JP2723554B2 - Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredient - Google Patents
Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredientInfo
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- JP2723554B2 JP2723554B2 JP25305588A JP25305588A JP2723554B2 JP 2723554 B2 JP2723554 B2 JP 2723554B2 JP 25305588 A JP25305588 A JP 25305588A JP 25305588 A JP25305588 A JP 25305588A JP 2723554 B2 JP2723554 B2 JP 2723554B2
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- general formula
- agricultural
- derivative
- triazole derivative
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、植物病害を防除する作用を有する活性成分
としての有用性を有するアシル化トリアゾール誘導体と
その製造法及び該アシル化トリアゾール誘導体を活性成
分として含有する農園芸用殺菌剤に関する。Description: TECHNICAL FIELD The present invention relates to an acylated triazole derivative having utility as an active ingredient having a function of controlling plant diseases, a method for producing the same, and the acylated triazole derivative as an active ingredient. The present invention relates to an agricultural and horticultural fungicide to be contained.
従来の技術 現在、種々の植物病害の農作物を与える損害は莫大な
ものがあり、また農薬による環境汚染の問題もしばしば
話題として取り上げられ、人々の関心を集めてきた。従
って、人畜、鳥類及び魚類に対する毒性が低く、有用植
物に対する薬害の少い、即取扱い上での安全性が高く環
境に対する影響が少く、しかも広範な植物病害に対して
優れた防除効果を示す農園芸用殺菌剤が求められてき
た。2. Description of the Related Art At present, the damage of crops caused by various plant diseases is enormous, and the problem of environmental pollution caused by pesticides has often been taken up as a topic, and has attracted people's attention. Therefore, it has low toxicity to humans, birds and fish, low phytotoxicity to useful plants, high safety in immediate handling, little impact on the environment, and excellent control of a wide range of plant diseases. Horticultural fungicides have been sought.
このような農園芸用殺菌剤としてトリアゾール誘導体
がすぐれた効果を有することが示されている。（特開昭
62−149667,特開昭63−156782。） 本発明者等は更に人畜等に対する毒性が低く取り扱い
上での安全性が高く、かつ広範な植物病害に対して優れ
た防除効果を示すアゾール誘導体について研究を行い、
多数のアゾール誘導体を合成し、それらの実用性につい
て検討を行った結果、アシル化トリアゾール誘導体が上
述した特性を有することを見出し、本発明をなすに至っ
た。It has been shown that triazole derivatives have excellent effects as such agricultural and horticultural fungicides. (JP
62-149667, JP-A-63-156782. The present inventors have further studied azole derivatives having low toxicity to humans and animals, high safety in handling, and an excellent control effect on a wide range of plant diseases,
As a result of synthesizing a large number of azole derivatives and examining their practicality, they have found that acylated triazole derivatives have the above-described properties, and have accomplished the present invention.
すなわち、本発明の目的は、農園芸用殺菌剤の活性成
分として有用な新規アシル化トリアゾール誘導体とその
製造法及び該アシル化トリアゾール誘導体を活性成分と
して含有する広汎な植物病害に対して優れた防除効果を
奏する農園芸用殺菌剤を提供することにある。That is, an object of the present invention is to provide a novel acylated triazole derivative useful as an active ingredient of an agricultural and horticultural fungicide, a method for producing the same, and excellent control of a wide range of plant diseases containing the acylated triazole derivative as an active ingredient. It is an object of the present invention to provide an agricultural and horticultural fungicide which is effective.
問題点を解決するための手段 本発明は 下記一般式（Ｉ）で示されるアシル化トリアゾール
誘導体と （式中、Ｘはハロゲン原子、C1〜C4のアルキル基、フェ
ニル基を表わす。またＲはC1〜C3のアルキル基を表わ
す。） 下記一般式（II）で示されるトリアゾール誘導体を （式中、Ｘはハロゲン原子、C1〜C4のアルキル基、フェ
ニル基を表わす。） 触媒の存在下に下記一般式（III）で示される酸無水
物とを反応させることにより上記一般式（Ｉ）で示され
るアシル化トリアゾール誘導体を製造する方法 Ｒ−CO−Ｏ−CO−Ｒ （III） （式中、ＲはC1〜C3のアルキル基を表わす。） 及び 上記一般式（Ｉ）で示されるアシル化トリアゾール
誘導体を活性成分として含有する農園芸用殺菌剤であ
る。Means for Solving the Problems The present invention relates to an acylated triazole derivative represented by the following general formula (I): (Wherein, X is a halogen atom, an alkyl group of C 1 -C 4, a phenyl group. The R represents an alkyl group of C 1 -C 3.) The triazole derivative represented by the following general formula (II) (In the formula, X represents a halogen atom, a C 1 -C 4 alkyl group, or a phenyl group.) By reacting with an acid anhydride represented by the following general formula (III) in the presence of a catalyst, method (wherein, R represents an alkyl group of C 1 ~C 3.) R- CO-O-CO-R (III) to produce the acylated triazole derivative represented by formula (I) and the general formula (I ) Is an agricultural and horticultural fungicide containing an acylated triazole derivative represented by the formula (1) as an active ingredient.
本発明に係る上記アシル化トリアゾール誘導体は文献
未載の新規化合物であって、それを例示すると表１に示
すとおりであるが、これに限定されるものではない。The above-mentioned acylated triazole derivative according to the present invention is a novel compound not described in any literature, and examples thereof are shown in Table 1, but are not limited thereto.
その理化学的性質を表１に併記する。 The physicochemical properties are also shown in Table 1.
表１に示した各化合物のNMRスペクトルはTMSを内部基
準にして測定し、下記の記号で示した。 The NMR spectrum of each compound shown in Table 1 was measured using TMS as an internal standard, and indicated by the following symbols.
ｓ…一重線、ｄ…二重線、ｔ…三重線、ｍ…多重線、
ｂ…ブロードライン、Ｊ…カップリング定数（単位、H
z） なお、表１に例示した各化合物の赤外吸収スペクトル
を添付図（第１図〜第６図）に示した。s: singlet, d: doublet, t: triplet, m: multiplet,
b: Broad line, J: Coupling constant (unit, H
z) The infrared absorption spectrum of each compound exemplified in Table 1 is shown in the attached drawings (FIGS. 1 to 6).
本発明に係る上記の一般式（Ｉ）で示されるアシル化
トリアゾール誘導体は下記方法により製造される。The acylated triazole derivative represented by the above general formula (I) according to the present invention is produced by the following method.
前記一般式（II）で示されるトリアゾール誘導体を希
釈剤および触媒の存在下に、前記一般式（III）で示さ
れる酸無水物と反応させることにより、前記一般式
（Ｉ）で示される目的のアシル化トリアゾール誘導体が
得られる。By reacting the triazole derivative represented by the general formula (II) with an acid anhydride represented by the general formula (III) in the presence of a diluent and a catalyst, the objective compound represented by the general formula (I) is obtained. An acylated triazole derivative is obtained.
ここで出発物質として用いる一般式（II）で示される
トリアゾール誘導体は、公知化合物であって、特開昭62
−149667に記載されている化合物が使用され得る。The triazole derivative represented by the general formula (II) used as a starting material here is a known compound and is disclosed in
The compounds described in -149667 may be used.
本発明に係る一般式（Ｉ）で示される化合物は一般式
（II）および一般式（III）で示される化合物を希釈剤
の存在で反応させることが好ましい。一般式（II）で示
される化合物としては無水酢酸，無水プロピオン酸，無
水酪酸等が好ましく使用される。希釈剤としてはベンゼ
ン，トルエン，キシレン，ヘキサン等の炭化水素類；塩
化メチレン，クロロホルム，四塩化炭素等のハロゲン化
炭化水素類；ジエチルエーテル，ジイソプロピルエーテ
ル，テトラヒドロフラン等のエーテル類を例示し得る。The compound represented by the general formula (I) according to the present invention is preferably reacted with the compounds represented by the general formulas (II) and (III) in the presence of a diluent. As the compound represented by the general formula (II), acetic anhydride, propionic anhydride, butyric anhydride and the like are preferably used. Examples of the diluent include hydrocarbons such as benzene, toluene, xylene, and hexane; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; and ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran.
希釈剤を使用せず一般式（III）で示される酸無水物
を溶媒として利用するということも可能である。この場
合には一般式（III）で示される酸無水物を適当に過剰
量使用する必要がある。It is also possible to use an acid anhydride represented by the general formula (III) as a solvent without using a diluent. In this case, it is necessary to use an appropriate excess of the acid anhydride represented by the general formula (III).
なお、本発明に係る一般式（Ｉ）の製造法では例えば
トリエチルアミン，ピリジン,N,N−ジメチル−４−ピリ
ジンアミンの如き触媒を使用することが好ましく、特に
トリエチルアミンとN,N−ジメチル−４−ピリジンアミ
ンの両者を併用することが好ましい。In the production method of the general formula (I) according to the present invention, it is preferable to use a catalyst such as, for example, triethylamine, pyridine, N, N-dimethyl-4-pyridineamine, and in particular, triethylamine and N, N-dimethyl-4. It is preferable to use both of -pyridineamine.
本発明に係る製造法を実施するには例えば前記一般式
（II）で示されるトリアゾール類を前記の希釈剤に溶か
したものに前記一般式（III）で示される酸無水物を一
般式（II）で示される化合物に対して1.0〜3.0当量、前
記の触媒を0.04〜2.0当量それぞれ加えて反応させるこ
とが好ましい。また前記の希釈剤の代わりに、前記一般
式（III）で示される酸無水物を用いてもよい。In order to carry out the production method according to the present invention, for example, a triazole represented by the above general formula (II) is dissolved in the above diluent and an acid anhydride represented by the above general formula (III) is mixed with the acid anhydride represented by the above general formula (II). It is preferable to add 1.0 to 3.0 equivalents of the compound represented by the formula (1) and 0.04 to 2.0 equivalents of the above-mentioned catalyst, respectively, to carry out the reaction. Further, an acid anhydride represented by the general formula (III) may be used in place of the diluent.
この際の反応温度は溶媒としての希釈剤の凝固点から
沸点までの任意の温度を適用し得るが、０℃乃至50℃の
範囲の温度で反応を行うことが好ましい。また反応時間
は10〜30時間の範囲であって、攪拌下に反応を行うこと
が好ましい。The reaction temperature at this time may be any temperature from the freezing point to the boiling point of the diluent as a solvent, but the reaction is preferably performed at a temperature in the range of 0 ° C to 50 ° C. The reaction time is in the range of 10 to 30 hours, and the reaction is preferably performed with stirring.
上記反応の終了後、得られた反応混合物を、氷水中に
注ぎ、酢酸エチル，クロロホルム，ベンゼン等の有機溶
剤により抽出して有機層を分離し、次いで該有機層を酸
水溶液，アルカリ水溶液，飽和食塩水でそれぞれ洗浄し
て乾燥した後、溶媒を減圧下に留去し、得られた残渣を
精製処理することにより、目的とする化合物を得る。な
お精製処理はシリカゲルカラムクロマトグラフィー等に
付することにより行い得る。After the completion of the above reaction, the obtained reaction mixture was poured into ice water, extracted with an organic solvent such as ethyl acetate, chloroform, benzene or the like to separate an organic layer. After washing with a saline solution and drying, the solvent is distilled off under reduced pressure, and the obtained residue is purified to obtain the target compound. The purification treatment can be performed by subjecting to silica gel column chromatography or the like.
次に、本発明に係る前記一般式（Ｉ）を有するアシル
化トリアゾール誘導体の農園芸用殺菌剤の活性成分とし
ての有用性について説明する。Next, the usefulness of the acylated triazole derivative having the general formula (I) according to the present invention as an active ingredient of an agricultural and horticultural fungicide will be described.
上記アシル化トリアゾール誘導体は下記に示す広範囲
な植物病害に対して優れた防除効果を奏する。The acylated triazole derivative exhibits an excellent controlling effect on a wide range of plant diseases shown below.
イネのいもち病（Pyricularia oryzae）、 イネのごま葉枯病（Cochliobolus miyabeanus）、 イネの白葉枯病（Xanthomonas oryzae）、 イネの紋枯病（Rhizoctonia solani）、 イネの小黒菌核病（Helminthosporium sigmoideum）、 イネの馬鹿苗病（Gibberella fujikuroi）、 リンゴのうどんこ病（Podosphaera leucotricha） リンゴの黒星病（Venturia inaequalis）、 リンゴのモニリア病（Monilinia mali）、 リンゴの斑点落葉病（Alternaria mali）、 リンゴの腐らん病（Valsa mali）、 ナシの黒斑病（Alternaria kikuchiana）、 ナシのうどんこ病（Phyllactinia pyri）、 ナシの赤星病（Gymnosporangium asiaticum）、 ナシの黒星病（Venturia nashicola）、 ブドウのうどんこ病（Uncinula necator）、 ブドウのさび病（Phakopsora ampelopsidis）、 ブドウの晩腐病（Glomerella cingulata）、 オオムギのうどんこ病（Erysiphe graminis f.sp.horde
i）、 オオムギの雲形病（Rhynchosporium secalis f.sp.hord
ei）、 オオムギの黒さび病（Puccinia graminis）、 オオムギの黄さび病（Puccinia striiformis）、 コムギの赤さび病（Puccinia recondita）、 コムギの葉枯病（Septoria tritici）、 コムギの黄さび病（Puccinia striiformis）、 コムギのうどんこ病（Erysiphe graminis f.sp.tritic
i）、 ウリ類のうどんこ病（Sphaerotheca fuliginea）、 ウリ類の炭そ病（Colletotrichum lagenarium）、 スイカのつる割病（Fusarium oxysporum f.sp.niveu
m）、 キュウリのつる割病（Fusarium oxysporum f.sp.cucume
rinum）、 ダイコンの萎黄病（Fusarium oxysporum f.sp.raphan
i）、 トマトのうどんこ病（Erysiphe cichoracearum）、 トマトの輸紋病（Alternaria solani）、 ナスのうどんこ病（Erysiphe cichoracearum）、 イチゴのうどんこ病（Sphaerotheca humuli）、 タバコのうどんこ病（Erysiphe cichoracearum）、 タバコの赤星病（Alternaria longipes）、 テンサイの褐斑病（Cercospora beticola）、 ジャガイモの夏疫病（Alternaria solani）、 ダイズの褐紋病（Septoria glycines）、 ダイズの紫斑病（Cercospora kikuchii）、 核果類果樹の灰星病（Monilinia fructicola）、 種々の作物をおかす灰色かび病（Botrytis cinerea）及
び 菌核病（Sclerotinia sclerotiorum） などに対して活性を有する。Rice blast (Pyricularia oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice white blight (Xanthomonas oryzae), rice sheath blight (Rhizoctonia solani), rice small scab (Helminthosporium sigmoideum) , Rice idiot disease (Gibberella fujikuroi), Apple powdery mildew (Podosphaera leucotricha) Apple scab (Venturia inaequalis), Apple monilia disease (Monilinia mali), Apple spot leaf rot (Alternaria mali), Apple Rot rot (Valsa mali), Pear black spot (Alternaria kikuchiana), Pear powdery mildew (Phyllactinia pyri), Pear scab (Gymnosporangium asiaticum), Pear scab (Venturia nashicola), Grape powdery mildew (Uncinula necator), Grape rust (Phakopsora ampelopsidis), Grape late rot (Glomerella cingulata), Barley powdery mildew (Erysiphe graminis f.sp.horde)
i), barley scald (Rhynchosporium secalis f.sp.hord)
ei), black rust of barley (Puccinia graminis), yellow rust of barley (Puccinia striiformis), red rust of wheat (Puccinia recondita), leaf wilt of wheat (Septoria tritici), yellow rust of wheat (Puccinia striiformis) ), Wheat powdery mildew (Erysiphe graminis f.sp.tritic)
i), Powdery mildew on cucumber (Sphaerotheca fuliginea), Anthracnose on cucumber (Colletotrichum lagenarium), Fusarium wilt on watermelon (Fusarium oxysporum f.sp.niveu)
m), Cucumber vine disease (Fusarium oxysporum f.sp.cucume
rinum), yellow radish of radish (Fusarium oxysporum f.sp.raphan)
i), Tomato powdery mildew (Erysiphe cichoracearum), Tomato blight (Alternaria solani), Eggplant powdery mildew (Erysiphe cichoracearum), Strawberry powdery mildew (Sphaerotheca humuli), Tobacco powdery mildew (Erysiphe) cichoracearum), tobacco scab (Alternaria longipes), sugar beet brown spot (Cercospora beticola), potato summer blight (Alternaria solani), soybean brown spot (Septoria glycines), soybean purple spot (Cercospora kikuchii), It has activity against ash disease (Monilinia fructicola) on drupe fruits, gray mold disease (Botrytis cinerea) on various crops, and sclerotinia (Sclerotinia sclerotiorum).
前記一般式（Ｉ）で示されるアシル化トリアゾール誘
導体の化合物を農園芸用殺菌剤として適用するには、該
化合物をそのまま、又は担体（希釈剤）と混合して粉
剤、水和剤、粒剤、乳剤、ならびに液剤等の形態として
有利に使用し得る。更に、必要に応じて上記担体のほか
に展着剤、乳化剤、湿展剤、固着剤等の助剤を添加する
ことにより効果を一層確実にすることも勿論可能であ
る。To apply the compound of the acylated triazole derivative represented by the general formula (I) as a fungicide for agricultural and horticultural use, the compound may be used as it is or mixed with a carrier (diluent), powder, wettable powder, granule , Emulsions, and liquid preparations. Further, if necessary, in addition to the above-mentioned carrier, an auxiliary agent such as a spreading agent, an emulsifier, a wetting agent, and a fixing agent may be added to further ensure the effect.
担体（希釈剤）及び助剤の種類、アシル化トリアゾー
ル誘導体との混合比は広い範囲において選択することが
できる。The type of the carrier (diluent) and the auxiliary agent, and the mixing ratio with the acylated triazole derivative can be selected in a wide range.
因に、本化合物は、1,2,4−トリアゾール環を含有し
ているので、無機酸塩、有機酸塩もしくは金属錯塩等の
形態でも使用し得る。Incidentally, since the present compound contains a 1,2,4-triazole ring, it can be used in the form of an inorganic acid salt, an organic acid salt or a metal complex salt.
また、本化合物には、シクロペンタン骨格の１位と２
位に不斉炭素が存在するので、シス体とトランス体の幾
何異性体ならびに光学異性体等の立体異性体が存在し得
るが、本発明ではこれら全ての単独の異性体ならびに各
異性体の任意の比率での混合物をも包含するものであ
る。In addition, the present compound has 1-position and 2-position of the cyclopentane skeleton.
Since there is an asymmetric carbon at the position, stereoisomers such as geometric isomers of cis- and trans-forms and optical isomers may exist. In the present invention, all of these single isomers and any of the respective isomers are optional. And the mixture in the ratio of
したがって、本発明に係る農園芸用殺菌剤は、これら
異性体の単独又は、混合物を活性成分として含有するも
のを包含するものであると理解すべきである。Therefore, it should be understood that the agricultural and horticultural fungicides according to the present invention include those containing these isomers alone or as a mixture as active ingredients.
発明の効果 本発明のアシル化トリアゾール誘導体は一般式（II）
のOH基を に置換した新規なトリアゾール誘導体である。これらの
化合物はそのまま、又は各種担体と混合し種々の形態で
農園芸用殺菌剤として使用することができる。本発明の
農園芸用殺菌剤は後記の実施例から明らかなように、極
めて広範囲の植物病害に対してすぐれた防除効果を奏す
る。しかも植物病害のうち、いくつかの病害に対しては
予防的な防除効果のみならず治療的効果をも奏する。Effect of the Invention The acylated triazole derivative of the present invention has the general formula (II)
Of the OH group Is a novel triazole derivative substituted with These compounds can be used as agricultural or horticultural fungicides as they are or in a mixture with various carriers in various forms. The agricultural and horticultural fungicide of the present invention has an excellent control effect on an extremely wide range of plant diseases, as is apparent from the examples described later. In addition, some of the plant diseases have not only a preventive control effect but also a therapeutic effect.
以下、本発明に係るアシル化トリアゾール誘導体の具
体的な製造法及び該誘導体を活性成分として利用した農
園芸用殺菌剤の具体例を示してその効果を説明する。Hereinafter, the effect of the acylated triazole derivative according to the present invention will be described with reference to a specific production method and a specific example of an agricultural and horticultural fungicide using the derivative as an active ingredient.
実施例１ ｃ−２−［（４−クロロフエニル）メチル］−１−（1H
−1,2,4−トリアゾール−１−イルメチル）−ｒ−１−
シクロペンチルアセテート（表１に示した番号１の化合
物）の製造 ｃ−２−［（４−クロロフエニル）メチル］−１−
（1H−1,2,4−トリアゾール−１−イルメチル）−ｒ−
１−シクロペンタノール500mgに、無水酢酸0.6ml,トリ
エチルアミン0.6ml,N,N−ジメチル−４−ピリジンアミ
ン16mgをそれぞれ加え、室温で14時間攪拌した。Example 1 c-2-[(4-chlorophenyl) methyl] -1- (1H
-1,2,4-triazol-1-ylmethyl) -r-1-
Preparation of cyclopentyl acetate (compound No. 1 shown in Table 1) c-2-[(4-chlorophenyl) methyl] -1-
(1H-1,2,4-triazol-1-ylmethyl) -r-
To 500 mg of 1-cyclopentanol, 0.6 ml of acetic anhydride, 0.6 ml of triethylamine, and 16 mg of N, N-dimethyl-4-pyridineamine were added, and the mixture was stirred at room temperature for 14 hours.
得られた反応混合物を氷水中に注ぎ、酢酸エチルで抽
出して有機層を得、該有機層を1N塩酸，飽和炭酸水素ナ
トリウム水溶液，飽和食塩水でそれぞれ洗浄した後、無
水硫酸ナトリウムで乾燥し、次いで減圧下に溶媒を留去
した。The obtained reaction mixture was poured into ice water and extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with 1N hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, and saturated saline, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure.
得られた残渣をシリカゲルカラムクロマトグラフィー
（展開溶媒:n−ヘキサン：酢酸エチル＝1:1）に付して
精製し、標題化合物270mgを得た。（収率47.6％） このようにして得られた化合物のNMRスペクトルデー
ターを１表に、赤外吸収スペクトルを第１図に示す。The obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 1: 1) to obtain 270 mg of the title compound. (Yield 47.6%) The NMR spectrum data of the compound thus obtained is shown in Table 1, and the infrared absorption spectrum is shown in FIG.
実施例２ ｃ−２−［（４−クロロフエニル）メチル］−１−（1H
−1,2,4−トリアゾール−１−イルメチル）−ｒ−１−
シクロペンチルプロピオネート（表１に示した番号６の
化合物）の製造 ｃ−２−［（４−クロロフエニル）メチル］−１−
（1H−1,2,4−トリアゾール−１−イルメチル）−ｒ−
１−シクロペンタノール500mgに、無水プロピオン酸0.5
ml,トリエチルアミン0.5ml,N,N−ジメチル−４−ピリジ
ンアミン10mgをそれぞれ加え、室温で25時間攪拌した。Example 2 c-2-[(4-chlorophenyl) methyl] -1- (1H
-1,2,4-triazol-1-ylmethyl) -r-1-
Preparation of cyclopentyl propionate (compound No. 6 shown in Table 1) c-2-[(4-chlorophenyl) methyl] -1-
(1H-1,2,4-triazol-1-ylmethyl) -r-
1-cyclopentanol 500 mg, propionic anhydride 0.5
ml, 0.5 ml of triethylamine and 10 mg of N, N-dimethyl-4-pyridineamine were added, and the mixture was stirred at room temperature for 25 hours.
得られた反応混合物を氷水中に注ぎ、酢酸エチルで抽
出して有機層を得、該有機層を1N塩酸，飽和炭酸水素ナ
トリウム水溶液，飽和食塩水でそれぞれ洗浄した後、無
水硫酸ナトリウムで乾燥し、次いで減圧下に溶媒を留去
した。The obtained reaction mixture was poured into ice water and extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with 1N hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, and saturated saline, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure.
得られた残渣をシリカゲルカラムクロマトグラフィー
に付して精製し、標題化合物330mgを得た。（収率55.9
％）。The obtained residue was purified by silica gel column chromatography to obtain 330 mg of the title compound. (Yield 55.9
%).
このようにして得られた化合物のNMRスペクトルデー
ターを１表に、赤外吸収スペクトルを第６図に示す。The NMR spectrum data of the compound thus obtained is shown in Table 1, and the infrared absorption spectrum is shown in FIG.
次に、上記アシル化トリアゾール誘導体を活性成分と
して含有する農園芸用殺菌剤の製剤処方及び病原菌防除
試験例を示す。Next, the formulation of an agricultural and horticultural fungicide containing the acylated triazole derivative as an active ingredient and a test example for controlling pathogenic bacteria will be described.
実施例3:粉 剤 重量部 本発明化合物（化合物番号１） 3 ク レ ー 40 タ ル ク 57 を粉砕混合し、散粉として使用する。Example 3: Powder by weight Compound of the present invention (Compound No. 1) 3 Clay 40 Talk 57 is pulverized and mixed and used as dusting.
実施例4:水和剤 重量部 本発明化合物（化合物番号１） 50 リグニンスルホン酸塩 5 アルキルスルホン酸塩 3 珪 藻 土 42 を粉砕混合して水和剤とし、水で希釈して使用する。Example 4: wettable powder (parts by weight) The compound of the present invention (compound No. 1) 50 ligninsulfonate 5 alkylsulfonate 3 diatomaceous earth 42 is pulverized and mixed to obtain a wettable powder, which is diluted with water and used.
実施例5:粒 剤 重量部 本発明化合物（化合物番号３） 5 ベントナイト 43 ク レ ー 45 リグニンスルホン酸塩 7 を均一に混合し更に水を加えて練り合わせ、押し出し式
造粒機で粒状に加工乾燥して粒剤とする。Example 5: Granules (parts by weight) Compound of the present invention (Compound No. 3) 5 Bentonite 43 Cray 45 Lignin sulfonate 7 is uniformly mixed, further added with water, kneaded, and processed into granules by an extrusion granulator and dried. Into granules.
実施例6:乳 剤 重量部 本発明化合物（化合物番号６） 20 ポリオキシエチレンアルキルアリルエーテル 10 ポリオキシエチレンソルビタンモノラウレート 3 キ シ レ ン 67 を均一に混合溶解して乳剤とする。Example 6: Emulsion Part by weight The compound of the present invention (Compound No. 6) 20 polyoxyethylene alkyl allyl ether 10 polyoxyethylene sorbitan monolaurate 3 xylene 67 are uniformly mixed and dissolved to form an emulsion.
実施例7:コムギ赤さび病防除試験 径10cmの素焼鉢を用いて栽培した第２葉期の幼苗コム
ギ（品種；農林64号、16本／鉢 ３鉢処理区使用）に、
実施例４に示した水和剤形態のものを水で所定濃度に希
釈懸濁し、5ml/鉢の割合で散布した。散布葉風乾後、り
病葉より採取したコムギ赤さび病菌夏胞子の懸濁液を噴
霧接種し20〜23℃高湿度条件下に24時間保った。その後
ガラス温室内に放置し、接種から７〜10日後にコムギ赤
さび病の病斑面積率を調査し、下記式により防除価を算
出した。Example 7: Wheat Leaf Rust Control Test The second leaf stage young seedling wheat (cultivar: Norin 64, 16 / pot, using three pot treatment areas) cultivated using a 10 cm diameter unglazed pot,
The wettable powder shown in Example 4 was diluted and suspended with water at a predetermined concentration, and sprayed at a ratio of 5 ml / pot. After air-spraying of the sprayed leaves, a suspension of euspores of wheat leaf rust collected from the diseased leaves was spray-inoculated and kept at 20 to 23 ° C. under high humidity for 24 hours. Then, it was left in a glass greenhouse, 7 to 10 days after the inoculation, the lesion area ratio of wheat leaf rust was investigated, and the control value was calculated by the following formula.
結果は表２に示す。 The results are shown in Table 2.
実施例8:コムギうどんこ病防除試験 径10cmの素焼体を用いて栽培した第２葉期の幼苗コム
ギ（品種；農林64号、16本／鉢、３鉢 処理区使用）
に、実施例４の如き水和剤形態のものを所定濃度に水で
希釈懸濁し、１鉢当り5ml散布した。散布葉風乾後、り
病葉から採取したコムギうどんこ病菌胞子の懸濁液を噴
霧接種し、20〜24℃高湿度条件下に24時間保ちその後は
温室内に放置した。接種後９〜11日目にコムギうどんこ
病の病斑面積率を調査し、下記式により防除価を算出し
た。 Example 8: Wheat Powdery Mildew Control Test Young seedling wheat of the second leaf stage cultivated using an unglazed body having a diameter of 10 cm (variety: Norin 64, 16 / pot, using three pots in the treatment area)
Then, the wettable powder in the form of Example 4 was diluted and suspended with water to a predetermined concentration, and sprayed at 5 ml per pot. After air-spraying of the sprayed leaves, a suspension of wheat powdery mildew spores collected from the diseased leaves was spray-inoculated, kept at 20 to 24 ° C. under high humidity for 24 hours, and then left in a greenhouse. 9 to 11 days after the inoculation, the lesion area ratio of wheat powdery mildew was investigated, and the control value was calculated by the following formula.
結果は表３に示す。 The results are shown in Table 3.
実施例９ 各種病原菌に対する抗菌性試験 本例は、本発明によるアゾール誘導体の化合物の各種
植物病原菌に対する抗菌性を試験した結果を示したもの
である。 Example 9 Test of antibacterial activity against various pathogenic bacteria This example shows the results of testing the antibacterial activity of the compound of the azole derivative according to the present invention against various plant pathogenic bacteria.
試験方法： 本発明化合物を、所定濃度となるように、ジメチル
スルホキシドに溶解し、その0.6mlと、60℃前後のPSA培
地60mlを100ml三角フラスコ内でよく混合し、シャーレ
内に流し固化させた。一方、予め平板培地上で培養した
供試菌を直径4mmのコルクボーラーでうちぬき、上記の
薬剤含有平板培地上に接種した。接種後、各菌の生育適
温にて１〜３日間培養し、菌の生育を菌そう直径で測定
し、薬剤無添加区における菌の生育と比較して下記式に
従い菌糸伸長抑制率を求めた。Test method: The compound of the present invention was dissolved in dimethyl
The solution was dissolved in sulfoxide, and 0.6 ml of the solution was well mixed with 60 ml of a PSA medium at about 60 ° C. in a 100 ml Erlenmeyer flask. The mixture was poured into a petri dish and solidified. On the other hand, test bacteria previously cultured on a plate medium were punched out with a cork borer having a diameter of 4 mm, and inoculated on the above-mentioned drug-containing plate medium. After inoculation, each strain was cultured at an appropriate growth temperature for 1 to 3 days, the growth of the bacteria was measured by the diameter of the bacteria, and the rate of inhibition of hyphal elongation was determined according to the following formula in comparison with the growth of the bacteria in the drug-free group. .
Ｒ＝100（dc−dt）/dc 式中 R ＝菌糸伸長抑制率（％） dc＝無処理平板上菌そう直径 dt＝薬剤処理平板上菌そう直径 をそれぞれ示す。 R = 100 (dc-dt) / dc In the equation, R = inhibition rate of hyphal elongation (%) dc = bacterial cell diameter on untreated plate dt = bacterial cell diameter on drug-treated plate
結果を次の基準に従って生育阻害度を５段階評価し、
表４に示した。Based on the results, the degree of growth inhibition was evaluated in five steps according to the following criteria.
The results are shown in Table 4.
生育阻害度 ５ 菌糸伸長抑制率が100％〜90％以上のもの ４ 菌糸伸長抑制率が90％未満〜70％以上のもの ３ 菌糸伸長抑制率が70％未満〜40％以上のもの ２ 菌糸伸長抑制率が40％未満〜20％以上のもの １ 菌糸伸長抑制率が20％未満のもの Growth inhibition 5 Hyphal elongation inhibition rate of 100% to 90% or more 4 Hyphal elongation inhibition rate of less than 90% to 70% or more 3 Hyphal elongation inhibition rate of less than 70% to 40% or more 2 Hyphal elongation Inhibition rate of less than 40% to 20% or more 1. Hyphal elongation inhibition rate of less than 20%
添付した図面は本発明に係る表１の化合物番号１〜６の
化合物の赤外吸収スペクトルを示す。 第１図は化合物番号１、第２図は化合物番号２、第３図
は化合物番号３、第４図は化合物番号４、第５図は化合
物番号５、第６図は化合物番号６の化合物の赤外吸収ス
ペクトルを示す。The attached drawings show the infrared absorption spectra of the compounds Nos. 1 to 6 in Table 1 according to the present invention. 1 is Compound No. 1, FIG. 2 is Compound No. 2, FIG. 3 is Compound No. 3, FIG. 4 is Compound No. 4, FIG. 5 is Compound No. 5, and FIG. 3 shows an infrared absorption spectrum.
Claims (3)
ニル基を表わす。またＲはC1〜C3のアルキル基を表わ
す） で示されるアシル化トリアゾール誘導体。1. The compound of the general formula (I) (Wherein X represents a halogen atom, a C 1 -C 4 alkyl group or a phenyl group, and R represents a C 1 -C 3 alkyl group).
ニル基を表わす。） で示されるトリアゾール誘導体を触媒の存在下に 一般式（III） Ｒ−CO−Ｏ−CO−Ｒ （III） （式中、ＲはC1〜C3のアルキル基を表わす） で示される酸無水物と反応させることを特徴とする 一般式（Ｉ） （式中、Ｘはハロゲン原子、C1〜C4のアルキル基、フェ
ニル基を表わす。またＲはC1〜C3のアルキル基を表わ
す。） で示されるアシル化トリアゾール誘導体の製造法。2. A compound of the general formula (II) (Wherein, x represents a halogen atom, an alkyl group of C 1 -C 4, a phenyl group.) In the general formula of the triazole derivative in the presence of a catalyst represented (III) R-CO-O -CO-R ( III) (wherein R represents a C 1 -C 3 alkyl group), and reacted with an acid anhydride represented by the following general formula (I): (Wherein, X represents a halogen atom, a C 1 -C 4 alkyl group or a phenyl group. R represents a C 1 -C 3 alkyl group.) A process for producing an acylated triazole derivative represented by the formula:
ニル基を表わす。またＲはC1〜C3のアルキル基を表わ
す。） で示されるアシル化トリアゾール誘導体を活性成分とし
て含有する農園芸用殺菌剤。3. A compound of the general formula (I) (In the formula, x represents a halogen atom, a C 1 -C 4 alkyl group or a phenyl group. R represents a C 1 -C 3 alkyl group.) Agricultural and horticultural fungicides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25305588A JP2723554B2 (en) | 1988-10-07 | 1988-10-07 | Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25305588A JP2723554B2 (en) | 1988-10-07 | 1988-10-07 | Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02101067A JPH02101067A (en) | 1990-04-12 |
| JP2723554B2 true JP2723554B2 (en) | 1998-03-09 |
Family
ID=17245856
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25305588A Expired - Lifetime JP2723554B2 (en) | 1988-10-07 | 1988-10-07 | Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredient |
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|---|---|
| JP (1) | JP2723554B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04202188A (en) * | 1990-11-30 | 1992-07-22 | Kureha Chem Ind Co Ltd | Optically active triazole derivative and agent for agricultural and horticultural use |
| JP2016522800A (en) | 2013-04-12 | 2016-08-04 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | New triazoline thione derivatives |
| US9822099B2 (en) | 2013-04-12 | 2017-11-21 | Bayer Cropscience Aktiengesellschaft | Triazole derivatives |
| EP3201188A1 (en) | 2014-10-02 | 2017-08-09 | Bayer CropScience Aktiengesellschaft | Novel triazole derivatives useful as fungicides |
| WO2016156282A1 (en) | 2015-04-02 | 2016-10-06 | Bayer Cropscience Aktiengesellschaft | Novel triazole compounds for controlling phytopathogenic harmful fungi |
| EA201792151A1 (en) | 2015-04-02 | 2018-04-30 | Байер Кропсайенс Акциенгезельшафт | NEW 5-SUBSTITUTED IMIDAZOLE DERIVATIVES |
| EP3277674B1 (en) | 2015-04-02 | 2019-09-11 | Bayer CropScience Aktiengesellschaft | Triazol derivatives as fungicides |
| EA201990690A1 (en) | 2016-09-13 | 2019-10-31 | COMBINATIONS OF ACTIVE COMPOUNDS CONTAINING A 5-SUBSTITUTED IMIDAZOLE DERIVATIVE | |
| WO2018050535A1 (en) | 2016-09-13 | 2018-03-22 | Bayer Cropscience Aktiengesellschaft | Active compound combinations |
| US20200045972A1 (en) | 2016-09-29 | 2020-02-13 | Bayer Cropscience Aktiengesellschaft | Novel 5-substituted imidazolylmethyl derivatives |
| AR109545A1 (en) | 2016-09-29 | 2018-12-19 | Bayer Cropscience Ag | TRIAZOL DERIVATIVES |
| CN109983000A (en) | 2016-09-29 | 2019-07-05 | 拜耳作物科学股份公司 | The imidazolyl methyl-derivatives that new 5- replaces |
| AR109696A1 (en) | 2016-09-29 | 2019-01-16 | Bayer Cropscience Ag | TRIAZOL DERIVATIVES |
| BR112019006451A2 (en) | 2016-09-29 | 2019-06-25 | Bayer Ag | substituted derivatives of 1.5 imidazoles as fungicides for plant protection. |
| WO2018060076A1 (en) | 2016-09-29 | 2018-04-05 | Bayer Cropscience Aktiengesellschaft | Novel triazole derivatives |
| MX2019003714A (en) | 2016-09-29 | 2019-06-24 | Bayer Cropscience Ag | Novel 5-substituted imidazolylmethyl derivatives. |
| JP2020506950A (en) | 2017-02-08 | 2020-03-05 | バイエル アクチェンゲゼルシャフトＢａｙｅｒ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | Triazolethione derivative |
| WO2019091898A1 (en) | 2017-11-09 | 2019-05-16 | Bayer Aktiengesellschaft | Process for the preparation of 5-substituted imidazole derivatives and manganese compounds useful therefor |
| EP3710432A1 (en) | 2017-11-13 | 2020-09-23 | Bayer Aktiengesellschaft | Tetrazolylpropyl derivatives and their use as fungicides |
| WO2019162228A1 (en) | 2018-02-21 | 2019-08-29 | Bayer Aktiengesellschaft | 1-(5-substituted imidazol-1-yl)but-3-en derivatives and their use as fungicides |
-
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- 1988-10-07 JP JP25305588A patent/JP2723554B2/en not_active Expired - Lifetime
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