JP3697075B2 - Trifluoromethanesulfonylanilide derivative, process for producing the same, and herbicide containing the same as an active ingredient - Google Patents

Description

で表わされるトリフルオロメタンスルホニルアニリド誘導体及びその塩を提供するものである。
【０００７】
前記式（Ｉ）で表わされる化合物は、文献未載の新規化合物であり、例えば反応式
【化６】

（式中のＸはハロゲン原子である）
に従い、２‐置換アニリン誘導体（ＩＩ）にトリフルオロメタンスルホニルハライド又はトリフルオロメタンスルホン酸無水物を反応させることによって得られる。
【０００８】
【発明の実施の形態】
本発明のトリフルオロメタンスルホニルアニリド誘導体は、前記式（Ｉ）で表わされる構造を有している。
【０００９】
次に、式（Ｉ）で表わされる化合物の塩は、この化合物のスルホニルアミド基部分と塩基との塩であり、このような塩としては、ナトリウム塩、カリウム塩などを挙げることができる。
【００１０】
この式（Ｉ）で表わされる化合物及びその塩は、例えば前記の化６で示される反応式に従い、式（ＩＩ）で表わされる２‐置換アニリン誘導体にトリフルオロメタンスルホニルハライド又はトリフルオロメタンスルホン酸無水物を反応させ、所望に応じその生成物を常法に従い塩に変えることによって製造することができる。
【００１１】
この反応は、通常、不活性溶媒、例えばペンタン、ヘキサン、シクロヘキサンなどの脂肪族又は脂環式炭化水素類、トルエン、キシレンなどの芳香族炭化水素類、ジクロロメタン、クロロホルムなどのハロゲン化炭化水素類、メタノール、エタノールなどのアルコール類、ジエチルエーテル、テトラヒドロフラン、１，４‐ジオキサンなどのエーテル類、アセトン、メチルエチルケトンなどのケトン類、酢酸メチル、酢酸エチルなどのエステル類、アセトニトリル、プロピオニトリルなどのニトリル類、さらにはＮ，Ｎ‐ジメチルホルムアミド、ジメチルスルホキシド、スルホランなどの非プロトン性極性溶媒及びこれらの混合溶媒中、塩基の存在下で行われる。
この際用いられる塩基は、この種の反応に慣用されているもの、例えば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化カルシウムなどのアルカリ土類金属水酸化物、さらにはトリメチルアミン、トリエチルアミン、Ｎ，Ｎ‐ジメチルアニリン、ピリジンなどの有機塩基であり、中でもトリエチルアミンが好ましい。
反応温度としては−７０〜２５０℃、好ましくは−７０〜４０℃の範囲で選ばれる。反応時間は原料化合物の種類や反応温度などに左右されるが、５分〜７日間程度である。
【００１２】
この原料として用いられる式（ＩＩ）で表わされる化合物は、例えば、「ジャーナル・オブ・ケミカル・リサーチズ（Ｊ．Ｃｈｅｍ．Ｒｅｓｅａｒｃｈｅｓ）」，１９７７年，第１８６ページ又は「ヘテロサイクルズ（Ｈｅｔｅｒｏｃｙｃｌｅｓ）」，第３８巻，第１号，第１２５ページに記載されている製造方法に準じた方法により、以下に示す反応順序に従って、対応する２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（２‐ニトロフェニル）アセトニトリル（ＩＩＩ）から容易に製造することができる。
【００１３】
【化７】

