CN113908864A - 用于法尼烯偶联的催化体系和角鲨烷制备方法 - Google Patents
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Abstract
本发明涉及用于法尼烯偶联的催化体系和角鲨烷制备方法,包含:采用用于法尼烯偶联的催化体系催化法尼烯进行偶联反应,以制备角鲨烯;将角鲨烯通过催化加氢还原反应,制备合成角鲨烷。和现有技术相比,本发明以过渡金属构成的催化体系催化法尼烯偶联来制备角鲨烯,并通过氢气还原得到角鲨烷,具有简单易合、热稳定性好、可简单分离的优势。
Description
技术领域
本发明涉及化学原料制备领域,具体地说是一种用于法尼烯偶联的催化体系和角鲨烷制备方法。
背景技术
角鲨烯存在于我们的皮脂膜中,在人体内参与胆因醇的生物合成以及多种生化反应,促进生物氧化以及机体的新陈代谢。合成角鲨烯通过催化加氢可得到无色无味无毒的异构直链烷烃结构的角鲨烷产品,是一种无色无味,结构稳定优质护肤成分。合成的角鲨烷不仅有保湿作用,还能修复肌肤屏障、抗衰老氧化、促进形成代谢、抗菌抑菌,与天然角鲨烷相比它价格便宜,合成工艺也简单。传统制备角鲨烷的方法是通过异丁烯正离子聚合,得到饱和线型聚异丁烯,通常其分子量较大,其中只有分子量在300左右的低聚异丁烯才是目标产物,这就需要后期将分子量300左右的馏分收集出来催化加氢,才能得到角鲨烷产品。还有一个问题就是传统的催化体系对合成分子量在300左右聚异丁烯选择性<15%,导致目标产物产率很低。
同时,以异戊二烯(特开2008-13477)、金合欢基醋酸酯(Chem Lett,1985,3,315)、金合欢醇(Tetrahedron Lett,1990,31,4831)、金合欢基溴(Tetrahedron Lett,1983,24,921)等为原料的化学合成方法被开发出来,但都因为条件苛刻、后处理繁琐等而没有工业化价值。因此,选择合适的单体以及开发该单体定向聚合成角鲨烷的催化体系尤为重要。鉴于此,特提出此发明。
本发明涉及的法尼烯(Farnesene),又称金和欢烯,是一种由三个异戊二烯组成的链状倍半萜烯类化合物,在日化、农业、化工、能源和医药等领域有着广泛的应用。相比于异丁烯难以定向合成高产率的低分子量角鲨烷产品,本发明涉及的普通过渡金属催化剂就能催化法尼烯偶联以获得角鲨烯,分子量在400左右,产率高达90%。并进一步通过催化加氢,定量生成角鲨烷。与以往的方法相比,大大减少非目标大分子量副产,提升反应效率。
发明内容
本发明为解决现有的问题,旨在提供一种用于法尼烯偶联的催化体系和角鲨烷制备方法。
为了达到上述目的,本发明提供的一种用于法尼烯偶联的催化体系,其主催化剂为乙酸钯(Pd(OAc)2)、氯化钯(PdCl2)、乙酰丙酮钯(Pd(acac)2)、(1,5-环辛二烯)氯化钯(PdCl2(cod))、三氟乙酸钯(Pd(TFA)2)、[1,1’-双(二苯基膦基)二茂铁]二氯化钯(PdCl2(dppf))、二(三苯基膦)氯化钯(PdCl2(PPh3)2)、乙酸镍(Ni(OAc)2)、氯化镍(NiCl2)、乙酰丙酮镍(Ni(acac)2)、(1,5-环辛二烯)氯化镍(NiCl2(cod))、三氟乙酸镍(Ni(TFA)2)、[1,1’-双(二苯基膦基)二茂铁]二氯化镍(NiCl2(dppf))和二(三苯基膦)氯化镍(NiCl2(PPh3)2)中的一种或若干种。
进一步地,可根据最终反应产物的收率和纯度,催化剂优选乙酸钯(Pd(OAc)2)、(1,5-环辛二烯)氯化钯(PdCl2(cod))、三氟乙酸钯(Pd(TFA)2)、乙酸镍(Ni(OAc)2)、氯化镍(NiCl2)、乙酰丙酮镍(Ni(acac)2)和(1,5-环辛二烯)氯化镍(NiCl2(cod))中的一种或若干种。
进一步地,助催化剂为三苯基膦(PPh3),三甲基膦((CH3)3P),三环己基膦((C6H12)3P)中的一种或若干种。
进一步地,助催化剂的与主催化剂的摩尔量比为(1.0-3.0):1或(1.0-2.0):1。
本发明还提供一种角鲨烷的制备方法,其特征在包含如下步骤:
a)采用上述催化体系催化法尼烯进行偶联反应,以制备角鲨烯;
b)将角鲨烯通过催化加氢还原反应,制备合成角鲨烷。
进一步地,a)中在偶联反应的同时加入助剂,所述助剂为甲酸钠、乙酸钠、碳酸钠中的任何一种或多种。
进一步地,a)中反应完毕后,加水淬灭,分离角鲨烯和催化剂残余物。
进一步地,助剂与主催化剂摩尔量比为(10-50):1,优选(30-50):1。
本发明的过渡金属构成的催化体系具备中等催化活性,能够定向催化两分子法尼烯的偶联。该催化体系可以高选择性的实现分子量在400-410左右的角鲨烯的制备,但催化剂的用量、反应温度、反应时间等因素对角鲨烯的产率具有极大影响。助催化剂和助剂的用量对角鲨烯的收率具有非常大的影响,同时会在反应体系中产生三聚及四聚的副产物。
进一步地,a)中法尼烯偶联反应的温度为30℃~150℃,优选70℃~80℃。若温度过高,会导致催化剂失活、产率明显降低;若温度太低,反应活性会显著降低。
进一步地,a)中法尼烯偶联反应的时间为8h~72h,优选18h~22h。
进一步地,b)中角鲨烯在醇类溶剂中利用氢气进行还原,其压力为0.2~2.0MPa,优选0.2~0.8Mpa。
进一步地,b)中醇类溶剂为乙醇或异丙醇。
进一步地,b)中加氢还原反应的催化剂为雷尼镍或钯炭(Pd/C)。
进一步地,法尼烯单体摩尔浓度为0.5mol L-1~2.5mol L-1,优选摩尔浓度为0.5mol L-1~1mol L-1。
和现有技术相比,本发明以过渡金属构成的催化体系催化法尼烯偶联来制备角鲨烯,并通过氢气还原得到角鲨烷,具有简单易合、热稳定性好、可简单分离的优势;本发明使用简单的催化体系就能够实现法尼烯的高效偶联,选择性高达90%以上;本发明对反应体系进行了优化,在保证经济效益与高收率的同时,筛选出了最佳反应条件:反应过程中对底物的区域选择性更高,角鲨烷的纯度也相应更高;本发明涉及的合成工艺简单,具有很好的可操作性,适用于工业化生产的需求;法尼烯作为一种生物质单体更加符合绿色环保、持续发展理念。
说明书附图
图1是制备角鲨烷反应方程的示意图。
具体实施方式
下面结合实施例对本发明的具体实施方法作进一步描述。该实施例用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
本发明通过使用一种简单易合、热稳定性好、可简单分离的催化体系,实现了法尼烯的选择性偶联,以制备角鲨烯,并进一步催化加氢得到合成角鲨烷。本发明在提高对产物选择性的同时,也获得较高的产率。
以下以β-法尼烯为例,对本发明催化体系的原理作阐述。β-法尼烯的结构如下图:
β-法尼烯在镍或钯金属化合物的催化下发生偶联反应,主要生成以下四种结构的二聚体化合物:
(A)
(6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene
(B)
(6E,11E,18E)-2,6,19,23-tetramethyl-10,15-dimethylenetetracosa-2,6,11,18,22-pentaene
(C)
(6E,11E,17E)-2,6,18,22-tetramethyl-10-methylene-14-vinyltricosa-2,6,11,17,21-pentaene
(D)
(6E,10Z,12E,17E)-2,6,14,18,22-pentamethyl-10-vinyltricosa-2,6,10,12,17,21-hexaene
其中,化合物A(即角鲨烯)和B(即异角鲨烯)是最主要的偶联产物,它们加氢还原后得到的产物一致,既是所期待得到的最终产品角鲨烷。上述偶联阶段的产物化合物A和化合物B的比值在1:3至1:10之间。参见图1,角鲨烷制备过程中具体的反应方程式如图所示。
实施例一:
在50mL反应瓶中,加入NiCl2(PPh3)2(320mg,0.4893mmol),PPh3(256.7mg,0.9787mmol),HCOONa(665.6mg,9.7867mmol),置换气三次确保反应瓶内氧气被排除。N2流通情况下注入法尼烯6.0mL(24.4667mmol,1mmolmL-1),并注入18.52mL异丙醇做溶剂,再次置换气排除氧气。在70℃下搅拌反应23h,停止聚合。将反应液用硅藻土过滤,收集滤液,抽干溶剂得到黄棕色油状物,称重为4.7890g。对该黄棕色油状物进行GC-Mass分析,角鲨烯的选择性94%,收率90.0%。
实施例二:
在50mL反应瓶中,加入NiCl2(33.03mg,0.2447mmol),PPh3(128.3mg,0.4893mmol),Na2CO3(518.6mg,4.893mmol),置换气三次确保反应瓶内氧气被排除。N2流通情况下注入法尼烯6.0mL(24.4667mmol,1mmolmL-1),并注入18.52mL四氢呋喃做溶剂,再次置换气排除氧气。在85℃下搅拌反应18h,停止聚合。将反应液用硅藻土过滤,收集滤液,抽干溶剂得到黄棕色油状物,称重为4.1089g。对该黄棕色油状物进行GC-Mass分析,角鲨烯的选择性84%,收率60.8%。
实施例三:
在50mL反应瓶中,加入Pd(OAc)2(27.46mg,0.1223mmol),PPh3(64.2mg,0.2447mmol),Na2CO3(259.3mg,2.4467mmol),置换气三次确保反应瓶内氧气被排除。N2流通情况下注入法尼烯6.0mL(24.4667mmol,1mmolmL-1),并注入18.52mL异丙醇做溶剂,再次置换气排除氧气。在60℃下搅拌反应60h,停止聚合。将反应液用硅藻土过滤,收集滤液,抽干溶剂得到黄棕色油状物,称重为3.9018g。对该黄棕色油状物进行GC-Mass分析,角鲨烯的选择性91%,收率71.0%。
实施例四:
在50mL反应瓶中,加入PdCl2(PPh3)2(343.49mg,0.4893mmol),PPh3(256.7mg,0.9787mmol),NaCOOH(665.6mg,9.7867mmol),置换气三次确保反应瓶内氧气被排除。N2流通情况下注入法尼烯6.0mL(24.4667mmol,1mmolmL-1),并注入18.52mL异丙醇做溶剂,再次置换气排除氧气。在120℃下搅拌反应7h,停止聚合。将反应液用硅藻土过滤,收集滤液,抽干溶剂得到黄棕色油状物,称重为2.3508g。对该黄棕色油状物进行GC-Mass分析,角鲨烯的选择性87%,收率90.9%。
实施例五:
在100mL的不锈钢高压釜中,加入上述各实施例所得的黄棕色的角鲨烯混合物和异丙醇,同时加入角鲨烯混合物1wt%的Pd/C。通入氢气,保持压力在0.3MPa。常温搅拌24小时后停止反应,放出高压釜中的氢气,回收Pd/C而得到无色溶液,除去溶剂后得到无色粘稠液体。精馏后得到目标产物角鲨烷。GC-Ms分析,角鲨烷的含量不低于95%。
在上述实施例、数据之外,本领域技术人员基于对各化合物的性能,可以充分得出在相近似反应条件下,在本发明的保护范围内均能够得出可预期的技术效果。并且上述仅为本发明的优选实施方式,应指出的是,对于本行业内的普通技术技术人员而言,在本发明的原理之下可以由一些改进和替换,该改进和替换也应视为本发明的保护范围。
Claims (10)
