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CN111905836B - 一种多孔塑料化学试剂载体及其制备方法和应用 - Google Patents

一种多孔塑料化学试剂载体及其制备方法和应用 Download PDF

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CN111905836B
CN111905836B CN202010819698.5A CN202010819698A CN111905836B CN 111905836 B CN111905836 B CN 111905836B CN 202010819698 A CN202010819698 A CN 202010819698A CN 111905836 B CN111905836 B CN 111905836B
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CN111905836A (zh
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胥波
齐义舟
李婷婷
齐培州
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Shanghai Group Wave Intelligent Instrument Technology Co ltd
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Abstract

本发明提供了一种多孔塑料化学试剂载体及其制备方法和应用。本发明采用的技术方案制备的化学试剂载体改变了化学试剂的使用形态，使不易操作和难于精确称量的固体，半固体和粘稠液体也能方便的量取，制备工艺简便且制备过程中并未引入对于环境不友好的溶剂，故易易工业化生产且环保效果更佳。

Description

一种多孔塑料化学试剂载体及其制备方法和应用
技术领域
本发明涉及化学试剂负载技术领域，具体涉及一种多孔塑料化学试剂载体及其制备方法和应用。
背景技术
化学合成在医药、农药、精细化工、材料、传感器、航空航天等各个领域的运用越来越广泛。尽管取得了重大进展，但化学合成目前仍是一个有相当危险性的，劳动密集型的行业。特别是处理危险化学品时固有的安全隐患，这使得化学合成自动化领域的化学家趋之若鹜。尽管自动化彻底改变了许多工业和实验室工作，但在实际应用中，化学合成的完全自动化仍具有很高的挑战性,在大多数学校和工业实验室中，绝大部分化学实验仍然由人工完成。对于自动化机器来说，许多常规的化学药品处理任务仍然很困难，下载或设计合成方案，并且可以在本地合成机中完全自动执行，是合成化学家的梦想。
由于化学合成中涉及的化学品种类繁多，且称取少量或微量化学试剂时非常耗时耗力，因此实现自动合成，首先需要将数千种试剂标准化，尤其是试剂的剂量标准化，利于算法控制的机器人系统使用。对于低粘度液体的自动化移取相对容易，然而，固体、半固体和粘稠液体试剂却面临很大的挑战。近年来自动化的合成方面取得了很大进展，但国内外相关研究都没有相对通用的方法来处理成千上万，形态各异的化学品，因此无法实现高度自动化的合成。
发明内容
为克服现有技术缺陷，本发明提供了一种超高分子量多孔塑料化学试剂载体及其制备方法和应用，具体采用以下技术方案：
本发明第一方面提供了一种多孔塑料化学试剂载体，其为多孔的固体块状结构；
进一步的，所述多孔塑料化学试剂载体为药片样圆柱结构、球形结构或立方体结构；进一步优选的，所述的药片样圆柱结构多孔塑料化学试剂载体，其孔容为0.3～0.6ml/g，且其总孔隙面积为20～25m2/g，其平均孔径为70～80nm，其在0.5～1psi下的体积密度0.5～1.0g/ml，其孔隙率为20～30％；优选的，其孔容为0.4298ml/g；其总孔隙面积为23.780m2/g；其平均孔径为72.3nm；其在0.5～1psi下的体积密度0.6069g/ml；其孔隙率为26.0850％；
