CN111205184A - 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法 - Google Patents

一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法 Download PDF

Info

Publication number
CN111205184A
CN111205184A CN201911272015.2A CN201911272015A CN111205184A CN 111205184 A CN111205184 A CN 111205184A CN 201911272015 A CN201911272015 A CN 201911272015A CN 111205184 A CN111205184 A CN 111205184A
Authority
CN
China
Prior art keywords
reaction
acetate
pentenyl
tetradeca
synthesis
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.)
Pending
Application number
CN201911272015.2A
Other languages
English (en)
Inventor
王敏
孙效
钟江春
原超楠
袁谷城
杨宇雄
边庆花
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Agricultural University
Original Assignee
China Agricultural University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Agricultural University filed Critical China Agricultural University
Priority to CN201911272015.2A priority Critical patent/CN111205184A/zh
Publication of CN111205184A publication Critical patent/CN111205184A/zh
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/28Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/292Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/10Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/54Quaternary phosphonium compounds
    • C07F9/5442Aromatic phosphonium compounds (P-C aromatic linkage)
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09Geometrical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于绿色农药合成技术领域,公开了一种新的合成(9Z,12E)‑十四碳‑9,12‑二烯‑1‑醇乙酸酯的方法。该方法以丙二酸和9‑溴‑1‑壬醇为两种起始原料。丙二酸与丙醛在哌啶乙酸盐存在下发生Knoevenagel缩合反应,生成(E)‑3‑戊烯酸,然后经氢化铝锂还原得到(E)‑3‑戊烯‑1‑醇,再经过溴代反应,与三苯基膦在乙腈中回流制得(E)‑3‑戊烯基三苯基溴化膦。9‑溴‑1‑壬醇经过PCC氧化反应得到9‑溴壬醛,然后和乙酸钾反应得到9‑乙酰氧基壬醛。最后(E)‑3‑戊烯基三苯基溴化膦与9‑乙酰氧基壬醛发生过Wittig反应制得(9Z,12E)‑十四碳‑9,12‑二烯‑1‑醇乙酸酯。本发明利用丙二酸与丙醛的Knoevenagel缩合反应构建E‑型双键,具有反应条件温和,对环境友好、合成路线简捷等优点。

