TW201127286A - Ketone compound and herbicide containing the same - Google Patents
Ketone compound and herbicide containing the same Download PDFInfo
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- TW201127286A TW201127286A TW99140140A TW99140140A TW201127286A TW 201127286 A TW201127286 A TW 201127286A TW 99140140 A TW99140140 A TW 99140140A TW 99140140 A TW99140140 A TW 99140140A TW 201127286 A TW201127286 A TW 201127286A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
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Abstract
Description
201127286 六、發明說明： 【發明所屬之技術領域】 本發明是有關酮化合物及含有該酮化合物的除草劑。 【先前技術】 成為除草劑之有效成分的化合物之開發正廣泛推展中， 已發現具有防除雜草之效力（以下亦稱為雜草防除效力）之 化合物。例如，在 The pesticide Manual Thirteenth Ed i d i on中已介紹多種成為除草劑有效成分的化合物。 【發明内容】 [發明欲解決之課題] 本發明之課題是提供具有優良之雜草防除效力的化 合物。 [解決課題之手段] 本發明人發現式（I)所示之酮化合物具有雜草防除效 力，遂而完成本發明。 亦即，本發明係以下者。 [1] 一種酮化合物，係如式（I)所示（以下，稱為本發明化合 物）。201127286 VI. Description of the Invention: [Technical Field to Which the Invention Is Along] The present invention relates to a ketone compound and a herbicide containing the ketone compound. [Prior Art] The development of a compound which is an active ingredient of a herbicide is being widely developed, and a compound having an effect of controlling weeds (hereinafter also referred to as weed control effect) has been found. For example, various compounds which become active ingredients of herbicides have been described in The Pesticide Thirteenth Ed i d on. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a compound having excellent weed control efficiency. [Means for Solving the Problem] The present inventors have found that the ketone compound represented by the formula (I) has weed control effect, and has completed the present invention. That is, the present invention is as follows. [1] A ketone compound represented by the formula (I) (hereinafter referred to as a compound of the present invention).
[2]—種[1]所述之酮化合物的製造方法，其具有使式（II) 所示化合物與間氣過氧苯曱酸（m-chloroperbenzoic acid)進行反應之步驟。 4 322535 201127286[2] The process for producing a ketone compound according to [1], which comprises the step of reacting a compound represented by the formula (II) with m-chloroperbenzoic acid. 4 322535 201127286
[3] —種除草劑’其含有fl]所述之酮化合物與不活性載體。 [4] 二種雜草之防除方法，係將[丨]所述之酮化合物的有效 里施用在雜草、雜草生長之土壤、或是雜草將來可能生 長之土壌中。 [5] 種[1]所述之_化合物的用途，係用於防除雜草。 [6] —種化合物，係如式（11)所示。[3] A herbicide which contains a ketone compound described by fl] and an inactive carrier. [4] The method for controlling two kinds of weeds is to effectively apply the ketone compound described in [丨] to weeds, soil in which weeds grow, or in soils where weeds may grow in the future. [5] The use of the compound according to [1] for controlling weeds. [6] A compound which is represented by the formula (11).
[7]-種⑻所狀化合㈣製造料，其具有使式（ιιι) 所示化合物與式⑽所示化合物在路易斯酸存在下進 行反應之步驟：[7]- (8) A compound of the formula (4) having a step of reacting a compound of the formula (?) with a compound of the formula (10) in the presence of a Lewis acid:
(III)(III)
(IV) [式中’X表示鹵原子]。 [8]如m所述的製造方法’其中，路易斯 本發明化合物因為具有雜草 .，、虱化鋁。 早防除效力’故為有用之除 322535 201127286 草劑的有效成分。 【實施方式】 本發明化合物可藉由例如以下之製造法而製造。 (製造法1) 式⑴所示之本發明化合物’係可藉由使式⑼所示 化合物與間氯過氧苯甲酸進行反應而製造：(IV) [wherein 'X represents a halogen atom>. [8] A production method as described in " wherein, the Lewis compound of the present invention has weeds, aluminum halide. Early control effectiveness 'is therefore useful 322535 201127286 active ingredients of grass. [Embodiment] The compound of the present invention can be produced, for example, by the following production method. (Production Method 1) The compound of the present invention represented by the formula (1) can be produced by reacting a compound represented by the formula (9) with m-chloroperoxybenzoic acid:
該反應通常是在溶劑中進行。 反應中使用之溶劑，例如可列舉：氣仿等齒化烴。 相對於式（11)所示化合物1莫耳，在反應中使用的間 氣過氧苯曱酸之量通常是2至4莫耳之比率。 該反應之反應溫度通常是一2〇°C至40。〇的範圍。該反 應之反應時間通常是在1至10小時的範圍。 反應結束後，例如，將反應混合物注入水中，經有機 溶劑萃取後，藉由將有機層進行乾燥、濃縮等之後處理操 作，可單離出本發明化合物。所單離之本發明化合物亦可 藉由再結晶、管柱層析法（c〇lumn chromatography)等而更 進一步精製。 6 322535 201127286 (製造法2) 式（II)所示化合物，係可藉由使式（in)所示化合物 與式（IV)所示化合物在路易斯酸存在下進行反應而製造： Ο C1This reaction is usually carried out in a solvent. The solvent used in the reaction may, for example, be a hydrocarbon such as a gas-like hydrocarbon. The amount of the gas benzoic acid used in the reaction is usually a ratio of 2 to 4 moles relative to the compound 1 mole represented by the formula (11). The reaction temperature of the reaction is usually from 2 ° C to 40 ° C. The scope of the cockroach. The reaction time of the reaction is usually in the range of 1 to 10 hours. After completion of the reaction, for example, the reaction mixture is poured into water, and after extraction with an organic solvent, the organic layer is dried, concentrated, and the like, and the compound of the present invention can be isolated. The isolated compound of the present invention can be further purified by recrystallization, column chromatography or the like. 6 322535 201127286 (Production Method 2) A compound of the formula (II) can be produced by reacting a compound of the formula (in) with a compound of the formula (IV) in the presence of a Lewis acid: Ο C1
