CN113248357B - 一种通过脱氢芳樟醇重排反应制备柠檬醛的方法 - Google Patents
一种通过脱氢芳樟醇重排反应制备柠檬醛的方法 Download PDFInfo
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Abstract
本发明公开了一种以脱氢芳樟醇为原料重排合成柠檬醛的方法，包括：以脱氢芳樟醇为原料，在溶剂甲苯和有机酸4‑叔丁基苯甲酸的存在下，加入催化体系MoO2(acac)2和Ph3PO，催化Meyer‑Schuster重排反应，得到柠檬醛。本发明所用的催化剂系统能以较高的活性和选择性，以较为理想的转化率和产率得到柠檬醛，且反应过程绿色环保，不产生有害且具有臭味的硫醇与硫醚。该催化体系为柠檬醛的制备提供了一个改良方法，避免了使用亚砜类化合物，有着良好的应用前景。
Description
技术领域
本发明属于有机合成技术领域，涉及一种柠檬醛的制备方法，具体涉及一种通过脱氢芳樟醇重排反应制备柠檬醛的方法。
背景技术
柠檬醛，化学名3,7-二甲基-2,6-辛二烯醛,有顺反两种同分异构体,分别为香叶醛(E-柠檬醛)和橙花醛(Z-柠檬醛),是一种淡黄色透明液体,具有浓郁的柠檬香气,可用于化妆品、食用香精。柠檬醛还是合成紫罗兰酮系列产品的原料,后者又是合成维生素A及类胡萝卜素系列的关键中间体。
柠檬醛
国内的柠檬醛产品主要从植物精油中提取，受到原料限制，无法大规模进行连续生产。柠檬醛也可以通过一些化学方法进行合成，有报道使用异戊烯醛与3-甲基-2-丁烯-1-醇作为起始原料合成柠檬醛；而脱氢芳樟醇通过迈耶-舒斯特重排反应合成柠檬醛是最具有原子经济性的一个方法，而且工艺的流程简单，条件相对温和，国内外已经报道了许多方法，主要有使用钒、钛、钼金属催化脱氢芳樟醇的重排反应。
使用异戊烯醛与3-甲基-2-丁烯-1-醇作为起始原料合成柠檬醛，具体的步骤是通过缩合、裂解等合成柠檬醛。
迈耶-舒斯特重排反应(Meyer-Schuster rearrangement)是在酸的催化作用下，炔丙醇发生重排异构，得到α,β-不饱和羰基化合物，同时也会发生Rupe重排反应生成α,β-不饱和甲基酮。该反应与Meyer-Schuster反应为竞争反应。
其中，R1和R2分别代表氢原子或脂肪族或芳香族基团。
G.Saucy等人使用了银或铜离子对乙酸脱氢芳樟酯的催化重排制备了丙二烯乙酸酯和二乙酸酯的化合物，它们可通过水解得到柠檬醛。
US3912656使用了一种以三苯基硅氧基氧化钒与三苯基硅醇组成的催化剂，以高沸点的烷烃作为溶剂，在140oC下反应，脱氢芳樟醇的转化率和柠檬醛的收率都可达到97%。该催化剂在经过10次套用以后，转化率下降为95%，收率不变。但是三苯基硅氧基氧化钒容易水解，反应条件较为苛刻，该催化剂还需要大量昂贵的三苯基硅醇。
CN105289751使用了钛酸酯和氯化亚铜组合的催化剂，在酸性助催化剂的存在下，在有机溶剂中进行脱氢芳樟醇的重排发育，反应温度90~130oC，反应3~5小时，柠檬醛收率85-98%。该催化剂必须在无水的条件下保存，要求条件苛刻。
CN1170801使用了钼化合物MoO2X2和二烷基-或二芳基亚砜组成的催化剂系统，在pK值范围在4.0~6.5之间的有机酸存在下，且在非极性质子惰性有机溶剂中进行脱氢芳樟醇的重排反应。重排温度在90~120oC之间，反应时间约7小时，柠檬醛收率77~87%。但是DMSO在酸存在时加热会产生少量的甲硫醇、二甲硫醚等具有恶臭气味的化合物，无法在目前以绿色环保为主流的工业上实现应用。
发明内容
针对现有技术的不足，本发明的目的在于提供一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，通过选用具有较高活性和选择性的催化体系进行重排反应，可获得理想的转化率和目标产物的收率。原料和催化剂来源方便，反应过程中绿色环保，不会产生有害且具有臭味的硫醇与硫醚，对柠檬醛的制备具有良好的经济效益和应用前景。
本发明是通过以下技术方案实现的：
一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，包括以下步骤：以脱氢芳樟醇为原料，在溶剂和有机酸的存在下，在由MoO2(acac)2和Ph3PO构成的催化体系的催化下进行Meyer-Schuster重排反应制备得到柠檬醛。
进一步的，所述催化体系中MoO2(acac)2的用量为脱氢芳樟醇的1~5mol%。
进一步的，所述的催化体系中Ph3PO的用量为脱氢芳樟醇的18~22mol%。
进一步的，所述脱氢芳樟醇与溶剂的重量比为1：20~25。
进一步的，所述的溶剂为甲苯。
进一步的，所述有机酸与脱氢芳樟醇的摩尔比为0.8~1.2：5。
进一步的，所述的有机酸为4-叔丁基苯甲酸。
