JPH0672931A - P-menthane-2-methyl-3,8-diol and p-menthane-2-methylene-3,8-diol - Google Patents
P-menthane-2-methyl-3,8-diol and p-menthane-2-methylene-3,8-diolInfo
- Publication number
- JPH0672931A JPH0672931A JP26821991A JP26821991A JPH0672931A JP H0672931 A JPH0672931 A JP H0672931A JP 26821991 A JP26821991 A JP 26821991A JP 26821991 A JP26821991 A JP 26821991A JP H0672931 A JPH0672931 A JP H0672931A
- Authority
- JP
- Japan
- Prior art keywords
- menthane
- diol
- methylene
- formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、それ自体実質的に無臭
の化合物であって、有害生物忌避剤として極めて優れた
持続効果を有する新規化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound which itself is substantially odorless and has an extremely long-lasting effect as a pest repellent.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】蚊等の
有害生物から身を守るために、有害生物忌避剤として
Ｎ，Ｎ−ジエチルトルアミドが広く用いられている。ま
た、ｐ−メンタン−３，８−ジオールにも強い忌避効果
があることが知られている（特開昭６０−１９９８０４
号公報）。2. Description of the Related Art N, N-diethyltoluamide is widely used as a pest repellent in order to protect oneself from pests such as mosquitoes. It is also known that p-menthane-3,8-diol has a strong repellent effect (Japanese Patent Laid-Open No. 60-199804).
Issue).
【０００３】しかしながら、前者のＮ，Ｎ−ジエチルト
ルアミドは特異な臭いを有し、また後者のｐ−メンタン
−３，８−ジオールは忌避効果の持続性に欠ける等の問
題がある。このため、上記のような問題を解決しうる新
規な有害生物忌避剤の開発が望まれていた。However, the former N, N-diethyltoluamide has a peculiar odor, and the latter p-menthane-3,8-diol has a problem that the repellent effect is not persistent. Therefore, it has been desired to develop a new pest repellent capable of solving the above problems.
【０００４】本発明の目的は、優れた有害生物忌避効果
を有し、不快臭の無い有害忌避剤として有用な新規化合
物を提供することにある。An object of the present invention is to provide a novel compound having an excellent pest repellent effect and useful as a pest repellent having no unpleasant odor.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記事情
に鑑み、有害生物忌避剤として強い効果を有し、且つ特
異な臭いを有しない新しい有害生物忌避剤を開発すべく
鋭意研究した結果、新規化合物の合成に成功し、またこ
の化合物が優れた有害生物忌避効果の持続性を有するこ
とを見出した。即ち本発明は、下記構造式SUMMARY OF THE INVENTION In view of the above circumstances, the present inventors have earnestly studied to develop a new pest repellent having a strong effect as a pest repellent and having no peculiar odor. As a result, they have succeeded in synthesizing a novel compound and found that this compound has an excellent pest repellent effect persistence. That is, the present invention has the following structural formula
【化３】 で表されるｐ−メンタン−２−メチル−３，８−ジオー
ル、及び下記構造式[Chemical 3] P-menthane-2-methyl-3,8-diol represented by
【化４】 で表されるｐ−メンタン−２−メチレン−３，８−ジオ
ールである。[Chemical 4] Is p-menthane-2-methylene-3,8-diol.
【０００６】以下、本発明の構成の詳細について説明す
る。本発明のｐ−メンタン−２−メチル−３，８−ジオ
ール（以下、ＭＭＤと略称する）は、２，３，７−トリ
メチル−６−オクテナール（以下、ＴＯと略称する）を
硫酸等の酸水溶液と混合撹拌することにより得ることが
できる。また、本発明のｐ−メンタン−２−メチレン−
３，８−ジオール（以下、ＭＭＥＤと略称する）は、
３，７−ジメチル−２−メチレン−６−オクテナール
（以下、ＤＭＯと略称する）を硫酸等の酸水溶液と混合
撹拌することにより得ることができる。The details of the configuration of the present invention will be described below. The p-menthane-2-methyl-3,8-diol (hereinafter abbreviated as MMD) of the present invention is obtained by converting 2,3,7-trimethyl-6-octenal (hereinafter abbreviated as TO) into an acid such as sulfuric acid. It can be obtained by mixing with an aqueous solution and stirring. In addition, p-menthane-2-methylene- of the present invention
3,8-diol (hereinafter abbreviated as MMED) is
It can be obtained by mixing 3,7-dimethyl-2-methylene-6-octenal (hereinafter abbreviated as DMO) with an aqueous acid solution such as sulfuric acid and stirring.
