JP2004002363A - Ester compound and its application - Google Patents
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- JP2004002363A JP2004002363A JP2003098931A JP2003098931A JP2004002363A JP 2004002363 A JP2004002363 A JP 2004002363A JP 2003098931 A JP2003098931 A JP 2003098931A JP 2003098931 A JP2003098931 A JP 2003098931A JP 2004002363 A JP2004002363 A JP 2004002363A
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- 0 CC(C)(C1C=*)C1C(OCc(c(F)c(c(COC)c1F)F)c1F)=O Chemical compound CC(C)(C1C=*)C1C(OCc(c(F)c(c(COC)c1F)F)c1F)=O 0.000 description 2
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、エステル化合物およびその用途に関する。
【０００２】
【発明が解決しようとする課題】
本発明は、優れた有害生物防除効力を有する化合物を提供することを課題とする。
【０００３】
【課題を解決するための手段】
本発明者は優れた有害生物防除効力を有する化合物を見出すべく鋭意検討した結果、後記式（１）で示される化合物が優れた有害生物防除効力を有することを見出し、本発明を完成した。
【０００４】
即ち、本発明は、式（１）
【化２】
【０００５】
【発明の実施の形態】
本発明化合物にはシクロプロパン環上に存在する２個の不斉炭素原子に由来する異性体、および二重結合に由来する異性体が存在するが、本発明にはその各々および任意の異性体比率である化合物が含まれる。
【０００６】
本発明化合物の形態としては例えば以下のものが挙げられる。
【化３】
式（１）において、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランス配置である化合物；
式（１）において、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がシス配置である化合物；
式（１）において、シクロプロパン環３位の置換基に存在する二重結合の相対配置がＺ配置である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスである化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がシスである化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランス配置であり、シクロプロパン環３位の置換基に存在する二重結合の相対配置がＺ配置である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がシス配置であり、シクロプロパン環３位の置換基に存在する二重結合の相対配置がＺ配置である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものに富む化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものが８０％以上である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものが９０％以上である化合物。
【０００７】
本発明化合物は例えば以下に示す方法により製造することができる。
式（２）
【化４】
【化５】
該反応は通常塩基の存在下、溶媒中で行われる。
該反応に用いられる溶媒としては例えば、ヘキサン、ヘプタン、オクタン、トルエン等の炭化水素類、ジエチルエーテル、テトラヒドロフラン等のエーテル類およびこれらの混合物があげられる。
該反応に用いられる塩基としては例えば、ナトリウムメトキシド、カリウム−ｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシド類、水素化ナトリウム、水素化カリウム等のアルカリ金属水素化物、およびナトリウムビストリメチルシリルアミド、リチウムビストリメチルシリルアミド、リチウムビスイソプロピルアミド等のアルカリ金属アミド類が挙げられる。
反応に用いられる試剤の量は、式（２）で示されるアルデヒド化合物１モルに対して、式（３）で示される化合物が通常０．８〜１．５モルの割合であり、塩基が通常０．８〜１．５モルの割合である。
反応時間は通常瞬時〜７２時間の範囲、反応温度は通常−８０〜８０℃の範囲である。
反応終了後は反応混合物を水に注加し、有機溶媒抽出して、得られた有機層を乾燥、濃縮する等の後処理操作を行うことにより本発明化合物を単離することができる。単離した本発明化合物はクロマトグラフィー等によりさらに精製することもできる。
【０００８】
式（２）で示されるアルデヒド化合物は例えば式（４）
【化６】
【０００９】
本発明化合物はまた、式（５）
【化７】
【化８】
【００１０】
式（４）で示される化合物は例えばヨーロッパ特許公開ＥＰ１００４５６９Ａ１号公報に記載の化合物であり、該公報に記載の方法で製造することができる。式（５）で示される２，３，５，６−テトラフルオロ−４−メトキシメチルベンジルアルコールは例えば特開昭５６−９７２５１号公報に記載の化合物であり、該公報に記載の方法で製造することができる。
式（６）で示されるカルボン酸化合物は例えばＡｇｒ．Ｂｉｏｌ．Ｃｈｅｍ．，３４，１１１９（１９７０）に記載された化合物であり、該文献に記載された方法で製造することができる。
【００１１】
本発明化合物が効力を有する有害生物としては、例えば昆虫やダニ等の節足動物があげられ、具体的には例えば以下の害虫等があげられる。
鱗翅目害虫
ニカメイガ、コブノメイガ、ノシメコクガ等のメイガ類、ハスモンヨトウ、アワヨトウ、ヨトウガ等のヨトウ類、モンシロチョウ等のシロチョウ類、コカクモンハマキ等のハマキガ類、シンクイガ類、ハモグリガ類、ドクガ類、ウワバ類、カブラヤガ、タマナヤガ等のアグロティス属害虫 （Ａｇｒｏｔｉｓ ｓｐｐ．）、ヘリコベルパ属害虫 （Ｈｅｌｉｃｏｖｅｒｐａ ｓｐｐ．）、ヘリオティス属害虫 （Ｈｅｌｉｏｔｈｉｓ ｓｐｐ．）、コナガ、イチモンジセセリ、イガ、コイガ等
【００１２】
双翅目害虫
アカイエカ、コガタアカイエカ等のイエカ類、ネッタイシマカ、ヒトスジシマカ等のヤブカ類、シナハマダラカ等のハマダラカ類、ユスリカ類、イエバエ、オオイエバエ、ヒメイエバエ等のイエバエ類、クロバエ類、ニクバエ類、タネバエ、タマネギバエ等のハナバエ類、ミバエ類、ショウジョウバエ類、チョウバエ類、ノミバエ類、アブ類、ブユ類、サシバエ類、ヌカカ類等
【００１３】
網翅目害虫
チャバネゴキブリ、クロゴキブリ、ワモンゴキブリ、トビイロゴキブリ、コバネゴキブリ等
【００１４】
膜翅目害虫
アリ類、スズメバチ類、アリガタバチ類、カブラハバチ等のハバチ類等
【００１５】
隠翅目害虫
イヌノミ、ネコノミ、ヒトノミ等
【００１６】
シラミ目害虫
ヒトジラミ、ケジラミ、アタマジラミ、コロモジラミ等
【００１７】
等翅目害虫
ヤマトシロアリ、イエシロアリ等
【００１８】
半翅目害虫
ヒメトビウンカ、トビイロウンカ、セジロウンカ等のウンカ類、ツマグロヨコバイ、タイワンツマグロヨコバイ等のヨコバイ類、アブラムシ類、カメムシ類、コナジラミ類、カイガラムシ類、グンバイムシ類、キジラミ類等
【００１９】
鞘翅目害虫
ヒメカツオブシムシ、ヒメマルカツオブシムシ、ウエスタンコーンルートワーム、サザンコーンルートワーム等のコーンルートワーム類、ドウガネブイブイ、ヒメコガネ等のコガネムシ類、コクゾウムシ、イネミズゾウムシ、ワタミゾウムシ、アズキゾウムシ等のゾウムシ類、チャイロコメノゴミムシダマシ、コクヌストモドキ等のゴミムシダマシ類、イネドロオイムシ、キスジノミハムシ、ウリハムシ等のハムシ類、シバンムシ類、ニジュウヤホシテントウ等のエピラクナ属 （Ｅｐｉｌａｃｈｎａ ｓｐｐ．）、ヒラタキクイムシ類、ナガシンクイムシ類、カミキリムシ類、アオバアリガタハネカクシ等
