JPS6259699B2 - - Google Patents

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Publication number
JPS6259699B2
JPS6259699B2 JP9569979A JP9569979A JPS6259699B2 JP S6259699 B2 JPS6259699 B2 JP S6259699B2 JP 9569979 A JP9569979 A JP 9569979A JP 9569979 A JP9569979 A JP 9569979A JP S6259699 B2 JPS6259699 B2 JP S6259699B2
Authority
JP
Japan
Prior art keywords
compound
methanol
reaction
benzisothiazoline
synthesis
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
Application number
JP9569979A
Other languages
Japanese (ja)
Other versions
JPS5620580A (en
Inventor
Fumio Kai
Michiaki Iwata
Yukio Suzuki
Tetsuo Watanabe
Masao Seki
Taiji Sekizawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Meiji Seika Kaisha Ltd
Original Assignee
Meiji Seika Kaisha Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Meiji Seika Kaisha Ltd filed Critical Meiji Seika Kaisha Ltd
Priority to JP9569979A priority Critical patent/JPS5620580A/en
Priority to PH24348A priority patent/PH17237A/en
Priority to BR8004671A priority patent/BR8004671A/en
Publication of JPS5620580A publication Critical patent/JPS5620580A/en
Publication of JPS6259699B2 publication Critical patent/JPS6259699B2/ja
Granted legal-status Critical Current

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  • Thiazole And Isothizaole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