(II)(II)
(III)(III)
(IV) [式中，X表示氣、溴等鹵原子]。 該反應通常是在溶劑中進行。 反應中使用之路易斯酸，例如可列舉：氣化紹。 反應中使用之溶劑可列舉如：氣仿等齒化烴。 在反應中使用之試劑之量，相對於式⑴1;>所示化合 物1莫耳，式（IV)所示化合物通常是丨至2莫耳之比率， 路易斯酸通常是1至2莫耳之比率。 ’ 該反應之反應溫度通常是—2{rc至靴的範圍。該反 應之反應時間通常是在1至1 〇小時的範圍。 溶 作 反應結束後，例如，將反應混合物注入水中， 劑萃取後’藉由將有制進行賴、濃料之後處 ，可單離出式（II)所示化合物。所單離之式（⑴所示化 7 322535 201127286 合物可不經精製而使用在下一步驟中。 (參考製造法1) 式（III)所示化合物，係可藉由使式（V)所示化合物與 硫化物鹽進行反應而製造：(IV) [wherein, X represents a halogen atom such as a gas or a bromine]. This reaction is usually carried out in a solvent. The Lewis acid used in the reaction may, for example, be gasification. The solvent used in the reaction may, for example, be a hydrocarbon such as a gas-like hydrocarbon. The amount of the reagent to be used in the reaction is usually from 丨 to 2 mol, and the Lewis acid is usually from 1 to 2 mol per mol of the compound of the formula (1); ratio. The reaction temperature of the reaction is usually in the range of -2{rc to the boot. The reaction time for this reaction is usually in the range of 1 to 1 hour. After the completion of the reaction, for example, the reaction mixture is poured into water, and after the agent is extracted, the compound represented by the formula (II) can be isolated by leaving the residue and the concentrate. The formula (1) shown in (1) can be used in the next step without purification. (Refer to Production Method 1) The compound of the formula (III) can be represented by the formula (V). The compound is produced by reacting with a sulfide salt:
該反應通常是在溶劑中進行。 反應中使用之溶劑，例如可列舉：1-曱基-2-吡咯啶 酮（1-methyl-2-pyrrolidone)等非質子性極性化合物。 該反應中使用之硫化物鹽，例如可列舉：硫化納9水 合物。 相對於式（V)所示化合物1莫耳，在反應中使用之硫 化物鹽的量通常是1至4莫耳之比率。 該反應之反應溫度通常是0°C至180°C的範圍。該反 應之反應時間通常是在1至20小時的範圍。 反應結束後，例如，將反應混合物注入水中，經有機 溶劑萃取後，藉由將有機層進行乾燥、濃縮等之後處理操 作，可單離出式（III)所示化合物。所單離之式（III)所示 化合物可藉由管柱層析法等而更進一步精製。所單離之式 8 322535 201127286 (III)所示化合物亦可不經精製而使用在下一步驟中。 (參考製造法2) • 式（V)所示化合物，係可藉由使式（VI)所示化合物與 對甲苯石黃醯氯（p-toluenesulfonyl chloride)進行反應而 製造：This reaction is usually carried out in a solvent. The solvent to be used in the reaction may, for example, be an aprotic polar compound such as 1-methyl-2-pyrrolidone. The sulfide salt used in the reaction may, for example, be sodium sulfide sulfide hydrate. The amount of the sulfide salt used in the reaction is usually a ratio of 1 to 4 moles relative to the compound 1 mole of the formula (V). The reaction temperature of the reaction is usually in the range of from 0 °C to 180 °C. The reaction time of the reaction is usually in the range of 1 to 20 hours. After completion of the reaction, for example, the reaction mixture is poured into water, and after extraction with an organic solvent, the organic layer is dried, concentrated, and the like, and the compound of the formula (III) can be isolated. The compound represented by the formula (III) which is isolated can be further purified by column chromatography or the like. The isolated compound 8 322535 201127286 The compound shown in (III) can also be used in the next step without purification. (Refer to Production Method 2) • A compound of the formula (V) can be produced by reacting a compound of the formula (VI) with p-toluenesulfonyl chloride:
該反應通常是在吡啶等鹼性溶劑中進行。 相對於式（VI)所示化合物1莫耳，該反應中使用之對 曱苯磺醯氯的量通常是1至4莫耳之比率。 該反應之反應溫度通常是_10°C至50°C的範圍。該反 應之反應時間通常是在1至10小時的範圍。 反應結束後，例如，將反應混合物注入水中，經有機 溶劑萃取後，藉由將有機層進行乾燥、濃縮等之後處理操 作，可單離出式（V)所示化合物。所單離之式（V)所示化合 物係可藉由管柱層析法等而更進一步精製。所單離之式（V) 所示化合物亦可不經精製而使用在下一步驟中。 式（VI)所示化合物’例如可依據journai 〇fThis reaction is usually carried out in an alkaline solvent such as pyridine. The amount of p-toluenesulfonyl chloride used in the reaction is usually a ratio of 1 to 4 moles relative to the compound 1 mole of the formula (VI). The reaction temperature of the reaction is usually in the range of _10 ° C to 50 ° C. The reaction time of the reaction is usually in the range of 1 to 10 hours. After completion of the reaction, for example, the reaction mixture is poured into water, and after extraction with an organic solvent, the organic layer is dried, concentrated, and the like, and the compound of the formula (V) can be isolated. The compound represented by the formula (V) which is isolated can be further purified by column chromatography or the like. The compound of the formula (V) which is isolated can also be used in the next step without purification. The compound represented by the formula (VI) can be, for example, based on journai 〇f