【００２０】
総翅目害虫
ミナミキイロアザミウマ、ミカンキイロアザミウマ、ハナアザミウマ等
【００２１】
直翅目害虫
ケラ、バッタ等
【００２２】
ダニ類
コナヒョウヒダニ、ヤケヒョウヒダニ等のヒョウヒダニ類、ケナガコナダニ、ムギコナダニ等のコナダニ類、チリニクダニ、イエニクダニ、サナアシニクダニ等のニクダニ類、クワガタツメダニ、フトツメダニ等のツメダニ類、ホコリダニ類、マルニクダニ類、イエササラダニ類、ナミハダニ、カンザワハダニ、ミカンハダニ、リンゴハダニ等のハダニ類、フタトゲチマダニ等のマダニ類
【００２３】
本発明の有害生物防除剤は本発明化合物そのものでもよいが、通常は本発明化合物を製剤化されている。
その製剤としては、例えば油剤、乳剤、水和剤、フロアブル剤（水中懸濁剤、水中乳濁剤等）、粉剤、粒剤、エアゾール剤、加熱蒸散剤（殺虫線香、電気殺虫マット、吸液芯型加熱蒸散殺虫剤等）、加熱燻煙剤（自己燃焼型燻煙剤、化学反応型燻煙剤、多孔セラミック板燻煙剤等）、非加熱蒸散剤（樹脂蒸散剤、含浸紙蒸散剤等）、煙霧剤（フォッキング等）、ＵＬＶ剤および毒餌があげられる。
【００２４】
製剤化の方法としては、例えば以下の方法をあげることができる。
（１）本発明化合物を固体担体、液体担体、ガス状担体、餌等と混合し、必要があれば界面活性剤その他の製剤用補助剤を添加・加工する方法。
（２）本発明化合物を有効成分を含有していない基材に含浸する方法。
（３）本発明化合物と基材を混合した後に成形加工する方法。
これらの製剤には、本発明化合物を、製剤形態にもよるが、通常、重量比で０．００１〜９５％含有する。
【００２５】
製剤化の際に用いられる担体としては、例えば固体担体｛粘土類（カオリンクレー、珪藻土、合成含水酸化珪素、ベントナイト、フバサミクレー、酸性白土等）、タルク類、セラミック、その他の無機鉱物（セリサイト、石英、硫黄、活性炭、炭酸カルシウム、水和シリカ、モンモリロナイト等）、化学肥料（硫安、燐安、硝安、尿素、塩安等）等｝、液体担体｛水、アルコール類（メタノール、エタノール等）、ケトン類（アセトン、メチルエチルケトン等）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン、メチルナフタレン、フェニルキシリルエタン等）、脂肪族炭化水素類（ヘキサン、シクロヘキサン、灯油、軽油等）、エステル類（酢酸エチル、酢酸ブチル等）、ニトリル類（アセトニトリル、イソブチロニトリル等）、エーテル類（ジイソプロピルエーテル、ジオキサン等）、酸アミド類（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等）、ハロゲン化炭化水素類（ジクロロメタン、トリクロロエタン、四塩化炭素等）、ジメチルスルホキシド、植物油（大豆油、綿実油等）等｝、およびガス状担体｛フロンガス、ブタンガス、ＬＰＧ（液化石油ガス）、ジメチルエーテル、炭酸ガス等｝があげられる。
【００２６】
界面活性剤としては、例えば、アルキル硫酸エステル類、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アルキルアリールエーテル類、アルキルアリールエーテル類のポリオキシエチレン化物、ポリエチレングリコールエーテル類、多価アルコールエステル類、及び糖アルコール誘導体があげられる。
【００２７】
その他の製剤用補助剤としては、固着剤、分散剤及び安定剤等、例えばカゼイン、ゼラチン、多糖類（デンプン、アラビアガム、セルロース誘導体、アルギン酸等）、リグニン誘導体、ベントナイト、合成水溶性高分子（ポリビニルアルコール、ポリビニルピロリドン）、ポリアクリル酸等、ＢＨＴ（２，６−ジ−ｔ−ブチル−４−メチルフェノール）、およびＢＨＡ（２−ｔ−ブチル−４−メトキシフェノールと３−ｔ−ブチル−４−メトキシフェノールとの混合物）があげられる。
【００２８】
殺虫線香の基材としては、例えば木粉、粕粉等の植物性粉末とタブ粉、スターチ、グルテイン等の結合剤との混合物があげられる。
【００２９】
電気殺虫マットの基材としては、例えばコットンリンターを板状に固めたもの、およびコットンリンターとパルプとの混合物のフィリブルを板状に固めたものがあげられる。
【００３０】
自己燃焼型燻煙剤の基材としては、例えば、硝酸塩、亜硝酸塩、グアニジン塩、塩素酸カリウム、ニトロセルロース、エチルセルロース、木粉等の燃焼発熱剤、アルカリ金属塩、アルカリ土類金属塩、重クロム酸塩、クロム酸塩等の熱分解刺激剤、硝酸カリウム等の酸素供給剤、メラミン、小麦デンプン等の支燃剤、珪藻土等の増量剤及び合成糊料等の結合剤があげられる。
【００３１】
化学反応型燻煙剤の基材としては、例えば、アルカリ金属の硫化物、多硫化物、水硫化物、酸化カルシウム等の発熱剤、炭素質物質、炭化鉄、活性白土などの触媒剤、アゾジカルボンアミド、ベンゼンスルホニルヒドラジド、ジニトロペンタメチレンテトラミン、ポリスチレン、ポリウレタン等の有機発泡剤、および天然繊維片、合成繊維片等の充填剤があげられる。
【００３２】
非加熱蒸散剤の基材としては、例えば、熱可塑性樹脂、および紙（濾紙、和紙等）があげられる。
【００３３】
毒餌の基材としては、例えば、穀物粉、植物油、糖、結晶セルロース等の餌成分、ジブチルヒドロキシトルエン、ノルジヒドログアセチック酸等の酸化防止剤、デヒドロ酢酸等の保存料、トウガラシ末等の子どもやペットによる誤食防止剤、及びチーズ香料、タマネギ香料、ピーナッツオイル等の害虫誘引性香料があげられる。
【００３４】
本発明の有害生物防除方法は通常、本発明の有害生物防除剤を有害生物または有害生物の生息場所に施用することにより行われる。
【００３５】
本発明の有害生物防除剤の施用方法としては、例えば以下の方法があげられ、本発明の有害生物防除剤の形態、使用場所等に応じて適宜選択できる。
（１）本発明の有害生物防除剤をそのまま有害生物又は有害生物の生息場所に処理する方法。
（２）本発明の有害生物防除剤を水等の溶媒で希釈した後に、有害生物又は有害生物の生息場所に散布処理する方法。
この場合には、通常、乳剤、水和剤、フロアブル剤、マイクロカプセル製剤等に製剤化された本発明の有害生物防除剤を本発明化合物の濃度が０．１〜１００００ｐｐｍとなるように希釈する。
（３）本発明の有害生物防除剤を有害生物の生息場所で加熱し、有効成分を揮散させる方法。
この場合、本発明化合物の施用量、施用濃度はいずれも本発明の有害生物防除剤の形態、施用時期、施用場所、施用方法、有害生物の種類、被害状況等に応じて適宜定めることができる。
【００３６】
本発明の有害生物防除剤は他の殺虫剤、殺線虫剤、土壌害虫防除剤、殺菌剤、除草剤、植物成長調節剤、忌避剤、共力剤、肥料、土壌改良材と混用または併用することもできる。
【００３７】
かかる殺虫剤、殺ダニ剤の有効成分としては、例えば、フェニトロチオン、フェンチオン、ダイアジノン、クロルピリホス、アセフェート、メチダチオン、ジスルホトン、ＤＤＶＰ、スルプロホス、シアノホス、ジオキサベンゾホス、ジメトエート、フェントエート、マラチオン、トリクロルホン、アジンホスメチル、モノクロトホス、エチオン等の有機リン系化合物、
【００３８】
ＢＰＭＣ、ベンフラカルブ、プロポキスル、カルボスルファン、カルバリル、メソミル、エチオフェンカルブ、アルジカルブ、オキサミル、フェノチオカルブ等のカーバメート系化合物、
【００３９】
エトフェンプロックス、フェンバレレート、エスフェンバレレート、フェンプロパトリン、シペルメトリン、ペルメトリン、シハロトリン、デルタメトリン、シクロプロトリン、フルバリネート、ビフェンスリン、２−メチル−２−（４−ブロモジフルオロメトキシフェニル）プロピル（３−フェノキシベンジル）エ−テル、トラロメトリン、シラフルオフェン、ｄ−フェノトリン、シフェノトリン、ｄ−レスメトリン、アクリナスリン、シフルトリン、テフルトリン、トランスフルスリン、テトラメトリン、アレスリン、ｄ−フラメトリン、プラレトリン、エンペントリン、５−（２−プロピニル）フルフリル ２，２，３，３−テトラメチルシクロプロパンカルボキシレート等のピレスロイド化合物、
【００４０】
