-dimethylformamide, and potassium carbonate was dissolved therein. 2.5 g (18.4 mmol) was added at room temperature. To this solution, 2.3 g (18.4 mmol) of dimethyl sulfate was added dropwise at room temperature and stirred at the same temperature for 16 hours. The reaction mixture was poured into 60 ml of water and extracted three times with 50 ml of ethyl acetate. The collected organic layer was washed with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel chromatography (ethyl acetate: n-hexane = 1: 9), and methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2 -3.1 g of methoxyiminoacetate was obtained as a pale yellow oil (yield 82%).
[0035]
Production Example 2: Synthesis of methyl 2- (4-chloro-3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate (Compound No. 21)
0.7 g (2.3 mmol) of methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate synthesized in Production Example 1 was dissolved in 10 ml of acetone, Dichloro-5,5-dimethylhydantoin 0.5 g (2.3 mmol) was added at room temperature and stirred at the same temperature for 16 hours. Thereafter, the solvent was distilled off, the residue was purified by silica gel chromatography (ethyl acetate: n-hexane = 1: 9), and methyl 2- (4-chloro-3-methyl-5- (4-chlorophenyl) pyrazole- 1.7 g of 1-yl) -2-methoxyiminoacetate was obtained as a colorless oil (yield 89%).
[0036]
Production Example 3: Synthesis of methyl 2- (4-bromo-3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate (Compound No. 22)
1.1 g (3.6 mmol) of methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate synthesized in Production Example 1 was dissolved in 10 ml of acetone, Dichloro-5,5-dimethylhydantoin 0.7 g (2.5 mmol) was added at room temperature and stirred at the same temperature for 16 hours. Thereafter, the solvent was distilled off, and the residue was purified by silica gel chromatography (ethyl acetate: n-hexane = 1: 9), and methyl 2- (4-bromo-3-methyl-5- (4-chlorophenyl) pyrazole- 1.2 g of 1-yl) -2-methoxyiminoacetate was obtained as a colorless oil (yield 89%).
[0037]
Production Example 4: Synthesis of methyl 2- (4-iodo-5-methyl-3- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate (Compound No. 23)
1.0 g (3.2 mmol) of methyl 2- (5-methyl-3- (4-chlorophenyl) pyrazol-1-yl) -2-methoxyiminoacetate synthesized in Production Example 1 was dissolved in 15 ml of methylene chloride, and 0.8 g of iodine was obtained. (3.2 mmol) was added, and then 0.3 g (3.2 mmol) of 70% nitric acid was added dropwise at room temperature, followed by stirring at the same temperature for 16 hours. The reaction mixture was poured into 60 ml of water, the methylene chloride layer was separated, and the water bath was extracted 3 times with 50 ml of methylene chloride. The collected organic layer was washed with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel chromatography (ethyl acetate: n-hexane = 1: 4), and methyl 2- (4-iodo-3-methyl-5- (4-chlorophenyl) pyrazole-1- Yl) -2-methoxyiminoacetate (2.1 g) was obtained as an oil (yield 97%).
[0038]
Reference Example: Synthesis of methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2-hydroxyiminoacetate
10.0 g (51.9 mmol) of 5-methyl-3- (4-chlorophenyl) pyrazole was dissolved in 60 ml of N, N-dimethylformamide, and 6.5 g (78.0 mmol) of sodium bicarbonate was added at room temperature. To this solution, a solution of 10.7 g (78.0 mmol) of methyl 2-chloro-2-hydroxyiminoacetate in 10 ml of N, N-dimethylformamide was quickly added dropwise at room temperature. The solution was then heated to 100 ° C. and heated at the same temperature for 1 hour. The solution cooled to room temperature was poured into 100 ml of water and extracted three times with 50 ml of ethyl acetate, and the combined organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel chromatography (ethyl acetate: n-hexane = 1: 2), and methyl 2- (3-methyl-5- (4-chlorophenyl) pyrazol-1-yl) -2 -Hydroxyiminoacetate 3.6 g (12.3 mmol: 24% yield) and its positional isomer methyl 2- (5-methyl-3- (4-chlorophenyl) pyrazol-1-yl) -2-hydroxyiminoacetate 5.4 g (18.4 mmol: yield 35%) were obtained.
[0039]
Test example
Next, test examples of the compounds of the present invention as agricultural and horticultural fungicides will be described.
The control effect was determined by visual observation of the disease area ratio, disease length, and number of lesions at the time of the investigation, and the control index was shown in the following five levels. The evaluation criteria were in accordance with this evaluation criteria unless otherwise specified.
Index 5: No lesions are observed,
Index 4: Disease area rate, disease length, number of lesions is less than 1 to 10% of the untreated group,
Index 3: Disease area ratio, disease length, number of lesions is less than 10-30% of untreated area,
Index 2: Disease area ratio, disease length, and number of lesions are 30 to less than 50% of the untreated area,
Index 1: Disease area rate, disease length, number of lesions is 50 to less than 100% of untreated area,
Index 0: The disease area ratio, disease length, and number of lesions are the same as in the untreated group.
[0040]
Test Example 1: Worm powdery mildew control test
Cucumbers of 3 leaf stage (variety: Hikari No. 3 type P) grown in a plastic pot having a diameter of 6 cm were sprinkled with inoculated with conidia of Sphaerotheca fuliginea. Three days later, the active ingredient compound was diluted with water containing Tween 20 and an amount equivalent to 200 liters / 10a of a chemical solution prepared to 500 ppm was sprayed using a spray gun. Thereafter, the pot was kept in the greenhouse, and the lesion areas formed on the first and second true leaves were examined 12 days after the inoculation, and the control index was determined according to the aforementioned evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed the index 5: 3, 4, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 24, 25, 26, 28, 29, 30, 32, 33, 34, 40, 41, 44, 45, 46, 64, 65.