【００１４】
すなわち、式（ＩＩ）の化合物は、例えば２‐ニトロフェニルアセトニトリル誘導体に２‐ハロゲノ又はアルキルスルホニル‐４，６‐ジメトキシピリミジンを塩基の存在下反応させるか、あるいは２‐ハロゲノニトロベンゼン誘導体に２‐（４，６‐ジメトキシピリミジン‐２‐イル）アセトニトリルを塩基の存在下反応させることにより得られる２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（２‐ニトロフェニル）アセトニトリル（ＩＩＩ）を、酸化的脱シアノ化して、式（ＩＶ）の化合物を生成させ、次いでこの化合物のニトロ基をアミノ基に還元して式（Ｖ）の化合物を形成させ、さらにこの化合物のカルボニル基をヒドロキシメチル基に還元することによって製造することができる。
【００１５】
この式（ＩＩＩ）の化合物を式（ＩＶ）の化合物に変える酸化的脱シアノ化は、先ず酸化剤により酸化したのち、塩基で処理することにより行われる。
この反応は通常、不活性溶媒、例えばペンタン、ヘキサン、シクロヘキサンなどの脂肪族又は脂環式炭化水素類、トルエン、キシレンなどの芳香族炭化水素類、ジクロロメタン、クロロホルムなどのハロゲン化炭化水素類、ジエチルエーテル、テトラヒドロフラン、１，４‐ジオキサンなどのエーテル類、アセトン、メチルエチルケトンなどのケトン類、酢酸メチル、酢酸エチルなどのエステル類、アセトニトリル、プロピオニトリルなどのニトリル類、Ｎ，Ｎ‐ジメチルホルムアミド、ジメチルスルホキシド、スルホランなどの非プロトン性極性溶媒、水及びこれらを組み合わせた混合溶媒中で行われる。
第一段階で用いる酸化剤としては、例えばｍ‐クロロ過安息香酸などの有機過酸類がある。
また、第二段階で用いる塩基としては、この種の反応に慣用されるもの、例えば水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化カルシウムなどのアルカリ土類金属水酸化物、さらにはトリメチルアミン、トリエチルアミン、Ｎ，Ｎ‐ジメチルアニリン、ピリジンなどの有機塩基が用いられる。
反応温度は−７０〜２５０℃、好ましくは−２０〜４０℃の範囲から選ばれる。反応時間は使用される酸化剤、塩基の種類及び反応温度などに左右されるが、通常５分〜７日間である。
【００１６】
次に、このようにして得られた前記式（ＩＶ）で表わされるカルボニル誘導体のニトロ基をアミノ基に還元して式（Ｖ）のアニリン誘導体とする反応は、触媒の存在下に、還元剤により行うことができる。
この反応は、通常、不活性溶媒、例えばメタノール、エタノールなどのアルコール類や、ジエチルエーテル、テトラヒドロフラン、１，４‐ジオキサンなどのエーテル類や、酢酸メチル、酢酸エチルなどのエステル類や、アセトニトリル、プロピオニトリルなどのニトリル類や、Ｎ，Ｎ‐ジメチルホルムアミド、ジメチルスルホキシド、スルホランなどの非プロトン性極性溶媒、水及びこれらの混合溶媒中で行われる。
また、還元剤としては、例えば鉄、亜鉛、スズなどの金属類が、触媒としては、例えば酢酸などの有機酸類が用いられる。
この反応は、２０℃ないし溶媒の沸点の範囲の温度で行われる。反応時間は、還元剤や触媒の種類、反応温度などに左右されるが、通常５分〜７日間である。
【００１７】
最後に、このようにして得られた式（Ｖ）で表わされるアニリン誘導体のカルボニル基をヒドロキシメチル基へ変換して式（ＩＩ）の化合物を製造する還元反応は、例えば水素化ホウ素ナトリウムのようなアルカリ金属水素錯化合物を還元剤として用いて行われる。
この反応は、通常不活性溶媒、例えばペンタン、ヘキサン、シクロヘキサンなどの脂肪族又は脂環式炭化水素類、トルエン、キシレンなどの芳香族炭化水素類、ジクロロメタン、クロロホルムなどのハロゲン化炭化水素類、メタノール、エタノールなどのアルコール類、ジエチルエーテル、テトラヒドロフラン、１，４‐ジオキサンなどのエーテル類、酢酸メチル、酢酸エチルなどのエステル類、アセトニトリル、プロピオニトリルなどのニトリル類、さらにはＮ，Ｎ‐ジメチルホルムアミド、ジメチルスルホキシド、スルホランなどの非プロトン性極性溶媒、水及びこれらの混合溶媒を用いることができる。
この反応は、−７０℃ないし溶媒の沸点の範囲、好ましくは−２０〜４０℃の範囲の温度で行うのがよく、また、反応時間は、還元剤の種類や反応温度などに左右されるが、通常５分〜７日間である。
【００１８】
次に、前記式（Ｉ）で表わされる化合物を有効成分とする本発明の除草剤は、該化合物それ自体のみを用いてもよいが、粉剤、水和剤、乳剤、微粒剤、顆粒など、一般の除草剤に慣用されている剤型に製剤することができる。
この際に用いられる賦形剤、添加剤としては、通常の除草剤の製剤に慣用されているものの中から、使用目的に応じ任意に選ぶことができる。
すなわち、製剤化に際して用いられる担体としては、例えばタルク、ベントナイト、クレー、カオリン、けいそう土、ホワイトカーボン、バーミキュライト、炭酸カルシウム、消石灰、けい砂、硫安、尿素などの固体担体や、イソプロピルアルコール、キシレン、シクロヘキサン、メチルナフタレンなどの液体担体などが挙げられる。
【００１９】
また、界面活性剤又は分散剤としては、例えば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、アルキル硫酸エステル塩、アルキルアリールスルホン酸塩ホルマリン縮合物、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などが挙げられる。
補助剤としては、例えばカルボキシメチルセルロース、ポリエチレングリコール、アラビアゴムなどが挙げられる。
【００２０】
この除草剤の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。
本発明の除草剤は茎葉散布、土壌施用又は水面施用などの形で使用される。
本発明の除草剤における有効成分の配合割合については使用目的に応じて適宜選ばれるが、粉剤又は粒剤とする場合は０．０１〜１０重量％、好ましくは０．０５〜５重量％の範囲で選ぶのがよい。また、乳剤及び水和剤とする場合は１〜５０重量％、好ましくは５〜３０重量％の範囲で選ぶのがよい。
【００２１】
本発明の除草剤の施用量は使用される化合物の種類、対象雑草、発生傾向、環境条件、使用する剤型等によって変わるが、粉剤又は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０．１ｇ〜５ｋｇ，好ましくは１ｇ〜１ｋｇの範囲で選ぶのがよい。また、乳剤又は水和剤のように液状で使用する場合は、０．１〜５０，０００ｐｐｍ、好ましくは１０〜１０，０００ｐｐｍの範囲で選ぶのがよい。
また、本発明の除草剤は、必要に応じて殺虫剤、殺菌剤、他の除草剤、植物生長調節剤、肥料などと併用してもよい。
【００２２】
【実施例】
次に、実施例、製剤例、試験例により本発明をさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００２３】
参考例１；２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（３‐メトキシメチル‐２‐ニトロフェニル）アセトニトリルの製造
６０％水素化ナトリウム１１．２ｇ（０．２８モル）をＮ，Ｎ‐ジメチルホルムアミド１００ｍｌに懸濁させ氷水浴で１０℃以下に冷却し、撹拌しながら２‐（４，６‐ジメトキシピリミジン‐２‐イル）アセトニトリル２５ｇ（０．１４モル）をＮ，Ｎ‐ジメチルホルムアミド１００ｍｌに溶解させた溶液を滴下した。滴下終了後、室温下で水素の発生がなくなるまで撹拌した。再び氷水浴中で１０℃以下に冷却し、撹拌しながら、２‐クロロ‐６‐メトキシメチルニトロベンゼン２８ｇ（０．１４モル）をＮ，Ｎ‐ジメチルホルムアミド１００ｍｌに溶解させたものを滴下した。室温にて１２時間撹拌後、反応液を氷水に注加し、１０重量％塩酸で酸性にした後、酢酸エチルで抽出した。有機層を飽和食塩水、水で洗浄した後、乾燥、減圧濃縮し、析出した粗結晶をエタノール、イソプロピルエーテル混合溶媒で洗浄することにより、２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（３‐メトキシメチル‐２‐ニトロフェニル）アセトニトリル３１ｇ（収率６４％）を赤褐色粉末（融点１１２〜１１３℃）として得た。
