JP4023721B2 - Sexual stimulant for the long-horned beetle - Google Patents
Sexual stimulant for the long-horned beetle Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は、ゴマダラカミキリの防除あるいは発生予察のための新規化合物および性刺激剤に関する。
【0002】
【従来の技術】
フトカミキリ亜科に属するゴマダラカミキリは、その幼虫および成虫のいずれもが柑橘類やプラタナス等を食害する、これらの植物の大害虫である。すなわち、ゴマダラカミキリは、その幼虫が柑橘類やプラタナスなど多種の木本植物の幹部及び地下部に食入して形成層付近を食害すると共に、成虫が茎葉部を食害することによって樹勢を著しく弱める。このような加害形態によって、樹木を枯死に至らしめることも珍しくない。
【0003】
しかもゴマダラカミキリは、発生時期が数ヶ月と長期にわたる上、産卵が樹皮下になされるので殺虫剤による防除が困難である。また、果樹や街路樹に対する殺虫剤の使用には多くの制限がある。従って、ゴマダラカミキリを効果的に防除するためには、殺虫剤に代わる新たな防除手段が求められている。
【0004】
一方、近年多くの害虫について、殺虫剤等による防除の代替法としてフェロモンを利用した防除法が研究された結果、誘引性の性フェロモンを用いて、害虫の発生消長調査や交信撹乱法などによる害虫防除が実用化されている。
【0005】
フェロモンを利用した害虫防除法は、該フェロモンによって防除対象害虫を誘殺あるいは正常な生殖行動を攪乱することによって対象害虫を防除するものである。該方法は、対象害虫以外の生物に対する安全性の面等において、優れた方法である。
【0006】
ゴマダラカミキリに関しても、本出願人らの出願による15−メチルヘントリアコンタンおよび/または4−メチルオクタコサンを活性成分として含有する性刺激剤に係る発明が特許第3079259号として、既に特許付与されている。
また、これら以外の炭化水素類、すなわち、ヘプタコサン、ノナコサン、4−メチルヘキサコサン、9−メチルヘプタコサン、9−メチルノナコサンおよび15−メチルヘントリトリアコンタンも、ゴマダラカミキリ雌性フェロモンの成分であることが明らかになっている。
【0007】
しかしながら、ゴマダラカミキリの雌性フェロモンは、上記活性成分以外にもにも活性成分を含むものであると考えられていた。したがって、該未同定成分の特定、およびそれらの合成方法の確立が望まれている。
【0008】
【発明が解決しようとする課題】
したがって、本発明の課題は、ゴマダラカミキリの性刺激剤のための新規化合物の探索によって、新規な成分の取得およびそれを用いた性刺激剤を提供することにある。
【0009】
【課題を解決するための手段】
本発明者らは、上記事情に鑑みゴマダラカミキリの雌性フェロモンに関して鋭意研究を行った結果、ゴマダラカミキリの雌性フェロモンは3つの化合物群によって構成され、その1群には従来知られていなかった新規ケトン類が含有されていることを見出し、当該物質の同定に成功するとともに、それらがゴマダラカミキリに対する優れた性刺激活性を有することを見出し、本発明を完成するに至った。
【0010】
すなわち、本発明は、10-ヘプタコサノンに関する。
また、本発明は、(Z)-18-ヘプタコセン-10-オンに関する。
さらに、本発明は、(18Z,21Z)-18,21-ヘプタコサジエン-10-オンに関する。
また、さらに本発明は、(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンに関する。
そして、本発明は、10-ヘプタコサノン、(Z)-18-ヘプタコセン-10-オン、 (18Z,21Z)-18,21-ヘプタコサジエン-10-オンおよび(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンからなる群からの1種または2種以上を有効成分として含むことを特徴とする、ゴマダラカミキリの性刺激剤に関する。
【0011】
