Article信州大学農学部紀要 20(1): 127-132(1983)departmental bulletin pape

KATO,  Yoshiaki

KAYAHARA,  Hiroshi

TOMIDA,  Ichiro

English

Shinshu University Institutional Repository

Studies on Pheromones of Female Eri-Silk Moth, Ⅰ.            Preparation of C6-C11 2-Alkenyl           Triphenylphosphonium Bromides   By Ichiro TOMIDA, Yoshiaki KATO and Hiroshi KAYAHARA        Laboratoi:y of Biochemistry, Dopt. of Agricultural Chemisti:y,         Faculty of Agriculture, Shinshu University, Minamiminowa,                     Kamiina, Nagano, 399-45        (Journal of the Fac, Agric. Shinshu Unlv. 18,i27-130(!983))   Some Ci6-Ci7 conjugated alkadienals assumed to have pheromonal activity towardmale Eri-silk moth, Philosamia cNnthia ricini, based on our earlier studies.i,2) Weproposed to prepare tkese subs£ances and in this paper describe syntheses of thetieled compounds, which are intermediate in the syntheses. The syntheses werecarried out in the conventional way (scheme)4) : Propargyloxy tetrahydropyran (!)was condensed with alkyl bromides (2) using the classical Na in liq. ammoRia methodto give alkynyloxy tetrahydropyran (3), which were then hydrolyzed to the cor-respoRding free alcohols (4). These were converted either to the (Z)-alkenols (5(Z))by hydrogenation over Lind}ar catalyse5) or to the (E)-alkenols (5(E)) by treatingwith lithium tetrahydroaluminate according to tlte Rossi's procedure.6) Eack productwas converted to the corresponding bromides (6(Z) or 6(E)) on treatment with 47%HBr aq, and these were then converted to the corresponding triphenylphosphoniumbromides (7).   The lntermediate compounds, 3,4,5 and 6, were characterized by IR- andNMR- spectral analyses. As far as observed from spectral data, allylic rearrange-ment product could not be detected in 6, aRd, however, the stereoselectivity of P,r-double bond seems to be not distinctly retained in the brominatioR as revealedfrom IR-spectra. The final products 7 were at any rate obtained as analysis-puresubstances. Their NMR-analyses were also satisfactorily coincident to the structures,although the geometrical purity can not be critically detected. These products were,however, used for tke further syntheses, because it was not absolutely necessaryto use the geometrically absolutely pure substances for our present purpose.3)                     EXPERIMENTAL PROCEDURES   Mps and bps were not corrected. PMR spectra were taken on a Hitachi R-241983iEii 4 JEi 30 N il2tr128 ts Y･I･I Jk i}ft me 4}(ir ]Eas ttil pt nyl 20 ig UX 1 lli'･ (1983)      Fig 1. General Scheme for Syntheses of Alkenyl Triphenylphosphonlum          Brornide          CH3-(CH2).-i-Br -- HCE-:C-CHrOTHP a 2--7I n               2 tNaliiq. NH3 : 2          CH3-(CH2).-rC!:CC}IrOTgP 3 e s                                                      di6                    S p-tosyl-Off/MeOH e 7                                                      f8          CH3{CH2)n-suaCEiiC-CH2-OH 4                       1) Mndlar cat. (Z)    l                                   (E)        2) LiAIH,          CH3KCH2)nmrCH :CHrmCH2-OH 5(Z) or 5(E)                    t }IBr aq          CH3--<CH2)n-rCH=:CH-Cg2-Br 6(Z) or 6<E)                    t P(C6E,),/DMF          CH3-(CH2)nmrCH==Cg-CH2-P"(C6Hs)3･Br- 7(Z) or 7(E)(60MHz) NMR-spectrometer, TMS as standard in CDCI3. For taking IR-spectra aHitachi EPI spectrometer was used, liquids as fiIm and solids matter as KBr-discs.   1) 2--(2'-alfeynyloxy)-tetrahydropyran (3a-f) : To liq. NH3 at -400 were addedaccording to the Lit.4) 2-propargyloxy tetrahydropyraR (bpi2660), a crystal of ferrlcRitrate and metaliic sodium (1. 5eq) under stirring. Upon discharge of the blue colour,the corresponding aikyl bromide 2a-f was added to this soltttion and stirred for 4h.The reaction mixture was then treated as described in the Lit.4) and the reactionproduct fractionally distilied. Yield : 51-61%; Bp (OC/mmHg): a 126/8, b 118/10, c113/1.5, d 127/O.4, e 148/1.0 and f 152/1.8; IR(cmffi): C=-C 2200--2230(w), NMR(6)4.05-4.18 (t,fJ:2Hz, ==C-C-H,-O) 4.67-4.76 (b-s, H-C-C).                                        -oAa   2) .ElydrolNsis of Pyitcznyl ether to alleynol (4a-f) : The corresponding pyraRyl ether3a-f (40m mole) was dissolved in MeOH (85ml) containing p-toluene suifoRic acid(2.5m mole). The solution was allowed to stand overnight under stirring. ThereactioR mixture was then treated in the usrkal manner and the neutral fractioRfractionaily distiiled. Yield: 76-96%; Bp (OC/mmHg): a 84/18, h 80/16, c 100/15,d 85/O.3, e 114/4 and f 101/O.2; IR (cmmi):OH 3350, CiiiiC 2200-2220 (w);NMR(6):4.1-4.2 (t, f=2}Iz, :==CH-CmaH,-O); TLC (Rf):O.5-O.6.   3) Hlrydrogenation of alkynol to (Z)-2-alfeenol (5a-f(Z)): It was carriecl out inMeOH usually by using Lindlar catalyst5) poisoned with a smail amount of quinoline.I. ToMIDA, Y. KATo, E[. KAyAHARA : Studies on Pheromones of Fernale Eri-Silk ])v(!oth 129Yield; 69-84%;Bp (OC/mmHg): a 58/12, b 75-6/14, c 87/18, d 101-2/12, e 85-6/O.3and f 102/O.7; IR(cmffi): OH 3320-3330 C==C 1650-1660 (w); NMR(6):3. 8-4.1 (d, fM5Hz or m, =='C}i{-C}-[{2-O), 5. CF-5.9 (m, CH== CH); TLC (Rf):O.51-O.59.   4) Hlydrogenation of alhynol to (E)-2-alleenol (5b-f(E)): According and analogousto the Lit. 6) the corresponding alkyRol 4b-f was reduced to (E) -alkenol l(5b-f(E )) withexcess of LiAIH` in the mixture of tetrahydrofuran and diglyme. 5a(E) was com-mercially available. Yield:29-63%;Bp (OC/mmHg):b 82/18, c 94-5/15, d 76.5/O.4,e 89/O.7 and f 102/O.8; IR(cm-i): OH 3300-3340, CmC 1670-1680 and 960-980(s);NMR(o"):3.6-4.1 (b-d or m, ==CH-C!!2-O) 5.4-5.7 (m, CH=:CH);TLC (Rf):O.45-O. 59.   5) Bromination of alkenol to alfeenNl bromide (6a-f(Z) and 6a-f(E)): The corres-ponding alkenol (5a-f(Z) and 5a-f(E) (10m mole) was treated with a mixture (44 ml)of 47% HBr aq and 95% H2S04 (10: 1) for 3 days at room temperature under stirring.The reaction rnixture was treated in the usual way and the neutrai fractlon frac-tionally distilled. Yield;56-88% ; Bp(OC/mmHg):a(Z) 42/12, b(Z) 68/16, c(Z) 81-2/17, d(Z) 104/18, e<Z) 90/2.0, f(Z) 93-4/O.6, a(E) 40/13, b(E) 75/20, c(E) 82/14,d(E) 95/14, e(E) 84-5/1.2 and f(E) 92-3/O.6; IR(cm-i): C==C 164e-1660 (w) 960 (mor w in h-f(Z), s in a-f(E)) 720-750 (s or m in b-f(Z), w or very w in a-e(E)and m in f(E)). NMR (6):3.7-4.0 (m, =CH-CHww2-Br) 5.1-6.1 (m, CH==CH, moresimply splitted patterR in b-f(E).   6) 2-Alfeenyl triphenylPhosphoniunz bremide (7a-f(Z) and 7a-f(E)) : Tke correspon-ding alkenyi bromide (6a-£(Z) and 6a-f(E) (20rn mole) and triphenyl phosphine (1.1eq) were disso!ved in benzene (30ml) and allowed to stand for 2-3 days at roomtempeyature (A) or refluxed for 2 days (B) or better dissolved in dirr}ethyl formamide(30 ml) and refiuxed for 3h at 1400C (C). The precipitated crystals were separatedand refluxed in abs.ether for 5h to give white crystals. Yield:40-89%;Mp (OC) andreaction conditions:a(Z) 120 (A) (Lit.`) 127-130), b(Z) 129-131(A), c(Z) 139-9(A), d(Z)121-139 (A), e(Z) sirup(B), f(Z) 98-102 (adhesive solid matter) (C), a(E) 143(A),b(E) 141-6 (A) <Lit.9) 156), c(E) 177-180 (A), d(E) 174-5(A), (Lit.8) l70), e(E) 116-120(B) and f(E) 99-104 (adhesive solid rnatter) (C); NMR (S):4.3-4.9 (m or dd, J==7and 15 Hz) 4.9-6.3 (m, CH==CH) 7. 1-8.5 (m, (C6Hs)3). All compounds were elemen-tal-analytically pure except a(Z).                             REFERENCES1) I. Tomida and S. Ishii, APf>. Ent. Zool., 3, 103 (1968).130 信州大学農学部紀要　第20巻第1考’（1983）））））））＞23456781．Tom三da，、4gガ。．．翫oJ，αzθ甥．，45，2135（1981）。1。Tomida，　Y．　Kato　and　H．　Kayahara，．ハFαo．14gガ。．　S砺π3伽σ癖〃．18，133（1983）。R．Truscheit　and　K，£三ter，42zπ．4．　C加勉．，658，65（1962）．H．Liadlar，1ノθ1四．　C痂7π．〆i6’α，35，446（1952）．R。Rossi　and　A，　Carpita，　Syη酌g3ゴ3，561（1977）．F．Bohlmann　and　H，・G．　Viehe，　C加甥．　Bθア．，88．1245（1955＞．F．Boh互mann　aad　H．一G．　Viehe，0乃θ吻．　Bθ7．，88，1347（1955），1．’roMIDA，　Y．　KATo，　H。　KAYAHARA：Stud三es◎n　Pheromones　of　Fe鶏ale　Eri－Silk　M◎出　131摘 要エリ蚕雌フェロモンに関する研究　ⅠC6～C11の2-アルケニルトリフェニルホスホニウム塩の調製富田一郎・加藤喜章・茅原紘信州大学農学部　生物化学研究室　我々は以前の研究において，エリ蚕の雌の性フェロモンはC16～C三7の共役二重結合をもったアルヵジェニル化合物であろうと推定したが，本報ではその合成中間物質である標題の化合物の合成について報告する。合成は従来の方法で行った。すなわち，プロパルギルァルコールのテトラヒドロピラニルエーテルを出発物質とし，これに液安中ナトリウムを用いて各種炭素数のアルキルブロマイドを作用させて，2一アルキニル化合物とする。これを一度遊離のアルコールに戻したのち，リンドラー角虫媒を用いた接触還元でZ体，またRossiの過剰の水素化アルミニウムリチウムを用いる還元法でE体の2一アルケノールに導いた。各々はブロマイドにしたのち，トリフェニルポスフィンと作用させて，標題の化合物に導き，元素分析一致の生成物を得た。各段階における精製，収量，スペクトルデータによる確認について記載した。

Studies on Pheromones of Female Eri-Silk Moth, I. Preparation of C₆-C₁₁ 2-Alkenyl Triphenyiphosphonium Bromides

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Studies on Pheromones of Female Eri-Silk Moth, I. Preparation of C₆-C₁₁ 2-Alkenyl Triphenyiphosphonium Bromides

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