CN109020937A - 一种(e)-7-十二碳烯-1-醇乙酸酯的合成方法 - Google Patents

一种(e)-7-十二碳烯-1-醇乙酸酯的合成方法 Download PDF

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CN109020937A
CN109020937A CN201810946831.6A CN201810946831A CN109020937A CN 109020937 A CN109020937 A CN 109020937A CN 201810946831 A CN201810946831 A CN 201810946831A CN 109020937 A CN109020937 A CN 109020937A
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dodecylene
tetrahydro
acetic ester
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钟江春
马思捷
边庆花
王敏
周云
侯文博
李杨帆
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Abstract

本发明属于昆虫信息素合成技术领域，公开了一种新的合成(E)‑7‑十二碳烯‑1‑醇乙酸酯的方法。该方法以6‑溴‑1‑己醇为起始原料，先与2,3‑二氢吡喃反应，得到1‑四氢吡喃氧基‑6‑溴己烷，接着在正丁基锂的存在下，与1‑己炔发生偶联反应生成1‑四氢吡喃氧基‑7‑十二碳炔。然后在二乙二醇二甲醚中，经四氢铝锂还原，得到(E)‑1‑四氢吡喃氧基‑7‑十二碳烯。再利用对甲苯磺酸脱去四氢吡喃保护基，合成(E)‑7‑十二碳烯‑1‑醇，最后与乙酰氯反应，得到目标物(E)‑7‑十二碳烯‑1‑醇乙酸酯。本发明合成路线简捷，反应条件温和，总产率为49％。

Description

一种(E)-7-十二碳烯-1-醇乙酸酯的合成方法
技术领域
本发明属于昆虫信息素合成技术领域，具体涉及一种新的合成(E)-7-十二碳烯-1-醇乙酸酯的方法。
背景技术
(E)-7-十二碳烯-1-醇乙酸酯((E)-dodec-7-enyl acetate，式1)是植物害虫Argyroploce leucotreta(Meyrick)性信息素的主要成分，可用于该类害虫的生物防治(Read,J.S.；Warren,F.L.；Hewitt,P.H.Chem.Commun.1968,792-793.Read,J.S.；Hewitt,P.H.；Warren,F.L.；Myberg,A.C.J.Insect Physiol.1974,20,441-450.)。(E)-7-十二碳烯-1-醇乙酸酯也是葡萄蔓蛾(Lobesia botrana)性信息素的次要成分，可显著增加主要成分(7Z,9E,11)-十二碳三烯-1-醇乙酸酯的引诱雄蛾的能力(Witzgall,P.；Tasin,M.；Buser,H.-R.；Wegner-Kiss,G.；Mancebon,V.S.M.；Ioriatti,C.；Baeckman,A.-C.；Bengtsson,M.；Lehmann,L.；Francke,W.J.Chem.Ecol.2005,31,2923-2932.)。另外，(E)-7-十二碳烯-1-醇乙酸酯还是秋季黏虫Spodoptera frugiperda(Smith)性信息素的活性成分(Batista-Pereira,L.G.；Stein,K.；Paula,A.F.；Moreira,J.A.；Cruz,I.；Figueiredo,M.d.L.C.；Perri,J.,Jr.；Correa,A.G.J.Chem.Ecol.2006,32,1085-1099.)。
(E)-7-十二碳烯-1-醇乙酸酯是一类重要的昆虫信息素，具有显著的生理活性，但在昆虫体内含量极少，而且提取困难，限制了其在防治农作物病虫害领域的应用研究。因此，研究其化学合成具有重要的意义。目前合成(E)-7-十二碳烯-1-醇乙酸酯的方法主要包括Wittig反应法、格氏试剂偶联法、烯基硼烷法以及烯烃复分解法。
(1)Wittig反应法是利用正丁醛与含酯基的Wittig试剂反应，构建E型双键，然后经酯还原、溴代、偶联、脱保护基等多步反应，得到(E)-7-十二碳烯-1-醇，最后与乙酸酐反应，实现(E)-7-十二碳烯-1-醇乙酸酯的合成(Canevet,C.；Roeder,T.；Vostrowsky,O.；Bestmann,H.J.Chem.Ber.1980,113,1115-1120.)。
(2)格氏试剂偶联法是在金属钯配位化合物的催化下利用烯基碘或烯基溴与格氏试剂发生偶联反应构建E型双键，然后经硼氢化氧化、酯化等多步反应，得到(E)-7-十二碳烯-1-醇乙酸酯(Yen,Y.-P.；Chen,P.-H.J.Chin.Chem.Soc.(Taipei)1999,46,87-90.Rossi,R.；Carpita,A.Tetrahedron Lett.1986,27,2529-2532.)。
(3)烯基硼烷法是利用炔烃与硼烷反应生成烯基硼烷，然后用甲醇钠处理，再经氧化、酯化等多步反应得到(E)-7-十二碳烯-1-醇乙酸酯(Brown,H.C.；Lee,H.D.；Kulkarni,S.U.J.Org.Chem.1986,51,5282-5286.Brown,H.C.；Basavaiah,D.；Singh,S.M.；Bhat,N.G.J.Org.Chem.1988,53,246-250.)。
(4)烯烃复分解法是在苯氧氯化钨与四烷基锡的共同催化下，1-己烯与7-辛烯-1-醇乙酸酯发生烯烃复分解反应，直接得到(E)-7-十二碳烯-1-醇乙酸酯(Crisp,G.T.；Collis,M.P.Aust.J.Chem.1988,41,935-942.)。
虽然关于合成(E)-7-十二碳烯-1-醇乙酸酯的研究已有一些文献报道，但仍然存在反应条件苛刻，反应步骤繁琐等问题。因此，研究新的、反应条件温和的、简捷的合成(E)-7-十二碳烯-1-醇乙酸酯的方法，具有重要的意义。
发明内容
本发明旨在提供一种新的合成(E)-7-十二碳烯-1-醇乙酸酯的方法。本发明以6-溴-1-己醇为起始原料，在对甲苯磺酸催化下，先与2,3-二氢吡喃反应，得到四氢吡喃保护的溴代醇2，接着在正丁基锂的存在下，与1-己炔发生偶联反应生成四氢吡喃保护的炔醇3。然后在二乙二醇二甲醚中，经四氢铝锂还原，得到四氢吡喃保护的烯醇4。再利用对甲苯磺酸脱去四氢吡喃保护基，合成(E)-7-十二碳烯-1-醇5，最后与乙酰氯反应，得到目标物(E)-7-十二碳烯-1-醇乙酸酯。本发明合成路线简捷，反应条件温和，总产率为49％。本发明合成(E)-7-十二碳烯-1-醇乙酸酯的合成路线参见式2。
本发明(E)-7-十二碳烯-1-醇乙酸酯的方法包括如下步骤。
(1)1-四氢吡喃氧基-6-溴己烷2的合成
将6-溴-1-己醇1与2,3-二氢吡喃溶于二氯甲烷，加入对甲苯磺酸，室温下搅拌反应过夜。反应完成后，用饱和Na2CO3水溶液洗涤反应液，分液。水相用二氯甲烷萃取，合并有机相，无水Na2SO4干燥。减压浓缩，粗产物经硅胶柱色谱纯化，制得1-四氢吡喃氧基-6-溴己烷2。
(2)1-四氢吡喃氧基-7-十二碳炔3的合成
氩气保护下，将1-己炔溶于四氢呋喃，-40℃下滴加正丁基锂的正己烷溶液，搅拌反应2h，加入1-四氢吡喃氧基-7-十二碳炔3。将反应液自然升温至室温，继续搅拌反应24h。反应完成后，在0℃下用水淬灭反应，分液，水相用乙醚萃取。合并有机相，无水Na2SO4干燥。减压浓缩，粗产物经硅胶柱色谱纯化，制得1-四氢吡喃氧基-7-十二碳炔3。
(3)(E)-1-四氢吡喃氧基-7-十二碳烯4的合成
氩气保护下，在四氢铝锂的二乙二醇二甲醚溶液中，加入1-四氢吡喃氧基-7-十二碳炔3，搅拌均匀。将反应液温度升至150℃，继续搅拌回流反应24h。反应完成后，在0℃下用甲醇与含水氯化铵淬灭反应。抽滤，固体用乙醚洗涤，滤液用水洗涤后分液。合并有机相，无水Na2SO4干燥。减压浓缩，粗产物经硅胶柱色谱纯化制得(E)-1-四氢吡喃氧基-7-十二碳烯4。
(4)(E)-7-十二烯碳-1-醇5的合成
将(E)-1-四氢吡喃氧基-7-十二碳烯4与对甲苯磺酸溶于甲醇，室温搅拌反应30min。反应完成后，用饱和Na2CO3水溶液淬灭反应。分液，水相用二氯甲烷萃取。合并有机相，无水Na2SO4干燥。减压浓缩，粗产物经硅胶柱色谱纯化，制得(E)-7-十二烯碳-1-醇5。
(5)(E)-7-十二碳烯-1-醇乙酸酯的合成
氩气保护下，将(E)-7-十二烯醇5和三乙胺溶于二氯甲烷，在0℃下缓慢滴加乙酰氯，将反应液温度自然升至室温，继续搅拌反应过夜。反应完成后，加水淬灭反应。分液，水相用二氯甲烷萃取。合并有机相，无水Na2SO4干燥。减压浓缩，粗产物经硅胶柱色谱纯化，制得(E)-7-十二碳烯-1-醇乙酸酯。
具体实施方式
实施例1
1-四氢吡喃氧基-6-溴己烷2的合成
将6-溴己醇1(1.0g,5.52mmol)与2,3-二氢吡喃(0.95g,11.03mmol)加入二氯甲烷(10mL)，搅拌溶解。然后加入对甲苯磺酸(0.1g,0.58mmol)，室温下搅拌反应过夜。反应完成后，将反应混合液用饱和Na2CO3水溶液(20mL)洗涤，分液。水相用二氯甲烷(3×20mL)萃取，合并有机相。无水Na2SO4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1-四氢吡喃氧基-6-溴己醇2，为淡黄色液体(1.36g,产率93％)。1H NMR(300MHz,CDCl3)δ4.55(t,J＝3.5Hz,1H),3.84–3.70(m,2H),3.41–3.35(m,4H),1.87–1.37(m,14H)；13C NMR(75MHz,CDCl3)δ98.53,67.04,62.01,33.49,32.40,30.42,29.21,27.65,25.14,19.35.
实施例2
1-四氢吡喃氧基-7-十二碳炔3的合成
氩气保护下，将1-己炔(0.79g,9.6mmol)加入四氢呋喃(20mL)，室温下搅拌溶解。将混合溶液温度降至-40℃，缓慢滴加正丁基锂(4mL,2.4M正己烷溶液,9.6mmol)。在-40℃下搅拌反应2h，然后加入1-四氢吡喃氧基-6-溴己烷2(1.27g,4.8mmol)，将反应液自然升温至室温，继续搅拌反应24h。反应完成后，将反应液温度降至0℃，用少量水淬灭反应，分液，水相用乙醚(3×10mL)萃取。合并有机相，无水Na2SO4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100:1)纯化，制得1-四氢吡喃氧基-7-十二碳炔3，为淡黄色液体(1.21g，产率95％)。1H NMR(300MHz,CDCl3)δ4.55(t,J＝3.5Hz,1H),3.88–3.67(m,2H),3.51–3.32(m,2H),2.14–2.09(m,4H),1.83–1.31(m,18H),0.88(t,J＝7.1Hz,3H)；13C NMR(75MHz,CDCl3)δ98.46,79.83,79.68,67.19,61.92,30.90,30.42,29.31,28.75,28.32,25.45,25.16,21.55,19.32,18.34,18.06,13.24.
实施例3
(E)-1-四氢吡喃氧基-7-十二碳烯4的合成
氩气保护下，在四氢铝锂(114mg,3mmol)的二乙二醇二甲醚(40mL)溶液中，加入1-四氢吡喃氧基-7-十二碳炔3(266mg,1mmol)，搅拌均匀。将反应液温度升至150℃，继续搅拌回流反应24h。反应完成后，将反应液温度降至0℃，用甲醇(2mL)与含水氯化铵淬灭反应。抽滤，固体用乙醚(30mL)洗涤，滤液用水(30mL)洗涤后分液。合并有机相，无水Na2SO4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110:1)纯化，制得(E)-1-四氢吡喃氧基-7-十二碳烯4，为淡黄色液体(174mg,产率65％)。1H NMR(300MHz,CDCl3)δ5.39–5.34(m,2H),4.57(t,J＝3.5Hz,1H),3.87–3.69(m,2H),3.51–3.36(m,2H),1.97–1.95(m,4H),1.59–1.53(m,8H),1.33–1.29(m,10H),0.88(t,J＝6.9Hz,3H)；13C NMR(75MHz,CDCl3)δ130.06,129.89,98.49,67.32,61.98,32.18,31.93,31.49,30.45,29.39,29.24,28.64,25.77,25.18,21.84,19.36,13.60.
实施例4
(E)-7-十二碳烯-1-醇的合成5
将(E)-1-四氢吡喃氧基-7-十二碳烯4(268mg,1mmol)与对甲苯磺酸(18mg,0.1mmol)加入甲醇(5mL)，搅拌溶解后，在室温下继续搅拌反应30min。反应完成后，用饱和Na2CO3水溶液淬灭反应，分液，水相用二氯甲烷(3×20mL)萃取。合并有机相，无水Na2SO4干燥。减压浓缩得粗产物。粗产物经硅胶柱色谱(石油醚/乙酸乙酯50:1)纯化，制得(E)-7-十二碳烯-1-醇5，为油状液体(158mg,产率86％)。1H NMR(300MHz,CDCl3)δ5.38–5.33(m,2H),3.63(t,J＝6.1Hz,2H),2.03–1.97(m,4H),1.56–1.29(m,12H),0.88(t,J＝6.9Hz,3H)；13CNMR(75MHz,CDCl3)δ130.13,129.81,62.66,32.41,32.15,31.92,31.47,29.23,28.56,25.25,21.84,13.59.
实施例5
(E)-7-十二碳烯-1-醇乙酸酯的合成
氩气保护下，将(E)-7-十二碳烯-1-醇5(184mg,1mmol)和三乙胺(0.85mL,6mmol)加入二氯甲烷(10mL)，搅拌溶解。将混合溶液温度降至0℃，缓慢滴加乙酰氯(236mg,3mmol)。将反应液温度自然升至室温，继续搅拌反应过夜。反应完成后，用少量水淬灭反应，分液，水相用二氯甲烷(3×10mL)萃取。合并有机相，无水Na2SO4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(E)-7-十二碳烯-1-醇乙酸酯，为无色液体(199mg,产率88％)。1H NMR(300MHz,CDCl3)δ5.39–5.36(m,2H),4.04(t,J＝6.8Hz,2H),2.04(s,3H),2.03–1.95(m,4H),1.64–1.60(m,2H),1.32–1.28(m,10H),0.88(t,J＝7.0Hz,3H)；13C NMR(75MHz,CDCl3)δ170.83,130.19,129.72,64.27,32.11,31.91,31.47,29.12,28.37,28.23,25.43,21.83,20.64,13.58.

