JPS632261B2

JPS632261B2 -

Info

Publication number: JPS632261B2
Application number: JP6396880A
Authority: JP
Inventors: Mitsumasa Yamazaki; Hideo Maeda; Yasunari Sakuraba
Original assignee: Hodogaya Chemical Co Ltd
Current assignee: Hodogaya Chemical Co Ltd
Priority date: 1980-05-16
Filing date: 1980-05-16
Publication date: 1988-01-18
Also published as: JPS56161373A

Description

[Detailed description of the invention]

本発明は特定のピリジルオキシ安息香酸アミド
誘導体及びそのピリジルオキシ安息香酸アミド誘
導体を含有する除草剤に関するものである。本発明者らは、ピリジルオキシ安息香酸系の化
合物について除草活性を種々検討した結果、特定
のピリジルオキシ安息香酸アミド誘導体に特異な
作用を見い出し、本発明を完成させるに至つた。すなわち本発明は、二つの発明からなり、その
第一の発明は、次の一般式に示すピリジルオキシ
安息香酸アミド誘導体であり、また第二の発明
は、そのピリジルオキシ安息香酸アミド誘導体を
有効成分とする除草剤である。一般式（式中のＲ、R′は、水素原子、低級アルキル基、
または低級アルケニル基を、Ｘはハロゲン原子
を、ｎは０ないし３の整数を示す。）本発明に係るピリジルオキシ安息香酸アミド誘
導体の代表的なものを次に示すが、本発明はこれ
らのみに限定されるものではない。 The present invention relates to specific pyridyloxybenzoic acid amide derivatives and herbicides containing the pyridyloxybenzoic acid amide derivatives. As a result of various studies on herbicidal activity of pyridyloxybenzoic acid compounds, the present inventors discovered a unique action of a specific pyridyloxybenzoic acid amide derivative, and completed the present invention. That is, the present invention consists of two inventions, the first invention is a pyridyloxybenzoic acid amide derivative represented by the following general formula, and the second invention is a pyridyloxybenzoic acid amide derivative represented by the following general formula. It is a herbicide that general formula (R and R' in the formula are hydrogen atoms, lower alkyl groups,
or a lower alkenyl group, X represents a halogen atom, and n represents an integer of 0 to 3. ) Representative pyridyloxybenzoic acid amide derivatives according to the present invention are shown below, but the present invention is not limited thereto.