【００２４】
参考例２；２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（３‐メトキシメチル‐２‐ニトロフェニル）アセトニトリルの製造
６０％水素化ナトリウム１１．２ｇ（０．２８モル）をＮ，Ｎ‐ジメチルホルムアミド１００ｍｌに懸濁させ氷水浴で１０℃以下に冷却し、撹拌しながら３‐メトキシメチル‐２‐ニトロフェニルアセトニトリル２９ｇ（０．１４モル）をＮ，Ｎ‐ジメチルホルムアミド１００ｍｌに溶解させた溶液を滴下した。滴下終了後、室温下で水素の発生がなくなるまで撹拌した。再び氷水浴中で１０℃以下に冷却し、撹拌しながら４，６‐ジメトキシ‐２‐メチルスルホニルピリミジン３０ｇ（０．１４モル）を加え、室温下で１２時間撹拌後、反応液を氷水に注加し、１０重量％塩酸で酸性にした後、析出した粗結晶をろ別し、水及びエタノール−イソプロピルエーテル混合溶媒で洗浄することにより、２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（３‐メトキシメチル‐２‐ニトロフェニル）アセトニトリル４２ｇ（収率８７％）を、赤褐色粉末（融点１１２〜１１３℃）として得た。
【００２５】
参考例３；（４，６‐ジメトキシピリミジン‐２‐イル） ３‐メトキシメチル‐２‐ニトロフェニルケトンの製造
参考例１又は２で得た２‐（４，６‐ジメトキシピリミジン‐２‐イル）‐２‐（３‐メトキシメチル‐２‐ニトロフェニル）アセトニトリル３．５ｇ（１０ミリモル）と５０重量％ｍ‐クロロ過安息香酸６．０ｇ（１７ミリモル）とをクロロホルム３０ｍｌに溶解させ、室温下で１２時間撹拌した。次いで１０重量％水酸化ナトリウム水溶液１５ｍｌを加え、室温下で１時間撹拌した後、クロロホルム５０ｍｌを加え、有機層を５重量％希塩酸、飽和食塩水で洗浄後、乾燥した。溶媒を減圧留去し、結晶残渣をエタノール−ジイソプロピルエーテルで洗浄することにより、（４，６‐ジメトキシピリミジン‐２‐イル） ３‐メトキシメチル‐２‐ニトロフェニルケトン２．８ｇ（収率８４％）を、白色粉末（融点１１１〜１１３℃）として得た。
【００２６】
参考例４；２‐［（４，６‐ジメトキシピリミジン‐２‐イル）カルボニル］‐６‐メトキシメチルアニリンの製造
参考例３で得た（４，６‐ジメトキシピリミジン‐２‐イル） ３‐メトキシメチル‐２‐ニトロフェニルケトン３．３ｇ（１０ミリモル）と、鉄粉３ｇ（５４ミリモル）と、水２０ｍｌと、酢酸エチル１５０ｍｌと、酢酸１ｍｌとの混合物を５０℃で５時間反応させた。反応液中の不溶物をろ過助剤を用いてろ別し、有機層を飽和食塩水で洗浄後、乾燥した。溶媒を減圧留去し、結晶残渣をジイソプロピルエーテルで洗浄することにより、２‐［（４，６‐ジメトキシピリミジン‐２‐イル）カルボニル］‐６‐メトキシメチルアニリン２．４ｇ（収率８０％）を、黄色結晶（融点１００〜１０１℃）として得た。
【００２７】
参考例５；２‐［（４，６‐ジメトキシピリミジン‐２‐イル）ヒドロキシメチル］‐６‐メトキシメチルアニリンの製造
参考例４で得た２‐［（４，６‐ジメトキシピリミジン‐２‐イル）カルボニル］‐６‐メトキシメチルアニリン３．１ｇ（１０ミリモル）をテトラヒドロフランと水との等量混合溶媒５０ｍｌに溶解させ、室温で撹拌しながら水素化ホウ素ナトリウム０．６ｇ（１６ミリモル）を加え、さらに２時間室温で撹拌を続けた。氷水５０ｍｌを加え、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄、乾燥した。溶媒を減圧留去し、結晶残渣をジイソプロピルエーテルで洗浄することにより、２‐［（４，６‐ジメトキシピリミジン‐２‐イル）ヒドロキシメチル］‐６‐メトキシメチルアニリン２．８ｇ（収率９２％）を、白色粉末（融点４０〜４２℃）として得た。
【００２８】
実施例
参考例５で得た２‐［（４，６‐ジメトキシピリミジン‐２‐イル）ヒドロキシメチル］‐６‐メトキシメチルアニリン４．０ｇ（１３．１ミリモル）と、トリエチルアミン１．５ｇ（１４．８ミリモル）とをジクロロメタン３０ｍｌに溶解させ、−５０℃にて撹拌しながらトリフルオロメタンスルホン酸無水物４．０ｇ（１４．２ミリモル）を滴下した。−５０〜０℃にて３時間撹拌を続けた後、反応液を氷水中に注加し、ジクロロメタンで抽出した。有機層を５重量％希塩酸、飽和食塩水で洗浄、乾燥の後、溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィー［溶出溶媒、酢酸エチル：ヘキサン＝１：３（容量比）］で分離精製することにより、２‐［（４，６‐ジメトキシピリミジン‐２‐イル）ヒドロキシメチル］‐６‐メトキシメチルトリフルオロメタンスルホニルアニリド３．８ｇ（収率６６％）を、無色粒状結晶（融点９１〜９２℃）として得た。
【００２９】
製剤例１ 水和剤
実施例で得た化合物１０重量部にポリオキシエチレンオクチルフェニルエーテル０．５重量部、β‐ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩０．５重量部、けいそう土２０重量部及びクレー６９重量部を混合粉砕して水和剤を調製した。
【００３０】
製剤例２ 水和剤
実施例で得た化合物１０重量部にポリオキシエチレンオクチルフェニルエーテル０．５重量部、β‐ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩０．５重量部、けいそう土２０重量部、ホワイトカーボン５重量部及びクレー６４重量部を混合粉砕して水和剤を調製した。
【００３１】
製剤例３ 水和剤
実施例で得た化合物１０重量部にポリオキシエチレンオクチルフェニルエーテル０．５重量部、β‐ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩０．５重量部、けいそう土２０重量部、ホワイトカーボン５重量部及び炭酸カルシウム６４重量部を混合粉砕して水和剤を調製した。
【００３２】
製剤例４ 乳剤
実施例で得た化合物３０重量部にキシレンとイソホロンの等量混合物６０重量部及びポリオキシエチレンソルビタンアルキレートとポリオキシエチレンアルキルアリールポリマーとアルキルアリールスルホネートの等量混合物１０重量部を混合して乳剤を調製した。
【００３３】
製剤例５ 粒剤
実施例で得た化合物１０重量部、タルクとベントナイトを１：３の重量比で混合した増量剤８０重量部、ホワイトカーボン５重量部、及びポリオキシエチレンソルビタンアルキレートとポリオキシエチレンアルキルアリールポリマーとアルキルアリールスルホネートの等量混合物５重量部に水１０重量部を加え、よく練ってペースト状としたものを直径０．７ｍｍのふるい穴から押し出して乾燥したのち、０．５〜１ｍｍの長さに切断して粒剤を調製した。
【００３４】
試験例１ 水田湛水処理による除草効果試験
１００ｃｍ²のプラスチックポットに水田土壌を充填し、代掻きしたのち、タイヌビエ（Ｅｃ）、コナギ（Ｍｏ）及びホタルイ（Ｓｃ）の各種子を０．５ｃｍの深さに播種し、水深３ｃｍに湛水した。翌日、製剤例１に準じて調製した水和剤の所定有効成分量（ｇ／１０アール）を水で希釈し、水面に滴下処理した。次いで温室内で育成し、処理後２８日目に以下の基準に従って除草効果を評価した。その結果を表１に示す。
【００３５】
なお、比較のために式
【化８】

で示される２‐［（４，６‐ジメトキシピリミジン‐２‐イル）ヒドロキシメチル］‐Ｎ‐トリフルオロメタンスルホニルアニリド（ＷＯ９６／４１７９９号の化合物番号１０−１１１のもの）を用い、同様の試験を行い、その結果を表１に併記した。
【００３６】
除草効果（生育抑制程度）及び薬害の基準
５：９０％以上の除草効果、薬害
４：７０％以上９０％未満の除草効果、薬害
３：５０％以上７０％未満の除草効果、薬害
２：３０％以上５０％未満の除草効果、薬害
１：１０％以上３０％未満の除草効果、薬害
０：１０％未満の除草効果、薬害
【００３７】
【表１】

【００３８】
試験例２ 水田湛水処理による除草効果試験
２００ｃｍ²のプラスチックポットに水田土壌を充填し、代掻きしたのち、タイヌビエ（Ｅｃ）、ホタルイ（Ｓｃ）の各種子を０．５ｃｍの深さに播種し、ウリカワ（Ｓａ）、ミズガヤツリ（Ｃｙ）の地下茎を埋め込み、さらに２葉期の水稲（Ｏｒ）を移植深度２ｃｍで２本移植し、水深３ｃｍに湛水した。翌日、製剤例１に準じて調製した水和剤の所定有効成分量（ｇ／１０アール）を水で希釈し、水面に滴下処理した。次いで温室内で育成し、処理後２８日目に試験例１と同じ基準により除草効果及び薬害程度を評価した。その結果を表２に示す。
【００３９】
【表２】

【００４０】
試験例３ 水田湛水処理による除草効果試験
２００ｃｍ²のプラスチックポットに水田土壌を充填し、代掻きしたのち、タイヌビエ（Ｅｃ）の種子を０．５ｃｍの深さに播種し、タイヌビエが１葉期、２葉期及び３葉期になった時点で、製剤例１に準じて調製した水和剤の所定有効成分量（ｇ／１０アール）を水で希釈し、水面に滴下処理した。次いで、温室内で育成し、処理後２８日目に試験例１と同様の基準により除草効果を評価した。その結果を表３に示す。
【００４１】
【表３】

【００４２】
試験例４ 催奇形性試験
「毒性に関する試験成績を作成するに当たっての指針」（農林水産省）に記載された方法に準じ、実施例で得た化合物及び試験例１で用いたのと同じ比較化合物を秤量後、０．５％カルボキシメチルセルロース水溶液に懸濁し、それぞれＳＤ系妊娠ラット１０頭に対して、妊娠６日目から１５日目まで連続的に強制経口投与した。また、対照群には０．５％カルボキシメチルセルロース水溶液のみを投与した。各化合物の投与量はＳＤ系非妊娠ラット３頭を用いて、１０日間連続投与予備試験を行い、投与可能な最大耐量とした。妊娠２０日目に母体を帝王切開し、子宮内検査（生存胎児数、吸収胚数、死亡胎児数、性比、胎児重量）及び胎児外表検査を行った。また、胎児を７０％エタノールで固定し、軟部組織を水酸化カリウムで融解後、骨格をアリザリンレッドＳで染色し、骨格検査を行った。その結果を表４に示す。これらの検査において、全く異常が認められなかった場合を合格、少しでも異常が認められた場合は不合格とした。
【００４３】
【表４】

