CN106543074B - 一种一维手性Cu(II)链状配合物及其制备方法与应用 - Google Patents
一种一维手性Cu(II)链状配合物及其制备方法与应用 Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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Abstract
本发明公开了一种一维手性Cu(II)链状配合物及其制备方法,其制备方法包括,首先合成手性有机配体L,然后配位合成手性Cu(II)分子构筑单元,最后将手性Cu(II)分子构筑单元与2,6‑吡啶二羧酸溶于甲醇中反应,反应结束后经程序降温降至室温得红色一维手性Cu(II)链状配合物。本发明由手性配体经过配位反应最终获得一维手性Cu(II)链状配合物,丰富了手性金属配合物家族,为进一步研究其应用打下基础;本发明反应温度温和,反应步骤简单,产率较高,便于工业化规模生产。所述一维手性Cu(II)链状配合物作为分子材料在手性领域富有应用价值。
Description
技术领域
本发明属于不对称合成技术领域,具体涉及一种一维手性Cu(II)链状配合物及其制备方法和应用。
背景技术
手性是自然界的基本特征。手性分子与人类生理和生活息息相关,特定的手性分子具有某些特殊的光学或电子学特性,是组成高科技产品的关键物质。而自然界中所存在的物质来自于动植物,这就表现出其有限性及局限性,因而如何更为经济和高选择性地合成手性分子以满足人们日益增长的需求,则是不对称合成的焦点和难点。
经过近数十年来的研究,人们发现金属离子与手性配体平衡过程中所产生的手性金属配合物因其结构多样化,在光、电、磁、催化、吸附等具有优良性质而吸引各国化学家的广泛兴趣,因此制备手性金属配合物一直是国内外研究的热点。然而该类化合物的合成比较困难,一般手性配合物的获得可以通过手性模板的诱导得到,但这种方法得到的手性配合物的偶然性较大,另外的方法是直接通过手性配体来直接合成手性配合物,这种方法得到手性配合物的几率较大,所以一般手性配合物的获得多为直接由手性配体配位得到。但截至目前,人们合成手性金属配合物仍然较少,无法满足科学研究及实际生产的需要。因此,设计和制备合成新的手性金属配合物仍然是化学合成领域研究的重点。
发明内容
本发明的目的在于克服现有技术的不足,提供一种一维手性Cu(II)链状配合物及其制备方法。
为实现上述目的,具体的,本发明采用下述技术方案:
一种手性有机配体L,所述手性有机配体L,其化学命名为:(3E,3’E)-3,3’(1,2-二苯乙烷基)二亚乙基氮杂2(1-(4-吡啶-4苯丁1酮)),其左旋配体LR的化学命名为:
(3E,3’E)-3,3’((1R,1R)-1,2-二苯乙烷基)二亚乙基氮杂2(1-(4-吡啶-4苯丁1酮)),右旋配体LS的化学命名为:(3E,3’E)-3,3’((1S,1S)-1,2-二苯乙烷基)二亚乙基氮杂2(1-(4-吡啶-4苯丁1酮)),所述LR和LS的分子结构如下:
所述手性有机配体L的合成方法,包括以下步骤:
(1)在氮气保护下,以对溴苯乙酮和对吡啶硼酸碳酸钾和Pd(PPh3)4为反应原料在无水乙醇、水和甲苯的混合溶液中加热回流,冷却,分液,弃去水相,减压蒸除溶剂,柱层析提纯即得制备中间体A,其中,所述对溴苯乙酮和对吡啶硼酸碳酸钾和Pd(PPh3)4的摩尔质量比为1:(1~1.2):(0.3~0.5);所述混合溶液中无水乙醇、水和甲苯的体积比为3:2:3;所述中间体A为4-吡啶基苯乙酮,所述中间体A结构如下式所示;
(2)在氮气保护下,将中间体A与氢化钠在无水THF的溶液中加热反应一段时间后,再缓慢加入乙酸乙酯,制备中间体B,所述中间体A、氢化钠和乙酸乙酯的摩尔质量比为1:1~1.2:2,优选的,所述中间体A、氢化钠和乙酸乙酯的摩尔质量比为1:1.164:2;所述中间体B为4-吡啶基苯乙酰丙酮,所述中间体B的结构式如下式所示;
(3)将中间产物B与手性1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得手性有机配体L,具体的,将中间产物B与手性1R,2R-1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得到手性对映配体LR或将中间产物B与1S,2S-1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得到手性对映配体LS;其中,所述中间产物B与手性1,2-二苯基乙二胺的摩尔质量比为2:0.8~1.2,优选为2:1。
有机配体L的应用,其作为合成手性Cu(II)分子构筑单元的有机配体。
所述手性Cu(II)分子构筑单元,其结构简式为:[CuL],其实验式为C44H36CuN4O2,其左旋手性Cu(II)分子构筑单元1R和右旋手性Cu(II)分子构筑单元1S单晶结构如图1所示,所述手性Cu(II)分子构筑单元结晶属于正交晶系,P212121空间群,flack参数分别是0.01(2)(1R)和-0.009(19)(1S),中心Cu(II)为平面四方的四配位方式,Cu-N和Cu-O键长分别是和键角O(1)-Cu(1)-N(2)和N(2)-Cu(1)-N(1)分别是167.82(9)和85.78(9)。所述手性Cu(II)分子构筑单元其左旋手性Cu(II)分子构筑单元1R和右旋手性Cu(II)分子构筑单元1S具体晶体数据见表1。
表1 1R和1S的晶体学数据
所述手性Cu(II)分子构筑单元的制备方法为:
将Cu(OAc)2溶于MeOH,然后再加入手性有机配体L,室温搅拌,过滤真空干燥即得;其中,所述Cu(OAc)2与手性有机配体L的摩尔质量比为1:1~1.2,优选为1:1。
优选的,所述的室温是指15-25℃条件。
手性Cu(II)分子构筑单元作为合成一维手性Cu(II)链状配合物的应用。
所述一维手性Cu(II)链状配合物,其实验式为C106H74Cu4N10O16,所述一维手性Cu(II)链状配合物其左旋一维手性Cu(II)链状配合物2R和右旋一维手性Cu(II)链状配合物2S单晶结构如图2所示,所述一维手性Cu(II)链状配合物结晶属于正交晶系,P1空间群,flack参数分别是0.027(13)(2R)和0.00(3)(2S),其在手性Cu(II)分子构筑单元中的Cu仍然保持4配位的配位方式,Cu-O和Cu-N的键长范围分别为和 一维手性Cu(II)链状配合物中未配位的吡啶上的N原子与另外的Cu(II)配位,此Cu(II)与2,6-吡啶二羧酸再配位后形成一个手性的一维链状配合物,该Cu(II)为5配位的四角锥形配位结构。在平面上的Cu-N和Cu-O键长为和 轴向上Cu-N键长范围为如果为τ值为100则Cu的配位结构是一个理想的三角双锥结构,为τ值为0则其为四方锥的配位模式。通过计算2R的Cu(II)τ值为0.026(Cu1)和0.034(Cu(3)),而2S的τ值为0.006(Cu1)和0.003(Cu2),这说明2R和2S是一个比较理想的四方锥配位模式。所述一维手性Cu(II)链状配合物其左旋一维手性Cu(II)链状配合物2R和右旋一维手性Cu(II)链状配合物2S的具体晶体数据见表2。
表2 2R和2S的晶体学数据
一维手性Cu(II)链状配合物2R和2S的圆二色光谱性质显示,在300和410nm处为负Cotton效应,而在250nm和330nm处显示正Cotton效应。CD谱上很好的镜面关系说明配合物2R和2S为对映异构体,表明所述一维手性Cu(II)链状配合物具有作为手性分子材料的应用价值。
所述一维手性Cu(II)链状配合物的制备方法为:
将手性Cu(II)分子构筑单元与2,6-吡啶二羧酸溶于甲醇中反应,反应结束后经程序降温降至室温得红色一维手性Cu(II)链状配合物;其中,所述手性Cu(II)分子构筑单元与2,6-吡啶二羧酸的摩尔质量比为1:0.8~1.2,优选为1:1。
本发明公开了所述一维手性Cu(II)链状配合物作为分子材料在手性材料领域中的应用。
本发明的有益效果:
(1)本发明由手性配体经过配位反应最终获得一维手性Cu(II)链状配合物,丰富了手性金属配合物家族,为进一步研究其应用打下基础;
(2)本发明反应温度温和,反应步骤简单,产率较高,便于工业化规模生产;
(3)本发明一维手性Cu(II)链状配合物不仅表现在本身的结构新颖上,其对映异构体良好的镜面关系表明其作为分子材料在手性领域富有应用价值。
附图说明
图1是手性Cu(II)分子构筑单元的的单晶结构图;
图2是一维手性Cu(II)链状配合物的单晶结构图;
图3是本发明实施例1手性有机配体LR的单晶结构图;
图4是本发明实施例1手性有机配体L的红外谱图;
图5是本发明实施例1手性有机配体L的核磁图;
图6是本发明实施例2手性Cu(II)分子构筑单元的红外谱图;
图7是本发明实施例2手性Cu(II)分子构筑单元1R的圆二色谱图
图8是本发明实施例2手性Cu(II)分子构筑单元1S的红外谱图;
图9是本发明实施例2手性Cu(II)分子构筑单元1S的圆二色谱图;
图10是本发明实施例3的一维手性Cu(II)链状配合物2R的红外谱图;
图11是本发明实施例3一维手性Cu(II)链状配合物2R的圆二色谱图;
图12是本发明实施例3一维手性Cu(II)链状配合物2S的红外谱图;
图13是本发明实施例3一维手性Cu(II)链状配合物2S的圆二色谱图;
具体实施方式
结合实施例对本发明作进一步的说明,应该说明的是,下述说明仅是为了解释本发明,并不对其内容进行限定。
实施例1:手性有机配体LR或对映体LS的制备
具体的制备步骤如下:
(1)氮气保护下,以对溴苯乙酮(1.99g,10mmol)和对吡啶硼酸(1.23g,10mmol)碳酸钾(40.00mmol,5.53g)和四-(三苯基磷)钯(0.50mmol,0.57g),80mL(EtOH:H2O:甲苯=3:2:3)混合液于250mL三口瓶中,加热回流48h。冷却,分液,弃去水相,减压蒸除溶剂,得粗产品,柱层析分离(乙酸乙酯,甲醇)得黄色固体2.58g,即为中间体A,产率:80.1%。
(2)N2保护下,中间体A(1.97g,10mmol),氢化钠(0.28g,11.64mmol),置于100ml三口瓶中,缓慢加入50ml无水THF作溶剂,加热至80℃,80℃恒温搅拌1h,然后用注射器缓慢注乙酸乙酯(1.76g,20mmol),反应体系继续在80℃恒温搅拌。TLC跟踪,反应结束后反应体系中倒入100ml乙酸乙酯,混合溶液用盐水洗三次(3×100ml),水相用100ml乙酸乙酯萃取,合并有机相,加入无水硫酸镁干燥,过滤,减压除去溶剂,得中间体B,晾干后硅胶柱层析(乙酸乙酯),得浅黄色固体2.22g,产率71.1%
(3)中间体B(4.78g,20momol),手性1R,2R-1,2-二苯基乙二胺或1S,2S-1,2-二苯基乙二胺(2.12g,10mmol),乙酸2滴,置于50ml乙醇中,回流1小时,得到黄色固体,过滤,得粗产品,柱层析分离(二氯甲烷/甲醇:10/1)得黄色固体5.18g,即为有机配体LR或LS,产率:70.1%。
对本实施例制备的有机配体L进行结构表征,其配体LR的单晶图如图3所示,IR如图4所示,核磁图如图5所示。
实施例2:手性Cu(II)分子构筑单元的合成
将实施例1制备的有机配体LR或者LS(69.1mg,0.10mmol),醋酸铜(19.9mg,0.10mmol),溶于5mL甲醇中,室温搅拌2小时,得红色块状晶体[CuL],产量75.7mg,产率81%(以L为基准)。
我们通过IR,CD的性质表征了该化合物,结果分别见图6-9。
实施例3:一维手性Cu(II)链状配合物的合成
将实施例2制备的手性Cu分子构筑单元(71.6mg,0.1mmol),1,5-二羧基吡啶(16.7mg,0.1mmol)),溶于2mL甲醇中,置于5ml小试管中,120℃条件下恒温72小时,经50小时程序降温至室温,得红色块状晶体即一维手性Cu(II)链状配合物,产量48.6mg,产率55%(以L为基准)。
我们通过IR,CD的性质表征了该化合物,结果分别见图10-13,需要特别指出的是,一维手性Cu(II)链状配合物2R和2S的圆二色光谱性质显示,在300和410nm处为负Cotton效应,而在250nm和330nm处显示正Cotton效应。CD谱上很好的镜面关系说明配合物2R和2S为对映异构体。
上述虽然结合实施例对本发明的具体实施方式进行了描述,但并非对本发明保护范围的限制,所属领域技术人员应该明白,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (5)
1.一种一维手性Cu(II)链状配合物结晶的制备方法,其特征在于,包括如下步骤:
将手性Cu(II)分子构筑单元结晶与2,6-吡啶二羧酸溶于甲醇中反应,反应结束后经程序降温降至室温得红色一维手性Cu(II)链状配合物结晶;其中,所述手性Cu(II)分子构筑单元结晶与2,6-吡啶二羧酸的摩尔质量比为1:0.8~1.2;
其中,
一维手性Cu(II)链状配合物结晶属于正交晶系,P1空间群,flack参数分别是0.027(13)(2R)和0.00(3)(2S),其在手性Cu(II)分子构筑单元中的Cu仍然保持4配位的配位方式,Cu-O和Cu-N的键长范围分别为 和一维手性Cu(II)链状配合物中未配位的吡啶上的N原子与另外的Cu(II)配位,此Cu(II)与2,6-吡啶二羧酸再配位后形成一个手性的一维链状配合物,该Cu(II)为5配位的四角锥形配位结构;在平面上的Cu-N和Cu-O键长为和轴向上Cu-N键长范围为
手性Cu(II)分子构筑单元,其结构简式为:[CuL],其结构式如下所示:
所述手性Cu(II)分子构筑单元结晶属于正交晶系,P212121空间群,flack参数分别是0.01(2)(1R)和-0.009(19)(1S),中心Cu(II)为平面四方的四配位方式,Cu-N和Cu-O键长分别是和 键角O(1)-Cu(1)-N(2)和N(2)-Cu(1)-N(1)分别是167.82(9)和85.78(9);
制备方法包括:
将Cu(OAc)2溶于MeOH,然后再加入手性有机配体L,室温搅拌,过滤真空干燥即得手性Cu(II)分子构筑单元结晶;其中,所述Cu(OAc)2与手性有机配体L的摩尔质量比为1:1~1.2,所述的室温是指15-25℃条件;
所述手性有机配体L,其左旋配体LR和右旋配体LS分子结构式如下:
手性有机配体L,合成包括以下步骤:
(1)在氮气保护下,以对溴苯乙酮和对吡啶硼酸碳酸钾和Pd(PPh3)4为反应原料在无水乙醇、水和甲苯的混合溶液中加热回流,冷却,分液,弃去水相,减压蒸除溶剂,柱层析提纯即得制备中间体A,其中,所述对溴苯乙酮和对吡啶硼酸碳酸钾和Pd(PPh3)4的摩尔质量比为1:(1~1.2):(0.3~0.5);所述混合溶液中无水乙醇、水和甲苯的体积比为3:2:3;所述中间体A为4-吡啶基苯乙酮,所述中间体A结构如下所示:
(2)在氮气保护下,将中间体A与氢化钠在无水THF的溶液中加热反应一段时间后,再缓慢加入乙酸乙酯,制备中间体B,所述中间体A、氢化钠和乙酸乙酯的摩尔质量比为1:1~1.2:2,所述中间体B的结构式如下所示:
(3)将中间产物B与手性1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得手性有机配体L,具体的,将中间产物B与手性1R,2R-1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得到手性对映配体LR或将中间产物B与1S,2S-1,2-二苯基乙二胺加热反应,过滤,柱层析提纯即得到手性对映配体LS;其中,所述中间产物B与手性1,2-二苯基乙二胺的摩尔质量比为2:0.8~1.2。
2.如权利要求1所述的制备方法,其特征在于,所述手性Cu(II)分子构筑单元结晶与2,6-吡啶二羧酸的摩尔质量比为1:1。
3.如权利要求1所述的制备方法,其特征在于,所述Cu(OAc)2与手性有机配体L的摩尔质量比为1:1。
4.如权利要求1所述的制备方法,其特征在于,所述中间体A、氢化钠和乙酸乙酯的摩尔质量比为1:1.164:2。
5.如权利要求1所述的制备方法,其特征在于,所述中间产物B与手性1,2-二苯基乙二胺的摩尔质量比为2:1。
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