【発明の詳細な説明】 〔〕 発明の背景 技術分野 本発明は、新規化合物およびその用途に関す
る。さらに具体的には、本発明は、新規なベンゾ
イソチアゾリン誘導体およびそれを有効成分とす
る植物病害防除剤に関する。 現在、絞枯病防除薬剤として広範囲に使用され
ている抗生物質剤は各地で耐性菌の出現が伝えら
れ、あるいは、薬効不足が指摘されるなど、今後
の継続使用に大きな懸念が持たれはじめている。
また一方、砒素剤であるアソジン剤も絞枯病防除
剤として使用されているが、有効成分のなかに重
金属化合物が含まれているため、人畜に対する毒
性ならびに環境汚染の点から使用規制の方向にあ
るなど、既存防除薬剤には多くの難点があり、新
しい型の防除薬剤開発が各界から強く要望されて
いる。 〔〕 発明の概要 要 旨 本発明は、新規なベンゾイソチアゾリン誘導体
を提供することによつて上記の点に解決を与えよ
うとするものである。 従つて、本発明による3−イミノ−1,2−ベ
ンゾイソチアゾリン−1,1−ジオキシド誘導体
は、一般式 (式中、Rはそれぞれエチル基またはイソプロ
ピル基を示す)で示されるものである。 また、本発明による植物病害防除剤は、一般式 (式中、Rはそれぞれエチル基またはイソプロ
ピル基を示す)で示される化合物を有効成分とす
るものである。 効 果 本発明による新規化合物は一般に広範囲の農園
芸作物病害に防除活性を示すが、特にイネ絞枯病
ならびにトマトおよびキウリの立枯病にすぐれた
防除効果を有している。 この新規化合物は重金属を含まない極めて低毒
性の合成化合物であつて、人畜ならびに魚類に対
する毒性は実用上全くなく、また作物に対する薬
害も認められない。従つて、この化合物は、前記
した既存薬剤の欠点を補なうに充分な作用性を有
するものと考えられる。 〔〕 発明の具体的説明 1 化合物 本発明による化合物は、一般式()で示され
る。 (式中、Rはそれぞれエチル基またはイソプロ
ピル基を示す。以下の各々の式についても同じ) 一般式()の化合物のうち、Rがともにエチ
ル基およびイソプロピル基であるもの、すなわち
下記の化合物(1)および(2)が代表的である。 化合物 (1) 2−(2′,6′−ジエチルフエニル)−3−イミ
ノ−1,2−ベンゾイソチアゾリン−1,1
−ジオキシド 化合物 (2) 2−(2′,6′−ジイソプロピルフエニル)−3
−イミノ−1,2−ベンゾイソチアゾリン−
1,1−ジオキシド 2 化合物の製造 本発明化合物は、式()中の希望の置換基な
いし結合の導入ないし形成に合目的的な任意の方
法によつて合成することができる。 適当な合成法の一つは、下記の反応式(A)に示さ
れる反応によるものであつて、2−シアノベンゼ
ンスルホン酸の水酸基に関しての反応性誘導体、
たとえばハロゲニド、特にクロリド()、と
2,6−ジアルキルアニリン()とを反応させ
て、目的物()を得る方法である。中間体
()は、目的意識的にこれをつくつてもあるい
はつくらなくてもよい。 化合物()と()との反応はハロゲン化水
素の発生を併なうものであるから、種々の有機塩
基ないし無機塩基の酸捕捉剤の存在下に行なうの
が好ましい。また、反応は、化合物()〜
()および場合により使用する酸捕捉剤の少な
くともいずれかを所望濃度に溶解ないし分散させ
ることができ、しかもこの反応を実質的に阻害し
ない溶媒ないし分散媒の存在下に行なうことがで
きる。その場合に、過剰量の化合物()を酸捕
捉剤兼溶媒ないし分散媒として利用することがで
きる。 この反応を行なうときの具体的な反応条件その
他は、後記実験例の記載およびJ.Chem.Soc.82
1594(1960)(文献1)またはKhim.Geterotsikl.
Soedin.No.12,1632(1978)(文献2)の方法に準
じて適宜選定すればよい。なお、原料の一つであ
る化合物()は、たとえばBeilstein
Handbuch der organischen ChemieXI,376(文
献3)の記載の方法に準じて合成することができ
る。 適当な合成法の他の一つは、下記の反応式(B)で
示される反応によるものであつて、式()の2
−シアノ−N−(2′,6′−ジアルキルフエニル)−
ベンゼンスルホン酸アミドの閉環反応によつて目
的物()を得る方法である。 この閉環反応は加熱によつて行なうこともでき
るし、また反応の触媒として酸や塩基を使用する
ことによつて実施することもできる。反応Aの場
合と同様に適当な溶媒ないし分散媒を使用するこ
とができる。 具体的な反応条件その他は、後記実験例の記載
および前記文献1の方法に準じて適宜選定すれば
よい。 3 化合物の有用性−植物病害防除剤 本発明による植物病害防除剤は、活性成分が前
記の化合物()であることに留意すべきことを
除けば、農園芸用薬剤、特に殺菌剤、として採用
しうる任意の形態ないし使用態様をとることがで
きる。 具体的には、たとえば、本発明の化合物をその
まままたは、固体粉末、その他の適当な担体を用
いて希釈し、必要に応じて展着剤等の補助剤を加
えて使用するか、あるいは農薬製造に一般的に使
用されている方法によつて各種の液体または固体
担体を混合し、必要ならば湿展剤、展着剤、分散
剤、乳化剤、固着剤などの補助剤を加えて、水和
剤、液剤、乳剤、粉剤、粒剤などの製剤形態にし
て使用することができる。 これらの製剤を製造するに当つて、液体担体と
しては、本発明の化合物に対して溶剤となるもの
または補助剤によつて分散もしくは溶解させ得る
ものが用いられる。たとえば、ケロシン、ジオキ
サン、アセトン、ジメチルスルオキサイド、動植
物油、および界面活性剤など、固体担体としては
粘土、カオリン、タルク、珪藻土、シリカ、炭酸
カルシウム、重炭酸カルシウムなどが用いられ
る。 このようにして得られる製剤中の有効成分の含
量は、広い範囲で変更することができる。たとえ
ば、液剤として使用する場合の液中濃度は
10ppm〜500ppm程度が適当であり、粉剤あるい
は粒剤の場合は本発明の化合物を1%〜20%程度
の範囲で含有することが望ましい。このような濃
度よりも高濃度に製剤化して、使用時に希釈する
ようにすることができることもいうまでもない。
また、事情が許せば、製剤化に際しては両立性の
他の農園芸用薬剤または肥料を混合することもで
きる。 本発明による防除剤は、作物の茎葉に散布して
用いることができるほか、水面や水中あるいは土
壌表面や土壌中に施用して用いることもできる。
その場合に、両立性の農園芸用薬剤ないし肥料を
混用することができる。そのような農園芸用薬剤
には、たとえば、殺菌剤、殺虫剤、除草剤、植物
生長調整剤などがある。 施用量は対象病害の種類および程度、対象作物
の種類、施用態様その他によつて変化するが、土
壌に施す場合の例を挙げれば10アール当り0.1Kg
〜10Kg程度の施用量が一般に適当である。 4 実験例 1 化合物の合成 合成例1 化合物(1)の合成 2−シアノベンゼンスルホン酸クロリド2.01g
と2,6−ジエチルアニリン1.5gとをピリジン
6ml中に加え、撹拌下に1時間加熱環流した。ピ
リジンを減圧留去して得られた残留物に、氷冷下
にメタノールを加え、析出する白色の結晶を過
し、少量のメタノールで洗つて、2−(2′,6′−
ジエチルフエニル)−3−イミノ−1,2−ベン
ゾイソチアゾリン−1,1−ジオキシド1.1g
(収率35%)を得た。 (1) 融点136〜137℃(再結晶溶媒メタノール)。 (2) 赤外吸収スペクトル(Nujol)(cm-1) 3230(NH),1651(C=N),1348,1328,
1270,1249,1216,1170,1122,1074,967,
860,808,776,758,747 (3) NMRスペクトル(DMSO−d6−TMS)δ 8.48〜6.98(7H、多重線と巾広いシグナル、
芳香環プロトン)、2.51(4H、四重線、J=7.5
Hz,−CH2 −CH3×2)、1.08(6H、三重線、
J=7.5Hz,−CH2−CH3 ×2) (4) 元素分析値(%) C17H18N2O2S(314.4) 計算値 C64.95,H5.77,N8.91 分析値 C64.56,H5.63,N8.92 (5) Massスペクトルm/e 314(M+),285(M−C2H5),235,91。 合成例2 化合物(1)の合成 2−シアノベンゼンスルホン酸クロリド2.01g
を2,6−ジエチルアニリン3.0gとを混合し、
撹拌しながら150℃に加熱した。発熱して反応
し、透明な溶液は間もなく固化した。直ちに加熱
をやめて放冷し、メタノールを加え、析出する結
晶を過して少量のメタノールで洗つて、化合物
(1)の中間体である2−シアノ−N−(2′,6′−ジ
エチルフエニル)−ベンゼンスルホンアミド(一
般式()に於てR=エチル基の化合物)1.3g
を得た。 (1) 融点131.5〜133℃(再結晶溶媒メタノー
ル)。 (2) 赤外吸収スペクトル(Nujol)(cm-1) 3230(NH),2260(C≡N),1660,1586,
1406,1334,1264,1197,1158,1132,1068,
1038,971,946,684,606 (3) NMRスペクトル(DMSO−d6−TMS)δ 8.05〜6.78(7H、多重線、芳香環プロト
ン)、2.30(4H、四重線、J=7Hz,−CH2
CH3×2)、0.93(6H、三重線、J=7Hz,−
CH2−CH3 ×2) (4) Massスペクトルm/e 314(M+) (5) 元素分析値(%) C17H18N2O2S(314.4) 計算値 C64.95,H5.77,N8.91 分析値 C64.87,H5.80,N8.88 こゝに得られた中間体200mgをジオキサン3ml
を溶かし、トリエチルアミン0.1mlを加えて、1
時間加熱、還流した。溶媒を留去して得られた油
状物は間もなく結晶化した。この結晶は、先に合
成例1で得られた化合物(1)に一致した。収量200
mg。 合成例3 化合物(1)の合成 2−シアノベンゼンスルホン酸クロリド10gと
2,6−ジエチルアニリン7.5gとをジオキサン
40mlに溶かし、トリエチルアミン6gを加えて、
3時間加熱還流した。溶媒を留去して得られた褐
色の油状物を水で数回洗い、最後にメタノール30
mlを加えて結晶化させ、これを過し、少量のメ
タノールで洗つて、粗製の化合物(1)8gを得た。
こゝに得られた粗製の化合物(1)1gを取り、これ
をメタノール30mlに熱時溶解させ、不溶物を熱時
過して除き、液を氷冷し、析出する白色結晶
を過した。液を濃縮乾固して得られた固体
を、含水メタノールで再結晶して、目的物56mgが
得られた。この物質は、合成例1および2で得ら
れた化合物(1)に一致した。 合成例4 化合物(2)の合成 2−シアノベンゼンスルホン酸クロリド2.1g
と2,6−ジイソプロピルアニリン1.77gとをピ
リジン30mlに溶かし、浴温180℃で2時間加熱還
流した。ピリジンを留去して得られた褐色の油状
物にメタノール15mlを加えて氷冷撹拌し、析出す
る白色の結晶を過し、少量のメタノールで洗つ
て、2−(2′,6′−ジイソプロピルフエニル)−3
−イミノ−1,2−ベンゾイソチアゾリン−1,
1−ジオキシド1.5gを得た。 (1) 融点195〜196℃(再結晶溶媒メタノール)。 (2) 赤外吸収スペクトル(Nujol)(cm-1) 3320(NH),1651(C=N),1467,1368,
1353,1332,1320,1270,1187,1160,1110,
1063,927,862,842,806,773,753,651,
608,588,553。 (3) NMRスペクトル(DMSO−d6−TMS)δ 8.44〜7.08(7H、多重線、芳香環プロト
ン)、2.90(2H、多重線、J=7Hz,−C
(CH32×2)、1.16(6H、二重線、J=7Hz,
−CH(CH3 )、1.02(6H、二重線、J=
7Hz,−CH(CH3 ) (4) Massスペクトルm/e 342(M+),299(M−CH(CH32),235。 (5) 元素分析値(%) C19H22N2O2S(342.46) 計算値 C66.63,H6.48,N8.18 分析値 C66.67,H6.48,N8.18 合成例5 化合物(2)の合成 2,6−ジイソプロピルアニリン6.48gと2−
シアノ−ベンゼンスルホン酸クロリド4.2gとを
混合し、浴温140℃で撹拌しながら加熱した。透
明な溶液は、次第に固化した。内温120℃に達し
内容物が完全に固化したときに加熱をやめ、放冷
し、メタノール30mlを加えてスラリー状とし、析
出している無色の結晶を過し、冷メタノールで
洗つて、2.8gの2−シアノ−N−(2′,6′−ジイ
ソプロピルフエニル)−ベンゼンスルホンアミド
の結晶が得られた。 (1) 融点175〜176.5(分解)(再結晶溶媒メタノ
ール)。 (2) 赤外吸収スペクトル(Nujol)(cm-1) 3240(NH),2260(C≡N),1589,1408,
1339,1260,1185,1161,1131,1104,1066,
928,804,773,756,703,688,625,600,
571。 (3) NMRスペクトル(DMSO−d6−TMS)δ 8.05〜6.82(7H、多重線、芳香環プロト
ン)、2.97(2H、七重線、J=6.5Hz,−C
(CH32×2),0.91(12H、二重線、J=6.5
Hz、−CH(CH3 )×2)。 (4) 元素分析値(%) C19H22N2O2S(342.46) 計算値 C66.63,H6.48,N8.18 分析値 C66.56,H6.52,N8.13 (5) Massスペクトルm/e 342(M+),299(M−CH(CH32),176 こゝに得られた2−シアノ−N−(2′,6′−ジ
イソプロピルフエニル)−ベンゼンスルホンアミ
ド500mgをジオキサン10mlに溶解し、トリエチル
アミン0.3mlを加えて、1時間加熱還流した。溶
媒を留去して得られた油状物は間もなく結晶化し
た。この結晶は、合成例4で得られた化合物(2)に
一致した。収量500mg。 2 製剤化 製剤例1 水和剤 2−(2′,6′−ジアルキルフエニル)−3−イミ
ノ−1,2−ベンゾイソチアゾリン−1,1−
ジオキシド 20重量部 クレー 10 〃 硅藻土 65 〃 リグニンスルフオン酸 3 〃 ポリオキシエチレンアルキルアリルエーテル
2 〃 上記の成分物質を均一に混合粉砕して、水和剤
組成物をつくり、所定濃度で10アール当り100〜
150リツトル散布する。 製剤例2 粉剤 2−(2′,6′−ジアルキルフエニル)−3−イミ
ノ−1,2−ベンゾイソチアゾリン−1,1−
ジオキシド 3重量部 ステアリン酸カルシウム 1 〃 無水珪酸粉末 1 〃 クレー 48 〃 タルク 47 〃 上記の成分を混合粉砕して得た粉剤組成物を、
10アール当り4Kg散布する。 製剤例3 粒剤 2−(2′,6′−ジアルキルフエニル)−3−イ
ミノ−1,2−ベンゾイソチアゾリン−1,1
−ジオキシド 8重量部 クレー 89 〃 カルボキシメチルセルローズ 3 〃 上記の成分物質を混合し、適当量の水を加えて
練合成型ののち乾燥してなる粒剤組成物を、10ア
ール当り3Kg散粒する。 3 薬効試験 試験例1 イネ絞枯病の防除効果試験 1/5000アールのワグネルポツトで栽培した穂孕
期の水稲(品種十石)に、前記製剤例1により製
造した水和剤を所定濃度の散布液に調整したもの
を、薬剤散布装置スプレーガン(3Kg/cm2)を使
用して、70ml/3ポツトの割合で散布した。 当日接種区は、風乾後たゞちに、ペプトン加用
馬鈴薯煎汁寒天培地に48時間平面培養して得た絞
枯病菌を径0.5cmのコルクボーラーで打抜いた含
菌糸寒天片を株の中心、地表面から15cmのところ
へ挿入して接種を行なつた。また、侵入の予防効
果をみるため行なつた散布後7日目接種区は、薬
液散布風乾後、7日間にわたつてガラス温室内に
静置したのちに、上記当日接種区に準じた方法で
接種を行なつた。 接種後は、当日接種区および7日後接種区の両
区とも、絞枯病菌の侵入進展を助長するためポツ
ト毎にビニル円筒で覆い、日中30℃および夜間24
℃のガラス温室に静置して発病させ、接種処理10
日後に発病径の病斑長を測定し、次式に従つて防
除価を算出した。また薬害の発生状況は、同時に
観察によつて行なつた。 防除価=(1−処理区の平均病斑長/無処理区の平均
病斑長)×100 結果は、下表に示した通りであつた。 【表】 試験例2 苗立枯病防除試験 苗立枯病菌(リゾクトニア菌A型菌)を馬鈴
薯煎汁寒天培地上で培養し、3倍量の米糠ととも
に混合磨砕して、接種源をつくつた。供試作物と
してトマト(品種ひかり)ならびにキユウリ(品
種さつきみどり)を用い、殺菌畑土壌をつめた1/
5000アールワグネルポツトに20粒/ポツトの芽出
し種子を播種および覆土し、上記の接種源と殺菌
畑土とを等量混合したものをその上に均一に散布
して接種を行なつた。接種後、28℃の恒温室に48
時間静置したのち、製剤例1の本発明の化合物を
所定濃度に調整して潅注液とし、ポツト当り100
mlのこの薬液をビペツトで地表面に均一に注下施
用した。その後、接種菌の侵入進展を容易にする
ため、30℃〜28℃のガラス温室に搬入し、ポツト
内土壌の湿度をやゝ乾燥気味の状態で経過させて
発病させた。調査は、播種3週間後までの発芽数
および健全苗数を調べて、播種粒数に対する発芽
率および発芽数に対する健全苗率を算出した。 結果は、下表に示す通りであつた。 【表】
DETAILED DESCRIPTION OF THE INVENTION [] BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to novel compounds and their uses. More specifically, the present invention relates to a novel benzisothiazoline derivative and a plant disease control agent containing the same as an active ingredient. Antibiotics, which are currently widely used to control bacterial blight, have been reported to be resistant to bacteria in various places, or lack efficacy, and there are growing concerns about their continued use in the future. .
On the other hand, Asozin, an arsenic agent, is also used as a blight control agent, but its use is being regulated due to its toxicity to humans and livestock and environmental pollution, as it contains heavy metal compounds in its active ingredients. There are many drawbacks to existing insecticides, such as the presence of insecticides, and there is a strong demand from various fields for the development of new types of insecticides. [] Summary of the Invention The present invention seeks to solve the above-mentioned problems by providing a novel benzisothiazoline derivative. Therefore, the 3-imino-1,2-benzisothiazoline-1,1-dioxide derivative according to the invention has the general formula (wherein R represents an ethyl group or an isopropyl group, respectively). Furthermore, the plant disease control agent according to the present invention has the general formula (In the formula, R represents an ethyl group or an isopropyl group, respectively) as an active ingredient. Effects The novel compound according to the present invention generally exhibits control activity against a wide range of agricultural and horticultural crop diseases, but has particularly excellent control effects against rice blight and damping-off of tomatoes and cucumbers. This new compound is an extremely low-toxic synthetic compound that does not contain heavy metals, has no practical toxicity to humans, livestock, or fish, and has no phytotoxicity to crops. Therefore, this compound is considered to have sufficient activity to compensate for the drawbacks of the existing drugs mentioned above. [] Detailed Description of the Invention 1 Compound The compound according to the present invention is represented by the general formula (). (In the formula, each R represents an ethyl group or an isopropyl group. The same applies to each of the following formulas.) Among the compounds of general formula (), those in which R is both an ethyl group and an isopropyl group, that is, the following compounds ( 1) and (2) are typical. Compound (1) 2-(2',6'-diethylphenyl)-3-imino-1,2-benzisothiazoline-1,1
-dioxide compound (2) 2-(2',6'-diisopropylphenyl)-3
-Imino-1,2-benzisothiazoline-
Preparation of 1,1-dioxide 2 compound The compound of the present invention can be synthesized by any method suitable for introducing or forming a desired substituent or bond in formula (). One suitable synthesis method is by the reaction shown in the following reaction formula (A), in which a reactive derivative with respect to the hydroxyl group of 2-cyanobenzenesulfonic acid,
For example, the desired product (2) is obtained by reacting a halide, particularly chloride (2), with 2,6-dialkylaniline (2). The intermediate () may or may not be created intentionally. Since the reaction between compounds () and () involves the generation of hydrogen halide, it is preferably carried out in the presence of an acid scavenger of various organic or inorganic bases. Also, the reaction is the compound () ~
(2) and at least one of the optionally used acid scavenger can be dissolved or dispersed to a desired concentration and can be carried out in the presence of a solvent or dispersion medium that does not substantially inhibit this reaction. In that case, an excess amount of the compound () can be used as an acid scavenger and also as a solvent or a dispersion medium. Specific reaction conditions and other details for carrying out this reaction can be found in the experimental examples below and in J.Chem.Soc. 82 ,
1594 (1960) (Reference 1) or Khim.Geterotsikl.
It may be appropriately selected according to the method of Soedin. No. 12, 1632 (1978) (Reference 2). Note that the compound (), which is one of the raw materials, is
It can be synthesized according to the method described in Handbuch der organischen Chemie XI , 376 (Reference 3). Another suitable synthesis method is by the reaction shown in the following reaction formula (B), in which 2 of the formula () is
-Cyano-N-(2',6'-dialkyl phenyl)-
This is a method for obtaining the target product () by ring-closing reaction of benzenesulfonic acid amide. This ring-closing reaction can be carried out by heating or by using an acid or a base as a reaction catalyst. As in the case of reaction A, a suitable solvent or dispersion medium can be used. Specific reaction conditions and other conditions may be appropriately selected according to the description of the experimental examples described later and the method of the above-mentioned document 1. 3. Usefulness of Compound - Plant Disease Control Agent The plant disease control agent according to the present invention is employed as an agricultural and horticultural agent, especially a fungicide, except that the active ingredient is the above-mentioned compound (). It can take any possible form or usage mode. Specifically, for example, the compound of the present invention may be used as it is, or diluted with a solid powder or other suitable carrier, and if necessary, an auxiliary agent such as a spreading agent may be added thereto, or the compound may be used in the production of agricultural chemicals. Hydration is achieved by mixing various liquid or solid carriers according to methods commonly used in It can be used in the form of formulations such as tablets, liquids, emulsions, powders, and granules. In producing these preparations, the liquid carrier used is one that serves as a solvent for the compound of the present invention, or one that can be dispersed or dissolved with the aid of an auxiliary agent. For example, kerosene, dioxane, acetone, dimethyl sulfoxide, animal and vegetable oils, and surfactants, and solid carriers such as clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, calcium bicarbonate, and the like are used. The content of active ingredient in the preparations thus obtained can be varied within a wide range. For example, when used as a liquid agent, the concentration in the liquid is
Approximately 10 ppm to 500 ppm is appropriate, and in the case of powders or granules, it is desirable to contain the compound of the present invention in a range of approximately 1% to 20%. It goes without saying that the formulation can be formulated at a higher concentration than this and diluted before use.
In addition, if circumstances permit, other compatible agricultural and horticultural chemicals or fertilizers may be mixed into the formulation. The pesticidal agent according to the present invention can be used by spraying on the foliage of crops, and can also be applied to water surfaces, water, soil surfaces, and soil.
In this case, compatible agricultural and horticultural chemicals or fertilizers may be used. Such agricultural and horticultural chemicals include, for example, fungicides, insecticides, herbicides, and plant growth regulators. The amount of application varies depending on the type and severity of the target disease, the type of target crop, the mode of application, etc., but an example when applying to soil is 0.1 kg per 10 ares.
Application rates of ~10Kg are generally appropriate. 4 Experimental Example 1 Synthesis of Compound Synthesis Example 1 Synthesis of Compound (1) 2-cyanobenzenesulfonic acid chloride 2.01g
and 1.5 g of 2,6-diethylaniline were added to 6 ml of pyridine, and heated under reflux for 1 hour with stirring. Methanol was added to the residue obtained by distilling off pyridine under reduced pressure under ice cooling, the precipitated white crystals were filtered, washed with a small amount of methanol, and 2-(2',6'-
1.1 g of (diethylphenyl)-3-imino-1,2-benzisothiazoline-1,1-dioxide
(yield 35%). (1) Melting point: 136-137°C (recrystallization solvent: methanol). (2) Infrared absorption spectrum (Nujol) (cm -1 ) 3230 (NH), 1651 (C=N), 1348, 1328,
1270, 1249, 1216, 1170, 1122, 1074, 967,
860, 808, 776, 758, 747 (3) NMR spectrum (DMSO-d6-TMS) δ 8.48-6.98 (7H, multiplet and broad signal,
aromatic ring proton), 2.51 (4H, quartet, J=7.5
Hz, −CH 2 −CH 3 ×2), 1.08 (6H, triple line,
J=7.5Hz, −CH 2 −CH 3 ×2) (4) Elemental analysis value (%) C 17 H 18 N 2 O 2 S (314.4) Calculated value C64.95, H5.77, N8.91 Analysis Values C64.56, H5.63, N8.92 (5) Mass spectrum m/e 314 (M + ), 285 (MC 2 H 5 ), 235, 91. Synthesis Example 2 Synthesis of compound (1) 2-cyanobenzenesulfonic acid chloride 2.01g
was mixed with 3.0 g of 2,6-diethylaniline,
It was heated to 150°C with stirring. The reaction was exothermic and the clear solution soon solidified. Immediately stop heating and allow to cool, add methanol, filter the precipitated crystals and wash with a small amount of methanol to remove the compound.
1.3 g of 2-cyano-N-(2',6'-diethylphenyl)-benzenesulfonamide (compound where R=ethyl group in general formula ()), which is the intermediate of (1)
I got it. (1) Melting point: 131.5-133°C (recrystallization solvent: methanol). (2) Infrared absorption spectrum (Nujol) (cm -1 ) 3230 (NH), 2260 (C≡N), 1660, 1586,
1406, 1334, 1264, 1197, 1158, 1132, 1068,
1038, 971, 946, 684, 606 (3) NMR spectrum (DMSO-d6-TMS) δ 8.05-6.78 (7H, multiplet, aromatic ring proton), 2.30 (4H, quartet, J = 7Hz, -C H 2