【００４４】
【発明の効果】
本発明化合物は低薬量で適用草種及び適用期幅の広い除草活性を有し、特にイネ科の雑草に対し優れた防除効果を有するとともに、催奇形性がないなど哺乳動物に対する安全性が高い除草剤として有用な新規物質である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel trifluoromethanesulfonylanilide derivative or a salt thereof, a production method thereof, and a herbicide containing the same as an active ingredient.
[0002]
[Prior art]
To date, it has been known that sulfonylanilide derivatives having a pyrimidinyl-containing group in the 2-position, such as 2-pyrimidinylmethyl-substituted or N-trifluoromethanesulfonyl derivatives of 2-pyrimidinyloxy or thiooxy-substituted anilines have herbicidal activity No. 7-501053 and WO93 / 09099).
It is also known that an N-trifluoromethanesulfonyl derivative of aniline having a pyrimidinylhydroxymethyl group at the 2-position of the phenyl group has a plant growth regulating action (WO96 / 41799).
However, it is not known that a sulfonylanilide derivative having a pyrimidinyl-containing group at the 2-position of the phenyl group and further having a methoxymethyl group at the 6-position has a herbicidal action.
[0003]
By the way, in recent years, in paddy rice cultivation, there is a problem of controlling harmful plant species that are generated in paddy fields and difficult to effectively control with conventional herbicides, so-called difficult-to-control weeds. These weeds are heterogeneous and must therefore be controlled over a long period of time. In addition, grass weeds other than rice belonging to the same family as rice, such as Tainubie, are also observed over a long period of time, and their growth is vigorous, so their control is also an important issue. At present, no herbicide has been developed which has high activity against these weeds and can be controlled at the same time. Therefore, it is hoped to develop drugs that have high herbicidal activity on grasses, including difficult-to-control weeds, can control a wide range of weeds in paddy fields for a long period of time, and are highly safe for mammals. It is rare.
[0004]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a novel compound that is effective in removing a wide range of weeds including difficult-to-control weeds that occur in paddy fields and that is useful as a safe herbicide for mammals. It was made for the purpose.
[0005]
[Means for Solving the Problems]
As a result of extensive research to develop a novel compound having herbicidal activity, the present inventors have found that an aniline having a pyrimidinylhydroxymethyl group at the 2-position of the phenyl group and a methoxymethyl group at the 6-position. Based on this finding, N-trifluoromethanesulfonyl derivatives have a low dose and a wide range of herbicidal activity, and are particularly effective against grass weeds, as well as being highly safe for mammals. The present invention has been made.
[0006]
That is, the present invention is a compound having a herbicidal activity.

The trifluoromethanesulfonyl anilide derivative | guide_body represented by these, and its salt are provided.
[0007]
The compound represented by the formula (I) is a novel compound not described in any literature, for example, the reaction formula:

(X in the formula is a halogen atom)
The 2-substituted aniline derivative (II) is reacted with trifluoromethanesulfonyl halide or trifluoromethanesulfonic anhydride.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The trifluoromethanesulfonyl anilide derivative of the present invention has a structure represented by the formula (I) .
[0009]
Next, the salts of the compounds of formula (I) is a sulfonyl amide group moiety and salts with bases of the compounds, Examples of such salts include sodium salts, Ru and the like can be illustrated potassium salt.
[0010]
The compound represented by the formula (I) and a salt thereof, for example, according to the reaction formula shown in the chemical formula 6 above, are converted to a 2-substituted aniline derivative represented by the formula (II) by trifluoromethanesulfonyl halide or trifluoromethanesulfonic anhydride. And the product can be converted into a salt according to a conventional method if desired.
[0011]
This reaction is usually carried out in an inert solvent, for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, Alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, and nitriles such as acetonitrile and propionitrile Further, it is carried out in the presence of a base in an aprotic polar solvent such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and a mixed solvent thereof.
Bases used in this case are those conventionally used for this type of reaction, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, and Organic bases such as trimethylamine, triethylamine, N, N-dimethylaniline, pyridine, etc. Among them, triethylamine is preferable.
The reaction temperature is selected in the range of −70 to 250 ° C., preferably −70 to 40 ° C. The reaction time depends on the type of raw material compound and the reaction temperature, but is about 5 minutes to 7 days.
[0012]
The compound represented by the formula (II) used as the raw material is, for example, “Journal of Chemical Research” (1977), page 186 or “Heterocycles”. , 38, No. 1, page 125, according to the reaction sequence shown below, the corresponding 2- (4,6-dimethoxypyrimidin-2-yl) -2 It can be easily produced from-(2-nitrophenyl) acetonitrile (III).
[0013]
[Chemical 7]

