CN114591185B - 一种乙二醇和硝基芳烃选择性制备氨基醇的方法 - Google Patents
一种乙二醇和硝基芳烃选择性制备氨基醇的方法 Download PDFInfo
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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Abstract
本发明提供一种乙二醇和硝基芳烃选择性制备氨基醇的方法，属于均相催化技术领域。以硝基芳烃和乙二醇为底物，通过调控碱的种类和用量、催化剂用量选择性催化生成N‑羟乙基芳胺类化合物或N,N‑二羟乙基芳胺类化合物的方法。本发明的优点是：该体系以硝基芳烃作为底物，以廉价低毒的乙二醇为溶剂和底物，高效、高选择性合成氨基醇产物，步骤经济性和原子经济性高，水为唯一副产物，符合绿色化学的要求；本反应体系可通过调控碱种类和用量、催化剂用量，高选择性地合成N‑羟乙基芳胺类化合物或N,N‑二羟乙基胺类化合物；本反应体系中所用的铱配合物催化剂制备方法简单，成本较低，稳定性好。该发明为氨基醇的绿色、高选择性合成提供了一种新方法。
Description
技术领域
本发明属于均相催化技术领域，涉及到铱配合物催化乙二醇和硝基芳烃选择性生成氨基醇产物反应，特别涉及到一种硝基芳烃和乙二醇为底物，通过调控碱的种类和用量、催化剂用量选择性催化生成N-羟乙基芳胺类化合物或N,N-二羟乙基芳胺类化合物的方法。
背景技术
氨基醇及其衍生物是合成药物、染料、手性助剂等的重要中间体。N-羟乙基芳胺是其中非常重要的一类化合物，例如利伐沙班中间体可合成抗凝血药物，分散橙30是一种效果优良的染料，埃文斯助剂作为最广泛使用的手性助剂之一，通常用于羟醛缩合以及Diele-Alder反应中。
氨基醇的传统制备方法中，最经典的方法是氨基酸还原，往往需要使用大量的还原剂，如四氢铝锂或硼氢化钠等，反应会产生大量废物；苯胺和环氧烷烃的开环反应也是合成氨基醇的有效手段，但需要使用环氧乙烷类危险有毒试剂；此外，氨基醇还可以通过卤化物与乙醇胺偶联反应制得，这种反应会生成卤代盐副产物，原子经济性差，不符合绿色化学的要求。因此开发温和、环保、高效的合成方法制备氨基醇类化合物一直是化学领域的热点之一。
近年来，过渡金属催化的以绿色廉价的醇为原料的借氢反应，由于其优异的原子经济性，被广泛地应用于C-C、C-N键构建。1981年，Grigg和Watanabe等人将借氢策略应用到均相体系(J.Chem.Soc.,Chem.Commun.,1981,611-612；Tetrahedron Lett.,1981,22,2667-2670)。受此启发，Beller、Fujita、Yamaguchi等课题组开发了许多芳胺类和醇类构建C-N键的反应体系(Tetrahedron Lett.,2006,47,8881-8885；Org.Lett.,2002,4,2691-2694；J.Am.Chem.Soc.,2010,132,15108-15111)。2016年，Takacs等人报道了一种膦配体钌催化的芳胺和二元醇合成氨基醇的方法(ACS Catal.,2016,6,2205-2210)，但该体系存在所用膦配合物合成困难且不稳定、甲苯溶剂有毒、反应条件较苛刻等缺点。
硝基化合物是制备芳胺类的重要原料，因此，采用硝基化合物还原为胺串联N-烷基化反应具有原子经济性、步骤经济性、环境友好等优点，有着重要的研究意义和应用潜力。醇借氢还原硝基化合物构建C-N键的一般过程如下：(1)在过渡金属配合物作用下醇脱氢生成醛，过渡金属配合物生成金属氢化物；(2)金属氢化物还原硝基化合物生成胺；(3)醛和胺缩合生成亚胺中间体；(4)金属氢化物还原亚胺中间体生成最终的N-烷基化产物。近年来，Bhaumik、Kundu、Beller等人通过合成高活性的过渡金属配合物，开发了许多醇类借氢还原硝基芳烃构建C-N键的反应(J.Colloid Interface Sci.,2016,472,202-209；Chem.Commun.,2018,54,6883-6886；Angew.Chem.Int.Ed.,2019,58,5417-5421)。2019年，Kundu报道了一种铱配合物催化二醇借氢还原2-硝基芳胺类化合物高效合成喹喔啉产物的反应(Green Chem.,2019,21,1999-2004)。但目前为止，二元醇借氢还原硝基化合物合成氨基醇产物尚未见报道。利用高效催化剂，以廉价安全的乙二醇做原料和溶剂，利用醇脱除的氢还原硝基芳烃一步合成氨基醇产物，符合步骤和原子经济性，可以在较温和的条件下高效、高选择性地制备氨基醇产物。
