CN114534791B - 一种多功能非均相催化剂及其制备方法和应用 - Google Patents
一种多功能非均相催化剂及其制备方法和应用 Download PDFInfo
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 24
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Classifications
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- 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
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- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
本发明公开了一种多功能非均相催化剂及其制备方法和应用,该多功能非均相催化剂的是将金属合金包裹在金属有机骨架孔中,利用配体来修饰金属有机骨架材料,通过配位将手性脯氨酸连接在金属有机骨架的金属节点上,得到多功能非均相催化剂。该多功能非均相催化剂可用于催化芳香醇氧化‑Suzuki偶联‑不对称羟醛多步连续反应。本发明的多功能非均相催化剂具有非均相性,充分利用MOFs的催化活性位点,可以最大限度地减少化学废物、缩短操作时间并避免反应中间体的分离和纯化等。本发明操作条件温和,所制备的多功能非均相催化剂具有稳定、催化活性高及循环性能好等优点。
Description
技术领域:
本发明涉及一种多功能非均相催化剂及其制备方法和应用,属于有机催化材料技术领域。
背景技术:
当前,人们越来越关注日益严重的能源短缺和环境污染问题。必须开发一种综合考虑经济可行性与环境完整性的可持续发展模式。尤其是可持续化学科学发展涉及的新技术和高效工艺,被认为是解决环境问题的有效手段。提高催化效率、减少浪费、使用环保试剂是绿色化学的关键因素。从可持续化学的角度来看,连续反应是高效、环保的化学合成方法。连续反应由单锅系统中进行的两个或多个连续独立反应组成,无需分离和纯化中间体。反应可以由单个催化剂顺序催化,但这种方法通常仅限于具有相似机制的反应。更常见的是,连续反应由两种催化剂或具有两种或多种活性位点的多功能催化剂促进。多功能催化剂是指一种可同时催化多种反应的物质,该物质具备多重催化活性中心,在其作用下,一个反应过程中可完成多种不同类型的催化反应。反应物被第一类催化剂活化产生中间体,再由第二类催化剂催化得到最终产物。因此,连续反应不仅减少了能源消耗和浪费,而且最大限度地减少了溶剂和试剂的使用。这些优势使连续反应成为可持续的绿色过程,说明了效率和原子经济的概念。单一催化剂通常需要拥有多功能活性位点,依次完成每一步反应。然而,由于分子复杂性的增加以及活性位点在每个反应条件下保持高稳定性的要求,在分子水平上设计和构建具有两个或多个活性位点的多功能催化剂仍然是一个巨大的挑战。
由于具备结构多样性、均匀催化中心、可调节的孔径和孔隙率、可调节的热稳定性和易清楚阐明结构与功能关系的晶体性质等特性,MOFs已然成为均相催化剂和非均相催化剂之间的桥梁。当前,MOFs多功能催化剂在催化剂领域占据一席之地,引起了绿色化学科研工作者的极大兴趣。MOFs多功能性催化剂通常具有两个或多个活性位点,这些孤立催化位点的空间分布是需要精确设计的,以便催化因子执行其不同功能,尤其是对于一些不相容的催化活性基团。另外,在所有连续步骤反应过程中,这些活性位点应稳定存在,不易失活。由此可见,设计和开发用于串联反应的基于MOFs的多功能催化剂仍然是一项巨大的挑战。
发明内容
发明目的:本发明的第一个目的是提供了一种用于多步连续反应的多功能非均相催化剂,本发明的第二个目的是提供了该多功能非均相催化剂的制备方法,本发明的第三个目的是提供了该多功能非均相催化剂在芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应中的应用。
技术方案:本发明所述的一种多功能非均相催化剂,所述的多功能非均相催化剂为金属有机骨架材料CuCo@UiO-67-Pd-Pro,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro为内部包裹CuCo合金(CuCo NPs)的金属有机骨架材料UiO-67-Pd-Pro,所述金属有机骨架材料UiO-67-Pd-Pro包括正八面体UiO-67和键合在正八面体UiO-67的任意一条或者多条棱上的[(2,2'-联吡啶-5,5'-二甲酸)钯(II)]二氯化物,所述正八面体UiO-67的锆簇节点上配位有手性脯氨酸。
进一步地,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro粒子的粒径为正八面体对角之间的距离,其平均粒径为500-3000nm。
进一步地,所述的手性脯氨酸为L-脯氨酸。
进一步地,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro包裹Cu的含量为0.02~0.2mg/mg,包裹Co的含量为0.02~0.2mg/mg。
进一步地,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro骨架上Pd的含量为0.25~0.5μmol/mg。
进一步地,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro骨架上配位的手性脯氨酸为0.05-0.22mg/mg。
本发明所述的多功能非均相催化剂的制备方法采用一锅法合成,包含以下步骤:
将ZrCl4、4,4′-联苯二甲酸、含Pd(Ⅱ)配体和手性脯氨酸溶于DMF中,滴加冰醋酸,超声溶解,加入CuCo合金的DMF溶液,超声波处理,加热反应,离心分离得到固体物质,分别用DMF和丙酮清洗固体物质,真空干燥,用丙酮浸泡,加热真空下活化,得到活化后的多功能非均相催化剂金属有机骨架材料CuCo@UiO-67-Pd-Pro。
进一步地,所述ZrCl4、4,4′-联苯二甲酸、含Pd(Ⅱ)配体和手性脯氨酸摩尔比为1:(0.1~1):(0.1~0.33):1
进一步地,所述CuCo NPs的制备方法包含以下步骤:
将CuCl2·2H2O和CoCl2·6H2O溶于水得到混合溶液,将混合溶液加入到NaOH溶液中,搅拌,滴加入水合肼,搅拌,加热反应,离心分离,分别用水、乙醇、DMF进行洗涤,得到CuCo合金。
进一步地,所述含Pd(Ⅱ)配体的制备方法包含以下步骤:
(1)将(2,2'-联吡啶)-5,5'-二羧酸溶解在甲醇中,在冰浴条件下,加入浓硫酸。回流反应,将反应后的溶液转移至蒸馏水中,用Na2CO3调节pH,萃取,干燥、过滤,蒸发至干,得到白色固体产物即(2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc),结构式为:
(2)将(2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc)和PdCl2(CH3CN)2加入乙腈溶液,搅拌反应,过滤,洗涤,得到的橙黄色固体产物即[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物结构式为:
(3)将橙黄色固体产物[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物加入到四氢呋喃和乙醇的混合溶液中,加入NaOH水溶液,搅拌反应,将混合溶液酸化,获得黄色固体,分别用H2O和甲醇洗涤,得到黄色产物即为含Pd(Ⅱ)配体,结构式为:
本发明还包括所述多功能非均相催化剂在芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应中的应用。
进一步地,所述芳香醇为4-溴苯甲醇、4-氯苯甲醇、4-羟基苯甲醇或4-氨基苯甲醇。
进一步地,所述应用包括以下步骤:
(1)将芳香醇和多功能非均相催化剂混合,加入叔丁基过氧化氢和乙腈,在10℃-50℃和空气氛围下反应,采用薄层色谱法对反应进行检测,反应完成后减压蒸发,得到反应物;
(2)在反应物中加入苯硼酸、无机碱、乙醇、水,在25℃-100℃和空气氛围下反应,采用薄层色谱法对反应进行检测,反应完成后,加入HCl中和K2CO3,减压下蒸发,得到残留物;
(3)在残留物中加入环戊酮、二氯甲烷、水,在20℃-(-20℃)和空气氛围下搅拌反应,采用薄层色谱法对反应进行检测,反应完成后减压蒸发。
进一步地,步骤(1)中所述芳香醇、多功能非均相催化剂、叔丁基过氧化氢和乙腈的固液比为(0.25~1)mmol:(20~80)mg:(100~400)μL:(1~4)mL。
进一步地,步骤(2)中,所述反应物、苯硼酸、无机碱、K2CO、HCl、乙醇和水的固液比为(0.25~1)mmol:(0.3~1.2)mmol:(0.1~0.4)mmol:(0.2~0.8)mmol:(1~4)mL:(0.5~2)mL:(0.5~2)mL。
进一步地,步骤(2)中,所述残留物、环戊酮、二氯甲烷和水固液比为(0.25~1)mmol::(0.22~0.88)mL:(0.95~3.8)mL:(0.05~0.2)mL。