Description

一种合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的方法
技术领域
本发明属于绿色农药合成技术领域,具体涉及一种合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的方法。
背景技术
(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(式1)是植物害虫印度谷螟(Plodiainterpunctella Hübner)性信息素的主要成分,可用于该类害虫的综合防治(Brady,U.E.;Tumlinson,J.H.,III;Brownlee,R.G.;Silverstein,R.M.Science 1971,171,802-804.Kuwahara,Y.;Kitamura,C.;Takahashi,S.;Hara,H.;Ishii,S.;Fukami,H.Science1971,171,801-802.)。(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯也是烟草粉螟(Ephestiaelutella Hübner)性信息素的次要成分(Brady,U.E.;Nordlund,D.A.Life Sci.1971,10,797-801.Brady,U.E.Life Sci.1973,13,227-235.)。另外,(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯还是草地贪夜蛾(Spodoptera frugiperda Smith)性信息素的活性成分,具有吸引雄虫的生理活性(Jacobson,M.;Redfern,R.E.;Jones,W.A.;Aldrige,M.H.Science1970,170,542-544.)。
Figure BDA0002314455770000011
(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯虽然具有显著的生理活性,但在植物害虫雌虫体内含量很少,极难提取,阻碍了其在植物病虫害生物防治领域的应用研究。因此,研究(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成具有重要的意义。目前合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的方法主要包括“sila-Cope”消除法、环丙基乙醇开环法、反式烯酸酯法与烯烃复分解反应法。
(1)“sila-Cope”消除法是以2-乙基吡啶为原料,先与叔丁基二甲基氯硅烷、碘甲烷反应,然后经硼氢化钠还原、与碘甲烷反应,得到四氢吡啶盐,接着用CsF处理发生“sila-Cope”消除,得到(2Z,5E)-1-二甲氨基-2,5-庚二烯,最后经格氏偶联、脱保护与乙酰化等多步反应制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(Bac,N.V.;Langlois,Y.J.Am.Chem.Soc.1982,104,7666-7667.)。
(2)环丙基乙醇开环法是以1-环丙基乙醇为原料,先与溴化氢反应构建E型双键,得到(E)-5-溴-2-戊烯,然后与三苯膦反应得到季鏻盐,最后与羰基酯发生Wittig反应构建Z型双键,制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(Bestmann,H.J.;Koschatzky,K.H.;Plenchette,A.;Suess,J.;Vostrowsky,O.Liebigs Ann.Chem.1982,536-544.)。
(3)反式烯酸酯法是以(E)-3-戊烯酸甲酯为原料,先经还原、溴代,然后与三苯膦反应生成季鏻盐,再与羰基酯发生Wittig反应构建Z型双键,制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(Hornyanszky,G.;Rohaly,J.;Novak,L.Synth.Commun.2008,38,1533-1540.)。
(4)烯烃复分解反应法是在钌催化剂下,(Z)-9-十八碳烯-1-醇与反式1,4-己二烯发生烯烃复分解反应,直接得到(9Z,12E)-十四碳-9,12-二烯-1-醇,然后乙酰化制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(Herbert,M.B.;Marx,V.M.;Pederson,R.L.;Grubbs,R.H.Angew.Chem.,Int.Ed.2013,52,310-314.)。
(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成研究虽然已取得较大进展,但仍然存在许多问题,例如:反应条件苛刻、反应路线冗长、试剂毒性较大等。因此,研究路线简捷、反应条件温和、对环境友好的合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的新方法,具有重要的理论意义与应用价值。
发明内容
本发明旨在提供一种合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的新方法。该方法以丙二酸和9-溴-1-壬醇为两种起始原料。丙二酸与丙醛在哌啶乙酸盐存在下发生Knoevenagel缩合反应,生成反式戊烯酸2,然后经氢化铝锂还原得到戊烯醇3,再经过溴代反应,与三苯基膦在乙腈中回流制得季鏻盐4。9-溴-1-壬醇经过PCC氧化反应得到溴代醛6,然后和乙酸钾反应得到羰基酯7。最后季鏻盐4和羰基酯7发生过Wittig反应制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯。本发明合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成路线参见式2。
Figure BDA0002314455770000021
本发明合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的方法包括如下步骤。
(1)(E)-3-戊烯酸2的合成
氩气保护下,在丙二酸、哌啶、冰醋酸与DMSO的混合液中,滴加丙醛,升温至40℃,反应2h后,升温至100℃,反应8h。反应结束后,用冷水淬灭反应。水相用乙醚萃取,合并有机相,经水洗和饱和氯化钠水溶液洗涤。干燥后减压浓缩,最后经硅胶柱色谱纯化,制得(E)-3-戊烯酸2。
(2)(E)-3-戊烯-1-醇3的合成
氩气保护下,在氢化铝锂与四氢呋喃的混合物中,滴加(E)-3-戊烯酸2的四氢呋喃溶液。升温至室温,反应8h。反应结束后,用氢氧化钠水溶液淬灭反应。反应混合物经硅藻土抽滤,并用乙醚洗涤滤饼。滤液经水洗和饱和氯化钠水溶液洗涤,干燥后减压浓缩,最后利用常压蒸馏纯化,制得(E)-3-戊烯-1-醇3。
(3)(E)-3-戊烯基三苯基溴化膦4的合成。
氩气保护下,在(E)-3-戊烯-1-醇3、四溴化碳与二氯甲烷的混合液中,滴加三苯基膦的二氯甲烷溶液。升温至室温反应5h,反应结束后,减压脱溶。残余物经硅藻土抽滤,无水乙醚洗涤滤饼。滤液减压浓缩,制得(E)-5-溴-2-戊烯粗产物。
氩气保护下,将三苯基膦、乙腈和(E)-5-溴-2-戊烯粗产物的混合液,回流反应48h。反应结束后,减压浓缩,最后经硅胶柱色谱纯化,制得(E)-3-戊烯基三苯基溴化膦4。
(4)9-溴壬醛6的合成
氩气保护下,在PCC氧化剂和硅胶的混合物中加入二氯甲烷,搅拌均匀,滴加9-溴-1-壬醇的二氯甲烷溶液,升温至室温,反应4h。反应结束后,减压脱溶,残余物经硅藻土抽滤,无水乙醚洗涤滤饼。滤液减压浓缩,最后经硅胶柱色谱纯化,制得9-溴壬醛6。
(5)9-乙酰氧基壬醛7的合成
在9-溴壬醛6与乙酸钾的混合物中加入DMF,升温至120℃,反应2h。反应结束后,加水淬灭反应。分液,水相用乙醚萃取,合并有机相。经水洗和饱和氯化钠水溶液洗涤,干燥后减压浓缩。最后经硅胶柱色谱纯化,制得9-乙酰氧基壬醛7。
(6)(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成
氩气保护下,将(E)-3-戊烯基三苯基溴化膦4的四氢呋喃溶液降温至-78℃,滴加双(三甲基硅基)氨基钠,反应1h。再滴加9-乙酰氧基壬醛7的四氢呋喃溶液,升温至室温,反应24h。反应结束后,用饱和氯化铵水溶液淬灭反应。分液,水相乙醚萃取,合并有机相。经水洗和饱和氯化钠溶液洗涤,干燥后减压浓缩。最后经硅胶柱色谱纯化,制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯。
具体实施方式
实施例1
(E)-3-戊烯酸2的合成
氩气保护下,向装有回流冷凝管的100mL三口瓶中依次加入丙二酸(10.40g,100mmol)、哌啶(0.086g,1mmol)、冰醋酸(0.060g,1mmol)与DMSO(40mL),室温下搅拌溶解,缓慢滴加丙醛(2.90g,50mmol)。滴完后,升温至40℃,搅拌反应2h,然后升温至100℃,继续反应8h。反应结束后,将反应混合液降至室温。加冷水(30mL)淬灭反应,分液。水相用乙醚(3×30mL)萃取,合并有机相。有机相依次用水(3×100mL)与饱和氯化钠水溶液(100mL)洗涤。无水硫酸钠干燥后减压浓缩,得到粗产物。粗产物经硅胶柱色谱(石油醚/乙酸乙酯2:1)纯化,制得淡黄色液体化合物(E)-3-戊烯酸2(7.01g,产率70%)。1H NMR(300MHz,CDCl3)δ10.61(s,1H),5.68–5.47(m,2H),3.07(ddd,J=4.5,2.3,1.3Hz,2H),1.72–1.69(m,3H).13CNMR(75MHz,CDCl3)δ178.75,130.01,121.94,37.74,17.82.
实施实例2
(E)-3-戊烯-1-醇3的合成
氩气保护下,在200mL Schlenk反应瓶中加入四氢铝锂(1.39g,36.62mmol),然后加入四氢呋喃(60mL),搅拌均匀。冰浴冷却下缓慢滴加(E)-3-戊烯酸2(2.82g,28.17mmol)的四氢呋喃溶液(20mL)。滴完后,将反应混合液逐渐升温至室温,搅拌反应8h。反应结束后,冰浴冷却下缓慢滴加20%氢氧化钠水溶液(3mL)淬灭反应。反应混合物用硅藻土抽滤,用乙醚(500mL)洗涤滤饼,滤液依次用水(50mL)和饱和氯化钠水溶液(100mL)洗涤。无水硫酸钠干燥后,减压浓缩得到粗产物。粗产物经常压蒸馏纯化,收集沸点135~150℃馏分,得到无色液体化合物(E)-3-戊烯-1-醇3(2.06g,产率85%)。1H NMR(300MHz,CDCl3)δ5.60–5.38(m,2H),3.61(t,J=6.4Hz,2H),2.28–2.21(m,2H),2.17(br s,1H),1.68(ddt,J=6.3,2.5,1.2Hz,3H).13C NMR(75MHz,CDCl3)δ128.09,127.10,61.93,35.84,17.85.
实施实例3
(E)-3-戊烯基三苯基溴化膦4的合成。
氩气保护下,在200mL Schlenk反应瓶中依次加入(E)-3-戊烯-1-醇3(2.00g,23.22mmol)、四溴化碳(11.55g,34.83mmol)和二氯甲烷(60mL),室温下搅拌溶解。冰浴冷却下缓慢滴加三苯基膦(18.27g,69.66mmol)的二氯甲烷溶液(50mL)。滴完后,将反应混合液自然升温至室温,继续搅拌反应5h。反应结束后,将反应液浓缩得到粗产物。粗产物经硅藻土抽滤,用乙醚(500mL)洗涤滤饼,滤液减压浓缩,制得浅黄色液体化合物(E)-5-溴-2-戊烯粗产物(2.98g,粗产率86%)。
氩气保护下,向装有回流冷凝管的100mL三口瓶中依次加入三苯基膦(2.64g,10.07mmol)、无水乙腈(60mL)和(E)-5-溴-2-戊烯粗产物(1.00g,6.71mmol),搅拌溶解。将反应液温度升温至85℃,继续回流反应48h。反应结束后,将反应液温度降至室温,减压浓缩得到粗产物。粗产物经硅胶柱色谱(二氯甲烷/甲醇10:1)纯化,制得黏稠化合物(E)-3-戊烯基三苯基溴化膦4(1.77g,产率64%)。1H NMR(300MHz,CDCl3)δ7.87–7.70(m,15H),5.58–5.41(m,2H),3.82–3.73(m,2H),2.47–2.36(m,2H),1.54(d,J=6.0Hz,3H).13C NMR(75MHz,CDCl3)δ134.94,133.53,130.42,130.25,128.16,127.39,118.53,117.39,25.41,23.11,17.43.
实施实例4
9-溴壬醛6的合成
氩气保护下,在200mL Schlenk反应瓶中加入PCC氧化剂(8.69g,40.32mmol)和硅胶(8.69g),然后加入二氯甲烷(70mL),搅拌均匀。冰浴冷却下缓慢滴加9-溴-1-壬醇(3.00g,13.44mmol)的二氯甲烷溶液(20mL)。滴完后,将反应液自然升温至室温,搅拌反应4h。反应结束后,减压浓缩,经硅藻土抽滤,用无水乙醚(500mL)洗涤滤饼。滤液减压浓缩得到粗产物,粗产物经硅胶柱色谱(石油醚/乙酸乙酯40:1)纯化,制得淡黄色液体化合物9-溴壬醛6(2.47g,产率83%)。1H NMR(300MHz,CDCl3)δ9.77(s,1H),3.41(t,J=6.8Hz,2H),2.43(t,J=7.3Hz,2H),1.87–1.83(m,2H),1.65–1.61(m,2H),1.50–1.32(m,8H).13C NMR(75MHz,CDCl3)δ202.72,43.73,33.79,32.65,29.03,28.91,28.42,27.95,21.89.
实施实例5
9-乙酰氧基壬醛7的合成
在50mL反应瓶中依次加入9-溴壬醛6(2.34g,10.58mmol)、乙酸钾(1.14g,1.16mmol)和DMF(20mL),搅拌溶解,将反应液升温至120℃,继续搅拌反应2h。反应结束后,将反应混合液温度降至室温,加水(30mL)淬灭反应。分液,水相用乙醚(3×40mL)萃取,合并有机相。有机相依次用水(3×40mL)和饱和氯化钠水溶液(50mL)洗涤,无水硫酸钠干燥,减压浓缩得到粗产物。粗产物经硅胶柱色谱(石油醚/乙酸乙酯20:1)纯化,制得淡黄色液体化合物9-乙酰氧基壬醛7(1.53g,产率72%)。1H NMR(300MHz,CDCl3)δ9.77(t,J=1.8Hz,1H),4.05(t,J=6.7Hz,2H),2.43(td,J=7.3,1.8Hz,2H),2.05(s,3H),1.66–1.59(m,4H),1.40–1.33(m 8H).13C NMR(75MHz,CDCl3)δ202.80,171.25,64.54,43.78,28.94,28.87,28.49,25.76,24.57,21.95,20.91.
实施实例6
(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成
氩气保护下,在100mL Schlenk反应瓶中加入(E)-3-戊烯基三苯基溴化膦4(1.70g,4.13mmol)和无水四氢呋喃(40mL),搅拌溶解。将混合液温度降温至-78℃,缓慢滴加双(三甲基硅基)氨基钠(2.1mL,2M THF溶液,4.2mmol),滴完后,搅拌1h。然后滴加9-乙酰氧基壬醛7(0.83g,4.13mmol)的四氢呋喃溶液(5mL)。滴完后,将反应液缓慢升温至室温,继续搅拌反应24h。反应结束后,冰浴下滴加饱和氯化铵水溶液(20mL)淬灭反应。分液,水相用乙醚(3×30mL)萃取,合并有机相。有机相依次用水(50mL)和饱和氯化钠水溶液(50mL)洗涤,无水硫酸钠干燥。减压浓缩得到粗产物,粗产物经硅胶柱色谱(石油醚/乙酸乙酯80:1)纯化,制得淡黄色液体化合物(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯(0.58g,产率56%)。1H NMR(300MHz,CDCl3)δ5.46–5.30(m,4H),4.05(t,J=6.8Hz,2H),2.73–2.70(m,2H),2.04(s,3H),2.02–1.99(m,2H),1.65–1.64(m,5H),1.36–1.30(m,10H).13C NMR(75MHz,CDCl3)δ171.07,130.28,129.56,127.64,124.98,64.54,30.37,29.55,29.31,29.16,29.10,28.56,27.01,25.84,20.89,17.79.

Claims (5)

1.一种合成(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的方法,其特征在于包括如下步骤:以丙二酸和9-溴-1-壬醇为两种起始原料;丙二酸与丙醛在哌啶乙酸盐存在下发生Knoevenagel缩合反应,生成(E)-3-戊烯酸,然后经氢化铝锂还原得到(E)-3-戊烯-1-醇,再经过溴代反应,与三苯基膦在乙腈中回流制得(E)-3-戊烯基三苯基溴化膦;9-溴-1-壬醇经过PCC氧化反应得到9-溴壬醛,然后和乙酸钾反应得到9-乙酰氧基壬醛;最后(E)-3-戊烯基三苯基溴化膦与9-乙酰氧基壬醛发生过Wittig反应制得(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯。
2.根据权利要求1所述的(9Z,12E)-十四碳-9,12-二烯-1-醇乙酸酯的合成方法,其特征在于合成(E)-3-戊烯酸的方法为:氩气保护下,在丙二酸、哌啶、冰醋酸与DMSO的混合液中,滴加丙醛,升温至40℃,反应2h后,升温至100℃,反应8h;反应结束后,用冷水淬灭反应;水相用乙醚萃取,合并有机相,经水洗和饱和氯化钠水溶液洗涤;干燥后减压浓缩,最后经硅胶柱色谱纯化,制得(E)-3-戊烯酸。
3.根据权利要求2所述的合成方法,其特征在于合成(E)-3-戊烯酸所用的反应溶剂为N,N-二甲基甲酰胺、甲苯、二甲基亚砜,优选二甲基亚砜。
4.根据权利要求2所述的合成方法,其特征在于合成(E)-3-戊烯酸的反应温度范围为25-120℃,优选100℃。
5.根据权利要求2所述的合成方法,其特征在于合成(E)-3-戊烯酸所使用的催化剂为氢氧化钠、碳酸钠、磷酸氢二铵、哌啶,优选哌啶。
CN201911272015.2A 2019-12-12 2019-12-12 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法 Pending CN111205184A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911272015.2A CN111205184A (zh) 2019-12-12 2019-12-12 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911272015.2A CN111205184A (zh) 2019-12-12 2019-12-12 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法

Publications (1)

Publication Number Publication Date
CN111205184A true CN111205184A (zh) 2020-05-29

Family

ID=70783833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911272015.2A Pending CN111205184A (zh) 2019-12-12 2019-12-12 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法

Country Status (1)

Country Link
CN (1) CN111205184A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620913A (zh) * 2021-07-26 2021-11-09 安徽华业香料股份有限公司 一种γ-壬烯内酯的合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5735681B2 (zh) * 1973-09-27 1982-07-30
CN103626657A (zh) * 2012-08-23 2014-03-12 昆明博鸿生物科技有限公司 印度谷螟性信息素9z,12e-十四碳二烯-1-醇乙酸酯的合成

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5735681B2 (zh) * 1973-09-27 1982-07-30
CN103626657A (zh) * 2012-08-23 2014-03-12 昆明博鸿生物科技有限公司 印度谷螟性信息素9z,12e-十四碳二烯-1-醇乙酸酯的合成

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANTONIO ORTIZ ET AL.: "Potential for use of synthetic sex pheromone for mating disruption of the olive pyralid moth, Euzophera pinguis", 《JOURNAL OF CHEMICAL ECOLOGY》 *
CHANGMING QIN ET AL.: "Rh2(R‑TPCP)4‑Catalyzed Enantioselective [3+2]-Cycloaddition between Nitrones and Vinyldiazoacetates", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620913A (zh) * 2021-07-26 2021-11-09 安徽华业香料股份有限公司 一种γ-壬烯内酯的合成方法

Similar Documents

Publication Publication Date Title
CN107417505B (zh) α-卤代四甲基环己酮及其与(2,3,4,4-四甲基环戊基)甲基羧酸酯的制备方法
EP0004621B1 (de) Verfahren zur mehrstufigen Synthese von Zeaxanthin und Alloxanthin über Cyclohexanon- und Cyclohexanolderivate; Cyclohexanon- und Cyclohexanolderivate
CN109456182B (zh) (5z,7e)-十二碳-5,7-二烯-1-醇及其乙酸酯与丙酸酯的合成
Li et al. Metal-mediated two-atom carbocycle enlargement in aqueous medium
CN111205184A (zh) 一种合成(9z,12e)-十四碳-9,12-二烯-1-醇乙酸酯的方法
Giuseppone et al. Tandem Mukaiyama Michael–aldol reactions catalysed by samarium diiodide
CN110937985B (zh) 一种姜酮酚的合成方法
CN109970534B (zh) 一种合成桃小食心虫性信息素的方法
Konno et al. Stereoselective synthesis of trifluoromethylated compounds via Johnson-Claisen and Eshenmoser-Claisen rearrangements
Hansen et al. A facile formal synthesis of volicitin
Tellier et al. Stereospecific synthesis of 1, 5-dien-3-ynes and 1, 3, 5-trienes application to the stereochemical identification of trienic sex pheromones
WO2022260168A1 (ja) ヒドロキシチエノイミダゾール誘導体、ビニルスルフィド誘導体、n-ブチリデンスルフィド誘導体、及び飽和直鎖炭化水素置換チエノイミダゾール誘導体の製造方法
CN112079679B (zh) 黄星天牛性信息素(r,z)-21-甲基-8-三十五碳烯不对称全合成方法
JP2002348260A (ja) 2,7−ジメチル−2,4,6−オクタトリエナールモノアセタールの製造方法
US4064183A (en) Synthesis of vitamin A, intermediates and conversion thereof to vitamin A
KR101939863B1 (ko) 1,3,3-트라이메틸-2-(3-메틸펜트-2-엔-4-이닐)사이클로헥스-1-엔의 제조 방법
JP6553553B2 (ja) 2,6−ジメチル−1,5−ヘプタジエン−3−オール及び2,6−ジメチル−1,5−ヘプタジエン−3−イル=アセテートの製造方法
Bernard et al. A highly stereocontrolled formal total synthesis of (±)-and of (−)-grandisol by 1, 4-conjugated addition of organocopper reagents to cyclobutylidene derivatives
US4547586A (en) Preparation of 2-isopropenyl-or 2-isopropylidenyl-3-hexenoates from chrysanthemic acid esters
Ducoux et al. An efficient and stereoselective synthesis of insect pheromones by way of nickel-catalyzed Grignard reactions. Syntheses of gossyplure and pheromones of Eudia pavonia and Droxophila melanogaster.
JP2790915B2 (ja) アルカトリエン化合物の製造方法
Tsuboi et al. Stereoselective synthesis of 3, 5-alkadienoic esters from 2, 4-dienoic isomers.
Yanchang et al. A novel synthesis of trans-γ, δ-unsaturatedtrifluoromethyl ketones
JP3918120B2 (ja) 3,7−ジメチル−2,6−オクタジエン−4−オリドの製造方法
CN109699646B (zh) 一种水稻螟虫信息素成分的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200529