CN102875579B - 一种铜氮配合物及其用途 - Google Patents
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- 239000000126 substance Substances 0.000 claims abstract description 6
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Abstract
一种铜氮配合物摩尔比为2.08：1的2-氧代-1-吡咯烷基丙腈与一水合乙酸铜在无水乙醇溶剂中制备的如以下化学式所示的配合物：
Description
一、技术领域
本发明涉及一种金属有机配位化合物(配合物)及其用途，特别涉及含氮的金属有机配合物及其用途，确切地说是一种由2-氧代-1-吡咯烷基丙腈与一水合乙酸铜制备的氮铜配合物及其作为催化剂的应用。
二、背景技术
铜配合物上的配体按能提供配位原子的个数分为单齿配体和多齿配体，导致其合成了多种单核或多核的铜配合物.铜(Ⅱ)可以与单齿、三齿或多齿配体配位，进而形成单核、双核以及多核配合物。氨是典型的单齿配体，与铜(Ⅱ)形成配合物的通式为CuX2·nNH3(n＝2,4,5,6)。正常情况下，铜(Ⅱ)可以与四个配体鳌合，例如CuCl2和吡啶分子鳌合，形成的Cu(Py)2Cl2可以稳定地存在于吡啶中。在Cu(NH3)4(NO3)2晶种中，4个NH3近似正方形(Cu-N＝200pm)，两个O处于稍不等的位置(约250pm)。双(二甲基氨乙基)甲胺、三吡啶是典型双、三齿配体，与铜(Ⅱ)形成的配合物通式为：[CuLX2]和[CuLXY]，其构型为畸变的三角双锥构型。铜(Ⅱ)与空间位阻较大的三(2-氨乙基)胺形成八面体配合物分子。另外铜(Ⅱ)与O、S都有较强的亲和力，铜(II)和8-羟基喹啉、槲皮素、高氯酸[三(2-苯并咪唑亚甲基)胺]咪唑、1，4-噻恶烷等均能产生稳定的配离子。
自人类有历史记载以来，铜及其配合物即用作药物。铜是人体必需的金属元素。人体的正常代谢过程需要它们，但无法体内合成，因此，需要每天从饮食摄取和吸收。生物药学家和研究者以极大的努力彻底地了解铜及其配合物在生物体系中的作用，希望获得更多地信息以利于人类疾病的预防和治疗。铜是日常生活中最常见的金属之一，也是一种非常重要的生命微量元素在人体中分布于器官与组织中，对于维持人的生命活动发挥着重要作用，人体缺乏铜会引起多种疾病，故适当的摄入铜是有益的。由于铜对人体的重要性，近年来成为引人注目的研究对象迄今为止，不断有新的铜配合物合成，配合物的合成方法及配合物的物理化学性质、晶体结构以及配合物的抗菌活性是目前研究热点之一。
由于铜具有可变化合价，在生命体中可以参与电子传递、氧化还原等一系列过程，具有特殊的生物活性.Schiff碱铜配合物的医药活性，特别是在抗菌、抗肿瘤方面一直是人们关注的热点。合成筛选出高效、低毒的抑菌剂,研究其抗肿瘤、抑制细胞增殖的原理、构效关系及影响因素是目前研究的主要方向。金属配合物对人体产生作用主要是通过有机药物分子进入人体后,与人体内的微量元素、细菌、病毒或者癌细胞中的金属蛋白、金属酶有核酸间相互作用,促进机体正常代谢的恢复或破坏病原体的正常代谢。当前金属配合物在医学和药学研究中已经得到广泛应用。例如槲皮素合铜配合物显示较强的抗癌活性CuCl2·2H2O与DNA作用时，能够插入DNA的碱基对之间，存在插入键合模式.可能正是由于这种插入键合的作用，影响了DNA分子的内部构型，抑制了DNA分子的进一步遗传与复制，从而抑制癌细胞的恶性生长以达到抗癌效果。
随着有机化学的发展，金属有机化合物在有机合成中的应用愈来愈广，是现在有机化学中极为活跃的领域之一，已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性配体及含金属催化剂的设计，从而使反应具有高效和高对映选择性。
1、手性双噁唑啉配体一金属配合物催化不对称环丙烷化
催化不对称环丙烷比反应，即利用手性配体一金属配合物催化重氮化合物与烯烃的环加成反应，是合成光活性环丙烷结构化合物的重要手段。1990年，Masmune等分别利用手性双噁唑啉配体—铜配合物催化环丙烷化反应，均得到了很高的对映选择性。
2、手性铜催化剂一催化烯烃发生不对称环丙烷化反应
日本住友公司用手性铜催化剂催化烯烃发生不对称环丙烷化反应，合成了二肽抑制剂Cilastatin。
参考文献：
[1]Holmes F,Jones K M,et al.Complex-forming agents similar to 2,2’-bipyridyl.Part I.Someligands containing imidazole[J].J Chem Soc,1961,4790-4794.
[2]樊志,文欣,周卫红,刘小兰,缪方明.三(2-苯并咪唑亚甲基)胺铜(Ⅱ)配合物的合成、晶体结构和量子化学研究.无机化学学报,1999年9月,第5期:602-606.
[3]谭君.槲皮素合铜(Ⅱ)配合物的配位化学研究.重庆教育学院学报,2006年11月，第19卷第6期:11-15.
[4]李钦玲.过渡金属配合物在手性药物合成中的应用.青海科技，2007年第1期：45-49。
三、发明内容
本发明旨在提供一种铜氮金属有机配合物以应用于不对称催化领域，所要解决的技术问题遴选2-氧代-1-吡咯烷基丙腈作为配体并合成铜氮配合物。
本发明所称的铜氮配合物是由2-氧代-1-吡咯烷基丙腈与一水合乙酸铜在无水乙醇溶剂中制备的如以下化学式所示的配合物：
化学名称：2-氧代-1-吡咯烷基丙腈乙酸铜，简称配合物。
本配合物的合成方法是由摩尔比为2.08：1的2-氧代-1-吡咯烷基丙腈与一水合乙酸铜在无水乙醇溶剂中加热搅拌回流24小时,热过滤，将滤液旋干，用无水乙醇和正己烷重结晶，一天后出现蓝色晶体。
本配合物在亨利反应中显示较好的催化性能。
Henry反应是Louis Henry于1895年最早发现并命名的。它是基于羰基和含有α-活泼氢的硝基烷烃类化合物之间的碳碳键形成反应，其产物是一类含β-硝基醇的双官能团化合物。到目前为止它仍然是一种经典的碳碳键形成反应。Henry反应中，含α-活泼氢的硝基化合物在碱等夺质子试剂作用下成为碳负离子，再进攻羰基形成新的碳碳键，而得到双官能团化合物β-硝基醇。
四、附图说明
图1是本配合物的单晶衍射图。
五、具体实施方式
1、2-氧代-1-吡咯烷基丙腈乙酸铜配合物的合成
称取一水合醋酸铜0.8415g(0.0048mol)，2-氧代-1-吡咯烷基丙腈1.30ml(0.01mol)于100ml圆底烧瓶中，加入30ml无水乙醇，搅拌回流24h，热过滤，将滤液旋干，用无水乙醇和正己烷重结晶，一天后出现蓝色晶体。元素分析结果如下：理论值：C，41.31；H，5.04；N，8.76，实测值：C，41.17；H，5.25；N，8.44；IR(KBr)3439(s)，2970(s)，2251(m)，1611(s)，1422(s)，1305(m)，1044(w)，684(w)。
在显微镜下选取合适大小的单晶在室温下进行X-射线单晶衍射实验，在293k温度下，在Oxford X-射线单晶衍射仪上，用经石墨单色器单色化的MoKa射线(λ＝0.71073A)以w-Theta扫描方式收集衍射数据。对所得数据进行Lp因子及经验吸收校正，晶体结构由直接法解出，衍射数据还原和结构解析工作分别使用SAINT-5.0和SHELXS-97程序完成晶体结构解析:配合物(Ⅱ)进行X单晶衍射测试的晶体大小为0.20×0.15×0.10mm3，三斜晶系，空间点群p-1，α＝105.852(3)°，β＝103.083(4)°，γ＝95.377(3)°，Z＝1，Dcalc＝1.568Mg/m3，F(000)＝330。
2-氧-1-吡咯烷基丙腈铜配合物(Ⅱ)是以[Cu2(C7H10N2O)2(OAc)4]为单元，每个单元内含2个直接相连的Cu离子，Cu离子与2个乙酸根的4个O原子和2个2-氧-1-吡咯烷基丙腈分子中的O分别配位，配位数为6。Cu(1)-O(4)、Cu(1)-O(3)#1、Cu(1)-O(2)、Cu(1)-O(5)#1、Cu(1)-O(1)、Cu(1)-Cu(1)#1的键长分别为 (对称法则：-x+1,-y+1,-z；-x+1,-y+1,-z)
配合物的晶体数据如下：
配合物晶体的键长数据表
配合物晶体的键角数据表
2、本配合物在亨利反应中作为催化剂的应用
2-Nitro-1-phenylethanol的制备
2-硝基-1苯基乙醇的制备
取0.15mmol配合物(I)(催化用量为15％)于25mL的小烧瓶中，加入2毫升的甲醇溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL的硝基甲烷，常温搅拌，反应72小时，用石油醚/二氯甲烷淋洗，进行柱层析,转化率：73％，1H NMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH)。
Claims (1)
1.一种由以下化学式所示的铜氮配合物该配合物，在293k温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属三斜晶系,空间群P-1，晶胞参数α＝105.852(3)°.β＝103.083(3)°；γ＝95.377(3)°。
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