进一步的，所述的药片样圆柱结构多孔塑料化学试剂载体规格为：内径5.1～9mm且高2.5～4mm；更进一步的，所述的药片样圆柱结构多孔塑料化学试剂载体的重量为30mg/片或150mg/片；
进一步的，所述多孔塑料为具有高耐磨性及高度化学惰性的材料，包括但不限于超高分子量多孔聚乙烯、超高分子量多孔聚丙烯、超高分子量聚四氟乙烯或超高分子量聚偏四氟乙烯；
进一步的，所述化学试剂为固体试剂或液体试剂；更进一步的，所述固体试剂为可溶性固体或不溶性固体；更进一步的，所述液体试剂包括但不限于粘性液体；
本发明的第二方面提供了上述多孔塑料化学试剂载体的制备方法，包括以下步骤：将上述塑料粉末加入到圆柱状不锈钢磨具中，在常压下加热至140～155℃，然后迅速降温至室温，退模后即得；
进一步的，所述多孔塑料粉末的直径为10～100μm，其分子量大于100万；
进一步的，所述圆柱状不锈钢磨具的内径为5.1～9mm，高为2.5～4mm；具体地，所述圆柱状不锈钢磨具的尺寸：内径为5.1mm且高为2.5mm、内径为7.4mm且高为2.5mm或内径为9mm且高为4mm；
本发明的第三方面提供了一种多孔塑料化学试剂载体的用途，其特征在于，将其用于负载化学试剂；
进一步的，所述化学试剂为固体试剂或液体试剂；更进一步的，所述固体试剂为可溶性固体试剂或不溶性固体试剂；更进一步的，所述液体试剂包括但不限于非粘性液体试剂或粘性液体试剂。
本发明的第四方面提供了一种多孔塑料化学试剂，包括上述多孔塑料化学试剂载体以及其负载的化学试剂，进一步的，所述多孔塑料化学试剂载体负载的化学试剂的物质的量是确定的；
进一步的，所述多孔塑料化学试剂载体负载的化学试剂的物质的量为0.001μmol～10.0mol；更进一步的，所述多孔塑料化学试剂载体负载的化学试剂的物质的量为0.01μmol～1.0mol；更进一步的，所述多孔塑料化学试剂载体负载的化学试剂的物质的量为0.001μmol、0.002μmol、0.005μmol、0.01μmol、0.02μmol、0.05μmol、0.1μmol、0.2μmol、0.5μmol、1μmol、2μmol、5μmol、10μmol、20μmol、50μmol、100μmol、200μmol、500μmol、1mmol、2mmol、5mmol、10mmol、20mmol、50mmol、100mmol、200mmol、500mmol或1mol；
进一步的，所述多孔塑料化学试剂为多孔可溶性固体试剂、多孔不溶性固体试剂或多孔液体试剂；更进一步的，所述多孔液体试剂包括但不限于多孔非粘性液体试剂或多孔粘性液体试剂；
进一步的，所述多孔可溶性固体试剂的制备方法包括以下步骤：
S1：将可溶性固体溶于其质量0.1％～100％的低沸点良溶剂中配成溶液；优选的，所述良溶剂包括但不限于乙醇、氯仿或水；
S2：用移液装置移取步骤S1获得的溶液滴于上述多孔塑料化学试剂载体上，待所述溶液完全吸附于所述载体后，得负载溶液多孔载体；优选的，所述移液装置为移液枪；
S3：在压强为1mmHg、温度为0～60℃下，真空干燥步骤S2获得的负载溶液多孔载体，待溶剂挥发完，即得多孔可溶性固体试剂；
进一步的，所述多孔可溶性固体试剂中，所述多孔塑料化学试剂载体负载的可溶性固体试剂的物质的量为0.001μmol～10.0mol；更进一步的，所述多孔塑料化学试剂载体负载的可溶性固体试剂物质的量为0.01μmol～1.0mol；更进一步的，所述多孔塑料化学试剂载体负载的可溶性固体试剂物质的量为0.001μmol、0.002μmol、0.005μmol、0.01μmol、0.02μmol、0.05μmol、0.1μmol、0.2μmol、0.5μmol、1μmol、2μmol、5μmol、10μmol、20μmol、50μmol、100μmol、200μmol、500μmol、1mmol、2mmol、5mmol、10mmol、20mmol、50mmol、100mmol、200mmol、500mmol或1mol；