ニトロイミダゾリジン誘導体、アセタミプリド等のＮ−シアノアミジン誘導体、エンドスルファン、γ−ＢＨＣ、１，１−ビス（クロロフェニル）−２，２，２−トリクロロエタノール等の塩素化炭化水素化合物、クロルフルアズロン、テフルベンズロン、フルフェノクスロン等のベンゾイルフェニルウレア系化合物、フェニルピラゾール系化合物、メトキサジアゾン、ブロモプロピレート、テトラジホン、キノメチオネート、ピリダベン、フェンピロキシメート、ジアフェンチウロン、テブフェンピラド、ポリナクチンコンプレックス〔テトラナクチン、ジナクチン、トリナクチン〕、ピリミジフェン、ミルベメクチン、アバメクチン、イバーメクチン、およびアザジラクチンがあげられる。
【００４１】
忌避剤としては、例えば、３，４−カランジオール、Ｎ，Ｎ−ジエチル−ｍ−トルアミド、１−メチルプロピル ２−（２−ヒドロキシエチル）−１−ピペリジンカルボキシラート、ｐ−メンタン−３，８−ジオール、およびヒソップ油などの植物精油等があげられる。
【００４２】
共力剤としては、例えば、ビス−（２，３，３，３−テトラクロロプロピル）エーテル（Ｓ−４２１）、Ｎ−（２−エチルヘキシル）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド（ＭＧＫ−２６４）、およびα−［２−（２−ブトキシエトキシ）エトキシ］−４，５−メチレンジオキシ−２−プロピルトルエン（ピペロニルブトキシド）があげられる。
【００４３】
【実施例】
以下、製造例、製剤例及び試験例等により本発明さらに詳しく説明するが、本発明はこれらの例に限定されるものではない。
【００４４】
まず、本発明化合物の製造例を示す。
製造例
窒素雰囲気下、テトラヒドロフラン６ｍｌにジエチル（１−シアノエチル）ホスホナート０．５４ｇを溶解し、約０℃で、ナトリウムビス（トリメチルシリル）アミドのテトラヒドロフラン溶液（１ｍｏｌ／ｌ）２．８ｍｌを加え、３０分間攪拌した。そこに、式（７）で示される
【化９】
【化１０】
【００４５】
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ）δ（ｐｐｍ）：１．２１（ｓ，３Ｈ，Ｚ＋Ｅ体）、１．３２（ｓ，３Ｈ，Ｚ＋Ｅ体）、１．７３（ｍ，１Ｈ，Ｚ＋Ｅ体）、１．９６（ｓ，３Ｈ、Ｚ＋Ｅ体）、２．２０（ｍ，１／３Ｈ，Ｅ体）、２．４７（ｍ，２／３Ｈ，Ｚ体）、３．４１（ｓ，３Ｈ，Ｚ＋Ｅ体）、４．５９（ｓ，２Ｈ，Ｚ＋Ｅ体）、５．２６（ｓ，２Ｈ，Ｚ＋Ｅ体）、５．７８（ｍ，２／３Ｈ，Ｚ体）、６．０１（ｍ，１／３Ｈ，Ｅ体）
【００４６】
参考製造例１
テトラヒドロフラン１０ｍｌに４−メトキシメチル−２，３，５，６−テトラフルオロベンジルアルコール１．０ｇ及びピリジン０．４２ｇを溶解し、氷冷下で３−（２−メチル−１−プロペニル）−２，２−ジメチルシクロプロパンカルボン酸塩化物｛立体異性体比率 （１Ｒ）−トランス体：（１Ｒ）−シス体：（１Ｓ）−トランス体：（１Ｓ）−シス体＝９３．９：２．５：３．５：０．１｝０．９ｇを加え、さらに室温で８時間攪拌した。その後、反応混合物を氷水約５０ｍｌ中に注加し、酢酸エチル８０ｍｌで２回抽出した。有機層を合わせて飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した後、減圧下濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、４−メトキシメチル−２，３，５，６−テトラフルオロベンジル ３−（２−メチル−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレート１．４ｇを得た。
【００４７】
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ）δ（ｐｐｍ）：１．１３（ｓ，３Ｈ）、１．２６（ｓ，３Ｈ）、１．３８（ｄ，１Ｈ）、１．６９（ｂｒｓ，６Ｈ）、２．１０（ｄｄ，１Ｈ）、３．４０（ｓ，３Ｈ）、４．５９（ｓ，２Ｈ）、４．８７（ｄ，１Ｈ）、５．２４（ｄｄ，２Ｈ）
【００４８】
テトラヒドロフラン２５ｍｌと１，４−ジオキサン１５０ｍｌとの混合溶媒に４−メトキシメチル−２，３，５，６−テトラフルオロベンジル ３−（２−メチル−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレート１５．４ｇを溶解し、室温で四酸化オスミウム１．０ｇを加え、さらにメタ過ヨウ素酸ナトリウム２４．０ｇを水５０ｍｌに溶解した溶液を加えた後、２時間加熱還流した。その後、反応混合物を水約２００ｍｌに注加し、酢酸エチル２００ｍｌで２回抽出した。有機層を合わせて１％チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した後、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、４−メトキシメチル−２，３，５，６−テトラフルオロベンジル ３−ホルミル−２，２−ジメチルシクロプロパンカルボキシレート１０．４ｇを得た。
【００４９】
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ）δ（ｐｐｍ）：１．３０（ｓ，３Ｈ）、１．３６（ｓ，３Ｈ）、２．４７（ｍ，２Ｈ）、３．４１（ｓ，３Ｈ）、４．５９（ｓ，２Ｈ）、５．２６（ｓ，２Ｈ）、９．５９（ｓ，１Ｈ）
【００５０】
次に製剤例を示す。なお、部は重量部を示す。
製剤例１
本発明化合物２０部をキシレン６５部に溶解し、ソルポール３００５Ｘ（東邦化学登録商標）１５部を加え、よく攪拌混合して、乳剤を得る。
【００５１】
製剤例２
本発明化合物４０部にソルポール３００５Ｘ ５部を加え、良く混合してカープレックス＃８０（合成含水酸化珪素、塩野義製薬登録商標）３２部、３００メッシュ珪藻土２３部を加え、ジュースミキサーで攪拌混合して、水和剤を得る。
【００５２】
製剤例３
本発明化合物 １．５部およびトクシールＧＵＮ（合成含水酸化珪素、株式会社トクヤマ製）１部、リアックス８５Ａ（リグニンスルホン酸ナトリウム、Ｗｅｓｔ ｖａｃｏ ｃｈｅｍｉｃａｌｓ社製）２部、ベントナイト富士（ベントナイト、ホウジュン社製）３０部および勝光山Ａクレー（カオリンクレー、勝光山鉱業所社製）６５．５部をよく粉砕混合し、水を加えてよく練り合わせた後、押出し造粒機で造粒し、乾燥して、１．５％粒剤を得る。
【００５３】
製剤例４
本発明化合物１０部、フェニルキシリルエタン１０部およびスミジュールＬ−７５（トリレンジイソシアネート、住友バイエルウレタン社製）０．５部を混合した後、アラビアガムの１０％水溶液２０部中に加え、ホモミキサーで攪拌して、平均粒径２０μｍのエマルジョンを得る。ここにエチレングリコール２部を加え、さらに６０℃の温浴中で２４時間攪拌してマイクロカプセルスラリーを得る。一方、ザンサンガム０．２部、ビーガムＲ（アルミニウムマグネシウムシリケート、三洋化成製）１．０部をイオン交換水５６．３部に分散させて増粘剤溶液を得る。上記マイクロカプセルスラリー４２．５部および増粘剤溶液５７．５部を混合して、マイクロカプセル剤を得る。
【００５４】
製剤例５
本発明化合物１０部とフェニルキシリルエタン１０部とを混合した後、ポリエチレングリコールの１０％水溶液２０部中に加え、ホモミキサーで攪拌して、平均粒径３μｍのエマルジョンを得る。一方、ザンサンガム０．２部、ビーガムＲ（アルミニウムマグネシウムシリケート、三洋化成製）１．０部をイオン交換水５８．８部に分散させて増粘剤溶液を得る。上記エマルジョン溶液４０部及び増粘剤溶液６０部を混合してフロアブル剤を得る。
【００５５】
製剤例６
本発明化合物５部をカープレックス＃８０（合成含水酸化珪素微粉末、塩野義製薬登録商標）３部、ＰＡＰ（モノイソプロピルホスフェートとジイソプロピルホスフェートとの混合物）０．３部及びタルク（３００メッシュ）９１．７部を加え、ジュースミキサーで攪拌混合し、粉剤を得る。
【００５６】
製剤例７
本発明化合物０．１部をジクロロメタン１０部に溶解し、これを脱臭灯油８９．９部に混合して、油剤を得る。
【００５７】
製剤例８
本発明化合物１部、ジクロロメタン５部及び脱臭灯油３４部を混合溶解し、エアゾール容器に充填し、バルブ部分を取付けた後、該バルブ部分を通じて噴射剤（液化石油ガス）６０部を加圧充填して、油性エアゾールを得る。
