JP3775816B2 - Carbohydroxymoylazole derivatives or salts thereof and insecticides - Google Patents
Carbohydroxymoylazole derivatives or salts thereof and insecticides Download PDFInfo
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- JP3775816B2 JP3775816B2 JP05649995A JP5649995A JP3775816B2 JP 3775816 B2 JP3775816 B2 JP 3775816B2 JP 05649995 A JP05649995 A JP 05649995A JP 5649995 A JP5649995 A JP 5649995A JP 3775816 B2 JP3775816 B2 JP 3775816B2
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- compound
- carbohydroxymoylazole
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- formula
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- 150000003839 salts Chemical class 0.000 title claims description 10
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- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
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- 125000003545 alkoxy group Chemical group 0.000 claims description 3
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- 125000002071 phenylalkoxy group Chemical group 0.000 claims description 2
- 125000005554 pyridyloxy group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
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- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
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- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
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Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、カルボヒドロキシモイルアゾール誘導体又はその塩及びこれを有効成分として含有する殺虫剤に関するものである。
【０００２】
【従来の技術】
ベンズヒドロキシモイルアゾール誘導体は、有害昆虫に活性を有することが知られている（例えば、特開平１−３０８２６０号公報明細書および国際公開ＷＯ９２０９５８１公報明細書）。また、本明細書と類似の化合物が特開昭６０−８７２６９号公報明細書に記載されているが、殺菌活性を示すとの記載しか無く、殺虫活性については何ら知られていない。
【０００３】
【発明が解決しようとする課題】
近年、既存の市販殺虫剤は残留、蓄積、環境汚染等の問題から使用が規制されたり、長期使用によって抵抗性害虫が発生し、効力の薄れたものも出ている。そのため低薬量において高い効力を有し、安全性に優れ且つ抵抗性害虫にも有用な殺虫剤の開発が望まれている。
【０００４】
【課題を解決するための手段】
本発明者らは、種々のアルカンカルボン酸のカルボヒドロキシモイルアゾール誘導体を合成し、その生理活性について検討を重ねた。その結果、本発明化合物が種々の有害昆虫類、特に感受性及び抵抗性ウンカ類並びにヨコバイ類、アブラムシ類及びカメムシ類等の半翅目害虫に対して、極めて優れた殺虫活性を有することを見いだし本発明を完成したものである。即ち、本発明は一般式〔Ｉ〕
【０００５】
【化３】
【０００６】
【化４】
【０００７】
