CN115304463A - 一种苹果蠹蛾信息素的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation 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
- C07C29/136—Preparation 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
- C07C29/14—Preparation 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 a —CHO group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于昆虫信息素合成技术领域，提供了一种苹果蠹蛾信息素主要成分(8E,10E)‑十二碳二烯‑1‑醇的合成方法，包括如下步骤：（1）以乙醛为起始原料，通过1‑乙基‑3‑甲基咪唑硫酸氢盐催化缩合，生成关键中间体2,4‑二己烯‑1‑醛；（2）将（1）中生成的中间体2,4‑二己烯‑1‑醛经硼氢化钠还原醛羰基为羟基得到中间体2,4‑己二烯‑1‑醇（山梨基醇）；（3）该醇在乙酸酐、三乙胺存在下反应生成中间体山梨基乙酸酯；（4）山梨基乙酸酯与格氏试剂反应，猝灭反应后经萃取、洗涤、干燥、浓缩、柱层析制得(8E,10E)‑十二碳二烯‑1‑醇。本发明利用一锅法合成(8E,10E)‑十二碳二烯‑1‑醇，其优点在于合成成本低，合成路线简捷，反应条件温和，对环境友好。
Description
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(8E,10E)-十二碳二烯-1-醇的一锅法合成方法。
背景技术
苹果蠹蛾(Cydia pomonElla)属鳞翅目卷蛾科，是世界重大入侵害虫之一，其适应性、抗逆性以及繁殖能力极强，主要为害苹果、山楂、梨等经济植物。自苹果蠹蛾于上世纪五十年代首次被报道入侵我国后，对我国西北部等地区的水果生产造成了极其恶劣的影响，且其近年来有不断向其他地区扩张的趋势。目前对于苹果蠹蛾的防治措施主要有农业综合防治，刮除树皮、刷涂白剂、破坏越冬环境等；杀虫灯物理防治诱捕除虫；喷施氯氰菊酯等进行化学防治，使用性诱剂进行生物防治等，其中，使用性信息素进行生物防治的方法最为高效、环保。
七十年代初，苹果蠹蛾首次被鉴定出(8E,10E)-十二碳二烯-1-醇是其信息素的主要活性成分。虽然苹果蠹蛾信息素活性十分显著，但其在成虫体内含量极低，单纯从昆虫体内提取信息素投入病虫害防治的应用并不现实。因此，研究苹果蠹蛾信息素的化学合成方法具有重要的应用价值。
目前合成(8E,10E)-十二碳二烯-1-醇，即苹果蠹蛾信息素的方法主要包括Wittig反应法、烯烃硼氢化法、炔化物还原法以及格氏偶联法等。此外，专利CN201910194423.4报道了一种从山梨酸钾酯出发得到山梨基乙酸酯通过酯交换反应生成目标产物的方法。虽然关于合成苹果蠹蛾信息素(8E,10E)-十二碳二烯-1-醇的研究已有一些成功事例，但仍然存在需要步骤冗长、反应原料成本高等问题。因此，研究一种简捷、低成本合成(8E,10E)-十二碳二烯-1-醇的方法，仍然具有重要的理论意义与应用价值。
发明内容
有鉴于此，本发明提供了一种苹果蠹蛾信息素(8E,10E)-十二碳二烯-1-醇的制备方法，包括以下步骤：
1、2,4-己二烯醛(2)的制备
取适量溶剂，将催化剂、助剂与乙醛(1)按比例投入高压反应釜中，混合均匀后通氮气保护，随后分批次逐滴滴加乙醛(1)到反应釜中，加入完毕后继续反应一段时间，静置温度下降至室温，得到2,4-己二烯醛(2)，不经处理用于下一步反应。
上述溶剂为二氯甲烷、无水乙醇、环己烷、四氢呋喃、丁醇、异丁醇中的至少一种；
上述助剂为吡啶、三乙胺、三乙醇胺中的至少一种，其用量范围为乙醛的 1％-3％，可选1.2％-1.5％，优选1.2％；
上述催化剂为1-乙基-3-甲基咪唑硫酸氢盐，其用量范围为乙醛的1％- 5％，可选1％-2％，优选1.5％；
上述反应温度可选50-110℃，优选70-80℃；
上述反应时间可选0.5-12h，优选0.5-2h：
2、2,4-二己烯-1-醇(3)的制备
将硼氢化钠溶液在室温下分批次逐滴滴加到上述中反应液中，加入完毕后继续反应一段时间，纯化后得到2,4-二己烯-1-醇(3)。
上述硼氢化钠溶液中硼氢化钠固体和水的比例为1:30，反应时间可选 0.5-12h，优选0.5-2h；
3、山梨基乙酸酯的制备(4)
将(2)中所得2,4-二己烯-1-醇(3)与乙酸酐在三乙胺作用反应6-8h，纯化后得山梨基乙酸酯(4)。
上述反应中2,4-二己烯-1-醇与乙酸酐的比例为1:1.5-1.8
上述反应温度可选20-80℃，优选50-60℃；
上述反应溶剂为上述溶剂为二氯甲烷、无水乙醇、环己烷、四氢呋喃、乙酸乙酯中的至少一种；
4、(8E,10E)-十二碳二烯-1-醇的制备