【００５８】
製剤例９
本発明化合物０．６部、キシレン５部、脱臭灯油３．４部及びアトモス３００（乳化剤、アトラスケミカル社登録商標）１部を混合溶解したものと、水５０部とをエアゾール容器に充填し、バルブ部分を通じて噴射剤（液化石油ガス）４０部を加圧充填して、水性エアゾールを得る。
【００５９】
製剤例１０
本発明化合物０．３ｇをアセトン２０ｍｌに溶解し、これと線香用基材（タブ粉：粕粉：木粉＝４：３：３の割合で混合したもの）９９．７ｇとを均一に攪拌混合した後、水１００ｍｌを加え、十分練り合わせたものを成型乾燥し、殺虫線香を得る。
【００６０】
製剤例１１
本発明化合物０．８ｇ、ピペロニルブトキシド０．４ｇにアセトンを加えて溶解し、全部で１０ｍｌとする。この溶液０．５ｍｌを２．５ｃｍ×１．５ｃｍ、厚さ０．３ｃｍの電気殺虫マット用基材（コットンリンターとパルプの混合物のフィリブルを板状に固めたもの）に均一に含浸させて、電気殺虫マット剤を得る。
【００６１】
製剤例１２
本発明化合物３部を脱臭灯油９７部に溶解して液剤を得、これを塩化ビニル製容器に入れ上部をヒーターで加熱できるようにした吸液芯（無機粉体をバインダーで固め、焼結したもの）を挿入することにより、吸液芯型加熱蒸散装置に用いるパーツを得る。
【００６２】
製剤例１３
本発明化合物１００ｍｇを適量のアセトンに溶解し、４．０ｃｍ×４．０ｃｍ、厚さ１．２ｃｍの多孔セラミック板に含浸させて、加熱燻煙剤を得る。
【００６３】
製剤例１４
本発明化合物１００μｇを適量のアセトンに溶解し、２ｃｍ×２ｃｍ、厚さ０．３ｍｍの濾紙に均一に塗布した後、アセトンを風乾して、常温揮散剤を得る。
【００６４】
次に、本発明化合物が有害生物防除剤の有効成分として有効であることを試験例として示す。
【００６５】
試験例１
前記製造例にて製造した本発明化合物０．０２５部をジクロロメタン１０部に溶解し、これを脱臭灯油８９．９９７５部に混合して、０．０２５％油剤を調製した。
イエバエ成虫（雄雌各５頭）を一辺７０ｃｍの立方体チャンバー内に放ち、前記本発明化合物の０．０２５％油剤０．７ｍｌを該チャンバー側面の小窓からスプレーガンを用いて８．８×１０４Ｐａの圧力でチャンバー内に散布した。その後１０分後まで経時的にノックダウンした虫数をカウントした。供試虫の半数がノックダウンするのに要する時間は１．０分であった。
【００６６】
試験例２
前記製造例にて製造した本発明化合物０．００６２５部をジクロロメタン１０部に溶解し、これを脱臭灯油８９．９９３７５部に混合して、０．００６２５％油剤を調製した。
イエバエ成虫（雄雌各５頭）を一辺７０ｃｍの立方体チャンバー内に放ち、前記本発明化合物の０．００６２５％油剤０．７ｍｌを該チャンバー側面の小窓からスプレーガンを用いて８．８×１０４Ｐａの圧力でチャンバー内に散布した。その後１０分後まで経時的にノックダウンした虫数をカウントした（２反復）。供試虫の半数がノックダウンするのに要する時間は平均１．１分であった。
前記で製造した本発明化合物の代わりに、対照として国際公開第９９／３２４２６号パンフレットのＥｘａｍｐｌｅ１２に記載の化合物４−メトキシメチル−２，３，５，６−テトラフルオロベンジル （１Ｒ）−トランス−３−（２−フルオロ−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレートを用いて上記と同様の試験を行い、供試中の半数がノックダウンするのに要する時間は５．０分であった。
【００６７】
試験例３
本発明化合物｛（１Ｒ）−シス−（Ｅ）−体｝０．００６２５部をジクロロメタン１０部に溶解し、これを脱臭灯油８９．９９３７５部に混合して、０．００６２５％油剤を調製した。
アカイエカ（雌１０頭）を一辺７０ｃｍの立方体チャンバー内に放ち、前記本発明化合物の０．００６２５％油剤０．７ｍｌを該チャンバー側面の小窓からスプレーガンを用いて８．８×１０４Ｐａの圧力でチャンバー内に散布した。その後１０分後まで経時的にノックダウンした虫数をカウントした。供試虫の半数がノックダウンするのに要する時間は１．３分であった。
前記で製造した本発明化合物の代わりに、対照としてインド国公開特許第１５２３０６号公報記載の化合物３−フェノキシベンジル （１Ｒ）−シス−３−｛（Ｅ）−２−フルオロ−１−プロペニル｝−２，２−ジメチルシクロプロパンカルボキシレートを用いて上記と同様の試験を行い、供試中の半数がノックダウンするのに要する時間は８．０分であった。
【００６８】
【発明の効果】
本発明化合物は優れた有害生物防除効果を有することから、本発明化合物は有害生物防除剤の有効成分として有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an ester compound and its use.
[0002]
[Problems to be solved by the invention]
An object of the present invention is to provide a compound having an excellent pest control effect.
[0003]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to find a compound having an excellent pesticidal activity, and as a result, have found that a compound represented by the following formula (1) has an excellent pesticidal effect, and completed the present invention.
[0004]
That is, the present invention relates to formula (1)
Embedded image
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
In the compound of the present invention, there are isomers derived from two asymmetric carbon atoms present on the cyclopropane ring and isomers derived from the double bond, and in the present invention, each isomer and any isomer Compounds that are ratios are included.
[0006]
Examples of the form of the compound of the present invention include the following.
Embedded image
In the formula (1), compounds wherein the relative configuration between the substituent on the cyclopropane ring 1-position and the substituent on the cyclopropane ring 3 is trans-configuration;
In the formula (1), compounds wherein the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is a cis configuration;
In the formula (1), a compound in which the relative configuration of the double bond present in the substituent at the 3-position of the cyclopropane ring is Z configuration;
In the formula (1), compounds wherein the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position on the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is trans;
In the formula (1), compounds wherein the absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and the relative configuration between the substituent at the 1-position on the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is cis;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the relative configuration between the substituent at the 1-position on the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is the trans configuration, A compound in which the relative configuration of the double bond present in the substituent at the 3-position of the propane ring is the Z configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the relative configuration between the substituent at the 1-position on the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is the cis configuration, A compound in which the relative configuration of the double bond present in the substituent at the 3-position of the propane ring is the Z configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is trans. Compound;
In the formula (1), when the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position on the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is trans, % Or more compounds;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position on the cyclopropane ring is trans. % Or more.
[0007]
The compound of the present invention can be produced, for example, by the following method.
Equation (2)
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The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include hydrocarbons such as hexane, heptane, octane, and toluene; ethers such as diethyl ether and tetrahydrofuran; and mixtures thereof.
Examples of the base used in the reaction include alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; and sodium bistrimethylsilylamide and lithium bistrimethylsilylamide. And alkali metal amides such as lithium bisisopropylamide.
The amount of the reagent used in the reaction is such that the compound represented by the formula (3) is usually in a ratio of 0.8 to 1.5 mol per mol of the aldehyde compound represented by the formula (2), 0.8 to 1.5 moles.
The reaction time is usually in the range of instant to 72 hours, and the reaction temperature is usually in the range of -80 to 80C.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and drying and concentrating the obtained organic layer. The isolated compound of the present invention can be further purified by chromatography or the like.
[0008]
The aldehyde compound represented by the formula (2) is, for example, a compound represented by the formula (4)
Embedded image
[0009]
The compound of the present invention also has the formula (5)
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[0010]
The compound represented by the formula (4) is, for example, a compound described in European Patent Publication EP100004569A1, and can be produced by the method described in the publication. The 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol represented by the formula (5) is, for example, a compound described in JP-A-56-97251, and is produced by the method described in the publication. be able to.
The carboxylic acid compound represented by the formula (6) is described in, for example, Agr. Biol. Chem. , 34, 1119 (1970), and can be produced by the method described in the literature.
[0011]
Examples of pests against which the compound of the present invention is effective include arthropods such as insects and mites, and specific examples include the following pests.