【表】本発明の化合物は、例えば、下記方法によつて
製造される。こゝで使用するアルカリ性物質は、炭酸水素ナ
トリウム、炭酸ナトリウム、炭酸カリウム等の塩
基性の塩類、または、ピリジン、トリエチルアミ
ンおよび反応に使用する塩基自身のような有機塩
基性物質等が挙げられる。溶媒としては、水溶媒
中、または、アセトン、ベンゼン、トルエン、テ
トラヒドロフラン、ジオキサン等の有機溶媒が挙
げられる。反応終了後、目的化合物は常法に従つ
て反応混合物から容易に取得される。次に、本発明の化合物の合成例を記載する。合成例１Ｎ−メチル−３−（２−ピリジルオキシ）安息
香酸アミドメチルアミン40％水溶液1.55ｇをテトラヒドロ
フラン40mlに溶解させ、５℃以下に冷却しなが
ら、３−（２−ピリジルオキシ）安息香酸クロラ
イド2.34ｇを添加した。添加後室温で２時間撹拌
した。反応終了後反応混合物は水400mlに注ぎ、
析出した結晶を別し、良く水洗した。これを乾
燥して、Ｎ−メチル−３−（２−ピリジルオキシ）
安息香酸アミド2.05ｇを得た。収率89.9％、融点
91〜93℃であつた。元素分析値Ｃ％Ｈ％Ｎ％計算値 68.41 5.30 12.27 実験値 68.47 5.26 12.34 合成例２Ｎ−エチル−３−〔２−（６−クロルピリジルオ
キシ）〕安息香酸アミドエチルアミン70％水溶液1.29ｇをジオキサン30
mlに溶解させ、10℃以下に冷却しながら、ジオキ
サン10mlに溶解した３−〔２−（６−クロルピリジ
ルオキシ）〕安息香酸クロライド2.68ｇを滴下し
た。滴下後室温で１時間撹拌した。反応終了後反
応混合物は減圧下にてジオキサンを回収した。残
渣に塩化メチレンを加え水洗後、脱水して塩化メ
チレンを回収した。この残物にリグロインを加
え、Ｎ−エチル−３−〔２−（６−クロルピリジル
オキシ）〕安息香酸アミド2.11ｇを得た。収率
76.3％、融点70〜73℃であつた。元素分析値Ｃ％Ｈ％Ｎ％計算値 60.77 4.74 10.12 実験値 60.85 4.68 10.21 本発明の除草剤は、有効成分化合物を各種担体
と混合し、水和剤、乳剤、粉剤、粒剤などの形態
に製剤化して得られる。担体のうち、液状担体と
しては、通常の有機溶媒、固体担体としては、通
常の鉱物質微粉が使用される。また、製剤製造に
際して乳化性、分散性、展着性等を付与するため
に界面活性剤が添加される。さらに肥料、除草
剤、殺虫剤、殺菌剤などの農薬と混合して使用す
ることもできる。本発明の除草剤は、主として雑草の発芽および
生長を抑制し、特に湛水条件下における土壤処理
で、ノビエ、ミゾハコベおよびタマガヤツリなど
の雑草に卓越した防除効果を示し、しかも、移植
水稲に対する薬害はほとんど見られない、高度選
択性除草剤である。次に実施例によつて本発明の除草剤を説明す
る。実施例１（水和剤）ジークライト 97重量部ネオペレツクスパウダー（商標名：花王アトラス
(株)） 1.5重量部ソルポール800A（商標名：東邦化学工業(株)）
1.5重量部以上の成分を均一に粉砕混合して、水和剤用の
キヤリヤーを得た。得られた水和剤用キヤリヤー
90重量部と、Ｎ−メチル−３−（２−ピリジルオ
キシ）安息香酸アミド10重量部とを均一に粉砕混
合して、水和剤を得た。実施例２（乳剤）Ｎ−メチル−３−（２−ピリジルオキシ）安息香
酸アミド 10重量部シクロヘキサノン 30重量部キシレン 50重量部ソルポール800A（商標名：東邦化学工業(株)）
10重量部以上の成分を均一に混合溶解して、乳剤を得
た。試験例 1/15500アールの磁製ポツトに水田土壤をつめ、
表層にノビエ種子、ミゾハコベ種子およびタマガ
ヤツリ種子を播種し、代かきした後、２cmの深さ
に湛水した。さらに葉令２葉期の水稲苗（品種：
日本晴）を２本移植した。水稲移植後４日目に、
各被検化合物の水和剤および乳剤の水による希釈
液を、各薬剤の所定量だけ、水面に滴下処理し
た。薬剤処理後20日目に、ノビエ、ミゾハコベお
よびタマガヤツリに対する除草効果および移植水
稲に対する反応を下記の基準によつて観察調査を
行なつた。除草効果移植水稲の薬害０：無（効果なし） −：無害１：微 ±：微害２：小＋：小害３：中：中害４：大：大害５：極大（100％除草）この結果は、次の表に示すとおりであつて、本
発明の化合物を含有する除草剤は、除草効果が優
れ、かつ、水稲に対する薬害が殆んど認められな
い。[Table] The compound of the present invention is produced, for example, by the following method. Examples of the alkaline substance used here include basic salts such as sodium hydrogen carbonate, sodium carbonate, and potassium carbonate, and organic basic substances such as pyridine, triethylamine, and the base itself used in the reaction. Examples of the solvent include aqueous solvents and organic solvents such as acetone, benzene, toluene, tetrahydrofuran, and dioxane. After completion of the reaction, the target compound can be easily obtained from the reaction mixture according to a conventional method. Next, a synthesis example of the compound of the present invention will be described. Synthesis Example 1 N-Methyl-3-(2-pyridyloxy)benzoic acid amide Dissolve 1.55 g of 40% methylamine aqueous solution in 40 ml of tetrahydrofuran, and while cooling to below 5°C, dissolve 3-(2-pyridyloxy)benzoic acid. 2.34g of chloride was added. After the addition, the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the reaction mixture was poured into 400ml of water.
The precipitated crystals were separated and thoroughly washed with water. This was dried and N-methyl-3-(2-pyridyloxy)
2.05 g of benzoic acid amide was obtained. Yield 89.9%, melting point
The temperature was 91-93℃. Elemental analysis value C% H% N% Calculated value 68.41 5.30 12.27 Experimental value 68.47 5.26 12.34 Synthesis example 2 N-ethyl-3-[2-(6-chloropyridyloxy)]benzoic acid amide 1.29 g of ethylamine 70% aqueous solution was dissolved in dioxane 30
ml, and 2.68 g of 3-[2-(6-chloropyridyloxy)]benzoic acid chloride dissolved in 10 ml of dioxane was added dropwise while cooling to below 10°C. After the addition, the mixture was stirred at room temperature for 1 hour. After the reaction was completed, dioxane was recovered from the reaction mixture under reduced pressure. Methylene chloride was added to the residue, washed with water, and then dehydrated to recover methylene chloride. Ligroin was added to this residue to obtain 2.11 g of N-ethyl-3-[2-(6-chloropyridyloxy)]benzoic acid amide. yield
It was 76.3% and the melting point was 70-73°C. Elemental analysis value C% H% N% Calculated value 60.77 4.74 10.12 Experimental value 60.85 4.68 10.21 The herbicide of the present invention is prepared by mixing the active ingredient compound with various carriers and forming it into a wettable powder, emulsion, powder, granule, etc. Obtained by formulating it. Among the carriers, a usual organic solvent is used as the liquid carrier, and a usual mineral fine powder is used as the solid carrier. In addition, surfactants are added to impart emulsifying properties, dispersibility, spreading properties, etc. during preparation. Furthermore, it can be used in combination with agricultural chemicals such as fertilizers, herbicides, insecticides, and fungicides. The herbicide of the present invention mainly suppresses the germination and growth of weeds, and exhibits an outstanding control effect on weeds such as field weed, chickweed, and cypress, especially when treated with soil under flooded conditions.Moreover, it does not cause chemical damage to transplanted paddy rice. It is a highly selective herbicide that is rarely seen. Next, the herbicide of the present invention will be explained with reference to Examples. Example 1 (Hydrating agent) Zeeklite 97 parts by weight Neopellex powder (trade name: Kao Atlas
Co., Ltd.) 1.5 parts by weight Solpol 800A (trade name: Toho Chemical Industry Co., Ltd.)
A carrier for a wettable powder was obtained by uniformly pulverizing and mixing 1.5 parts by weight or more of the components. Obtained carrier for wettable powders
A wettable powder was obtained by uniformly pulverizing and mixing 90 parts by weight and 10 parts by weight of N-methyl-3-(2-pyridyloxy)benzoic acid amide. Example 2 (Emulsion) N-methyl-3-(2-pyridyloxy)benzoic acid amide 10 parts by weight Cyclohexanone 30 parts by weight Xylene 50 parts by weight Solpol 800A (trade name: Toho Chemical Industry Co., Ltd.)
An emulsion was obtained by uniformly mixing and dissolving 10 parts by weight or more of the components. Test example Fill a 1/15500 are porcelain pot with paddy soil,
Wild field seeds, Japanese chickweed seeds, and Japanese cypress seeds were sown on the surface layer, and after plowing, the soil was flooded to a depth of 2 cm. In addition, paddy rice seedlings at the second leaf stage (variety:
Two plants (Nipponbare) were transplanted. On the fourth day after transplanting paddy rice,
A predetermined amount of each drug was dropped onto the water surface by diluting the hydrating powder and emulsion of each test compound with water. On the 20th day after the chemical treatment, the herbicidal effects on wild grass, chickweed, and cypress and the response to transplanted paddy rice were observed and investigated according to the following criteria. Weeding effect Chemical damage to transplanted paddy rice 0: No (no effect) -: Harmless 1: Slight ±: Slight damage 2: Small +: Slight damage 3: Medium: Medium damage 4: Large: Large damage 5: Extremely large (100% weeding) The results are shown in the following table, and the herbicide containing the compound of the present invention has an excellent herbicidal effect and almost no phytotoxicity to paddy rice is observed.

【表】【table】

【table】

Claims

[Claims] 1. General formula (In the formula, R and R' represent a hydrogen atom, a lower alkyl group, or a lower alkenyl group, X represents a halogen atom, and n represents an integer of 0 to 3.) A pyridyloxybenzoic acid amide derivative represented by the following formula. 2 General formula (R and R' in the formula are hydrogen atoms, lower alkyl groups,
or a lower alkenyl group, X represents a halogen atom, and n represents an integer of 0 to 3. ) A herbicide containing a pyridyloxybenzoic acid amide derivative represented by: