CN104402934B - 2‑（二苯膦基乙基）‑（5,6,7,8‑四氢喹啉基）胺钌配合物的制备方法及其应用 - Google Patents

2‑（二苯膦基乙基）‑（5,6,7,8‑四氢喹啉基）胺钌配合物的制备方法及其应用 Download PDF

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CN104402934B
CN104402934B CN201410580979.4A CN201410580979A CN104402934B CN 104402934 B CN104402934 B CN 104402934B CN 201410580979 A CN201410580979 A CN 201410580979A CN 104402934 B CN104402934 B CN 104402934B
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刘庆彬
潘冰
刘博�
张福军
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Hebei Normal University
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Abstract

本发明公开了一种制备2‑（二苯膦基乙基）‑（5,6,7,8‑四氢喹啉基）钌胺配合物的方法，先制备配体2‑（二苯膦基乙基）‑（5,6,7,8‑四氢喹啉基）胺，再通过与RuHCl(CO)(PPh3)3和RuCl2(PPh3)3反应，制备得到不同结构的配合物1和配合物2。然后用含有2‑（二苯膦基乙基）‑（5,6,7,8‑四氢喹啉基）胺钌配合物1或配合物2催化氨基醇与二级醇或酮缩合反应，合成吡啶及喹啉衍生物。本发明的制备方法简单，稳定性好，催化剂催化活性高，用量仅为底物摩尔量的0.025%。用于吡啶和喹啉化合物的生产，方法简单、环境污染小、收率高、成本低。

Description

2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的制 备方法及其应用
技术领域
本发明涉及一种络合物的制备方法，具体就是2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的制备方法,以及将该配合物用于吡啶、喹啉等杂环化合物的合成，属于精细化学品制备技术领域。
背景技术
氮杂环化合物，特别是吡啶及喹啉的衍生物，在医药、农药及新材料领域得到广泛应用，尽管吡啶及喹啉的衍生物合成方法发表的很多，但由于环境保护意识越来越强，吡啶及喹啉衍生物的绿色合成方法在研究领域和工业界得到了广泛的关注。近年来，许多研究集中在有机金属催化的杂环化合物的合成上，有机金属催化具有反应效率高，环境污染小的特点。最近以色列的Milstein小组发展了有机金属催化的无受体脱氢反应（Acceptorless dehydrogenation (AD) reactions），该反应是用有机金属催化剂剪短C-H,N-H和O-H，形成活性中间体同时和其他底物发生耦合反应，形成新的化合物，该反应的特点是反应条件温和，无污染，副产物氢气可以作为新型能源燃料。是一种绿色环保合成工艺。Milstein小组（Srimani,D.; Ben-David,Y.; Milstein,D.Chem. Commun., 2013, 49,6632.）报道采用结构如下结构式所示的金属钌的配合物催化3-氨基丁醇与二级醇反应生成吡啶和喹啉的衍生物，取得较好的结果。
但催化剂的用量是底物的摩尔量0.5 % ，催化剂的用量很大，造成生产成本很高，不具有生产竞争力。另外德国的Kempe group小组（Michlik,S.; Kempe,R. Angew. Chem.Int. Ed. 2013, 52, 6326.）也报道采用结构如下式所示的金属铱的配合物催化3-氨基丁醇与醇反应生成吡啶和喹啉的衍生物，取得较高收率，但存在同样问题。
此外，催化剂采用贵金属铱，同时催化剂用量较大，为底物摩尔量的0.5%-1.5% 不太适合工业化生产的要求。
发明内容
本发明的目的在于提供一种2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的制备方法。
本发明的目的还在于提供一种2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的应用。
本发明是通过如下技术方案实现的。 2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物如下式（Ⅰ）所示：
式（Ⅰ）
其中，式（Ⅰ）配合物1：R=CO、R1=H；式（Ⅰ）配合物2：R= R1= Cl。
具体的，本发明2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的制备方法，包括以下步骤：
（1）配体2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺的制备
N2保护下，将5,6,7,8-四氢喹啉酮加入到烧瓶中，再加入2-（二苯基膦）乙胺和三乙酰氧基硼氢化钠，加入二氯甲烷作溶剂，溶液为淡黄色乳状物，室温下搅拌6h后，将反应液用饱和NaHCO3溶液猝灭，加水稀释，然后用乙酸乙酯萃取,萃取液用无水硫酸钠干燥，旋干后的粗品用乙酸乙酯：石油醚按体积比=1:10过柱得到黄色油状纯品，该纯品即2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺；
（2）配合物1的制备
将步骤（1）制得的2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺和RuHCl(CO)(PPh3)3溶入甲苯中，加热到117℃，回流10h，冷却至40℃继续搅拌2h后停止反应，过滤，用甲苯洗涤，干燥，得到灰白色固体，经ＮＭＲ、Ｘ－单晶衍射、元素分析确定为配合物1；
（3）配合物２的制备
N2保护下，将步骤（1）制得的2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺和RuCl2(PPh3)3溶入甲苯中，加热到100℃回流3h，溶液为黄色悬浮液，冷却后过滤，用乙醚洗涤，干燥后得到浅黄色固体，经ＮＭＲ、Ｘ－单晶衍射、元素分析确定为配合物2；
本发明给出的2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的应用如下：
（一）配合物1的应用
以配合物1作为催化剂，加入叔丁醇钾或叔丁醇钠为助催化剂，催化3-氨基-1-丁醇、环己醇或环己酮缩合，合成2-甲基5,6,7,8四氢化喹啉，步骤如下：
N2保护下，将3-氨基-1-丁醇、环己醇或环己酮、催化剂配合物1、叔丁醇钾或叔丁醇钠按比例放入单口瓶中，加入溶剂甲苯和四氢化喹啉（THF），混合物在117-135℃下加热回流24-72 h，反应完毕，加入水，用乙酸乙酯萃取，浓缩，用乙酸乙酯：石油醚按体积比=1:50过硅胶柱，得到浅黄色液体即为2-甲基5,6,7,8-四氢化喹啉。
本发明，配合物1的应用中，配合物1的用量为3-氨基-1-丁醇摩尔量的0.025%-0.333%。
本发明，配合物1的应用中，3-氨基-1-丁醇、环己醇或环己酮与叔丁醇钾或叔丁醇钠的最佳摩尔比为：1：2：2；
溶剂甲苯：ＴＨＦ最佳体积比为 ４：1。
（二）配合物2的应用
以配合物 2作为催化剂，加入叔丁醇钾或叔丁醇钠为助催化剂，催化氨基醇、二级醇缩合，合成吡啶或喹啉衍生物，步骤如下：
将氨基丁醇、二级醇、KOtBu和配合物2加入到甲苯和四氢呋喃按体积比(4:1)的混合溶剂中，在N2保护条件下加热到117℃，回流24-72小时，产品用硅胶柱纯化,以乙酸乙酯：正己烷的体积比为1:50为洗脱剂，得到产品吡啶或喹啉衍生物。
上述配合物2 用量为氨基丁醇摩尔量的0.025%-0.05%。
氨基丁醇、二级醇与叔丁醇钾或叔丁醇钠的最佳摩尔比为：1：2：2 ；溶剂甲苯：ＴＨＦ最佳体积比为 ４：1。
本发明取得的有益效果如下：
（1）本发明配合物1、配合物2制备方法步骤简单，能够大量制备，方法稳定性好；（2）本发明，配合物1、配合物2用于催化由氨基醇和二级醇缩合得到吡啶和喹啉化合物，方法简单、环境污染小、收率高,催化剂的用量仅为氨基醇摩尔量的0.025% ，用量少，成本低，有良好的工业化前景。
具体实施方式
以下实施例用于说明本发明。
实施例1 配体2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺的制备
N2保护下，将5,6,7,8-四氢喹啉酮1.47g(10mmol )加入到250ml圆底烧瓶中，再加入3g（13.2mmol）2-（二苯基膦）乙胺和4.43g（21mmol）的三乙酰氧基硼氢化钠。加入100mlDCE溶剂，溶液为淡黄色乳状物，33℃下搅拌6h后，将反应液用饱和NaHCO3溶液猝灭，加水稀释，用乙酸乙酯（3X30ml）萃取,萃取液用无水硫酸钠干燥，旋干得粗品3.32g。用乙酸乙酯：石油醚=1:10过柱子得黄色油状的纯品，产率：75%；核磁共振氢谱1HNMR(CDCl3,500MHZ)δ0.98(1H,d,C-H),1.69-2.36(6H,m,CH2CH2CH2), 2.73-2.85(4H,m,N-CH2CH2-P),3.76(1H,s, N-H), 7.04-8.37(13,m,py+ph)。即为2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺。
实施例2 配合物1的制备
化学反应式如下：
将0.6g(1.68mmol) 2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺和1.6g(1.68mmol)RuHCl(CO)(PPh3)3溶入30ml甲苯，回流10h, 然后冷却至40℃继续搅拌2h后停止反应。过滤，用甲苯洗涤，干燥，得灰白色固体0.94g。产率：75%；核磁共振氢谱1HNMR (CDCl3,500MHz)；δ-11.58(1H,t,Ru-H), 1.01(1H,m,C-H)，1.73-2.47(6H,m,CH2CH2CH2)， 3.59-4.04(4H,m,P-CH2CH2-N) 6.20-7.85(28H,m,Py+Ph). 元素分析 C42H40N2ORuP2: C, 67.10;H, 5.363; N, 3.726. 理论值: C, 61.51; H, 5,274; N,3.742. 红外光谱 IR(cm.-1) νC=O,1921。证明为配合物1。
实施例3 配合物2的制备
化学反应式如下：
（催化剂2）
N2保护下，在100ml单口瓶，将2g(2.087mmol)RuCl2(PPh3)3和0.75g(2.1mmol)2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺溶入100ml甲苯中，100℃回流3h，溶液为黄色悬浮液。过滤后用5ml乙醚洗涤，干燥得浅黄色固体1.08g.产率：65%。核磁共振氢谱1HNMR(CDCl3,500MHZ) 1.80-2.36(6H,m,CH2CH2CH2), 2.55-2.75(4H,m,N-CH2CH2-P), 3.47(1H,d,C-H), 5.92-7.66(28,m,py+ph). 元素分析C41H39Cl2N2RuP2: C,62.04; H,4.953; N,3.529. 计算值: C, 61.77; H, 5,159; N,3.341。证明产物为：2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基，三苯基膦基）二氯化钌配合物2。
实施例4 配合物1在催化3-氨基丁醇与环己醇反应合成2-甲基5,6,7,8四氢化喹啉中的应用
化学反应式如下：
以配合物1为催化剂，N2保护下，将3-氨基-1-丁醇、环己醇或环己酮、配合物1、叔丁醇 按下表中的比例放入50ml的单口瓶中，加入2ml甲苯和0.5mlTHF，混合物在135℃下加热回流，24-72小时，反应完毕，加入10ml水，用乙酸乙酯（3X10ml）萃取，浓缩，用乙酸乙酯：石油醚=2:1(体积比) TLC分析，用乙酸乙酯：石油醚=1:50（体积比）过硅胶柱，得到浅黄色液体，产率见下表1。
表1：Ru配合物1催化3-氨基丁醇与环己醇缩合成2-甲基5,6,7,8四氢化喹啉不同条件下的收率。
表1
说明：表1中反应10中的a 用环己酮替代环己醇的实验结果；反应11中的b用叔丁醇钠替代叔丁醇钾的结果。
实施例5 配合物2在催化3-氨基丁醇与环己醇反应合成2-甲基5,6,7,8四氢化喹啉中的应用
以配合物2为催化剂，N2保护下，将3-氨基-1-丁醇、环己醇或、配合物2、叔丁醇 按毫摩尔比为11.2:22.4:0.0028比例放入50ml的单口瓶中，加入2ml甲苯和0.5mlTHF，混合物在135℃下加热回流，24-72小时，反应完毕，加入10ml水，用乙酸乙酯（3X10ml）萃取，浓缩，用乙酸乙酯：石油醚=2:1(体积比) TLC分析，用乙酸乙酯：石油醚=1:50（体积比）过硅胶柱，得到浅黄色液体，2-甲基5,6,7,8-四氢化喹啉。产率：24小时30%；72小时71.9%。
实施例6 配合物1在催化不同的吡啶及喹啉衍生物合成中的应用
不同的氨基丁醇(22.4 mmol),二级醇(44.8 mmol) KOtBu (44.8 mmol) 和配合物1. 加入到甲苯和四氢呋喃(4:1)（体积比）的混合溶剂中,在氮气条件下回流24-72小时;产品用硅胶柱纯化,乙酸乙酯/正己烷为洗脱剂产品结果见下表2
表2：在配合物2的催化下用不同的氨基醇和醇反应合成吡啶和喹啉衍生物的结果,括号中数据为反应24小时收率。
表2

Claims (5)

1.一种2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的制备方法，其特征在于包括以下步骤：
（1）配体2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺的制备
N2保护下，将5,6,7,8-四氢喹啉酮加入到烧瓶中，再加入2-（二苯基膦）乙胺和三乙酰氧基硼氢化钠，加入二氯甲烷作溶剂，溶液为淡黄色乳状物，室温下搅拌6h后，将反应液用饱和NaHCO3溶液猝灭，加水稀释，然后用乙酸乙酯萃取,萃取液用无水硫酸钠干燥，旋干后的粗品用乙酸乙酯：石油醚按体积比=1:10过柱得到黄色油状的纯品，该纯品即2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺；
（2）配合物1的制备
将步骤（1）制得的2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺和RuHCl(CO)(PPh3)3溶入甲苯中，加热到117℃，回流10h，冷却至40℃继续搅拌2h后停止反应，过滤，用甲苯洗涤，干燥，得到灰白色固体，经ＮＭＲ、Ｘ－单晶衍射、元素分析确定为配合物1；
（3）配合物２的制备
N2保护下，将步骤（1）制得的2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺和RuCl2(PPh3)3溶入甲苯中，加热到100℃回流3h，溶液为黄色悬浮液，冷却后过滤，用乙醚洗涤，干燥后得到浅黄色固体，经ＮＭＲ、Ｘ－单晶衍射、元素分析确定为配合物2。
2.一种2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的应用，其特征在于：以如权利要求1所示的配合物1作为催化剂，加入叔丁醇钾或叔丁醇钠为助催化剂，催化3-氨基-1-丁醇、环己醇或环己酮缩合合成2-甲基-5,6,7,8-四氢化喹啉，步骤如下：
N2保护下，将3-氨基-1-丁醇、环己醇或环己酮、催化剂配合物1、叔丁醇钾或叔丁醇钠按比例放入单口瓶中，加入溶剂甲苯和THF，混合物在117-135℃下加热回流24-72 h，反应完毕，加入水，用乙酸乙酯萃取，浓缩，用乙酸乙酯：石油醚按体积比=1:50过硅胶柱，得到浅黄色液体即为2-甲基-5,6,7,8-四氢化喹啉；
其中，配合物1的摩尔用量为3-氨基-1-丁醇的0.025%-0.333%。
3.根据如权利要求2所述的配合物的应用，其特征在于3-氨基-1-丁醇、环己醇或环己酮、叔丁醇钾或叔丁醇钠的摩尔比比例为：1：2：2；溶剂甲苯：ＴＨＦ体积比为 ４：1。
4.一种2-（二苯膦基乙基）-（5,6,7,8-四氢喹啉基）胺钌配合物的应用，其特征在于：以如权利要求1所示的配合物2作为催化剂，加入叔丁醇钾或叔丁醇钠为助催化剂，催化氨基醇、二级醇缩合合成吡啶或喹啉衍生物，步骤如下：
将氨基丁醇、二级醇、KOtBu和配合物2加入到甲苯和四氢呋喃的混合溶剂中，在氮气条件下，反应温度为117-135℃，回流24-72小时，产品用硅胶柱纯化,用乙酸乙酯和正己烷混合溶剂为洗脱剂得产品吡啶或喹啉衍生物；
其中，配合物2 的摩尔用量为氨基丁醇0.025%-0.05%。
5.根据权利要求4所述的配合物的应用，其特征在于：氨基丁醇、二级醇、叔丁醇钾或叔丁醇钠的摩尔比比例为：1：2：2；反应溶剂甲苯：ＴＨＦ的体积比为 ４：1。
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