本明細書において、アルキル基としては、炭素数１〜６の直鎖又は枝分かれしたアルキル基、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基，ｎ−ペンチル基、ｎ−ヘキシル基等を挙げることができる。
【０００８】
アルコキシ基としては、それぞれアルキル部分が上記の意味を示す（アルキル）−Ｏ−基を例示できる。
【０００９】
ハロゲン原子とは、フッ素、塩素、臭素、ヨウ素原子を示す。
【００１０】
アルキレン基としては、例えばエチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基等を挙げることができる。
【００１１】
アルケニレン基としては、直鎖状アルケンの両端の炭素原子に結合する水素原子を１個ずつのぞいてできる２価基を意味し、例えば、ビニレン基、１−メチルエチニレン基、２−メチルエチニレン基、プロペニレン基、１−メチルプロペニレン基、２−メチルプロペニレン基、３−メチルプロペニレン基、２−ペンテニレン基等を挙げることができる。
【００１２】
ハロアルキル基としては、ハロゲン原子によって置換されたアルキル基を意味し、例えばトリフルオロメチル基、ペンタフルオロエチル基等を挙げることができる。
【００１３】
一般式〔Ｉ〕においてＡで示される置換基の、式Ａ−１で示される基としてはフェニル基、４−クロロフェニル基を、式Ａ−２で示される基としてはフリル基を、式Ａ−３で示される基としてはチオフェニル基を、式Ａ−４で示される基としてはナフチル基等を挙げることができる。
【００１４】
前記一般式〔Ｉ〕において、好ましい化合物群としてはＲがイソプロピル基を示し、Ａがフェニル基を示し、Ｘｎが水素原子、トリフルオロメチル基又はイソプロピルオキシ基を示し、Ｚは窒素原子を示し、Ｙがエチレン、トリメチレン基、テトラメチレン基を示し、ｎが０又は１を示す化合物があげられる。
【００１５】
一般式〔Ｉ〕で表されるカルボヒドロキシモイルアゾール誘導体はエントゲーゲン（ｅｎｔｇｅｇｅｎ）体、ツザーメン（ｚｕｓａｍｍｅｎ）体の二種の立体異性体が存在するが、本発明化合物はこれらの異性体及びこれらの異性体の任意の比率の混合物をも包含する。
【００１６】
次に、一般式〔Ｉ〕で表される本発明化合物の代表的な具体例を表１〜表５に例示する。尚、表中のアルケンの立体異性についてはエントゲーゲン体をＥ、ツザーメン体をＺ、エントゲーゲン体とツザーメン体の混合体をＥＺと略記してある。また、化合物番号は以後の記載において参照される。
【００１７】
【表１】
【表２】
【表３】
【表４】
【表５】
製造法Ａ
【００２２】
【化５】
【００２３】
一般式〔Ｉ〕で示される本発明化合物は一般式〔ＩＩ〕で示されるカルボヒドロキシモイルハライド化合物と、一般式〔ＩＩＩ〕で示されるイミダゾール又はトリアゾールとを塩基の存在下で反応させて製造することができる。本反応において、イミダゾール又はトリアゾールは塩基をかねて当量以上使用することもできる。また、使用することができる塩基としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物類、水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属の水酸化物類、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩類、炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属の重炭酸塩類などの無機塩基類、水素化ナトリウム、水素化カリウム等の金属水素化物類又はトリエチルアミン、Ｎ，Ｎ−ジメチルアニリン、ピリジン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン（ＤＢＵ）等の有機塩基類が挙げられる。
【００２４】
反応は必要ならば適当な希釈剤の存在下で行うことができる。使用できる希釈剤としては水又は不活性な有機溶媒、例えばアセトン、ブタノン等のケトン類、ベンゼン、トルエン、キシレン、クロロベンゼン等の芳香族炭化水素類、石油エーテル、リグロイン等の脂肪族炭化水素類、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、アセトニトリル、プロピオニトリル等のニトリル類又はＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、スルホラン等の非プロトン性極性溶媒等が挙げられる。反応温度は室温から反応系における還流温度までの任意の温度であり、好ましくは８０〜１５０℃である。反応時間は化合物により異なるが、２〜５時間反応させれば収率良く目的物を製造することができる。
【００２５】
尚、原料となる一般式〔ＩＩ〕で示されるカルボヒドロキシモイルハライド化合物は、次の反応式で示される方法で製造することができる。
【００２６】
【化６】
【００２７】