进一步的，所述多孔不溶性固体试剂的制备方法包括以下步骤：
S1：将不溶性固体试剂研磨成5微米以下的粉末；
S2：将上述粉末悬浮于其质量8～50倍的有机溶剂中，获得悬浮液，然后在0～30℃下，以300～600r/min的速率边搅拌边将上述悬浮液加入上述多孔塑料化学试剂载体，充分搅拌1～24h使所述粉末充分吸附至所述载体；优选的，所述有机溶剂包括但不限于乙醇、石油醚、甲苯、四氢呋喃或二氯甲烷；
S3：将S2获得的负载不溶性固体试剂后的载体在干净的、同样的有机溶剂中以同样地速率和温度继续搅拌10～24h，以洗去所述载体表面未吸附的粉末，即得多孔不溶性固体试剂；进一步的，所述多孔不溶性固体试剂中，所述多孔塑料化学试剂载体负载的不溶性固体试剂物质的量为0.001μmol～10.0mol；更进一步的，所述多孔塑料化学试剂载体负载的不溶性固体试剂物质的量为0.01μmol～1.0mol；更进一步的，所述多孔塑料化学试剂载体负载的不溶性固体试剂物质的量为0.001μmol、0.002μmol、0.005μmol、0.01μmol、0.02μmol、0.05μmol、0.1μmol、0.2μmol、0.5μmol、1μmol、2μmol、5μmol、10μmol、20μmol、50μmol、100μmol、200μmol、500μmol、1mmol、2mmol、5mmol、10mmol、20mmol、50mmol、100mmol、200mmol、500mmol或1mol。
进一步的，所述多孔液体试剂的负载方法包括以下步骤：
S1：直接用移液装置吸取液体试剂或吸取在低沸点良溶剂中稀释至所述液体试剂质量5～100倍的液体，并将其滴于所述多孔塑料化学试剂载体上，待所述载体充分吸附上述液体试剂后，得负载液体试剂多孔载体；优选的，所述移液装置为移液枪；
S2：在压强为1mmHg、温度为0～60℃下，真空干燥10～60min步骤S2获得的负载溶液多孔载体即得多孔液体试剂；进一步的，多孔液体试剂中，所述多孔塑料化学试剂载体负载的不溶性固体试剂物质的量为0.001μmol～10.0mol；更进一步的，所述多孔塑料化学试剂载体负载的不溶性固体试剂物质的量为0.01μmol～1.0mol；更进一步的，所述确定的液体试剂物质的量为0.01μmol、0.02μmol、0.05μmol、0.1μmol、0.2μmol、0.5μmol、1μmol、2μmol、5μmol、10μmol、20μmol、50μmol、100μmol、200μmol、500μmol、1mmol、2mmol、5mmol、10mmol、20mmol、50mmol、100mmol、200mmol、500mmol或1mol。
有益效果
本发明采用上述技术方案具有以下技术效果：
提升了化学试剂载体的强度和负载量：多孔塑料，尤其是超高分子量聚乙烯(HighDensity Polyethylene，缩写为HDPE)为白色粉末或颗粒状产品。无毒，无味，结晶度为80％～90％，软化点为125～l35℃，使用温度可达110℃；硬度、拉伸强度和蠕变性均优于低密度聚乙烯；耐磨性、电绝缘性、韧性及耐寒性较好；化学稳定性好，在室温条件下，不溶于任何有机溶剂，耐酸、碱和各种盐类的腐蚀低。故将其用于制备多孔聚合物化学试剂的载体具有以下优异的技术效果：
改变了化学试剂的使用形式，例如将液体或可溶性固体试剂变成固体试剂、将粘稠液体等很难处理的试剂变为固体试剂，方便使用、便于定量的同时，使得试剂也易与其它化学试剂分离；便于运输方便，并且能减少科研人员与有毒试剂的接触；显著提升了化学试剂的机械强度；其单位质量的负载量较大，利于化学反应的进行，可以广泛应用于各类化学反应。
本发明多孔塑料载体的制备方法更为简便：通过常压下加热烧结、降温等操作即可获得多孔塑料载体；负载化学试剂方法简便：通过常温常压下的滴加吸收或搅拌即可负载化学试剂；且制备过程中并未引入对于环境不友好的溶剂，环保效果更佳。
附图说明