【０００７】本発明のＭＭＤ及びＭＭＥＤを得るための
それぞれの原料物質である２，３，７−トリメチル−６
−オクテナール（ＴＯ）又は３，７−ジメチル−２−メ
チレン−６−オクテナール（ＤＭＯ）は、いずれもシト
ロネラールより容易に得られる化合物であることが知ら
れている（ＵＳＰ３，４６３，８１８号公報）。2,3,7-Trimethyl-6, which is each raw material for obtaining the MMD and MMED of the present invention
-Octenal (TO) or 3,7-dimethyl-2-methylene-6-octenal (DMO) is known to be a compound easily obtained from citronellal (USP 3,463,818). .
【０００８】上記の合成方法により得られるＭＭＤ及び
ＭＭＥＤは、いずれも臭いがほとんどなく、無色透明の
油状物である。The MMD and MMED obtained by the above-mentioned synthesis method are colorless and transparent oils with almost no odor.
【０００９】また、これらの油状物にカラム処理等を施
し、シス体及びトランス体を単離することにより結晶と
して取り出すこともできる。このＭＭＤ及びＭＭＥＤ
は、シス体及びトランス体のいずれでも蚊などの有害生
物に対し忌避効果に優れている。Further, these oily substances can be taken out as crystals by subjecting the oily substance to column treatment and the like to isolate the cis form and the trans form. This MMD and MMED
Is excellent in repellent effect against pests such as mosquitoes in both cis and trans forms.
【００１０】本発明の化合物を有功成分として、通常に
用いられる化粧料又は医薬品の基剤（ベース）に配合す
ることによって、種々の剤型の有害生物忌避剤を得るこ
とが可能である。そして、本発明の化合物の含有量は、
製剤形態、使用方法、その他の条件によって異なるが、
一般的にはその配合量を０．１％〜９０％、特に３％〜
２０％とすることが好ましいBy incorporating the compound of the present invention as a useful ingredient into a base of cosmetics or pharmaceuticals which is usually used, pest repellents of various dosage forms can be obtained. And the content of the compound of the present invention,
Depending on the formulation form, method of use, and other conditions,
Generally, the blending amount is 0.1% to 90%, especially 3% to
20% is preferable
【００１１】本発明の化合物は、ヒストジマカ等の蚊、
ヤスデ、ヨトウムシ、ナメクジ等の有害生物に使用され
る。The compounds of the present invention are mosquitoes such as Aedes albopictus,
It is used for pests such as millipedes, weevil and slugs.
【００１２】[0012]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。尚、以下における％表示は、特に指定しない
限り重量％を意味する。EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, unless otherwise specified, the% display in the following means% by weight.
【００１３】実施例１ ５０ｇのＴＯを２０％硫酸水溶液３００ｇ中に徐々に添
加した後、２０時間激しく混合撹拌した。この反応溶液
から１５０ｍｌのジエチルエーテルを用いて抽出し、ジ
エチルエーテル層を１０％炭酸ナトリウム水溶液１００
ｍｌにて２度洗浄した後、更に飽和食塩水１００ｍｌに
て２度洗浄した。Example 1 50 g of TO was gradually added to 300 g of a 20% sulfuric acid aqueous solution, and then vigorously mixed and stirred for 20 hours. The reaction solution was extracted with 150 ml of diethyl ether, and the diethyl ether layer was mixed with 100% sodium carbonate aqueous solution 100
After being washed twice with 100 ml of water, it was further washed twice with 100 ml of saturated saline.
【００１４】このジエチルエーテル層を無水炭酸ナトリ
ウムにて乾燥後、ジエチルエーテルを除去することによ
り、粗反応生成物を得た。この粗反応生成物をシリカゲ
ルカラムクロマトグラフィー（展開溶媒 ヘキサン／酢
酸エチル＝４／１）にて生成することにより、無色透明
の油状物４３ｇ（収率７４．５％）を得た。The diethyl ether layer was dried over anhydrous sodium carbonate and the diethyl ether was removed to obtain a crude reaction product. By producing this crude reaction product by silica gel column chromatography (developing solvent hexane / ethyl acetate = 4/1), 43 g (yield 74.5%) of a colorless transparent oily substance was obtained.
