CN111269114A - 草地贪夜蛾性信息素活性成分的合成方法 - Google Patents
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/54—Quaternary phosphonium compounds
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Abstract
本发明属于绿色农药合成技术领域,公开了合成草地贪夜蛾性信息素活性成分(Z)‑9‑十二碳烯‑1‑醇乙酸酯、(Z)‑9‑十四碳烯‑1‑醇乙酸酯与(Z)‑11‑十六碳烯‑1‑醇乙酸酯的新方法。该方法以溴代醇为起始原料,先与三苯膦生成羟基鏻盐,然后分别与丙醛、戊醛发生Wittig偶联反应,生成Z型烯醇,最后与乙酸酐发生乙酰化反应制得(Z)‑9‑十二碳烯‑1‑醇乙酸酯、(Z)‑9‑十四碳烯‑1‑醇乙酸酯与(Z)‑11‑十六碳烯‑1‑醇乙酸酯。该方法利用羟基鏻盐进行Wittig反应,省略了保护羟基与去保护两步,简化了合成路线,还具有对环境友好等优点。
Description
技术领域
本发明属于绿色农药合成技术领域,具体涉及草地贪夜蛾性信息素活性成分的合成方法。
背景技术
(Z)-9-十二碳烯-1-醇乙酸酯1、(Z)-9-十四碳烯-1-醇乙酸酯2与(Z)-11-十六碳烯-1-醇乙酸酯3(式1)是植物害虫草地贪夜蛾(Spodoptera frugiperda J.E,Smith)性信息素的主要活性成分,可用于该类害虫的干扰交配(Hirai,Y.;Mitchell,E.R.J.Chem.Ecol.1982,8,267-273.)、引诱雄虫(Meagher Robert,L.;Nagoshi Rodney,N.Environ.Entomol.2013,42,751-757.)与虫情监测(Cruz-Esteban,S.;Rojas Julio,C.;Gonzalez Francisco,J.J.Econ.Entomol.2018,111,1674-1681.)。1967年,Sparks等从草地贪夜蛾雌虫虫体中提取分离出(Z)-9-十四碳烯-1-醇乙酸酯(Sekul,A.A.;Sparks,A.N.J.Econ.Entomol.1967,60,1270-1272.)。随后,Mitchell等研究表明,(Z)-9-十二碳烯-1-醇乙酸酯也可以干扰草地贪夜蛾的交配(Mitchell,E.R.;Copeland,W.W.;Sparks,A.N.;Sekul,A.A.Environ.Entomol.1974,3,778-780.)。1986年,该课题组研究发现,草地贪夜蛾雌虫腺体提取物中还存在(Z)-11-十六碳烯-1-醇乙酸酯(Tumlinson,J.H.;Mitchell,E.R.;Teal,P.E.;Heath,R.R.;Mengelkoch,L.J.J.Chem.Ecol.1986,12,1909-1926.)。
(Z)-9-十二碳烯-1-醇乙酸酯、(Z)-9-十四碳烯-1-醇乙酸酯与(Z)-11-十六碳烯-1-醇乙酸酯虽然可用于草地贪夜蛾的综合防治,但难以提取,而且含量极低。因此,研究这些乙酸酯的合成具有重要的意义。合成乙酸酯1-3的关键是构建Z型碳-碳双键,文献报道的方法主要有炔烃Lindlar催化氢化法、烯烃复分解反应法、Wittig偶联法与Z型烯烃原料法。
(1)炔烃Lindlar氢化法是以正溴丁烷为原料,先与3-丁炔-1-醇发生亲核取代反应,然后经Lindlar催化氢化得到(Z)-3-辛烯-1-醇,再经溴代生成(Z)-1-溴-3-辛烯,最后经腙的双烷基化、脱THP保护基与乙酰化等多步反应制得(Z)-9-十四碳烯-1-醇乙酸酯(Mitra,R.B.;Reddy,G.B.Synthesis 1989,694-698.)。
(2)烯烃复分解反应法是在钌催化剂存在下,(Z)-9-十八碳烯-1-醇与1-丁烯发生烯烃复分解反应,直接得到(Z)-9-十二碳-1-醇,然后乙酰化制得(Z)-9-十二碳烯-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.)。