发明内容
本发明要解决的技术问题是提供一种乙二醇和硝基芳烃选择性制备氨基醇的方法。该反应使用的铱配合物结构简单稳定、催化效率高，适合大规模的工业化生产；以廉价易得的乙二醇为氢源和溶剂，安全经济，绿色环保；该体系具有高选择性，通过调控碱的种类和用量、催化剂用量可高选择性合成N-羟乙基芳胺类化合物或N,N-二羟乙基芳胺类化合物；催化体系对底物的普适性强，含各种官能团的硝基芳烃均能高效、高选择性地反应。以硝基苯为例，N-羟乙基苯胺分离收率最高为87％，N,N-二羟乙基苯胺分离收率为70％。
本发明的技术方案：
一种乙二醇和硝基芳烃选择性制备氨基醇的方法，在氮气保护下，将硝基芳烃、碱与铱配合物加入到乙二醇中，密封后置于60～120℃的油浴中，搅拌反应6～30h，停止反应后冷却至室温；用二氯甲烷萃取反应液，收集萃取液；减压除去二氯甲烷得粗产物，经薄层层析或柱层析分离提纯，得到N-羟乙基芳胺类化合物或N,N-二羟乙基芳胺类化合物；
反应通式如下：
R2＝F,Cl,Br,I,OH,CH3,CH2CH3,OCH3,CO2CH3。
所述的碱为叔丁醇钾、氢氧化钾、氢氧化钠、碳酸铯、碳酸钾或碳酸氢钠。
当制备N-羟乙基芳胺类化合物时，碱的用量为硝基芳烃用量的1.5-10倍，催化剂用量为硝基芳烃用量的0.5-2.5mol％，碱为碳酸铯。
当制备N,N-二羟乙基芳胺类化合物时，碱的用量为硝基芳烃用量的0.1-1.4倍，催化剂用量为硝基芳烃用量的1.5-5.0mol％，碱为氢氧化钾。
所述的铱配合物的结构如下：
R3,R4＝H,OCH3,OH,CH3
R6,R7＝H,OH,OCH3,CH3
R8,R9＝H,OH。
本发明的有益效果：
1、该反应体系以硝基芳烃和乙二醇为底物一步高选择性合成氨基醇，相比其他氨基醇的合成方法，反应条件更温和，经济实用性更好，原子经济性更高，且水为唯一的副产物，符合绿色化学要求；相比较用芳胺和二元醇合成该产物的反应体系，直接以上游原料硝基芳烃作为底物，符合步骤经济性，减少了中间处理过程，操作更简便。
2、本发明体系通过调控碱的种类和用量、催化剂用量高选择性合成N-羟乙基芳胺类化合物或N,N-二羟乙基芳胺类化合物。
3、本发明中乙二醇既是反应原料又是溶剂，是一种低毒、廉价的绿色溶剂，避免使用危险有毒试剂。
4、本发明所用的铱配合物制备方法简单，成本低，稳定性好，可高效催化硝基芳烃和乙二醇一步合成氨基醇产物。
附图说明
图1是配合物Cat.A的1H NMR谱图。
图2是配合物Cat.B的1H NMR谱图。
图3是N-羟乙基苯胺的1H NMR谱图。
图4是2-(1-萘基氨基)乙醇的1H NMR谱图。
图5是N,N-二羟乙基苯胺的1H NMR谱图。
图6是N,N-二羟乙基对甲苯胺的1H NMR谱图。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1：
(1)在氮气环境下，将0.08mmol(0.0172g)N-(4-羟基苯基)吡啶-2-甲酰胺和0.04mmol(0.0319g)[Cp*IrCl2]2加入到50mL单口瓶中,加入20mL无水甲醇，升温至60℃，搅拌反应18h，反应结束后，冷却至室温，旋转蒸发除去溶剂，真空干燥，得到0.0466g金属铱配合物Cat.A。
(2)在氮气保护下，将0.5mmol(0.0615g)硝基苯、1.0mmol(0.0560g)氢氧化钾，1.5mol％(0.0050g)Cat.A加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于60℃油浴中，搅拌反应24h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:2)分离提纯，得到N-羟乙基苯胺，产率为82％。
在上述其他条件不变的情况下，仅改变氢氧化钾用量，得到N-羟乙基苯胺产率如下：
实施例2：
在氮气保护下，将0.5mmol(0.0866g)1-硝基萘、1.0mmol(0.0560g)氢氧化钾，1.5mol％(0.0050g)Cat.A加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于110℃油浴中，搅拌反应6h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:2)分离提纯，得到产物2-(1-萘基氨基)乙醇，产率为80％。
在上述其他条件不变的情况下，仅改变碱的种类，得到2-(1-萘基氨基)乙醇产率如下：
实施例3：
在氮气保护下，将0.5mmol(0.0615g)硝基苯、1.0mmol(0.3258g)碳酸铯，1.5mol％(0.0050g)Cat.A加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于90℃油浴中，搅拌反应18h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:2)分离提纯，得到N-羟乙基苯胺，产率为87％。
在上述其他条件不变的情况下，仅改变Cat.A用量，得到N-羟乙基苯胺产率如下：
实施例4：
(1)在氮气环境下，将0.08mmol(0.0151g)6,6'-二羟基-2,2'-联吡啶、(0.08mmol(0.0382g)[Cp*Ir(OH2)3]SO4和15mL去离子水加入到50mL单口瓶中，室温搅拌反应24h。反应结束后，减压旋蒸除去溶剂，真空干燥，得到0.0403g金属铱配合物Cat.B。
(2)在氮气保护下，将0.5mmol(0.0615g)硝基苯、0.5mmol(0.0280g)氢氧化钾，2.0mol％(0.0063g)Cat.B加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于120℃油浴中，搅拌反应30h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:10)分离提纯，得到N,N-二羟乙基苯胺产物，产率为68％。
在上述其他条件不变的情况下，仅改变氢氧化钾用量，得到N,N-二羟乙基苯胺产率如下：
实施例5：
在氮气保护下，将0.5mmol(0.0686g)4-硝基甲苯、0.5mmol(0.0280g)氢氧化钾，2.0mol％(0.0066g)Cat.A加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于90℃油浴中，搅拌反应18h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:10)分离提纯，得到N,N-二羟乙基对甲苯胺产物，产率为78％。
在上述其他条件不变的情况下，仅改变碱的种类，得到N,N-二羟乙基对甲苯胺产率如下：
实施例6
在氮气保护下，将0.5mmol(0.0615g)硝基苯、0.5mmol(0.0280g)氢氧化钾，2.0mol％(0.0066g)Cat.A加入反应管中，随后加入1mL乙二醇，氮气置换三次后密闭反应管。将反应管置于90℃油浴中，搅拌反应18h。停止反应后冷却至室温，用二氯甲烷萃取三次，收集萃取液，减压旋蒸除去溶剂。经薄层层析或者柱层析(正己烷：乙酸乙酯＝1:10)分离提纯，得到N,N-二羟乙基苯胺，产率为70％。
在上述其他条件不变的情况下，仅改变Cat.A用量，得到N,N-二羟乙基苯胺产率如下：
Claims (4)
1.一种乙二醇和硝基芳烃选择性制备氨基醇的方法，其特征在于，在氮气保护下，将硝基芳烃、碱与铱配合物加入到乙二醇中，密封后置于60～120℃的油浴中，搅拌反应6～30h，停止反应后冷却至室温；用二氯甲烷萃取反应液，收集萃取液；减压除去二氯甲烷得粗产物，经薄层层析或柱层析分离提纯，得到N-羟乙基芳胺类化合物或N,N-二羟乙基芳胺类化合物；
反应通式如下：
所述的铱配合物的结构如下：
2.根据权利要求1所述的方法，其特征在于，所述的碱为叔丁醇钾、氢氧化钾、氢氧化钠、碳酸铯、碳酸钾或碳酸氢钠。
3.根据权利要求2所述的方法，其特征在于，
当制备N-羟乙基芳胺类化合物时，碱的用量为硝基芳烃用量的1.5-10倍，催化剂用量为硝基芳烃用量的0.5-2.5mol％，碱为碳酸铯。
4.根据权利要求2所述的方法，其特征在于，
当制备N,N-二羟乙基芳胺类化合物时，碱的用量为硝基芳烃用量的0.1-1.4倍，催化剂用量为硝基芳烃用量的1.5-5.0mol％，碱为氢氧化钾。
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