一般式〔ＩＶ〕で示されるヒドロキサム酸化合物を、五塩化燐、塩化チオニル等のハロゲン化剤と、ベンゼン、トルエン等の芳香族炭化水素類又はクロロホルム、四塩化炭素等のハロゲン化炭化水素類等の不活性溶媒の存在下反応させることにより製造できる。また、トリフェニルホスフィンと四塩化炭素又は四臭化炭素とからなるハロゲン化剤と、アセトニトリル、プロピオニトリル等のニトリル類又はベンゼン、クロロベンゼン等の芳香族炭化水素類等の不活性溶媒の存在下反応させることにより製造することもでき、この場合四塩化炭素および四臭化炭素は溶媒を兼ねることもできる。いずれの方法においても反応温度は、０℃から反応系における還流温度までの任意の温度であり、好ましくは５０〜８０℃である。反応時間は、化合物により異なるが、１〜６時間反応させればよい。
【００２８】
一般式〔ＩＶ〕で示されるヒドロキサム酸化合物は、対応するカルボン酸を公知の方法により、酸ハライド又は１−アシルイミダゾールとし、これにアルコキシアミンを反応させることにより製造することができる。
【００２９】
製造法Ｂ
一般式〔Ｉ〕で示される本発明化合物は、常法に従い塩化水素、硫酸、硝酸およびリン酸等の強酸を作用させることにより、各々の塩に導くことができる。
【００３０】
具体的には、例えば一般式〔Ｉ〕で示される本発明化合物を溶媒に溶解し、氷冷下ないし室温下に酸を気体あるいは水溶液にて１〜１．５当量加えて１０分〜１時間放置した後、減圧濃縮等の後処理を行い、必要に応じて再結晶等によって処理することにより塩を得られる。ここで反応溶媒としては、メタノール、エタノール等の低級アルコール、トルエン、ベンゼン等の芳香族炭化水素、エチルエーテル、テトラヒドロフラン、ジオキサン等のハロゲン化炭化水素類、アセトン等のケトン類、酢酸エチル等のエステル類、ヘキサン等の炭化水素類、水あるいはそれらの混合物等があげられる。
【００３１】
次に実施例を挙げて本発明化合物の製造法を具体的に説明する。
【００３２】
【実施例】
製造例１ １−（Ｏ−イソプロピル−５−フェニルペンタンカルボヒドロキシモイル）−１Ｈ−１，２，４−トリアゾール （化合物番号４）の製造
Ｏ−イソプロピル−５−フェニルペンタンカルボヒドロキシモイルクロリド７．０ｇ（２８ｍｍｏｌ）、１Ｈ−１，２，４−トリアゾール２．９ｇ（４０ｍｍｏｌ）及び炭酸カリウム４．６ｇ（３４ｍｍｏｌ）をジメチルスルホキシド１５０ｍｌに加え、１５０℃にて４時間加熱攪拌した。ついで反応混合物を室温まで自然冷却した後水に注ぎ、酢酸エチルにて抽出した。有機層を水洗後、無水硫酸マグネシウムにて乾燥し、溶媒を減圧下に除いた。残渣をカラムクロマトグラフィーにて精製して２０℃における屈折率１．５２２１の目的物２．４ｇ（収率３０％）を得た。
【００３３】
ＮＭＲデ−タ（６０ＭＨｚ，ＣＤＣｌ３溶媒，δ値：ｐｐｍ）
１．２８ （６Ｈ，ｄｄ）
１．５３〜１．７９ （４Ｈ，ｍ）
２．５２〜３．０９ （４Ｈ，ｍ）
４．０７〜４．６５ （１Ｈ，ｍ）
７．１６ （５Ｈ，ｓ）
７．９３ （１Ｈ，ｄ）
８．８７ （１Ｈ，ｄ）
【００３４】
製造例２ １−（Ｏ−イソプロピル−５−フェニルブタンカルボヒドロキシモイル）イミダゾール （化合物番号３）の製造
Ｏ−イソプロピル−５−フェニルブタンカルボヒドロキシモイルクロリド５．０ｇ（２０ｍｍｏｌ）、イミダゾール２．１ｇ（３０ｍｍｏｌ）及び炭酸カリウム３．３ｇ（２４ｍｍｏｌ）をジメチルスルホキシド１５０ｍｌに加え、１５０℃にて２時間加熱攪拌した。ついで反応混合物を室温まで自然冷却した後水に注ぎ、酢酸エチルにて抽出した。有機層を水洗後、無水硫酸マグネシウムにて乾燥し、溶媒を減圧下にて除いた。残渣をカラムクロマトグラフィーにて精製して２０℃における屈折率１．５３３１の目的物１．５ｇ（収率２８％）を得た。
【００３５】
ＮＭＲデ−タ（６０ＭＨｚ，ＣＤＣｌ３溶媒，δ値：ｐｐｍ）
１．２５ （６Ｈ，ｄ）
１．７５〜２．１５ （２Ｈ，ｍ）
２．５０〜２．９０ （４Ｈ，ｍ）
４．１０〜４．５７ （１Ｈ，ｍ）
７．０３〜７．１８ （７Ｈ，ｍ）
７．９３ （１Ｈ，ｄ）
【００３６】
本発明の殺虫剤は、一般式〔Ｉ〕で示されるカルボヒドロキシモイルアゾール誘導体又はその塩を有効成分としてなる。
【００３７】
本発明化合物を殺虫剤として使用するには本発明化合物それ自体で用いてもよいが、製剤化に一般的に用いられる担体、界面活性剤、分散剤又は補助剤等を配合して、粉剤、水和剤、乳剤、微粒剤又は粒剤等に製剤して使用することもできる。製剤化に際して用いられる担体としては、タルク、ベントナイト、クレー、カオリン、珪藻土、ホワイトカーボン、バーミキュライト、消石灰、珪砂、硫安、尿素等の固体担体、イソプロピルアルコール、キシレン、シクロヘキサノン、メチルナフタレン等の液体担体等があげられる。界面活性剤及び分散剤としては、アルキルベンゼンスルホン酸金属塩、ジナフチルメタンジスルホン酸金属塩、アルコール硫酸エステル塩、アルキルアリールスルホン酸塩、リグニンスルホン酸塩、ポリオキシエチレングリコールエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタンモノアルキレート等があげられる。補助剤としては、カルボキシメチルセルロース、ポリエチレングリコール、アラビアゴム等があげられる。使用に際しては適当な濃度に希釈して散布するか又は直接施用する。