【００１５】得られた油状物のマススペクトル測定にお
いては、〔親ピーク分子量〕−１８（Ｈ2 Ｏ由来）のピ
ークを認め、元素分析においては、Ｃ＝７０．８７％、
Ｈ＝１１．９３％の実測値（Ｃ，Ｈの理論値はＣ＝７
０．９２％、Ｈ＝１１．９０％）を示した。更に、赤外
吸収スペクトルの測定によって、３４００ｃｍ-1及び１
１８０ｃｍ-1に水酸基による強い吸収を確認した。ま
た、環状構造に由来する吸収である１４８０ｃｍ-1、９
２０ｃｍ-1〜９４０ｃｍ-1に吸収を確認した。その結
果、ＭＭＤの生成を確認した。In the mass spectrum measurement of the obtained oily substance, a peak of [parent peak molecular weight] -18 (derived from H 2 O) was observed, and in elemental analysis, C = 70.87%,
Measured value of H = 11.93% (theoretical value of C and H is C = 7
0.92%, H = 11.90%). Furthermore, by measuring the infrared absorption spectrum, 3400 cm -1 and 1
Strong absorption by a hydroxyl group was confirmed at 180 cm -1 . In addition, the absorption due to the ring structure is 1480 cm -1 , 9
It was confirmed absorption to 20cm -1 ~940cm -1. As a result, generation of MMD was confirmed.
【００１６】実施例２ ５０ｇのＤＭＯを２０％硫酸水溶液３００ｇ中に徐々に
添加した後、２０時間激しく混合撹拌した。この反応溶
液から１５０ｍｌのジエチルエーテルを用いて抽出し、
ジエチルエーテル層を１０％炭酸ナトリウム水溶液１０
０ｍｌにて２度洗浄した後、更に飽和食塩水１００ｍｌ
にて２度洗浄した。Example 2 50 g of DMO was gradually added to 300 g of a 20% sulfuric acid aqueous solution and then vigorously mixed and stirred for 20 hours. Extract from this reaction solution with 150 ml of diethyl ether,
Diethyl ether layer is 10% sodium carbonate aqueous solution 10
After washing twice with 0 ml, 100 ml of saturated saline solution was added.
It was washed twice in.
【００１７】このジエチルエーテル層を無水炭酸ナトリ
ウムにて乾燥後、ジエチルエーテルを除去することによ
り、粗反応生成物を得た。この粗反応生成物をシリカゲ
ルカラムクロマトグラフィー（展開溶媒 ヘキサン／酢
酸エチル＝４／１）にて生成することにより、無色透明
の油状物４３ｇ（収率７４．５％）を得た。The diethyl ether layer was dried over anhydrous sodium carbonate and the diethyl ether was removed to obtain a crude reaction product. By producing this crude reaction product by silica gel column chromatography (developing solvent hexane / ethyl acetate = 4/1), 43 g (yield 74.5%) of a colorless transparent oily substance was obtained.
【００１８】得られた油状物のマススペクトル測定にお
いては、〔親ピーク分子量〕−１８（Ｈ2 Ｏ由来）のピ
ークを認め、元素分析においては、Ｃ＝７１．７２％、
Ｈ＝１０．８８％の実測値（Ｃ，Ｈの理論値はＣ＝７
１．６９％、Ｈ＝１０．９４％）を示した。更に、赤外
吸収スペクトルの測定によって、３４００ｃｍ-1及び１
１８０ｃｍ-1に水酸基による強い吸収を確認した。ま
た、環状構造に由来する吸収である１４８０ｃｍ-1、９
２０ｃｍ-1〜９４０ｃｍ-1に吸収を確認した。その結
果、ＭＭＥＤの生成を確認した。In the mass spectrum measurement of the obtained oily substance, a peak of [parent peak molecular weight] -18 (derived from H 2 O) was observed, and in elemental analysis, C = 71.72%,
Measured value of H = 10.88% (theoretical value of C and H is C = 7
1.69% and H = 10.94%). Furthermore, by measuring the infrared absorption spectrum, 3400 cm -1 and 1
Strong absorption by a hydroxyl group was confirmed at 180 cm -1 . In addition, the absorption due to the ring structure is 1480 cm -1 , 9
It was confirmed absorption to 20cm -1 ~940cm -1. As a result, generation of MMED was confirmed.
【００１９】以下に本発明の応用例を示す。 応用例１，２及び比較例１，２ 〔リペルローション〕 下記表１の組成に従って、応用例１，２及び比較例１，
２のリペルローションを調製し、下記有害生物忌避試験
を実施した。尚、Ｎ，Ｎ−ジエチルトルアミドは従来よ
り有害生物忌避剤として用いられているものであり、ま
た、ｐ−メンタン−３，８−ジオールは高い忌避効果を
有することで知られている化合物である。The application examples of the present invention are shown below. Application Examples 1 and 2 and Comparative Examples 1 and 2 [Liper Lotion] Application Examples 1 and 2 and Comparative Example 1, according to the compositions in Table 1 below.
2 repel lotions were prepared and the following pest repellent test was conducted. Incidentally, N, N-diethyltoluamide has been conventionally used as a pest repellent, and p-menthane-3,8-diol is a compound known to have a high repellent effect. is there.
【００２０】[0020]
【表１】 [Table 1]
【００２１】有害生物忌避試験 （１）有害生物忌避効果及びその効果持続性の試験方法 ヒストジマカの成虫に対する忌避効果を調べるために以
下の試験を室温３０℃、湿度７０％の恒温室において行
った。左右の前腕に各試験試料を１０ｍｌ塗布した後、
羽化後５〜７日経過したヒストジマカの成虫の雌雄５０
匹づつが入った２０ｃｍ×１５ｃｍの袋状金網に、それ
ぞれの腕を１５分間差入れ吸血の時間を与えた。この施
行を、３０分、１時間、４時間、及び６時間後に行い、
吸血の時間内の吸血の跡の数を求め、次の式から忌避率
を算出した。Pest repellent test (1) Test method for pest repellent effect and its effect persistence The following test was carried out in a constant temperature room at room temperature of 30 ° C. and humidity of 70% to examine the repellent effect of Aedes albopictus on adults. After applying 10 ml of each test sample to the left and right forearms,
Adult male and female of Aedes albopictus 5 to 7 days after emergence
Each arm was inserted into a 20 cm × 15 cm bag-shaped wire net containing the individual animals for 15 minutes to give blood-sucking time. Do this after 30 minutes, 1 hour, 4 hours, and 6 hours,
The number of blood-sucking traces within the time of blood-sucking was obtained, and the repellency rate was calculated from the following formula.
【数１】 Ｘ：試験液を塗布しない場合の吸血の跡の数 Ｙ：試験液を塗布した場合の吸血の跡の数[Equation 1] X: Number of blood-sucking traces when test liquid was not applied Y: Number of blood-sucking traces when test liquid was applied
【００２２】（２）結果 前記応用例１，２及び比較例１，２について、上記ヒス
トジマカ成虫に対する吸血忌避試験を行った結果を表２
に示した。表２から明かなように、本発明のＭＭＤ及び
ＭＭＥＤは優れた有害生物忌避効果を奏し、しかもその
効果の持続性に優れていた。(2) Results Table 2 shows the results of the blood-sucking repellent test for the above adult Aedes albopictus for the above-mentioned Application Examples 1 and 2 and Comparative Examples 1 and 2.
It was shown to. As is clear from Table 2, the MMD and MMED of the present invention exhibited an excellent pest repellent effect, and the effect was excellent in sustainability.
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【発明の効果】以上記載のように、本発明は、有害生物
忌避剤として優れた効果とその持続性を有するｐ−メン
タン−２−メチル−３，８−ジオール及びｐ−メンタン
−２−メチレン−３，８−ジオールを提供するものであ
る。INDUSTRIAL APPLICABILITY As described above, the present invention provides p-menthane-2-methyl-3,8-diol and p-menthane-2-methylene having excellent effects as pest repellents and its longevity. -3,8-diol.
Claims (2)
ル。1. The following general structural formula: P-menthane-2-methyl-3,8-diol represented by:
ール。2. The following general structural formula: P-menthane-2-methylene-3,8-diol represented by:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26821991A JP2840145B2 (en) | 1991-09-18 | 1991-09-18 | p-menthan-2-methyl-3,8-diol and p-menthan-2-methylene-3,8-diol |
| US09/492,351 US6372804B1 (en) | 1991-09-02 | 2000-01-27 | Noxious-insect repellent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26821991A JP2840145B2 (en) | 1991-09-18 | 1991-09-18 | p-menthan-2-methyl-3,8-diol and p-menthan-2-methylene-3,8-diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0672931A true JPH0672931A (en) | 1994-03-15 |
| JP2840145B2 JP2840145B2 (en) | 1998-12-24 |
Family
ID=17455570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26821991A Expired - Fee Related JP2840145B2 (en) | 1991-09-02 | 1991-09-18 | p-menthan-2-methyl-3,8-diol and p-menthan-2-methylene-3,8-diol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2840145B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130255A (en) * | 1993-10-22 | 2000-10-10 | Ikemoto; Takeshi | Noxious-insect repellent |
-
1991
- 1991-09-18 JP JP26821991A patent/JP2840145B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130255A (en) * | 1993-10-22 | 2000-10-10 | Ikemoto; Takeshi | Noxious-insect repellent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2840145B2 (en) | 1998-12-24 |
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