进一步的，所述的催化重排反应在120~130oC下反应6~8小时。
本发明的MoO2(acac)2/Ph3PO催化脱氢芳樟醇重排循环的过程如下所示：
本发明的有益效果为：
本发明采用由MoO2(acac)2和Ph3PO构成的催化体系，催化脱氢芳樟醇的重排得到柠檬醛。同时，Ph3PO有助于维持Mo的VI价态，避免因为Mo被还原到低价态而导致的催化剂失活。
综上，本发明所用的催化剂具有较高的反应活性和选择性，通过催化重排，可获得理想的转化率和目标产物的收率；且原料、催化剂来源方便，反应过程中绿色环保，不会产生有害且具有臭味的硫醇与硫醚，对柠檬醛的制备具有良好的经济效益和应用前景。
具体实施方式
实施例1
将0.152g(1mmol)脱氢芳樟醇、3.26mg(0.01mmol)MoO2(acac)2、55.6mg(0.2mmol)Ph3PO、35.6mg(0.2mmol)4-叔丁基苯甲酸和4mL溶剂甲苯，加入厚壁耐压反应瓶中，密闭后，放入120oC油浴中反应7h后，通过薄层色谱法监测反应完全，通过1H-NMR内标法测定目标产物的产率，测得目标产物柠檬醛的产率为53%。
实施例2
将0.152g(1mmol)脱氢芳樟醇、4.89mg(0.015mmol)MoO2(acac)2、55.6mg(0.2mmol)Ph3PO、35.6mg(0.2mmol)4-叔丁基苯甲酸和4mL溶剂甲苯，加入厚壁耐压反应瓶中，密闭后，放入120oC油浴中反应7h后，通过薄层色谱法监测反应完全，通过1H-NMR内标法测定目标产物的产率，测得目标产物柠檬醛的产率为67%。
实施例3
将0.152g(1mmol)脱氢芳樟醇、9.78mg(0.03mmol)MoO2(acac)2、55.6mg(0.2mmol)Ph3PO、35.6mg(0.2mmol)4-叔丁基苯甲酸和4mL溶剂甲苯，加入厚壁耐压反应瓶中，密闭后，放入120oC油浴中反应7h后，通过薄层色谱法监测反应完全，通过1H-NMR内标法测定目标产物的产率，测得目标产物柠檬醛的产率为70%。
实施例4
将0.152g(1mmol)脱氢芳樟醇、16.3mg(0.05mmol)MoO2(acac)2、55.6mg(0.2mmol)Ph3PO、35.6mg(0.2mmol)4-叔丁基苯甲酸和4mL溶剂甲苯，加入厚壁耐压反应瓶中，密闭后，放入120oC油浴中反应7h后，通过薄层色谱法监测反应完全，通过1H-NMR内标法测定目标产物的产率，测得目标产物柠檬醛的产率为78%。
实施例5
将0.152g(1mmol)脱氢芳樟醇、3.26mg(0.01mmol)MoO2(acac)2、55.6mg(0.2mmol)Ph3PO、24.4mg(0.2mmol)苯甲酸和4mL溶剂甲苯，加入厚壁耐压反应瓶中，密闭后，放入120oC油浴中反应7h后，通过薄层色谱法监测反应完全，通过1H-NMR内标法测定目标产物的产率，测得目标产物柠檬醛的产率为53%。
Claims (8)
1.一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于，包括以下步骤：以脱氢芳樟醇为原料，在溶剂和有机酸的存在下，在由MoO2(acac)2和Ph3PO构成的催化体系的催化下进行Meyer-Schuster重排反应制备得到柠檬醛。
2.根据权利要求1所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述催化体系中MoO2(acac)2的用量为脱氢芳樟醇的1~5mol%。
3.根据权利要求1所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述的催化体系中Ph3PO的用量为脱氢芳樟醇的18~22mol%。
4.根据权利要求1所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述脱氢芳樟醇与溶剂的重量比为1：20~25。
5.根据权利要求1或4任意一项所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述的溶剂为甲苯。
6.根据权利要求1所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述有机酸与脱氢芳樟醇的摩尔比为0.8~1.2：5。
7.根据权利要求1或6任意一项所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述的有机酸为4-叔丁基苯甲酸。
8.根据权利要求1所述的一种通过脱氢芳樟醇重排反应制备柠檬醛的方法，其特征在于：所述的催化重排反应在120~130oC下反应6~8小时。
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