【００３８】
本発明の殺虫剤は茎葉散布、土壌施用、育苗箱施用又は水面施用等により使用することができる。有効成分の配合割合については必要に応じて適宜選ばれるが、粉剤又は粒剤とする場合は０．０５〜２０％（重量）、好ましくは０．１％〜１０％（重量）の範囲から適宜選ぶのがよい。乳剤又は水和剤とする場合は０．５〜８０％（重量）が適当である。好ましくは１〜６０％（重量）の範囲から適宜選ぶのがよい。
【００３９】
本発明の殺虫剤の施用量は使用される化合物の種類、対象害虫、発生傾向、被害の程度、環境条件、使用する剤型などによってかわるが、粉剤及び粒剤のようにそのまま使用する場合は、有効成分として１０アール当り０．０５ｇ〜５ｋｇ、好ましくは０．１ｇ〜１ｋｇの範囲から適宜選ぶのがよい。また、乳剤及び水和剤のように液状で使用する場合は、０．１〜５，０００ｐｐｍ、好ましくは１〜１，０００ｐｐｍの範囲から適宜選ぶのがよい。
【００４０】
本発明の殺虫剤は、他の殺虫剤、殺菌剤、肥料、植物生長調節剤を混合して使用することもできる。
【００４１】
次に、代表的な製剤例をあげて製剤方法を具体的に説明する。化合物、添加剤の種類及び配合比率は、これのみに限定されることなく広い範囲で変更可能である。以下の説明において、％は重量百分率を示す。
【００４２】
製剤例１ 乳剤
化合物番号（１）３０％、シクロヘキサノン２０％、ポリオキシエチレンアルキルアリールエーテル１１％、アルキルベンゼンスルホン酸カルシウム４％及びメチルナフタリン３５％を均一に溶解して乳剤とした。
【００４３】
製剤例２ 水和剤
化合物番号（２０）４０％、珪藻土１５％、クレー１５％、ホワイトカーボン２５％、ジナフチルメタンジスルホン酸ナトリウム２％及びリグニンスルホン酸ナトリウム３％を均一に混合粉砕して水和剤とした。
【００４４】
製剤例３ 粉剤
化合物番号（２７）２％、珪藻土５％及びクレー９３％を均一に混合粉砕して粉剤とした。
【００４５】
製剤例４ 粒剤
化合物番号（１０）５％、ラウリルアルコール硫酸エステルのナトリウム塩２％、リグニンスルホン酸ナトリウム５％、カルボキシメチルセルロース２％及びクレー８６％を均一に混合粉砕する。この混合物１００重量部に水２０重量部を加えて練合し、押出式造粒機を用いて１４〜３２メッシュの粒状に加工したのち、乾燥して粒剤とした。
【００４６】
【発明の効果】
本発明のカルボヒドロキシモイルアゾール誘導体又はその塩は、トビイロウンカ、セジロウンカ、ヒメトビウンカ等のウンカ類、ツマグロヨコバイ、ミドリヒメヨコバイ等のヨコバイ類、ワタアブラムシ、モモアカアブラムシ、ダイコン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、クワコナカイガラムシ等のカイガラムシ類、クモヘリカメムシ、チャバネアオカメムシ等のカメムシ類、ツツジグンバイ等のグンバイムシ類及びナシキジラミ、リンゴキジラミ等のキジラミ類等の半翅目害虫、コナガ、シロイチモジヨトウ、ハスモンヨトウ等の鱗翅目害虫、イエバエ、アカイエカ等の双翅目害虫、イネミズゾウムシ、アズキゾウムシ、ウリハムシ等の鞘翅目害虫、ワモンゴキブリ、チャバネゴキブリ等の直翅目害虫ならびにナミハダニ、カンザワハダニ、ミカンハダニ等のハダニ類の防除に有効である。特に感受性及び抵抗性ウンカ類並びにヨコバイ類、アブラムシ類及びカメムシ類等の半翅目害虫に対し、極めて優れた防除効果を示す。
【００４７】
次に本発明化合物の奏する効果について試験例をもって説明する。尚、使用した比較薬剤ａは特開昭６０−８７２６９号公報明細書記載の化合物である。この比較薬剤は供試化合物と同様に製剤して使用した。
【００４８】
比較薬剤ａ：１−（Ｏ−メチル−ピバロヒドロキシモイル）イミダゾール
【００４９】
試験例１ ツマグロヨコバイ殺虫試験
製剤例２に準じて調製した水和剤を５００ｐｐｍの濃度に水で希釈した。その薬液にイネ茎葉を浸漬し、風乾後、試験管に静置した。その中にツマグロヨコバイ幼虫５頭を放ち、脱脂綿で栓をした。その後、２５℃の恒温室に置き、６日後に死虫数を調査し、死虫率を算出した。求めた死虫率は表６の基準に従い評価し、結果を表７に示した。尚、試験は２連制で行った。
【００５０】
【表６】
【表７】
試験例２ トビイロウンカ殺虫試験
製剤例２に準じて調製した水和剤を５００ｐｐｍの濃度に水で希釈した。その薬液にイネ茎葉を浸漬し、風乾後、試験管に静置した。その中にトビイロウンカ幼虫５頭を放ち、脱脂綿で栓をした。その後、２５℃の恒温室に置き、６日後に死虫数を調査し、死虫率を算出した。求めた死虫率は表６の基準に従い評価し、結果を表８に示した。尚、試験は２連制で行った。
【００５３】
【表８】
試験例３ ワタアブラムシ殺虫試験
製剤例２に準じて調製した水和剤を１００ｐｐｍの濃度に水で希釈した。その薬液に、予めワタアブラムシ若虫を接種しておいたキュウリ苗を浸漬し、風乾した後、２５℃の恒温室に置いた。３日後に死虫数を調査し、死虫率を算出した。求めた死虫率は表６の基準に従い評価し、結果を表９に示した。尚、試験は２連制で行った。
【００５５】
【表９】
[Industrial application fields]
The present invention relates to a carbohydroxymoylazole derivative or a salt thereof and an insecticide containing this as an active ingredient.
[0002]
[Prior art]
Benzhydroxymoylazole derivatives are known to have activity against harmful insects (for example, JP-A-1-308260 and International Publication WO9209581). Moreover, although a compound similar to this specification is described in Unexamined-Japanese-Patent No. 60-87269, there is only description that it shows bactericidal activity, and no insecticidal activity is known.
[0003]
[Problems to be solved by the invention]
In recent years, the use of existing commercially available insecticides has been restricted due to problems such as residue, accumulation and environmental pollution, and resistant pests have been generated due to long-term use, and some of them are less effective. Therefore, development of an insecticide having high efficacy at a low dose, excellent safety, and useful for resistant pests has been desired.
[0004]
[Means for Solving the Problems]
The present inventors have synthesized carbohydroxymoylazole derivatives of various alkanecarboxylic acids and repeatedly studied their physiological activities. As a result, it has been found that the compounds of the present invention have extremely excellent insecticidal activity against various harmful insects, particularly sensitive and resistant planthoppers, and hemipod pests such as leafhoppers, aphids and stink bugs. The invention has been completed. That is, the present invention relates to the general formula [I]
[0005]
[Chemical 3]
[Formula 4]
[0007]
In this specification, as the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and the like can be given.
[0008]
Examples of the alkoxy group include (alkyl) -O- groups in which each alkyl moiety has the above meaning.
[0009]
A halogen atom represents a fluorine, chlorine, bromine or iodine atom.
[0010]
Examples of the alkylene group include an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
[0011]
The alkenylene group means a divalent group formed by removing one hydrogen atom bonded to carbon atoms at both ends of a linear alkene, for example, vinylene group, 1-methylethynylene group, 2-methylethynylene group, propenylene group 1-methylpropenylene group, 2-methylpropenylene group, 3-methylpropenylene group, 2-pentenylene group and the like.
[0012]
The haloalkyl group means an alkyl group substituted with a halogen atom, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.
[0013]
In the general formula [I], the substituent represented by A is a phenyl group, 4-chlorophenyl group as the group represented by formula A-1, a furyl group as the group represented by formula A-2, and the formula A- Examples of the group represented by 3 include a thiophenyl group, and examples of the group represented by the formula A-4 include a naphthyl group.
[0014]
In the general formula [I], as a preferred compound group, R represents an isopropyl group, A represents a phenyl group, Xn represents a hydrogen atom, a trifluoromethyl group or an isopropyloxy group, Z represents a nitrogen atom, Examples thereof include compounds in which Y represents ethylene, trimethylene group or tetramethylene group, and n represents 0 or 1.
[0015]
The carbohydroxymoylazole derivative represented by the general formula [I] has two stereoisomers, an entgegen isomer and a zusammen isomer, and the compound of the present invention includes these isomers and isomers thereof. Also includes mixtures of any proportion of the body.
[0016]
Next, typical specific examples of the compound of the present invention represented by the general formula [I] are illustrated in Tables 1 to 5. In the table, steric isomerism of alkenes is abbreviated as E. Engegen body, Z as tsusemen body, and EZ as a mixture of entgegen body and semen body. The compound number is referred to in the following description.
[0017]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
Manufacturing method A
[0022]
[Chemical formula 5]
[0023]
The compound of the present invention represented by the general formula [I] is produced by reacting a carbohydroxymoyl halide compound represented by the general formula [II] with an imidazole or triazole represented by the general formula [III] in the presence of a base. be able to. In this reaction, imidazole or triazole can also be used in an equivalent amount or more as a base. Examples of the base that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, and sodium carbonate. , Alkali metal carbonates such as potassium carbonate, inorganic bases such as sodium hydrogen carbonate, alkali metal bicarbonates such as potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride or triethylamine, N, And organic bases such as N-dimethylaniline, pyridine, and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU).
[0024]
If necessary, the reaction can be carried out in the presence of a suitable diluent. Diluents that can be used include water or inert organic solvents such as ketones such as acetone and butanone, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbons such as petroleum ether and ligroin, Aprotic polarities such as ethers such as diethyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, or N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane A solvent etc. are mentioned. The reaction temperature is an arbitrary temperature from room temperature to the reflux temperature in the reaction system, and preferably 80 to 150 ° C. Although the reaction time varies depending on the compound, the target product can be produced in good yield by reacting for 2 to 5 hours.
[0025]
The carbohydroxymoyl halide compound represented by the general formula [II] as a raw material can be produced by a method represented by the following reaction formula.
[0026]
[Chemical 6]
[0027]
Hydroxamic acid compound represented by the general formula [IV], halogenating agents such as phosphorus pentachloride and thionyl chloride, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as chloroform and carbon tetrachloride, etc. In the presence of an inert solvent. Also, in the presence of a halogenating agent comprising triphenylphosphine and carbon tetrachloride or carbon tetrabromide, and an inert solvent such as nitriles such as acetonitrile and propionitrile, or aromatic hydrocarbons such as benzene and chlorobenzene. In addition, carbon tetrachloride and carbon tetrabromide can also serve as a solvent. In any method, the reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably 50 to 80 ° C. Although reaction time changes with compounds, what is necessary is just to make it react for 1 to 6 hours.
[0028]
The hydroxamic acid compound represented by the general formula [IV] can be produced by converting the corresponding carboxylic acid into an acid halide or 1-acylimidazole by a known method and reacting this with an alkoxyamine.
[0029]
Manufacturing method B
The compound of the present invention represented by the general formula [I] can be led to each salt by the action of a strong acid such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid according to a conventional method.