图1空白化学试剂载体的实物照片以及扫描SEM图
图2实施例2制备的Pd/C@tab的形貌特征
图3试剂片与试剂粉末的动力学图比较
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1制备超高分子量多孔聚乙烯化学试剂载体
方法如下：将直径为50μm、分子量大于100万的超高分子量聚乙烯粉末加入到内径为5.1、7.4或9mm、高为2.5mm或4mm的圆柱状不锈钢磨具中，在常压下加热至150℃，然后迅速降温至室温，退模后即得。制备获得的超高分子量多孔聚乙烯化学试剂载体硬度高，在搅拌过程中几乎不破裂，但可以用锋利的刀切割制备成各种形状，本发明实施例1制备获得两种直径的催化剂载体实物照片如图1a所示；将获得载体置于扫描电镜下，获得的SEM图像如图1b所示。
实施例2定量制备多孔聚乙烯化学试剂片
(1)Pd(OAc)2试剂片的制备：称取6.74mg Pd(OAc)2溶于600μL的氯仿中混合均匀配制成Pd(OAc)2溶液，用移液枪分别精密吸取上述溶液20μL分别滴加于30个空白负载片(尺寸：直径5.1mm*高2.5mm，30毫克/片)上，充分吸收后，真空干燥后制得的试剂片中Pd(OAc)2的含量为1μmol/片。
(2)XPhos试剂片的制备：称取14.28mg XPhos溶于600μL的氯仿中混合均匀配制成XPhos溶液，用移液枪分别精密吸取上述溶液20μL分别滴加于30个空白负载片(尺寸：直径5.1mm*高2.5mm，30毫克/片)上，充分吸收后，真空干燥后制得的试剂片中XPhos的含量为1μmol/片。
(3)K3PO4试剂片的制备：称取636.80mg K3PO4溶于1.8mL的水中混合均匀，分别于30个空白负载片上(尺寸：9.0mm*4mm，150毫克/片)用移液枪滴加60μL溶液，再滴加20μL乙醇驱使水溶液被负载片吸收，真空干燥后制得的试剂片K3PO4的含量为0.1mmol/片。
(4)各种配体试剂片的制备。制备方法同上述K3PO4的制备。分别将PPh3，SPhos，XtantPhos，DPEPhos，Dppf配成相应的氯仿溶液，制备成试剂片(尺寸：直径5.1mm*高2.5mm，30毫克/片)，配体含量均为1μmol/片。
(5)叔丁醇钠试剂片的制备：制备方法同上述K3PO4的制备。称取叔丁醇钠,配成THF溶液分别制备0.05mmol/片(尺寸：直径5.1mm*高2.5mm，30毫克/片)和0.2mmol/片(尺寸：直径5.1mm*高2.5mm，30毫克/片)两种规格的试剂片。制备方法同上述K3PO4的制备。
(6)Pd/C试剂片的制备：将600.0mg微Pd/C粉末(市售，Pd含量为10wt/wt％)研磨成粒径≤5μm的粉末，然后将粉末悬浮于150ml乙醇中，然后边搅拌边加入100片(尺寸：直径5.1mm*高2.5mm，30毫克/片)多孔塑料化学试剂载体，所述搅拌速率为500r/min，所述搅拌温度为室温，所述搅拌时间为24h；充分搅拌使试剂充分负载至所述载体，直到悬浮液变澄清，然后取出负载后的实际再在干净的100mL乙醇中以同样的速率和温度继续搅拌12h，以洗去所述催化剂载体表面上多余的试剂，即得Pd/C@tab，所述载体对微米Pd/C的最大负载量为2μmol/片；制备获得定量Pd/C@tab照片如图2所示。
实施例3.Suzuki反应及其动力学研究
在一支反应管中加入粉末试剂底物4-溴苯甲醚(0.1mmol,18.7mg)，1-萘硼酸(0.1mmol,17.2mg)，以及实施例2制备的醋酸钯试剂片(1片)，XPhos试剂片(2片)，K3PO4试剂片(2片)，乙醇水溶液(乙醇：水体积比为9：1)1.5mL；在另一支反应管中加入粉末试剂4-溴苯甲醚(0.1mmol,18.7mg)，1-萘硼酸(0.1mmol,17.2mg)，醋酸钯(1μmol，0.22mg),XPhos(2μmol，0.95mg),K3PO4(0.2mmol，42.45mg)，乙醇水溶液(乙醇：水体积比为9：1)1.5mL。两支反应管同时在60℃下搅拌，在反应分别进行15min、30min、1h、2h、4h时，分别取反应液用GC-MS检测反应转化率，得到反应动力学图(如图3所示)，从图3中可以看出，采用醋酸钯试剂片、XPhos试剂片以及K3PO4试剂片和醋酸钯、XPhos以及K3PO4粉末分别进行反应，两个反应在同一时刻转化率极其相似，证明试剂片的引入没有影响试剂的释放和反应的速率。