Claims (3)

1.一种(E)-7-十二碳烯-1-醇乙酸酯的合成方法，其特征在于包括如下步骤：6-溴-1-己醇先与2,3-二氢吡喃反应，得到1-四氢吡喃氧基-6-溴己烷，接着与1-己炔发生偶联反应生成1-四氢吡喃氧基-7-十二碳炔，然后经四氢铝锂还原，得到(E)-1-四氢吡喃氧基-7-十二碳烯，再利用对甲苯磺酸脱去四氢吡喃保护基，合成(E)-7-十二碳烯-1-醇，最后与乙酰氯反应，得到(E)-7-十二碳烯-1-醇乙酸酯。
2.根据权利要求1所述的一种(E)-7-十二碳烯-1-醇乙酸酯的合成方法，其特征在于氩气保护下，将1-己炔溶于四氢呋喃，-40℃下滴加正丁基锂的正己烷溶液，搅拌反应2h，加入1-四氢吡喃氧基-7-十二碳炔，在室温下继续搅拌反应24h，在0℃下淬灭反应，经分液、萃取、干燥、减压浓缩，最后用硅胶柱色谱纯化，制得1-四氢吡喃氧基-7-十二碳炔。
3.根据权利要求1所述的一种(E)-7-十二碳烯-1-醇乙酸酯的合成方法，其特征在于氩气保护下，在四氢铝锂的二乙二醇二甲醚溶液中，加入1-四氢吡喃氧基-7-十二碳炔，在150℃下回流反应24h，在0℃下淬灭反应，经抽滤、洗涤、分液、干燥、减压浓缩，最后用硅胶柱色谱纯化，制得(E)-1-四氢吡喃氧基-7-十二碳烯。
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