JP4512928B2 - N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients - Google Patents
N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients Download PDFInfo
- Publication number
- JP4512928B2 JP4512928B2 JP36239899A JP36239899A JP4512928B2 JP 4512928 B2 JP4512928 B2 JP 4512928B2 JP 36239899 A JP36239899 A JP 36239899A JP 36239899 A JP36239899 A JP 36239899A JP 4512928 B2 JP4512928 B2 JP 4512928B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituent
- atom
- acid amides
- insecticides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 C*=C(*)Nc1nnc(*)[s]1 Chemical compound C*=C(*)Nc1nnc(*)[s]1 0.000 description 1
Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、新規なN-チアジアゾリルシクロアルカンカルボン酸アミド類および該N-チアジアゾリルシクロアルカンカルボン酸アミド類を有効成分として含有する殺虫、殺ダニ剤に関する。
【０００２】
【従来の技術】
農園芸分野では、各種害虫の防除を目的とした様々な殺虫剤が開発され実用に供されている。しかしながら、従来汎用されている農園芸用殺虫剤は殺虫効果、殺虫スペクトラム、あるいは残効性等の点において必ずしも満足すべきものではない。また、施用回数や施用薬量の低減等の要求を満足しているとは言えないものであった。
また、従来汎用の農薬に対して抵抗性を獲得した害虫の出現も問題となっている。例えば、野菜、果樹、花卉、茶、ムギ類およびイネ等の栽培において、様々な型の農薬、例えば、カーバメート系、ピレスロイド系、ベンゾイルウレア系、有機塩素系、有機リン系農薬等に抵抗性を獲得した種々の害虫が各地で出現しており、これらの害虫に起因する各種病害虫の防除が年々困難になっている。その為、従来汎用の農園芸用殺虫剤に抵抗性を獲得した各種害虫に対しても低薬量で十分な防除効果を示し、しかも環境への悪影響が少ない新規な殺虫剤の開発が切望されている。殺ダニ剤についても、従来汎用の殺ダニ剤に抵抗性を示すダニ類に対して優れた防除効果を示し、安全性の高い殺ダニ剤の開発が期待されている。
一方、生理活性を示す化合物に関しては多くの報告が成されており、例えば特開昭 48-44433 号公報、特開昭 50-117934号公報、米国特許4092148 には除草活性を有するN-チアジアゾリルシクロアルカンカルボン酸アミド類が記載されているが、殺虫、殺ダニ活性については全く記載がない。
【０００３】
【発明が解決しようとする課題】
本発明の課題は、従来の殺虫剤や殺ダニ剤に抵抗性を示す各種害虫に対しても高い防除効果を示し、殺虫、殺ダニ剤の有効成分として有用な化学物質を提供することにある。また、本発明の別の課題は、上記の特徴を有し、且つ、残留毒性や環境汚染等の問題が軽減された安全性の高い殺虫、殺ダニ剤を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者等は上記の課題を解決すべく鋭意検討した結果、酸残基がハロゲン原子またはシアノ基で置換されたシクロアルキル基である新規なN-チアジアゾリルシクロアルカンカルボン酸アミド類が上記の特徴を有する化合物であることを見出し、本発明を完成するに至った。即ち、本発明の要旨は、下記一般式 （Ｉ）
【０００５】
【化３】
【化４】
（式中、Ｒ1 は水素原子またはＣ1-Ｃ4 のアルキル基を示し、Ｒ2 は水素原子、ハロゲン原子またはＣ1-Ｃ4 のアルキル基を示し、Ｘ1 はハロゲン原子を示す。Ｒ3 およびＲ4 はそれぞれ独立に水素原子、Ｃ1-Ｃ4 のアルキル基またはハロゲン原子を示し、Ｘ2 はハロゲン原子またはシアノ基を示す。ｎは１−５の整数を示す。）で表される置換基を示し、Ｙは水素原子、Ｃ1-Ｃ5 のハロアルキル基、Ｃ1-Ｃ4 のハロアルキルチオ基、Ｃ1-Ｃ4 のアルキルチオ基、Ｃ1-Ｃ4 のアルコキシ基、ハロゲン原子、Ｃ1-Ｃ4 のアルキル基、置換基を有してもよいフェニル基、置換基を有してもよいベンジル基または置換基を有しても良いベンジルチオ基を示す。・−は結合手を示す。｝で表されるＮ−チアジアゾリルシクロアルカンカルボン酸アミド類および該N-チアジアゾリルシクロアルカンカルボン酸アミド類を有効成分として含有する殺虫・殺ダニ剤に存する。
【０００７】
前述の如く特開昭 48-44433 号公報にはN-チアジアゾリルシクロプロパンカルボン酸アミド類の記載はあるが、シクロプロパン部位に置換基を有する化合物については全く記載がない。特開昭 50-117934号公報はN-チアジアゾリルシクロプロパンカルボン酸アミド類の記載はあるが、シクロプロパン部位の置換基はメチル基に限られており、シクロプロパン部位に少なくとも１個のハロゲン原子あるいはシアノ基を有する一般式（Ｉ）の化合物は記載されていない。また、米国特許4092148 にはN-チアジアゾリルシクロアルカンカルボン酸アミド類の記載はあるが、シクロアルカン部位に置換基を有する化合物については全く記載がない。このように、シクロアルカン部位がハロゲン原子またはシアノ基で置換された N-チアジアゾリルシクロアルカンカルボン酸アミド類は全く知られていなかった。