Lepidopteran pests
Japanese beetles such as Japanese syrup, Kobunomeiga and Noshimekokuga, Spodoptera such as Spodoptera litura, Armyworm, Spodoptera litura, White butterflies such as White butterfly, Scarlet beetles such as Kokakumon hamaki, Singing moths, Lepidoptera, Scarabaeidae, Orophoridae Genus pests (Agrotis spp.), Helicoverpa spp., Heliotis pests (Heliothis spp.), Conaga, Ichimon dissely, Iga, Koiga, etc.
[0012]
Diptera pests
Musca domestica such as Culex pipiens and Culex pipiens, Aedes aegypti such as Aedes aegypti and Aedes albopictus, Anopheles such as Aedes albopictus, Mussels, house flies such as house flies, houseflies and gypsophila, houseflies such as house flies, flies and flies, and flies , Drosophila, Drosophila, Flies, flies, blackflies, sand flies, brassicae, etc.
[0013]
Reptile pests
German cockroaches, black cockroaches, brown cockroaches, common brown cockroaches, small cockroaches, etc.
[0014]
Hymenoptera pests
Ants, hornets, wasps, and wasps such as wasps
[0015]
Insect pests
Dog flea, cat flea, human flea, etc.
[0016]
Louse pests
Lice, lice, head lice, body lice, etc.
[0017]
Isoptera pests
Yamato termite, house termite, etc.
[0018]
Hemiptera pests
Planthoppers such as brown planthopper, brown planthopper, brown groundhopper, etc., leafhoppers such as leafhopper leafhopper, leafhopper leafhopper, aphids, stinkbugs, whiteflies, scale insects, hornworms, lice, etc.
[0019]
Coleoptera pests
Corn rootworms such as corn beetle, beetle beetle beetle, western corn rootworm, southern corn rootworm, etc. Tenebrion beetles such as Pterodactyla, rice beetle, leaf beetle, beetle beetle, leaf beetle, etc., genus Epiracuna spp.
[0020]
Pterodactyl pests
Thrips palmi, Thrips palmi, Thrips palmi, etc.
[0021]
Orthoptera pest
Viper, grasshopper, etc.
[0022]
Mites
Dermatophagoids such as Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinus , Spider mites such as apple spider mites, ticks such as red tick
[0023]
The pest control agent of the present invention may be the compound of the present invention itself, but usually the compound of the present invention is formulated.
Examples of the preparations include oils, emulsions, wettable powders, flowables (suspension in water, emulsions in water, etc.), powders, granules, aerosols, and heat-transpiration agents (insect sticks, electric insecticidal mats, liquid absorption). Core-type heat-transpiration insecticide, etc.), Heat-smoking agent (Self-combustion-type smoker, Chemical-reaction-type smoker, Perforated ceramic plate smoker, etc.), Non-heat-evaporation agent (Resin evaporation agent, Impregnated paper evaporation agent) Etc.), aerosols (such as foking), ULV agents and baits.
[0024]
Examples of the method of formulation include the following methods.
(1) A method in which the compound of the present invention is mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, and the like, and if necessary, a surfactant and other formulation auxiliaries are added and processed.
(2) A method of impregnating a base material containing no active ingredient with the compound of the present invention.
(3) A method in which the compound of the present invention and a substrate are mixed and then molded.
These preparations usually contain 0.001 to 95% by weight of the compound of the present invention, depending on the form of the preparation.
[0025]
Carriers used in the formulation include, for example, solid carriers such as clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, montmorillonite, etc.), chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.), liquid carriers, water, alcohols (methanol, ethanol, etc.), Ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, phenylxylylethane, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (Ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyroni Ryl, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), Dimethyl sulfoxide, vegetable oils (soy oil, cottonseed oil, etc.), and gaseous carriers {fluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, etc.}.
[0026]
Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyoxyethylenated alkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters, And sugar alcohol derivatives.
[0027]
Other pharmaceutical auxiliaries include fixing agents, dispersants and stabilizers such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers ( BHT (2,6-di-t-butyl-4-methylphenol), and BHA (2-t-butyl-4-methoxyphenol and 3-t-butyl-) such as polyvinyl alcohol, polyvinylpyrrolidone) and polyacrylic acid. A mixture with 4-methoxyphenol).
[0028]
Examples of the base material for the insecticidal incense include a mixture of a plant powder such as wood flour and lees flour and a binder such as tub flour, starch and glutein.
[0029]
Examples of the base material of the electric insecticidal mat include those obtained by solidifying cotton linter in a plate shape and those obtained by solidifying a filible of a mixture of cotton linter and pulp in a plate shape.
[0030]
Examples of the base material of the self-combustion type smoke agent include combustion exothermic agents such as nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, wood flour, alkali metal salts, alkaline earth metal salts, and heavy metals. Examples thereof include chromate, a pyrolysis stimulant such as chromate, an oxygen supply agent such as potassium nitrate, a flame retardant such as melamine and wheat starch, a bulking agent such as diatomaceous earth, and a binder such as synthetic paste.
[0031]
As the base material of the chemical reaction type smoke agent, for example, exothermic agents such as sulfides of alkali metals, polysulfides, hydrosulfides, calcium oxide, etc., catalysts such as carbonaceous substances, iron carbide, activated clay, azo Organic foaming agents such as dicarbonamide, benzenesulfonylhydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.
[0032]
Examples of the base material of the non-heated evaporant include a thermoplastic resin and paper (filter paper, Japanese paper, etc.).
[0033]
Examples of the bait bait include, for example, bait ingredients such as cereal flour, vegetable oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguacetic acid; preservatives such as dehydroacetic acid; and pepper powder. Examples include an anti-feeding agent for children and pets, and a pest-inducing flavor such as cheese flavor, onion flavor, and peanut oil.
[0034]
The pest control method of the present invention is usually carried out by applying the pest control agent of the present invention to a pest or a habitat of a pest.
[0035]
The method for applying the pesticidal agent of the present invention includes, for example, the following methods, which can be appropriately selected depending on the form, place of use, and the like of the pesticidal agent of the present invention.
(1) A method of treating a pest or a habitat of a pest as it is with the pest control agent of the present invention.
(2) A method of diluting the pest control agent of the present invention with a solvent such as water, and then spraying the diluted pest on a pest or a habitat of the pest.
In this case, the pesticidal agent of the present invention, usually formulated into an emulsion, a wettable powder, a flowable, a microcapsule preparation, or the like, is diluted so that the concentration of the compound of the present invention is 0.1 to 10000 ppm. .
(3) A method in which the pest control agent of the present invention is heated in a habitat of a pest to volatilize an active ingredient.
In this case, the application amount and application concentration of the compound of the present invention can be appropriately determined according to the form of the pest control agent of the present invention, the application time, the application place, the application method, the type of pest, the damage situation, and the like. .