向上述山梨基乙酸酯中加入适量二甲基甲酰胺溶液和20％稀硫酸溶液，在-10℃下缓慢加入如下所示格氏试剂，不断搅拌，升至室温后反应0.5h后用饱和氯化铵溶液猝灭后加入硼氢化钠还原，后经萃取、洗涤、干燥、浓缩、柱层析得到产物(8E,10E)-十二碳二烯-1-醇。
本发明提供的制备方法过程简单，能够高效率、低成本获得目标产物苹果蠹蛾信息素，合成工艺简洁、原料易得、生产成本较低，适合于放量生产。
与现有技术相比，本发明具有如下有益效果：本发明苹果蠹蛾信息素(8E,10E)-十二碳二烯-1-醇的合成所需的原料易得且价格低廉，合成路径简单，产率较高。合成的产物经田间试验验证具有较高的活性，专一性强，对人畜无害，环境友好，使用方便。本发明可准确应用于苹果蠹蛾等害虫的虫情测报及大量诱捕等方面，可以达到高效、绿色防治害虫的目的。
具体实施方式
实施例1
将三乙胺(0.1520g,0.0015mol)，4-二甲氨基吡啶(0.1220g,0.0010mol)投入二氯甲烷溶液(50ml)中，将其混合均匀后通氮气保护，控制温度为 70℃。向该混合反应液中缓慢滴加乙醛(5.2860g，0.1200mol)，反应2h后静置到室温，得到2,4-己二烯醛2.8832g。
2,4-己二烯醛，收率25.0％；1H NMR(500MHz,CDCl3)δ:9.68(d,1H),7.44 (m,1H),6.28(m,2H),5.80(m,1H),1.58(t,J＝20Hz,3H)；13C NMR(75MHz,CDCl3)δ:193.3,151.9,136.8,130.2(2C),19.3；HR-MS(ESI)m/z:Calcd for C6H8O {[M+H]+}97.1378,found96.1329。
将1:30硼氢化钠水溶液在室温下分批次逐滴滴加到上述反应液中，加入完毕后继续反应2h后加水淬灭反应，、乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸钠干燥、浓缩，生成2,4二己烯-1-醇。向上述产物中加入适量二甲基甲酰胺溶液和20％稀硫酸溶液，在室温下缓慢加入格氏试剂，不断搅拌，反应 0.5h后用饱和氯化铵溶液猝灭，经萃取、洗涤、干燥、浓缩、柱层析得到产物(8E,10E)-十二碳二烯-1-醇3.8820g。
(8E,10E)-十二碳二烯-1-醇，收率71.0％；1H NMR(500MHz,CDCl3)δ:6.03 (m,2H),5.65-5.91(m,2H),4.70(d,1H),3.61(t,J＝15.3Hz,2H),2.16(m,2H), 1.58(m,5H),1.26-1.43(m,8H)；13C NMR(75MHz,CDCl3)δ:132.2,130.3,128.6, 126.9,62.5,33.8,32.1,29.9(3C),25.5,19.3；HR-MS(ESI)m/z:Calcd for C6H8O {[M+H]+}183.1726,found 183.1705。
实施例2
将三乙胺(0.1520g,0.0015mol)，溴化铜(0.2330g,0.0010mol)投入四氢呋喃溶液(50ml)中，将其混合均匀后通氮气保护，控制温度为70℃。向该混合反应液中缓慢滴加乙醛(5.2860g，0.1200mol)，反应2h后静置到室温，得到2,4-己二烯醛2.4225g，产率21％。
将1:30硼氢化钠水溶液在室温下分批次逐滴滴加到上述反应液中，加入完毕后继续反应2h后加水淬灭反应，、乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸钠干燥、浓缩，生成2,4二己烯-1-醇。向上述产物中加入适量二甲基甲酰胺溶液和20％稀硫酸溶液，在室温下缓慢加入格氏试剂，不断搅拌，反应 0.5h后用饱和氯化铵溶液猝灭，经萃取、洗涤、干燥、浓缩、柱层析得到产物(8E,10E)-十二碳二烯-1-醇3.1698g，产率69％。
以上所述，仅为本发明较为理想的具体实施方式，但本发明的保护范围并局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。
Claims (2)
1.一种(8E,10E) 十二碳二烯-1-醇的合成方法，其特征在于一锅法合成，包括如下步骤：以乙醛为原料并通氮气保护，在溶剂、催化剂和助剂的作用下，发生缩合反应，得到2,4-己二烯醛，随后经硼氢化钠还原，得到2,4-己二烯-1-醇（山梨基醇），再与乙酸酐反应，制得山梨基乙酸酯，最后再与格氏试剂反应，制得(8E,10E) 十二碳二烯-1-醇。
2.根据权利要求1所述的合成方法，其特征在于合成2,4-己二烯醛所用的溶剂为二氯甲烷、无水乙醇、环己烷、四氢呋喃、丁醇、异丁醇中的至少一种；合成2,4-己二烯醛所用的催化剂为1-乙基-3-甲基咪唑硫酸氢盐，其用量范围为乙醛的1-5%；合成2,4-己二烯醛所用的助剂为吡啶、三乙胺、三乙醇胺中的至少一种，用量为乙醛的1-3%；合成2,4-己二烯醛的反应温度可选50-110℃，优选70-80℃；反应时间可选0.5-12h，优选0.5-2h。
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