CH 3 ×2), 0.93 (6H, triple line, J=7Hz, -
CH 2 −CH 3 ×2) (4) Mass spectrum m/e 314 (M + ) (5) Elemental analysis value (%) C 17 H 18 N 2 O 2 S (314.4) Calculated value C64.95, H5 .77, N8.91 Analysis value C64.87, H5.80, N8.88 200 mg of the obtained intermediate was added to 3 ml of dioxane.
Dissolve it, add 0.1ml of triethylamine, and make 1
Heat to reflux for an hour. The oil obtained by evaporation of the solvent crystallized shortly after. This crystal corresponded to compound (1) obtained previously in Synthesis Example 1. Yield 200
mg. Synthesis Example 3 Synthesis of Compound (1) 10 g of 2-cyanobenzenesulfonic acid chloride and 7.5 g of 2,6-diethylaniline were mixed in dioxane.
Dissolve in 40ml, add 6g of triethylamine,
The mixture was heated under reflux for 3 hours. The brown oil obtained by distilling off the solvent was washed several times with water, and finally diluted with methanol 30
ml was added to cause crystallization, which was filtered and washed with a small amount of methanol to obtain 8 g of crude compound (1).
1 g of the crude compound (1) thus obtained was taken and dissolved in 30 ml of methanol while hot, insoluble matter was removed by heating, the liquid was cooled on ice, and the precipitated white crystals were filtered. The solid obtained by concentrating the liquid to dryness was recrystallized from aqueous methanol to obtain 56 mg of the desired product. This substance corresponded to compound (1) obtained in Synthesis Examples 1 and 2. Synthesis Example 4 Synthesis of compound (2) 2-cyanobenzenesulfonic acid chloride 2.1g
and 1.77 g of 2,6-diisopropylaniline were dissolved in 30 ml of pyridine and heated under reflux at a bath temperature of 180°C for 2 hours. 15 ml of methanol was added to the brown oil obtained by distilling off the pyridine, and the mixture was stirred under ice cooling. The precipitated white crystals were filtered, washed with a small amount of methanol, phenyl)-3
-imino-1,2-benzisothiazoline-1,
1.5 g of 1-dioxide was obtained. (1) Melting point: 195-196°C (recrystallization solvent: methanol). (2) Infrared absorption spectrum (Nujol) (cm -1 ) 3320 (NH), 1651 (C=N), 1467, 1368,
1353, 1332, 1320, 1270, 1187, 1160, 1110,
1063, 927, 862, 842, 806, 773, 753, 651,
608, 588, 553. (3) NMR spectrum (DMSO-d6-TMS) δ 8.44-7.08 (7H, multiplet, aromatic ring proton), 2.90 (2H, multiplet, J=7Hz, -CH
(CH 3 ) 2 × 2), 1.16 (6H, double line, J = 7Hz,
-CH( CH3 ) 2 ), 1.02(6H, double line, J=
7Hz, -CH( CH3 ) 2 ) (4) Mass spectrum m/e 342(M + ), 299(M-CH( CH3 ) 2 ), 235. (5) Elemental analysis value (%) C 19 H 22 N 2 O 2 S (342.46) Calculated value C66.63, H6.48, N8.18 Analysis value C66.67, H6.48, N8.18 Synthesis example 5 Synthesis of compound (2) 6.48g of 2,6-diisopropylaniline and 2-
4.2 g of cyano-benzenesulfonic acid chloride was mixed with the mixture and heated with stirring at a bath temperature of 140°C. The clear solution gradually solidified. When the internal temperature reaches 120℃ and the contents are completely solidified, stop heating, leave to cool, add 30ml of methanol to make a slurry, filter out the colorless crystals that have precipitated, and wash with cold methanol.2.8 g of 2-cyano-N-(2',6'-diisopropylphenyl)-benzenesulfonamide crystals were obtained. (1) Melting point 175-176.5 (decomposed) (recrystallization solvent methanol). (2) Infrared absorption spectrum (Nujol) (cm -1 ) 3240 (NH), 2260 (C≡N), 1589, 1408,
1339, 1260, 1185, 1161, 1131, 1104, 1066,
928, 804, 773, 756, 703, 688, 625, 600,
571. (3) NMR spectrum (DMSO-d6-TMS) δ 8.05-6.82 (7H, multiplet, aromatic ring proton), 2.97 (2H, septet, J=6.5Hz, -CH
(CH 3 ) 2 × 2), 0.91 (12H, double line, J = 6.5
Hz, -CH( CH3 )×2). (4) Elemental analysis value (%) C 19 H 22 N 2 O 2 S (342.46) Calculated value C66.63, H6.48, N8.18 Analysis value C66.56, H6.52, N8.13 (5) Mass spectrum m/e 342 (M + ), 299 (M-CH (CH 3 ) 2 ), 176 2-cyano-N-(2',6'-diisopropylphenyl)-benzenesulfone obtained here 500 mg of amide was dissolved in 10 ml of dioxane, 0.3 ml of triethylamine was added, and the mixture was heated under reflux for 1 hour. The oil obtained by evaporation of the solvent crystallized shortly after. This crystal corresponded to compound (2) obtained in Synthesis Example 4. Yield 500mg. 2 Formulation Formulation Example 1 Wettable powder 2-(2',6'-dialkyl phenyl)-3-imino-1,2-benzisothiazoline-1,1-
Dioxide 20 parts by weight Clay 10 〃 Diatomaceous earth 65 〃 Lignosulfonic acid 3 〃 Polyoxyethylene alkyl allyl ether
2〃 Make a wettable powder composition by uniformly mixing and pulverizing the above component materials, and prepare a wettable powder composition with a predetermined concentration of 100 to 100% per 10 ares.
Spread 150 liters. Formulation Example 2 Powder 2-(2',6'-dialkyl phenyl)-3-imino-1,2-benzisothiazoline-1,1-
Dioxide 3 parts by weight Calcium stearate 1 Anhydrous silicic acid powder 1 Clay 48 Talc 47 A powder composition obtained by mixing and pulverizing the above components,
Spray 4 kg per 10 ares. Formulation Example 3 Granules 2-(2',6'-dialkyl phenyl)-3-imino-1,2-benzisothiazoline-1,1
- Dioxide 8 parts by weight Clay 89 〃 Carboxymethyl cellulose 3 〃 The above ingredients are mixed, an appropriate amount of water is added, kneaded into a mold, and then dried to obtain a granule composition, which is powdered at 3 kg per 10 ares. . 3 Medicinal Efficacy Test Test Example 1 Rice Shrinkage Blight Control Efficacy Test A predetermined concentration of the hydrating powder produced in Formulation Example 1 was sprayed on paddy rice (variety Jukoku) at the heading stage grown in a 1/5000 are Wagner pot. The mixture was sprayed at a rate of 70 ml/3 pots using a spray gun (3 kg/cm 2 ), a chemical spraying device. Immediately after air-drying the inoculated areas on the same day, the strangulation blight bacteria obtained by flat culture on a peptone-added potato decoction agar medium for 48 hours was punched out using a cork borer with a diameter of 0.5 cm. Inoculation was performed by inserting the tube into the center, 15 cm from the ground surface. In addition, the inoculated areas on the 7th day after spraying, which were carried out to check the effectiveness of preventing invasion, were air-dried after spraying the chemical solution, and then allowed to stand in a glass greenhouse for 7 days, and then treated in the same manner as the inoculated areas on the same day. Inoculation was carried out. After inoculation, each pot was covered with a vinyl cylinder and kept at 30°C during the day and at 24°C at night in both the same-day and 7-day post-inoculation areas to encourage the invasion of strangle blight bacteria.
Let stand in a glass greenhouse at ℃ and inoculate 10
Days later, the lesion length of the disease onset diameter was measured, and the control value was calculated according to the following formula. At the same time, the occurrence of drug damage was also observed. Control value = (1 - average lesion length of treated area/average lesion length of untreated area) x 100 The results were as shown in the table below. [Table] Test Example 2 Seedling damping-off control test Seedling damping-off bacterium (Rhizoctonia type A bacterium) was cultured on a potato decoction agar medium, mixed and ground with three times the amount of rice bran to prepare an inoculum. Ivy. Tomatoes (variety: Hikari) and cucumbers (variety: Satsuki Midori) were used as test crops.
Twenty sprouted seeds per pot were sown in a 5,000 Ahl Wagner pot and covered with soil, and a mixture of equal amounts of the above-mentioned inoculum and sterilized field soil was uniformly spread over the pot for inoculation. After inoculation, store in a constant temperature room at 28℃ for 48 hours.
After standing for a period of time, the compound of the present invention of Formulation Example 1 was adjusted to a predetermined concentration to prepare an irrigation solution, and 100 mg/pot was prepared.
ml of this chemical solution was poured uniformly onto the ground surface using a pipette. Thereafter, in order to facilitate the invasion and progress of the inoculated bacteria, the plants were transported to a glass greenhouse at a temperature of 30°C to 28°C, and the soil in the pot was kept in a slightly dry state to develop the disease. In the investigation, the number of germination and the number of healthy seedlings up to three weeks after sowing were investigated, and the germination rate relative to the number of sown grains and the percentage of healthy seedlings relative to the number of germination were calculated. The results were as shown in the table below. 【table】

Claims (1)

【特許請求の範囲】 1 一般式 (式中、Rはそれぞれエチル基またはイソプロ
ピル基を示す)で示される3−イミノ−1,2−
ベンゾイソチアゾリン−1,1−ジオキシド誘導
体。 2 一般式 (式中Rはそれぞれエチル基またはイソプロピ
ル基を示す)で示される化合物を有効成分とする
植物病害防除剤。
[Claims] 1. General formula 3-imino-1,2- (wherein R represents an ethyl group or an isopropyl group, respectively)
Benzisothiazoline-1,1-dioxide derivative. 2 General formula A plant disease control agent containing a compound represented by the following formula (in which R represents an ethyl group or an isopropyl group) as an active ingredient.
JP9569979A 1979-07-27 1979-07-27 3-imino-1,2-benzoisothiazoline-1,1-dioxide derivative and plant blight control agent comprising the same as active constituent Granted JPS5620580A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9569979A JPS5620580A (en) 1979-07-27 1979-07-27 3-imino-1,2-benzoisothiazoline-1,1-dioxide derivative and plant blight control agent comprising the same as active constituent
PH24348A PH17237A (en) 1979-07-27 1980-07-25 3-imino-1,2-benzoisothiazoline-1,1-dioxide derivatives and preventives or remedies for plant diseases containing the same
BR8004671A BR8004671A (en) 1979-07-27 1980-07-25 PREVENTIVE OR REMEDY FOR PLANT DISEASES

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9569979A JPS5620580A (en) 1979-07-27 1979-07-27 3-imino-1,2-benzoisothiazoline-1,1-dioxide derivative and plant blight control agent comprising the same as active constituent

Publications (2)

Publication Number Publication Date
JPS5620580A JPS5620580A (en) 1981-02-26
JPS6259699B2 true JPS6259699B2 (en) 1987-12-12

Family

ID=14144741

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9569979A Granted JPS5620580A (en) 1979-07-27 1979-07-27 3-imino-1,2-benzoisothiazoline-1,1-dioxide derivative and plant blight control agent comprising the same as active constituent

Country Status (2)

Country Link
JP (1) JPS5620580A (en)
PH (1) PH17237A (en)

Also Published As

Publication number Publication date
PH17237A (en) 1984-07-03
JPS5620580A (en) 1981-02-26

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