また、これら公知の化合物は除草活性を有することは知られているが、その酸残基をハロゲン原子またはシアノ基で置換されたシクロアルキル基にすることにより、生理活性が如何に変化するかは知られておらず、まして、本発明に示す如き優れた殺虫、殺ダニ活性が出現することは全く知られていなかった。
【０００８】
【発明の実施の形態】
以下、本発明を詳細に説明する。
一般式（Ｉ）で表される本発明化合物の置換基 Ｒ1 は、水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等のＣ1-Ｃ4のアルキル基を示す。中でもＲ1 としては、水素原子が好ましい。Ｒ2 は水素原子；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等のＣ1-Ｃ4のアルキル基を示す。中でもＲ2 としてはメチル基、エチル基が好ましい。Ｘ1 はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を示す。中でもＸ1 としては塩素原子が好ましい。Ｒ3 および Ｒ4はそれぞれ独立に水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等のＣ1-Ｃ4のアルキル基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を示す。中でもＲ3、Ｒ4としては水素原子およびメチル基が好ましい。Ｘ2 はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基を示す。ｎは１−５の整数を示す。
【０００９】
Ｙは水素原子；トリフルオロメチル基、ジフルオロメチル基、トリクロロメチル基、ペンタフルオロエチル基、ペルフルオロプロピル基、ペルフルオロブチル基、ペルフルオロペンチル基等のＣ1-Ｃ5のハロアルキル基；ジフルオロメチルチオ基、トリフルオロメチルチオ基、トリクロロメチルチオ基、ペンタフルオロエチルチオ基、ペルフルオロプロピルチオ基等のＣ1-Ｃ4 のハロアルキルチオ基；メチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、イソブチルチオ基、sec-ブチルチオ基、tert-ブチルチオ基等のＣ1-Ｃ4のアルキルチオ基；メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基等のＣ1-Ｃ4のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等のＣ1-Ｃ4のアルキル基；フェニル基、クロロフェニル基、トリフルオロメチルフェニル基等の置換基を有してもよいフェニル基；ベンジル基、クロロベンジル基、ジクロロベンジル基等の置換基を有してもよいベンジル基；ベンジルチオ基、クロロベンジルチオ基、tert-ブチルベンジルチオ基等の置換基を有してもよいベンジルチオ基を示す。中でもＹとしては、Ｃ1-Ｃ5 のペルフルオロアルキル基、特にＣ3-Ｃ4 のペルフルオロアルキル基が好ましい。ＡとしてはＡ−１で示される基、またはＡ−２で示される基において、ｎが４の基が好ましく、特にＡ−１で示される基が好ましい。
一般式（Ｉ）で示される本発明の化合物は新規化合物であり、例えば下記反応に従って製造することができる。
【００１０】
【化５】
（上記式中、ＡおよびＹは前記一般式（Ｉ）で定義した通りであり、Ｚは塩素原子または臭素原子を示す。）
即ち、一般式（ＩＩ）で示されるカルボン酸ハロゲン化物と一般式 （ＩＩＩ）で示される 2-アミノ-1,3,4-チアジアゾール類とを、塩基の存在下または非存在下、好ましくは溶媒を用いて、5〜150 ℃で反応させる。溶媒としては、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；クロロホルム、ジクロロメタン等のハロゲン化炭化水素類；水；酢酸エチル、酢酸メチル等のエステル類；またはテトラヒドロフラン、アセトニトリル、ジオキサン、N,N-ジメチルホルムアミド、N-メチルピロリドン、ジメチルスルホキシド、ピリジン等の極性溶媒等が用いられる。塩基としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸カリウム等の無機塩類；ピリジン、トリエチルアミン等のアミン類等が用いられる。反応後、目的物である一般式 (I) で表される化合物を単離するには、水に溶解する溶媒を用いた場合は、減圧下溶媒を留去し、水を加えた後、水に不溶のベンゼン、トルエン、キシレン等の芳香族炭化水素；クロロホルム、ジクロロメタン等のハロゲン化炭化水素；酢酸エチル等のエステル類で抽出し、飽和食塩水で洗浄後、無水硫酸ナトリウム、無水硫酸マグネシウム等の乾燥剤で乾燥し、減圧下で溶媒を留去すれば良い。水に不溶の溶媒を用いた場合は、反応混合物に水を加えた後分液し、有機層を飽和食塩水で洗浄後、無水硫酸ナトリウム、無水硫酸マグネシウム等の乾燥剤で乾燥し、減圧下で溶媒を留去すれば良い。
溶媒留去後得られた残渣を、再結晶、懸濁洗浄、カラムクロマトグラフィー等で精製すれば目的物である一般式（Ｉ）で表される化合物が得れらる。
【００１２】
一般式 (II) で示される化合物は、対応するカルボン酸を塩化チオニル、五塩化リン、オキシ塩化リン、三塩化リン等で処理することにより製造できる。一般式 （ＩＩ）で示される化合物に対応するカルボン酸は、一部は市販されており、容易に入手することができる。また、例えば、1,1,2-トリブロモシクロプロパンカルボン酸はTetrahedron, 52, 3409 (1996) に記載の方法；1-ブロモシクロプロパンカルボン酸は J. Org. Chem., 54, 6096 (1989) に記載の方法；2,2-ジクロロシクロプロパンカルボン酸類は特開昭 62-201855 号公報 に記載の方法で製造することができる。一般式 (III) で表される化合物は一部は市販されており、容易に入手することができる。また、例えば、特開昭 57-77603 号公報または薬学会誌、72 巻、376 頁 (1952) 等に記載された方法に準じて合成することができる。