[0036]
The pest control agent of the present invention is mixed or used in combination with other insecticides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, repellents, synergists, fertilizers, soil improvement materials. You can also.
[0037]
Examples of the active ingredients of such insecticides and acaricides include, for example, fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulfophos, cyanophos, dioxabenzophos, dimethoate, fentoate, malathion, trichlorfon, azinphos-methyl, Organophosphorus compounds such as monocrotophos and ethion,
[0038]
Carbamate-based compounds such as BPMC, benfracarb, propoxur, carbosulfan, carbaryl, mesomil, ethiophenecarb, aldicarb, oxamyl, phenothiocarb,
[0039]
Etofenprox, fenvalerate, esfenvalerate, fenpropatrin, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprothrin, fluvalinate, bifenthrin, 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3 -Phenoxybenzyl) ether, tralomethrin, silafluofen, d-phenothrin, cyphenothrin, d-resmethrin, acrinasulin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, allethrin, d-framethrin, praletrin, empentrin, 5- (2- Pyrethroid compounds such as propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate,
[0040]
Nitroimidazolidine derivatives, N-cyanoamidine derivatives such as acetamiprid, endosulfan, γ-BHC, chlorinated hydrocarbon compounds such as 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol, chlorfluazuron, teflubenzuron, Benzoylphenylurea compounds such as flufenoxuron, phenylpyrazole compounds, methoxadiazon, bromopropylate, tetradiphon, quinomethionate, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, polynactin complex (tetranactin, dinactin, trinactin), pyrimidifene , Milbemectin, abamectin, ivermectin, and azadirachtin.
[0041]
Examples of repellents include 3,4-caranediol, N, N-diethyl-m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate, p-menthane-3,8 -Essential oils such as diols and vegetable oils such as hyssop oil.
[0042]
Examples of the synergist include bis- (2,3,3,3-tetrachloropropyl) ether (S-421) and N- (2-ethylhexyl) bicyclo [2.2.1] hept-5-ene. -2,3-dicarboximide (MGK-264), and [alpha]-[2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene (piperonylbutoxide).
[0043]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, Test Examples, and the like, but the present invention is not limited to these Examples.
[0044]
First, Production Examples of the compound of the present invention will be described.
Manufacturing example
Under a nitrogen atmosphere, 0.54 g of diethyl (1-cyanoethyl) phosphonate was dissolved in 6 ml of tetrahydrofuran, and at about 0 ° C., 2.8 ml of a solution of sodium bis (trimethylsilyl) amide in tetrahydrofuran (1 mol / l) was added, followed by stirring for 30 minutes. . There, it is shown by equation (7)
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[0045]
1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.21 (s, 3H, Z + E), 1.32 (s, 3H, Z + E), 1.73 (m, 1H, Z + E), 1.96 (s, 3H, Z + E form), 2.20 (m, 1 / 3H, E form), 2.47 (m, 2 / 3H, Z form), 3.41 (s, 3H, Z + E form), 4.59 ( s, 2H, Z + E form), 5.26 (s, 2H, Z + E form), 5.78 (m, 2 / 3H, Z form), 6.01 (m, 1 / 3H, E form)
[0046]
Reference Production Example 1
1.0 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol and 0.42 g of pyridine were dissolved in 10 ml of tetrahydrofuran, and 3- (2-methyl-1-propenyl) -2,2 was dissolved in ice. 2-dimethylcyclopropanecarboxylic acid chloride 酸 塩 stereoisomer ratio (1R) -trans form: (1R) -cis form: (1S) -trans form: (1S) -cis form = 93.9: 2.5: 3.5: 0.1｝ 0.9 g was added, and the mixture was further stirred at room temperature for 8 hours. Thereafter, the reaction mixture was poured into about 50 ml of ice water and extracted twice with 80 ml of ethyl acetate. The organic layers were combined, washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxy. A rate of 1.4 g was obtained.
[0047]
1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.13 (s, 3H), 1.26 (s, 3H), 1.38 (d, 1H), 1.69 (brs, 6H), 2.10 (dd, 1H), 3.40 (s, 3H), 4.59 (s, 2H), 4.87 (d, 1H), 5.24 (dd, 2H)
[0048]
In a mixed solvent of 25 ml of tetrahydrofuran and 150 ml of 1,4-dioxane, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxy. After dissolving 15.4 g of a rate, 1.0 g of osmium tetroxide was added at room temperature, a solution of 24.0 g of sodium metaperiodate dissolved in 50 ml of water was added, and the mixture was heated under reflux for 2 hours. Thereafter, the reaction mixture was poured into about 200 ml of water and extracted twice with 200 ml of ethyl acetate. The organic layers were combined, washed successively with a 1% aqueous sodium thiosulfate solution, a saturated aqueous sodium hydrogen carbonate solution and saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to obtain 10.4 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate.
[0049]
1 H-NMR (CDCl 3 , TMS) δ (ppm): 1.30 (s, 3H), 1.36 (s, 3H), 2.47 (m, 2H), 3.41 (s, 3H), 4.59 (s, 3H) 2H), 5.26 (s, 2H), 9.59 (s, 1H)
[0050]
Next, formulation examples are shown. In addition, a part shows a weight part.
Formulation Example 1
Dissolve 20 parts of the compound of the present invention in 65 parts of xylene, add 15 parts of Solpol 3005X (registered trademark of Toho Kagaku) and mix well with stirring to obtain an emulsion.
[0051]
Formulation Example 2
To 40 parts of the compound of the present invention, 5 parts of Solpol 3005X were added and mixed well, and 32 parts of Carplex # 80 (synthetic silicon oxide containing hydroxide, Shionogi & Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth were added, followed by stirring and mixing with a juice mixer. To obtain a wettable powder.
[0052]
Formulation Example 3
1.5 parts of the compound of the present invention, 1 part of Tokusil GUN (synthetic hydrous silicon oxide, manufactured by Tokuyama Corporation), 2 parts of Liax 85A (sodium ligninsulfonate, manufactured by West Vaco Chemicals), bentonite Fuji (manufactured by Bentonite, Hojoun) 30 parts and 65.5 parts of Katsumitsuyama A clay (kaolin clay, manufactured by Katsumitsu Mining Co., Ltd.) are well pulverized and mixed, water is added and kneaded well, and the mixture is granulated by an extruder and dried. 1.5% granules are obtained.
[0053]
Formulation Example 4
After mixing 10 parts of the compound of the present invention, 10 parts of phenylxylylethane and 0.5 part of Sumidur L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co.), the mixture was added to 20 parts of a 10% aqueous solution of gum arabic, Stir with a homomixer to obtain an emulsion having an average particle size of 20 μm. 2 parts of ethylene glycol is added thereto, and the mixture is further stirred for 24 hours in a warm bath at 60 ° C. to obtain a microcapsule slurry. On the other hand, 0.2 part of Xanthan gum and 1.0 part of Vegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. 42.5 parts of the microcapsule slurry and 57.5 parts of the thickener solution are mixed to obtain a microcapsule.
