CN106831879B - 1,1-二吡唑甲烷双核锰聚合物及其原位脱羧合成方法及应用 - Google Patents
1,1-二吡唑甲烷双核锰聚合物及其原位脱羧合成方法及应用 Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 22
- 239000011572 manganese Substances 0.000 title claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 title claims description 8
- 238000010189 synthetic method Methods 0.000 title claims description 8
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- 238000006555 catalytic reaction Methods 0.000 claims description 8
- HOGKYJGTZSXWFI-UHFFFAOYSA-N 2,2-bis(1h-pyrazol-5-yl)acetic acid Chemical class C=1C=NNC=1C(C(=O)O)C1=CC=NN1 HOGKYJGTZSXWFI-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 10
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- 239000000376 reactant Substances 0.000 description 3
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- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
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- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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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Abstract
本发明公开了一种1,1‑二吡唑甲烷双核锰聚合物，还提供了该化合物的制备方法及催化应用。本发明具有工艺简单、成本低廉、化学组分易于控制、重复性好并且产量高，催化效果优良等优点。
Description
技术领域
本发明属于化学合成及催化应用领域，特别涉及一种1,1-二吡唑甲烷双核锰聚合物的原位脱羧合成方法及应用。
背景技术
不对称硅腈化反应是近年来发展起来的一类不对称催化合成反应，该反应主要用来合成手性氰醇。手性氰醇是一类具有广泛用途的有机合成中间体，它的两个官能团经过多步转化，可以合成一系列光学纯的手性化产物，分别是α-羟基酸，α-羟基醛，α-羟基酮，β-羟基胺，α-氨基酸等；氰醇也是合成许多药物的起始原料，如心血管扩张药物等；氰醇还是一些天然产物和农药的重要组成片断，例如，糖苷杏仁苷等。因此，研究新催化剂和新制备技术，探索新不对称催化硅腈化反应过程是一项既有理论价值又有应用前景的工作。合成手性氰醇的方法很多，主要包括生物和化学两种方法。化学方法主要是手性试剂催化醛或酮的不对称硅腈化反应。
但是，目前此类催化剂存在着诸多问题和缺陷，如催化剂合成工艺及结构复杂，催化机理不明确，影响反应转化率和对映选择性的因素诸多，如温度、催化剂用量、时间、底物适应性等；选择的腈源或催化剂具有毒性，对人体有害，且有时反应速度较慢。所以，如何进一步合成新型催化剂，提高其活性，明确其催化机理，同时提高反应转化率和对映选择性，是今后发展的趋势之一。
近年来出现了原位合成技术，即在一定条件下，通过化学反应，在反应体系内生成一种或者几种新型的化合物，通过原位合成，可以获得其他合成方法难以得到的化合物。而新型吡唑烷聚合物是被广泛应用于不对称催化、电致发光和储气吸附的金属有机框架，对寻找优异的可替代的多功能材料具有指导意义。目前，报道过的硅腈化非均相催化剂如双核二聚Salen钛配合物催化剂，铜金属配合物框架催化剂等存在着转化率低，反应速度慢等缺点。而本发明提供的双核锰配合物很好地克服了上述缺点，有着优良的催化性能。
发明内容
本发明的目的就是为了提供一种吡唑烷基锰过渡金属聚合物及应用，该化合物通过原位脱羧反应得到并应用于硅腈化非均相催化反应中，具有优良的催化性能。
本发明采用的技术方案为：一种1,1-二吡唑甲烷双核锰聚合物，该聚合物结构式如下式(I)所示：
本发明还提供了上述1,1-二吡唑甲烷双核锰聚合物的原位脱羧合成方法，包括以下步骤：
(1)MnCl2·4H2O和1,1-二吡唑乙酸在乙腈中室温搅拌5-10分钟；
(2)步骤(1)的溶液于110-140℃下反应100-150h，过滤、洗涤，即得单晶级1,1-二吡唑甲烷双核锰聚合物，产率78-85％；
反应方程式如下：
作为优选，所述MnCl2·4H2O和1,1-二吡唑乙酸的重量比为：1.02-1.05。
本发明还提供了一种1,1-二吡唑甲烷双核锰聚合物的应用，催化剂(1)在室温条件、二氯甲烷溶剂中催化芳香醛(如苯甲醛)和三甲基氰硅烷参与的硅腈化反应中具有良好的催化性能。
有益效果：与现有技术相比，本发明具有以下优点：
(1)合成方法上，本发明克服了溶剂法的缺点，具有工艺简单，成本低廉、化学组分易于控制、重复性好并且产量高等优点。
(2)合成的催化剂结构简单，是一种开放式的结构，能显著提高其催化活性。
(3)在苯甲醛硅腈化催化反应中，催化转化率高，相比报道的杂化催化剂或羧酸类金属配合物催化剂，其具有稳定性高、条件温和、能重复利用，既经济又环保的优点。
附图说明
图1为1,1-二吡唑甲烷双核锰聚合物的结构图。
具体实施方法
下面结合具体实施方式和说明书附图进一步阐明本发明的内容。
本发明使用的化合物来源：
1,1-二吡唑乙酸(本实验室合成)，其它均为商业化产品。
实施例1
(1)将0.197克分析纯MnCl2·4H2O和0.192克分析纯1,1-二吡唑乙酸溶于10毫升的无水乙腈溶液中；
(2)将步骤(1)中的溶液在室温下搅拌5分钟至反应物全部溶解且澄清；
(3)将步骤(2)制得的溶液转移到聚四氟乙烯反应釜中在110℃反应100小时，降温至室温，开釜，过滤，用无水乙腈洗涤，得到单晶级1,1-二吡唑甲烷双核锰聚合物，产率78-85％。
并用X-射线单晶衍射、红外光谱、质谱、核磁共振氢谱/碳谱确认其结构式为：
分析所得的1,1-二吡唑甲烷双核锰聚合物的基本数据：
X-射线单晶衍射表征，解析结构图(如图1)。
实施例2
(1)将0.256克分析纯MnCl2·4H2O和0.245克分析纯1,1-二吡唑乙酸溶于12毫升的无水乙腈溶液中；
(2)将步骤(1)中的溶液在室温下搅拌5分钟至反应物全部溶解且澄清；
(3)将步骤(2)制得的溶液转移到聚四氟乙烯反应釜中在120℃反应120小时，降温至室温，开釜，过滤，用无水乙腈洗涤，得到单晶级1,1-二吡唑甲烷双核锰聚合物，产率78-85％。
实施例3
(1)将0.380克分析纯MnCl2·4H2O和0.360克分析纯1,1-二吡唑乙酸溶于15毫升的无水乙腈溶液中；
(2)将步骤(1)中的溶液在室温下搅拌10分钟至反应物全部溶解且澄清；
(3)将步骤(2)制得的溶液转移到聚四氟乙烯反应釜中在140℃反应150小时，降温至室温，开釜，过滤，用无水乙腈洗涤，得到单晶级1,1-二吡唑甲烷双核锰聚合物，产率78-85％。
实施例4
1,1-二吡唑甲烷双核锰聚合物参与的催化反应式如下：
1)催化剂的活化：将催化剂(1)用球磨机研磨，浸入三氯甲烷中3天，倾滤，100度下真空干燥2-4小时，待用。
1,1-二吡唑甲烷双核锰聚合物的催化应用：用2.4mol％量的催化剂(1)在室温条件下催化苯甲醛与三甲基腈硅烷的加成反应，如上反应式。用气相色谱-质谱联用仪监控反应，2小时后，转化率可达到30％，24小时后达到85-90％。重复利用此催化剂2-3次后，其最终转化率仍能达到较高的水平，大约50-65％。同时，空白实验显示，即不加入催化剂(1)时，反应48小时后，只有大约1％的转化率。电感耦合等离子体原子发射光谱测试显示，催化剂的损失率极低，大约0.5wt％，说明此催化剂具有良好的稳定性。另一组对比实验，用基于苯三甲酸配位形成的铜配位聚合物在用量相同的前提下，反应72小时，转化率达到50-60％；用无机-有机复合杂化催化剂，在提高用量到10mol％、提高温度到50度的条件下，其转化率最高到75％。综上，本发明所提供的催化剂(1)的催化性能明显优于对比的两种催化剂，是一种高效、优良且可多次利用的硅腈化非均相催化剂。
应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (4)
1.一种1,1-二吡唑甲烷双核锰聚合物，其特征在于：该聚合物结构式如下式(I)所示：
2.根据权利要求1所述的1,1-二吡唑甲烷双核锰聚合物的原位脱羧合成方法，其特征在于：包括以下步骤：
(1)MnCl2·4H2O和1,1-二吡唑乙酸在乙腈中室温搅拌5-10分钟；
(2)步骤(1)的溶液于110-140℃下反应100-150h，过滤、洗涤，即得单晶级1,1-二吡唑甲烷双核锰聚合物，产率78-85％。
3.根据权利要求2所述的一种1,1-二吡唑甲烷双核锰聚合物的原位脱羧合成方法，其特征在于：所述MnCl2·4H2O和1,1-二吡唑乙酸的所用重量比为：1.02-1.05：1。
4.一种如权利要求1所述的1,1-二吡唑甲烷双核锰聚合物的应用，其特征在于：所述1,1-二吡唑甲烷双核锰聚合物在硅腈化非均相催化反应中有优良的催化效果。
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