[0041]
Test Example 2: Rice Blast Control Test
Using a spray gun, an equivalent amount of 200 liters / 10a of chemical solution prepared by diluting the active ingredient compound with water containing Tween 20 in three-leaf rice (cultivar: Koshihikari) grown in a plastic pot with a diameter of 9 cm was prepared. Scattered. On the next day, a conidial spore suspension of rice blast (Pyricularia oryzae) was spray-inoculated. After the pot was kept in a 23 ° C. wet chamber for 24 hours and then kept in the greenhouse for 7 days, the number of lesions on the inoculated leaves was examined, and the control index was determined according to the above-mentioned evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed index 5: 3, 4, 10, 11, 12, 15, 16, 17, 18, 24, 25, 26, 28, 32, 33, 34, 40, 41, 44, 45, 46, 64, 65.
[0042]
Test Example 3: Cucumber downy mildew control test
Spray the cucumber (variety: Hikari No. 3 type P) in the 3 leaf stage grown in a plastic pot with a diameter of 6 cm, and dilute the active ingredient compound with water containing Tween 20 to make a chemical solution equivalent to 200 liter / 10a. Sprayed with a gun. 20 ml of chemical solution adjusted to 500 ppm was sprayed using a spray gun. The next day, the seedlings were inoculated with a zoospore suspension of Pseudoperonospora cubensis. The pot was kept in a humid chamber at 22 ° C. for 18 hours and then kept in a greenhouse for 5 days to investigate the lesion length, and the control index was determined according to the above evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed index 5: 2,3,4,6,10,11,12,13,15,16,17,18,20,21,24,25,26,28,29,30, 32, 33, 34, 40, 41, 44, 45, 46, 64, 65.
[0043]
Test Example 4: Rice Blight Disease Control Test
Using a spray gun, an equivalent amount of 200 liters / 10a of chemical solution prepared by diluting the active ingredient compound with water containing Tween 20 in three-leaf rice (cultivar: Koshihikari) grown in a plastic pot with a diameter of 9 cm was prepared. Scattered. 20 ml of chemical solution prepared to 500 ppm was sprayed using a spray gun. The next day, the fungus of Rhizoctonia solani grown on PDA medium was punched with a cork borer and inoculated by sticking it to the leaf sheath. After holding the pot in a wet chamber at 28 ° C. for 24 hours and then in the greenhouse for 3 days, the length of lesions was investigated, and the control index was determined according to the aforementioned evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed index 5: 11, 12, 13, 15, 16, 17, 18, 21, 24, 25, 26, 28, 29, 30, 32, 33, 34, 40, 41, 44, 45, 46, 64, 65.
[0044]
Test Example 5: Chinese cabbage black spot disease prevention test
A spray gun with a chemical equivalent to 200 liters / 10a prepared by diluting the active ingredient compound with water containing Tween 20 in 5-leaf cabbage grown in a 6 cm diameter plastic pot (variety: Nozaki No. 2) Used to spray. The next day, spray inoculation was carried out with a conidial suspension of Alternaria brassicae. After the pot was kept in a wet room at 24 ° C. for 3 days and then kept in the greenhouse for 1 day, the diseased area ratio of the inoculated leaves was investigated, and the control index was determined according to the above-mentioned evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed index 5: 3, 4, 5, 10, 11, 12, 13, 15, 16, 17, 18, 24, 25, 26, 28, 29, 30, 32, 33, 34, 40, 41, 44, 45, 46, 64, 65.
[0045]
Test Example 6: Cucumber gray mold control test
An effective ingredient compound is diluted with water containing Tween 20 in a cotyledon cucumber (variety: Hikari No. 3 P-type) grown in a plastic pot with a diameter of 9 cm, and spray gun is used in an amount equivalent to 200 liters / 10a of chemical solution prepared to 500 ppm. It sprayed using. The next day, a conidial spore suspension of Botrytis cinerea was spray-inoculated. After the pot was kept in a humid chamber at 22 ° C. for 24 hours and then kept in the greenhouse for 2 days, the number of lesions on the inoculated leaves was examined, and the control index was determined according to the above evaluation criteria. As a result, the following compounds showed an index of 5 at 500 ppm.
This invention compound number which showed index 5: 2,3,4,10,11,12,13,15,16,17,18,24,25,26,28,29,30,32,33,34, 40, 41, 44, 45, 46, 64, 65.
[0046]
【The invention's effect】
The novel substituted pyrazole derivative of the present invention exhibits excellent control effects on prevention, treatment, and osmotic transfer for a wide range of plant diseases, while it exhibits safety and excellent bactericidal effects on crops. Useful as a disinfectant.

Claims (3)

Formula (I)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkenyl group, a cyano group, an alkoxycarbonyl group, a nitro group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, Or

(Wherein R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
R ² represents a hydrogen atom, an alkyl group, a phenyl group, a cycloalkyl group, a haloalkyl group, a halogen atom, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group,
R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ⁴ represents an alkyl group having 1 to 6 carbon atoms,
Ar represents a phenyl group or a substituted phenyl group. ]
A substituted pyrazole derivative represented by: Formula (II)

(Wherein R ¹ , R ² , R ⁴ and Ar have the same meanings as defined in claim 1), a general formula characterized by reacting with a alkylating agent in the presence of a base (I)

(Wherein R ³ represents the same meaning as described in claim 1 and the other symbols represent the same meaning as described above).   An agricultural and horticultural fungicide containing one or more of the substituted pyrazole derivatives according to claim 1 as an active ingredient.