Article信州大学農学部紀要 20(2): 213-218(1983)departmental bulletin pape

KATO,  Yoshiaki

KAYAHARA,  Hiroshi

TAKAGI,  Kazumasa

TOMIDA,  Ichiro

English

Shinshu University Institutional Repository

Studies on Pheromones of Female Eri-Silk Moth, Ⅲ   Synthesis of (6 Z, 11 Z) - 6, 11-Hexadecadienal and     Its Activity as Pheromone Mimics toward                 Male Eri-Silk MothBy Ichiro TOMIDA, Kazumasa TAKAGI, Yoshiaki KATO            and Hiroshi KAYAHARA Laboratof:y of Biological Chemist7:y, Fac. Agric., Shinshtt Uitiv.   The titie compound has electroantennographically exciting activityi) toward thema}e eri-silk moth, as does also (6E,11Z)-6, 11-hexadecadienal, a compoRent ofthe pherornone from female Anthereae PolNPhemacs2), and has recently been synthe-sized by Bestmann et al. 3) As a model compound*" for the study of pheromone fromfemale eri-sill< moth, Philosamia cynthia ricini, we also tried to synthesize the titlecompound by the following way as was schemed below:     Cs-componentCRa-(CH2)4igP" (CeHs)3'Br-               g         silazide methodCs-componentaO OH        ,CHr(CH,),-C}I=:CHKCK,),-OH        iPCcCH,-(CH,),-Cff==CH-<CH2),--CHO        l siiazide23   4methodC6-componentHOKCH,),-OH   sBrKCH2)a-OH   i5BrM･ (C6Hs)3P "-<CH2)a-ON 6                   sCK3{CH2)e-CH :CE[-(CHD)3-CH =CH-(CH,),-OK                   S pccCK,-(CH,),-Cfl==CH--(CH,),-CE[=CK-(CH,),-CHO                Fig. 1.t78We disconnected the target compound into three fragments (Cs+Cs+C6) and the* Part ll see Lit.a)      '":ts (6E, 11Z)-6, 11-Hexadecadienal is electroantennographically more active than (6Z, 11Z)-isomer toward the antenna of male eri-sillc mothsi>; the latter was, however, sele- cted 'for this work as it was considered to be more easily prepared.1983tEii 9 A 28 H ead!!l-214 GY･1･iJk e}!ii,gegkeeg*iil･if ts20tsas2-･Stt- (1983)synthons were coupled to each other by means of the Wittig reaction under Z-selective conditions (siiazide method).4) Thus we have reached the dienol com-pound 7 directly after the second Wittig reaction by using an unprotected hydroxy-phosphonium compound as the C6-component.    Cs+Cs-component 4 was prepared accerding te the Lit.5,6) : X was condeRsedwith 2 by using the Z-selective Wittig reaction4) to give 3. An oily product 3 waspurified either by the preparative tlc (in the case of small scale) or by the Si02-column chromatography (in the case of large scale). It was then converted to 4 bymeans of Corey's oxidation method.7)    5 was obtained by the usual method from 1 ,6-hexanediol, while 6 was preparedby treating 5 with triphenyl phosphine at 9(>-100eC under nitrogen without anysolvent. The reaction product was solid, owing to its highiy hygroscopic nature,however, this solid matter 6 was directly condensed wlth 4 again under Z-selectivereaction conditions. The product obtained after puri'fication by preparative tlc wasspectroscopically assigned as 7 (14%). 7 was tken oxidized with pyridinlum chloro-chrornate7) to give the target compound 8. The structure o'f this product wasestabiished spectroscopically after puyification using preparative tlc (yield, 55%).   Tke synthesized product 8 was assayed on the male eri-silk moths. As expected,it showed the pheromonally stimulating action and the response pattern was ldenticalwith that by the pheromone extract itself from the female eri-silk moths. Theactivity of this product was then determined by using the conventional wing fltitter-ing test using 20 specimens of the inaie eri-siik moth.8) The positive response inthe individual test was estimated when the animai started to vibrate his wingscharacteristically within about 20 sec after the test glass rod was ptit iR froRt oftke antenna, and the test solution was decided as positlve when more thaR half ofthe test insects responded positively to it. The experlment was several times repii-cated and the minimum concentration of the product 8 was elucidated to be 100I.tg/ml <n-hexane). In tkis test such animals thae were sensi£ive up to 10-3 F. E.(female equivalent) were used.                      EXPERIMENTAL PROCEB{JgeES   iK-NMR-spectra : Hitachi R-24 (60MHz), TMS as standard. Mass spectrum:Shimazu GCMS-7eOO (70ev). IR-spectra : spectrophotometer Hitachi EPI-52.GLC:Hitachi 063, FID-detector, coiumR lm × 3mm ID and, uniess otherwisedescribed, OV-l7(5%). tlc:hexane/ethyl-methyl ketone (4:1 vol.)was thoroughlyused as developing solvent including preparative tlc. The spot was visualized byspraying with IO% H2S04.1. (Z)-5-decen-1-al (4):According to the procedure in the Lit.7) 35,6) was oxidized     I.ToMmA,K.TAKAG et al : Studies on Pheromones of Female Eri-Sill< Moth 215with pyridinium chlorochromate. An oil, bpg86-920(64%). Lit.5) bpu 100-1200 (53%), Lit.6) bpio 89-910 (70%). tlc: 1?f=O.89. GLC(1000): tR==2.0 min, a single peak.IR(film):S{P;i3000(CH=) 2700(CHO) 1730(HC==O) and no absorption at 960. NMR(CDCI,):o" O. 90(3H, t, fm5Hz, CH3) 1.05-!.7(6H, m, -CH,-× 3) 1.7-2.2(4H, m, CH,-C!l==CHC!I2)2.45 (2H, d-t, Cb-CHO> 5.1-5.6 (2H, m, CH=CH) 9.65 (IH, t, f==5Hz, CHO).2. 6-Bromohexanol (5): According to a related procedure in Lit.6) ,5 was preparedfrom 1, 6-hexanediol. AR oil, bpiollO-1160(71%). (Lit.iO) bpsl05-1060(81%). Lit.5)bp,, lll-ll80 (72%)). tlc: Rf==O.32. IR(film: fi,M,.-i 3300(OH). NMR(CCI,):o" 1.2-1.8(4K, m, -CH2-×2) 1.8-2.35 (4H, m, -CH2-×2) 3.33 (2H, t, 1==7Hz, CH2Br)3.48(2H, t, 1=6Hz, Cg,-OH) 4.0 (IH, s, OH).3. 6-ILydroxyhexyl triPhenNlphosPhonium bromide (6):5 aRd triphenyl phosphine (1 eq)were heatecl under nitrogen for 24h (bath temp. 90-1000). The reaction mixture (a hardmass) was recrystallized from chloroform and benzene. The crystals were hygroscopicin the atmosphere. It was then heated in ether uRder reflux for 15h. The soiidmatter (88%) was fully dyied in a desiccator and used directly in the next reaction.NMR(CDCI,):S 2.9 (IH, s, OH) 3. 0-4.0 (4H, m, CIi[2-OH, CU,-PPh3) 7.7(15H, s, PPh3).Found:C, 65.02;H, 6.37. Calcd. for C24H2oOPBr (444.4):C, 64.87;}l, 6.58%.4. (6Z,11Z)-6,11-Hexadecadien-1-ol (7): According to the procedure in Lit.4), tothe solution o£ sodium bis (trimethysiiyl) amide (1.5 eq) iR Na-dry THF was added6 (4. 00g, 9. 0m mole) with stirring under argon to give the corresponding ylid. Afterfurther stirring for 1/4h the solution was chiiled in dry-ice/methanol mixture(-500) and 4(1.39g, leq) was added under argoii. The stirring was continued over-night. The reaction mixture was concentrated i,n vacuo, the residue was stirred withn-hexane and allowed to stand in an ice-box overnight. The precipitate was filteredoff, the filtrate was washed successively with 2N HCI aq, sat. NaHC03 aq and 10% NaHS03 aq, dried over Na2S04 and evaporated in vacuo. The residue was puri'fiedby preparative tlc. 7 was obtained as an oil (O.30g, l4%). tlc:Rf =O.55. GLC(1600):tR=:4.7min, a single peak. IR(film):C.M..-i 3350 (OH) 3000 (CH==) 800 (C =C) and noabsorption at 960. NMR(CCk):6 O.9(3H, t, f=6Hz, CH3) 1.06-1.67 (12H, m,-CH2-×6) 1.67-2.25 (8H, m, C!l!,-CH==CH-Ck!, ×2) 2.35 (IH, s, OH)3.5 (2H, t, 1 :6Hz,CEIE2-OH) 5.27(4H, t, 1==4.6Hz, CH=CH ×2).5. (6Z,11Z)-6,U-Llexadecadien-1-al (8): In the same manner as described in1,7 was oxidized with pyridinium ch!orochromate. The product was purified bymeaRs of preparative tlc. An oil (55%). tlc:Rf==O.90 GLC (1600):tR==3.6miR,216 kY･l･I Jit egE St., agk jss ttE ee ee 20 ig fik.t 2-Fv (1983)accompanied with one smalKmpure peak in the range apart from the main peak.IR(film) : kllP.-' 3000(CN==) 2700(CHO) 1730(C==O). No absorption at 960. NMR(CC14) :o" O.9 (3H, t, f= 6Kz, CH3) 1. 0--1.6 (8H, m, CII2-CK =CH-Cg2 × 2) 2. 15-2. 55 (2H,m, Clj2-CHO) 5.31 (4H, t, f=5Hz, Cff=CH ×2) 9.67(IH, t, f= 1.6Hz, CHO). MS:rn/Z 236<M", 8%)･                           AcknowSedgemaents   We are indebted to thank Prof. }I.J. Bestmann (Erlangen University) and Dr.D.R. Hall (London, Tropical Products Institute) for their kind informatlon about theaRtennographical studies and the related experixnental procedures. These experimentswere performed partially with financial heip from the Science Promoting Associationof Nagano Prefecture. For the measuring of mass spectrum we are also thanl<fulto Dr. D. Karasawa (Shinshu University, Dept. of Agricultural Chemistry).                             REgeERewCES 1. H.J. Bestmann, private communication. cf. Part. rr.I. Tomida, Y. Kato and H. kayahara, f. Fac. Agn'c. Shinshu Univ., 2e, 133 (1983).2. J. Kochansky, J. Tette, E.F. Taschenberg, R.T. Carde, K.E. Kaissling and W.L. Loeloffs, J. Insect Physiol., 21, 1977 (1975).3. H.J. Bestmann and O.Vostorwsl{y, Chem. Phys. LiPids., 2aj, 335 (1979).4. H.J. Bestmann, W. Stransl<y and O.Vostrowsky, Chem. Ber., 189, 1694 (1976).s. K.H. Keschatzky, "9octoral Thesis" (Erlangen, 1979).6. H.J. Bestmann and K. Li, Tetrahedron Lett., 4941 (1981).7. E.J. Corey and j.W. Suggs, Tetrahedron Lett., 2647 (1975).s. I. Tomida and S. Ishii, APp. Ent. Zool., 3, 103 (1968).9. 0rg. Synth., Coll. Vol. Iil, p.446.Io. F. Degering and L.G. Eoatri.crht, J. Amer. Chem. Soc., 72, 5137 (1950).工．ToMIDA，　K：，　TAKAGIθ’α♂：Studies　o且P王ユeromo！1es　of　Female　Eri・Si11ζMoth　　217商手 要　　　　エリ蚕雌フェロモンに関する研究Ⅲ（6Z,11Z）-6，11-ヘキサデカジェナールの合成と，それのエリ蚕蛾雄に対するフェロモンミミクス　　　　　　　　　　　としての活性度富田一郎・高木一全・加藤喜章・茅原紘信州大学農学部　生物化学研究室　標題の化合物は，サク蚕の一種Anthereae　polyphemusの雌から得られるフェロモン成分の1つである（6Z，三1Z）一6，11一ヘキサデカジエナールとともに，エリ蚕P観05α珈αoッη’屠αr読短の雄馬に対して電磁触角的に活性を示す物質である。我々は標題の化合物をエリ蚕の性フェロモンの研究のモデル化合物の1つとして合成を試みた。すなわち，ペンチルトリフェニルホスホニウムブロマイドからシラジド法で得られるイリドに対し，5一ヒドロキシペンタナールをZ選択的ウイティヒ反応の条件で縮合し，（Z）一5一デセンー1一オールを得，これを酸化して相当するアルデヒドにした。一方，6一プロモヘキサノールから6一ヒドロキシヘキシル　トリフェニルホスホニウムブロマイドとし，これを上記で得たアルデヒドと：再びZ選択的ウィティヒ反応で縮合し，（6Z，11Z）一6－11一ヘキサデカジェノールに一挙に導き，更に酸化して糖当するアルデヒド，すなわち目的物に導いた。このものはかスクロマトグラフ的タこは少量の不純ピークを伴うが，主ピークに関してはZ，Zの単一幾何異性体と結論された。このものはエリ蚕の雄蛾に対して，天然のフェロモン抽出物と全く岡様の反応パターンを惹き起した。そして，従来の羽捲：きテスト法では100μg／m♂の低濃度までの活性度を示した。なお，このとき使用したエリ蚕雄蛾は雌中陣抽出液を10－3濃度まで希釈しても，それに対し感応するものであった。

Studies on Pheromones of Female Eri-Silk Moth, III. Synthesis of (6Z, 11Z)-6,11-Hexadecadienal and Its Activity as Pheromone Mimics toward Male Eri-Silk Moth

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Studies on Pheromones of Female Eri-Silk Moth, III. Synthesis of (6Z, 11Z)-6,11-Hexadecadienal and Its Activity as Pheromone Mimics toward Male Eri-Silk Moth

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