JP2886669B2 - For stabilizing water-soluble pheromone compounds - Google Patents
For stabilizing water-soluble pheromone compoundsInfo
- Publication number
- JP2886669B2 JP2886669B2 JP2305750A JP30575090A JP2886669B2 JP 2886669 B2 JP2886669 B2 JP 2886669B2 JP 2305750 A JP2305750 A JP 2305750A JP 30575090 A JP30575090 A JP 30575090A JP 2886669 B2 JP2886669 B2 JP 2886669B2
- Authority
- JP
- Japan
- Prior art keywords
- sex pheromone
- acetate
- unsaturated double
- double bond
- stabilizing
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本願発明は、交信撹乱防除法による害虫の駆除に有用
な、不飽和二重結合を有する性フェロモン化合物の安定
化方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for stabilizing a sex pheromone compound having an unsaturated double bond, which is useful for controlling pests by a communication disturbance control method.
（従来の技術） 近年、害虫の農薬に対する抵抗性の増加や農薬を扱う
者に対する毒性が問題になってきている。この問題に対
処するため、生物学的害虫駆除法が研究されており、こ
の方法の一つとして害虫の雌が放出する性フェロモンを
化学的に合成し、これを利用する交信撹乱防除法が提案
されている。この防除法においては特公昭61−16361号
公報に記載の徐放体のように性フェロモンを長期間一定
の量放出させることが必要である。しかし、リンシ目害
虫の性フェロモン物質の多くは不飽和二重結合を有する
高級脂肪族誘導体であるため、長期間野外条件下に放置
すると、二重結合が容易に酸化、異性化および重合など
で変質してしまう。(Prior Art) In recent years, increased resistance of pests to pesticides and toxicity to pesticide handlers have become problems. In order to address this problem, biological pest control methods have been studied, and one of these methods is to propose a method of chemically synthesizing sex pheromones released by female pests and using this to control communication disruption. Have been. In this control method, it is necessary to release a constant amount of sex pheromone for a long period of time as in the sustained-release body described in JP-B-61-16361. However, many of the sex pheromone substances of the order Pests of Pterygium are higher aliphatic derivatives having unsaturated double bonds, and when left under outdoor conditions for a long period of time, the double bonds are easily oxidized, isomerized and polymerized. It will change.
これを防ぐため製剤中に酸化防止剤や紫外線吸収剤を
添加する方法が提案された。例えば、Journal of Chemi
cal Ecolo−gy,Vol.14,No.8,1659（1988）には、酸化防
止剤としてジ−ｔ−ブチルヒドロキシトルエンやｔ−ブ
チルヒドロキシアニソールを使用し、これに２−ヒドロ
キシ−４−メトキシベンゾフェノンなどの紫外線吸収剤
を性フェロモン物質に添加使用すると、さらに安定性が
向上すると報告されている。また、特公昭63−12452号
公報には紫外線吸収剤としてベンゾフェノン系化合物を
用い、これに酸化防止剤と第三級アミン化合物を添加使
用することにより、高級脂肪族アルデヒド化合物の安定
性が向上すると報告されている。In order to prevent this, a method of adding an antioxidant or an ultraviolet absorber to the preparation has been proposed. For example, Journal of Chemi
Cal Ecolo-gy, Vol. 14, No. 8, 1659 (1988) uses di-t-butylhydroxytoluene or t-butylhydroxyanisole as an antioxidant, and uses 2-hydroxy-4-methoxy as an antioxidant. It has been reported that when an ultraviolet absorber such as benzophenone is added to a sex pheromone substance, the stability is further improved. In addition, JP-B-63-12452 discloses that the stability of a higher aliphatic aldehyde compound is improved by using a benzophenone-based compound as an ultraviolet absorber and adding and using an antioxidant and a tertiary amine compound. It has been reported.
確かに特定の酸化防止剤や紫外線吸収剤では、単独で
使用するよりも混合使用の方が不飽和二重結合を有する
性フェロモン化合物の安定性の向上に役立つが、現在知
られている酸化防止剤と紫外線吸収剤の組合せでは実用
上充分な安定化効果は得られていない。したがって、さ
らに安定化効果の高い安定剤が望まれているが、数多く
ある安定剤をどのように組合せれば最も有効かというこ
とまでは知られていない。Certainly, with certain antioxidants and UV absorbers, mixed use can help improve the stability of sex pheromone compounds with unsaturated double bonds rather than using them alone. A practically sufficient stabilizing effect has not been obtained with a combination of an agent and an ultraviolet absorber. Therefore, although a stabilizer having a higher stabilizing effect has been desired, it is not known how many stabilizers are most effective when combined.
（発明が解決しようとする課題） したがって、本発明の目的は不飽和二重結合を有する
性フェロモン化合物の安定性の向上に有用な添加物の組
合せを提供するにある。(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a combination of additives useful for improving the stability of a sex pheromone compound having an unsaturated double bond.
（課題を解決するための手段） 本発明による不飽和二重結合を有する性フェロモン化
合物の安定化方法は、これに、２−（２′−ヒドロキシ
−５′−メチルフェニル）ベンゾトリアゾールとヒドロ
キノン誘導体とを、好ましくはそれぞれ0.1〜10重量％
の割合で添加混合することを特徴とするものであり、こ
のヒドロキノン誘導体として下記一般式（１） で示されるヒドロキノン誘導体（ここにR1はｔ−ブチル
基またはｔ−アミル基を、R2は水素原子、ｔ−ブチル基
またはｔ−アミル基を示す）を使用することを好適とす
るものである。(Means for Solving the Problems) The method for stabilizing a sex pheromone compound having an unsaturated double bond according to the present invention comprises two steps: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and a hydroquinone derivative. And preferably 0.1 to 10% by weight, respectively.
Wherein the hydroquinone derivative has the following general formula (1): Wherein R 1 represents a t-butyl group or a t-amyl group, and R 2 represents a hydrogen atom, a t-butyl group or a t-amyl group. is there.
以下、本発明の詳細を説明する。 Hereinafter, details of the present invention will be described.
本発明者らは不飽和二重結合を有する性フェロモン化
合物が、二重結合の酸化や異性化、重合などを起しやす
いことから、これを防止するため、各種安定剤の組合せ
を鋭意検討した結果、２−（２′−ヒドロキシ−５′−
メチルフェニル）ベンゾトリアゾールとヒドロキノン誘
導体とを組合せたものが最も優れていること、また、こ
のヒドロキノン誘導体には上記一般式（１）で表わされ
るヒドロキノン誘導体が最も好適であることを見出し本
発明に到達した。The present inventors have intensively studied combinations of various stabilizers in order to prevent sex pheromone compounds having an unsaturated double bond from being liable to cause oxidation, isomerization, and polymerization of the double bond, and to prevent this. As a result, 2- (2'-hydroxy-5'-
It has been found that a combination of (methylphenyl) benzotriazole and a hydroquinone derivative is the most excellent, and that the hydroquinone derivative represented by the above general formula (1) is most suitable for this hydroquinone derivative, and the present invention has been achieved. did.
本発明において安定剤として使用される２−（２′−
ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾー
ルとヒドロキノン誘導体とは、それぞれ混合されること
が重要であり、この混合物に他の安定剤をさらに混合し
て使用してもよい。2- (2'-) used as a stabilizer in the present invention
It is important that the (hydroxy-5'-methylphenyl) benzotriazole and the hydroquinone derivative are mixed with each other, and other stabilizers may be further mixed with this mixture and used.
この安定剤の不飽和二重結合を有する性フェロモン化
合物に対する使用量は、それぞれ0.1〜10重量％の割合
であって、これが0.1％未満では効果が少なく、また10
重量％を超えて使用してもこれ以上の効果の向上が見込
めないため経済的に好ましくない。The amount of the stabilizer to be used for the sex pheromone compound having an unsaturated double bond is 0.1 to 10% by weight, respectively. If the amount is less than 0.1%, the effect is small.
Even if it is used in excess of weight%, no further improvement in the effect can be expected, which is economically undesirable.
この酸化防止剤にはｔ−ブチルヒドロキノン、ジ−ｔ
−ブチルヒドロキノン、ジ−ｔ−アミルヒドロキノン、
ジ−ｔ−ブチルレゾルシン、ヒドロキノン、などが例示
されるが、高級脂肪族誘導体である性フェロモンに対す
る相溶性や安定化効果の点からは、上記一般式で表され
るヒドロキノン誘導体が望ましい。The antioxidants include t-butylhydroquinone, di-t
-Butylhydroquinone, di-t-amylhydroquinone,
Examples thereof include di-t-butyl resorcin, hydroquinone, and the like. From the viewpoint of compatibility and stabilizing effect with a higher aliphatic derivative sex pheromone, a hydroquinone derivative represented by the above general formula is desirable.
本発明が適用される不飽和二重結合を有する性フェロ
モン化合物には、Ｚ−７−ドデセニルアセテート、Ｚ−
８−ドデセニルアセテート、Ｚ−９−ドデセニルアセテ
ート、E,Z−7,9−ドデカジエニルアセテート、E,E−8,1
0−ドデカジエノール、Ｅ−４−トリデセニルアセテー
ト、Ｚ−９−テトラデセニルアセテート、Ｚ−９−テト
ラデセノール、Ｚ−11−テトラデセニルアセテート、Z,
E−9,11−テトラデカジエニルアセテート、Z,E−9,12−
テトラデカジエニルアセテート、Ｚ−11−ヘキサデセニ
ルアセテート、Z,Z−7,11−ヘキサデカジエニルアセテ
ート、E,E,7−4,6,10−ヘキサデカトリエニルアセテー
ト、Z,Z−3,13−オクタデカジエニルアセテート、E,Z−
3,13−オクタデカジエニルアセテート、Z,13−イコセン
−10−オンなどが例示される。これらの中でも通常不安
定とされている、不飽和二重結合を２個以上含む化合物
に対して本発明の安定効果が高い。The sex pheromone compound having an unsaturated double bond to which the present invention is applied includes Z-7-dodecenyl acetate, Z-
8-dodecenyl acetate, Z-9-dodecenyl acetate, E, Z-7,9-dodecadienenyl acetate, E, E-8,1
0-dodecadienol, E-4-tridecenyl acetate, Z-9-tetradecenyl acetate, Z-9-tetradecenol, Z-11-tetradecenyl acetate, Z,
E-9,11-tetradecadienyl acetate, Z, E-9,12-
Tetradecadienyl acetate, Z-11-hexadecenyl acetate, Z, Z-7,11-hexadecadienyl acetate, E, E, 7-4,6,10-hexadecatrienyl acetate, Z, Z-3,13-octadecadienyl acetate, E, Z-
Examples thereof include 3,13-octadecadienyl acetate and Z, 13-icosen-10-one. Among these, compounds having two or more unsaturated double bonds, which are usually unstable, have a high stabilizing effect of the present invention.
（実施例） 以下、本発明の具体的な態様を実施例および比較例に
より説明するが、本発明はこれに限定されるものではな
い。EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
内径1mm、外径2mm、長さ20cmのガラス管内に、次表に
示す性フェロモン化合物と安定剤の混合物の100mgを充
填した後、両端に栓をして野外の直射日光の当る場所に
６月から３ヵ月間曝露した。その後、開封して混合液を
取り出し、変性しないで残存している性フェロモン量を
内部標準法ガスクロマトグラフィーによって定量して、
充填時の性フェロモンに対する残存率を求めた。After filling 100mg of the mixture of the sex pheromone compound and the stabilizer shown in the following table in a glass tube of 1mm inner diameter, 2mm outer diameter and 20cm length, plug both ends and put it in a place exposed to direct sunlight in June. For 3 months. After that, open and take out the mixed solution, determine the amount of sex pheromone remaining without denaturation by internal standard method gas chromatography,
The residual ratio to the sex pheromone at the time of filling was determined.
表より、実施例の組合せでは比較例に比べ性フェロモ
ンの残存率が高く顕著な安定化効果のあることが判っ
た。From the table, it was found that the residual ratio of sex pheromone was higher in the combination of the examples than in the comparative example, and there was a remarkable stabilizing effect.
なお、各例で用いた性フェロモン、安定剤は次の通り
である。The sex pheromone and stabilizer used in each example are as follows.
・性フェロモン I :E,7−7,9−ドデカジエニルアセテート、 II :Z,Z−7,11−ヘキサデカジエニルアセテート、 III:Z,E−9,12−テトラデカジエニルアセテート、 ・安定剤 HMBT:2−（２′−ヒドロキシ−５′−メチルフェニル）
ベンゾトリアゾール、 （酸化防止剤） TBH:t−ブチルヒドロキノン、 BHA:t−ブチルヒドロキシアニソール （その他） HMBP:2−ヒドロキシ−４−メトキシベンゾフェノン （発明の効果） 本発明によれば、請求項１記載の不飽和二重結合を有
する性フェロモン化合物の安定性の向上に最も有効に作
用する。Sex pheromone I: E, 7-7,9-dodecadienenyl acetate, II: Z, Z-7,11-hexadecadienenyl acetate, III: Z, E-9,12-tetradecadienyl acetate, .Stabilizer HMBT: 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, (antioxidant) TBH: t-butylhydroquinone, BHA: t-butylhydroxyanisole (others) HMBP: 2-hydroxy-4-methoxybenzophenone (Effect of the Invention) According to the present invention, the present invention most effectively acts to improve the stability of the sex pheromone compound having an unsaturated double bond.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 左口 龍一 新潟県中頚城郡頚城村大字西福島28番地 の１ 信越化学工業株式会社合成技術研 究所内 (56)参考文献 特開 昭59−51232（ＪＰ，Ａ) 特開 昭56−95101（ＪＰ，Ａ) 特開 昭62−108801（ＪＰ，Ａ) 特開 平３−112903（ＪＰ，Ａ) 特開 昭57−72904（ＪＰ，Ａ) 特公 昭36−10466（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) A01N 37/02 A01N 25/22 A01N 63/00 C09K 15/08 C09K 15/24 C07C 69/145 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Ryuichi Left Exit 28, Nishifukushima, Oaza, Kushiro-mura, Nakatsukujo-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References JP-A-59-51232 JP, A) JP-A-56-95101 (JP, A) JP-A-62-108801 (JP, A) JP-A-3-112903 (JP, A) JP-A-57-72904 (JP, A) (Showa 36-10466) (JP, B1) (58) Fields investigated (Int. Cl. 6 , DB name) A01N 37/02 A01N 25/22 A01N 63/00 C09K 15/08 C09K 15/24 C07C 69/145 CA (STN) REGISTRY (STN) WPIDS (STN)
Claims (2)
テート、アルコール、ケトンから選択される性フェロモ
ン化合物に、２−（２′−ヒドロキシ−５′−メチルフ
ェニル）ベンゾトリアゾールと下記一般式（１）で表さ
れるヒドロキノン誘導体とを添加、混合することを特徴
とする性フェロモン化合物の安定化方法。 （ただしR1はｔ−ブチル基またはｔ−アミル基を、R2は
水素原子、ｔ−ブチル基またはｔ−アミル基を示す。） (1) a sex pheromone compound selected from higher aliphatic acetates, alcohols and ketones having an unsaturated double bond, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and the following general formula: A method for stabilizing a sex pheromone compound, comprising adding and mixing the hydroquinone derivative represented by (1). (However, R 1 represents a t-butyl group or a t-amyl group, and R 2 represents a hydrogen atom, a t-butyl group or a t-amyl group.)
ェニル）ベンゾトリアゾールとヒドロキノン誘導体と
が、不飽和二重結合を有する性フェロモン化合物に対
し、それぞれ0.1〜10重量％の割合で添加混合される請
求項１記載の性フェロモン化合物の安定化方法。2. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and a hydroquinone derivative are added at a ratio of 0.1 to 10% by weight, respectively, based on the sex pheromone compound having an unsaturated double bond. The method for stabilizing a sex pheromone compound according to claim 1, which is mixed.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2305750A JP2886669B2 (en) | 1990-11-09 | 1990-11-09 | For stabilizing water-soluble pheromone compounds |
| DE19914136832 DE4136832C2 (en) | 1990-11-09 | 1991-11-08 | Process for stabilizing a pheromone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2305750A JP2886669B2 (en) | 1990-11-09 | 1990-11-09 | For stabilizing water-soluble pheromone compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04178308A JPH04178308A (en) | 1992-06-25 |
| JP2886669B2 true JP2886669B2 (en) | 1999-04-26 |
Family
ID=17948898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2305750A Expired - Fee Related JP2886669B2 (en) | 1990-11-09 | 1990-11-09 | For stabilizing water-soluble pheromone compounds |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2886669B2 (en) |
| DE (1) | DE4136832C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3184851B2 (en) * | 1992-09-09 | 2001-07-09 | 信越化学工業株式会社 | For stabilizing water-soluble pheromone compounds |
| DE19528529A1 (en) * | 1995-08-03 | 1997-02-06 | Bayer Ag | Pesticides |
| US6540991B2 (en) * | 2001-04-06 | 2003-04-01 | 3M Innovative Properties Company | Stabilized active materials |
-
1990
- 1990-11-09 JP JP2305750A patent/JP2886669B2/en not_active Expired - Fee Related
-
1991
- 1991-11-08 DE DE19914136832 patent/DE4136832C2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4136832C2 (en) | 2003-07-03 |
| DE4136832A1 (en) | 1992-05-14 |
| JPH04178308A (en) | 1992-06-25 |
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