JP2002234876A - 6-(1-fluoroethyl)-5-iodo-4-alkylaminopyrimidine derivative, method for producing the same and agricultural/ horticultural pest-controlling agent - Google Patents
6-(1-fluoroethyl)-5-iodo-4-alkylaminopyrimidine derivative, method for producing the same and agricultural/ horticultural pest-controlling agentInfo
- Publication number
- JP2002234876A JP2002234876A JP2001031160A JP2001031160A JP2002234876A JP 2002234876 A JP2002234876 A JP 2002234876A JP 2001031160 A JP2001031160 A JP 2001031160A JP 2001031160 A JP2001031160 A JP 2001031160A JP 2002234876 A JP2002234876 A JP 2002234876A
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- fluoroethyl
- iodo
- compound
- agricultural
- alkylaminopyrimidine
- Prior art date
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、農園芸用の有害生
物防除剤として有用である新規な6−(1−フルオロエ
チル)−5−ヨード−4−アルキルアミノピリミジン誘
導体に関するものである。[0001] The present invention relates to a novel 6- (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative which is useful as a pesticide for agricultural and horticultural use.
【0002】[0002]
【従来の技術】本発明の6−(1−フルオロエチル)−
5−ヨード−4−アルキルアミノピリミジン誘導体は新
規化合物であり、農園芸用の有害生物防除活性を有する
ことも知られていない。BACKGROUND OF THE INVENTION 6- (1-Fluoroethyl)-of the present invention
A 5-iodo-4-alkylaminopyrimidine derivative is a novel compound and is not known to have pest control activity for agricultural and horticultural purposes.
【0003】[0003]
【発明が解決しようとする課題】本発明の課題は、新規
な6−(1−フルオロエチル)−5−ヨード−4−アル
キルアミノピリミジン誘導体、その製法及びそれを有効
成分とする農園芸用の有害生物防除剤を提供することで
ある。An object of the present invention is to provide a novel 6- (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative, a method for producing the same and an agricultural and horticultural product containing the same as an active ingredient. It is to provide a pesticide.
【0004】[0004]
【課題を解決するための手段】本発明者らは、前記の課
題を解決するために検討した結果、新規な6−(1−フ
ルオロエチル)−5−ヨード−4−アルキルアミノピリ
ミジン誘導体が顕著な農園芸用の殺虫,殺ダニ,殺線虫
及び殺菌活性を有することを見出し、本発明を完成し
た。即ち、本発明は次の通りである。第1の発明は、次
式(1):The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, a novel 6- (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative is remarkable. The present invention has been found to have an insecticidal, acaricidal, nematicidal and fungicidal activity for agricultural and horticultural purposes, and completed the present invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):
【0005】[0005]
【化4】 Embedded image
【0006】(式中、Rは、炭素原子数1〜20個の直
鎖状又は分岐状アルキル基を表わし;*は、不斉炭素原
子を表わす。)で示される6−(1−フルオロエチル)
−5−ヨード−4−アルキルアミノピリミジン誘導体に
関するものである。第2の発明は次式(2):(Wherein, R represents a linear or branched alkyl group having 1 to 20 carbon atoms; * represents an asymmetric carbon atom). )
It relates to a -5-iodo-4-alkylaminopyrimidine derivative. The second invention provides the following formula (2):
【0007】[0007]
【化5】 Embedded image
【0008】(式中、*は、前記と同義である。)で示
される4−クロロ−6−(1−フルオロエチル)−5−
ヨードピリミジンと次式(3):(Wherein * has the same meaning as described above.) 4-chloro-6- (1-fluoroethyl) -5-
Iodopyrimidine and the following formula (3):
【0009】[0009]
【化6】 Embedded image
【0010】(式中、Rは、前記と同義である。)で示
されるアルキルアミン類とを反応させることを特徴とす
る前記の式(1)で示される6−(1−フルオロエチ
ル)−5−ヨード−4−アルキルアミノピリミジン誘導
体の製法に関するものである。第3の発明は、前記の式
(1)で示される6−(1−フルオロエチル)−5−ヨ
ード−4−アルキルアミノピリミジン誘導体を有効成分
とする農園芸用の有害生物防除剤に関するものである。Wherein R is as defined above, and reacted with an alkylamine represented by the formula (1), wherein 6- (1-fluoroethyl)- The present invention relates to a method for producing a 5-iodo-4-alkylaminopyrimidine derivative. The third invention relates to a pesticide for agricultural and horticultural use containing a 6- (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative represented by the above formula (1) as an active ingredient. is there.
【0011】[0011]
【発明の実施の形態】以下、本発明について詳細に説明
する。前記の各化合物で表した各種の置換基は、次の通
りである。Rは炭素原子数1〜20個の直鎖状又は分岐
状アルキル基である。*は、不斉炭素原子である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The various substituents represented by the above compounds are as follows. R is a linear or branched alkyl group having 1 to 20 carbon atoms. * Is an asymmetric carbon atom.
【0012】Rにおける炭素原子数1〜20個のアルキ
ル基としては、直鎖状又は分岐状のアルキル基を挙げる
ことができるが;i−プロピル基,sec−ブチル基,
n−アミル基,n−オクチル基,2−エチルヘキシル
基,n−ノニル基,n−デシル基,1−エチルノニル
基,n−テトラデシル基が好ましい。Examples of the alkyl group having 1 to 20 carbon atoms for R include a linear or branched alkyl group; i-propyl group, sec-butyl group,
An n-amyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 1-ethylnonyl group and n-tetradecyl group are preferred.
【0013】本発明の化合物(1)はアミノ基を有して
いるので、これに由来する酸付加塩も本発明に含まれ
る。酸付加塩を形成する酸としては、例えば、塩酸,臭
化水素酸,硝酸,硫酸,リン酸などの無機酸;ギ酸,シ
ュウ酸,フマル酸,アジピン酸,ステアリン酸,オレイ
ン酸,アコニット酸などのカルボン酸;メタンスルホン
酸,ベンゼンスルホン酸、p−トルエンスルホン酸など
のスルホン酸;サッカリンなどを挙げることができる。Since the compound (1) of the present invention has an amino group, an acid addition salt derived therefrom is also included in the present invention. Examples of the acid forming an acid addition salt include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, and phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, aconitic acid, and the like. And sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; and saccharin.
【0014】また、本発明の化合物(1)は*で示した
不斉炭素原子原子を含むので、これらに由来する個々の
光学異性体、ラセミ体,ジアステレオマー体又はそれら
の混合物のいずれも本発明に含まれる。前記の本発明の
化合物(1)の合成法を、さらに詳細に述べる。 〔合成法〕合成法は、化合物(2)と化合物(3)と
を、溶媒中、塩基存在下で反応させて化合物(1)を得
る方法である。Since the compound (1) of the present invention contains an asymmetric carbon atom indicated by *, any of the individual optical isomers, racemates, diastereomers or mixtures thereof derived therefrom Included in the present invention. The synthesis of the compounds of the present invention of (1), described in further detail. [Synthesis method] The synthesis method is a method of reacting compound (2) with compound (3) in a solvent in the presence of a base to obtain compound (1).
【0015】溶媒の種類としては、本反応に直接関与し
ないものであれば特に限定されず、例えば、ベンゼン,
トルエン,キシレン,メチルナフタリン,石油エーテ
ル,リグロイン,ヘキサン,クロルベンゼン,ジクロル
ベンゼン,クロロホルム,ジクロルエタン,トリクロル
エチレンのような塩素化された又はされていない芳香
族、脂肪族、脂環式の炭化水素類;テトラヒドロフラ
ン,シオキサン,ジエチルエーテルなどのようなエーテ
ル類;アセトニトリル,プロピオニトリルなどのような
ニトリル類;アセトン,メチルエチルケトンなどのよう
なケトン類;N,N−ジメチルホルムアミド,ジメチル
スルフォキシド,スルフォラン,N,N−ジメチルイミ
ダゾリジノン,N−メチルピロリドンなどのような非プ
ロトン性極性溶媒;及び前記溶媒の混合物などを挙げる
ことができる。The type of the solvent is not particularly limited as long as it does not directly participate in the present reaction.
Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic hydrocarbons such as toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, chloroform, dichloroethane, trichloroethylene Ethers such as tetrahydrofuran, siloxane, diethyl ether, etc .; nitriles such as acetonitrile, propionitrile, etc .; ketones such as acetone, methyl ethyl ketone, etc .; N, N-dimethylformamide, dimethyl sulfoxide, sulfolane , N, N-dimethylimidazolidinone, N-methylpyrrolidone and the like; aprotic polar solvents; and mixtures of the above solvents.
【0016】溶媒の使用量は、化合物(2)が5〜80
重量%になるようにして使用することができるが;10
〜70重量%が好ましい。塩基の種類としては、特に限
定されず、有機及び無機塩基、例えばトリエチルアミン
のような第3級アミン、DBUなどの有機塩基、アルカ
リ金属及びアルカリ土類金属の水素化物、水酸化物、炭
酸塩、炭酸水素塩などの無機塩基を挙げることができる
が;トリエチルアミンのような有機塩基が好ましい。塩
基の使用量は、化合物(2)に対して1〜5倍モルであ
るが;1.2〜2.0倍モルが好ましい。The amount of the solvent used is such that the compound (2)
Weight percent can be used; however, 10
~ 70% by weight is preferred. The type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, organic bases such as DBU, hydrides, hydroxides, carbonates of alkali metals and alkaline earth metals, Mention may be made of inorganic bases such as hydrogen carbonate; organic bases such as triethylamine are preferred. The amount of the base to be used is 1 to 5 moles compared to the compound (2); preferably 1.2 to 2.0 moles.
【0017】反応温度は、特に限定されないが、室温か
ら使用する溶媒の沸点以下の温度範囲内であり;60〜
110℃が好ましい。反応時間は、前記の濃度,温度に
よって変化するが;通常0.5〜8時間である。原料化
合物の使用量は、化合物(2)に対して化合物(3)
が、1.0〜5倍モルであるが;1〜1.1倍モルが好
ましい。本発明で用いる化合物(2)は、特願2000
−384776号公報の記載に準じて次式に示す方法で
製造することができる。The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower;
110 ° C. is preferred. The reaction time varies depending on the above concentration and temperature; it is usually 0.5 to 8 hours. The amount of the starting compound used is the compound (3) based on the compound (2).
Is 1.0 to 5 times mol; preferably 1 to 1.1 times mol. Compound (2) used in the present invention is described in
It can be manufactured by the method shown in the following formula according to the description of JP-384776.
【0018】[0018]
【化7】 Embedded image
【0019】(式中、*は、前記と同義である。) 化合物(4)は、例えば、特開平−171834号公報
に記載の方法に準じて、次式に示す方法で製造できる。(In the formula, * has the same meaning as described above.) The compound (4) can be produced, for example, by the method shown in the following formula according to the method described in JP-A-171834.
【0020】[0020]
【化8】 Embedded image
【0021】化合物(3)は、市販品を使用するか、又
は次式に示す方法によって製造することができる。Compound (3) can be a commercially available product or can be produced by the method shown in the following formula.
【0022】[0022]
【化9】 Embedded image
【0023】(式中、Rは、前記と同義であり、Xはク
ロル原子又はブロモ原子を表す。) 以上のようにして製造された目的の化合物(1)は、反
応終了後、抽出,濃縮,ロ過などの通常の後処理を行
い、必要に応じて再結晶,各種クロマトグラフィーなど
の公知の手段で適宣精製することができる。(Wherein, R has the same meaning as described above, and X represents a chloro atom or a bromo atom.) The target compound (1) produced as described above is extracted and concentrated after completion of the reaction. After the usual post-treatments such as filtration and filtration, if necessary, purification can be carried out by known means such as recrystallization and various types of chromatography.
【0024】〔防除効果〕本発明の化合物(1)で防除
効果が認められる農園芸用有害生物としては、農園芸害
虫〔例えば、半翅目(ウンカ類,ヨコバイ類,アブラム
シ類,コナジラミ類など)、鱗翅目(ヨトウムシ類,コ
ナガ,ハマキムシ類,メイガ類,シンクイムシ類,モン
シロチョウなど)、鞘翅目(ゴミムシダマシ類,ゾウム
シ類,ハムシ類,コガネムシ類など)、ダニ目(ハダニ
科のミカンハダニ,ナミハダニなど、フシダニ科のミカ
ンサビダニなど)〕、線虫(ネコブセンチュウ,シスト
センチュウ,ネグサレセンチュウ,シンガレセンチュ
ウ,マツノザイセンチュウなど)、ネダニ、衛生害虫
(例えば、ハエ,カ,ゴキブリなど)、貯蔵害虫(例え
ば、コクヌストモドキ類,マメゾウムシ類など)、木材
害虫(例えば、イエシロアリ,ヤマトシロアリ,ダイコ
クシロアリなどのシロアリ類、ヒラタキクイムシ類、シ
バンムシ類、シンクイムシ類、カミキリムシ類、キクイ
ムシ類など)を挙げることができ、また、農園芸病原菌
(例えば、コムギ赤さび病,大麦うどんこ病,キュウリ
べと病,イネいもち病,トマト疫病など)を挙げること
ができる。[Pest control effect] The pests for agricultural and horticultural use which are effective in controlling the compound (1) of the present invention include agricultural and horticultural pests such as Hemiptera (Cyberidae, leafhoppers, aphids, whiteflies, etc.). ), Lepidoptera (Coleoptera, Scarabaeidae, Coleoptera, Scarabaeidae, Scarabaeidae, White butterfly), Coleoptera (Tenebrionidae, Weevil, Chrysomelidae, Scarabaeidae, etc.), Acaridae (Acari (Acari: Tetranychidae, Tetranychidae), etc.) ), Nematodes (e.g., root-knot nematodes, cyst nematodes, nexare nematodes, singare nematodes, pine wood nematodes), nematodes, sanitary pests (e.g., fly, mosquito, cockroach, etc.), storage pests (e.g. For example, woodpeckers, beetles and the like, wood pests (for example, Examples include termites such as ants, Yamato termites, and beetle termites, leaf bark beetles, beetles, beetles, sink beetles, longhorn beetles, bark beetles, etc., and agricultural and horticultural pathogens (eg, wheat leaf rust, barley udonko) Disease, cucumber downy mildew, rice blast, tomato late blight, etc.).
【0025】〔有害生物防除剤〕本発明の農園芸用の有
害生物防除剤は、特に、殺虫・殺ダニ及び殺線虫効果が
顕著であり、化合物(1)の1種以上を有効成分として
含有するものである。化合物(1)は、単独で使用する
こともできるが、通常は常法によって、担体,界面活性
剤,分散剤,補助剤などを配合(例えば、粉剤,乳剤,
微粒剤,粒剤,水和剤,油性の懸濁液,エアゾールなど
の組成物として調製する)して使用することが好まし
い。[Pest control agent] The pest control agent for agricultural and horticultural use of the present invention has a remarkable insecticidal / miticidal and nematicidal effect, and contains at least one compound (1) as an active ingredient. It contains. The compound (1) can be used alone, but is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powder, emulsion,
(Prepared as a composition such as fine granules, granules, wettable powders, oily suspensions, and aerosols).
【0026】担体としては、例えば、タルク,ベントナ
イト,クレー,カオリン,ケイソウ土,ホワイトカーボ
ン,バーミキュライト,消石灰,ケイ砂,硫安,尿素な
どの固体担体;炭化水素(ケロシン,鉱油など)、芳香
族炭化水素(ベンゼン,トルエン,キシレンなど)、塩
素化炭化水素(クロロホルム,四塩化炭素など)、エー
テル類(ジオキサン,テトラヒドロフランなど)、ケト
ン類(アセトン,シクロヘキサノン,イソホロンな
ど)、エステル類(酢酸エチル,エチレングリコールア
セテート,マレイン酸ジブチルなど)、アルコール類
(メタノール,n−ヘキサノール,エチレングリコール
など)、極性溶媒(ジメチルホルムアミド,ジメチルス
ルホキシドなど)、水などの液体担体;空気,窒素,炭
酸ガス,フレオンなどの気体担体(この場合には、混合
噴射することができる)などを挙げることがでる。Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbon Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.
【0027】本剤の動植物への付着,吸収の向上,薬剤
の分散,乳化,展着などの性能を向上させるために使用
できる界面活性剤や分散剤としては、例えば、アルコー
ル硫酸エステル類,アルキルスルホン酸塩,リグニンス
ルホン酸塩,ポリオキシエチレングリコールエーテルな
どを挙げることができる。そして、その製剤の性状を
改善するためには、例えば、カルボキシメチルセルロー
ス,ポリエチレングリコール,アラビアゴムなどを補助
剤として用いることができる。本剤の製造では、前記の
担体,界面活性剤,分散剤及び補助剤をそれぞれの目的
に応じて、各々単独で又は適当に組み合わせて使用する
ことができる。Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion, emulsification, and spreading of drugs include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. And the properties of the formulation
For improvement, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as adjuvants. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes.
【0028】本発明の化合物(1)を製剤化した場合の
有効成分濃度は、乳剤では通常1〜50重量%,粉剤で
は通常0.3〜25重量%,水和剤では通常1〜90重
量%,粒剤では通常0.5〜5重量%,油剤では通常
0.5〜5重量%,エアゾールでは通常0.1〜5重量
%である。これらの製剤を適当な濃度に希釈して、それ
ぞれの目的に応じて、植物茎葉,土壌,水田の水面に散
布するか、又は直接施用することによって各種の用途に
供することができる。When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% by weight for wettable powders. % For granules, usually 0.5 to 5% by weight for oils, usually 0.5 to 5% by weight for oils, and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.
【0029】[0029]
【実施例】以下、本発明を参考例及び実施例によって具
体的に説明する。なお、これらは、本発明の範囲を限定
するものではない。 参考例1〔化合物(5)の合成法〕 6−(1−フルオロエチル)−4−ピリミドンの合成 4−フルオロ−3−オキソペンタン酸メチルエステル
(93.3g)をメタノール(1000ml)に溶解
し、28%ナトリウムメチラート/メタノール溶液(3
65g)とホルムアミジン酢酸塩(98.4g)を順次
加え、40℃で12時間加熱還流した。反応終了後、1
0℃以下に冷却し、濃硫酸(95.1g)と水(85
g)の混合液を添加した。次いで、50℃で30分撹拌
し、不溶物を濾別し、濾液を減圧下に濃縮した。得られ
た残渣をイソプロパノールで再結晶することによって、
無色結晶である目的化合物を58g得た。 m.p.170.0〜171.5℃EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these do not limit the scope of the present invention. Reference Example 1 [Synthesis of Compound (5)] Synthesis of 6- (1-fluoroethyl) -4-pyrimidone Methyl 4-fluoro-3-oxopentanoate (93.3 g) was dissolved in methanol (1000 ml). , 28% sodium methylate / methanol solution (3
65 g) and formamidine acetate (98.4 g) were sequentially added, and the mixture was heated under reflux at 40 ° C. for 12 hours. After the reaction is over, 1
After cooling to 0 ° C. or less, concentrated sulfuric acid (95.1 g) and water (85
g) was added. Then, the mixture was stirred at 50 ° C. for 30 minutes, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure. By recrystallizing the obtained residue with isopropanol,
58 g of the target compound as colorless crystals was obtained. m. p. 170.0-171.5 ° C
【0030】参考例2〔化合物(6)の合成法〕 6−(1−フルオロエチル)−5−ヨード−4−ピリミ
ドンの合成 ヨード(50.8g)を酢酸(500ml)に加え、室
温撹拌下に塩素(15g)を吹き込み調製した1塩化ヨ
ウ素の酢酸溶液を、6−(1−フルオロエチル)−4−
ピリミドン(56.8g)の酢酸(150ml)溶液に
室温撹拌下に滴下し、6時間撹拌した。反応終了後、減
圧下に酢酸を留去し、水(300ml)を加え溶解し、
2N水酸化ナトリウム及び飽和炭酸水素ナトリウム水溶
液でpH5に調整する。析出した結晶を濾集し、水洗、
乾燥し、淡黄土色結晶の目的物85gを得た。更に、酢
酸エチル−ヘキサンによる再結晶で精製することによっ
て、無色小針状結晶である目的化合物を76.0g得
た。 m.p.195〜196℃Reference Example 2 [Synthesis of Compound (6)] Synthesis of 6- (1-fluoroethyl) -5-iodo-4-pyrimidone Iodine (50.8 g) was added to acetic acid (500 ml), and the mixture was stirred at room temperature. Acetic acid solution of iodine monochloride prepared by blowing chlorine (15 g) into 6- (1-fluoroethyl) -4-
The solution was added dropwise to a solution of pyrimidone (56.8 g) in acetic acid (150 ml) with stirring at room temperature, and the mixture was stirred for 6 hours. After the completion of the reaction, acetic acid was distilled off under reduced pressure, and water (300 ml) was added to dissolve.
Adjust to pH 5 with 2N sodium hydroxide and saturated aqueous sodium bicarbonate. The precipitated crystals are collected by filtration, washed with water,
After drying, 85 g of the target product as pale ocher crystals was obtained. Further, the residue was purified by recrystallization from ethyl acetate-hexane to obtain 76.0 g of the target compound as colorless small needle crystals. m. p. 195-196 ° C
【0031】参考例3〔化合物(2)の合成法〕 4−クロロ−6−(1−フルオロエチル)−5−ヨード
ピリミジンの合成 6−(1−フルオロエチル)−5−ヨード−4−ピリミ
ドン(53.6g)を酢酸エチル(180ml)に加
え、N,N−ジメチルフォルムアミド(1.5g)を添
加し、70℃に加温撹拌する。次いで、チオニルクロラ
イド(28.6g)を滴下し、3時間撹拌して反応を完
結した。反応混合物冷却後、氷冷水に加え、2N水酸化
ナトリウムでpH4に調整し、酢酸エチル層を分取し、
水洗、無水硫酸ナトリウムで乾燥した。次いで、減圧下
溶媒を留去し、得られた残渣を減圧蒸留で精製すること
によって、淡黄色液体である目的物を54.6g得た。 b.p.116〜118℃/4mmHgReference Example 3 [Synthesis of compound (2)] Synthesis of 4-chloro-6- (1-fluoroethyl) -5-iodopyrimidine 6- (1-fluoroethyl) -5-iodo-4-pyrimidone (53.6 g) was added to ethyl acetate (180 ml), N, N-dimethylformamide (1.5 g) was added, and the mixture was heated and stirred at 70 ° C. Next, thionyl chloride (28.6 g) was added dropwise, and the mixture was stirred for 3 hours to complete the reaction. After cooling the reaction mixture, the mixture was added to ice-cold water, adjusted to pH 4 with 2N sodium hydroxide, and the ethyl acetate layer was separated.
Washed with water and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure, and the obtained residue was purified by vacuum distillation to obtain 54.6 g of the desired product as a pale yellow liquid. b. p. 116-118 ° C / 4mmHg
【0032】実施例1〔化合物(1)の合成法〕 (1)6−(1−フルオロエチル)−5−ヨード−4−
(i−プロピルアミノ)ピリミジン(化合物4)の合成 i−プロピルアミン(0.4g)とトリエチルアミン
(0.6g)をトルエン20mlに溶解し、4−クロロ
−6−(1−フルオロエチル)−5−ヨードピリミジン
(1.5g)を加え、約80℃で3時間加熱撹拌した。
反応終了後、トリエチルアミン塩酸塩を濾別し、減圧下
溶媒を留去し、得られた残渣をシリカゲルカラムクロマ
トグラフィー(ワコーゲルC−200,n−ヘキサン:
酢酸エチル=3:1溶出)で精製することによって、無
色粉状結晶である目的物を1.4g得た。Example 1 [Synthesis of Compound (1)] (1) 6- (1-Fluoroethyl) -5-iodo-4-
Synthesis of (i-propylamino) pyrimidine (compound 4) i-propylamine (0.4 g) and triethylamine (0.6 g) were dissolved in 20 ml of toluene, and 4-chloro-6- (1-fluoroethyl) -5 was dissolved. -Iodopyrimidine (1.5 g) was added, and the mixture was heated and stirred at about 80 ° C for 3 hours.
After completion of the reaction, triethylamine hydrochloride was separated by filtration, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C-200, n-hexane:
Purification with ethyl acetate (3: 1 elution) yielded 1.4 g of the desired product as colorless powdery crystals.
【0033】m.p.88〜90℃1 H−NMR(CDCl3,δppm) 1.26〜1.28(6H,d)、1.59〜1.71
(3H,d−d)、4.25〜4.36(1H,m)、
5.39(1H,b)、5.68〜5.90(1H,d
−q)、8.52(1H,s)、M. p. 88 to 90 ° C 1 H-NMR (CDCl 3 , δ ppm) 1.26 to 1.28 (6H, d), 1.59 to 1.71
(3H, dd), 4.25 to 4.36 (1H, m),
5.39 (1H, b), 5.68 to 5.90 (1H, d
-Q), 8.52 (1H, s),
【0034】(2)6−(1−フルオロエチル)−5−ヨ
ード−4−(n−テトラデシルアミノ)ピリミジン(化
合物16)の合成 n−テトラデシルアミン(1.1g)とトリエチルアミ
ン(0.6g)をトルエン20mlに溶解し、4−クロ
ロ−6−(1−フルオロエチル)−5−ヨードピリミジ
ン(1.5g)を加え、約80℃で3時間加熱撹拌し
た。反応終了後、トリエチルアミン塩酸塩を濾別し、減
圧下溶媒を留去し、得られた残渣をシリカゲルカラムク
ロマトグラフィー(ワコーゲルC−200,n−ヘキサ
ン:酢酸エチル=3:1溶出)で精製することによっ
て、淡橙色粉状結晶である目的物を2.1g得た。(2) Synthesis of 6- (1-fluoroethyl) -5-iodo-4- (n-tetradecylamino) pyrimidine (compound 16) n-tetradecylamine (1.1 g) and triethylamine (0.1 g) were used. 6 g) was dissolved in toluene (20 ml), 4-chloro-6- (1-fluoroethyl) -5-iodopyrimidine (1.5 g) was added, and the mixture was heated and stirred at about 80 ° C. for 3 hours. After completion of the reaction, triethylamine hydrochloride was separated by filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (Wakogel C-200, n-hexane: ethyl acetate = 3: 1 elution). As a result, 2.1 g of the target product as pale orange powdery crystals was obtained.
【0035】m.p.35〜36℃1 H−NMR(CDCl3,δppm) 0.86〜0.90(3H,t)、1.26(20H,
s)、1.59〜1.70(4H,m)、3.46〜
3.52(4H,m)、5.59(1H,b)、5.6
8〜5.90(1H,d−q)、8.45(1H,s)M. p. 35-36 ° C. 1 H-NMR (CDCl 3 , δ ppm) 0.86-0.90 (3H, t), 1.26 (20H,
s), 1.59-1.70 (4H, m), 3.46-
3.52 (4H, m), 5.59 (1H, b), 5.6
8 to 5.90 (1H, dq), 8.45 (1H, s)
【0036】(3)表1中のその他の化合物(1)の合成 前記(1)及び(2)に記載の方法に準じて、表1中のその他
の化合物(1)を合成した。以上のように合成した化合
物(1)及びそれらの物性を表1に示す。(3) Synthesis of Other Compound (1) in Table 1 According to the method described in the above (1) and (2), other compound (1) in Table 1 was synthesized. Table 1 shows the compounds (1) synthesized as described above and their physical properties.
【0037】[0037]
【表1】 [Table 1]
【0038】実施例2〔製剤の調製〕 (1)粒剤の調製 化合物(1)を5重量部、ベントナイト35重量部,タ
ルク57重量部,ネオレックスパウダー(商品名;花王
株式会社製)1重量部及びリグニンスルホン酸ソーダ2
重量部を均一に混合し、次いで少量の水を添加して混練
した後、造粒,乾燥して粒剤を得た。Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, Neorex powder (trade name; manufactured by Kao Corporation) 1 Parts by weight and sodium lignin sulfonate 2
The parts by weight were uniformly mixed and then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.
【0039】(2)水和剤の調製 化合物(1)を10重量部,カオリン70重量部,ホワ
イトカーボン18重量部,ネオレックスパウダー(商品
名;花王株式会社製)1.5重量部及びデモール(商品
名;花王株式会社製)0.5重量部を均一に混合し、次
いで粉砕して水和剤を得た。(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neorex powder (trade name, manufactured by Kao Corporation) and Demol 0.5 parts by weight (trade name, manufactured by Kao Corporation) were uniformly mixed and then pulverized to obtain a wettable powder.
【0040】(3)乳剤の調製 化合物(1)を20重量部及びキシレン70重量部に、
トキサノン(商品名;三洋化成工業製)10重量部を加
えて均一に混合し、溶解して乳剤を得た。(3) Preparation of emulsion Compound (1) was added to 20 parts by weight and 70 parts by weight of xylene.
Toxanone (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.) (10 parts by weight) was added, mixed uniformly, and dissolved to obtain an emulsion.
【0041】(4)粉剤の調製 化合物(1)を粉5重量部,タルク50重量部及びカオ
リン45重量部を均一に混合して粉剤を得た。(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of the compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin.
【0042】実施例3〔効力試験〕 (1)アオムシに対する効力試験 実施例2に準じて調製した表1に示す化合物(1)の各
水和剤を界面活性剤(0.01%)を含む水で1000
ppmに希釈し、これら各薬液中にキャベツ葉片(5c
m×5cm)を30秒浸漬し、各プラスチックカップに
一枚ずつ入れて風乾した。次に、これらカップ内に各々
10頭のアオムシ(3齢幼虫)を放って蓋をし、25℃
の定温室に放置し、2日後に各カップの生死虫数を数え
て死虫率を求めた。この結果、化合物9,11,12,
15,16が、80%以上の殺虫活性を示した。Example 3 [Efficacy Test] (1) Efficacy Test for Stink Caterpillars Each of the wettable powders of compound (1) shown in Table 1 prepared according to Example 2 contains a surfactant (0.01%). 1000 with water
ppm, and the cabbage leaf pieces (5c
m × 5 cm) for 30 seconds, placed in each plastic cup one by one, and air-dried. Next, 10 caterpillars (3rd instar larvae) were released into each of these cups, and the cups were capped.
After 2 days, the number of live and dead insects in each cup was counted to determine the mortality. As a result, Compounds 9, 11, 12,
15, 16 showed an insecticidal activity of 80% or more.
【0043】(2)モモアカアブラムシに対する効力試験 実施例2に準じて調製した表1に示す化合物(1)の各
水和剤を界面活性剤(0.01%)を含む水で100p
pmに希釈し、これら各薬液中にキャベツ葉片(5cm
×5cm)を30秒浸漬し、各プラスチックカップに一
枚ずつ入れて風乾した。次に、これらカップ内に各々1
0頭のモモアカアブラムシ(無翅雌成虫)を放って蓋を
し、25℃の定温室に放置し、3日後に各カップの無翅
雌成虫及び幼虫の生死数を数えて死虫率を求めた。この
結果、化合物6,9,11,12,15,16が、80
%以上の殺虫活性を示した。(2) Efficacy test against peach aphid [Table 1] Each wettable powder of compound (1) shown in Table 1 prepared according to Example 2 was added to water containing a surfactant (0.01%) in 100 p.
pm and the cabbage leaf pieces (5 cm
× 5 cm) was immersed for 30 seconds, placed one by one in each plastic cup, and air-dried. Next, one in each of these cups
0 peach aphids (wingless female adults) were released, covered, and allowed to stand in a constant temperature room at 25 ° C. After 3 days, the mortality of the wingless female adults and larvae in each cup was counted to determine the number of dead and larvae. I asked. As a result, Compounds 6, 9, 11, 12, 15, 16 were converted to 80
% Or more insecticidal activity.
【0044】(3)抗菌試験 表1に示す化合物(1)のアセトン溶液を、最終濃度4
0ppmとなるようにPDA(ポテトデキストロース寒
天)培地に混入させ平板培地を作製した。予めPDA平
板培地に生育させたスモモ灰星病菌、イネいもち病菌の
菌叢をメスで1mm四方に切り取り、作製した薬剤入り
平板培地へ接種した。25℃、暗黒下で3日間培養し、
薬剤無添加区と菌叢直径を比較し、以下の式で菌叢生育
阻止率(%)を求めた。(3) Antibacterial test Acetone solution of compound (1) shown in Table 1 was added to a final concentration of 4
A plate culture medium was prepared by mixing a PDA (potato dextrose agar) medium at 0 ppm. The flora of Plum yellow rot and rice blast, which had been grown on a PDA plate medium in advance, were cut into a 1 mm square with a scalpel and inoculated into the prepared plate medium containing the drug. Culture at 25 ° C in the dark for 3 days,
The microflora diameter was compared with the non-added group, and the microbial growth inhibition rate (%) was determined by the following formula.
【0045】[0045]
【数1】 (Equation 1)
【0046】効果の判定は、菌叢阻止率が95〜100
%を5,85〜95%を4,85〜70%を3,45〜
70%を2,10〜45を1,10〜0%を0として、
5〜0の6段階で行った。この結果、スモモ灰星病菌に
対して化合物4〜6,9〜12,15,16が4以上の
効果を示し、イネいもち病菌対して化合物4,6,9,
11,12,15,16が3以上の効果を示した。The effect was determined when the inhibition rate of the bacterial flora was 95 to 100.
% To 5,85 to 95%, 4,85 to 70% to 3,45 to
70%, 2,10-45 and 1,10-0% as 0,
The test was performed in 6 stages of 5 to 0. As a result, Compounds 4 to 6, 9 to 12, 15, and 16 showed an effect of 4 or more on Plum rot fungi, and Compounds 4, 6, 9 and
11, 12, 15, and 16 showed three or more effects.
【0047】[0047]
【発明の効果】本発明の新規な6−(1−フルオロエチ
ル)−5−ヨード−4−アルキルアミノピリミジン誘導
体は、優れた農園芸用の有害生物防除効果を有するもの
である。The novel 6- (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative of the present invention has an excellent agricultural and horticultural pest control effect.
Claims (3)
状アルキル基を表わし;*は、不斉炭素原子を表わ
す。)で示される6−(1−フルオロエチル)−5−ヨ
ード−4−アルキルアミノピリミジン誘導体。(1) The following formula (1): (Wherein, R represents a linear or branched alkyl group having 1 to 20 carbon atoms; * represents an asymmetric carbon atom) 6- (1-fluoroethyl) -5 -Iodo-4-alkylaminopyrimidine derivatives.
れる4−クロロ−6−(1−フルオロエチル)−5−ヨ
ードピリミジンと次式(3): 【化3】 (式中、Rは、請求項1の記載と同義である。)で示さ
れるアルキルアミン類とを反応させることを特徴とする
請求項1記載の式(1)で示される6−(1−フルオロ
エチル)−5−ヨード−4−アルキルアミノピリミジン
誘導体の製法。2. The following formula (2): (Wherein * has the same meaning as in claim 1) and 4-chloro-6- (1-fluoroethyl) -5-iodopyrimidine represented by the following formula (3): (Wherein R has the same meaning as described in claim 1). 6- (1-) represented by the formula (1) according to claim 1, characterized by reacting with an alkylamine represented by the formula (1). Production method of (fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative.
(1−フルオロエチル)−5−ヨード−4−アルキルア
ミノピリミジン誘導体を有効成分とする有害生物防除
剤。Wherein the formula (1) according to claim 1 6-
A pest control agent comprising a (1-fluoroethyl) -5-iodo-4-alkylaminopyrimidine derivative as an active ingredient.
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JP2006104150A (en) * | 2004-10-07 | 2006-04-20 | Ube Ind Ltd | 4-anilinopyrimidine derivative and antibacterial agent |
JP2006188462A (en) * | 2005-01-07 | 2006-07-20 | Ube Ind Ltd | 4-(homo)piperazinylpyrimidine derivative and antibacterial agent |
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JP2006188462A (en) * | 2005-01-07 | 2006-07-20 | Ube Ind Ltd | 4-(homo)piperazinylpyrimidine derivative and antibacterial agent |
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