JPH0458441B2

JPH0458441B2 -

Info

Publication number: JPH0458441B2
Application number: JP4025983A
Authority: JP
Inventors: Yoji Takahashi; Kenji Yoshida; Toyohiko Yotsuya
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Kasei Corp
Priority date: 1983-03-11
Filing date: 1983-03-11
Publication date: 1992-09-17
Also published as: JPS59164706A

Description

[Detailed description of the invention]

本発明はカーバメート系化合物を有効成分とす
る害虫忌避剤に関するものである。従来、害虫忌避剤としては、Ｎ、Ｎ−ジエチル
−ｍ−トルアミド（以下、DEETという。）が一
般に広く使用されているが、薬効の点で未だ満足
すべきものではない。本発明者らは従来殺虫剤として知られているカ
ーバメート系化合物について害虫忌避効果に関し
て検討を行なつたところ、ｍ−トリル−Ｎ−メチ
ルカーバメート（以下、MTMCという。）等の殺
虫剤として実用されているカーバメート系化合物
は害虫回避効果を殆ど示さず、殺虫効果が低くて
殺虫剤としての実用性のないＮ−フエニルカーバ
メート類、Ｎ−シクロヘキシルカーバメート類な
どが非常に高い害虫忌避効果を示すことを見い出
し、本発明に到達したものである。すなわち、本発明の要旨は一般式〔〕（式中、R¹はシクロヘキシル基または炭素原子
数１〜４のアルキル基、ハロゲン、メトキシ基お
よびエトキシ基から選ばれる１〜３個の置換基を
有していてもよいフエニル基を表わし、R²は炭
素原子数１〜６のアルキル基を表わし、Ｘおよび
Ｙはイオウまたは酸素を表わす。）で示されるカ
ーバメートを有効成分とする害虫忌避剤にある。以下に本発明を詳細に説明する。本発明の害虫忌避剤の有効成分であるカーバメ
ートは前記一般式〔〕で示される化合物であ
り、R¹で表わされる置換フエニル基の具体例と
してはｐ−クロロフエニル基、ｍ−クロロフエニ
ル基、ｐ−フルオロフエニル基、ｍ−ブロモフエ
ニル基、３，４−ジクロロフエニル基、２，６−
ジクロロフエニル基、２，４，６−トリクロロフ
エニル基等の１〜３個のハロゲンにより置換され
たフニニル基、ｐ−トリル基、ｍ−トリル基、
２，３−キシリル基、２，４−キシリル基、２，
６−キシリル基、メシチル基、ｐ−クメニル基、
ｐ−ブチルフエニル基等の炭素原子数１〜４のア
ルキル基を１〜３個有するフエニル基、ｐ−アニ
シル基、１−メチル−４−エトキシフエニル基等
のメトキシ基あるいはエトキシ基を置換基として
有するフエニル基などが挙げられる。またR²で
表わされる炭素原子数１〜６のアルキル基として
は、メチル基、エチル基、プロピル基、イソプロ
ピル基、ブチル基、イソブチル基、ｔ−ブチル
基、ペンチル基、イソペンチル基、ヘキシル基、
イソヘキシル基等が挙げられる。前記一般式〔〕で示されるカーバメートのな
かでも特に好ましいものはR¹がフエニル基また
はシクロヘキシル基であつて、Ｘがイオウ、Ｙが
酸素であつて、R²がメチル基、エチル基または
炭素原子数３〜６の分岐鎖アルキル基であるカー
バメートである。これら化合物の使用量は、有効成分化合物とし
て１m²あたり10〜1000mg、好ましくは50〜500mg
である。適用害虫としては、ゴキブリ、黒アリ、シロア
リ、蚊、ダニ、ハエ、イガ、コクゾウムシ等に対
して有効であるが、特にゴキブリ、黒アリ、ダニ
に対し強力な回避作用を示す。本発明の害虫忌避剤は、一般家庭の台所、食堂
等のみならず、ホテル、レストラン、病院等の厨
房、収納家具内等広い用途を有する。これら化合物は、常法に従つて各種の形態例え
ば液剤、粉剤、粒剤等にして使用できる。液剤の場合の担体としては、例えば水、エチル
アルコール、メチルアルコール等のアルコール
類、アセトン、メチルエチルケトン等のケトン
類、テトラヒドロフラン、ジオキサン等のエーテ
ル類、ヘキサン、ケロシン、パラフイン、ベンゼ
ン、トルエン等の炭化水素類が挙げられる。粉剤及び粒剤の場合の担体としては、例えばケ
イ酸、カオリン、珪藻土、タルク、殿粉等が挙げ
られる。また、本発明化合物は、適宜の溶媒に稀釈し木
材、プラスチツクス、繊維、ワツクス類に含浸、
塗布してもよい。更に、公知の殺虫剤、殺菌剤、
防黴剤等を組合せることもできる。以下に実施例により本発明を更に具体的に説明
する。実施例１、比較例１（コナダニに対する忌避効果）表−５に示す化合物の0.5％アセトン溶液を黒
色紙（５×５cm）に0.5mlあて処理する（忌避剤
として１ｇ／m²相当）。あらかじめ、シヤーレ
（９cm）にケナガコナダニの飽和培地（培地は朝
日麦酒株式会社製の乾燥酵母エビオスを使用）を
約４ｇ入れておく。この上に、ダンボール紙（６
×６cm）、上記の忌避剤処理黒色紙、それに無処
理の黒色紙（３×３cm）の順に静かに重ねて設置
する。24時間後に、無処理の紙上のダニの数を調
査し、忌避効果を判定した。実験は２回くり返し
て行つた。結果を表−１に示した。 The present invention relates to an insect repellent containing a carbamate compound as an active ingredient. Conventionally, N,N-diethyl-m-toluamide (hereinafter referred to as DEET) has been widely used as an insect repellent, but it is still unsatisfactory in terms of medicinal efficacy. The present inventors investigated the pest repellent effects of carbamate compounds, which are conventionally known as insecticides, and found that m-tolyl-N-methylcarbamate (hereinafter referred to as MTMC) and other insecticides have been put to practical use. Carbamate-based compounds, which have been found in many countries, have almost no insect repellent effect, while N-phenyl carbamates, N-cyclohexyl carbamates, etc., which have low insecticidal effects and are not practical as insecticides, have extremely high insect repellent effects. This is what led to the present invention. That is, the gist of the present invention is the general formula [] (In the formula, R ¹ represents a cyclohexyl group or a phenyl group optionally having 1 to 3 substituents selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a methoxy group, and an ethoxy group, ² represents an alkyl group having 1 to 6 carbon atoms, and X and Y represent sulfur or oxygen. The present invention will be explained in detail below. Carbamate, which is an active ingredient of the pest repellent of the present invention, is a compound represented by the above general formula [], and specific examples of the substituted phenyl group represented by R ¹ include p-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, and p-chlorophenyl group. Fluorophenyl group, m-bromophenyl group, 3,4-dichlorophenyl group, 2,6-
a dichlorophenyl group, a p-tolyl group, a m-tolyl group substituted with 1 to 3 halogens such as a 2,4,6-trichlorophenyl group,
2,3-xylyl group, 2,4-xylyl group, 2,
6-xylyl group, mesityl group, p-cumenyl group,
A phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms such as p-butylphenyl group, p-anisyl group, methoxy group or ethoxy group such as 1-methyl-4-ethoxyphenyl group as a substituent Examples include phenyl groups. Further, as the alkyl group having 1 to 6 carbon atoms represented by ^R2 , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group,
Examples include isohexyl group. Among the carbamates represented by the above general formula [], particularly preferred are those in which R ¹ is a phenyl group or a cyclohexyl group, X is sulfur, Y is oxygen, and R ² is a methyl group, an ethyl group, or a carbon atom. It is a carbamate which is a branched alkyl group of number 3 to 6. The usage amount of these compounds is 10 to 1000 mg, preferably 50 to 500 mg per 1 m ² as the active ingredient compound.
It is. It is effective against pests such as cockroaches, black ants, termites, mosquitoes, mites, flies, burrs, and weevils, but it shows a particularly strong evasion effect against cockroaches, black ants, and mites. The pest repellent of the present invention has a wide range of uses, not only in general household kitchens and cafeterias, but also in the kitchens of hotels, restaurants, hospitals, etc., and in storage furniture. These compounds can be used in various forms such as liquids, powders, granules, etc. according to conventional methods. Examples of carriers for liquid preparations include water, alcohols such as ethyl alcohol and methyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and hydrocarbons such as hexane, kerosene, paraffin, benzene and toluene. Examples include: Examples of carriers for powders and granules include silicic acid, kaolin, diatomaceous earth, talc, and starch. The compound of the present invention can also be diluted in an appropriate solvent and impregnated into wood, plastics, fibers, waxes, etc.
May be applied. Furthermore, known insecticides, fungicides,
Antifungal agents and the like can also be combined. The present invention will be explained in more detail below with reference to Examples. Example 1, Comparative Example 1 (Repellent effect on white mites) 0.5 ml of a 0.5% acetone solution of the compounds shown in Table 5 was applied to black paper (5 x 5 cm) for treatment (equivalent to 1 g/m ² as a repellent). In advance, approximately 4 g of a saturated medium for woolly mites (dried yeast Ebios manufactured by Asahi Beer Co., Ltd. is used as the medium) is placed in a 9 cm Siare (9 cm). On top of this, put cardboard paper (6
x 6 cm), the above-mentioned repellent-treated black paper, and untreated black paper (3 x 3 cm) in this order. After 24 hours, the number of mites on the untreated paper was counted to determine the repellent effect. The experiment was repeated twice. The results are shown in Table-1.

【表】【table】

【表】実施例２、比較例２実施例１と同じ方法で、さらに低薬量（１ｇ／
m²、0.25ｇ／m³、0.0625ｇ／m²）での検討を行
い、表−２に示す結果を得た。[Table] Example 2, Comparative Example 2 Using the same method as Example 1, a lower dose (1 g/
m ² , 0.25 g/m ³ , 0.0625 g/m ² ), and the results shown in Table 2 were obtained.

【表】実施例３、比較例３（ゴキブリに対する忌避効果）表−３に記載した化合物のアセトン溶液（有効
成分0.5％、0.12％）を直径11cmの円型ロ紙に２
ml処理する（忌避剤として、約１ｇ／m²、0.25
ｇ／m²相当）。風乾したのち、スチロール製透明
容器〔35×25.5×６cm（高さ）〕の一方の角に置
く。対照として同じ大きさの無処理のロ紙をもう
一方の角に置く。両ロ紙の中央に、角砂糖（約４
ｇ）を置く。さらに木製シエルター〔９×15×
1.5cm（高さ）〕を両ロ紙から等距離の位置に置
き、この中にチヤバネゴキブリの成虫30頭（雌
15、雄15）を入れる。一定日数後に角砂糖の重量
を計り、摂食された量を知る。回避率は下式で求
めた。なお砂糖以外に、水を与えた。Ａ−Ｂ／Ａ×100（％）Ａ：無処理区の摂食量Ｂ：処理区の摂食量[Table] Example 3, Comparative Example 3 (Repellent effect on cockroaches) An acetone solution of the compounds listed in Table 3 (active ingredients 0.5%, 0.12%) was placed on a circular piece of paper with a diameter of 11 cm.
ml treatment (as a repellent, approximately 1 g/m ² , 0.25
g/ ^m2 equivalent). After air drying, place it in one corner of a transparent styrofoam container [35 x 25.5 x 6 cm (height)]. As a control, place an untreated piece of paper of the same size in the other corner. Place a sugar cube (approximately 4
g). Furthermore, wooden shelter [9×15×
1.5cm (height)] at the same distance from both sides of the paper, and place 30 adult German cockroaches (female) inside.
15, male 15). Weigh the sugar cubes after a certain number of days to find out how much was consumed. The evasion rate was calculated using the formula below. In addition to sugar, water was also given. A-B/A×100 (%) A: Intake amount in untreated area B: Intake amount in treated area

【表】実施例４、比較例４（アリに対する忌避効果）表−４に記載した各化合物の種々の濃度のアセ
トン溶液を調製し、長方形（８×13cm）の紙に
前記アセトン溶液２mlを均一に塗布して風乾した
のち両面接着テープでガラス板に固定した。同じ
大きさの紙をもう一枚用意し、無処理のまま先
の紙と長辺を接するように同じガラス板に固定
した。ポリ塩化ビニル製カツプ（10〜13cmφ、9.5cm
ｈ）の底面（10cmφ）を刳貫き内壁に流動パラフ
インを塗布したのち、上記のガラス板に固定した
二枚の紙でつくられている長方形の中央に、カ
ツプで覆われる円内の未処理紙と処理済紙の
面積が等しくなるように伏せて置いた。上記カツプ内にヒメアリ10頭を放ち、一定時間
経過後のヒメアリの存在位置を調査し、その結果
を表−４に示した。なお、本実験においては濃度１％が20mg／100
cm²の忌避剤使用量に該当する。[Table] Example 4, Comparative Example 4 (Repellent effect on ants) Acetone solutions of various concentrations of each compound listed in Table 4 were prepared, and 2 ml of the acetone solution was uniformly spread on a rectangular (8 x 13 cm) piece of paper. After applying it to a glass plate and letting it air dry, it was fixed to a glass plate using double-sided adhesive tape. Another sheet of paper of the same size was prepared and fixed to the same glass plate with its long sides touching the first sheet without any treatment. PVC cup (10~13cmφ, 9.5cm
Hollow out the bottom (10cmφ) of h) and apply liquid paraffin to the inner wall, then place the untreated paper in the circle covered by the cup in the center of the rectangle made of the two sheets of paper fixed to the glass plate mentioned above. and the treated paper were placed face down so that their areas were equal. Ten lesser ants were released into the cup, and the locations of the lesser ants were investigated after a certain period of time. The results are shown in Table 4. In addition, in this experiment, the concentration of 1% is 20mg/100
Corresponds to the amount of repellent used in cm ² .

【表】実施例５、比較例５（蚊に対する忌避効果） 30メツシユの金網を15cm×12cmに切り、これを
２つ折りにして７cm×11cmのかごをつくつた。こ
のなかに体重20ｇ前後のマウスを入れて固定し、
これを所定の数のアカイエカを入れた金網かご
（30cm×30cm×30cm）のなかにつるした。マウスを固定したかごにはあらかじめ表−５の
化合物のエタノール溶液を一定量処理し、無処理
区にはエタノールのみを処理した。観察は、その時点で吸血中のものも含めて、所
定時間経過ごとに累積吸血蚊数をカウントした。なお、試験は14時頃に開始して、翌日11時頃に
終了した。結果を表−５に示した。[Table] Example 5, Comparative Example 5 (Mosquito repellent effect) A 30-mesh wire mesh was cut into 15 cm x 12 cm and folded in half to make a 7 cm x 11 cm basket. Place a mouse weighing around 20g in this and secure it.
This was hung in a wire mesh basket (30 cm x 30 cm x 30 cm) containing a predetermined number of Culex mosquitoes. The cage in which the mouse was fixed was treated in advance with a fixed amount of an ethanol solution of the compound shown in Table 5, and the untreated area was treated with ethanol alone. For observation, the cumulative number of blood-feeding mosquitoes was counted at predetermined intervals, including mosquitoes currently sucking blood. The test started at around 2:00 p.m. and ended at around 11:00 the next day. The results are shown in Table-5.

【table】

Claims

[Claims] 1. General formula (In the formula, R ¹ represents a cyclohexyl group or a phenyl group optionally having 1 to 3 substituents selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a methoxy group, and an ethoxy group, ² represents an alkyl group having 1 to 6 carbon atoms, and X and Y represent sulfur or oxygen.) An insect repellent containing a carbamate as an active ingredient.