JPS6021966B2 - Insecticides and their manufacturing methods - Google Patents
Insecticides and their manufacturing methodsInfo
- Publication number
- JPS6021966B2 JPS6021966B2 JP4992482A JP4992482A JPS6021966B2 JP S6021966 B2 JPS6021966 B2 JP S6021966B2 JP 4992482 A JP4992482 A JP 4992482A JP 4992482 A JP4992482 A JP 4992482A JP S6021966 B2 JPS6021966 B2 JP S6021966B2
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- Pyrrole Compounds (AREA)
- Indole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式(1)で示される置換酢酸ヱステルを有
効成分として含有することを特徴とする殺虫剤およびそ
の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insecticide characterized by containing a substituted acetic acid ester represented by the general formula (1) as an active ingredient, and a method for producing the same.
で示される新規道モ奥酢酸ェステル有効成分として含有
することを特徴とする殺虫剤。(式中、Lnは1〜2の
整数を表わし、R,は水素原子、ハロゲン原子、メチル
基、ブロバルギル基、メトキシ基、メチレンジオキシ基
、カルボビニルオキシ基又はカルボェチニルオキシ基を
表わす。An insecticide characterized by containing a novel acetic acid ester as an active ingredient. (In the formula, Ln represents an integer of 1 to 2, and R represents a hydrogen atom, a halogen atom, a methyl group, a brobargyl group, a methoxy group, a methylenedioxy group, a carbovinyloxy group, or a carboethynyloxy group. .
R2は一般式(0)、(m)で表わされる基又はフター
ルィミドメチル基もしくは4ーチェニル−3−クロロ−
2−プテニルー1ーィル基を表わす。ここにR3はアリ
ル基、プロパルギル基又はペンタジェニル基であり、R
4は水素原子又はニトリル基を表わし、R5はプロパル
ギル基又はペンジル基を表わす。R2 is a group represented by the general formula (0) or (m), a phthalimidomethyl group, or 4-chenyl-3-chloro-
Represents a 2-putenyl-1-yl group. Here, R3 is an allyl group, a propargyl group, or a pentagenyl group, and R
4 represents a hydrogen atom or a nitrile group, and R5 represents a propargyl group or a penzyl group.
)現在使用されている殺虫剤としては、有機リン剤、カ
ーバメート系化合物、ピレスロィド化合物があげられる
が、本発明者はこれらのグループの中でもビレスロィド
系化合物について長年研究を重ねてきた。) Currently used insecticides include organic phosphorus agents, carbamate compounds, and pyrethroid compounds, and among these groups, the present inventor has conducted research on pyrethroid compounds for many years.
これ等殺虫剤は家庭衛生および農業面において非常に役
立って釆た一方、環境汚染食品公害等の問題が生じ、毒
性が低く、食物への残留が少なく、又効果の面では優れ
たものが望まれる。この要望に答えるものとしてピレス
ロィド系化合物が最も有望視されるが、従来のピレスロ
ィド系化合物は家庭衛生面には充分利用し得たが、農業
面へは発展がむずかしく、この点に留意して本発明者等
が更に広く研究を進めた結果、本発明記載の直換酢酸ヱ
ステルがピレスロィド系化合物と類似した活性をもち、
温血動物に対する毒性の低いことを知った。本発明は以
上の如き知見に基づいて完成されたものである。While these insecticides have been very useful in household hygiene and agriculture, they have caused problems such as environmental contamination and food pollution, and it is desirable to have low toxicity, less residue in food, and better efficacy. It will be done. Pyrethroid compounds are considered to be the most promising as a solution to this demand, but while conventional pyrethroid compounds have been sufficiently useful for household hygiene, it is difficult to develop them into agricultural applications. As a result of further extensive research by the inventors, it was found that the direct converted acetic acid ester described in the present invention has an activity similar to that of pyrethroid compounds,
I learned that it has low toxicity to warm-blooded animals. The present invention was completed based on the above findings.
本発明で有効成分として用いる上記式(1)で示される
化合物はヱステル製造の一般方法に準じて一般式(式中
n、R,は前記と同様の意味を有する)で表わされるカ
ルボン酸あるいはその反応性誘導体と一般式(V)、(
の)で表わされるアルコール又はフタールイミドメタノ
ールもしくは4−チエニルー3−クロロー2‐ブテニル
アルコール(式中、R3、R4、R5は前記と同様の意
味を有する。The compound represented by the above formula (1) used as an active ingredient in the present invention is a carboxylic acid represented by the general formula (where n, R, have the same meanings as above) or its Reactive derivatives and general formula (V), (
or phthalimidomethanol or 4-thienyl-3-chloro-2-butenyl alcohol (wherein R3, R4, and R5 have the same meanings as above).
)もしくはそのハライド又はスルホキシレートと反応さ
せることによって調製しえる。カルポン酸の反応性誘導
体としては酸ハラィド、酸無水物、低級アルキルェステ
ル、アルカリ金属塩などがあげられる。また一般式(1
)で示される置換酢酸ェステルにはQ位炭素に由来する
光学異性体が存在するが、これらのェステルも全て本発
明に含まれることはもちろんである。反応は適当な溶媒
中で必要により脱酸剤または触媒としての有機または無
機塩基または酸の存在下に必要により加熱下に行なわれ
る。上記式で示される化合物の代表例を示すが、本発明
はもちろんこれらのみに限定されるものではない。) or its halide or sulfoxylate. Examples of reactive derivatives of carboxylic acid include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Also, the general formula (1
The substituted acetate represented by ) has optical isomers derived from the carbon at the Q position, and it goes without saying that all of these esters are included in the present invention. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizing agent or catalyst, and optionally with heating. Representative examples of the compounds represented by the above formula are shown below, but the present invention is of course not limited to these.
3ーアリル−2′−メチルシクoベンター2ーエンー4
′−オンー1′−イルーQ−イソプロピル−(フエノキ
シ)アセテート n轡 1.55603・4′・5・6
ーテトラヒドロフタルイミドメチルーQ−イソプロピル
−(4ーメトキシフエノキシ)アセテート n谷 1.
55705ープoパルギル−2−フリルメチル一Q−イ
ソプロピルー(3・4−〆チレンジオキシフエノキシ)
アセテート n答 1.52303ーベンタジエニルー
2−メチルシクロベンター2ーエン−4′ーオソ−1′
−イルーQ−イソプロピル−(4ープロパルギルフエノ
キシ)アセテート n蟹 1.熱765−ペンジルー3
′ーフリルメチル−Qーイソプロピルー(4−力ルポビ
ニルオキシフエノキシ)アセテート n客 1.498
95−ペンジルーQ′−シアノ−3′ーフリルメチル
Q−イソプ。3-allyl-2'-methylcycloventer-2-en-4
'-one-1'-yl-Q-isopropyl-(phenoxy)acetate n轡 1.55603・4′・5・6
-Tetrahydrophthalimidomethyl-Q-isopropyl-(4-methoxyphenoxy)acetate n valley 1.
55705-pargyl-2-furylmethyl-Q-isopropyl(3,4-ethylenedioxyphenoxy)
Acetate n Answer 1.52303-bentadienyl-2-methylcyclobenter-2-ene-4'-otho-1'
-IruQ-isopropyl-(4-propargylphenoxy)acetate n crab 1. Heat 765-Penjiru 3
'-Furylmethyl-Q-isopropyl(4-lupovinyloxyphenoxy)acetate n customer 1.498
95-penzyl-Q'-cyano-3'-furylmethyl
Q-Isop.
ビル(4−カルボエチニルオキシフエノキシ)アセテー
ト n律 1.56033ーブロパルギルー2−メチル
シクロベンタ−2ーエン−4′ーオンー1′−イル−Q
ーイソプロピルー(2・4−ジクロロフエノキシ)アセ
テートn登 1.54935ーベンジルーQ′−シアノ
−3′ーフリルメチル一Q−イソプロピル(フエノキシ
)アセテートn容 1.54674′ーチエニル−3′
−クロロー2′−ブテン−1′−イル−Qーイソブロピ
ルー(4−メトキシフエ/キシ)アセテート n轡 1
.52磯5ーベンジル−3′−フリルメチル−Qーイソ
プロピル−(4ーメトキシフエノキシ)アセテートn登
1.52035ーベンジル−Q′ーシアノ−3′ーフ
リルメチルーQーイソプロピルー(2・4−ジクロロフ
エノキシ)アセテート n客 1.5571本発明で有
効成分として用いる新規化合物は、Z有機溶剤一般に易
溶である。Biru(4-carboethynyloxyphenoxy)acetate n rule 1.56033-bropargyl-2-methylcyclobent-2-ene-4'-one-1'-yl-Q
-isopropyl(2,4-dichlorophenoxy)acetate n volume 1.54935-benzyl-Q'-cyano-3'-furylmethyl-Q-isopropyl(phenoxy)acetate n volume 1.54674'-thienyl-3'
-Chloro 2'-buten-1'-yl-Q-isopropyru(4-methoxyphe/xy)acetate n轡 1
.. 52 Iso 5-benzyl-3'-furylmethyl-Q-isopropyl-(4-methoxyphenoxy)acetate n 1.52035-benzyl-Q'-cyano-3'-furylmethyl-Q-isopropyl-(2,4-dichlorophenoxy)acetate 1.5571 The novel compound used as an active ingredient in the present invention is generally easily soluble in Z organic solvents.
従って散布用殺虫剤としては乳剤、油剤、粉剤、水和剤
、エアゾール剤などとして用いることができ、又木粉そ
の他適当な基材と混合して蚊取線香の如き嫌蒸用殺虫剤
としても使用できる。又この有効成分を適当な有Z機溶
剤に溶解して台紙に濠ませ、適当な加熱体により有効成
分を加熱蒸散させるいわゆる電気蚊取として利用する場
合もすぐれた効果を示す。以下本発明化合物について合
成例をあげて詳細に説明する。合成例 1
Q−ィソプロピルーフェノキシ酢酸クロライド2.22
を乾燥ベンゼン15泌に溶解し、これに3−アリルー2
−メチルシクロベンター2ーエン−4−オンー1ーオー
ル1.5夕を乾燥ベンゼン20の‘に溶解したものを加
え、さらに縦合助剤として乾燥ピリジン3の‘を加える
とピリジン塩酸塩の結晶が析出する。Therefore, as an insecticide for spraying, it can be used as an emulsion, oil, powder, wettable powder, aerosol, etc. It can also be mixed with wood flour or other suitable base material to be used as an anti-vaporizing insecticide such as mosquito coils. Can be used. It also shows excellent effects when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in a suitable Z organic solvent and soaked in a mount, and the active ingredient is heated and evaporated using a suitable heating element. The compounds of the present invention will be explained in detail below by giving synthesis examples. Synthesis example 1 Q-isopropylphenoxyacetic acid chloride 2.22
was dissolved in 15% of dry benzene, and 3-aryl-2
- Adding 1.5 parts of methylcyclobent-2-en-4-on-1-ol dissolved in 20 parts of dry benzene, and then adding 3 parts of dry pyridine as a coalescence aid, crystals of pyridine hydrochloride precipitated. do.
。密栓して室温で一夜放置後ピリジン塩酸塩を炉別した
後、ベンゼン溶液をぼう硝で乾燥後、ベンゼンを蟹去し
て粘調透明な3′ーァリルー2−シク○ベンタ−2ーエ
ン−4′ーオン−1′ーイル Q−イソプロピルー(フ
ヱノキシ)アセテート3.2夕を得た。n色。1.55
60
合成例 2
Q−イソプロピル−(3・4ーメチレンジオキシフェノ
キシ)酢酸2.5夕と5ープロパルギル−2−フリルメ
チルアルコール1.4夕をベンゼン150の‘に溶解し
、溶液を激しくかく拝しつつ濃硫酸5の‘を加える。. After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed by a furnace, and the benzene solution was dried with sodium sulfate, and the benzene was removed to give a viscous and transparent 3'-aryl-2-cyclobenta-2-ene-4'. -1'-yl Q-isopropyl(phenoxy)acetate 3.2 hours was obtained. N colors. 1.55
60 Synthesis Example 2 2.5 parts of Q-isopropyl-(3,4-methylenedioxyphenoxy)acetic acid and 1.4 parts of 5-propargyl-2-furyl methyl alcohol were dissolved in 150 parts of benzene, and the solution was stirred vigorously. Add 5' of concentrated sulfuric acid while stirring.
かく梓下に還流加熱し、共沸によって出る水を脱水剤に
よって除く。ベンゼンは時々補充し、約4時間反応を行
う。ついで反応溶液を重曹水、食塩水で洗膝後ベンゼン
を減圧下に留去し、5′−プロパルギルー2′ーフリル
メチル o−イソプロピルー(3・4一メチレジオキシ
フエノキシ)アセテート3.02を得た。n色o l.
5230合成例 3Qーイソプロピルー(4ーカルポビ
ニルオキシフェノキシ)酢酸のメチルェステル2.8夕
と5−ペンジルー3ーフリルメチルアルコール1.9夕
を乾燥トルェン100の【に溶解し、水酸化ナトリウム
0.12を触媒として添加し、加熱縄拝した。The mixture is heated under reflux and the water produced by azeotropy is removed using a dehydrating agent. Benzene is replenished from time to time and the reaction is carried out for about 4 hours. Then, the reaction solution was washed with a sodium bicarbonate solution and a saline solution, and the benzene was distilled off under reduced pressure to obtain 3.02% of 5'-propargyl-2'-furylmethyl o-isopropyl-(3,4-methyledioxyphenoxy) acetate. Obtained. n color o l.
5230 Synthesis Example 2.8 parts of methyl ester of 3Q-isopropyl-(4-carpovinyloxyphenoxy)acetic acid and 1.9 parts of 5-penzyl-3-furyl methyl alcohol were dissolved in 100 parts of dry toluene, and 0.12 parts of sodium hydroxide was added. It was added as a catalyst and heated.
トルェンと共鱗して留出するメタノールを除去する。冷
却後冷水に注加してトルェン層を分液し、減圧下にトル
ェンを蟹去して粘調透明な5′ーベンジルー3′ーフリ
ルメチル Qーイソブロピルー(4−力ルポビニルオキ
シフエノキシ)アセテート3.7夕を得た。n律 1.
4斑9合成例 4
qーィソプロピルー4ーメトキシフェノキシ酢酸のナト
リウム塩2.5夕と3・4・5・6ーテトラヒドロフタ
ルイミドメチルクロライド2.2夕をベンゼン50の‘
に溶解し、環流下に3時間窒素気流中で反応させた後反
応液を冷却し、析出する食塩を炉別したのち、食塩水で
充分洗練後、ぼう硝で乾燥し、ベンゼンを減圧下に蟹去
して3′・4′・5・6−テトラヒドロフタルイミドメ
チル Q−イソプロピルー(4ーメトキシフエノキシ)
アセテート3.1夕を得た。Methanol co-scaled with toluene and distilled out is removed. After cooling, the toluene layer was separated by pouring it into cold water, and the toluene was removed under reduced pressure to obtain viscous and transparent 5'-benzyl-3'-furylmethyl Q-isobropyru(4-polvinyloxyphenoxy) acetate. I got 7 nights. n rule 1.
Synthesis Example 4 2.5% of sodium salt of qisopropyl-4-methoxyphenoxyacetic acid and 2.2% of 3,4,5,6-tetrahydrophthalimidomethyl chloride were mixed with 50% of benzene.
After reacting in a nitrogen stream for 3 hours under reflux, the reaction solution was cooled, and the precipitated salt was separated in a furnace, thoroughly purified with brine, dried with sulfur salt, and the benzene was removed under reduced pressure. 3', 4', 5, 6-tetrahydrophthalimidomethyl Q-isopropyl (4-methoxyphenoxy)
3.1 ml of acetate was obtained.
n色。1.5570合成例 5
Qーイソプロピルー(4ーメトキシフエノキシ)酢酸の
無水物4.4夕と4−チェニル−3−クロロー2ープテ
ンー1−オール1.6夕を乾燥ピリジン50の‘に溶解
し、室温下一晩縄拝した。N colors. 1.5570 Synthesis Example 5 4.4 parts of Q-isopropyl-(4-methoxyphenoxy)acetic anhydride and 1.6 parts of 4-chenyl-3-chloro-2-buten-1-ol were dissolved in 50 parts of dry pyridine. , I prayed the rope overnight at room temperature.
翌日反応液を氷水に注加し、エーテルを用いて抽出し、
エーテル溶液を重曹水、食塩水で充分洗総後、ぼう硝で
乾燥し、エーテルを減圧下に留去して4′ーチニルー3
′ークロロー2′ーブテン−1′ーイル Q−イソプロ
ピルー(4ーメトキシフエノキシ)アセテート3.3夕
を得た。n801.5288次に合成例1〜5と同様の
方法で下表の化合物を得た。表中、ェステル化法の欄で
a、b、c、d、eは下記の意味を有する。a:酸クロ
ラィドによるェステル化法
b:不活性溶媒中、濃硫酸による酸とアルコールとの脱
水ェステル化法c:不活性溶媒中、水素化ナトリウムま
たはアルカリ金属アルコキシドを触媒とするヱステル交
換によるヱステル化法d:酸のアルカリ金属、銀または
有機第三級塩基の塩とアルコールのハラィ日こよるェス
テル化法e:酸無水物によるヱステル化法
なお化合物は前記化合物例の番号で示す。The next day, the reaction solution was poured into ice water and extracted with ether.
After thoroughly washing the ether solution with a sodium bicarbonate solution and a saline solution, it was dried over salt solution, and the ether was distilled off under reduced pressure to obtain 4'-tinyl-3.
3.3 ml of '-chloro-2'-buten-1'-yl Q-isopropyl(4-methoxyphenoxy)acetate was obtained. n801.5288 Next, the compounds shown in the table below were obtained in the same manner as in Synthesis Examples 1 to 5. In the table, a, b, c, d, and e in the esterification method column have the following meanings. a: Esterification method using acid chloride b: Dehydration esterification method between acid and alcohol using concentrated sulfuric acid in an inert solvent c: Esterification method by transesterification using sodium hydride or an alkali metal alkoxide as a catalyst in an inert solvent Method d: Esterification of an alkali metal, silver or organic tertiary base salt of an acid with an alcohol; e: Esterification with an acid anhydride. The compounds are indicated by the numbers of the above compound examples.
又本発明の瞳ま奥酢酸ェステルはこれにNーオクチルビ
シクロヘプテンジカルボキシイミド(商品名MGK−2
64)、N−オクチルビシクロヘプテンジカルボキシイ
ミドとアルキルアリールスルホン酸塩との混合物(商品
名MGK一5026)、オクタクロロジプロピルエーテ
ル、ピベロニルブトキサイドなどの共力剤を加えると、
その殺虫効力を一層高めることができる。In addition, the pupil acetate of the present invention is N-octylbicycloheptenedicarboximide (trade name MGK-2).
64), by adding a synergist such as a mixture of N-octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK-5026), octachlorodipropyl ether, piveronyl butoxide, etc.
Its insecticidal efficacy can be further enhanced.
さらに本発明化合物の2種以上の配合使用によって、よ
りすぐれた防除効果を発現させることも可能であり、他
の殺虫剤たとえばスミチオン、DDVP、ダイアジノン
、サリチオン、シュアサィドなどの有機リン剤、1−ナ
フチルーN−メチルカーバメイト、3・4−ジメチルフ
エニル−Nーメチルカーバメイト、2−イソプロポキシ
フエニルーNーメチルカーバメイトなどのカーバメィト
剤、ピレトリン、アレスリン、フタルスリン、レスメト
リン、フラメトリン、フエノスリン、バーメスリン、フ
エンバレレートなどのシクロプロバンカルボン酸ェステ
ル剤、2・6ージターシヤリープチルー4−メチルフエ
ノ−ル(BHT)、2・6−ジターシヤリーブチルフェ
ノールなどのフェノール系、フェニルーQ−ナフチルア
ミン、フエニル−Bーナフチルアミンなどのアミン系酸
化防止剤、またバダン、ガルェクロン、ランネート等の
殺虫剤あるし、は殺ダニ剤、殺菌剤、殺線虫剤、除草剤
、植物生長調整剤、肥料その他の農薬を混合することに
よって効力のすぐれた多目的組成物が得られ、労力の省
力化、薬剤間の相乗効果も充分期待し得るものである。
次に本発明化合物の毅虫試験成績を示す。試験例 1
本発明化合物m〜(11)を各々30%、キシロール5
0%、ソルポールSM−200(東邦化学登録商標名)
20%の配合による乳剤を調製した。Furthermore, by using two or more of the compounds of the present invention in combination, it is possible to achieve a more excellent control effect, and other insecticides such as organic phosphorus agents such as sumithion, DDVP, diazinon, salithion, and sureside, and 1-naphthyl Carbamate agents such as N-methyl carbamate, 3,4-dimethylphenyl-N-methyl carbamate, 2-isopropoxyphenyl-N-methyl carbamate, pyrethrin, allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, vermethrin, fenvalerate cycloprobane carboxylic acid esters such as 2,6-ditertiarybutyl-4-methylphenol (BHT), phenolics such as 2,6-ditertiarybutylphenol, phenyl-Q-naphthylamine, phenyl-B-naphthylamine, etc. By mixing amine antioxidants, insecticides such as badan, galecron, and lannate, acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals. A multipurpose composition with excellent efficacy can be obtained, labor saving, and synergistic effects between drugs can be fully expected.
Next, the test results of the compounds of the present invention will be shown. Test Example 1 30% each of compounds m to (11) of the present invention, xylol 5
0%, Solpol SM-200 (Toho Chemical registered trademark name)
An emulsion with a 20% blend was prepared.
これら乳剤と対照市販薬剤として1ーナフチルーNーメ
チルカーバメート30%乳剤の水による300倍希釈液
をポット植えの稲に10の【/ポットでスプレ−をし、
金網円筒でおおし、、その中にッマグロョコバィ10匹
を放ち、1日後に生死を観察した結果、いずれの薬剤も
90%以上の致死率を示した。試験例 2本発明化合物
の各0.2%白灯溶液を調製し、イエバエを用いて長沢
式噂霧降下法に従い滋下仰転率より相対有効度を算出し
たところ、次の如くである。These emulsions and a 30% diluted solution of a 30% naphthyl-N-methyl carbamate emulsion in water were sprayed on rice plants planted in pots in 10 [//pots].
The cylinder was covered with a wire mesh cylinder, and 10 black-spotted black flies were released into the cylinder. After one day, they were observed to see whether they were alive or dead. As a result, all drugs had a mortality rate of over 90%. Test Example 2 A 0.2% white light solution of each of the compounds of the present invention was prepared, and the relative effectiveness was calculated from the rate of supination using house flies according to the Nagasawa-type mist descent method, and the results were as follows.
供試薬剤番号は前記有効成分例のものと同一である。試
験例 3
本発明化合物について0.2%の白灯溶液風、0.2%
とピベロニールプトキサィド0.8%の白灯溶液【8)
、0.1%とフタルスリン0.1%の白灯溶液に}につ
いて試験例2と同様に試験を行った。The sample drug number is the same as that of the active ingredient example above. Test Example 3 For the compound of the present invention, 0.2% white light solution, 0.2%
and piveronyl ptoxide 0.8% white lamp solution [8]
, 0.1% and 0.1% phthalthrin in a white lamp solution} was tested in the same manner as in Test Example 2.
試験例 4
殺虫成分として0.5%含有する蚊取線香を作り、アカ
ィェカの成虫を滋下仰転せしめる効果を試験した。Test Example 4 Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in making adult Acaea mosquitoes supine.
この実験は防虫科学1虎巻(1951年)第176頁長
沢、勝田の方法に従い、前記線香の相対有効度を算出し
たところ次の如くである。供試薬剤番号は前記有効成分
例のものと同一で以上の試験例から、本発明化合物はす
ぐれた生物活性を有し、異性体の存在するものについて
は光学異性体を分割すればさらにすぐれた効果を発輝す
るものである。This experiment was carried out in accordance with the method of Nagasawa and Katsuta, Insect Control Science 1, Compact Volume (1951), p. 176, and the relative effectiveness of the incense sticks was calculated as follows. The test drug number is the same as that of the active ingredient example above. From the above test examples, the compound of the present invention has excellent biological activity, and if it has isomers, it can be further improved by separating the optical isomers. It is something that makes the effect shine.
これらのことから本発明殺虫剤はツマグロョコバィ、ウ
ンカ類、ニカメィ虫、ョトウムシ類、コナガ、ヤガ、モ
ンシロチョウ、ハマキムシ類、アブラムシ類、カィガラ
ムシ類等の農業害虫、コクゾウ等の貯穀害虫、ダニ類等
の防除にきわめて有効である。又ピレスロィド系殺虫剤
と同様低毒性であるため、収穫前の作物、家庭園芸用、
食品関係等にも利用できる点ですぐれた化合物である。
以下本発明の殺虫剤の調製および効果を実施例をもって
説明するが、もちろん下記例によって本発明の範囲が限
定されるものではない。Based on these facts, the insecticide of the present invention is effective for controlling agricultural pests such as blackhoppers, planthoppers, black beetles, cutworms, diamondback moths, nocturnal moths, cabbage beetles, leaf beetles, aphids, and scale insects, grain storage pests such as brown elephants, and mites. It is extremely effective. Also, like pyrethroid insecticides, it has low toxicity, so it can be used for crops before harvest, home gardening, etc.
It is an excellent compound in that it can also be used in food-related applications.
The preparation and effects of the insecticide of the present invention will be explained below with reference to examples, but the scope of the present invention is of course not limited to the following examples.
実施例 1
本発明化合物‘1’、‘2’、(51、【8’および(
11)の各々2礎都、ソルポールSM一200(前述に
同じ)20部、キシロール6礎部を加えて各々の乳剤を
得る。Example 1 Compounds of the present invention '1', '2', (51, [8' and (
Add 2 parts of each of 11), 20 parts of Solpol SM-200 (same as above), and 6 parts of Xylene to obtain each emulsion.
上記の各乳剤の1on音希釈液を、モモアカアブラムシ
の発生した大根畑に150そ/1位散布した。2豚の調
査で・散布前密度の砂下略欧、減少していた。A 1 ton diluted solution of each of the above emulsions was sprayed 150/1 on a radish field infested with green peach aphid. A survey of two pigs revealed that the density before spraying had almost decreased under the sand.
実施例 2
本発明化合物【31、‘41、{6}および00の各々
0.2部、それらに各々フタルスリン0.4部、オクタ
クロロジブロピルェーテル1.庇都、BHTO.1部を
精製灯油28.3部に溶解してエアゾール容器に充填し
、バルブ部分を取り付けた後、該バルブ部分を通じて噴
射剤(綱ヒ石油ガス)7側を刀旺充填してヱアゾールを
得る。Example 2 0.2 parts each of the compounds of the present invention [31, '41, {6} and 00, 0.4 parts each of phthalthrine, and 1.0 parts of octachlorodibropylether. Eikoto, BHTO. 1 part is dissolved in 28.3 parts of refined kerosene and filled into an aerosol container, a valve part is attached, and a propellant (oil gas) 7 is filled through the valve part to obtain aerosol.
上記のエアゾールを15×20弧のべニア板面に5秒庵
瓢贋覆し、チャバネゴキブリ成虫を1時間接触させると
いずれも2日後には80%以上のチヤバネゴキブリを毅
虫することができた。実施例 3
本発明化合物‘21、{51、‘7}および■の各々0
.5夕、それらに各々MGK一50261.0部を除虫
菊抽出柏粉、木粉、デン粉などの蚊取線香用基材聡.5
夕と均一に混合して、公知の方法により蚊取線香を得る
。When the above aerosol was applied to the surface of a 15 x 20 arc plywood board for 5 seconds and adult German cockroaches were left in contact for 1 hour, more than 80% of the German cockroaches were able to be destroyed after 2 days. . Example 3 Each of the compounds of the present invention '21, {51, '7} and ■0
.. On the 5th evening, 50261.0 parts of MGK was added to each of the pyrethrum extract base materials for mosquito coils such as oak powder, wood powder, and starch powder. 5
A mosquito coil is obtained by a known method.
実施例 4
本発明化合物【3’、【41、‘71、【91および(
11)の各々0.1夕、それらに各々ピベロニールブト
キサイド0.05夕、BHTO.03夕をアセトンに溶
解し、1.5×2.4肌の繊維板に均一に吸着させ、風
乾して電気蚊取用マットを得る。Example 4 Compounds of the present invention [3', [41, '71, [91 and (
11), 0.1 night each of them, 0.05 night each of piveronyl butoxide, BHTO. 03 was dissolved in acetone, uniformly adsorbed onto a 1.5×2.4 fiber board, and air-dried to obtain an electric mosquito repellent mat.
実施例 5
本発明化合物‘1}、‘2’、【4’、【7ーおよび0
0の各々10部、それらに各々1−ナフチル−N−メチ
ルカーバメィト2碇部を加え、各々ソルポールSM−2
00(前述に同じ)5部をよく混合し、300メッシュ
タルク65部を加え楢債器中で充分櫨梓混合して各々の
水和剤を得る。Example 5 Compounds of the present invention '1}, '2', [4', [7- and 0
10 parts of each of Solpol SM-2 and 2 parts of 1-naphthyl-N-methylcarbamate were added to each of Solpol SM-2.
00 (same as above) were mixed thoroughly, 65 parts of 300 mesh talc was added, and the mixture was thoroughly mixed in a clay vessel to obtain each wettable powder.
実施例 6
本発明化合物{3}、【51、脚および(11)の各々
0.1部に各々白灯油を加えて溶解し、全体を100部
とすれば各々の油剤を得る。Example 6 White kerosene is added to 0.1 part of each of the compounds of the present invention {3}, [51, leg, and (11)] to dissolve them, and the total amount is 100 parts to obtain each oil solution.
実施例 7
本発明化合物【3}、側、‘9’および(11)の各々
5部、リグニンスルホン酸ソーダ5部、フバサミクレー
85部に水5部を加えてよく糠合し、造粒機で整形し、
乾燥すれば粒剤を得る。Example 7 5 parts of water were added to 5 parts each of the compounds of the present invention [3}, '9' and (11), 5 parts of sodium lignin sulfonate, and 85 parts of Fubasamiclay, and the mixture was thoroughly brazed and granulated using a granulator. Shaped,
When dried, granules are obtained.
実施例 8
本発明化合物‘1}、{2}、‘4}、‘7}および‘
10の各々1部に各々3・4ージメチルフェニルーNー
メチルカーバメィト2部を加え、アセトン2の都‘こ溶
解して、300メッシュクレー97部を加え橘簿器中で
よく縄浮浪舎した後、アセトンを蒸発除去すれば各々の
粉剤を得る。Example 8 Compounds of the present invention '1}, {2}, '4}, '7} and'
Add 2 parts of 3,4-dimethylphenyl-N-methylcarbamate to 1 part of each of 10, dissolve in 2 parts of acetone, add 97 parts of 300 mesh clay, and mix well in a Tachibana cup. After that, the acetone is removed by evaporation to obtain each powder.
Claims (1)
することを特徴とする殺虫剤。 (式中、nは1〜2の整数を表わし、R_1は水素原子
、ハロゲン原子、メチル基、プロパルギル基、メトキシ
基、メチレンジオキシ基、カルボビニルオキシ基又はカ
ルボエチニルオキシ基を表わす。 R_2は一般式(II)、(III)で表わされる基又は
フタールイミドメチル基もしくは4−チエニル−3−ク
ロロ−2−ブテニル−1−イル基を表わす。▲数式、化
学式、表等があります▼ ここにR_3はアリル基、プロパルギル基又はペンタ
ジエニル基であり、R_4は水素原子又はニトリル基を
表わし、R_5はプロパルギル基又はベンジル基を表わ
す。 )2 特許請求の範囲第1項記載の一般式(I)で示さ
れる新規置換酢酸エステルとピレスロイド用共力剤とを
有効成分として含有することを特徴とする殺虫剤。 3 下記一般式(IV)で示されるカルボン酸またはその
反応性誘導体と、一般式(V)、(VI)で表わされるア
ルコール又はフタールイミドメタノールもしくは4−チ
エニル−3−クロロ−2−ブテニルアルコール、あるい
はそのハライド又はスルホキシレートとを反応させて、
特許請求の範囲第1項に記載の一般式(I)で示される
新規置換酢酸エステルをを得ることを特徴とする殺虫剤
の製法。 ▲数式、化学式、表等があります▼ (ここにn、R_1、R_2、R_3、R_4、R_5
は特許請求の範囲第1項記載と同じ意味を表わす。 )[Scope of Claims] 1. An insecticide characterized by containing a novel substituted acetate ester represented by the general formula (numerical formula, chemical formula, table, etc.) as an active ingredient. (In the formula, n represents an integer of 1 to 2, and R_1 represents a hydrogen atom, a halogen atom, a methyl group, a propargyl group, a methoxy group, a methylenedioxy group, a carbovinyloxy group, or a carboethynyloxy group. R_2 represents Represents a group represented by general formula (II) or (III) or a phthalimidomethyl group or a 4-thienyl-3-chloro-2-butenyl-1-yl group. ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Here R_3 represents an allyl group, a propargyl group, or a pentadienyl group, R_4 represents a hydrogen atom or a nitrile group, and R_5 represents a propargyl group or a benzyl group. )2 General formula (I) according to claim 1 An insecticide characterized by containing a novel substituted acetate represented by: and a pyrethroid synergist as active ingredients. 3 A carboxylic acid represented by the following general formula (IV) or a reactive derivative thereof, and an alcohol or phthalimide methanol or 4-thienyl-3-chloro-2-butenyl represented by the general formulas (V) and (VI). By reacting alcohol, or its halide or sulfoxylate,
A method for producing an insecticide, which comprises obtaining a novel substituted acetate represented by the general formula (I) according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (here n, R_1, R_2, R_3, R_4, R_5
has the same meaning as in claim 1. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4992482A JPS6021966B2 (en) | 1982-03-26 | 1982-03-26 | Insecticides and their manufacturing methods |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4992482A JPS6021966B2 (en) | 1982-03-26 | 1982-03-26 | Insecticides and their manufacturing methods |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14760175A Division JPS582202B2 (en) | 1975-12-10 | 1975-12-10 | Satsuki Yuzai Oyobi Sono Seihou |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5896004A JPS5896004A (en) | 1983-06-07 |
JPS6021966B2 true JPS6021966B2 (en) | 1985-05-30 |
Family
ID=12844556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4992482A Expired JPS6021966B2 (en) | 1982-03-26 | 1982-03-26 | Insecticides and their manufacturing methods |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6021966B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2001256652B2 (en) | 2001-03-23 | 2007-03-01 | Bimal Arya | Coiled fumigant set |
-
1982
- 1982-03-26 JP JP4992482A patent/JPS6021966B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5896004A (en) | 1983-06-07 |
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