[0054]
Formulation Example 5
After mixing 10 parts of the compound of the present invention and 10 parts of phenylxylylethane, the mixture is added to 20 parts of a 10% aqueous solution of polyethylene glycol, and stirred with a homomixer to obtain an emulsion having an average particle size of 3 μm. On the other hand, 0.2 part of Xanthan gum and 1.0 part of Vegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution. 40 parts of the above emulsion solution and 60 parts of the thickener solution are mixed to obtain a flowable agent.
[0055]
Formulation Example 6
5 parts of the compound of the present invention were mixed with 3 parts of carplex # 80 (synthetic silicon hydroxide fine powder, Shionogi & Co., Ltd.), 0.3 parts of PAP (a mixture of monoisopropyl phosphate and diisopropyl phosphate), and talc (300 mesh) 91. Add 7 parts and stir and mix with a juice mixer to obtain a powder.
[0056]
Formulation Example 7
0.1 part of the present compound is dissolved in 10 parts of dichloromethane and mixed with 89.9 parts of deodorized kerosene to obtain an oil.
[0057]
Formulation Example 8
One part of the compound of the present invention, 5 parts of dichloromethane and 34 parts of deodorized kerosene are mixed and dissolved, filled in an aerosol container, a valve is attached, and 60 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve. To obtain an oily aerosol.
[0058]
Formulation Example 9
An aerosol container was charged with a mixture of 0.6 part of the compound of the present invention, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier, registered trademark of Atlas Chemical Co.), and 50 parts of water. 40 parts of a propellant (liquefied petroleum gas) is charged under pressure through a valve part to obtain an aqueous aerosol.
[0059]
Formulation Example 10
0.3 g of the compound of the present invention is dissolved in 20 ml of acetone, and 99.7 g of a base material for incense sticks (mixed in a ratio of 4: 3: 3 of tab powder: meal powder: wood powder) is uniformly stirred and mixed. After that, 100 ml of water was added, and the mixture was sufficiently kneaded and molded and dried to obtain an insecticide incense stick.
[0060]
Formulation Example 11
Acetone is added and dissolved in 0.8 g of the compound of the present invention and 0.4 g of piperonyl butoxide to make a total of 10 ml. 0.5 ml of this solution is uniformly impregnated in a 2.5 cm × 1.5 cm, 0.3 cm thick substrate for an electric insecticidal mat (a fibril of a mixture of cotton linter and pulp solidified into a plate), Obtain an electric insecticidal matting agent.
[0061]
Formulation Example 12
A solution was obtained by dissolving 3 parts of the compound of the present invention in 97 parts of deodorized kerosene. The liquid was put into a vinyl chloride container, and the upper portion was heated with a heater. ) To obtain the parts used in the liquid-absorbing core type heat evaporation device.
[0062]
Formulation Example 13
100 mg of the compound of the present invention is dissolved in an appropriate amount of acetone and impregnated in a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate to obtain a heated smoker.
[0063]
Formulation Example 14
100 μg of the compound of the present invention is dissolved in an appropriate amount of acetone and uniformly applied to a filter paper having a size of 2 cm × 2 cm and a thickness of 0.3 mm, and then the acetone is air-dried to obtain a room temperature volatile agent.
[0064]
Next, Test Examples show that the compound of the present invention is effective as an active ingredient of a pesticidal agent.
[0065]
Test example 1
0.025 part of the compound of the present invention produced in the above Production Example was dissolved in 10 parts of dichloromethane, and this was mixed with 89.9975 parts of deodorized kerosene to prepare a 0.025% oil solution.
Housefly adults (5 males and 5 females) were released into a cubic chamber 70 cm on a side, and 0.7 ml of 0.025% oil solution of the compound of the present invention was sprayed through a small window on the side of the chamber using a spray gun at 8.8 × 10 5 4 It was sprayed into the chamber at a pressure of Pa. Thereafter, the number of insects knocked down with time was counted until 10 minutes later. The time required for half of the test insects to knock down was 1.0 minute.
[0066]
Test example 2
0.00625 parts of the compound of the present invention produced in the above Production Example was dissolved in 10 parts of dichloromethane, and this was mixed with 89.99375 parts of deodorized kerosene to prepare a 0.00625% oil solution.
A housefly adult (five males and 5 females) was released into a cubic chamber 70 cm on a side, and 0.7 ml of a 0.00625% oil solution of the compound of the present invention was sprayed through a small window on the side of the chamber using a spray gun at 8.8 × 10 5. 4 It was sprayed into the chamber at a pressure of Pa. After that, the number of insects knocked down over time was counted up to 10 minutes later (2 repetitions). The time required for half of the test insects to knock down was an average of 1.1 minutes.
Instead of the compound of the present invention produced as described above, as a control, the compound 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl (1R) -trans-3 described in Example 12 of WO 99/32426. The same test as above was performed using-(2-fluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, and the time required for half of the test to be knocked down was 5.0 minutes. there were.
[0067]
Test example 3
0.00625 parts of the compound of the present invention {(1R) -cis- (E) -form} was dissolved in 10 parts of dichloromethane and mixed with 89.99375 parts of deodorized kerosene to prepare a 0.00625% oil solution.
A Culex pipiens (10 females) is released into a cubic chamber having a side of 70 cm, and 0.7 ml of the 0.00625% oil solution of the compound of the present invention is sprayed through a small window on the side of the chamber using a spray gun at 8.8 × 10 5 4 It was sprayed into the chamber at a pressure of Pa. Thereafter, the number of insects knocked down with time was counted until 10 minutes later. The time required for half of the test insects to knock down was 1.3 minutes.
Instead of the compound of the present invention prepared above, the compound 3-phenoxybenzyl (1R) -cis-3-{(E) -2-fluoro-1-propenyl}-described in Indian Patent Publication No. 152306 is used as a control. A test similar to the above was performed using 2,2-dimethylcyclopropanecarboxylate, and the time required for half of the test to be knocked down was 8.0 minutes.
[0068]
【The invention's effect】
Since the compound of the present invention has an excellent pest control effect, the compound of the present invention is useful as an active ingredient of a pesticide.
Claims (3)
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| JP2003098931A JP4285045B2 (en) | 2002-04-12 | 2003-04-02 | Ester compounds and uses thereof |
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| JP2002110348 | 2002-04-12 | ||
| JP2003098931A JP4285045B2 (en) | 2002-04-12 | 2003-04-02 | Ester compounds and uses thereof |
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| Publication Number | Publication Date |
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| JP2004002363A true JP2004002363A (en) | 2004-01-08 |
| JP4285045B2 JP4285045B2 (en) | 2009-06-24 |
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