本发明通过一锅法合成策略,构建了中孔UiO-67,通过孔包封将CuCo NPs进行固定化,并将Pd(II)配体锚定在UiO-67骨架结构上,将L-脯氨酸连接在Zr簇节点上,从而得到多功能非均相催化剂,其在芳香醇氧化-Suzuki偶联-不对称羟醛缩合多步连续反应中具有良好的催化活性。芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应分为三个步骤:StepI芳香醇氧化反应、Step II Suzuki偶联反应、StepIII不对称羟醛反应。芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应流程如下式所示:
有益效果:与现有技术相比,本发明有以下显著优点:
(1)本发明中将CuCo NPs包裹在UiO-67孔中,解决了固定化及后续反应过程中CuCo NPs浸出的问题。
(2)本发明用Pd(Ⅱ)配体修饰UiO-67,使UiO-67结合了催化位点,解决了催化剂在有机溶剂中损失的问题。
(3)本发明将L-脯氨酸通过配位连接到UiO-67的锆簇节点上,使均相催化剂L-脯氨酸变为非均相催化剂,解决了均相催化剂循环次数低的问题。
(4)本发明所制备的多功能非均相催化剂在芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应中具有良好的催化活性。
附图说明
图1为多功能非均相催化剂结构示意图;
图2为CuCo NPs、UiO-67、UiO-67-Pd、UiO-67-Pd-Pro、CuCo@UiO-67-Pro、CuCo@UiO-67-Pd、CuCo@UiO-67-Pd-Pro及循环使用三次后CuCo@UiO-67-Pd-Pro的粉末X射线衍射图。
具体实施方式
下面结合附图对本发明的技术方案作进一步的说明。
实施例1
1、制备前驱体CuCo NPs
(1)将CuCl2·2H2O(51mg,0.3mmol)和CoCl2·6H2O(68mg,0.3mmol)溶于去离子水中,将混合溶液加入到相同体积的0.4M NaOH溶液中。搅拌约15分钟后,将85%水合肼(0.375mL)逐滴加入到混合物中并剧烈搅拌。约25分钟后,将混合溶液转移到不锈钢高压釜中。将高压釜密封在120℃的烘箱中恒温反应6小时。反应结束后,将最终产物用蒸馏水、C2H5OH、DMF溶液洗涤(3×10mL),最后通过离心收集得到CuCo NPs。将CuCo NPs加入DMF(5mL),超声10分钟,备用。
2、制备含Pd(Ⅱ)配体
(1)将(2,2'-联吡啶)-5,5'-二羧酸(500mg,2mmol)的甲醇(30mL)溶液置于冰浴中,缓慢加入浓硫酸(2mL)。回流过夜后,将溶液转移至40mL水中,形成白色浆液。用Na2CO3将混合液的pH调节至7。然后用氯仿对产物进行萃取,无水硫酸镁干燥、过滤并蒸发至干,得到白色固体产物2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc),其结构是如下:
(2)在装有PdCl2(CH3CN)2(130mg,0.5mmol)和(2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc)(136mg,0.5mmol)的圆底烧瓶中加入8mL CH3CN溶液,并在65℃下搅拌24小时。过滤,收集得到的黄色固体,并用CH3CN洗涤,最后在100℃下真空干燥12小时,得到橙黄色固体[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物,其结构式如下:
(3)将[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物(120mg,0.27mmol)加入到四氢呋喃(10mL)和乙醇(10mL)的混合溶液中,再往混合液中加入3M NaOH水溶液(10mL),70℃下搅拌5小时。待溶液冷却至室温后,将混合液酸化至pH=1,获得黄色固体,并用H2O和甲醇洗涤,得到黄色产物含Pd(Ⅱ)配体,其结构是如下:
3、制备CuCo@UiO-67-Pd-Pro
将ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,97mg,0.4mmol)、含Pd(Ⅱ)配体(84mg,0.2mmol)、和手性脯氨酸(345mg,3mmol)、溶于DMF中,滴加冰醋酸(2mL),超声10分钟,充分溶解。然后将CuCo合金的DMF溶液(5mL)滴加到上述溶液中,超声波处理30min,将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥。然后用丙酮浸泡3天,在120℃动态真空下活化24h,得到活化后的CuCo@UiO-67-Pd-Pro。
4、金属有机骨架材料CuCo@UiO-67-Pd-Pro骨架上Pd元素含量的测定
将实施例1得到的金属有机骨架材料CuCo@UiO-67-Pd-Pro采用电感耦合等离子体质谱仪(ICP)测试骨架上Pd元素含量,得到金属骨架材料CuCo@UiO-67-Pd-Pro骨架上Pd元素含量为0.5μmol/mg。
5、金属有机骨架材料CuCo@UiO-67-Pd-Pro包裹Cu NPs的含量测定
将实施例1得到金属有机骨架材料CuCo@UiO-67-Pd-Pro采用电感耦合等离子体质谱仪(ICP)测试催化剂包裹的Cu元素含量,得到金属骨架材料CuCo@UiO-67-Pd-Pro包裹的Cu元素含量为0.2mg/mg。
6、金属有机骨架材料CuCo@UiO-67-Pd-Pro包裹Co NPs的含量测定
将实施例1得到金属有机骨架材料CuCo@UiO-67-Pd-Pro采用电感耦合等离子体质谱仪(ICP)测试催化剂包裹的Co元素含量,得到金属骨架材料CuCo@UiO-67-Pd-Pro包裹的Co元素含量为0.2mg/mg。
7、金属有机骨架材料CuCo@UiO-67-Pd-Pro配位的手性脯氨酸的含量测定
将实施例1得到金属有机骨架材料CuCo@UiO-67-Pd-Pro采用核磁共振测试催化剂配位的手性脯氨酸含量,得到金属骨架材料CuCo@UiO-67-Pd-Pro配位的手性脯氨酸的含量为0.22mg/mg。
实施例2多功多功能非均相催化剂对不同芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应
1、多功能非均相催化剂对4-溴苯甲醇氧化-Suzuki偶联-不对称羟醛多步连续反应
称取47mg的4-溴苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pd-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(19:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表1所示。
2、多功能非均相催化剂对4-氯苯甲醇氧化-Suzuki偶联-不对称羟醛多步连续反应
称取36mg的4-氯苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pd-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(19:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表1所示。
3、多功能非均相催化剂对4-羟基苯甲醇氧化-Suzuki偶联-不对称羟醛多步连续反应
称取31mg的4-羟基苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pd-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(19:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表1所示。
4、多功能非均相催化对剂4-氨基苯甲醇氧化-Suzuki偶联-不对称羟醛多步连续反应
称取31mg的4-氨基苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pd-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(19:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表1所示。(a.分离产率,b.手性AD-H柱,1mL min-1,正己烷:异丙醇=90:10)。
表1芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应条件及收率
由表1可以看出,所值得的多功能催化剂CuCo@UiO-67-Pd-Pro在催化芳香醇氧化反应具有很好的催化性能,芳香醇氧化反应的最高收率达到94%;多功能催化剂CuCo@UiO-67-Pd-Pro在Suzuki偶联反应中也有着很好的催化性能,收率达到95%;此外,制得的多功能催化剂CuCo@UiO-67-Pd-Pro在不对称羟醛反应中也有着非常好的催化性能,其中虽然收率不是太高,但是eeanti值可达到94%,显示出了多功能催化剂CuCo@UiO-67-Pd-Pro很好的催化活性。
实施例3多功能非均相催化剂的循环使用
在进行了实施例2中芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应后,离心收集固体催化剂,并用乙醇洗涤干燥后,接着将其用于下一个芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应中继续使用。如此循环三次,将循环使用过后的固体多功能非均相催化剂CuCo@UiO-67-Pd-Pro洗涤干燥后,进行粉末XRD衍射测试,结果如图2所示。图2为CuCo NPs、UiO-67、UiO-67-Pd、UiO-67-Pd-Pro、CuCo@UiO-67-Pro、CuCo@UiO-67-Pd、CuCo@UiO-67-Pd-Pro及循环使用三次后CuCo@UiO-67-Pd-Pro的粉末X射线衍射图,其中h为循环使用三次后CuCo@UiO-67-Pd-Pro粉末X射线衍射图,由图2中h可以看出,在经过了三次循环使用后,多功能催化剂CuCo@UiO-67-Pd-Pro仍然保持着很好的晶形结构。
对比例1制备UiO-67
称取ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,145mg,0.6mmol)溶于DMF(15mL)中,滴加冰醋酸(2mL),超声10分钟,充分溶解。将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥得到UiO-67。
对比例2制备UiO-67-Pd
称取ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,97mg,0.4mmol)、Pd(Ⅱ)配体(84mg,0.2mmol)溶于DMF(15mL)中,滴加冰醋酸(2mL),超声10分钟,充分溶解。将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥得到UiO-67-Pd。
对比例3制备UiO-67-Pd-Pro
称取ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,97mg,0.4mmol)、Pd(Ⅱ)配体(84mg,0.2mmol)、L-脯氨酸(345mg,3mmol)溶于DMF(15mL)中,滴加冰醋酸(2mL),超声10分钟,充分溶解。将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥得到UiO-67-Pd-Pro。
对比例4制备CuCo@UiO-67-Pro
称取ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,145mg,0.6mmol)、手性脯氨酸(345mg,3mmol)溶于DMF中,滴加冰醋酸(2mL),超声10分钟,充分溶解。然后将CuCo合金的DMF溶液(5mL)滴加到上述溶液中,超声波处理30min,将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥得到CuCo@UiO-67-Pro。
对比例5制备CuCo@UiO-67-Pd
称取ZrCl4(140mg,0.6mmol)、4,4′-联苯二甲酸(H2bpdc,97mg,0.4mmol)、Pd(Ⅱ)配体(84mg,0.2mmol)溶于DMF中,滴加冰醋酸(2mL),超声10分钟,充分溶解。然后将CuCo合金的DMF溶液(5mL)滴加到上述溶液中,超声波处理30min,将混合物溶液转移到聚四氟乙烯高压反应釜中,在120℃烘箱中反应24小时。反应结束后,固体产物通过离心收集,分别用DMF和丙酮(3×10mL)进行清洗以除去未反应物质及其他杂质,真空条件下干燥得到CuCo@UiO-67-Pd。
实施例4UiO-67、UiO-67-Pd、UiO-67-Pd-Pro、CuCo@UiO-67-Pro、CuCo@UiO-67-Pd、CuCo@UiO-67-Pd-Pro的粉末X射线衍射分析
对实施例1得到的CuCo@UiO-67-Pd-Pro、实施例3得到的循环使用三次后CuCo@UiO-67-Pd-Pro、对比例1得到的UiO-67、对比例2得到的UiO-67-Pd、对比例3得到的UiO-67-Pd-Pro、对比例4得到的CuCo@UiO-67-Pro、对比例5得到的CuCo@UiO-67-Pd进行粉末X射线衍射测试(测试角度范围为5-50°,扫描速度为5°/min)。结果如图2所示。图2为CuCo NPs、UiO-67、UiO-67-Pd、UiO-67-Pd-Pro、CuCo@UiO-67-Pro、CuCo@UiO-67-Pd、CuCo@UiO-67-Pd-Pro及循环使用三次后CuCo@UiO-67-Pd-Pro的粉末X射线衍射图,其中,a为CuCo NPs标准卡,b为UiO-67标准卡,c为UiO-67,d为UiO-67-Pd,e为UiO-67-Pd-Pro,f为CuCo@UiO-67-Pro,g为CuCo@UiO-67-Pd,h为CuCo@UiO-67-Pd-Pro,i为循环使用三次后CuCo@UiO-67-Pd-Pro。由图2可知,在2θ为5-10°区间,a中两条数值的虚线为CuCo NPs的出峰位置,可以看出f的CuCo@UiO-67-Pro,g的CuCo@UiO-67-Pd,h的CuCo@UiO-67-Pd-Pro,i的循环使用三次后CuCo@UiO-67-Pd-Pro。中均出现了CuCo NPs特征峰,说明CuCo NPs成功包裹在有机金属骨架UiO-67中。而由UiO-67标准卡比对可以看出,UiO-67-Pd、UiO-67-Pd-Pro、CuCo@UiO-67-Pro、CuCo@UiO-67-Pd、CuCo@UiO-67-Pd-Pro均出现了UiO-67结构的特征峰,表明所制备的样品均具有优异的结晶度,并且CuCo@UiO-67-Pd-Pro在进行了三次循环使用后仍保持了原有的结晶度。因此CuCo@UiO-67-Pd-Pro在进行了三次循环使用后仍有很好催化性能。
对比例6不同实验条件下芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应对比试验
1、未包裹CuCo NPs实验
称取47mg的4-溴苯甲醇(0.25mmol)和20mg的对比例3得到的UiO-67-Pd-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(20:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或ChiralcelOD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表2所示。
2、未键合Pd元素实验
称取47mg的4-溴苯甲醇(0.25mmol)和20mg的对比例4得到的CuCo@UiO-67-Pro,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(20:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表2所示。
3、未配位L-脯氨酸实验
称取47mg的4-溴苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pd,加入100微升叔丁基过氧化氢和1mL乙腈,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(20:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有Chiralpak AD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表2所示。
对比例7不同氧化剂代替叔丁基过氧化氢实验
1、H2O2和O2代替叔丁基过氧化氢实验
称取47mg的4-溴苯甲醇(0.25mmol)和20mg的CuCo@UiO-67-Pro,加入到1mL乙腈中,在O2氛围中或者加入100微升H2O2作为氧化剂,在30℃下反应8h。采用薄层色谱法对反应进行监测。反应完成后,通过真空旋蒸从反应混合物中除去叔丁基过氧化氢和溶剂,得到残留物。将37mg苯硼酸(0.3mmol)、14mg无机碱K2CO3(0.1mmol)、1mL乙醇与H2O(1:1)混合溶液添加到残留物中,在80℃下反应10小时,采用薄层色谱法对反应进行监测。反应完成后选用HCl中和K2CO3,并在减压下蒸发除去混合溶剂,得到残留物。将0.22mL环戊酮(2.5mmol)和1mL二氯甲烷与H2O混合溶剂(20:1)添加到残留物中,-20℃下搅拌反应6天。当连续反应结束后,选用硅胶柱色谱法提纯,有机相在真空条件下浓缩。以石油醚/乙酸乙酯(10:1-5:1)为洗脱剂,用柱色谱法在硅胶上对残留物进行纯化,得到催化产物。采用具有ChiralpakAD-H或Chiralcel OD-H色谱柱的高效液相色谱测定产物的ee值。其中,各步骤反应时间、收率及ee值如表2所示。
表2不同条件下芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应对比试验
