JPH0247977B2 - * E ** 4 ** Z ** 100TETORADEKAJENIRUASETAATO * SONOSEIZOHOOYOBISONOKAGOBUTSUTO * Z ** 100TETORADESENIRUASETAATOOJUKOSEIBUNTOSURUKONCHUJUINZAI - Google Patents
* E ** 4 ** Z ** 100TETORADEKAJENIRUASETAATO * SONOSEIZOHOOYOBISONOKAGOBUTSUTO * Z ** 100TETORADESENIRUASETAATOOJUKOSEIBUNTOSURUKONCHUJUINZAIInfo
- Publication number
- JPH0247977B2 JPH0247977B2 JP25520184A JP25520184A JPH0247977B2 JP H0247977 B2 JPH0247977 B2 JP H0247977B2 JP 25520184 A JP25520184 A JP 25520184A JP 25520184 A JP25520184 A JP 25520184A JP H0247977 B2 JPH0247977 B2 JP H0247977B2
- Authority
- JP
- Japan
- Prior art keywords
- following formula
- acetate
- ether
- formula
- reacted
- 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 - Lifetime
Links
- -1 (1-hydroxyhexyl)triphenylphosphonium bromide Chemical compound 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- NKUYBINSWIGLKM-VURMDHGXSA-N C(C)(=O)OC(CCCCC\C=C/C=C)CCCC Chemical compound C(C)(=O)OC(CCCCC\C=C/C=C)CCCC NKUYBINSWIGLKM-VURMDHGXSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- 244000197975 Solidago virgaurea Species 0.000 claims description 6
- 235000000914 Solidago virgaurea Nutrition 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 241000894007 species Species 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- LAXUVNVWTBEWKE-UHFFFAOYSA-N (Z)-10-Tetradecen-1-ol acetate Natural products CCCC=CCCCCCCCCCOC(C)=O LAXUVNVWTBEWKE-UHFFFAOYSA-N 0.000 claims description 4
- LAXUVNVWTBEWKE-WAYWQWQTSA-N 10Z-Tetradecenyl acetate Chemical compound CCC\C=C/CCCCCCCCCOC(C)=O LAXUVNVWTBEWKE-WAYWQWQTSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005667 attractant Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000031902 chemoattractant activity Effects 0.000 claims description 4
- 230000021736 acetylation Effects 0.000 claims description 3
- 238000006640 acetylation reaction Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- BHAHVSKDYRPNIR-PLNGDYQASA-N (z)-dec-6-enal Chemical compound CCC\C=C/CCCCC=O BHAHVSKDYRPNIR-PLNGDYQASA-N 0.000 claims description 2
- SIJLYRDVTMMSIP-UHFFFAOYSA-N 4-Bromo-1-butanol Chemical compound OCCCCBr SIJLYRDVTMMSIP-UHFFFAOYSA-N 0.000 claims description 2
- GBSLQEKRRMETIB-UHFFFAOYSA-N dec-6-en-1-ol Chemical compound CCCC=CCCCCCO GBSLQEKRRMETIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- PZYHLENTJZMOQC-UHFFFAOYSA-N 1-bromohexan-1-ol Chemical compound CCCCCC(O)Br PZYHLENTJZMOQC-UHFFFAOYSA-N 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- IOUUIFSIQMVYKP-UHFFFAOYSA-N Tetradecyl acetate Chemical compound CCCCCCCCCCCCCCOC(C)=O IOUUIFSIQMVYKP-UHFFFAOYSA-N 0.000 description 9
- 239000000877 Sex Attractant Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 241000607479 Yersinia pestis Species 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 241000220225 Malus Species 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UECPLNNAVLEZGO-CCEZHUSRSA-N [(e)-tetradec-1-enyl] acetate Chemical compound CCCCCCCCCCCC\C=C\OC(C)=O UECPLNNAVLEZGO-CCEZHUSRSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002044 hexane fraction Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002420 orchard Substances 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MMFCJPPRCYDLLZ-CMDGGOBGSA-N (2E)-dec-2-enal Chemical compound CCCCCCC\C=C\C=O MMFCJPPRCYDLLZ-CMDGGOBGSA-N 0.000 description 1