(3)Wittig偶联法以11-溴-1-十一醇为原料,先用THP保护羟基,然后与三苯膦反应生成THP保护的羟基鏻盐,再与丁醛发生Wittig偶联反应构建Z型双键,得到(Z)-16-四氢吡喃氧基-11-十六碳烯,最后经脱THP保护基与乙酰化反应,制得(Z)-11-十六碳烯-1-醇乙酸酯(Wang,A.-j.;Zhang,K.-X.;Gao,Y.-l.;Weng,A.-z.;Wang,L.-y.;Zhang,Y.-h.;Zhang,Z.;She,D.-m.;Ning,J.;Mei,X.-d.Pest Manage.Sci.2019,75,1045-1055.)。
(4)Z型烯烃原料法是以(Z)-11-十六碳烯-1-醇甲酸酯为原料,先经四氢铝锂还原,然后与乙酸酐反应,制得(Z)-11-十六碳烯-1-醇乙酸酯(Nesnerova,P.;Sebek,P.;Macek,T.;Svatos,A.Green Chem.2004,6,305-307.)。
关于草地贪夜蛾性信息素活性成分乙酸酯1-3的合成研究虽然已有一些文献报道,但仍然存在反应路线冗长、试剂毒性较大、需要昂贵的Z型烯烃原料等问题。因此,寻找路线简捷、反应条件温和、对环境友好的合成方法,具有重要的研究意义。
发明内容
本发明旨在提供合成草地贪夜蛾性信息素活性成分乙酸酯1-3的新方法。该方法以溴代醇4a与4b为起始原料,先与三苯膦生成羟基鏻盐5a与5b,然后分别与丙醛、戊醛发生Wittig偶联反应,生成Z型烯醇6-8,最后与乙酸酐发生乙酰化反应制得(Z)-9-十二碳烯-1-醇乙酸酯1、(Z)-9-十四碳烯-1-醇乙酸酯2与(Z)-11-十六碳烯-1-醇乙酸酯3。该方法利用羟基鏻盐进行Wittig反应,省略了保护羟基与去保护两步,简化了合成路线,还具有对环境友好等优点。本发明合成草地贪夜蛾性信息素活性成分乙酸酯1-3的合成路线参见式2。
本发明合成草地贪夜蛾性信息素活性成分乙酸酯1-3的方法包括如下步骤。
(1)季鏻盐5a的合成
氩气保护下,将三苯膦、乙腈和9-溴-1-壬醇4a的混合液,加热至回流,反应48h。反应结束后,减压浓缩除去乙腈,最后用硅胶柱色谱纯化,制得季鏻盐5a。
(2)季鏻盐5b的合成
氩气保护下,将三苯膦、乙腈和11-溴-1-十一醇4b的混合液,加热至回流,反应48h。反应结束后,减压浓缩除去乙腈,最后用硅胶柱色谱纯化,制得季鏻盐5a。
(3)(Z)-9-十二碳烯-1-醇6的合成。
氩气保护下,将季鏻盐5a的四氢呋喃溶液,降温至-78℃,滴加六甲基二硅基氨基钠,搅拌反应1h。再滴入丙醛,升温至室温,继续搅拌反应24h。反应结束后,用饱和氯化铵水溶液淬灭反应。分液,水相用乙醚萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-9-十二碳烯-1-醇6。
(4)(Z)-9-十四碳烯-1-醇7的合成
氩气保护下,将季鏻盐5a的四氢呋喃溶液,降温至-78℃,滴加六甲基二硅基氨基钠,搅拌反应1h。再滴入戊醛,升温至室温,继续搅拌反应24h。反应结束后,用饱和氯化铵水溶液淬灭反应。分液,水相用乙醚萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-9-十四碳烯-1-醇7。
(5)(Z)-11-十六碳烯-1-醇8的合成
氩气保护下,将季鏻盐5b的四氢呋喃溶液,降温至-78℃,滴加六甲基二硅基氨基钠,搅拌反应1h。再滴入戊醛,升温至室温,继续搅拌反应24h。反应结束后,用饱和氯化铵水溶液淬灭反应。分液,水相用乙醚萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-11-十六碳烯-1-醇8。
(6)(Z)-9-十二碳烯-1-醇乙酸酯1的合成
氩气保护下,在(Z)-9-十二碳烯-1-醇6、二氯甲烷与三乙胺的混合液中,冰浴冷却下滴加乙酸酐,升温至室温,搅拌反应8h。反应结束后,用水淬灭反应。分液,水相用二氯甲烷萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-9-十二碳烯-1-醇乙酸酯1。
(7)(Z)-9-十四碳烯-1-醇乙酸酯2的合成
氩气保护下,在(Z)-9-十四碳烯-1-醇7、二氯甲烷与三乙胺的混合液中,冰浴冷却下滴加乙酸酐,升温至室温,搅拌反应8h。反应结束后,用水淬灭反应。分液,水相用二氯甲烷萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-9-十四碳烯-1-醇乙酸酯2。
(8)(Z)-11-十六碳烯-1-醇乙酸酯3的合成
氩气保护下,在(Z)-11-十六碳烯-1-醇8、二氯甲烷与三乙胺的混合液中,冰浴冷却下滴加乙酸酐,升温至室温,搅拌反应8h。反应结束后,用水淬灭反应。分液,水相用二氯甲烷萃取,合并有机相。有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-11-十六碳烯-1-醇乙酸酯3。
具体实施方式
实施例1
季鏻盐5a的合成
氩气保护下,向装有回流冷凝管的100mL三口瓶中加入三苯膦(1.760g,6.7mmol)、无水乙腈(40mL)和9-溴-1-壬醇4a(1.000g,4.5mmol),搅拌溶解,加热至回流反应48h。反应结束后,降至室温,减压浓缩除去乙腈。残留物用硅胶柱色谱(二氯甲烷/甲醇10:1)纯化,制得浅黄色油状物季鏻盐5a(1.980g,产率91%)。13C NMR(75MHz,CDCl3)δ134.9,134.9,133.4,133.3,130.4,130.3,118.5,117.4,62.1,32.3,30.1,29.9,28.7,28.6,28.5,25.3,22.8,22.3,22.2,22.1.HRMS(APCI-TOF):理论值C27H35OBrNaP[M+Na]+508.1501,实测值508.1202.
实施实例2
季鏻盐5b的合成
氩气保护下,向装有回流冷凝管的50mL三口瓶中加入三苯膦(0.787g,3.0mmol)、无水乙腈(20mL)和11-溴-1-十一醇4b(0.502g,2.0mmol),搅拌溶解,加热至回流反应48h。反应结束后,降至室温,减压浓缩除去乙腈。残留物用硅胶柱色谱(二氯甲烷/甲醇10:1)纯化,制得浅黄色油状物季鏻盐5b(0.849g,产率83%)。1H NMR(300MHz,CDCl3)δ7.86–7.71(m,15H),3.60–3.55(m,4H),3.04(brs,1H),1.62–1.47(m,6H),1.27–1.19(m,12H).13C NMR(75MHz,CDCl3)δ134.6,134.5,133.0,132.9,130.1,129.9,118.1,117.0,61.7,32.1,29.8,29.6,28.8,28.7,28.6,28.4,25.2,22.5,21.8.HRMS(APCI-TOF):理论值C29H39OBrP[M+H]+513.1916,实测值513.1788.
实施实例3
(Z)-9-十二碳烯-1-醇6的合成
氩气保护下,向250mL Schlenk反应瓶中加入季鏻盐5a(8.000g,16.5mmol)和无水四氢呋喃(100mL),搅拌溶解,降温至-78℃,缓慢滴加六甲基二硅基氨基钠(16.5mL,2.0M四氢呋喃溶液,33.0mmol),在-78℃下搅拌反应1h,再加入丙醛(1.920g,33.0mmol),缓慢升温至室温,继续搅拌反应24h。反应结束后,冰浴冷却下滴加饱和氯化铵水溶液(40mL)淬灭反应,分液,水相用乙醚(3×60mL)萃取,合并有机相。有机相依次用水(100mL)和饱和氯化钠水溶液(100mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯5:1)纯化,制得淡黄色液体(Z)-9-十二碳烯-1-醇6(1.550g,产率51%)。1H NMR(300MHz,CDCl3)δ5.40–5.27(m,2H),3.62(t,J=6.7Hz,2H),2.06–1.98(m,5H),1.58–1.30(m,12H),0.95(t,J=7.5Hz,3H).13C NMR(75MHz,CDCl3)δ131.5,129.2,62.8,32.7,29.7,29.4,29.4,29.1,27.0,25.7,20.4,14.3.HRMS(APCI-TOF):理论值C12H25O[M+H]+185.1900,实测值185.1901.
实施实例4
(Z)-9-十四碳烯-1-醇7的合成
氩气保护下,向250mL Schlenk反应瓶中加入季鏻盐5a(8.000g,16.5mmol)和无水四氢呋喃(100mL),搅拌溶解,降温至-78℃,缓慢滴加六甲基二硅基氨基钠(16.5mL,2.0M四氢呋喃溶液,33.0mmol),在-78℃下搅拌反应1h,再滴加戊醛(2.840g,33.0mmol),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(40mL)淬灭反应,分液,水相用乙醚(3×60mL)萃取,合并有机相。有机相依次用水(100mL)和饱和氯化钠水溶液(100mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯5:1)纯化,制得淡黄色液体(Z)-9-十四碳烯-1-醇7(2.327g,产率66%)。1H NMR(300MHz,CDCl3)δ5.36–5.33(m,2H),3.62(t,J=6.7Hz,2H),2.02–1.99(m,5H),1.56–1.53(m,2H),1.35–1.30(m,14H),0.90(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ129.8,129.7,62.8,32.7,31.9,29.7,29.4,29.3,29.16,27.1,26.8,25.7,22.8,13.9.HRMS(APCI-TOF):理论值C14H28ONa[M+Na]+235.2032,实测值235.2040.
实施实例5
(Z)-11-十六碳烯-1-醇8的合成
氩气保护下,向100mL Schlenk反应瓶中加入季鏻盐5b(1.026g,2.0mmol)和无水四氢呋喃(20mL),搅拌溶解,降温至-78℃,缓慢滴入加六甲基二硅基氨基钠(2.0mL,2M四氢呋喃溶液,4.0mmol),在-78℃下搅拌1h,再滴戊醛(0.120g,1.3mmol),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(10mL)淬灭反应,分液,水相用乙醚(3×15mL)萃取,合并有机相。有机相依次用水(40mL)和饱和氯化钠水溶液(40mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯5:1)纯化,制得淡黄色液体(Z)-11-十六碳烯-1-醇8(0.168g,产率54%)。1H NMR(300MHz,CDCl3)δ5.36–5.33(m,2H),3.62(t,J=6.7Hz,2H),2.17(brs,1H),2.04–2.00(m,4H),1.60–1.50(m,2H),1.35–1.28(m,18H),0.90(t,J=6.9Hz,3H).13C NMR(75MHz,CDCl3)δ129.8,129.8,62.9,32.7,31.9,29.7,29.6,29.52,29.48,29.4,29.2,27.1,26.9,25.7,22.3,13.9.HRMS(APCI-TOF):理论值C16H32ONa[M+Na]+263.2345,实测值263.2355.
实施实例6
(Z)-9-十二碳烯-1-醇乙酸酯1的合成
氩气保护下,向100mL Schlenk反应瓶中加入(Z)-9-十二碳烯-1-醇6(1.471g,8.0mmol)、无水二氯甲烷(40mL)、无水三乙胺(4.790g,47.3mmol),冰浴下缓慢滴加乙酸酐(2.420g,23.7mmol)。滴完后,升温至室温,搅拌反应8h。反应结束后,加水(20mL)淬灭反应,分液,水相用二氯甲烷(3×30mL)萃取,合并有机相。有机相依次用水(3×70mL)和饱和氯化钠水溶液(70mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯80:1)纯化,制得淡黄色液体(Z)-9-十二碳烯-1-醇乙酸酯1(1.715g,产率95%)。1H NMR(300MHz,CDCl3)δ5.56–5.10(m,2H),4.05(t,J=6.8Hz,2H),2.06(s,3H),2.04–1.90(m,4H),1.64–1.30(m,12H),0.96(t,J=6.5Hz,3H).13C NMR(75MHz,CDCl3)δ171.1,131.5,129.2,64.6,29.7,29.3,29.2,29.1,28.6,27.0,25.9,20.9,20.5,14.3.HRMS(APCI-TOF):理论值C14H27O2[M+H]+227.2006,实测值227.2008.
实施实例7
(Z)-9-十四碳烯-1-醇乙酸酯2的合成
氩气保护下,向100mL Schlenk反应瓶中加入(Z)-9-十四碳烯-1-醇7(2.228g,10.5mmol)、无水二氯甲烷(50mL)与无水三乙胺(6.380g,63.0mmol),冰浴下缓慢滴加乙酸酐(3.216g,31.5mmol),滴完后,升温至室温,搅拌反应8h。反应结束后,加水(30mL)淬灭反应,分液,水相用二氯甲烷(3×40mL)萃取,合并有机相。有机相依次用水(3×80mL)和饱和氯化钠水溶液(80mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯80:1)纯化,制得淡黄色液体(Z)-9-十四碳烯-1-醇乙酸酯2(2.557g,产率96%)。1H NMR(300MHz,CDCl3)δ5.36–5.32(m,2H),4.05(t,J=6.8Hz,2H),2.04(s,3H),2.03–1.99(m,4H),1.64–1.59(m,2H),1.34–1.30(m,14H),0.90(t,J=7.0Hz,3H).13C NMR(75MHz,CDCl3)δ171.0,129.8,129.7,64.5,31.9,29.7,29.3,29.2,29.1,28.6,27.1,26.8,25.8,22.3,20.9,13.9.HRMS(APCI-TOF):理论值C16H30O2Na[M+Na]+277.2138,实测值277.2142.
实施实例8
(Z)-11-十六碳烯-1-醇乙酸酯3的合成
氩气保护下,向10mL Schlenk管中加入(Z)-11-十六碳烯-1-醇8(0.103g,0.43mmol)、无水二氯甲烷(4mL)与无水三乙胺(0.263g,2.6mmol),冰浴下缓慢滴加乙酸酐(0.133g,1.3mmol),滴完后,升温至室温,搅拌反应8h。反应结束后,加水(8mL)淬灭反应,分液,水相用二氯甲烷(3×10mL)萃取,合并有机相。有机相依次用水(3×20mL)和饱和氯化钠水溶液(30mL)洗涤,无水硫酸钠干燥后减压浓缩除去溶剂。残余物用硅胶柱色谱(石油醚/乙酸乙酯80:1)纯化,制得浅黄色液体(Z)-11-十六碳烯-1-醇乙酸酯3(0.114g,产率94%)。1HNMR(300MHz,CDCl3)δ5.35(t,J=4.6Hz,2H),4.05(t,J=6.8Hz,2H),2.04(s,3H),2.01–1.99(m,3H),1.64–1.57(m,2H),1.35–1.28(m,18H),0.88(t,J=4.6Hz,3H).13C NMR(75MHz,CDCl3)δ171.0,129.8,129.7,64.6,31.9,29.7,29.49,29.47,29.46,29.23,29.21,28.6,27.1,26.9,25.9,22.3,20.9,13.9.HRMS(APCI-TOF):理论值C18H34O2Na[M+Na]+305.2451,实测值305.2465.
Claims (5)
1.合成草地贪夜蛾性信息素活性成分(Z)-9-十二碳烯-1-醇乙酸酯、(Z)-9-十四碳烯-1-醇乙酸酯与(Z)-11-十六碳烯-1-醇乙酸酯的方法,其特征在于包括如下步骤:以9-溴-1-壬醇4a与11-溴-1-十一醇4b为起始原料,先与三苯膦生成羟基鏻盐5a与5b,然后分别与丙醛、戊醛发生Wittig偶联反应,生成Z型烯醇6、7与8,最后与乙酸酐发生乙酰化反应制得(Z)-9-十二碳烯-1-醇乙酸酯、(Z)-9-十四碳烯-1-醇乙酸酯与(Z)-11-十六碳烯-1-醇乙酸酯。
2.根据权利要求1所述的(Z)-9-十二碳烯-1-醇乙酸酯、(Z)-9-十四碳烯-1-醇乙酸酯与(Z)-11-十六碳烯-1-醇乙酸酯的合成方法,其特征在于合成Z型烯醇6、7与8方法为:氩气保护下,将碱加入季鏻盐5a或5b的有机溶剂溶液,搅拌均匀;再滴入丙醛或戊醛,继续搅拌反应;反应结束后,用饱和氯化铵水溶液淬灭反应,分液,水相用乙醚萃取,合并有机相;有机相经洗涤、干燥与减压浓缩,最后用硅胶柱色谱纯化,制得(Z)-9-十二碳烯-1-醇6、(Z)-9-十四碳烯-1-醇7与(Z)-11-十六碳烯-1-醇8。
3.根据权利要求2所述的合成方法,其特征在于合成Z型烯醇6、7与8的反应溶剂为四氢呋喃、乙醚、甲苯与二氯甲烷,优选四氢呋喃。
4.根据权利要求2所述的合成方法,其特征在于合成Z型烯醇6、7与8所用的碱为氢化钠、碳酸钾、叔丁醇钾、苯基锂、正丁基锂与六甲基二硅基氨基钠,优选六甲基二硅基氨基钠。
5.根据权利要求2所述的合成方法,其特征在于合成Z型烯醇6、7与8的反应温度为-80-25℃,优选-78℃。
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