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由表2可以看出,与No.4相比,No1.中显示在催化剂未包裹CuCo NPs时,芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应无法进行,均没有收率;No.2中显示在未键合Pd(II)时,多步连续反应中仅有芳香醇氧化反应可以进行,并且收率可以达到93%,而Suzuki偶联和不对称羟醛反应均无法进行,均没有收率;No.3中显示在未配位L-脯氨酸时,芳香醇氧化和Suzuki偶联均可以发生反应,而不对称羟醛反应无法进行,No.5中用不同种类的催化剂代替叔丁基过氧化氢进行实验,实验结果显示,H2O2和O2在该多步连续反应中的氧化效果很差,更加证明了叔丁基过氧化氢才是该多步连续反应更合适的氧化剂。
Claims (10)
1.一种多功能非均相催化剂,其特征在于,所述的多功能非均相催化剂为金属有机骨架材料CuCo@UiO-67-Pd-Pro,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro为内部包裹CuCo合金的金属有机骨架材料UiO-67-Pd-Pro,所述金属有机骨架材料UiO-67-Pd-Pro包括正八面体UiO-67和键合在正八面体UiO-67的任意一条或者多条棱上的[(2,2'-联吡啶-5,5'-二甲酸)钯(II)]二氯化物,所述正八面体UiO-67的锆簇节点上配位有手性脯氨酸。
2.根据权利要求1所述的多功能非均相催化剂,其特征在于,所述手性脯氨酸为L-脯氨酸。
3.根据权利要求1所述的多功能非均相催化剂,其特征在于,所述金属有机骨架材料CuCo@UiO-67-Pd-Pro上Cu的含量为0.02~0.2mg/mg,Co的含量为0.02~0.2mg/mg,Pd的含量为0.25~0.5μmol/mg,手性脯氨酸含量为0.05-0.22mg/mg。
4.根据权利要求1-3任一项所述的多功能非均相催化剂的制备方法,其特征在于,包含以下步骤:将ZrCl4、4,4′-联苯二甲酸、含Pd(Ⅱ)配体和手性脯氨酸溶于DMF中,滴加冰醋酸,超声溶解,加入CuCo合金的DMF溶液,超声波处理,加热反应,离心分离得到固体物质,分别用DMF和丙酮清洗固体物质,真空干燥,用丙酮浸泡,加热真空下活化,得到活化后的多功能非均相催化剂金属有机骨架材料CuCo@UiO-67-Pd-Pro。
5.根据权利要求4所述的多功能非均相催化剂的制备方法,其特征在于,所述ZrCl4、4,4′-联苯二甲酸、含Pd(Ⅱ)配体和手性脯氨酸摩尔比为1:1:0.1:1~1:0.1:0.33:1。
6.根据权利要求4所述的多功能非均相催化剂的制备方法,其特征在于,所述CuCo合金的制备方法包含以下步骤:将CuCl2·2H2O和CoCl2·6H2O溶于水得到混合溶液,将混合溶液加入到NaOH溶液中,搅拌,滴加入水合肼,搅拌,加热反应,离心分离,分别用水、乙醇、DMF进行洗涤,得到CuCo 合金。
7.根据权利要求4所述的多功能非均相催化剂的制备方法,其特征在于,所述含Pd(Ⅱ)配体的制备方法包含以下步骤:
(1)将(2,2'-联吡啶)-5,5'-二羧酸溶解在甲醇中,在冰水浴条件下,加入浓硫酸,回流反应,将反应后的溶液转移至蒸馏水中,用Na2CO3调节pH,萃取,干燥、过滤,蒸发至干,得到白色固体产物即(2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc);
(2)将(2,2'-联吡啶)-5,5'-二甲酸酯(Me2bpydc)和PdCl2(CH3CN)2加入乙腈溶液,搅拌反应,过滤,洗涤,得到的橙黄色固体产物即[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物;
(3)将橙黄色固体产物[(5,5'-二甲氧基羧基-2,2'-联吡啶)钯(II)]二氯化物加入到四氢呋喃和乙醇的混合溶液中,加入NaOH水溶液,搅拌反应,将混合溶液酸化,获得黄色固体,分别用H2O和甲醇洗涤,得到黄色产物即为含Pd(Ⅱ)配体。
8.权利要求1-3任一项所述的多功能非均相催化剂在芳香醇氧化-Suzuki偶联-不对称羟醛多步连续反应中的应用。
9.根据权利要求8所述的应用,其特征在于,所述芳香醇为4-溴苯甲醇、4-氯苯甲醇、4-羟基苯甲醇或4-氨基苯甲醇。
10.根据权利要求8所述的应用,其特征在于,包括以下步骤:
(1)将芳香醇和多功能非均相催化剂混合,加入叔丁基过氧化氢和乙腈,在10℃~50℃和空气氛围下反应,采用薄层色谱法对反应进行检测,反应完成后减压蒸发,得到反应物;
(2)在反应物中加入苯硼酸、无机碱、乙醇、水,在25℃~100℃和空气氛围下反应,采用薄层色谱法对反应进行检测,反应完成后,加入HCl中和K2CO3,减压下蒸发,得到残留物;
(3)在残留物中加入环戊酮、二氯甲烷、水,在20℃~ -20℃和空气氛围下搅拌反应,采用薄层色谱法对反应进行检测,反应完成后减压蒸发。
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