[0030]
Specifically, for example, the compound of the present invention represented by the general formula [I] is dissolved in a solvent, and an acid is added in an amount of 1 to 1.5 equivalents in a gas or an aqueous solution under ice cooling or room temperature, and 10 minutes to 1 hour. After allowing to stand, a salt can be obtained by performing post-treatment such as concentration under reduced pressure and, if necessary, recrystallization or the like. Here, the reaction solvent includes lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and benzene, halogenated hydrocarbons such as ethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, and esters such as ethyl acetate. , Hydrocarbons such as hexane, water or a mixture thereof.
[0031]
Next, an Example is given and the manufacturing method of this invention compound is demonstrated concretely.
[0032]
【Example】
Production Example 1 Production of 1- (O-isopropyl-5-phenylpentanecarbohydroxymoyl) -1H-1,2,4-triazole (Compound No. 4) 7.0 g of O-isopropyl-5-phenylpentanecarbohydroxymoyl chloride (28 mmol) 2.9 g (40 mmol) of 1H-1,2,4-triazole and 4.6 g (34 mmol) of potassium carbonate were added to 150 ml of dimethyl sulfoxide, and the mixture was heated and stirred at 150 ° C. for 4 hours. The reaction mixture was then naturally cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 2.4 g (yield 30%) of the desired product having a refractive index of 1.5221 at 20 ° C.
[0033]
NMR data (60 MHz, CDCl 3 solvent, δ value: ppm)
1.28 (6H, dd)
1.53 to 1.79 (4H, m)
2.52 to 3.09 (4H, m)
4.07 to 4.65 (1H, m)
7.16 (5H, s)
7.93 (1H, d)
8.87 (1H, d)
[0034]
Production Example 2 Production of 1- (O-isopropyl-5-phenylbutanecarbohydroxymoyl) imidazole (Compound No. 3) 5.0 g (20 mmol) of O-isopropyl-5-phenylbutanecarbohydroxymoyl chloride, 2.1 g of imidazole ( 30 mmol) and 3.3 g (24 mmol) of potassium carbonate were added to 150 ml of dimethyl sulfoxide, and the mixture was heated and stirred at 150 ° C. for 2 hours. The reaction mixture was then naturally cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 1.5 g (yield 28%) of the desired product having a refractive index of 1.5331 at 20 ° C.
[0035]
NMR data (60 MHz, CDCl 3 solvent, δ value: ppm)
1.25 (6H, d)
1.75 to 2.15 (2H, m)
2.50 to 2.90 (4H, m)
4.10 to 4.57 (1H, m)
7.03-7.18 (7H, m)
7.93 (1H, d)
[0036]
The insecticide of the present invention comprises a carbohydroxymoylazole derivative represented by the general formula [I] or a salt thereof as an active ingredient.
[0037]
In order to use the compound of the present invention as an insecticide, the compound of the present invention may be used as it is, but it contains a carrier, surfactant, dispersant, or auxiliary agent generally used for formulation, It can also be used in the form of wettable powders, emulsions, fine granules or granules. Carriers used for formulation include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, liquid carriers such as isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene, etc. Can be given. Surfactants and dispersants include alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate esters, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryls. Examples include ether and polyoxyethylene sorbitan monoalkylate. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. In use, dilute to an appropriate concentration and spray or apply directly.
[0038]
The insecticide of the present invention can be used by foliage application, soil application, nursery box application, water surface application, and the like. The blending ratio of the active ingredient is appropriately selected as necessary, but in the case of powder or granule, it is appropriately selected from the range of 0.05 to 20% (weight), preferably 0.1% to 10% (weight). It is good to choose. In the case of an emulsion or wettable powder, 0.5 to 80% (weight) is appropriate. Preferably, it is appropriately selected from the range of 1 to 60% (weight).
[0039]
The application rate of the insecticide of the present invention varies depending on the type of compound used, the target pest, the occurrence tendency, the degree of damage, the environmental conditions, the dosage form to be used, etc. The active ingredient is appropriately selected from the range of 0.05 g to 5 kg, preferably 0.1 g to 1 kg per 10 ares. Further, when used in a liquid form such as an emulsion and a wettable powder, it may be appropriately selected from the range of 0.1 to 5,000 ppm, preferably 1 to 1,000 ppm.
[0040]
The insecticide of the present invention can be used by mixing with other insecticides, fungicides, fertilizers, and plant growth regulators.
[0041]
Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description,% indicates weight percentage.