本発明者らは、ゴマダラカミキリの雄成虫に対して顕著な活性を有する成分を雌成虫から抽出分画し、前記のとおり活性画分が3群あることを同定し、該活性画分の1群に含有される成分数を特定した上で、前記活性化合物はいずれも前記15−メチルヘントリアコンタンおよび4−メチルオクタコサンより極性が高く、複雑な構造有する化合物であったため、GC−MS、NMRおよび微量化学反応等を用いて、前記1群に含有される全活性化合物の構造を特定した。その結果、本発明者らは、新規化合物である10-ヘプタコサノン、(Z)-18-ヘプタコセン-10-オン、 (18Z,21Z)-18,21-ヘプタコサジエン-10-オンおよび(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンを見出した。
さらに本発明者らは、該新規化合物を化学合成したものが、ゴマダラカミキリ雄に顕著な活性を示すことを確認し、また、前記3群のうちの2群以上を含むもの、とくに3群の全てを含む組成物は、いずれかの群の成分を欠いたものより雄成虫に対する活性が遙かに優れたものであることを見出した。
本発明は、これらの知見に基づいて完成されたものである。
【0012】
本発明によるゴマダラカミキリ性刺激剤の各成分は、1〜2雌当量でも雄成虫に対する活性を示すのに対して、前記既知の炭化水素類(ヘプタコサン、ノナコサン、4−メチルヘキサコサン、4−メチルオクタコサン、9−メチルヘプタコサン、9−メチルノナコサン、15−メチルヘントリアコンタンおよび15−メチルヘントリトリアコンタン)は、8雌当量で活性を示す。すなわち、本発明の性刺激剤は、前記炭化水素類の1/8〜1/4に相当する処理量で雌成虫に対する刺激活性を有する点に特徴がある。
また、本発明によるゴマダラカミキリ性刺激剤の各成分は、相互に混合することによって、または前記4−メチルオクタコサンおよび/または15−メチルヘントリアコンタン等と混合することによって、その活性が相乗的に増強される。
【0013】
本発明に係る性刺激剤の活性成分である10-ヘプタコサノン、(Z)-18-ヘプタコセン-10-オン、 (18Z,21Z)-18,21-ヘプタコサジエン-10-オンおよび(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンは、小さな物体表面に処理することにより、ゴマダラカミキリ雄成虫がこれにふ節や触角などで接触したのち、それを抱き込みさらに腹部末端の先端を小物体の下部に押しつけるという一連の行動を引き起こす活性を示すものである。
【0014】
該活性は、長さ30mm、幅10mm、深さ10mm程度の様々な物体、例えば、ゼラチンカプセルやガラス片、金属片、プラスチック片などの表面に処理することによって発現させることができるが、それによって解発される前記一連の行動は、雌生体に対する行動と全く同一で区別できない。
また、前記成分は、後述するように、いずれも比較的簡単な方法によって合成が可能である。
したがって、本発明の各化合物は、ゴマダラカミキリ雄成虫の防除に適用可能な性刺激剤の成分として、極めて有効なものであると考えられる。
【0015】
【発明の実施の形態】
本発明のゴマダラカミキリの性刺激剤は、10-ヘプタコサノン、(Z)-18-ヘプタコセン-10-オン、 (18Z,21Z)-18,21-ヘプタコサジエン-10-オンおよび(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンからなる群からの1種または2種以上を含むものであれば、その成分に特に制限はない。
【0016】
こららの活性成分は、単独でも性刺激活性を有するが、これらを組み合わせると、それらの活性が相乗的に増強されるため好ましい。
また、これらの活性成分の活性は、4−メチルオクタコサンおよび15−メチルヘントリアコンタン等の炭化水素類等と併用することによっても増強されるため、該併用も好ましい。
【0017】
これらの活性成分は、前記のとおり、1〜2雌当量でもゴマダラカミキリ雄成虫に対して性刺激活性を示す。したがって、実防除場面においては、当該当量範囲の処理量もしくはそれ以上の処理量での使用が好適であると考えられる。
【0018】
次に、実施例を掲げ、活性成分物質の単離と同定、その活性試験並びに活性成分物質の合成例について詳細に説明するが、本発明はこの実施例に限定されるものではない。
【0019】
【実施例】
1)活性成分物質の単離及び同定
活性成分の追跡は、直径12mm、長さ35mmで両端を丸めたガラス棒(以下、俵型ガラス片という)の表面に塗布した試料に触れたゴマダラカミキリの雄の行動を観察する検定法によった。
野外から採集したゴマダラカミキリの雌成虫528頭分の鞘翅をエーテル800mlで3回それぞれ5分間抽出し、抽出物は合わせた。抽出物はヘキサンに転溶しシリカゲルカラムクロマトグラフィーにより分画し、順にヘキサンで溶出される画分(以下ヘキサン画分と記す)、10%酢酸エチルを含むヘキサンで溶出される画分(以下、10%酢酸エチル画分と記す)及び酢酸エチルで溶出される画分(以下、酢酸エチル画分と記す)を得た。
そこで、ヘキサン画分をガスクロマトグラフ直結質量分析計(GC-MS)を用いて分析し、質量スペクトルから、ヘプタコサン、ノナコサン、4-メチルヘキサコサン、4-メチルオクタコサン、9-メチルヘプタコサン、9-メチルノナコサン、15-メチルヘントリアコンタン、15-メチルトリトリアコンタンなど炭化水素類が含まれていることが判明した。
分画された画分(各1雌当量)の活性を試験したところ、10%酢酸エチル画分と合成炭化水素類(ヘプタコサン、ノナコサン、4-メチルヘキサコサン、4-メチルオクタコサン、9-メチルヘプタコサン、9-メチルノナコサン、15-メチルヘントリアコンタン、15-メチルトリトリアコンタンの混合物)及び酢酸エチル画分を混合することにより強い活性が得られた(表1)。
【0020】
【表1】
【0021】
次に10%酢酸エチル画分をGC-MS、高速液体クロマトグラフ(HPLC)、核磁気共鳴装置(NMR)を用いた機器分析や微量化学反応を組み合わせて分析したところ、この画分には10-ヘプタコサノン(以下、飽和ケトンと記す)、(Z)-18-ヘプタコセン-10-オン(以下、モノエンケトンと記す)、(18Z,21Z)-18,21-ヘプタコサジエン-10-オン(以下、ジエンケトンと記す)、 (18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オン(以下、トリエンケトンと記す)の成分が含まれていることが判明した。
【0022】
なお、各成分のマススペクトルを、それぞれ図1〜4に示す。
また、モノエンケトン、ジエンケトンおよびトリエンケトンのNMRデータは、それぞれ以下に示すとおりである。
モノエンケトン; 1H NMR (800MHz) d 0.877 (3H, t, J=7.2Hz, H-1), 0.881(3H, J=7,1Hz, H-27), 2.01 (4H, dt, J=6.9 and 5.9Hz, H-17 and H-20), 2.38 (4H, t, J=7.5Hz, H-9 and H-11), 5.33 (1H, ddt, J=11.0, 6.0 and 1.1Hz, H-18 or H-19), 5.36 (1H, ddt, J=11.0, 6.0 and 1.1Hz, H-19 or H-18).
ジエンケトン;1H NMR (800MHz) d 0.88 (3H, t, J=7.1Hz, H-1), 0.89 (3H, t, J=7.1Hz, H-27), 2.04 (4H, m, H-17 and H-23), 2.38 (4H, t, J=7.6Hz, H-9 and H-11), 2.77 (2H, dddd, J=7.2, 7.0, 1.6 and1.4Hz, H-20), 5.33 (1H, dtt, J=10.7, 7.2 and 1.6Hz, H-19 or H-21), 5.34 (1H, dtt, J=10.7, 7.0 and 1.4Hz, H-21 or H-19), 5.37 (1H, dtt, J=10.6, 6.9 and 1.4Hz, H-18 or H-22), 5.38 (1H, dtt, J=10.6, 7.2 and 1.6Hz, H-22 or H-18).
トリエンケトン; 1H NMR (800MHz) d 0.877 (3H, t, J=7.3Hz, H-1), 0.976(3H, J=7.5Hz, H-27), 2.05 (2H, dt, J=7.1 and 7.1Hz, H-17), 2.08 (2H, ddq, J=7.5, 7.2 and 0.7Hz, H-26), 2.38 (4H, t, J=7.5Hz, H-9 and H-11), 2.80 (4H, m, H-20 and H-23), 5.32 (1H, dtt, J=10.7, 7.2and 1.6Hz, H-24), 5.34 (1H, dtt, J=10.9, 7.0 and 1.4Hz, H-19), 5.36 (2H, ddt, J=11.5, 5.7 and 1.9Hz, H-21 and H-22), 5.38 (1H, dtt, J=10.6, 7.2 and 1.4Hz, H-25), 5.39 (1H, dtt, J=10.6, 7.2 and 1.6Hz, H-18).