【００１３】
一般式（Ｉ）で示される本発明化合物は各種の昆虫、ダニ類に対し防除活性を有する。特に本発明の化合物は、ハスモンヨトウ、コナガ、チャノコカクモンハマキ、コブノメイガ、ニカメイチュウ等の鱗翅目；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、チャノミドリヒメヨコバイ等のヨコバイ類、モモアカアブラムシ、ワタアブラムシ等のアブラムシ類、オンシツコナジラミ等のコナジラミ類、チャバネアオカメムシ等のカメムシ類等の半翅目；キスジノミハムシ、ウリハムシ、アズキゾウムシ等の甲虫目；イエバエ、アカイエカ等の双翅目；ワモンゴキブリ等の直翅目の昆虫の幼虫および成虫、ならびに、ナミハダニ、ミカンハダニ、ミカンサビダニ、チャノホコリダニ等のダニ目の卵、幼虫および成虫等の農園芸作物の害虫に対して高い防除効果を有しているので、農園芸用の殺虫剤および殺ダニ剤の有効成分として有用である。もっとも、本発明の化合物の防除対象となる昆虫、ダニは上記に例示したものに限定されることはない。
【００１４】
式（Ｉ）で示される本発明化合物を農園芸用の殺虫剤、殺ダニ剤として使用する場合は、単独で用いてもよいが、好ましくは当業界で汎用される農薬補助剤を用いて製造した組成物の形態で用いられる。農園芸用殺虫剤、殺ダニ剤の形態は特に限定されないが、例えば乳剤、水和剤、水溶剤、粉剤、フロアブル剤、細粒剤、粒剤、錠剤、油剤、噴霧剤、煙霧剤等の形態とすることが好適である。上記の化合物の一種または二種以上を有効成分として配合することができる。
農園芸用の殺虫剤、殺ダニ剤を製造するために用いられる農薬補助剤は、農園芸用の殺虫剤、殺ダニ剤の効果の向上、安定化、分散性の向上等の目的で、例えば、担体 (希釈剤)、展着剤、乳化剤、湿展剤、分散剤、崩壊剤等を用いることができる。
【００１５】
液体担体としては、水、トルエン、キシレン等の芳香族炭化水素、メタノール、ブタノール、グリコール等のアルコール類、アセトン等のケトン類、ジメチルホルムアミド等のアミド類、ジメチルスルホキシド等のスルホキシド類、メチルナフタレン、シクロヘキサン、動植物油、脂肪酸等を挙げることができる。また、固体担体としてはクレー、カオリン、タルク、珪藻土、シリカ、炭酸カルシウム、モンモリロナイト、ベントナイト、長石、石英、アルミナ、鋸屑、ニトロセルロース、デンプン、アラビアゴム等を用いることができる。
乳化剤、分散剤としては通常の界面活性剤を使用することができ、例えば、高級アルコール硫酸ナトリウム、ステアリルトリメチルアンモニウムクロライド、ポリオキシエチレンアルキルフェニルエーテル、ラウリルベタイン等の陰イオン系界面活性剤、陽イオン系界面活性剤、非イオン系界面活性剤、両性イオン系界面活性剤等を用いることができる。また、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルフェニルエーテル等の展着剤；ジアルキルスルホサクシネート等の湿展剤；カルボキシメチルセルロース、ポリビニルアルコール等の固着剤；リグニンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等の崩壊剤を用いることができる。
【００１６】
本発明の農園芸用殺虫、殺ダニ剤における有効成分の含有量は０．１〜９９．５重量％の範囲から選ばれ、製剤形態、施用方法等の種々の条件により適宜決定すればよいが、例えば、粉剤では約０．５〜２０重量％程度、好ましくは１〜１０重量％、水和剤では約１〜９０重量％程度、好ましくは１０〜８０重量％、乳剤では約１〜９０重量％程度、好ましくは１０〜４０重量％の有効成分を含有するように製造することが好適である。
例えば、乳剤の場合、有効成分である一般式（Ｉ）の化合物に対して溶剤および界面活性剤等を混合して原液の乳剤を製造することができ、更にこの原液を使用に際して所定濃度に水で希釈して施用することができる。水和剤の場合、有効成分の上記化合物、固形担体、および界面活性剤等を混合して原体を製造し、さらにこの原体を使用に際して所定濃度に水で希釈して施用することができる。粉剤の場合、有効成分の上記化合物、固形担体等を混合してそのまま施用することができ、粒剤の場合には、有効成分の上記化合物、固形担体、および界面活性剤等を混合して造粒することにより製造し、そのまま施用することができる。もっとも、上記の各製剤形態の製造方法は上記のものに限定されることはなく、有効成分の種類や施用目的等に応じて当業者が適宜選択することができるものである。
【００１７】
本発明の農園芸用殺虫、殺ダニ剤には、有効成分である本発明の化合物以外に、他の殺菌剤、殺虫剤、殺ダニ剤、除草剤、昆虫生育調整剤、肥料、土壌改良剤等の任意の有効成分を配合してもよい。本発明の農園芸用殺虫剤、および／または殺ダニ剤の施用方法は特に限定されるものではなく、茎葉散布、水面施用、土壌処理、種子処理等のいずれの方法でも施用することができる。例えば、茎葉散布の場合、５〜１０００ｐｐｍ、好ましくは１０〜５００ｐｐｍの濃度範囲の溶液を１０アール当たり１００〜２００リットル程度の施用量で用いることができる。水面施用の場合の施用量は通常、有効成分が ５〜１５% の粒剤では１０アール当たり１〜１０ｋｇである。土壌処理の場合、５〜１０００ｐｐｍの濃度範囲の溶液を１ｍ2当たり１〜１０リットル程度の施用量で用いることができる。種子処理の場合、種子重量 1 kg 当たり１０〜１０００ｐｐｍの濃度範囲の溶液を１０〜１００ｍｌ程度施用処理することができる。
【００１８】
【実施例】
以下、本発明を実施例、製剤例、試験例によりさらに具体的に説明するが、本発明は、その要旨を越えない限りこれらの例に限定されるものではない。
実施例１ ＜2,2-ジクロロ-1-メチル-N-(5-トリフルオロメチル-1,3,4-チアジアゾール-2-イル)シクロプロパンカルボン酸アミドの合成＞