[0042]
Formulation Example 1 Emulsion compound No. (1) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzenesulfonate 4% and methylnaphthalene 35% were uniformly dissolved to prepare an emulsion.
[0043]
Formulation Example 2 40% wettable powder compound number, 15% diatomaceous earth, 15% clay, 25% white carbon, 2% sodium dinaphthylmethane disulfonate and 3% sodium lignin sulfonate are mixed and ground uniformly. It was made into a Japanese medicine.
[0044]
Formulation Example 3 Dust Compound No. (27) 2%, diatomaceous earth 5%, and clay 93% were uniformly mixed and ground to obtain a powder.
[0045]
Formulation Example 4 Granule compound number (10) 5%, sodium lauryl alcohol sulfate 2%, sodium lignin sulfonate 5%, carboxymethylcellulose 2% and clay 86% are uniformly mixed and ground. 20 parts by weight of water was added to 100 parts by weight of the mixture, kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and dried to form granules.
[0046]
【The invention's effect】
The carbohydroxymoylazole derivatives or salts thereof of the present invention include planthoppers such as green planthopper, white-tailed planthopper, leafhopper, etc. Parasitoids such as whiteflies, scale insects such as stag beetle, spider helicopters, stink bugs such as Chabanaeokamushi; Lepidopterous insects such as lepidopterous insects, house fly, mosquito, etc., Coleoptera insects such as rice weevil, azuki beetle, cucumber weevil, straight insects such as cockroach, German cockroach Two-spotted spider mite Each time, kanzawai, is effective for controlling mites such as citrus red mite. In particular, it exhibits an extremely excellent control effect against sensitive and resistant planthoppers, and hemipod pests such as leafhoppers, aphids and stink bugs.
[0047]
Next, the effect of the compound of the present invention will be described with test examples. The comparative drug a used is a compound described in JP-A-60-87269. This comparative drug was formulated and used in the same manner as the test compound.
[0048]
Comparative agent a: 1- (O-methyl-pivalohydroxymoyl) imidazole
Test Example 1 A wettable powder prepared according to Example 2 of the leafhopper insecticide test preparation 2 was diluted with water to a concentration of 500 ppm. Rice stems and leaves were immersed in the chemical, air-dried, and then allowed to stand in a test tube. Five larvae of the leafhopper were released into it, and plugged with cotton wool. Then, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined and the dead insect rate was calculated. The obtained death rate was evaluated according to the criteria in Table 6 and the results are shown in Table 7. In addition, the test was performed by 2 continuous systems.
[0050]
[Table 6]
[Table 7]
Test Example 2 A wettable powder prepared according to Example 2 of the planthopper insecticide test preparation was diluted with water to a concentration of 500 ppm. Rice stems and leaves were immersed in the chemical, air-dried, and then allowed to stand in a test tube. Five of the brown planthopper larvae were released in it and plugged with absorbent cotton. Then, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined and the dead insect rate was calculated. The obtained death rate was evaluated according to the criteria in Table 6 and the results are shown in Table 8. In addition, the test was performed by 2 continuous systems.
[0053]
[Table 8]
Test Example 3 A wettable powder prepared according to Cotton Aphid Insecticide Test Formulation Example 2 was diluted with water to a concentration of 100 ppm. Cucumber seedlings previously inoculated with cotton aphid nymphs were immersed in the chemical solution, air-dried, and placed in a thermostatic chamber at 25 ° C. Three days later, the number of dead insects was investigated, and the death rate was calculated. The obtained death rate was evaluated according to the criteria in Table 6 and the results are shown in Table 9. In addition, the test was performed by 2 continuous systems.
[0055]
[Table 9]
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05649995A JP3775816B2 (en) | 1995-02-21 | 1995-02-21 | Carbohydroxymoylazole derivatives or salts thereof and insecticides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05649995A JP3775816B2 (en) | 1995-02-21 | 1995-02-21 | Carbohydroxymoylazole derivatives or salts thereof and insecticides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08225536A JPH08225536A (en) | 1996-09-03 |
| JP3775816B2 true JP3775816B2 (en) | 2006-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP05649995A Expired - Fee Related JP3775816B2 (en) | 1995-02-21 | 1995-02-21 | Carbohydroxymoylazole derivatives or salts thereof and insecticides |
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