[0014]
That is, the compound of the formula (II) can be prepared by reacting 2-halophenylacetonitrile derivative with 2-halogeno or alkylsulfonyl-4,6-dimethoxypyrimidine in the presence of a base, or 2-halogenonitrobenzene derivative with 2- ( 2- (4,6-Dimethoxypyrimidin-2-yl) -2- (2-nitrophenyl) acetonitrile (III) obtained by reacting 4,6-dimethoxypyrimidin-2-yl) acetonitrile in the presence of a base Is oxidatively decyanogenated to form a compound of formula (IV), then the nitro group of the compound is reduced to an amino group to form a compound of formula (V), and the carbonyl group of the compound is further converted to a hydroxy group. It can be produced by reduction to a methyl group.
[0015]
This oxidative decyanoation which converts the compound of formula (III) into the compound of formula (IV) is performed by first oxidizing with an oxidizing agent and then treating with a base.
This reaction is usually carried out in an inert solvent such as aliphatic or alicyclic hydrocarbons such as pentane, hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, diethyl Ethers such as ether, tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide and dimethyl The reaction is carried out in an aprotic polar solvent such as sulfoxide and sulfolane, water, and a mixed solvent obtained by combining these.
Examples of the oxidizing agent used in the first stage include organic peracids such as m-chloroperbenzoic acid.
As the base used in the second stage, those commonly used in this type of reaction, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, Furthermore, organic bases such as trimethylamine, triethylamine, N, N-dimethylaniline and pyridine are used.
The reaction temperature is selected from the range of -70 to 250 ° C, preferably -20 to 40 ° C. The reaction time depends on the oxidizing agent used, the type of base and the reaction temperature, but is usually 5 minutes to 7 days.
[0016]
Next, the reaction obtained by reducing the nitro group of the carbonyl derivative represented by the above formula (IV) to an amino group to obtain the aniline derivative of the formula (V) is carried out in the presence of a catalyst in the presence of a reducing agent. Can be performed.
This reaction is usually carried out in an inert solvent such as alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, esters such as methyl acetate and ethyl acetate, acetonitrile, It is carried out in nitriles such as pionitrile, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, water, and mixed solvents thereof.
Further, as the reducing agent, for example, metals such as iron, zinc and tin are used, and as the catalyst, for example, organic acids such as acetic acid are used.
This reaction is carried out at a temperature ranging from 20 ° C. to the boiling point of the solvent. The reaction time depends on the type of reducing agent and catalyst, the reaction temperature, etc., but is usually 5 minutes to 7 days.
[0017]
Finally, the reduction reaction for producing the compound of the formula (II) by converting the carbonyl group of the aniline derivative represented by the formula (V) thus obtained into a hydroxymethyl group is, for example, sodium borohydride. An alkali metal hydrogen complex compound is used as a reducing agent.
This reaction is usually performed in an inert solvent, for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, and methanol. , Alcohols such as ethanol, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, and N, N-dimethylformamide , Aprotic polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof can be used.
This reaction is preferably carried out at a temperature in the range of -70 ° C to the boiling point of the solvent, preferably in the range of -20 to 40 ° C, and the reaction time depends on the kind of the reducing agent and the reaction temperature. Usually, 5 minutes to 7 days.
[0018]
Next, the herbicide of the present invention containing the compound represented by the formula (I) as an active ingredient may be used alone, but powders, wettable powders, emulsions, fine granules, granules, etc. It can be formulated into a dosage form commonly used for general herbicides.
The excipients and additives used at this time can be arbitrarily selected from those commonly used in normal herbicidal formulations according to the purpose of use.
That is, as a carrier used in the formulation, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate, urea, isopropyl alcohol, xylene , Liquid carriers such as cyclohexane and methylnaphthalene.
[0019]
Examples of the surfactant or dispersant include alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alkyl sulfate ester salt, alkylaryl sulfonate formalin condensate, lignin sulfonate, polyoxyethylene glycol ether , Polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate and the like.
Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like.
[0020]
When using this herbicide, it is sprayed after diluting to an appropriate concentration or applied directly.
The herbicide of the present invention is used in the form of foliage application, soil application or water surface application.
The mixing ratio of the active ingredient in the herbicide of the present invention is appropriately selected according to the purpose of use, but in the case of powder or granule, it is 0.01 to 10% by weight, preferably 0.05 to 5% by weight. It is good to choose in. In the case of emulsions and wettable powders, the content is selected in the range of 1 to 50% by weight, preferably 5 to 30% by weight.
[0021]
The application rate of the herbicide of the present invention varies depending on the type of compound used, the target weed, the tendency to occur, the environmental conditions, the dosage form used, etc., but when used as it is as a powder or granule, as an active ingredient It is better to select in the range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares. Further, when used in a liquid form such as an emulsion or a wettable powder, it is selected within the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.
Moreover, you may use the herbicide of this invention together with an insecticide, a fungicide, another herbicide, a plant growth regulator, a fertilizer, etc. as needed.
[0022]
【Example】
Next, the present invention will be described in more detail with reference to Examples, Formulation Examples, and Test Examples, but the present invention is not limited to these examples.
[0023]
Reference Example 1; Preparation of 2- (4,6-dimethoxypyrimidin-2-yl) -2- (3-methoxymethyl-2-nitrophenyl) acetonitrile 11.2 g (0.28 mol) of 60% sodium hydride Suspended in 100 ml of N, N-dimethylformamide, cooled to 10 ° C. or lower with an ice water bath, and stirred with 25 g (0.14 mol) of 2- (4,6-dimethoxypyrimidin-2-yl) acetonitrile. -A solution dissolved in 100 ml of dimethylformamide was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature until no more hydrogen was generated. The mixture was again cooled to 10 ° C. or lower in an ice-water bath, and a solution prepared by dissolving 28 g (0.14 mol) of 2-chloro-6-methoxymethylnitrobenzene in 100 ml of N, N-dimethylformamide was added dropwise. After stirring at room temperature for 12 hours, the reaction solution was poured into ice water, acidified with 10% by weight hydrochloric acid, and extracted with ethyl acetate. The organic layer is washed with saturated brine and water, dried, concentrated under reduced pressure, and the precipitated crude crystals are washed with a mixed solvent of ethanol and isopropyl ether to give 2- (4,6-dimethoxypyrimidin-2-yl). This gave 31 g (64% yield) of 2--2- (3-methoxymethyl-2-nitrophenyl) acetonitrile as a reddish brown powder (melting point 112-113 ° C.).
[0024]
Reference Example 2; Preparation of 2- (4,6-dimethoxypyrimidin-2-yl) -2- (3-methoxymethyl-2-nitrophenyl) acetonitrile 11.2 g (0.28 mol) of 60% sodium hydride Suspended in 100 ml of N, N-dimethylformamide, cooled to below 10 ° C. in an ice water bath, and stirred with 29 g (0.14 mol) of 3-methoxymethyl-2-nitrophenylacetonitrile into 100 ml of N, N-dimethylformamide. The dissolved solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature until no more hydrogen was generated. Cool again to 10 ° C or lower in an ice-water bath, add 30 g (0.14 mol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine with stirring, stir at room temperature for 12 hours, and then pour the reaction solution into ice water. After adding and acidifying with 10% by weight hydrochloric acid, the precipitated crude crystals are filtered off and washed with water and ethanol-isopropyl ether mixed solvent to give 2- (4,6-dimethoxypyrimidin-2-yl). 42 g of 2--2- (3-methoxymethyl-2-nitrophenyl) acetonitrile (87% yield) was obtained as a reddish brown powder (melting point 112-113 ° C.).
[0025]
Reference Example 3; (4,6-dimethoxypyrimidin-2-yl) Preparation of 3-methoxymethyl-2-nitrophenyl ketone 2- (4,6-dimethoxypyrimidin-2-yl) obtained in Reference Example 1 or 2 2- (3-methoxymethyl-2-nitrophenyl) acetonitrile (3.5 g, 10 mmol) and 50 wt% m-chloroperbenzoic acid (6.0 g, 17 mmol) were dissolved in chloroform (30 ml) at room temperature. Stir for 12 hours. Next, 15 ml of a 10% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 1 hour. Then, 50 ml of chloroform was added, and the organic layer was washed with 5% by weight dilute hydrochloric acid and saturated brine and dried. The solvent was distilled off under reduced pressure, and the crystal residue was washed with ethanol-diisopropyl ether to give 2.8 g of (4,6-dimethoxypyrimidin-2-yl) 3-methoxymethyl-2-nitrophenyl ketone (84% yield). ) Was obtained as a white powder (melting point 111-113 ° C.).
[0026]
Reference Example 4; Preparation of 2-[(4,6-Dimethoxypyrimidin-2-yl) carbonyl] -6-methoxymethylaniline (4,6-Dimethoxypyrimidin-2-yl) 3-methoxy obtained in Reference Example 3 A mixture of 3.3 g (10 mmol) of methyl-2-nitrophenyl ketone, 3 g (54 mmol) of iron powder, 20 ml of water, 150 ml of ethyl acetate and 1 ml of acetic acid was reacted at 50 ° C. for 5 hours. Insoluble matter in the reaction solution was filtered off using a filter aid, and the organic layer was washed with saturated brine and dried. The solvent was distilled off under reduced pressure, and the crystalline residue was washed with diisopropyl ether to give 2.4 g of 2-[(4,6-dimethoxypyrimidin-2-yl) carbonyl] -6-methoxymethylaniline (yield 80%). Were obtained as yellow crystals (melting point 100-101 ° C.).
[0027]
Reference Example 5: Preparation of 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -6-methoxymethylaniline 2-[(4,6-dimethoxypyrimidin-2-yl obtained in Reference Example 4 ) Carbonyl] -6-methoxymethylaniline (3.1 g, 10 mmol) was dissolved in 50 ml of an equal amount of a mixed solvent of tetrahydrofuran and water, and 0.6 g (16 mmol) of sodium borohydride was added while stirring at room temperature. Stirring was continued for another 2 hours at room temperature. 50 ml of ice water was added and extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried. The solvent was distilled off under reduced pressure, and the crystalline residue was washed with diisopropyl ether to give 2.8 g of 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -6-methoxymethylaniline (yield 92% ) Was obtained as a white powder (melting point 40-42 ° C.).
[0028]
Example 4.0 g (13.1 mmol) of 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -6-methoxymethylaniline obtained in Reference Example 5 and 1.5 g (14. 8 mmol) was dissolved in 30 ml of dichloromethane, and 4.0 g (14.2 mmol) of trifluoromethanesulfonic anhydride was added dropwise with stirring at -50 ° C. After stirring at −50 to 0 ° C. for 3 hours, the reaction solution was poured into ice water and extracted with dichloromethane. The organic layer was washed with 5% by weight dilute hydrochloric acid and saturated brine, dried, the solvent was evaporated under reduced pressure, and the residue was separated by silica gel column chromatography [elution solvent, ethyl acetate: hexane = 1: 3 (volume ratio)]. By purification, 3.8 g (yield 66%) of 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -6-methoxymethyltrifluoromethanesulfonylanilide was obtained as colorless granular crystals (melting point 91- 92 ° C.).
[0029]
Formulation Example 1 10 parts by weight of the compound obtained in the wettable powder example 0.5 parts by weight of polyoxyethylene octylphenyl ether, 0.5 parts by weight of β-naphthalenesulfonic acid formalin condensate sodium salt, 20 parts by weight of diatomaceous earth And 69 parts by weight of clay was mixed and ground to prepare a wettable powder.
[0030]
Formulation Example 2 10 parts by weight of the compound obtained in the wettable powder example, 0.5 parts by weight of polyoxyethylene octylphenyl ether, 0.5 parts by weight of β-naphthalenesulfonic acid formalin condensate, 20 parts by weight of diatomaceous earth Then, 5 parts by weight of white carbon and 64 parts by weight of clay were mixed and pulverized to prepare a wettable powder.
[0031]
Formulation Example 3 10 parts by weight of the compound obtained in the wettable powder example, 0.5 parts by weight of polyoxyethylene octylphenyl ether, 0.5 parts by weight of β-naphthalenesulfonic acid formalin condensate sodium salt, 20 parts by weight of diatomaceous earth Then, 5 parts by weight of white carbon and 64 parts by weight of calcium carbonate were mixed and pulverized to prepare a wettable powder.
[0032]
Formulation Example 4 30 parts by weight of the compound obtained in Emulsion Example, 60 parts by weight of an equivalent mixture of xylene and isophorone and 10 parts by weight of an equivalent mixture of polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate An emulsion was prepared by mixing.
[0033]
Formulation Example 5 10 parts by weight of the compound obtained in the granule example, 80 parts by weight of a filler obtained by mixing talc and bentonite in a weight ratio of 1: 3, 5 parts by weight of white carbon, and polyoxyethylene sorbitan alkylate and polyoxy After adding 10 parts by weight of water to 5 parts by weight of an equal mixture of an ethylene alkylaryl polymer and an alkylaryl sulfonate, and thoroughly kneading it into a paste, it was extruded through a sieve hole having a diameter of 0.7 mm, dried, and then 0.5 to Granules were prepared by cutting to a length of 1 mm.
[0034]
Test Example 1 Herbicidal effect test by paddy paddy treatment After filling paddy field soil into a 100cm ² plastic pot and scratching, each child of Tainubie (Ec), Konagi (Mo) and Firefly (Sc) is 0.5cm deep. The seeds were seeded and submerged to a depth of 3 cm. On the next day, a predetermined active ingredient amount (g / 10 are) of the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. Subsequently, it was grown in a greenhouse, and the herbicidal effect was evaluated according to the following criteria on the 28th day after the treatment. The results are shown in Table 1.
[0035]
For comparison, the formula

A similar test was conducted using 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -N-trifluoromethanesulfonylanilide (compound No. 10-111 of WO 96/41799) represented by The results are also shown in Table 1.
[0036]
Herbicidal effect (growth inhibition degree) and phytotoxicity 5: 90% or more herbicidal effect, phytotoxicity 4: 70% to less than 90% herbicidal effect, phytotoxicity 3: 50% to 70% herbicidal effect, phytotoxicity 2:30 % To less than 50% herbicidal effect, phytotoxicity 1: 10% to less than 30% herbicidal effect, phytotoxicity 0: less than 10% herbicidal effect, phytotoxicity
[Table 1]

[0038]
Test Example 2 Herbicidal Effect Test by Paddy Paddy Treatment After filling paddy soil into a 200 cm ² plastic pot and scratching, seeds of Tainubie (Ec) and Firefly (Sc) were seeded to a depth of 0.5 cm, Underground stems of Urikawa (Sa) and Mitsugayatsuri (Cy) were embedded, and two rice plants (Or) at the second leaf stage were transplanted at a transplantation depth of 2 cm and submerged at a depth of 3 cm. On the next day, a predetermined active ingredient amount (g / 10 are) of the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. Subsequently, it was grown in a greenhouse, and the herbicidal effect and the degree of phytotoxicity were evaluated according to the same criteria as in Test Example 1 on the 28th day after treatment. The results are shown in Table 2.
[0039]
[Table 2]

[0040]
Test Example 3 Herbicidal Effect Test by Paddy Paddy Treatment After filling paddy soil in a 200 cm ² plastic pot and plowing, seeds of Tainubie (Ec) were sown to a depth of 0.5 cm. At the time of the second and third leaf stages, a predetermined amount (g / 10 are) of a wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. Then, it was grown in a greenhouse, and the herbicidal effect was evaluated on the 28th day after treatment according to the same criteria as in Test Example 1. The results are shown in Table 3.
[0041]
[Table 3]

[0042]
Test Example 4 According to the method described in the teratogenicity test “Guidelines for preparing test results on toxicity” (Ministry of Agriculture, Forestry and Fisheries), the compounds obtained in Examples and the same comparative compounds used in Test Example 1 Were weighed and suspended in a 0.5% aqueous carboxymethylcellulose solution and each of 10 SD pregnant rats was continuously orally administered by gavage from the 6th to the 15th day of pregnancy. Further, only 0.5% carboxymethylcellulose aqueous solution was administered to the control group. The dose of each compound was a preliminary administration test for 10 days using 3 SD non-pregnant rats, and set the maximum tolerable dose. On the 20th day of gestation, the mother was cesarean sectioned for intrauterine examination (number of live fetuses, number of resorbed embryos, number of dead fetuses, sex ratio, fetal weight) and external fetal examination. In addition, the fetus was fixed with 70% ethanol, the soft tissue was melted with potassium hydroxide, the skeleton was stained with alizarin red S, and the skeleton was examined. The results are shown in Table 4. In these inspections, when no abnormality was found at all, it was accepted, and when any abnormality was found, it was rejected.
[0043]
[Table 4]

[0044]
【The invention's effect】
The compound of the present invention has a herbicidal activity with a low dosage and a wide range of applicable herb species and application periods, and particularly has an excellent control effect against weeds of the grass family and has no teratogenicity and is safe for mammals. It is a novel substance useful as a high herbicide.

Claims (3)

formula

In trifluoromethanesulfonyl anilide derivative or a salt thereof. formula

In 2-substituted aniline derivative is reacted with trifluoromethanesulfonyl halide or trifluoromethanesulfonic acid anhydride represented, then characterized by changing the product to a salt thereof if desired,
formula

In trifluoromethanesulfonyl anilide derivative or a salt thereof represented.

Herbicides and trifluoromethanesulfonyl anilide derivative or a salt thereof as an active ingredient represented in.