2-アミノ-5-トリフルオロメチル-1,3,4-チアジアゾール０．５１ｇ、ピリジン０．４９ｇおよびジクロロメタン５ｍｌの混合物に、2,2-ジクロロ-1-メチルシクロプロパンカルボン酸クロリド０．７５ｇを加え、室温で１時間攪拌した。希塩酸を加え、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、得られた結晶をヘキサンで洗浄して、表−１記載の化合物 (No.5)０．３８ｇを得た。
mp 131-132 ℃；1H NMR (CDCl3, TMS, ppm) 1.65 (1H, d), 1.88 (3H, s), 2.46 (1H, d)。
【００１９】
実施例２ ＜1-ブロモ-N-(5-トリフルオロメチル-1,3,4-チアジアゾール-2-イル)シクロヘキサンカルボン酸アミドの合成＞
2-アミノ-5-トリフルオロメチル-1,3,4-チアジアゾール０．５１ｇ、炭酸カリウム０．４１ｇおよびトルエン１０ｍｌの混合物に、1-ブロモシクロヘキサンカルボン酸クロリド０．６８ｇを加え、室温で１０時間攪拌した。水を加え、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、得られた結晶をヘキサンで洗浄して、表−１記載の化合物 (No.1)０．５２ｇを得た。 mp 99-103.5 ℃。
なお、原料として使用した1-ブロモシクロヘキサンカルボン酸クロリドは以下の方法で合成した。
シクロヘキサンカルボン酸１２．８ｇに塩化チオニル１５ｍｌを加え、３０分間加熱還流した。塩化チオニルを留去後、減圧蒸留して、シクロヘキサンカルボン酸クロリド １３．４ｇを得た。bp 97-105 ℃ / 70 mmHg。
シクロヘキサンカルボン酸クロリド５．００ｇに臭素２．１ｍｌを加え、２時間加熱還流した。減圧蒸留して、1-ブロモシクロヘキサンカルボン酸クロリド６．５５ｇを得た。bp 95-100 ℃ / 3 mmHg。
【００２０】
実施例３
実施例１または２記載の方法に準じて、表−１記載の化合物を合成した。
【００２１】
【表１】
【表２】
【表３】
【表４】
以下、本発明化合物を有効成分として含む殺虫、殺ダニ剤の製剤例を示すが、本発明の使用形態はこれらに限定されるものではない。
製剤例１：水和剤
本発明の化合物２０重量部、カープレックス＃８０（ホワイトカーボン、塩野義製薬株式会社、商品名）２０重量部、ＳＴカオリンクレー（カオリナイト、土屋カオリン社、商品名）５２重量部、ソルポール９０４７Ｋ（アニオン性界面活性剤、東邦化学株式会社、商品名）５重量部、ルノックスＰ６５Ｌ（アニオン性界面活性剤、東邦化学株式会社、商品名）３重量部を配合し、均一に混合粉砕して、有効成分２０重量％の水和剤を得た。
【００２６】
製剤例２：粉剤
本発明の化合物２重量部、クレー（日本タルク社製）９３重量部、カープレックス＃８０（ホワイトカーボン、塩野義製薬株式会社、商品名）５重量部を均一に混合粉砕して、有効成分２重量％の粉剤を製造した。
製剤例３：乳剤
本発明の化合物２０重量部をキシレン３５重量部およびジメチルホルムアミド３０重量部からなる混合溶媒に溶解し、これにソルポール３００５Ｘ（非イオン性界面活性剤とアニオン性界面活性剤の混合物、東邦化学株式会社、商品名）１５重量部を加えて、有効成分２０重量％の乳剤を得た。
【００２７】
製剤例４：フロアブル剤
本発明の化合物３０重量部とソルポール９０４７Ｋ ５重量部、ソルボンＴ−２０（非イオン性界面活性剤、東邦化学株式会社、商品名）３重量部、エチレングリコール８重量部および水４４重量部をダイノミル（シンマルエンタープライゼス社製）で湿式粉砕し、このスラリー状混合物に１重量％キサンタンガム（天然高分子）水溶液１０重量部を加え、よく混合粉砕して、有効成分２０重量％のフロアブル剤を得た。
【００２８】
以下、本発明の化合物を有効成分として含む農園芸用殺虫、殺ダニ剤の試験例を示すが、本発明の使用形態は下記のものに限定されるものではない。
また、比較の為米国特許4092148 に記載の下記構造の化合物（比較化合物）を同様の試験に供した。
【００２９】
【化６】
試験例１：コナガの幼虫に対する殺虫効果
製剤例３の処方にしたがって製造した本発明殺虫剤の水希釈液中に、キャベツ切葉（直径６ｃｍ）を１分間浸漬した。浸漬後風乾しプラスチックカップ（内径７ｃｍ）に入れ、このカップ内にコナガの３令虫を５頭放虫した（１濃度、２反復）。２５℃の恒温室内に保持し、放虫４日後に幼虫の生死および苦悶を調査し、苦悶虫を１／２頭死として殺虫活性（％）を求めた。結果を表−２に示した（以下の表中、化合物Ｎｏ．は表−１に対応している）。
【００３１】
【表５】
試験例 2：ナミハダニの成虫に対する殺ダニ効果
水を入れた試験管 (容量 : ５０ｍｌ) に、初生葉１枚を残したいんげん苗の茎部を挿し、ナミハダニの雌成虫を１葉あたり１５頭接種した。接種１日後にハダニの寄生した葉を製剤例 3 の処方に従って製造した本発明殺ダニ剤の水希釈液に浸漬処理 (約５秒間) した (１濃度、２反復)。２５℃の恒温室内に保持し、処理後５日目にいんげん葉上のハダニ雌成虫数を調査し、その結果に基づき殺成虫率（％）を求めた。結果を表−３に示した。
【００３３】
【表６】
【発明の効果】
本発明の新規なN-チアジアゾリルシクロアルカンカルボン酸アミド類は、有害な昆虫、ダニ類に対して優れた防除効果を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to novel N-thiadiazolyl cycloalkanecarboxylic acid amides and insecticides and acaricides containing the N-thiadiazolyl cycloalkanecarboxylic acid amides as active ingredients.
[0002]
[Prior art]
In the field of agriculture and horticulture, various insecticides aimed at controlling various pests have been developed and put into practical use. However, conventionally used agricultural and horticultural insecticides are not necessarily satisfactory in terms of insecticidal effect, insecticidal spectrum, residual effect and the like. Moreover, it cannot be said that the request | requirements, such as the frequency | count of application and the reduction of an applied chemical quantity, are satisfied.
In addition, the appearance of pests that have acquired resistance to conventional general agricultural chemicals is also a problem. For example, it is resistant to various types of pesticides such as carbamates, pyrethroids, benzoylurea, organochlorine, organophosphorus pesticides in the cultivation of vegetables, fruit trees, flower buds, tea, wheat and rice. The acquired various pests appear in various places, and it is difficult to control various pests caused by these pests every year. For this reason, the development of new insecticides that show sufficient control effects at low doses and that have little negative impact on the environment is also eagerly desired against various insect pests that have acquired resistance to conventional agricultural and horticultural insecticides. ing. As for acaricides, it is expected to develop a highly safe acaricide that exhibits an excellent control effect against mites that are resistant to conventional general acaricides.
On the other hand, many reports have been made on compounds exhibiting physiological activity. For example, JP-A-48-44433, JP-A-50-117934, and US Pat. No. 4092148 disclose N-thiadiazo having herbicidal activity. Although rylcycloalkanecarboxylic acid amides are described, there is no description of insecticidal and acaricidal activity.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a chemical substance useful as an active ingredient of insecticides and acaricides, exhibiting a high control effect against various insect pests resistant to conventional insecticides and acaricides. . Another object of the present invention is to provide a highly safe insecticidal and acaricidal agent having the above-mentioned characteristics and reduced problems such as residual toxicity and environmental pollution.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that novel N-thiadiazolylcycloalkanecarboxylic acid amides in which the acid residue is a cycloalkyl group substituted with a halogen atom or a cyano group are as described above. As a result, the present invention has been completed. That is, the gist of the present invention is the following general formula (I)
[0005]
[Chemical 3]
[Formula 4]
(Wherein R 1 represents a hydrogen atom or a C 1 -C 4 alkyl group, R 2 represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl group, and X 1 represents a halogen atom. R 3 and R 4 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group or a halogen atom, X 2 represents a halogen atom or a cyano group, and n represents an integer of 1-5. represents a substituent that, Y is a hydrogen atom, C 1 -C haloalkyl group 5, haloalkylthio group having C 1 -C 4, alkylthio group of C 1 -C 4, alkoxy group of C 1 -C 4, halogen atoms , A C 1 -C 4 alkyl group, a phenyl group which may have a substituent, a benzyl group which may have a substituent or a benzylthio group which may have a substituent. -Indicates a bond. } And N-thiadiazolyl cycloalkanecarboxylic acid amides and insecticides and acaricides containing the N-thiadiazolyl cycloalkanecarboxylic acid amides as active ingredients.
[0007]
As described above, JP-A-48-44433 discloses N-thiadiazolyl cyclopropanecarboxylic acid amides, but does not describe any compound having a substituent at the cyclopropane moiety. JP-A-50-117934 discloses N-thiadiazolyl cyclopropanecarboxylic acid amides, but the substituent at the cyclopropane moiety is limited to a methyl group, and at least one halogen atom is present at the cyclopropane moiety. Compounds of general formula (I) having atoms or cyano groups are not described. US Patent 4092148 describes N-thiadiazolylcycloalkanecarboxylic acid amides, but does not describe any compound having a substituent at the cycloalkane moiety. Thus, N-thiadiazolyl cycloalkanecarboxylic acid amides in which the cycloalkane moiety is substituted with a halogen atom or a cyano group have not been known at all.
In addition, these known compounds are known to have herbicidal activity, but how the physiological activity is changed by changing the acid residue to a cycloalkyl group substituted with a halogen atom or a cyano group. It was not known, and it was never known that the excellent insecticidal and acaricidal activity as shown in the present invention appeared.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The substituent R 1 of the compound of the present invention represented by the general formula (I) is a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. C 1 -C 4 alkyl group of Among them, R 1 is preferably a hydrogen atom. R 2 is hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. C 1 -C 4 alkyl group of Among them, R 2 is preferably a methyl group or an ethyl group. X 1 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, chlorine atom is preferred as X 1 . R 3 and R 4 are each independently a hydrogen atom; a C 1 -C 4 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc .; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom are shown. Among these, as R 3 and R 4 , a hydrogen atom and a methyl group are preferable. X 2 represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group. n represents an integer of 1-5.
[0009]
Y is a hydrogen atom; a C 1 -C 5 haloalkyl group such as a trifluoromethyl group, difluoromethyl group, trichloromethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group; difluoromethylthio group, tri C 1 -C 4 haloalkylthio groups such as fluoromethylthio group, trichloromethylthio group, pentafluoroethylthio group, perfluoropropylthio group; methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, C 1 -C 4 alkylthio groups such as sec-butylthio group, tert-butylthio group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, etc. alkoxy C 1 -C 4; fluorine atom , A chlorine atom, a bromine atom, a halogen atom such as an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, C 1 -C 4 alkyl, such as tert- butyl A phenyl group which may have a substituent such as a phenyl group, a chlorophenyl group or a trifluoromethylphenyl group; a benzyl group which may have a substituent such as a benzyl group, a chlorobenzyl group or a dichlorobenzyl group; A benzylthio group which may have a substituent such as a group, a chlorobenzylthio group and a tert-butylbenzylthio group; Among them, Y is preferably a C 1 -C 5 perfluoroalkyl group, particularly a C 3 -C 4 perfluoroalkyl group. As A, the group represented by A-1 or the group represented by A-2 is preferably a group where n is 4, and particularly preferably a group represented by A-1.
The compound of the present invention represented by the general formula (I) is a novel compound and can be produced, for example, according to the following reaction.
[0010]
[Chemical formula 5]
(In the above formula, A and Y are as defined in the general formula (I), and Z represents a chlorine atom or a bromine atom.)
That is, the carboxylic acid halide represented by the general formula (II) and the 2-amino-1,3,4-thiadiazole represented by the general formula (III) are preferably used in the presence or absence of a base, preferably a solvent. To react at 5 to 150 ° C. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as ethyl acetate and methyl acetate. Or polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine and the like. Examples of the base include inorganic salts such as sodium hydroxide, potassium hydroxide and potassium carbonate; amines such as pyridine and triethylamine. After the reaction, in order to isolate the target compound represented by the general formula (I), when using a solvent that dissolves in water, the solvent is distilled off under reduced pressure, water is added, Insoluble in benzene, toluene, xylene, etc .; halogenated hydrocarbons such as chloroform, dichloromethane, etc .; extracted with esters such as ethyl acetate, washed with saturated brine, then anhydrous sodium sulfate, anhydrous magnesium sulfate, etc. And then the solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added to the reaction mixture, followed by liquid separation. The organic layer is washed with saturated brine, dried with a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and reduced pressure. And the solvent may be distilled off.
If the residue obtained after distilling off the solvent is purified by recrystallization, suspension washing, column chromatography or the like, the compound represented by the general formula (I) as the target product can be obtained.
[0012]
The compound represented by the general formula (II) can be produced by treating the corresponding carboxylic acid with thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus trichloride or the like. Some of the carboxylic acids corresponding to the compounds represented by the general formula (II) are commercially available and can be easily obtained. Further, for example, 1,1,2-tribromocyclopropanecarboxylic acid is a method described in Tetrahedron, 52, 3409 (1996); 1-bromocyclopropanecarboxylic acid is J. Org. Chem., 54, 6096 (1989). ); 2,2-dichlorocyclopropanecarboxylic acids can be produced by the method described in JP-A-62-201855. Some of the compounds represented by the general formula (III) are commercially available and can be easily obtained. Further, it can be synthesized according to the method described in, for example, JP-A-57-77603 or the Journal of Pharmaceutical Sciences, Vol. 72, p. 376 (1952).
[0013]
The compound of the present invention represented by the general formula (I) has a controlling activity against various insects and mites. In particular, the compounds of the present invention include Lepidoptera such as Lotus moth, Konaga, Chanocokakumonhamaki, Kononomeiga, Nikameichu, etc .; Hemiptera such as aphids, whitefly, etc., stink bugs, such as Chabanae stink bugs; Coleoptera, such as kissing flea beetles, urihamushi, azuki beetle; Insect larvae and adults as well as pests of ticks such as nymph mite, mandarin mite, citrus mite, chano mite, larvae and adult pests such as adult horticultural crops, Insecticides and acaricides It is useful as an active ingredient. However, the insects and mites that are targets for control of the compound of the present invention are not limited to those exemplified above.
[0014]
When the compound of the present invention represented by the formula (I) is used as an agricultural or horticultural insecticide or acaricide, it may be used alone, but preferably manufactured using an agricultural chemical auxiliary widely used in the industry. Used in the form of a composition. The forms of agricultural and horticultural insecticides and acaricides are not particularly limited, but for example, emulsions, wettable powders, aqueous solvents, powders, flowables, fine granules, granules, tablets, oils, sprays, fumes, etc. It is preferable to adopt a form. One or more of the above compounds can be blended as an active ingredient.
Agricultural and horticultural insecticides, agrochemical adjuvants used to produce acaricides are agricultural and horticultural insecticides, for the purpose of improving, stabilizing, improving dispersibility, etc. , Carriers (diluents), spreading agents, emulsifiers, wetting agents, dispersing agents, disintegrating agents and the like can be used.
[0015]
Examples of liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, Examples include cyclohexane, animal and vegetable oils, and fatty acids. As the solid carrier, clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.
Usable surfactants can be used as emulsifiers and dispersants, for example, higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, anionic surfactants such as lauryl betaine, cations Surfactants, nonionic surfactants, zwitterionic surfactants, and the like can be used. In addition, spreading agents such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl phenyl ether; wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate and sodium lauryl sulfate Disintegrants can be used.
[0016]
The content of the active ingredient in the agricultural and horticultural insecticides and acaricides of the present invention is selected from the range of 0.1 to 99.5% by weight, and may be appropriately determined according to various conditions such as the preparation form and application method. For example, about 0.5 to 20% by weight for powders, preferably about 1 to 10% by weight, about 1 to 90% by weight for wettable powders, preferably about 10 to 80% by weight, and about 1 to 90% for emulsions. It is preferable to produce the composition so as to contain about 10%, preferably 10 to 40% by weight of the active ingredient.
For example, in the case of an emulsion, a solvent and a surfactant can be mixed with the compound of the general formula (I), which is an active ingredient, to prepare a stock emulsion. It can be diluted and applied. In the case of a wettable powder, the active ingredient can be mixed with the above compound, a solid carrier, a surfactant and the like to produce an active ingredient, and this active ingredient can be diluted with water to a predetermined concentration before use. . In the case of powders, the above active compound, solid carrier and the like can be mixed and applied as they are. In the case of granules, the active ingredient can be mixed with the solid carrier, surfactant and the like. It can be manufactured by granulating and applied as it is. However, the manufacturing method of each of the above-mentioned preparation forms is not limited to the above-mentioned ones, and can be appropriately selected by those skilled in the art according to the type of active ingredient, application purpose, and the like.
[0017]
The agricultural and horticultural insecticides and acaricides of the present invention include other fungicides, insecticides, acaricides, herbicides, insect growth regulators, fertilizers, soil improvers in addition to the compounds of the present invention which are active ingredients. Arbitrary active ingredients, such as, may be mix | blended. The application method of the agricultural and horticultural insecticide and / or acaricide of the present invention is not particularly limited, and can be applied by any method such as foliage application, water surface application, soil treatment, and seed treatment. For example, in the case of foliage spraying, a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of about 100 to 200 liters per 10 ares. In the case of water surface application, the application amount is usually 1 to 10 kg per 10 ares for granules containing 5 to 15% of the active ingredient. In the case of soil treatment, a solution having a concentration range of 5 to 1000 ppm can be used at an application rate of about 1 to 10 liters per 1 m 2 . In the case of seed treatment, about 10 to 100 ml of a solution having a concentration range of 10 to 1000 ppm per 1 kg of seed weight can be applied.
[0018]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, Formulation Examples, and Test Examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Example 1 <Synthesis of 2,2-dichloro-1-methyl-N- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) cyclopropanecarboxylic acid amide>
To a mixture of 0.51 g of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, 0.49 g of pyridine and 5 ml of dichloromethane, 0.75 g of 2,2-dichloro-1-methylcyclopropanecarboxylic acid chloride was added. The mixture was further stirred at room temperature for 1 hour. Dilute hydrochloric acid was added and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crystals were washed with hexane to obtain 0.38 g of the compound (No. 5) described in Table-1.
mp 131-132 ° C; 1 H NMR (CDCl 3 , TMS, ppm) 1.65 (1H, d), 1.88 (3H, s), 2.46 (1H, d).
[0019]
Example 2 <Synthesis of 1-bromo-N- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) cyclohexanecarboxylic acid amide>
To a mixture of 0.51 g of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, 0.41 g of potassium carbonate and 10 ml of toluene was added 0.68 g of 1-bromocyclohexanecarboxylic acid chloride, and at room temperature for 10 hours. Stir. Water was added and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crystals were washed with hexane to obtain 0.52 g of the compound (No. 1) described in Table-1. mp 99-103.5 ° C.
The 1-bromocyclohexanecarboxylic acid chloride used as a raw material was synthesized by the following method.
15 ml of thionyl chloride was added to 12.8 g of cyclohexanecarboxylic acid, and the mixture was refluxed for 30 minutes. After distilling off thionyl chloride, it was distilled under reduced pressure to obtain 13.4 g of cyclohexanecarboxylic acid chloride. bp 97-105 ° C / 70 mmHg.
2.1 ml of bromine was added to 5.00 g of cyclohexanecarboxylic acid chloride, and the mixture was heated to reflux for 2 hours. Distillation under reduced pressure gave 6.55 g of 1-bromocyclohexanecarboxylic acid chloride. bp 95-100 ° C / 3 mmHg.
[0020]
Example 3
The compounds described in Table 1 were synthesized according to the method described in Example 1 or 2.
[0021]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
Hereinafter, although the formulation example of the insecticide and acaricide which contain this invention compound as an active ingredient is shown, the usage form of this invention is not limited to these.
Formulation example 1: wettable powder 20 parts by weight of the compound of the present invention, Carplex # 80 (white carbon, Shionogi Pharmaceutical Co., Ltd., trade name), ST kaolin clay (Kaolinite, Tsuchiya Kaolin, trade name) 52 parts by weight, 5 parts by weight of Solpol 9047K (anionic surfactant, Toho Chemical Co., Ltd., trade name) and 3 parts by weight of Lunox P65L (anionic surfactant, Toho Chemical Co., Ltd., trade name) are blended uniformly. To obtain a wettable powder of 20% by weight of the active ingredient.
[0026]
Formulation Example 2: Powder 2 parts by weight of the compound of the present invention, 93 parts by weight of clay (manufactured by Nippon Talc Co., Ltd.), and 5 parts by weight of Carplex # 80 (white carbon, Shionogi & Co., Ltd., trade name) are uniformly mixed and ground. Thus, a powder of 2% by weight of active ingredient was produced.
Formulation Example 3: Emulsion 20 parts by weight of the compound of the present invention was dissolved in a mixed solvent consisting of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and Solpol 3005X (a mixture of a nonionic surfactant and an anionic surfactant). Toho Chemical Co., Ltd., trade name) 15 parts by weight was added to obtain an emulsion of 20% by weight active ingredient.
[0027]
Formulation Example 4: Flowable Agent 30 parts by weight of the compound of the present invention, 5 parts by weight of Solpol 9047K, 3 parts by weight of sorbon T-20 (nonionic surfactant, Toho Chemical Co., Ltd., trade name), 8 parts by weight of ethylene glycol, and 44 parts by weight of water is wet pulverized with Dynomill (manufactured by Shinmaru Enterprises), 10 parts by weight of a 1% by weight xanthan gum (natural polymer) aqueous solution is added to this slurry mixture, and the mixture is thoroughly mixed and pulverized to obtain 20 parts by weight of active ingredients % Flowable agent was obtained.
[0028]
Hereinafter, test examples of agricultural and horticultural insecticides and acaricides containing the compound of the present invention as an active ingredient will be shown, but the usage forms of the present invention are not limited to the following.
For comparison, a compound having the following structure described in US Pat. No. 4092148 (comparative compound) was subjected to the same test.
[0029]
[Chemical 6]
Test Example 1: Insecticidal effect on larvae of moths Cabbage cut leaves (6 cm in diameter) were immersed for 1 minute in an aqueous diluted solution of the insecticide of the present invention produced according to the formulation of Preparation Example 3. After soaking, it was air-dried and placed in a plastic cup (inner diameter: 7 cm), and 5 third instar worms were released in this cup (1 concentration, 2 repetitions). It was kept in a constant temperature room at 25 ° C., and after 4 days of larvae, the mortality and bitterness of the larvae were investigated, and the insecticidal activity (%) was determined by halving the bitter worms. The results are shown in Table 2 (in the following table, Compound No. corresponds to Table 1).
[0031]
[Table 5]
Test example 2: Acaricide effect on adult worm spider mites In a test tube containing water (capacity: 50 ml), the stem of a bean seedling that left one primary leaf was inserted, and 15 adult worm spider mites were inoculated per leaf. did. One day after the inoculation, the mite-infested leaf was immersed in a water-diluted solution of the acaricide of the present invention produced according to the formulation of Preparation Example 3 (about 5 seconds) (1 concentration, 2 repetitions). It was kept in a constant temperature room at 25 ° C., and the number of adult spider mites on the green leaf was examined on the 5th day after the treatment, and the killing rate (%) was determined based on the result. The results are shown in Table-3.
[0033]
[Table 6]
【The invention's effect】
The novel N-thiadiazolyl cycloalkanecarboxylic acid amides of the present invention have an excellent control effect against harmful insects and mites.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36239899A JP4512928B2 (en) | 1999-12-21 | 1999-12-21 | N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36239899A JP4512928B2 (en) | 1999-12-21 | 1999-12-21 | N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001172271A JP2001172271A (en) | 2001-06-26 |
| JP4512928B2 true JP4512928B2 (en) | 2010-07-28 |
Family
ID=18476748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36239899A Expired - Fee Related JP4512928B2 (en) | 1999-12-21 | 1999-12-21 | N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4512928B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002154904A (en) * | 2000-11-13 | 2002-05-28 | Mitsubishi Chemicals Corp | N-thiadiazolylcarboxamides and insecticide and acaricide comprising the same as active ingredient |
| JP4742333B2 (en) * | 2000-11-13 | 2011-08-10 | 日本農薬株式会社 | N-thiadiazolylcyclopropanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50117934A (en) * | 1974-03-01 | 1975-09-16 | ||
| JPH11263782A (en) * | 1997-12-11 | 1999-09-28 | Mitsubishi Chemical Corp | N-thiadiazolycarboxamide derivative and insecticidal and acaricidal agent containing the same as active ingredient |
-
1999
- 1999-12-21 JP JP36239899A patent/JP4512928B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50117934A (en) * | 1974-03-01 | 1975-09-16 | ||
| JPH11263782A (en) * | 1997-12-11 | 1999-09-28 | Mitsubishi Chemical Corp | N-thiadiazolycarboxamide derivative and insecticidal and acaricidal agent containing the same as active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001172271A (en) | 2001-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2006022225A1 (en) | Optically active phthalamide derivative, agricultural or horticultural insecticide, and method of using the same | |
| WO1998045274A1 (en) | Pyrazole derivatives, process for preparing the same, intermediates, and pest control agent containing the same as active ingredient | |
| JP2005263809A (en) | N-aryl hydrazine derivative as insecticide and acaricide | |
| KR0140208B1 (en) | Pyridaginones having insecticidal and acaricidal activity | |
| JP2006527172A (en) | Use of isoindolinone derivatives as insecticides | |
| JPH1053583A (en) | Pyrazole compound and antimicrobial, insecticidal and acaricidal agent containing the same as active ingredient | |
| JPH0472830B2 (en) | ||
| KR20020035614A (en) | Insecticidal and acaricidal agents | |
| JP2003277362A (en) | Pyrazolecarboxamide, intermediate of the same and pest- controlling agent with the same as active ingredient | |
| JP4512928B2 (en) | N-thiadiazolylcycloalkanecarboxylic acid amides and insecticides and acaricides containing the same as active ingredients | |
| JPS58148805A (en) | N-oxalyl derivatives of n-methylcarbamates, manufacture and use as insecticide | |
| JPS63159372A (en) | Pyridazinone compound and insecticide, acaricide and nematocide | |
| JP2000226389A (en) | N-thiadiazolylpyrazolecarboxamide derivative and insecticide and acaricide containing the same as active ingredient | |
| JPH04334374A (en) | N-(2-thiazolyl)urea derivative, its production and insecticide containing the same compound | |
| JPH0368566A (en) | Derivative of 5-substituted 3-aryl inoxazole, its preparation and expellant medicine for controlling harmful organism containing same | |
| JP2002363164A (en) | Pyrazolecarboxamide compound, its intermediate and noxious organism controlling agent containing the compound as active component | |
| JP2005060255A (en) | Carboxamide compounds and pest control agent containing the same as active ingredient | |
| JPH10338676A (en) | Pyrazole derivative, its production, intermediate and pest controlling agent containing the same as active ingredient | |
| JPH11263782A (en) | N-thiadiazolycarboxamide derivative and insecticidal and acaricidal agent containing the same as active ingredient | |
| JP4565286B2 (en) | 6-haloalkyl-3- (substituted amino) -1,2,4-triazin-5-one derivatives, agricultural chemicals containing this as an active ingredient, and production intermediates thereof | |
| JPS63211270A (en) | Condensed imidazole compound and exterminating agent against harmful organism containing said compound | |
| JPH0692935A (en) | N-substituted indole derivative, its productin and insecticidal composition with the same as active ingredient | |
| JPH05286970A (en) | 2-acylamino-2-thiazolines and their production and pest controller | |
| JPH04312566A (en) | Ether derivative and insecticidal and acaricidal composition containing the same as active ingredient | |
| JPH09278775A (en) | Pyrazole compound and insecticide, acaricide and germicide containing the same as active ingredient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20060123 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20060123 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061211 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100421 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100427 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130521 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |