JPS6035343B2

JPS6035343B2 - 2-methylbenzimidazole derivatives and insecticides containing the same

Info

Publication number: JPS6035343B2
Application number: JP13119482A
Authority: JP
Inventors: 栄一桑野
Original assignee: KYUSHUDAIGAKUCHO
Current assignee: KYUSHUDAIGAKUCHO
Priority date: 1982-07-29
Filing date: 1982-07-29
Publication date: 1985-08-14
Also published as: JPS5921671A

Description

【発明の詳細な説明】本発明は２−メチルベンゾイミダゾール誘導体に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 2-methylbenzimidazole derivatives.

本発明の２−メチルベンゾィミダゾール誘導体は新規な
化合物で、次の一般式（式中のＲはメチル基又はエチル
基等の低級アルキル基を示す）で表わされる１一（３・
７ージメチルー７−アルコキシー２ーオクテニル）一２
ーメチルベンゾイミダゾールである。The 2-methylbenzimidazole derivative of the present invention is a novel compound represented by the following general formula (R in the formula represents a lower alkyl group such as a methyl group or an ethyl group).
7-dimethyl-7-alkoxy-2-octenyl)-2
-Methylbenzimidazole.

本発明者は本発明の新規化合物が極めて優れた殺虫効果
を有することを見出した。The present inventor has discovered that the novel compound of the present invention has an extremely excellent insecticidal effect.

それ故、本発明は本発明の新規化合物を活性成分として
含有する殺虫剤にも関するものである。The invention therefore also relates to insecticides containing the novel compounds of the invention as active ingredients.

本発明化合物は次のようにして製造する。以下、本発明
を例につきさらに詳細に説明する。The compound of the present invention is produced as follows. The invention will now be explained in more detail by way of example.

例１１一（３・７ージメチルー２・６ーオクタジエニル）−
２ーメチルベンゾイミダゾール（ロ式）の製造０．０１
モルの水素化ナトリウムを含む乾燥ジメチルホルムアミ
ドもこ等モル量の２−メチルベンゾィミダゾールを加え
、婿拝し溶解した。Example 1 1-(3,7-dimethyl-2,6-octadienyl)-
Production of 2-methylbenzimidazole (formula B) 0.01
An equimolar amount of 2-methylbenzimidazole was added to dry dimethylformamide containing a molar amount of sodium hydride and dissolved.

１時間後、０．０１モルのゲラニルク。After 1 hour, 0.01 mole of Geranilc.

リドを加え、さらに室温で３時間境拝した。然る後、反
応液に水を加え、生成物をエーテルで抽出した。エーテ
ル層を食塩水で洗浄し、無水流酸ソーダで乾燥後、減圧
下で溶媒を蟹去し、残留物をシリカゲルのカラムクロマ
トグラフィによって精製した。溶出は最初へキサンで行
ない、続いてへキサン対酌酸エチル比が３：１の混合溶
媒を用いた。目的物はへキサン対酌酸エチル比が３：１
の混合溶媒で溶出した。溶媒を減圧下で除去し、０式の
化合物を得た。収率７９％。第１図にロ式の化合物のＮ
ＭＲスペクトルを示す。元素分析値Ｃ日Ｎ実測値８０．０３９．０９１０．３１理論
値８０．５５９．０１１０．４４（Ｃ，８
日２４Ｎ２）例２，１−（３・７ージメチルー７ーメトキシ−２ーオクテニ
ル）−２−メチルベンゾイミダゾール（１式でＲがメチ
ル基のもの）の製造乾燥メタノール６地に０．０１モル
の酢酸水銀を懸濁させ、乾燥メタノール６の上に溶解し
た０式の化合物を室温で加て、そのまま室温で燈拝した
。Lido was added and the mixture was further incubated at room temperature for 3 hours. After that, water was added to the reaction solution, and the product was extracted with ether. The ether layer was washed with brine, dried over anhydrous sodium hydroxide, the solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel. Elution was first performed with hexane, followed by a mixed solvent with a hexane to ethyl chloride ratio of 3:1. The target product has a hexane to ethyl oxalate ratio of 3:1.
It was eluted with a mixed solvent of The solvent was removed under reduced pressure to obtain a compound of formula 0. Yield 79%. Figure 1 shows the N of the compound of formula B.
The MR spectrum is shown. Elemental analysis value C Day N Actual value 80.03 9.09 10.31 Theoretical value 80.55 9.01 10.44 (C,8
24N2) Example 2, Preparation of 1-(3,7-dimethyl-7-methoxy-2-octenyl)-2-methylbenzimidazole (formula 1, where R is methyl group) 0.01 mole of mercury acetate in 6 parts of dry methanol was suspended, and a compound of formula 0 dissolved on dry methanol 6 was added at room temperature, and the mixture was allowed to stand at room temperature.

２４時間後が‐水酸化ナトリウム溶液１０の‘を加え、
、次いで水素化ホウ素ナトリウム（０．０１５モル）を
溶解した洲−水酸化ナトリウム溶液１０の‘を加え、室
温で５時間蝿拝した。After 24 hours - add 10' of sodium hydroxide solution,
Then, 10 parts of a sodium hydroxide solution containing sodium borohydride (0.015 mol) was added, and the mixture was stirred at room temperature for 5 hours.

反応生成物はエーテルで抽出し、エーテル層を食塩水で
洗浄した後、無水硫酸ソーダで乾燥した。溶媒を減圧下
で留去し、残留物をシリカゲルカラムクロマトグラフィ
によって精製した。溶出は最初へキサン対エーテル比が
１：１の混合溶媒を用い、次いでへキサン対酌酸エチル
比が２：１の混合溶媒を用い、さらにへキサン対酌酸エ
チル比が１：２の混合溶媒を用いた。目的物はへキサン
−酢酸エチル比が１；２で溶出した。溶媒を減圧下で除
去し、１式の化合物がＲでメチル基のものを得た。収率
３７％。第２図２にこのもののＮＭＲスペクトルを示す
。元素分析値Ｃ日Ｎ実測値７５．５２９．３６８．９１理論値
７５．９６９．３９９．３２（Ｃ，虹２８
Ｎ２０）例３１一（３・７ージメチル−７ーエトキシー２−オクテニ
ル）一２−メチルベンゾイミダゾール（１式でＲがエチ
ル基のもの）の製造乾燥メタノールの代わりに乾燥エタ
ノール用いた他は例２の方法と全く同様の操作を行ない
１式の化合物でＲがエチル基のものを得た。The reaction product was extracted with ether, and the ether layer was washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography. For elution, first use a mixed solvent with a hexane to ether ratio of 1:1, then use a mixed solvent with a hexane to ethyl oxanate ratio of 2:1, and then use a mixed solvent with a hexane to ethyl chlorate ratio of 1:2. A solvent was used. The target product was eluted at a hexane-ethyl acetate ratio of 1:2. The solvent was removed under reduced pressure to obtain a compound of Formula 1 with R being a methyl group. Yield 37%. FIG. 2 shows the NMR spectrum of this product. Elemental analysis value C Day N Actual value 75.52 9.36 8.91 Theoretical value 75.96 9.39 9.32 (C, Rainbow 28
N20) Example 3 Production of 1-(3,7-dimethyl-7-ethoxy-2-octenyl)-2-methylbenzimidazole (formula 1, where R is an ethyl group) Example 2 except that dry ethanol was used instead of dry methanol A compound of Formula 1, in which R is an ethyl group, was obtained by carrying out exactly the same operation as in the method described above.

収率２６％。第３図にこのもののＮＭＲスペクトルを示
す。元素分析値Ｃ日Ｎ実測値７５．６８９．６４８．９１理論値
７６．４０９．６２８．９１（Ｃ２虹３州
２０）例４本発明化合物の殺虫効果をイエバエについて試験した。Yield 26%. FIG. 3 shows the NMR spectrum of this product. Elemental analysis value C Day N Actual value 75.68 9.64 8.91 Theoretical value 76.40 9.62 8.91 (C2 Rainbow 3 States 20) Example 4 The insecticidal effect of the compound of the present invention was tested on house flies.

結果を次の第１表に示す。イエバエは有機リン剤感受性
（ＷＨＯ、ＳＳＳ）及び抵抗性（第３夢の島系統のもの
）の雌成虫を用いた。試験は本発明化合物のアセトン溶
液（１仏そ）を局所施用することにより行なった。２細
時間後の死亡率を求め、５０％のイエバエが死亡する量
（ＬＤ則値）で効果を示した。The results are shown in Table 1 below. As for house flies, female adult flies that are organophosphate sensitive (WHO, SSS) and resistant (of the third Yume no Shima strain) were used. The test was carried out by topically applying an acetone solution (1 cup) of the compound of the present invention. The mortality rate after 2 minutes was determined, and the effect was indicated by the amount at which 50% of house flies died (LD law value).

第１表前掲の第１表から明らかなとおり、本発明化合物は感受
性イエバエに対して有機リン殺虫剤フェニトロチオンよ
り効力は劣るが、・マラチオンの２倍の活性を示した。Table 1 As is clear from Table 1 above, the compound of the present invention was less effective against susceptible house flies than the organophosphorus insecticide fenitrothion, but exhibited twice the activity of malathion.

また、有機リン剤抵抗性イエバエに対しても強い殺虫活
性を示し、フェニトロチオンの約６川音も強い殺虫活性
を示した。本発明の広汎な精神と視野を逸脱することな
く、本発明の種々な変更と修整が可能なこと勿論である
。It also showed strong insecticidal activity against organophosphate-resistant house flies, and fenitrothion about 60% also showed strong insecticidal activity. It will be understood that various changes and modifications may be made to the invention without departing from its broader spirit and scope.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明化合物の中間体のＮＭＲスペクトル図、
第２図及び第３図はそれぞれ本発明化合物のＮＭＲスペ
クトル図である。第１図第２図第３図FIG. 1 is an NMR spectrum diagram of an intermediate of the compound of the present invention,
FIGS. 2 and 3 are NMR spectra of the compounds of the present invention, respectively. Figure 1 Figure 2 Figure 3

Claims

【特許請求の範囲】１次の一般式 ▲数式、化学式、表等があります▼ （式中のＲはメチル基又はエチル基等の低級アルキル基
を示す）で表わされる１−（３・７−ジメチル−７−ア
ルコキシ−２−オクテニル）−２−メチルベンゾイミダ
ゾール。２次の一般式 ▲数式、化学式、表等があります▼ （式中のＲはメチル基又はエチル基等の低級アルキル基
を示す）で表わされる１−（３・７−ジメチル−７−ア
ルコキシ−２−オクテニル）−２−メチルベンゾイミダ
ゾールを有効成分として含有することを特徴とする殺虫
剤。[Claims] 1 1-(3.7- Dimethyl-7-alkoxy-2-octenyl)-2-methylbenzimidazole. 2. 1-(3,7-dimethyl-7-alkoxy- An insecticide characterized by containing 2-octenyl)-2-methylbenzimidazole as an active ingredient.