实施例4负载其它化学试剂的负载片
使用非常相似的方法，制备了如表1所示的试剂片：
实施例5：烯烃复分解反应
向反应瓶中加入1-辛烯的二氯甲烷(缩写为DCM)(2mL，0.1mol/L)溶液，丙烯酸乙酯(173.9μL，1.6mmol)和2片Grubbs催化剂负载片(0.001mmol/片)。将混合物在室温在氩气下搅拌5小时。取出片剂后，将反应混合物在高真空泵上蒸发，并将粗产物通过硅胶柱上的快速色谱法纯化(洗脱剂：己烷/乙酸乙酯v/v＝20:1)，得到化合物2-烯壬乙酯(35.4mg，产率为96％)。经过核磁图谱指认，化合物2-烯壬乙酯的1H-NMR(400MHz,CDCl3)δ：7.04-6.91(m,1H),5.81(d,J＝15.7Hz,1H),4.19(q,J＝6.8Hz,2H),2.19(d,J＝6.5Hz,2H),1.50-1.20(m,11H),0.89(t,J＝6.8Hz,3H)。
实施例6：光延反应
向反应瓶中加入对硝基苯甲酸的THF溶液，苯乙醇(24.0μL，0.2mmol)，2片PPh3-负载片(0.2mmol/片)和2片偶氮二甲酸二乙酯负载片(DEAD-负载片，0.2mmol/片)；将混合物在室温搅拌过夜，取出片剂后，将反应混合物在高真空泵上蒸发并将粗产物通过硅胶柱上的快速色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝10:1)，得到化合物对硝基苯甲酸苯乙酯(44.1mg,产率为81％)。经过核磁图谱指认，化合物对硝基苯甲酸苯乙酯的1H NMR(400MHz,CDCl3)：δ8.28(d,J＝8.7Hz,2H),8.17(d,J＝8.7Hz,2H),7.40-7.19(m,5H),4.59(t,J＝6.9Hz,2H),3.11(t,J＝6.9Hz,2H)。
实施例7：三氟甲基化反应
向反应瓶中添加苯甲酸甲酯(25.0μL，0.2mmol)，三氟甲基三甲基硅烷(缩写为TMS-CF3，32.5μL，0.23mmol)和1片氟化铯负载片(CsF-负载片，0.002mmol/片)，将混合物在室温搅拌，并通过19F NMR监测；完成后，将所得产物用乙醚(10mL)萃取，除去乙醚以得到产物三氟苯乙酮(44.1mg,产率为81％)，该产物经过核磁图谱指认，1H NMR(400MHz,CDCl3)δ8.08(d,J＝8.4Hz,2H),7.72(t,J＝6.9Hz,1H),7.56(t,J＝7.9Hz,2H)；19F NMR(400MHz,CDCl3)δ71.42(s)。
实施例8：环合反应
向反应瓶中加入无乙醇氯仿(0.5mol/L，1mL)，苯乙烯(23.0μL，0.2mmol)，和硝基甲基苯，1片1,4-二氮杂二环[2.2.2]辛烷(DABCO-负载片，0.1mmol/片)，将混合物在60℃下搅拌40小时。然后除去溶剂，将残余物溶解在乙醚(10mL)中，并用水(3×10mL)、NaOH(1M，3×10mL)和盐水(3×10mL)洗涤，有机层经Na2SO3干燥并浓缩；粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝10:1)，得到产物3,5-二苯基-4,5-二氢异恶唑呤(35.7mg,产率为80％)。该产物经过核磁图谱指认，1H NMR(400MHz,CDCl3)δ7.73-7.66(m,2H),7.45-7.29(m,8H),5.74(dd,J＝11.0,8.2Hz,1H),3.78(dd,J＝16.6,11.0Hz,1H),3.35(dd,J＝16.6,8.2Hz,1H).
实施例9：取代反应
向反应瓶中加入1'-溴-2'，3'，6'，2、3、4、6-庚基-邻-乙酰基-α-d-乳糖的乙腈溶液(0.1mol/L，2mL)，乙二醇(278.8μL，5mmol)和4片对甲苯磺酸银(AgOTs-负载片，0.1mmol/片)，将混合物在室温搅拌3小时，过滤固体后，蒸发溶剂，并将粗产物溶于乙酸乙酯(乙酸乙酯，5mL)，用水(3×5mL)洗涤溶液，并用乙酸乙酯(10mL)反萃取水层，合并的有机层经无水无水硫酸钠干燥并浓缩，粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝1：1)，得产物如式24所示的二糖(86.5mg,产率为65％)。该产物经过核磁图谱指认，该产物经过核磁图谱指认，1H NMR(400MHz,CDCl3)δ5.35(d,J＝3.4Hz,1H),5.21(t,J＝9.3Hz,1H),5.12(dd,J＝10.4,7.8Hz,1H),5.00-4.87(m,2H),4.58-4.45(m,3H),4.09(ddd,J＝23.6,11.7,5.2Hz,4H),3.92-3.82(m,2H),3.82-3.63(m,5H),2.16(s,3H),2.13(s,3H),2.08-2.03(m,12H),1.97(s,3H)。
实施例10：氢化反应
向反应瓶中，N-苄氧羰基-L-苯丙氨酸(N-Cbz-L-苯丙氨酸)的乙醇溶液溶液(0.1mol/L，2mL)，加入6片Pd/C-负载片(0.001mmol/片剂)。将混合物在H 2气氛(气球)下于室温搅拌4小时。取出片剂后，将合并的溶液真空浓缩，得到纯产物，无需进一步纯化即可得到产物苯丙氨酸(29.5mg,89％)。该产物经过核磁图谱指认，1H NMR(400MHz,D2O)δ7.44-7.26(m,5H),3.96(dd,J＝8.0,5.2Hz,1H),3.26(dd,J＝14.5,5.2Hz,1H),3.10(dd,J＝14.5,8.0Hz,1H)。
实施例5.还原胺化反应
向反应瓶中，将四氢-4H-吡喃-4-酮(18.5μL，0.2mmol)，苄胺(24.0μL，0.22mmol)和异丙醇钛(94.7μL，0.32mmol)加入并搅拌。在室温下3小时。之后，加入3片NaBH4-负载片(0.1mmol/片)。将混合物搅拌24小时。取出片剂后，加入氢氧化钠溶液，并将混合物用DCM(3×5mL)萃取，然后用盐水(5mL)洗涤。合并的有机层经无水无水硫酸钠干燥并浓缩。粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝5:1)，得到N-苄基-四氢吡喃-4-胺(35.8mg,产率为93％)。该产物经过核磁图谱指认，1H NMR(CDCl3)δ7.22-7.36(m,5H),3.98(d,J＝11.7Hz,2H),3.83(s,2H),3.38(t,J＝11.6Hz,2H),2.67-2.77(m,1H)),1.86(d,J＝11.5Hz,2H),1.38-1.50(m,2H)。
实施例5.缩合反应
向反应瓶中添加丙炔酸(13.5μL，0.22mmol)，N-甲基苯胺(21.7μL，0.2mmol)，1片二环己基碳二亚胺负载片(DCC-负载片，0.15mmol/片)和2片4-二甲氨基吡啶(DMAP-负载片，0.01mmol/片剂)和DCM(2mL)。将混合物在室温搅拌过夜。过滤固体后，将反应混合物在高真空泵上蒸发并将粗产物通过硅胶柱上的快速色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝10:1)，得到产物N-苯基-N-甲基-丙炔酸胺(27.8mg,产率为87％)。该产物经过核磁图谱指认，1H NMR(400MHz,CDCl3)δ7.45-7.36(m,3H),7.29(dd,J＝7.7,1.5Hz,2H),3.34(s,3H),2.81(s,1H)。
实施例5.还原反应
向反应瓶中添加雌酮的乙醇溶液(0.1mol/L，2mL)和2片NaBH4-负载片(0.1mmol/片剂)。将混合物在室温搅拌2h。取出片剂后，加入水(10mL)，并用乙酸乙酯(3×5mL)萃取水相。合并的有机层经无水硫酸钠干燥并浓缩。粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝2:1)，得到甾醇(49.5mg,产率为91％)。该产物经过核磁图谱指认，1H NMR(400MHz,Methanol-d4)δ7.07(d,J＝8.4Hz,1H),6.56-6.43(m,2H),3.65(t,J＝8.6Hz,1H),2.76(d,J＝5.0Hz,2H),2.29(d,J＝15.8Hz,1H),2.07-1.81(m,3H),1.69(dd,J＝7.0,2.6Hz,1H),1.57-1.13(m,8H),0.77(s,3H)。
实施例5.烯丙基化反应
向反应瓶中加入4-甲氧基苯酚36的DMF溶液(0.1mol/L，2mL)，烯丙基溴(20.8μL，0.24mmol)和2片K2CO3-负载片(0.2mmol/片).将混合物在70℃下搅拌16小时。取出片剂后，将反应用水(5mL)淬灭，并用乙醚(2×5mL)萃取。合并的有机萃取物用盐水(2×5mL)洗涤，经无水硫酸钠干燥并浓缩。粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝10:1)，得到对甲氧基苯酚烯丙基醚(32.1mg,产率为98％)。该产物经过核磁图谱指认，1HNMR(400MHz,CDCl3)δ6.88-6.79(m,4H),6.05(tdd,J＝17.3,10.6,5.3Hz,1H),5.40(ddd,J＝17.3,3.0Hz,1.3Hz,1H),5.27(ddd,J＝10.6,3.0Hz,1.3Hz,1H),4.48(td,J＝1.3and5.3Hz,2H),3.76(s,3H)。
实施例5.缩合反应
向反应瓶中注入双环[2.2.1]庚-5-烯-2-甲醛(23.7μL，0.2mol)，丙二腈(12.6μL，0.2mmol)，1片吡啶负载片(Py-载片，0.04mmol/片)，冰醋酸(2mL)。将混合物在室温搅拌过夜。取出片剂后，将反应用水(5mL)淬灭，并用乙酸乙酯(3×5mL)萃取。用水(10mL)洗涤合并的有机萃取物，经无水硫酸钠干燥并浓缩。粗产物通过硅胶柱色谱法纯化(洗脱液：己烷/乙酸乙酯v/v＝10:1)，得到产物双环[2.2.1]-5-庚烯-2-亚甲基丙二氰基(32.5mg,88％)。