1.一种用于法尼烯偶联的催化体系,其特征在于:其主催化剂为乙酸钯、氯化钯、乙酰丙酮钯、(1,5-环辛二烯)氯化钯、三氟乙酸钯、[1,1’-双(二苯基膦基)二茂铁]二氯化钯、二(三苯基膦)氯化钯、乙酸镍、氯化镍、乙酰丙酮镍、(1,5-环辛二烯)氯化镍、三氟乙酸镍、[1,1’-双(二苯基膦基)二茂铁]二氯化镍和二(三苯基膦)氯化镍中的一种或若干种。
2.根据权利要求1所述用于法尼烯偶联的催化体系,其特征在于:助催化剂为三苯基膦、三甲基膦、三环己基膦中的一种或若干种。
3.根据权利要求2所述用于法尼烯偶联的催化体系,其特征在于:所述助催化剂的与主催化剂的摩尔量比为(1.0-3.0):1或(1.0-2.0):1。
4.一种角鲨烷的制备方法,其特征在包含如下步骤:
a)采用如权利要求1-3任一所述的催化体系催化法尼烯进行偶联反应,以制备角鲨烯;
b)将角鲨烯通过催化加氢还原反应,制备合成角鲨烷。
5.根据权利要求4所述的角鲨烷的制备方法,其特征在于:a)中,在偶联反应的同时加入助剂,所述助剂为甲酸钠、乙酸钠、碳酸钠中的任何一种或多种。
6.根据权利要求5所述的角鲨烷的制备方法,其特征在于:助剂与主催化剂摩尔量比为(10-50):1或(30-50):1。
7.根据权利要求4-6任一所述的角鲨烷的制备方法,其特征在于:a)中,法尼烯偶联反应的温度为30℃~150℃或70℃~80℃。
8.根据权利要求4-6任一所述的角鲨烷的制备方法,其特征在于:a)中,法尼烯偶联反应的时间为8h~72h或18h~22h。
9.根据权利要求4所述的角鲨烷的制备方法,其特征在于:b)中,角鲨烯在醇类溶剂中利用氢气进行还原,其压力为0.2~2.0Mpa或0.2~0.8Mpa。
10.根据权利要求4所述的角鲨烷的制备方法,其特征在于:b)中,醇类溶剂为乙醇或异丙醇,和/或加氢还原反应的催化剂为雷尼镍或钯炭。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4228313A (en) * | 1977-12-29 | 1980-10-14 | Scm Corporation | Coupling reaction involving a Grignard and allylic halide |
US20110287988A1 (en) * | 2010-05-21 | 2011-11-24 | Karl Fisher | Squalane and isosqualane compositions and methods for preparing the same |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4228313A (en) * | 1977-12-29 | 1980-10-14 | Scm Corporation | Coupling reaction involving a Grignard and allylic halide |
US20110287988A1 (en) * | 2010-05-21 | 2011-11-24 | Karl Fisher | Squalane and isosqualane compositions and methods for preparing the same |
Non-Patent Citations (1)
Title |
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李锦春: "角鲨烷的合成与应用", 《精细化工》, vol. 4, pages 48 - 51 * |
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