【0023】
2)活性成分の合成方法
(A) 10-ヘプタコサノン(飽和ケトン)の合成例
10-ヘプタコサノンは図5に示した経路に従って合成した。以下具体的な合成法について説明する。オクタデカン酸(ステアリン酸)(1)(10.0g)をテトラヒドロフランに溶解し水素化リチウムアルミニウムと反応させた後クロロクロム酸ピリジニウムと反応させ液状のオクタデカナール(2)(9.8g)を得た。(2)(5.0g)はテトラヒドロフラン溶解させ臭化ノニルマグネシウムと反応させることにより液状の10-ヘプタコサノール(3)(10.5g)を得た。(3)はジクロロメタンに溶解させクロロクロム酸ピリジニウムと反応させ液状の10-ヘプタコサノン(4)(9.0g)を得た。該化合物のマススペクトルは、図1に示したゴマダラカミキリ雌成虫由来成分のものと一致した。
【0024】
(B) (Z)-18-ヘプタコセン-10-オン(モノエンケトン)の合成例
(Z)-18-ヘプタコセン-10-オンは図6に示した経路に従って合成した。以下具体的な合成法について説明する。(Z)-9−オクタデセン酸(オレイン酸)(5)(2.94g)をテトラヒドロフランに溶解し水素化リチウムアルミニウムと反応させた後クロロクロム酸ピリジニウムと反応させ液状の(Z)-9-オクタデセナール(6)(1.29g)を得た。(6)(0.5g)はテトラヒドロフラン溶解させ臭化ノニルマグネシウムと反応させることにより液状の(Z)-18-ヘプタコセン-10-オール(7)(1.05g)を得た。(7)はジクロロメタンに溶解させクロロクロム酸ピリジニウムと反応させ粗(Z)-18-ヘプタコセン-10-オン(8)(0.84g)を得、これをシリカゲルカラムクロマトグラフィーで精製して0.24gを得た。該化合物のNMRペクトルはゴマダラカミキリ雌成虫由来成分のものと一致した。さらに該化合物のマススペクトルは、図2に示したゴマダラカミキリ雌成虫由来成分のものと一致した。
【0025】
(C) (18Z,21Z)-18,21-ヘプタコサジエン-10-オン(ジエンケトン)の合成例
(18Z,21Z)-18,21-ヘプタコサジエン-10-オンは図7に示した経路に従って合成した。以下具体的な合成法について説明する。(9Z,12Z)-9,12−オクタデカジエン酸(リノール酸)(9)(2.95g)をテトラヒドロフランに溶解し水素化リチウムアルミニウムと反応させた後クロロクロム酸ピリジニウムと反応させ液状の(9Z,12Z)-9,12−オクタカジエナール(10)(0.85g)を得た。(10)(0.85g)はテトラヒドロフラン溶解させ臭化ノニルマグネシウムと反応させることにより液状の(Z18,Z21)-18,21-ヘプタコサジエン-10-オール(11)(1.83g)を得た。(11)はジクロロメタンに溶解させクロロクロム酸ピリジニウムと反応させ粗(18Z,21Z)-18,21-ヘプタコサジエン-10-オン(12)(1.24g)を得、これをシリカゲルカラムクロマトグラフィーで精製して0.37gを得た。該化合物のNMRペクトルはゴマダラカミキリ雌成虫由来成分のものと一致した。さらに該化合物のマススペクトルは、図3に示したゴマダラカミキリ雌成虫由来成分のものと一致した。
【0026】
(D)(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オン(トリエンケトン)の合成例
(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オンは図8に示した経路に従って合成した。以下具体的な合成法について説明する。(9Z,12Z,15Z)-9,12,15−オクタデカトリエン酸(アルファ-リノレン酸)(13)(10.0g)をテトラヒドロフランに溶解し水素化リチウムアルミニウムと反応させた後クロロクロム酸ピリジニウムと反応させ液状の(9Z,12Z,15Z)-9,12,15−オクタカトリエナール(14)(0.70g)を得た。(14)(0.70g)はテトラヒドロフラン溶解させ臭化ノニルマグネシウムと反応させることにより液状の(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オール(15)(1.12g)を得た。(15)(0.80g)はジクロロメタンに溶解させクロロクロム酸ピリジニウムと反応させ、生成物はシリカゲルカラムクロマトグラフィーで精製して液状の(18Z,21Z,24Z)-18,21,24-ヘプタコサトリエン-10-オン(16)(0.78g)を得た。該化合物のNMRペクトルはゴマダラカミキリ雌成虫由来成分のものと一致した。さらに該化合物のマススペクトルは、図4に示したゴマダラカミキリ雌成虫由来成分のものと一致した。
【0027】
3)活性成分の性刺激活性の確認試験
前記のように別途合成した前記飽和ケトン、モノエンケトン、ジエンケトン、トリエンケトン(各2雌当量)をで混合したものを、合成炭化水素類(各2雌当量;ヘプタコサン140μg、ノナコサン54μg、4−メチルヘキサコサン160μg、4−メチルオクタコサン256μg、9−メチルヘプタコサン132μg、9−メチルノナコサン134μg、15−メチルヘントリアコンタン136μgおよび15−メチルヘントリトリアコンタン92μg)及び酢酸エチル画分(2雌当量)と共に俵型ガラス片に塗布し、これに触れさせたゴマダラカミキリ雌の反応を視察した。雄は合成したケトン類の全部または一部を含有する成分を塗布した俵型ガラス片を抱え込み腹部を俵型ガラス片下部に向かって曲げるという行動を示した。該行動をとった供試虫の割合を反応率(%)としたものを下記に示す (表2)。
下表の結果から、飽和ケトン、モノエンケトン、ジエンケトン、トリエンケトンを含むサンプルに、ゴマダラカミキリ雄成虫に対する性刺激活性があることが明らかになった。
【0028】
【表2】
【図面の簡単な説明】
【図1】 飽和ケトンのマススペクトルを示す図である。
【図2】 モノエンケトンのマススペクトルを示す図である。
【図3】 ジエンケトンのマススペクトルを示す図である。
【図4】 トリエンケトンのマススペクトルを示す図である。
【図5】 飽和ケトンの合成経路の例を示す図である。
【図6】 モノエンケトンの合成経路の例を示す図である。
【図7】 ジエンケトンの合成経路の例を示す図である。
【図8】 トリエンケトンの合成経路の例を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel compound and a sex stimulant for controlling or predicting the occurrence of a longhorn beetle.
[0002]
[Prior art]
The long-horned beetle belongs to the subfamily of Beetle and is a large pest of these plants in which both larvae and adults feed on citrus fruits and plane trees. In other words, the long-horned beetle eats into the trunk and underground parts of various woody plants such as citrus fruits and plane trees, and damages the vicinity of the formation layer, while the adult worm damages the foliage of the stem and leaves. It is not uncommon to cause trees to die with this form of harm.
[0003]
Moreover, it is difficult to control pesticides with insecticides because the spawning period is as long as several months and eggs are laid under the tree. There are also many restrictions on the use of insecticides on fruit trees and street trees. Therefore, in order to effectively control the longhorn beetle, a new control means to replace the insecticide is required.
[0004]
On the other hand, as a result of research on the control method using pheromone as an alternative method of control by insecticides etc. for many pests in recent years, pesticides using insect attracting sex pheromone, pest control and investigation method Control has been put to practical use.
[0005]
The pest control method using a pheromone is to control the target pest by killing the target pest to be controlled or disturbing normal reproductive behavior with the pheromone. This method is an excellent method in terms of safety against organisms other than the target pests.
[0006]
As for the long-horned beetle, an invention relating to a sex stimulant containing 15-methylhentriacontane and / or 4-methyloctacosane as an active ingredient according to the applicant's application has already been granted as Patent No. 3079259. .
In addition, hydrocarbons other than these, that is, heptacosane, nonacosane, 4-methylhexacosane, 9-methylheptacosane, 9-methylnonacosane and 15-methylhentolitriacontane are also components of the female pheromone Has been revealed.
[0007]
However, it was considered that the female pheromone of the longhorn beetle contains an active ingredient in addition to the above active ingredients. Therefore, it is desired to identify the unidentified components and establish a synthesis method thereof.
[0008]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to obtain a novel component and provide a sexual stimulant using the same by searching for a novel compound for the sex stimulant of the longhorn beetle.
[0009]
[Means for Solving the Problems]
In light of the above circumstances, the present inventors have conducted intensive research on the female pheromone of the long-horned beetle. As a result, the female pheromone of the long-horned beetle is composed of three compound groups, and one group contains novel ketones that have not been known so far. The present inventors have found that it is contained, and succeeded in identifying the substance, and found that they have excellent sexual stimulating activity against the spotted longhorn beetle, thereby completing the present invention.
[0010]
That is, the present invention relates to 10-heptacosanone.
The present invention also relates to (Z) -18-heptacosen-10-one.
Furthermore, the present invention relates to (18Z, 21Z) -18,21-heptacosadien-10-one.
The present invention further relates to (18Z, 21Z, 24Z) -18,21,24-heptacosatrien-10-one.
The present invention relates to 10-heptacosanone, (Z) -18-heptacosen-10-one, (18Z, 21Z) -18,21-heptacosadien-10-one and (18Z, 21Z, 24Z) -18,21, The present invention relates to a sex stimulant for a long-horned beetle characterized by containing one or more members from the group consisting of 24-heptacosatrien-10-one as active ingredients.
[0011]
The present inventors extracted and fractionated a component having remarkable activity against adult males of the long-horned beetle from female adults, identified three groups of active fractions as described above, and one group of the active fractions Since the active compound was a compound having a more complicated structure and a higher polarity than the 15-methylhentriacontane and 4-methyloctacosane, the number of components contained in the GC-MS, NMR The structure of all active compounds contained in the
Furthermore, the present inventors have confirmed that the chemically synthesized compound of the novel compound exhibits remarkable activity in male tiger beetle males, and includes those containing two or more of the three groups, particularly all three groups. It has been found that the composition containing, is much more active against adult males than those lacking any group of components.
The present invention has been completed based on these findings.
[0012]
Each of the components of the spotted beetle stimulant according to the present invention exhibits activity against adult males even at 1 to 2 female equivalents, whereas the known hydrocarbons (heptacosane, nonacosane, 4-methylhexacosane, 4-methyloctasan) Cosane, 9-methylheptacosane, 9-methylnonacosane, 15-methylhentriacontane and 15-methylhentriatritan) show activity at 8 female equivalents. That is, the sex stimulant of the present invention is characterized in that it has stimulating activity against female adults at a treatment amount corresponding to 1/8 to 1/4 of the hydrocarbons.
In addition, each component of the spotted beetle stimulant according to the present invention is synergistically mixed with each other or mixed with 4-methyloctacosane and / or 15-methylhentriacontane. Be enhanced.
[0013]
10-heptacosanone, (Z) -18-heptacosen-10-one, (18Z, 21Z) -18,21-heptacosadien-10-one and (18Z, 21Z, 24Z) which are active ingredients of the sex stimulant according to the present invention ) -18,21,24-heptacosatrien-10-one is treated on the surface of a small object, so that the adult male larvae come into contact with it at the joints or antennal, and then embraced it, and further the abdominal terminal It shows the activity that causes a series of actions of pressing the tip against the lower part of a small object.
[0014]
The activity can be expressed by treating various objects having a length of about 30 mm, a width of 10 mm, and a depth of about 10 mm, such as gelatin capsules, glass pieces, metal pieces, plastic pieces, etc. The series of actions to be resolved are exactly the same as actions on a female living body and cannot be distinguished.
Further, as will be described later, the components can be synthesized by a relatively simple method.
Therefore, each compound of the present invention is considered to be extremely effective as a component of a sex stimulant that can be applied to the control of male adult longhorn beetle.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The sex stimulant for the long-horned beetle of the present invention is 10-heptacosanone, (Z) -18-heptacosen-10-one, (18Z, 21Z) -18,21-heptacosadien-10-one and (18Z, 21Z, 24Z)- The component is not particularly limited as long as it contains one or more from the group consisting of 18,21,24-heptacosatrien-10-one.
[0016]
These active ingredients alone have sex stimulating activity, but combining them is preferable because their activities are synergistically enhanced.
Moreover, since the activity of these active ingredients is also enhanced by using together with hydrocarbons such as 4-methyloctacosane and 15-methylhentriacontane, the combined use is also preferable.
[0017]
As described above, these active ingredients exhibit sexually stimulating activity against adult male larva even at 1 to 2 female equivalents. Therefore, in actual control situations, it is considered suitable to be used at a throughput in the equivalent range or higher.
[0018]
Next, although an Example is raised and isolation and identification of an active ingredient substance, its activity test, and the synthesis example of an active ingredient substance are demonstrated in detail, this invention is not limited to this Example.
[0019]
【Example】
1) Isolation and identification of active ingredient substance The active ingredient was traced by a male long-horned beetle that touched a sample coated on the surface of a glass rod with a diameter of 12 mm and a length of 35 mm rounded at both ends (hereinafter referred to as a bowl-shaped glass piece). It was based on the test method to observe the behavior.
The pods of 528 adult females of the longhorn beetle collected from the field were extracted 3 times with 800 ml of ether for 5 minutes each, and the extracts were combined. The extract was dissolved in hexane and fractionated by silica gel column chromatography, and the fraction eluted with hexane in order (hereinafter referred to as hexane fraction) and the fraction eluted with hexane containing 10% ethyl acetate (hereinafter, 10% ethyl acetate fraction) and a fraction eluted with ethyl acetate (hereinafter referred to as ethyl acetate fraction).
Therefore, the hexane fraction was analyzed using a gas chromatograph direct mass spectrometer (GC-MS). From the mass spectrum, heptacosan, nonacosan, 4-methylhexacosane, 4-methyloctacosane, 9-methylheptacosane, 9 It was found that hydrocarbons such as -methylnonacosane, 15-methylhentriacontane and 15-methyltritriacontane were contained.
When the activity of the fractions (one female equivalent each) was tested, 10% ethyl acetate fraction and synthetic hydrocarbons (heptacosane, nonacosan, 4-methylhexacosane, 4-methyloctacosane, 9-methyl) Strong activity was obtained by mixing heptacosane, 9-methylnonacosane, 15-methylhentriacontane, 15-methyltritriacontane) and ethyl acetate fraction (Table 1).
[0020]
[Table 1]
[0021]
Next, the 10% ethyl acetate fraction was analyzed by a combination of GC-MS, high performance liquid chromatograph (HPLC), instrumental analysis using a nuclear magnetic resonance apparatus (NMR) and a trace chemical reaction. -Heptacosanone (hereinafter referred to as saturated ketone), (Z) -18-heptacosen-10-one (hereinafter referred to as monoeneketone), (18Z, 21Z) -18,21-heptacosadien-10-one (hereinafter referred to as dieneketone) And (18Z, 21Z, 24Z) -18, 21, 24-heptacosatrien-10-one (hereinafter referred to as triene ketone).
[0022]
In addition, the mass spectrum of each component is shown in FIGS.
The NMR data of monoene ketone, diene ketone, and triene ketone are as shown below.
Monoenketone; 1 H NMR (800MHz) d 0.877 (3H, t, J = 7.2Hz, H-1), 0.881 (3H, J = 7,1Hz, H-27), 2.01 (4H, dt, J = 6.9 and 5.9Hz, H-17 and H-20), 2.38 (4H, t, J = 7.5Hz, H-9 and H-11), 5.33 (1H, ddt, J = 11.0, 6.0 and 1.1Hz, H-18 or H-19), 5.36 (1H, ddt, J = 11.0, 6.0 and 1.1Hz, H-19 or H-18).
Diene ketone; 1 H NMR (800 MHz) d 0.88 (3H, t, J = 7.1 Hz, H-1), 0.89 (3H, t, J = 7.1 Hz, H-27), 2.04 (4H, m, H-17 and H-23), 2.38 (4H, t, J = 7.6Hz, H-9 and H-11), 2.77 (2H, dddd, J = 7.2, 7.0, 1.6 and1.4Hz, H-20), 5.33 ( 1H, dtt, J = 10.7, 7.2 and 1.6Hz, H-19 or H-21), 5.34 (1H, dtt, J = 10.7, 7.0 and 1.4Hz, H-21 or H-19), 5.37 (1H, dtt, J = 10.6, 6.9 and 1.4Hz, H-18 or H-22), 5.38 (1H, dtt, J = 10.6, 7.2 and 1.6Hz, H-22 or H-18).
Triene ketone; 1 H NMR (800MHz) d 0.877 (3H, t, J = 7.3Hz, H-1), 0.976 (3H, J = 7.5Hz, H-27), 2.05 (2H, dt, J = 7.1 and 7.1Hz, H-17), 2.08 (2H, ddq, J = 7.5, 7.2 and 0.7Hz, H-26), 2.38 (4H, t, J = 7.5Hz, H-9 and H-11), 2.80 ( 4H, m, H-20 and H-23), 5.32 (1H, dtt, J = 10.7, 7.2and 1.6Hz, H-24), 5.34 (1H, dtt, J = 10.9, 7.0 and 1.4Hz, H- 19), 5.36 (2H, ddt, J = 11.5, 5.7 and 1.9Hz, H-21 and H-22), 5.38 (1H, dtt, J = 10.6, 7.2 and 1.4Hz, H-25), 5.39 (1H , dtt, J = 10.6, 7.2 and 1.6Hz, H-18).
[0023]
2) Synthesis method of active ingredient (A) Synthesis example of 10-heptacosanone (saturated ketone) 10-Heptacosanone was synthesized according to the route shown in FIG. A specific synthesis method will be described below. Octadecanoic acid (stearic acid) (1) (10.0 g) is dissolved in tetrahydrofuran, reacted with lithium aluminum hydride and then reacted with pyridinium chlorochromate to obtain liquid octadecanal (2) (9.8 g). It was. (2) (5.0 g) was dissolved in tetrahydrofuran and reacted with nonylmagnesium bromide to obtain liquid 10-heptacosanol (3) (10.5 g). (3) was dissolved in dichloromethane and reacted with pyridinium chlorochromate to obtain liquid 10-heptacosanone (4) (9.0 g). The mass spectrum of the compound was consistent with that of the component derived from the female adult beetle shown in FIG.
[0024]
(B) Synthesis example of (Z) -18-heptacosen-10-one (monoene ketone)
(Z) -18-heptacosen-10-one was synthesized according to the route shown in FIG. A specific synthesis method will be described below. (Z) -9-octadecenoic acid (oleic acid) (5) (2.94 g) was dissolved in tetrahydrofuran and reacted with lithium aluminum hydride, then reacted with pyridinium chlorochromate to form liquid (Z) -9-octadecenal (6) (1.29 g) was obtained. (6) (0.5 g) was dissolved in tetrahydrofuran and reacted with nonylmagnesium bromide to obtain liquid (Z) -18-heptacosen-10-ol (7) (1.05 g). (7) was dissolved in dichloromethane and reacted with pyridinium chlorochromate to give crude (Z) -18-heptacosen-10-one (8) (0.84 g), which was purified by silica gel column chromatography to give a 0. 24 g was obtained. The NMR spectrum of the compound coincided with that of a component derived from an adult female beetle. Further, the mass spectrum of the compound coincided with that of the component derived from the female adult beetle shown in FIG.
[0025]
(C) Synthesis example of (18Z, 21Z) -18,21-heptacosadien-10-one (diene ketone)
(18Z, 21Z) -18,21-heptacosadien-10-one was synthesized according to the route shown in FIG. A specific synthesis method will be described below. (9Z, 12Z) -9,12-octadecadienoic acid (linoleic acid) (9) (2.95 g) was dissolved in tetrahydrofuran, reacted with lithium aluminum hydride, then reacted with pyridinium chlorochromate to form a liquid ( 9Z, 12Z) -9,12-octacadienal (10) (0.85 g) was obtained. (10) (0.85 g) was dissolved in tetrahydrofuran and reacted with nonylmagnesium bromide to obtain liquid (Z18, Z21) -18,21-heptacosadien-10-ol (11) (1.83 g). (11) is dissolved in dichloromethane and reacted with pyridinium chlorochromate to obtain crude (18Z, 21Z) -18,21-heptacosadien-10-one (12) (1.24 g), which is purified by silica gel column chromatography. As a result, 0.37 g was obtained. The NMR spectrum of the compound coincided with that of a component derived from an adult female beetle. Further, the mass spectrum of the compound coincided with that of the component derived from the female adult beetle shown in FIG.
[0026]
(D) Synthesis example of (18Z, 21Z, 24Z) -18,21,24-heptacosatrien-10-one (triene ketone)
(18Z, 21Z, 24Z) -18,21,24-heptacosatrien-10-one was synthesized according to the route shown in FIG. A specific synthesis method will be described below. (9Z, 12Z, 15Z) -9,12,15-octadecatrienoic acid (alpha-linolenic acid) (13) (10.0 g) was dissolved in tetrahydrofuran and reacted with lithium aluminum hydride, and then pyridinium chlorochromate. To give liquid (9Z, 12Z, 15Z) -9,12,15-octacatrienal (14) (0.70 g). (14) (0.70 g) is dissolved in tetrahydrofuran and reacted with nonylmagnesium bromide to give a liquid (18Z, 21Z, 24Z) -18,21,24-heptacosatrien-10-ol (15) (1. 12 g) was obtained. (15) (0.80 g) is dissolved in dichloromethane and reacted with pyridinium chlorochromate, and the product is purified by silica gel column chromatography to obtain liquid (18Z, 21Z, 24Z) -18,21,24-heptacosa Trien-10-one (16) (0.78 g) was obtained. The NMR spectrum of the compound coincided with that of a component derived from an adult female beetle. Further, the mass spectrum of the compound coincided with that of the component derived from the female adult beetle shown in FIG.
[0027]
3) Confirmation test of sex stimulating activity of active ingredient A mixture of the saturated ketone, monoeneketone, dieneketone and trieneketone (2 female equivalents each) synthesized separately as described above was synthesized hydrocarbons (2 female equivalents each). 140 μg of heptacosan, 54 μg of nonacosane, 160 μg of 4-methylhexacosane, 256 μg of 4-methyloctacosane, 132 μg of 9-methylheptacosane, 134 μg of 9-methylnonacosane, 136 μg of 15-methylhentriacontane and 15-methylhentriatritan 92 μg) and the ethyl acetate fraction (2 female equivalents) were applied to a saddle-shaped glass piece, and the reaction of a long-horned beetle female touched by this was observed. The male showed the behavior of holding a bowl-shaped glass piece coated with a component containing all or part of the synthesized ketones and bending the abdomen toward the lower part of the bowl-shaped glass piece. The ratio of the test insects that took this behavior as the response rate (%) is shown below (Table 2).
From the results in the table below, it was revealed that samples containing saturated ketones, monoene ketones, diene ketones, and triene ketones have sexual stimulating activity against adult male beetles.
[0028]
[Table 2]
[Brief description of the drawings]
FIG. 1 is a diagram showing a mass spectrum of a saturated ketone.
FIG. 2 is a diagram showing a mass spectrum of a monoene ketone.
FIG. 3 is a diagram showing a mass spectrum of a diene ketone.
FIG. 4 is a diagram showing a mass spectrum of triene ketone.
FIG. 5 is a diagram showing an example of a synthetic pathway for saturated ketones.
FIG. 6 is a diagram showing an example of a monoene ketone synthesis route.
FIG. 7 is a diagram showing an example of a synthesis route of diene ketone.
FIG. 8 is a diagram showing an example of a synthesis route of triene ketone.
Claims (4)
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