该产物经过核磁图谱指认，1H NMR(400MHz,400MHz,CDCl3)δ6.85(d,J＝11.0Hz,1H),6.36(dd,J＝5.7,3.1Hz,1H),6.00(dd,J＝5.7,2.8Hz,1H),3.37-3.28(m,1H),3.07(d,J＝15.7Hz,2H),2.19(ddd,J＝12.4,9.1,3.5Hz,1H),1.60(d,J＝8.1Hz,1H),1.42(d,J＝8.7Hz,1H),0.96(ddd,J＝12.2,3.8,2.6Hz,1H)。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (3)

1.一种多孔塑料化学试剂载体，其特征在于，所述多孔塑料化学试剂载体为药片样圆柱结构，其孔容为0.3～0.6ml/g，且其总孔隙面积为20～25m2/g，其平均孔径为70～80nm，其在0.5～1psi下的体积密度0.5～1.0g/ml，其孔隙率为20～30％；且所述的药片样圆柱结构多孔塑料化学试剂载体规格为：内径5.1～9mm且高2.5～4mm；且所述的药片样圆柱结构多孔塑料化学试剂载体的重量为30mg/片或150mg/片；且所述多孔塑料为超高分子量多孔聚乙烯；
多孔塑料化学试剂载体的制备方法包括以下步骤：将多孔塑料粉末加入到圆柱状不锈钢磨具中，在常压下加热至140～155℃，然后迅速降温至室温，退模后即得，其中，所述多孔塑料粉末的直径为10～100μm，且其分子量大于100万，所述圆柱状不锈钢磨具的内径为5.1～9mm，且高为2.5～4mm。
2.一种多孔塑料化学试剂，其特征在于，权利要求1所述多孔塑料化学试剂载体以及其负载的化学试剂；所述多孔塑料化学试剂载体负载的化学试剂的物质的量为0.01μmol～1.0mol/片；所述多孔塑料化学试剂为多孔可溶性固体试剂、多孔不溶性固体试剂或多孔液体试剂；
其中，
所述多孔可溶性固体试剂的制备方法包括以下步骤：S1：将可溶性固体溶于其质量0.1％～100％的溶剂乙醇、氯仿或水中配成溶液；S2：用移液装置移取步骤S1获得的溶液滴于上述多孔塑料化学试剂载体上，待所述溶液完全吸附于所述载体后，得负载溶液多孔载体；S3：在压强为1mmHg、温度为0～60℃下，真空干燥步骤S2获得的负载溶液多孔载体，待溶剂挥发完，即得多孔可溶性固体试剂；
所述多孔不溶性固体试剂的制备方法包括以下步骤：S1：将不溶性固体试剂研磨成5微米以下的粉末；S2：将上述粉末悬浮于其质量8～50倍的有机溶剂乙醇、石油醚、甲苯、四氢呋喃或二氯甲烷中，获得悬浮液，然后在0～30℃下，以300～600r/min的速率边搅拌边将上述悬浮液加入上述多孔塑料化学试剂载体，充分搅拌1～24h使所述粉末充分吸附至所述载体；S3：将S2获得的负载不溶性固体试剂后的载体在干净的、同样的有机溶剂中以同样地速率和温度继续搅拌10～24h，以洗去所述载体表面未吸附的粉末，即得多孔不溶性固体试剂；
所述多孔液体试剂的制备方法包括以下步骤：S1：直接用移液装置吸取液体试剂或吸取在低沸点良溶剂中稀释至所述液体试剂质量5～100倍的液体，并将其滴于所述多孔塑料化学试剂载体上，待所述载体充分吸附上述液体试剂后，得负载液体试剂多孔载体；S2：在压强为1mmHg、温度为0～60℃下，真空干燥10～60min步骤S2获得的负载溶液多孔载体即得多孔液体试剂。
3.根据权利要求2所述的多孔塑料化学试剂，其特征在于，所述移液装置为移液枪。
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