Medicinal Chemistry(2007)Vol.50.(No·12)，p.2818 至 9 322535 201127286 2841記載之方法而製造。 本發明化合物有優良之雜草防除效力，可作為除草劑 之有效成分使用。作為本發明化合物對其有效力之雜草， 例如可列舉：稗草（价Vasing)、螢 蘭（SW/pi/s 力Roxb.var. 、陌上草 {Lindernia procumbens)、）k 反專{Sagittaria pygmaea) 等水田雜草。 本發明之除草劑含有本發明化合物與不活性載體。作 為在本發明之除草劑中所含有之不活性載體者，可列舉液 體載體及固體載體。 本發明之除草劑，通常是藉由將本發明化合物在適當 之液體載體中溶解或分散、或是將本發明化合物與適當之 固體载體混合、或是使本發明化合物吸附在適當之固體載 體中而製劑化者。本發明之除草劑之製_態，例如可列 舉.乳劑、液劑、油劑、水和劑、粉劑、粒劑、顆粒水和 劑、懸浮劑（F1_ble)、乾懸浮劑、轉移（jumper) 剤劑:在此等製劑中，係因應需求而添加乳化劑、分 散劑、展者劑、浸透劑(penetrant)、濕潤劑、結、辦 黏劑、防腐劑、抗氧化劑、著色劑等製劑補助劑。θ 至：重本之除草劑中，通常含有本發明化合物㈣ 作為液體载體者，可列舉如：水、醇類（例如·甲醇、 =1-丙醇、2-丙醇、及乙二醇)、酮類(例如：丙酮、 及曱土乙基_)、_(例如：二辦、四氧咬喃、乙二醇 322535 10 201127286 ·- 單曱基醚、二乙二醇單甲基醚、及丙二醇單甲基醚）、脂肪 族烴類（例如：己烧、辛烷、環己烷、燈油、燃料油、及機 • 械油）、芳香族烴類（例如：苯、曱苯、二曱苯、溶劑油 (solvent naphtha)、及甲基萘）、鹵化烴類（例如：二氣甲 烧、氣仿、及四氣化％L )、酿fee類（例如：二甲基曱醯胺、 一曱基乙酿胺、及N-曱基D比p各咬酮）、酉旨類（例如：醋酸乙 酯、醋酸丁酯、及脂肪酸甘油脂）、及腈類（例如：乙猜、 及丙腈）。 作為固體載體者，可列舉如：植物性粉末（例如：大 豆粉、煙草粉、麵粉、及木粉）、礦物性粉末（例如：高嶺 土、膨潤土（bentonite)、酸性白土、黏土等黏土類；滑石 粉、蠟石粉等滑石類；矽藻土、及雲母粉等二氧化矽類）、 氧化鋁、硫粉末、活性碳、糖類（例如：乳糖、及葡萄糖）、 無機鹽類（例如：碳酸鈣、及碳酸氫鈉）、及玻璃中空體。 在本發明之除草劑中相對於其全體，通常含有液體載 體或固體載體1至99重量％，以含有約10至99重量％之比 率為佳。 製劑化時所使用之乳化劑、分散劑、展著劑、浸透劑、 濕潤劑等通常是使用界面活性劑。該界面活性劑可舉例 如：烷基硫酸酯鹽、烷基芳基磺酸鹽、二烷基磺酸基琥站 酸鹽、聚氧伸乙基烷基芳基醚磷酸酯鹽、木質素磺酸鹽、 萘磺酸醋甲醛聚縮合物等陰離子系界面活性劑；以及聚氧 伸乙基燒基喊、聚氧伸乙基炫基芳基趟、聚氧伸乙基烧基 聚氧伸丙基嵌段聚合物、山梨糠醇酐脂肪酸酯等非離子性 322535 11 201127286 界面活性劑。在本發明之除草劑中相對於其全量，通常含 有界面活性劑〇. 1至5〇重量％，而以約〇· 1至25重量％之 比率為佳。 作為結合劑及增黏劑者，可列舉如：糊精、羧甲基纖 維素之鈉鹽、多敌酸高分子化合物、聚乙稀基π比略咬_、 聚乙烯基醇、木質素續酸納、木質素績酸j弓、聚丙稀酸鈉、 阿拉伯膠（gum arabic)、褐藻酸鈉、甘露糖醇、山梨糖醇、 膨潤土礦物質、聚丙烯酸與其衍生物、羧曱基纖維素之鈉 鹽、白碳、及天然之糖類衍生物（例如：三仙膠（Xanthan gum’又稱為玉米糖膠、黃原膠）、關華豆膠（Guar Gum)等）。 製劑中之本發明化合物的含有比率，例如是如下所 述。 1. 乳劑、水和劑、顆粒水和劑、液劑、水溶劑、懸浮劑、 錠劑、乾懸浮劑：通常是1至9〇重量％之比率。 2. 油劑、粉劑：通常是0. 〇1至10重量％之比率。 3. 粒劑、轉移劑：通常是0. 05至25重量％之比率。 乳劑、水和劑、顆粒水和劑、液劑、水溶劑、懸浮劑 等通常是以水等稀釋成約1〇〇至1〇〇, 〇〇〇倍後使用。 本發明之雜草的防除方法，係藉由將本發明化合物之 有效量施用在雜草、雜草生長之土壤、或雜草將來可能生 長之土壤中來進行。本發明之雜草的防除方法，通常係藉 由將本發明化合物之製劑施用在雜草、雜草生長之土壤、 或雜草將來可能生長之土壌中而進行。 將本發明化合物使用於防除雜草時的施用方法，可使 12 322535 201127286 用與通常習知的施用農藥之方法相同的方法。該施用方 法，例如可列舉如土壤處理、及莖葉處理。將本發明化合 物使用於防除雜草時，本發明化合物之施用量通常是相對 於施用場地每10000m2為1至5〇00g之比率。 本發明化合物可使用於水田之雜草防除。將本發明化 合物使用於水田之雜草防除時，本發明化合物之使用量， 通常是相對於水田每l〇〇QQm2為1至5〇〇〇g之比率。 本發明之除草劑在作為水田雜草防除用時，通常是在 雜草發芽前或在發芽後施用。 本發明化合物在經製劑化為乳劑、水和劑、顆粒水和 劑、水溶劑、懸浮劑、乾懸浮劑等時，本發明化合物濃度 是以成為0. 1至1000ppm之方式以水稀釋後，藉由散布而 施用。本發明化合物在經製劑化為液劑、油劑、粉劑、粒 劑、轉移劑、錠劑等時，通常，該製劑係直接施用。 本發明之除草劑，可因應需求而與1種以上之其他除 草劑、植物生長調節劑、殺菌劑、殺蟲劑、殺蟎劑、殺線 蟲劑等同時施用及/或混合後施用。 該其他除草劑的有效成分，可舉例如： (1) 苯氧基脂肪酸除草性化合物、 (2) 笨甲酸除草性化合物、 (3) 尿素除草性化合物、 (4) 二啡除草性化合物、 (5) 聯吡啶鏘（bipyridinium)除草性化合物、 (6) 經基笨甲腈除草性化合物、 13 322535 201127286 (7) 二硝基笨胺除草性化合物、 (8) 有機磷除草性化合物、 (9) 胺曱酸鹽（carbamate)除草性化合物、 (10) 醯胺除草性化合物、 (11) 氯乙酿笨胺（chi〇r〇acetani 1 ide)除草性化合物、 (12) 一笨基喊除草性化合物、 (13) 環狀醯亞胺除草性化合物、 (14) 吡唑除草性化合物、 (15) 三酮除草性化合物、 (16) 芳氧基苯氧基丙酸除草性化合物、 (17) 三酮肟除草性化合物、 (18) 績醯基尿素除草性化合物、 (19) 咪唾琳酮（imidazolinone)除草性化合物、及 (20) 嘧啶基氧基苯甲酸除草性化合物。 該殺菌劑之有效成分，可列舉如： (1) 多鹵烧基硫殺菌性化合物、 (2) 有機填殺菌性化合物、 (3) 苯并咪唑殺菌性化合物、 (4) 羧基醯胺殺菌性化合物、 (5 )酿基丙胺酸殺菌性化合物、 (6) 〇坐（azole)殺菌性化合物、 (7) 嗎淋（morpholine)殺菌性化合物、 (8) 嗜越果傘素類（strobulin)殺菌性化合物、 (9) 抗生素、及 14 322535 201127286 . (10)二硫胺曱酸鹽（dithiocarbamate)殺菌性化合物。 該殺蟲劑之有效成分，可列舉如： (1) 有機磷殺蟲性化合物、 (2) 胺甲酸鹽殺蟲性化合物、 (3) 擬除蟲菊酯（pyrethroid)殺蟲性化合物、 (4) 沙蠶毒素（nereist〇xin)殺蟲性化合物、 (5) 新尼古丁類（neonic〇tinoid)殺蟲性化合物、 (6) 苯甲醯基苯基尿素殺蟲性化合物、及 (7) 巨環内自旨（macrolide)殺蟲性化合物。 在本發明之除草劑中，也可混合色素、肥料（例如尿 素等）等。 本發明化合物在栽培稻類等作物之農耕地中，可防除 雜草。 [實施例] 以下，列舉製造例、參考例、製劑例及試驗例而更具 體說明本發明’但本發明並不侷限於此等例子。 (製造例1) 5〜笨甲醯基-4-氯-2, 3-二氫苯并[b]噻吩-1，1-二氧化物之 合成Manufactured by the method described in Medicinal Chemistry (2007) Vol. 50. (No. 12), p. 2818 to 9 322535 201127286 2841. The compound of the present invention has excellent weed control efficacy and can be used as an active ingredient of a herbicide. Examples of the weeds which are effective against the compound of the present invention include: Valerian (Vasing), Firefly (SW/pi/s force Roxb.var., Linden grass (Lindernia procumbens), k) Sagittaria pygmaea) and other paddy weeds. The herbicides of the invention comprise a compound of the invention and an inactive carrier. As the inactive carrier contained in the herbicide of the present invention, a liquid carrier and a solid carrier can be mentioned. The herbicide of the present invention is usually prepared by dissolving or dispersing the compound of the present invention in a suitable liquid carrier, or by mixing the compound of the present invention with a suitable solid carrier, or by adsorbing the compound of the present invention in a suitable solid carrier. Medium formulation. Examples of the herbicide of the present invention include emulsions, liquids, oils, water and agents, powders, granules, granule water and agents, suspending agents (F1_ble), dry suspending agents, and jumpers. Tincture: In these preparations, emulsifiers, dispersants, exhibiters, penetrants, humectants, knots, adhesives, preservatives, antioxidants, colorants, etc. are added as needed. Agent. θ to: a heavy herbicide, which usually contains the compound (IV) of the present invention as a liquid carrier, and examples thereof include water and alcohols (for example, methanol, =1-propanol, 2-propanol, and ethylene glycol). ), ketones (for example: acetone, and terpene ethyl _), _ (for example: two, four oxygen, ethylene glycol 322535 10 201127286 · - monodecyl ether, diethylene glycol monomethyl ether And propylene glycol monomethyl ether), aliphatic hydrocarbons (eg, hexane, octane, cyclohexane, kerosene, fuel oil, and mechanical oil), aromatic hydrocarbons (eg, benzene, toluene, Diphenylbenzene, solvent naphtha, and methylnaphthalene), halogenated hydrocarbons (eg, two gas, gas, and gasification of %L), stuffed fee (eg, dimethylhydrazine) Amines, monothioethylamines, and N-mercapto D ratios, and ketones, such as ethyl acetate, butyl acetate, and fatty acid glycerides, and nitriles (eg, B. And propionitrile). Examples of the solid carrier include vegetable powders (for example, soybean powder, tobacco powder, flour, and wood flour), mineral powders (for example, kaolin, bentonite, acid clay, clay, and the like; talc; Talc such as powder and wax powder; cerium oxide such as diatomaceous earth and mica powder; alumina, sulfur powder, activated carbon, sugars (for example, lactose and glucose), and inorganic salts (for example, calcium carbonate, And sodium bicarbonate), and a glass hollow body. In the herbicide of the present invention, it is usually contained in a liquid carrier or a solid carrier in an amount of from 1 to 99% by weight, preferably from about 10 to 99% by weight. An emulsifier, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, and the like used in the formulation are usually used as a surfactant. The surfactant may, for example, be an alkyl sulfate salt, an alkyl aryl sulfonate, a dialkyl sulfonate succinate, a polyoxyethyl aryl ether phosphate, or a lignin sulfonate. An anionic surfactant such as an acid salt, a naphthalenesulfonic acid acetal formaldehyde polycondensate; and an polyoxyalkylene alkyl group, a polyoxyethyl aryl aryl group, a polyoxyalkylene group, a polyoxyalkylene group Base block polymer, sorbitan fatty acid ester, etc. Nonionic 322535 11 201127286 surfactant. The herbicide of the present invention usually contains a surfactant of from 1 to 5 % by weight, based on the total amount thereof, and preferably from about 1 to 25% by weight. As the binder and the tackifier, for example, dextrin, sodium salt of carboxymethyl cellulose, polybasic acid polymer compound, polyethylene π ratio bite _, polyvinyl alcohol, lignin continued Sodium, lignin, jade, sodium polyacrylate, gum arabic, sodium alginate, mannitol, sorbitol, bentonite minerals, polyacrylic acid and its derivatives, carboxymethyl cellulose Sodium salt, white carbon, and natural sugar derivatives (for example: Xanthan gum (also known as corn candy, xanthan gum), Guanhua bean gum (Guar Gum), etc.). The content ratio of the compound of the present invention in the preparation is, for example, as described below. 1. Emulsions, water and agents, granule water and agents, liquids, aqueous solvents, suspensions, troches, dry suspensions: usually in a ratio of from 1 to 9% by weight. 2. Oil, powder: usually 0. 〇 1 to 10% by weight ratio. 3. granules, transfer agent: usually a ratio of 0.05 to 25% by weight. The emulsion, water and agent, granule water and agent, liquid agent, aqueous solvent, suspending agent, etc. are usually diluted with water or the like to about 1 Torr to 1 Torr, and used after doubling. The weed control method of the present invention is carried out by applying an effective amount of the compound of the present invention to weeds, soil in which weeds grow, or soil in which weeds may grow in the future. The method for controlling weeds of the present invention is usually carried out by applying a preparation of the compound of the present invention to weeds, soil in which weeds grow, or soils in which weeds may grow in the future. When the compound of the present invention is used in a method for controlling weed control, 12 322535 201127286 can be used in the same manner as the conventionally known method of applying a pesticide. Examples of the application method include soil treatment, and stem and leaf treatment. When the compound of the present invention is used for controlling weeds, the application amount of the compound of the present invention is usually a ratio of from 1 to 5,000 g per 10,000 m 2 of the application site. The compounds of the invention can be used to control weeds in paddy fields. When the compound of the present invention is used for weed control in paddy fields, the compound of the present invention is usually used in an amount of from 1 to 5 g per 1 〇〇QQm2 of the paddy field. The herbicide of the present invention is usually applied before weed germination or after germination when used as a weed control in paddy fields. When the compound of the present invention is formulated into an emulsion, a water and a granule, a granule water and a granule, an aqueous solvent, a suspension, a dry suspension, etc., the concentration of the compound of the present invention is diluted with water in a manner of from 0.1 to 1000 ppm. Applied by spreading. When the compound of the present invention is formulated into a liquid preparation, an oil preparation, a powder, a granule, a transfer agent, a lozenge or the like, usually, the preparation is directly applied. The herbicide of the present invention can be applied simultaneously and/or mixed with one or more other herbicides, plant growth regulators, bactericides, insecticides, acaricides, nematicides, and the like according to the demand. The active ingredient of the other herbicide may, for example, be: (1) a phenoxy fatty acid herbicidal compound, (2) a benzoic acid herbicidal compound, (3) a urea herbicidal compound, (4) a dimorphic herbicidal compound, ( 5) Bipyridinium herbicidal compound, (6) Herbicidal herbicidal compound, 13 322535 201127286 (7) Dinitromethane herbicidal compound, (8) Organophosphorus herbicidal compound, (9) ) Carbamate herbicidal compound, (10) guanamine herbicidal compound, (11) chitoside 〇 〇 〇 〇 〇 、 、 、 、 、 、 、 、 、 、 12 12 12 12 12 12 Compound, (13) cyclic quinone imide herbicidal compound, (14) pyrazole herbicidal compound, (15) triketone herbicidal compound, (16) aryloxyphenoxypropionic acid herbicidal compound, (17) a triketooxime herbicidal compound, (18) a mercapto urea herbicidal compound, (19) an imidazolinone herbicidal compound, and (20) a pyrimidinyloxybenzoic acid herbicidal compound. Examples of the active ingredient of the bactericide include: (1) a polyhalogenated sulphur sterilizing compound, (2) an organic bactericidal compound, (3) a benzimidazole bactericidal compound, and (4) a carboxy guanamine bactericidal property. Compound, (5) tyrosine bactericidal compound, (6) azole bactericidal compound, (7) morpholine bactericidal compound, (8) strobulin sterilization Compounds, (9) antibiotics, and 14 322535 201127286 . (10) Dithiocarbamate bactericidal compounds. Examples of the active ingredient of the insecticide include: (1) organophosphorus insecticidal compounds, (2) carbamate insecticidal compounds, and (3) pyrethroid insecticidal compounds, (4) Nereis 〇xin insecticidal compound, (5) neonicotinoid insecticidal compound, (6) benzhydrylphenyl urea insecticidal compound, and (7) ) Macrolide insecticidal compounds. In the herbicide of the present invention, a coloring matter, a fertilizer (e.g., urea, etc.), or the like may be mixed. The compound of the present invention can prevent weeds in the cultivation of crops such as rice. [Examples] Hereinafter, the present invention will be described more specifically by way of Production Examples, Reference Examples, Preparation Examples and Test Examples. However, the present invention is not limited to these examples. (Manufacturing Example 1) Synthesis of 5~stanomethyl-4-chloro-2,3-dihydrobenzo[b]thiophene-1,1-dioxide
將4-氣-2, 3-二氫苯并[b]噻吩1. 〇〇g與氯化鋁1. 20g 力口入氣仿1 Om 1中。在此混合物中’於冰冷下滴入苯曱醯氯 15 322535 201127286 •〇ml。將此混合物在冰冷下授拌2小時。在冰水2Gml中， 2反歧合物與㈣2Gml，其錢行分液。將有機層以 硫賴乾燥，並_濃縮。所得_經㈣膠（silica =1)管柱層析法（移動相：醋酸乙s|/己&"⑻而得5_ ，甲醯基4氣2,3-一氫苯并[b]嗟吩與7_苯甲醯基一 4一 氣H二氫苯并[_吩之混合物1.57g。纟20ml氯仿 中，於冰冷下加人5-苯甲醯基+氣_2, 3_二氫苯并[化塞吩 ,、7苯曱醯基-4-氣一2, 3-二氫苯并[b]嗟吩之混合物及7〇% 間氣過氧苯甲酸3._。將所得混合物在室溫巾攪拌6小 時。在反應混合物巾加人lml之鮮硫代硫義水溶液。 用40ml之飽和碳酸氫鈉水溶液洗淨此溶液4次以無水硫 酸鎂乾燥後減壓濃縮。所得之殘渣經中壓分離HpLC (醋酸 乙酯；己烷=從3: 7至1 : 1)而得i 31g之5_苯甲醯基_4_ 氣一2’3-二氫笨并[b]噻吩-1，1-二氧化物與0.10g之7-苯 甲醞基-4-氣-2, 3-二氫苯并[b]噻吩一l !—二氧化物。 5笨曱酿基-4-氣-2, 3-二氫笨并[b]嗔吩-1，1-二氧化物 H-NMR (CDC13) 6ppm:3. 45 (2H, t, J=6. 9Hz), 3. 62 (2H, t, J=6. 9Hz), 7. 4 9-7. 5 3 (3H, m), 7. 65 (1H, d, J = 7. 5Hz), 7. 6 6- 7. 8 0 (3H, m). 7-苯甲醯基-4-氣-2, 3-二氫苯并[b]噻吩-1，1-二氧化物 'H-NMR (CDC13) δρρπι:3. 44 (2 H, t, J=6. 9Hz), 3. 57 (2H，t, J=6. 9Hz), 7. 4 9-7. 5 2 (2H, m), 7. 57 (1H, d, J=8. OHz), 7. 6 2-7. 6 7 (2H, m), 7. 83-7. 8 5 (2H, m). 16 322535 201127286 以下，將本發明化合物之原料化合物的製造例當作參 考例表示。 "(參考例1) 2-氯-6 -氣苯基乙腈之合成4-g-2,3-dihydrobenzo[b]thiophene 1. 〇〇g and aluminum chloride 1. 20g force into the gas imitation 1 Om 1. In this mixture, phenylhydrazine chloride was added dropwise under ice-cold 15 322535 201127286 • 〇ml. The mixture was stirred for 2 hours under ice cooling. In 2Gml of ice water, 2 anti-alias and (4) 2Gml, the money is divided. The organic layer was dried over sulfur and concentrated. The obtained _ _ (4) gel (silica =1) column chromatography (mobile phase: acetic acid ethyl s | / hex &" (8) to get 5 _, formazan 4 gas 2,3- hydroxy benzo [b] The porphin and 7_benzylidene thiol- 4-H-hydrogen benzo[_ phenoxide mixture 1.57g. 纟 20ml chloroform, add 5-benzylidene group + gas 2, 3_ dihydrogen under ice cooling a mixture of benzo[beta], 7-phenylhydrazin-4-a-2,3-dihydrobenzo[b]porphin and 7% by weight of m-peroxybenzoic acid 3.. The mixture was stirred for 6 hours at room temperature, and 1 ml of a fresh thiosulphonic aqueous solution was added to the reaction mixture. The solution was washed 4 times with 40 ml of a saturated aqueous solution of sodium hydrogencarbonate and dried over anhydrous magnesium sulfate. Separation of HpLC (ethyl acetate; hexane = from 3:7 to 1:1) by medium pressure to obtain i 31g of 5_benzimidyl_4_ gas-2'3-dihydro benzo[b]thiophene- 1,1-dioxide and 0.10 g of 7-benzimidyl-4-gas-2,3-dihydrobenzo[b]thiophene-l!-dioxide. Gas-2, 3-dihydro benzo[b] porphin-1,1-dioxide H-NMR (CDC13) 6 ppm: 3.45 (2H, t, J = 6.9 Hz), 3. 62 ( 2H, t, J=6. 9Hz), 7. 4 9-7. 5 3 (3H, m), 7. 65 (1H, d, J = 7. 5Hz), 7. 6 6- 7. 8 0 (3H, m). 7-benzimidyl-4-a-2,3-dihydrobenzo[b] Thiophene-1,1-dioxide 'H-NMR (CDC13) δρρπι: 3.44 (2 H, t, J=6.9 Hz), 3. 57 (2H,t, J=6. 9Hz), 7 4 9-7. 5 2 (2H, m), 7. 57 (1H, d, J=8. OHz), 7. 6 2-7. 6 7 (2H, m), 7. 83-7. 8 5 (2H, m). 16 322535 201127286 Hereinafter, a production example of a raw material compound of the compound of the present invention is shown as a reference example. "Reference Example 1 Synthesis of 2-chloro-6-phenyl acetonitrile
將2-氯-6-氟苯甲基氣化物50. Og溶解到二曱基亞砜 300ml中。在此溶液中加入氰化鈉16. 0g並在23°C攪拌5 小時。將反應混合物加入1000ml水中，以三級丁基曱基醚 1000ml萃取。用飽和食鹽水1000ml洗淨有機層後，以無水 硫酸鎂乾燥，減壓濃縮而得47. 6g之2-氣-6-氟苯基乙腈。 ^-NMR (CDC13) 5ppm:3. 85 (2 H, s), 7. 08-7. 10 (1H, m), 7. 2 6- 7. 3 2 (2H, m). (參考例2)The 2-chloro-6-fluorobenzyl vapor 50. Og was dissolved in 300 ml of dimethyl sulfoxide. To the solution was added 16.0 g of sodium cyanide and stirred at 23 ° C for 5 hours. The reaction mixture was poured into 1000 ml of water and extracted with 1000 ml of butyl decyl ether. The organic layer was washed with saturated brine (1 ml), dried over anhydrous magnesium sulfate. ^-NMR (CDC13) 5ppm: 3.85 (2 H, s), 7. 08-7. 10 (1H, m), 7. 2 6- 7. 3 2 (2H, m). (Reference Example 2 )
2 -氯-6 -氣苯基醋酸之合成 /=^ yCOOH ΜSynthesis of 2-chloro-6-phenylphenylacetate /=^ yCOOH Μ
F 在150ml水中加入47. 6g之2_氣_6_氣苯基乙猜及96% 硫酸150ml。將此混合物在120°C攪拌12小時。在反應混 合物中加入水600ml，在室溫下放置2小時，進一步在冰 冷下冷卻30分鐘。將析出之固體過濾而收集之，以水300ml 洗淨，乾燥後得到2-氣-6-氟苯基醋酸49. 2g。 17 322535 201127286 iH_NMR(DMS〇-d6)5ppm:3.70(2H,s),7.20-7 28 (1H，m)，7. 3 0-7. 4 4 (2H, m). (參考例3) 2-(2-亂-6 -氟苯基）乙醇之合成F In 47 ml of water, 44.6 g of 2_gas_6_gas phenyl b and 96% of sulfuric acid 150 ml were added. The mixture was stirred at 120 ° C for 12 hours. 600 ml of water was added to the reaction mixture, and the mixture was allowed to stand at room temperature for 2 hours, and further cooled under ice cooling for 30 minutes. 2克。 The precipitated solid was collected by filtration, washed with water 300ml, dried to give 2- gas-6-fluorophenylacetic acid 49. 2g. 17 322535 201127286 iH_NMR(DMS〇-d6) 5ppm: 3.70(2H, s), 7.20-7 28 (1H, m), 7. 3 0-7. 4 4 (2H, m). (Reference Example 3) 2 Synthesis of -(2-ran-6-fluorophenyl)ethanol
在600ml四氫呋喃中加入24. 6g之2-氣-6-氟苯基醋 酸’其次’在冰冷下加入4. 20g之氫化鋁鋰（lithium aluminum hydride)。將此混合物在室溫中攪拌1小時。其 次’加熱回流3小時。將反應混合物冷卻到室溫為止。在 反應混合物中加入冰冷之水13m 1與四氫°夫南53m 1之混合 物。10分鐘後，將此混合物通過矽藻土（Celite)過濾，將 過濾殘渣以四氫呋喃300ml洗淨。將濾液減壓濃縮後而得 2-(2-氣-6-氣苯基）乙醇14. 8g。 ^-NMR (CDC13) δρρπι:1. 60 (1Η, br), 3. 08-3. l 1 (2H, m), 3. 8 4 — 3. 8 8 (2H, m), 6. 96 — 7： 00 (1H, m), 7. 12-7. 19 (2H, m). (參考例4) 對曱苯續酸2-(2-氯-6-氟苯基）乙酯之合成2,6 g of 2-gas-6-fluorophenylacetic acid was added to 600 ml of tetrahydrofuran. Next, 4.20 g of lithium aluminum hydride was added under ice cooling. This mixture was stirred at room temperature for 1 hour. The second was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature. To the reaction mixture was added a mixture of ice-cold water 13 m 1 and tetrahydro-funan 53 m 1 . After 10 minutes, the mixture was filtered through Celite, and filtered residue was washed with 300 ml of THF. 8克。 The filtrate was concentrated under reduced pressure to give 2-(2- gas-6-phenylphenyl) ethanol 14. 8g. ^-NMR (CDC13) δρρπι: 1. 60 (1Η, br), 3. 08-3. l 1 (2H, m), 3. 8 4 — 3. 8 8 (2H, m), 6. 96 — 7: 00 (1H, m), 7. 12-7. 19 (2H, m). (Reference Example 4) Synthesis of 2-(2-chloro-6-fluorophenyl)ethyl phthalate
厂 1 )^0~cH3 在87ml吡啶中加入2-(2-氣-6-氟苯基）乙醇29. 2g， 18 322535 201127286 其次，在冰冷下加入30. 0g之對曱苯磺醯氯。將此混合物 在室溫中攪拌5小時。在870ml水中加入反應混合物，以 第三丁基曱基醚870ml萃取。將有機層以3.讥鹽酸9〇〇ml 及飽和食鹽水900ml依序洗淨，以無水硫酸鎂乾燥，並減 壓濃縮，而得對曱苯磺酸2-(2-氯-6-氟苯基）乙酯47. 3g。 ^H-NMR (CDC13) 6ppm：2. 43 (3H, s), 3. 14 (2H, t, J = 7. 1Hz), 4. 21 (2H, t, J = 7. 1Hz)> 6 9〇_? 〇〇 (1H, m)，7. 12 —7. 15 (2H, m) 7 2 8 (2h，d 7Hz)，7. 71 (2H, d, J =8. 7HZ). (參考例5) 4-氣-2, 3-二氫苯并[b]嗔吩之合成 在470ml之1-甲基-2-吡咯啶酮中加入對甲苯磺酸 2-(2-氯-6-氟苯基）乙酯47. 〇g及硫化鈉9水合物4〇. 2g。 將此混合物在15(TC攪拌1〇小時。在94〇ml水中加入反應 混合物’以第三丁基甲基則偏萃取。有機層以飽和食 鹽水1000ml力淨2次後，以無水硫酸鎮乾燥，並減麼漠縮。 所得之殘潰經石夕膠管柱層析法（移動相：己院）而得u 6g 之4-氣-2, 3-二氫苯并[b]噻吩。 iH-NMR (CDC 1 3) (3 H, m). PPm: 3. 40 (4H, s), 6. 95-7 10 (參考例6) 5-苯甲醯基-4-氣-2,3-二氫苯并[_吩與7_笨甲酿基 322535 19 201127286 -4-氣-2, 3-二氫苯并[b]喧吩之合成 4-氯-2, 3-二氫笨并[b]噻吩37g之氯仿355ml溶液中 加入氯化紹粉末41· 6g。於其中在冰冷下滴入38. Og之苯 曱醯氣。將此混合物攪拌4小時。在533ml冰水中加入反 應混合物並分液。有機層以水178ml洗淨後，以無水硫酸 鎮乾燥，並減壓濃縮而得到82. 9g之殘漬。在此殘潰中， 加入二異丙基醚165ml與己烷165ml，將此混合物加熱回 OIL 30分鐘。反應混合物放冷至室溫，其次予以冰冷分 鐘。將析出之固體藉由過濾而收集，得到5_苯甲醯基_4_ 氯-2, 3-二氫苯并[b]噻吩與7一苯甲醯基_.4_氯_2, 3一二氫 苯并[b]噻吩之混合物46. 4g。將5-苯曱醯基-4-氣-2, 3-二氫苯并[b]噻吩與7一苯曱醯基_4_氣一2,3_二氫苯并[b] 噻吩之混合物40〇mg溶解到6ml之乙腈中，將所得溶液經 0DS中壓管柱[移動相：乙腈/水=86%/14%(容量分取， 得到5-苯甲酿基+氣_2, 3_二氫苯并[b]嗔吩35〇呢、卜 苯曱醯基-4-氣-2, 3-二氫苯并[b]噻吩3mg。 5-苯曱醯基-4-氣-2, 3-二氫苯并[b]噻吩1 。 。 。 。 。 。 。 。 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 This mixture was stirred at room temperature for 5 hours. The reaction mixture was added to 870 ml of water and extracted with 870 ml of butyl decyl ether. The organic layer was washed successively with 9 〇〇 ml of hydrazine hydrochloride and 900 ml of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 2-(2-chloro-6-fluor Phenyl)ethyl ester 47. 3g. ^H-NMR (CDC13) 6ppm: 2.43 (3H, s), 3. 14 (2H, t, J = 7. 1Hz), 4. 21 (2H, t, J = 7. 1Hz)> 6 9〇_? 〇〇(1H, m), 7. 12 —7. 15 (2H, m) 7 2 8 (2h, d 7Hz), 7. 71 (2H, d, J =8. 7HZ). ( Reference Example 5) Synthesis of 4-gas-2,3-dihydrobenzo[b] porphin 2-(2-chloro-6) p-toluenesulfonic acid was added to 470 ml of 1-methyl-2-pyrrolidone -Fluorophenyl)ethyl ester 47. 〇g and sodium sulfide 9 hydrate 4 〇. 2g. The mixture was stirred at 15 (TC for 1 hour. The reaction mixture was added to 94 〇ml of water to extract with a third butyl methyl group. The organic layer was washed twice with 1000 ml of saturated brine, and dried with anhydrous sulfuric acid, and The resulting residue was subjected to Shixi rubber column chromatography (mobile phase: shangyuan) to obtain 6 g of 4-gas-2,3-dihydrobenzo[b]thiophene. iH-NMR ( CDC 1 3) (3 H, m). PPm: 3. 40 (4H, s), 6. 95-7 10 (Reference Example 6) 5-Benzyl indenyl-4-gas-2,3-dihydrogen Synthesis of benzo[_phene and 7_ stupid 322535 19 201127286 -4- gas-2,3-dihydrobenzo[b] porphin 4-chloro-2,3-dihydro benzo[b] To a solution of 37 g of chloroform in 355 ml of chloroform was added 41. 6 g of a chlorinated powder, and 38.0 g of benzoquinone was added dropwise thereto under ice cooling. The mixture was stirred for 4 hours. The reaction mixture was added to 533 ml of ice water and liquid-separated. The organic layer was washed with 178 ml of water, dried over anhydrous sulfuric acid, and concentrated under reduced pressure to give a residue of 82.9 g. In this residue, 165 ml of diisopropyl ether and 165 ml of hexane were added, and the mixture was heated. Return to OIL for 30 minutes. Allow the reaction mixture to cool to room temperature, and then Cold minute. The precipitated solid was collected by filtration to give 5-benzoyl- 4-chloro-2,3-dihydrobenzo[b]thiophene and 7-benzoic acid yl. , a mixture of 3 - dihydrobenzo[b]thiophene 46. 4 g. 5-Benzenyl-4-gas-2,3-dihydrobenzo[b]thiophene and 7-benzoinyl-4 _ gas a mixture of 2,3_dihydrobenzo[b] thiophene 40 〇mg dissolved in 6 ml of acetonitrile, the resulting solution was passed through a 0DS medium pressure column [mobile phase: acetonitrile / water = 86% / 14% ( The capacity was fractionated to obtain 5-benzoic acid + gas 2, 3 - dihydrobenzo[b] porphin 35 oxime, phenylphenyl-4-pyrene-2,3-dihydrobenzo[ b] thiophene 3 mg. 5-phenylhydrazin-4-yl-2,3-dihydrobenzo[b]thiophene
P CIP CI
1 H-NMR (CDC J · 1 8 (2H, m), 7. m), 7· 8 1 〜7. 81 H-NMR (CDC J · 1 8 (2H, m), 7. m), 7· 8 1 to 7. 8
7-苯甲醯基-4-氯-2, 3-二氫苯并[b]噻吩 322535 20 201127286 ci7-Benzylmercapto-4-chloro-2,3-dihydrobenzo[b]thiophene 322535 20 201127286 ci
1 H-NMR (CDC13) δ (ppm):3. 34 〜3 46 (4H, m) 06 (1H, d, J=8. 29Hz), 7. 44-7. 5〇 (3H, m), 5 〜7. 6 0 (1 H, m), 7· 70 〜7. 7 2 ( 2 H, m). 其次’表不含有本發明化合物之製劑例。 (製劑例1) 將下述者予以混合粉碎而得到水和劑： 本發明化合物 50重量％ 木質素磺酸鈉 5重量％ 聚氧伸乙基烷基醚 5重量％ 白碳 5重量％ 黏土 (製劑例2) 35重量％ 將下述者予以混合 ，並加水混練且造粒而得到粒 本發明化合物 1. 5重量％ 木質素磺酸鈉 2重量％ 滑石 40重量％ 膨潤土 56. 5重量％ 其次，表示本發明化合物在雜草之防除上為有用 驗例。 之試 322535 21 201127286 (試驗例l) 在塑膠盆（$ 9cmxl0cm)中填塞泥土，加入水並把土， 靜置3天。在此盆中將良有陌上萆(UJndernia procimbens) 種子之泥土均勻地播種，在溫室内（20°C至25°C)放置6 天。在此盆中加入3cm深度之水。其次，在此盆中，將試 驗化合物以丙酮溶解後再以純水稀釋而成之藥液予以加入 預定之藥量份。藥劑處理3週後，觀察對於陌上草之除草 效果，進行11階段評估（0 :無作用至10 :完全枯殺）。結 果，本發明化合物是在4000g/ha之處理藥量顯示效力為8。 [產業上之可利用性] 本發明化合物具有雜草防除效力。藉由將本發明化合 物之有效量施用在雜草、雜草生長之土壤、或是雜草將來 可能生長之土壌中，可防除雜草。 【圖式簡單說明】 無 【主要元件符號說明】 無 22 3225351 H-NMR (CDC13) δ (ppm): 3.34 〜3 46 (4H, m) 06 (1H, d, J=8. 29Hz), 7. 44-7. 5〇(3H, m), 5 to 7.60 (1 H, m), 7·70 to 7. 7 2 ( 2 H, m). Next, the table does not contain a formulation example of the compound of the present invention. (Formulation Example 1) The following were mixed and pulverized to obtain water and an agent: 50% by weight of the compound of the present invention, 5 wt% of sodium lignosulfonate, polyoxyethylene ethyl ether, 5 wt%, white carbon, 5 wt%, clay ( 5重量% Next, Formulation Example 2) 5% by weight, followed by mixing with water, and granulating to obtain a granule of the present invention 1. 5 wt% sodium lignin sulfonate 2 wt% talc 40 wt% bentonite 55.6 wt% , indicating that the compound of the present invention is a useful test for weed control. Test 322535 21 201127286 (Test Example l) Fill the soil in a plastic basin ($9cmxl0cm), add water and leave the soil for 3 days. In this pot, the soil of the seed of UJndernia procimbens is uniformly sown and placed in a greenhouse (20 ° C to 25 ° C) for 6 days. A water of 3 cm depth was added to the pot. Next, in this pot, the test compound is dissolved in acetone and then diluted with pure water to be added to the predetermined dose. After 3 weeks of treatment, the herbicidal effect on the grass was observed, and an 11-stage evaluation was performed (0: no effect to 10: complete kill). As a result, the compound of the present invention showed a potency of 8 at a treatment amount of 4000 g/ha. [Industrial Applicability] The compound of the present invention has weed control efficacy. Weeds can be prevented by applying an effective amount of the compound of the present invention to weeds, soil in which weeds grow, or in soils where weeds may grow in the future. [Simple diagram description] None [Main component symbol description] None 22 322535
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| US8962584B2 (en) | 2009-10-14 | 2015-02-24 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd. | Compositions for controlling Varroa mites in bees |
| PE20130649A1 (en) | 2010-03-08 | 2013-07-13 | Monsanto Technology Llc | POLYNUCLEOTIDE MOLECULES FOR GENETIC REGULATION IN PLANTS |
| WO2013040033A1 (en) | 2011-09-13 | 2013-03-21 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10829828B2 (en) | 2011-09-13 | 2020-11-10 | Monsanto Technology Llc | Methods and compositions for weed control |
| US10806146B2 (en) | 2011-09-13 | 2020-10-20 | Monsanto Technology Llc | Methods and compositions for weed control |
| WO2013040057A1 (en) | 2011-09-13 | 2013-03-21 | Monsanto Technology Llc | Methods and compositions for weed control |
| MX348495B (en) | 2011-09-13 | 2017-06-14 | Monsanto Technology Llc | Methods and compositions for weed control. |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ294096B6 (en) * | 1995-01-20 | 2004-10-13 | Americanácyanamidácompany | Benzophenone compounds, process of their preparation, fungicidal agents containing thereof and plant protection method |
| JP2000178268A (en) * | 1998-10-06 | 2000-06-27 | Idemitsu Kosan Co Ltd | Triketone derivative and herbicide |
| JP2001288183A (en) * | 2000-04-04 | 2001-10-16 | Idemitsu Kosan Co Ltd | Benzoyl derivative having condensed ring and herbicide composition using the same |
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2010
- 2010-11-17 JP JP2010256509A patent/JP2011195561A/en active Pending
- 2010-11-18 WO PCT/JP2010/071070 patent/WO2011065451A1/en active Application Filing
- 2010-11-22 TW TW99140140A patent/TW201127286A/en unknown
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|---|---|
| WO2011065451A1 (en) | 2011-06-03 |
| JP2011195561A (en) | 2011-10-06 |
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