- BHAHVSKDYRPNIR-SNAWJCMRSA-N (e)-dec-6-enal Chemical compound CCC\C=C\CCCCC=O BHAHVSKDYRPNIR-SNAWJCMRSA-N 0.000 description 1
- LAXUVNVWTBEWKE-AATRIKPKSA-N 10E-Tetradecenyl acetate Chemical compound CCC\C=C\CCCCCCCCCOC(C)=O LAXUVNVWTBEWKE-AATRIKPKSA-N 0.000 description 1
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- AAAIZLQILBFRTJ-UHFFFAOYSA-N Pentadecyl acetate Chemical compound CCCCCCCCCCCCCCCOC(C)=O AAAIZLQILBFRTJ-UHFFFAOYSA-N 0.000 description 1
- 241000720470 Phyllonorycter Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MMFCJPPRCYDLLZ-UHFFFAOYSA-N dec-2-enal Natural products CCCCCCCC=CC=O MMFCJPPRCYDLLZ-UHFFFAOYSA-N 0.000 description 1
- 230000035613 defoliation Effects 0.000 description 1
- 230000005059 dormancy Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007758 mating behavior Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- ZDRNMODJXFOYMN-UHFFFAOYSA-N tridecyl acetate Chemical compound CCCCCCCCCCCCCOC(C)=O ZDRNMODJXFOYMN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明はキンモンホソガ及びその近縁種の誘引
物質として有用な新規化合物及びその製造法並び
にそれを有効成分とする誘引剤に関する。
キンモンホソガ（Phyllonorycter ringoniela）
はリンゴの重要害虫である。この害虫は表皮をヒ
ダ状にたぐり寄せ葉肉内で棚状組織を点状に食害
し、一葉に数頭寄生すると、リンゴの葉の生理的
な落葉を誘起し、果実の肥大や翌年の花芽の形成
を著しく阻害する被害をもたらす。本種の幼虫は
葉肉内に生息しているため、防除は殺虫剤に対す
る感受性の高い若令幼虫期に限られる。このた
め、本種の発生時期を的確に知ることはきわめて
重要である。
一方、最近多くの害虫についていわゆる性フエ
ロモンの化学構造が明らかにされておりこの性フ
エロモンを用いて害虫の発生消長調査が能率的に
行われるようになつてきている。性フエロモンと
は一般に雌成虫が分泌する化学物質で、同種の雄
成虫に対して種特異的な誘引作用を示す。このよ
うな誘引性の性フエロモンの化学構造を明らかに
し、その物質を化学合成して、いわゆる性誘引物
質として用いることにより、効率的に発生消長を
調査することが可能となる。さらに、この物質を
用いて大量の雄を誘殺したり、雌雄の交尾行動を
撹乱したりすることにより成虫期を対象とした害
虫の防除を行うこともできる。
本発明者らはこれらの事情にかんがみ、キンモ
ンホソガの性フエロモンの研究をおこない、キン
モンホソガの処女雌から雄に対する誘引活性を有
する成分を抽出し、その化学構造を決定した。さ
らに化学的に合成した化合物が、キンモンホソガ
に対して有効な誘引作用を示すことを知つた。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。
本発明における新規化合物は示性式：
で示されるものである。この化合物は。例えば以
下のような方法で合成することができる。
HO−C6H12−OH＋HBr
−→Br−C6H12−OH＋H2O
Br−C6H12−OH−（C6H5）3P
−→〔（C6H5）3P（C6H12−OH）〕Br
〔（C6H5）3P（C6H12−OH）〕Br＋ｎ−
C3H7CHO
ヴイテイツヒ反応
―――――――――→
C3H7−CH＝CH−C5H10−OH
HO−C4H8−OH＋HBr
−→Br−C4H8−OH
Br−C4H8−OH＋（C6H5）3P
−→〔（C6H5）3P（C4H8−OH）〕Br
この化合物をキンモンホソガ用誘引剤の有効成
分として使用する場合、種々の形態が可能であ
る。この化合物はきわめて微量で著効を奏するこ
と、及び揮発性の油状液であることから、そのま
まあるいはヘキサン等の適当な溶媒に溶解したも
のを適当な担体（各種合成高分子体、天然ゴム、
合成ゴム）に吸着させたり、これらの担体素材の
成型物に封入した形態で使用することが好まし
い。
有効成分の含有量は適宜に定めることができる
が、担体に吸着させたり担体素材成型物に封入す
る場合は、担体１ｇ中に0.1〜100mg程度が好まし
い。
このような有効成分を含有する担体あるいは担
体素材成型物を適当な支持体によつて、例えば、
その他の液体を入れた容器（バツトなど）上ある
いは適当な粘着物質を塗布した物体上またはその
付近に設置することによりキンモンホソガが誘引
され、容器（バツトなど）中に落下または粘着物
質に捕捉されて死亡する。
次に本発明に係わる化合物の単離とその構造決
定について説明する。
野外から採集した越冬蛹を休眠消去後、20℃に
全明下で加温し、羽化した成虫の雌を暗条件下に
８時間おいたのちジクロロメタンに浸漬した抽出
物を得た。試料の誘引活性はりんご園またはフラ
イト・トンネルを用いて雄蛾が誘引されるかどう
かにより調べた。
活性物質の単離は次のようにして行つた。101，
000雌からの抽出物をケン化し、不ケン化物と、
ケン化物に分けた。不ケン化物をフロリシルカラ
ムクロマトグラフイによりヘキサン、５％エーテ
ル／ヘキサン、15％エーテル／ヘキサン、25％エ
ーテル／ヘキサン、50％エーテル／ヘキサン、２
％メタノール／エーテル、４％酢酸／エーテルに
よつて順次溶出した。15％エーテル／ヘキサン、
25％エーテル／ヘキサンの２画分を混合後、アセ
チル化を行い、さらにフロリシルカラムクロマト
グラフイにより得られた５％エーテル／ヘキサン
画分につついて硝酸銀−シリカゲルカラムクロマ
トグラフイにかけ、１％エーテル／石油エーテ
ル、３％エーテル／石油エーテル、５％エーテ
ル／石油エーテル、10％エーテル／石油エーテ
ル、50％エーテル／石油エーテル、エーテルによ
り溶出される画分を得た。以上の画分について生
物検定を行つたところ、硝酸銀−シリカゲルカラ
ムクロマトグラフイで得られた５％エーテル／石
油エーテル（AG−３）、10％エーテル／石油エ
ーテル（AG−４）で溶出された２画分を混ぜ合
わせた場合にのみ活性が認められた。そこで、こ
の２画分をべつべつにガスクロマトグラフイによ
り精製を進めた。１％OV−１（1m）のカラムを
用い100から200℃、毎分５℃昇温条件下で分取し
た。この条件でトリデシルアセタート、テトラデ
シルアセタート、ペンタデシルアセタートはそれ
ぞれ、9.3分、11.2分、13.0分に溶出された。AG
−３画分の分取の結果9.9〜11.8分の間に、AG−
４画分では10.4〜11.4分のあいだに溶出された２
画分を混ぜ合わせた場合にのみ活性が認められ
た。次いで、この２画分を10％サーモン1000
（1.2m，195℃）カラムを用いて分取を行つた。
AG−３からの画分は4.3〜5.1分に、AG−４から
の画分は4.5〜5.4分のあいだに溶出される２ピー
クを混ぜ合わせた場合にのみ活性が認められた。
この条件でテトラデシルアセタートは3.8分に溶
出された。この２画分をガスクロマトグラフ−マ
スクロマトグラフイ（GC−MS）により分析し
たところ、AG−３からのピークはテトラデセニ
ルアセタート〔特徴ピーク（相対強度）：61（13），
82（100），194（13）〕、AG−４からのピークはテ
トラデカジエニルアセタート〔特徴ピーク（相対
強度）：61（４），67（100），192（４）〕であること
がわかつた。これらはそれぞれ、1.5μg，0.4μgの
量であつた。
これらの物質の２重結合の位置の決定は、オゾ
ン分解により生じるω−アセトキシアルデヒドを
GC−MSを用いて検出することで行つた。テト
ラデカジエニルアセタートはヒドラジンを用いて
２個の２重結合の片方を飽和にした後、オゾン分
解した。AG−３に含まれるテトラデセニルアセ
タートからはω−アセトキシデカナール〔特徴ピ
ーク（相対強度）：61（40），69（100），171（４），
CIでは215（100）〕が検出されたことから10位に
２重結合があることがわかつた。またAG−４か
らのテトラデセニルアセタート混合物の分析は試
料の量が少ない為、EIで61，CIで（Ｍ＋１）の
フラグメントピークを検出する方法で行い、10位
に２重結合を持つものがあることがわかつた。し
かし、もう１つの２重結合位置についてはわから
なかつたが、ガスクロマトグラフイでの極性、非
極性カラム上のテトラデシルアセタートとの溶出
時間の比較から非共役な位置にあると推定され
た。そこで、２重結合の位置が（３，10）、（４，
10）、（５，10）、（６，10）にあるジエンを合成
し、その生物活性を野外での誘引試験で調べた。
また、モノエンについてもその幾何異性は不明で
あつたので、この点に関してもその生物活性を野
外での誘引試験で調べた。その結果モノエンは
（Ｚ）−10−テトラデセニルアセタート、ジエンは
（Ｅ）−４，（Ｚ）−10−テトラデカジエニルアセタ
ートであることが明らかとなつた。更に、その誘
引力は処女雌とほぼ同等であつた。
実施例
（Ｅ）−４，（Ｚ）−10−テトラデカジエニルア
セタートの合成
１） HO−C6H12−OH＋HBr
〔〕
−→Br−C6H12−OH＋H2O
〔〕
１，６−ヘキサンジオール（）59ｇと臭化
水素酸90ｇを80℃で連続抽出しながら反応させ
て６−ブロモ−１−ヘキサノール（）を得
た。フロリシルカラムでジブロム化合物と未反
応物を除いた（収率52％）。
２） Br−C6H12−OH＋（C6H5）3P
〔〕
−→〔（C6H5）3P（C6H12−OH）〕Br
〔〕
１）で得た化合物（）47ｇとトリフエニル
ホスフインを200mlのアセトニトリルに溶かし、
２日間還流した。50ｇの（１−ヒドロキシヘキ
シル）トリフエニルホスホニウムブロマイド
（）が得られ収率は80％であつた。
３）
〔（C6H5）3P（C6H12−OH）〕Br＋ｎ−C3H7CHO
〔〕
−→C3H7−CH＝CH−C5H10−OH
〔〕
次いで乾燥した丸底フラスコに11.2ｇの（１
−ヒドロキシヘキシル）トリフエニルホスホニ
ウムブロマイド（）とそれぞれ20mlの無水エ
ーテルとテトラヒドロフラン、ブチルリチウム
ヘキサン溶液を加えた。１時間撹拌を続けた
後、1.8ｇのブチルアルデヒドを加え、さらに
１時間撹拌を続けて反応させた。水を加えた
後、エーテルで抽出した。フロリシルカラムに
より精製し、1.2ｇの６−デセン−１−オール
（）が得られた（収率38％）。
４）
２ｇの無水クロム酸に20mlのピリジンを加え
ておき、工程３）で得た化合物をゆつくり加え
酸化をおこなつた。フロリシルカラムにより精
製し、20％の収率で６−デセナールを得た。次
いで、硝酸銀シリカゲルカラムクロマトグラフ
イによつてＺ体、Ｅ体に分離し、（Ｚ）−６−デ
セナール（）を得た。
５） HO−C4H8−OH＋HBr 〔〕
−→Br−C4H8−OH 〔〕
１，４−ブタンジオール（）45ｇと臭化水
素酸90ｇを連続抽出しながら80℃で反応させて
４−ブロムブタン−１−オール（）を得た。
これからフロリシルカラムでジブロム化合物と
未反応物を除いた（収率20％）。
６） Br−C4H8−OH＋（C6H5）3P
（）
−→〔（C6H5）3P（C4H8−OH）〕Br
〔〕
工程５）で得た化合物（）15ｇをトリフエ
ニルホスフインを200mlのアセトニトリルに溶
かし、２日間還流し、（１−ヒドロキシブチル）
トリフエニルフオスホニウムブロマイド（）
を得た。（収率73％）。
７）
次いで乾燥した丸底フラスコに2.1ｇの（１
−ヒドロキシブチル）トリフエニルホスホニウ
ムブロマイド（）とそれぞれ20mlの無水エー
テルとテトラヒドロフラン、５mlのブチルリチ
ウムヘキサン溶液を加えた。１時間撹拌を続け
た後、工程４）で得られた160mgの（Ｚ）−６−
デセナール（）を加え、さらに１時間撹拌を
続けて反応させた。水を加えた後、エーテルで
抽出し、フロリシルカラムにより精製した。さ
らに、アセチル化後、硝酸銀シリカゲルカラム
クロマトグラフイによつて精製し12mgの（Ｅ）
−４，（Ｚ）−10−テトラデカジエニルアセター
トと31mgの（Ｚ）−４，（Ｚ）−10−テトラデカ
ジエニルアセタートを得た（収率16％）。
（Ｅ）−４，（Ｚ）−10−テトラデカジエニルア
セタートの物性は次のとおりである。
分子量 252
沸 点 119℃／0.12mmHg
屈折率 1.4655（17℃）
赤外吸収スペクトル（cm-1）（KBr錠剤）
3000（−CH＝CH−）
1735（−Ｃ＝０）
960（−CH＝CH−，トランス
Ｅ）
720（−CH＝CH−，シスＺ）
質量分析スペクトル
ｍ／ｚ 81（ベース）
192（Ｍ−AcOH）
試験例 １
合成化合物（Ｅ）−４，（Ｚ）−10−テトラデカ
ジエニルアセタート、または、その幾何異性体
10μgと（Ｚ）−10−テトラデセニルアセタート、
または、（Ｅ）−10−テトラデセニルアセタート
100μgとをプラスチツクキヤツプ（安元化成(株)
製）に含浸させ、これを粘着式のトラツプ上に置
きリンゴ園に設置した。比較のために誘引源を取
りつけないトラツプと２頭の処女雌を誘引源とし
たトラツプも設置し、捕獲数を調査した。
その結果を下表に示すが、これより（Ｅ）−４，
（Ｚ）−10−テトラデカジエニルアセタートと
（Ｚ）−10−テトラデセニルアセタートの混合物に
処女雌と同程度の誘引力が認められた。
The present invention relates to a novel compound that is useful as an attractant for the goldenrod moth and its related species, a method for producing the same, and an attractant containing the compound as an active ingredient. Phyllonorycter ringoniela
is an important pest of apples. This pest folds the epidermis and damages the shelf tissue within the mesophyll in dots. When several individuals infest one leaf, it induces physiological defoliation of apple leaves, causing fruit enlargement and the formation of next year's flower buds. It causes damage that significantly inhibits formation. Since the larvae of this species live within the mesophyll, control is limited to the young larval stage, which is highly sensitive to insecticides. For this reason, it is extremely important to accurately know when this species appears. On the other hand, the chemical structures of so-called sex pheromones for many pests have recently been clarified, and it has become possible to efficiently investigate the occurrence and fate of pests using these sex pheromones. Sex pheromones are chemical substances that are generally secreted by adult females and exhibit a species-specific attracting effect on adult males of the same species. By clarifying the chemical structure of such attractive sex pheromone, chemically synthesizing the substance, and using it as a so-called sex attractant, it becomes possible to efficiently investigate the development and development of sex pheromone. Furthermore, by using this substance to attract and kill a large number of males or to disrupt the mating behavior of males and females, it is also possible to control pests targeting the adult stage. In view of these circumstances, the present inventors conducted research on the sex pheromone of the goldenrod moth, extracted a component having male-attractive activity from virgin females of the goldenrod moth, and determined its chemical structure. Furthermore, we learned that a chemically synthesized compound exhibits an effective attracting effect on the goldenrod moth. The present invention was completed based on these findings. The novel compound in the present invention has the following formula: This is shown in . This compound is. For example, it can be synthesized by the following method. HO−C 6 H 12 −OH+HBr −→Br−C 6 H 12 −OH+H 2 O Br−C 6 H 12 −OH−(C 6 H 5 ) 3 P −→[(C 6 H 5 ) 3 P(C 6 H 12 −OH)]Br [(C 6 H 5 ) 3 P(C 6 H 12 −OH)]Br+n−
C 3 H 7 CHO Witeizg reaction――――――――――→ C 3 H 7 −CH=CH−C 5 H 10 −OH HO−C 4 H 8 −OH+HBr −→Br−C 4 H 8 −OH Br−C 4 H 8 −OH+(C 6 H 5 ) 3 P −→[(C 6 H 5 ) 3 P(C 4 H 8 −OH)〕Br When this compound is used as an active ingredient of an attractant for goldenrod moth, various forms are possible. Since this compound is effective in extremely small amounts and is a volatile oily liquid, it can be used directly or dissolved in an appropriate solvent such as hexane in an appropriate carrier (such as various synthetic polymers, natural rubber, etc.).
It is preferable to use it in the form of being adsorbed onto a synthetic rubber (synthetic rubber) or encapsulated in a molded product of these carrier materials. The content of the active ingredient can be determined as appropriate, but when adsorbed onto a carrier or encapsulated in a molded carrier material, the content is preferably about 0.1 to 100 mg per gram of the carrier. A carrier or carrier material molded product containing such an active ingredient is supported by a suitable support, for example,
By placing it on or near a container containing other liquids (such as a vat) or an object coated with a suitable sticky substance, the golden moth can be attracted and fall into the container (such as a vat) or become trapped by the sticky substance. die. Next, isolation of the compound according to the present invention and determination of its structure will be explained. After extinguishing dormancy, overwintering pupae collected from the field were warmed to 20°C under full light, and the emerged adult females were left in the dark for 8 hours, and then immersed in dichloromethane to obtain an extract. Attractive activity of the samples was examined by whether male moths were attracted using apple orchards or flight tunnels. Isolation of the active substance was carried out as follows. 101,
000 The extract from the female was saponified and the unsaponifiable matter was
Separated into saponified products. Unsaponifiables were collected by Florisil column chromatography in hexane, 5% ether/hexane, 15% ether/hexane, 25% ether/hexane, 50% ether/hexane, 2
% methanol/ether and 4% acetic acid/ether. 15% ether/hexane,
After mixing the two 25% ether/hexane fractions, acetylation was performed, and the 5% ether/hexane fraction obtained by florisil column chromatography was subjected to silver nitrate-silica gel column chromatography to obtain 1% Fractions eluted with ether/petroleum ether, 3% ether/petroleum ether, 5% ether/petroleum ether, 10% ether/petroleum ether, 50% ether/petroleum ether, and ether were obtained. When bioassay was performed on the above fractions, it was found that eluted with 5% ether/petroleum ether (AG-3) and 10% ether/petroleum ether (AG-4) obtained by silver nitrate-silica gel column chromatography. Activity was observed only when the two fractions were combined. Therefore, these two fractions were purified separately by gas chromatography. Fractionation was carried out using a 1% OV-1 (1 m) column from 100 to 200°C at a heating rate of 5°C per minute. Under these conditions, tridecyl acetate, tetradecyl acetate, and pentadecyl acetate were eluted at 9.3 minutes, 11.2 minutes, and 13.0 minutes, respectively. A.G.
-As a result of fractionation of 3 fractions, between 9.9 and 11.8 minutes, AG-
In the 4th fraction, 2 eluted between 10.4 and 11.4 minutes.
Activity was observed only when the fractions were combined. Next, add these two fractions to 10% Salmon 1000
(1.2 m, 195°C) column was used for fractionation.
Activity was observed only when the two peaks, eluted between 4.3 and 5.1 minutes for the fraction from AG-3 and between 4.5 and 5.4 minutes for the fraction from AG-4, were combined.
Under these conditions, tetradecyl acetate was eluted at 3.8 minutes. When these two fractions were analyzed by gas chromatography-mass chromatography (GC-MS), the peak from AG-3 was tetradecenyl acetate [characteristic peak (relative intensity): 61 (13),
82 (100), 194 (13)], and the peak from AG-4 is tetradecadienyl acetate [characteristic peak (relative intensity): 61 (4), 67 (100), 192 (4)]. I understood. These amounts were 1.5 μg and 0.4 μg, respectively. Determination of the positions of the double bonds in these substances has revealed that ω-acetoxyaldehyde produced by ozonolysis is
This was done by detecting using GC-MS. One of the two double bonds of tetradecadienyl acetate was saturated using hydrazine, and then ozonolysis was performed. From the tetradecenyl acetate contained in AG-3, ω-acetoxydecanal [characteristic peaks (relative intensity): 61 (40), 69 (100), 171 (4),
215 (100)] was detected by CI, indicating that there was a double bond at the 10th position. In addition, since the amount of sample is small, the analysis of the tetradecenyl acetate mixture from AG-4 was carried out by detecting the fragment peaks of 61 with EI and (M+1) with CI, which has a double bond at the 10th position. I found out that there was something. However, the position of the other double bond was not known, but it was presumed to be at a non-conjugated position from a comparison of elution times with tetradecyl acetate on polar and non-polar columns in gas chromatography. Therefore, the positions of the double bonds are (3, 10), (4,
The dienes shown in (10), (5,10), and (6,10) were synthesized and their biological activities were investigated in field attraction tests.
Furthermore, since the geometric isomerism of monoene was unknown, we also investigated its biological activity in this regard through an attraction test in the field. The results revealed that the monoene was (Z)-10-tetradecenyl acetate and the diene was (E)-4,(Z)-10-tetradecadienyl acetate. Moreover, its attractive power was almost the same as that of virgin females. Example (E)-4, Synthesis of (Z)-10-tetradecadienyl acetate 1) HO-C 6 H 12 -OH+HBr [] -→Br-C 6 H 12 -OH+H 2 O [] 1, 59 g of 6-hexanediol () and 90 g of hydrobromic acid were reacted at 80° C. with continuous extraction to obtain 6-bromo-1-hexanol (). The dibrome compound and unreacted substances were removed using a Florisil column (yield 52%). 2) Br−C 6 H 12 −OH+(C 6 H 5 ) 3 P [] −→ [(C 6 H 5 ) 3 P(C 6 H 12 −OH)] Br [] Compound obtained in 1) ( ) and triphenylphosphine in 200ml of acetonitrile,
It was refluxed for 2 days. 50 g of (1-hydroxyhexyl)triphenylphosphonium bromide () was obtained with a yield of 80%. 3) [(C 6 H 5 ) 3 P (C 6 H 12 −OH)] Br+n−C 3 H 7 CHO [] −→C 3 H 7 −CH=CH−C 5 H 10 −OH [] Then drying 11.2 g (1
-hydroxyhexyl) triphenylphosphonium bromide () and 20 ml each of anhydrous ether, tetrahydrofuran, and butyllithium hexane solutions were added. After stirring for 1 hour, 1.8 g of butyraldehyde was added, and stirring was continued for another 1 hour for reaction. After adding water, the mixture was extracted with ether. Purification was performed using a Florisil column to obtain 1.2 g of 6-decen-1-ol (yield: 38%). 4) 20 ml of pyridine was added to 2 g of chromic anhydride, and the compound obtained in step 3) was slowly added to carry out oxidation. Purification was performed using a Florisil column to obtain 6-decenal with a yield of 20%. Next, it was separated into Z form and E form by silver nitrate silica gel column chromatography to obtain (Z)-6-decenal (). 5) HO−C 4 H 8 −OH+HBr [] −→Br−C 4 H 8 −OH [] 45 g of 1,4-butanediol () and 90 g of hydrobromic acid were reacted at 80°C with continuous extraction. 4-bromobutan-1-ol () was obtained.
From this, the dibrome compound and unreacted substances were removed using a Florisil column (yield 20%). 6) Br−C 4 H 8 −OH+(C 6 H 5 ) 3 P () −→ [(C 6 H 5 ) 3 P(C 4 H 8 −OH)] Br [] Compound obtained in step 5) Dissolve 15g of triphenylphosphine in 200ml of acetonitrile and reflux for 2 days to obtain (1-hydroxybutyl)
Triphenylphosphonium bromide ()
I got it. (yield 73%). 7) Then add 2.1 g (1
-hydroxybutyl) triphenylphosphonium bromide (20 ml each of anhydrous ether and tetrahydrofuran, and 5 ml of butyllithium hexane solution were added. After continuing stirring for 1 hour, 160 mg of (Z)-6- obtained in step 4)
Decenal () was added and the reaction was continued with stirring for an additional hour. After adding water, the mixture was extracted with ether and purified using a Florisil column. Furthermore, after acetylation, 12 mg of (E) was purified by silver nitrate silica gel column chromatography.
-4,(Z)-10-tetradecadienyl acetate and 31 mg of (Z)-4,(Z)-10-tetradecadienyl acetate were obtained (yield 16%). The physical properties of (E)-4,(Z)-10-tetradecadienyl acetate are as follows. Molecular weight 252 Boiling point 119℃/0.12mmHg Refractive index 1.4655 (17℃) Infrared absorption spectrum (cm -1 ) (KBr tablet) 3000 (-CH=CH-) 1735 (-C=0) 960 (-CH=CH -, trans E) 720 (-CH=CH-, cis Z) Mass spectrometry spectrum m/z 81 (base) 192 (M-AcOH) Test example 1 Synthetic compound (E)-4, (Z)-10-tetra Decadienyl acetate or its geometric isomer
10 μg and (Z)-10-tetradecenyl acetate,
or (E)-10-tetradecenyl acetate
100μg and plastic cap (Yasumoto Kasei Co., Ltd.)
(manufactured in Japan) and placed it on an adhesive trap and installed it in an apple orchard. For comparison, we also set traps with no attraction source and traps with two virgin females as attraction sources, and investigated the number of fish caught. The results are shown in the table below, from which (E)-4,
A mixture of (Z)-10-tetradecadienyl acetate and (Z)-10-tetradecenyl acetate was found to have an attractive power comparable to that of virgin females.
【表】【table】
【表】【table】
Claims (1)
エニルアセタート。 ２ 次の諸工程： (a) １，６−ヘキサンジオール（）と臭化水素
酸を下式（）のごとく反応させて得られる６
−ブロモ−１−ヘキサノール（）をトリフエ
ニルホスフインと下式（）のごとく反応させ
て（１−ヒドロキシヘキシル）トリフエニルホ
スホニウムブロマイド（）を生成せしめる工
程； HO−C6H12−OH＋HBr 〔〕 −→Br−C6H12−OH＋H2O （） 〔〕 Br−C6H12−OH＋（C6H5）3P 〔〕 −→〔（C6H5）3P（C6H12−OH）〕Br （） 〔〕 (b) 前記工程で得られた（１−ヒドロキシヘキシ
ル）トリフエニルホスホニウムブロマイド
（）をウイテイツヒ反応を利用してブチルア
ルデヒドと下式（）のごとく反応させて、６
−デセン−１−オール（）を得る工程； 〔（C6H5）3P（C6H12−OH）〕Br＋ｎ−
C3H7CHO 〔〕 塩基 ――→ C3H7−CH＝CH−C5H10−OH （） 〔〕 (c) 前記工程で得られた６−デセン−１−オール
（）をクロム酸酸化した後、硝酸銀シリカゲ
ルカラムクロマトグラフイによつてＺ体、Ｅ体
に分離した後、（Ｚ）−６−デセナール（）を
得る工程； (d) １，４−ブタンジオールと臭化水素酸を下式
（）のごとく反応させて得た４−ブロムブタ
ン−１−オール（）をトリフエニルホスフイ
ンと下式（）のごとく反応させて（１−ヒド
ロキシブチル）トリフエニルホスホニウロブロ
マイド（）を生成せしめる工程； HO−C4H8−OH＋HBr 〔〕 −→Br−C4H8−OH （） 〔〕 Br−C4H8−OH＋（C6H5）3P 〔〕 −→〔（C6H5）3P（C4H8−OH）〕Br （） 〔〕 (e) 前記工程で得られた（Ｚ）−６−デセナール
（）とウイテイツヒ反応を利用して前記工程
（）で得られた（１−ヒドロキシブチル）ト
リフエニルホスホニウムブロマイド（）と下
式（）のごとく反応させて、（Ｅ）−４，（Ｚ）
−10−テトラデカジエン−１−オール（Ｘ）を
得、さらにアセチル化後、硝酸銀シリカゲルカ
ラムクロマトグラフイによつて（Ｅ）−４，
（Ｚ）−10−テトラデカジエニルアセタート
（）を得る工程； よりなることを特徴とする示性式： で表させれる（Ｅ）−４，（Ｚ）−10−テトラデカ
ジエニルアセタート（）を製造する方法。 ３ 示性式： で表される（Ｅ）−４，（Ｚ）−10−テトラデカジ
エニルアセタート（１）と（Ｚ）−10−テトラデ
セニルアセタートを有効成分とするキンモンホソ
ガ及びその近縁種に対する誘引剤。[Claims] 1 Indicative formula: (E)-4,(Z)-10-tetradecadienyl acetate. 2 Next steps: (a) 6 obtained by reacting 1,6-hexanediol () and hydrobromic acid as shown in the following formula ()
- A step of reacting bromo-1-hexanol () with triphenylphosphine as shown in the following formula () to produce (1-hydroxyhexyl)triphenylphosphonium bromide (); HO-C 6 H 12 -OH+HBr [] −→Br−C 6 H 12 −OH+H 2 O () [] Br−C 6 H 12 −OH+(C 6 H 5 ) 3 P [] −→[(C 6 H 5 ) 3 P(C 6 H 12 -OH)]Br () [] (b) The (1-hydroxyhexyl)triphenylphosphonium bromide () obtained in the above step is reacted with butyraldehyde using the Witteitz reaction as shown in the following formula (), 6
Step of obtaining -decen-1-ol (); [ ( C6H5 ) 3P ( C6H12 - OH)]Br+n-
C 3 H 7 CHO [] Base---→ C 3 H 7 -CH=CH-C 5 H 10 -OH () [] (c) 6-decen-1-ol () obtained in the above step is converted to chromium A step of obtaining (Z)-6-decenal () after acid oxidation and separation into Z form and E form by silver nitrate silica gel column chromatography; (d) 4-bromobutan-1-ol () obtained by reacting 1,4-butanediol and hydrobromic acid as shown in the following formula () is reacted with triphenylphosphine as shown in the following formula (). Step of producing (1-hydroxybutyl) triphenylphosphoniurobromide (); HO−C 4 H 8 −OH+HBr [] −→Br−C 4 H 8 −OH () [] Br−C 4 H 8 − OH+ (C 6 H 5 ) 3 P [] −→ [(C 6 H 5 ) 3 P (C 4 H 8 −OH)] Br () [] (e) (Z)-6 obtained in the above step -decenal () is reacted with (1-hydroxybutyl)triphenylphosphonium bromide () obtained in the above step () using the Witteig reaction as shown in the following formula () to form (E)-4, (Z )
-10-tetradecadien-1-ol (X) was obtained, and after further acetylation, (E)-4,
Step of obtaining (Z)-10-tetradecadienyl acetate (); An indicative formula characterized by: A method for producing (E)-4,(Z)-10-tetradecadienyl acetate () represented by: 3 Indicative formula: A drug containing (E)-4, (Z)-10-tetradecadienyl acetate (1) and (Z)-10-tetradecenyl acetate as active ingredients against the goldenrod moth and its related species. Attractant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25520184A JPH0247977B2 (en) | 1984-12-03 | 1984-12-03 | * E ** 4 ** Z ** 100TETORADEKAJENIRUASETAATO * SONOSEIZOHOOYOBISONOKAGOBUTSUTO * Z ** 100TETORADESENIRUASETAATOOJUKOSEIBUNTOSURUKONCHUJUINZAI |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25520184A JPH0247977B2 (en) | 1984-12-03 | 1984-12-03 | * E ** 4 ** Z ** 100TETORADEKAJENIRUASETAATO * SONOSEIZOHOOYOBISONOKAGOBUTSUTO * Z ** 100TETORADESENIRUASETAATOOJUKOSEIBUNTOSURUKONCHUJUINZAI |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61134347A JPS61134347A (en) | 1986-06-21 |
| JPH0247977B2 true JPH0247977B2 (en) | 1990-10-23 |
Family
ID=17275423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25520184A Expired - Lifetime JPH0247977B2 (en) | 1984-12-03 | 1984-12-03 | * E ** 4 ** Z ** 100TETORADEKAJENIRUASETAATO * SONOSEIZOHOOYOBISONOKAGOBUTSUTO * Z ** 100TETORADESENIRUASETAATOOJUKOSEIBUNTOSURUKONCHUJUINZAI |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247977B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5150233B2 (en) * | 2007-12-14 | 2013-02-20 | 信越化学工業株式会社 | Process for preparing olefin compound geometric isomer composition |
-
1984
- 1984-12-03 JP JP25520184A patent/JPH0247977B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61134347A (en) | 1986-06-21 |
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