CN111632599A - 一种磁性核壳材料催化剂的制备方法及其应用 - Google Patents
一种磁性核壳材料催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种磁性核壳材料催化剂制备方法及其应用，其特点是以葡萄糖和Fe3O4为原料制备核壳材料，在氯磺酸/二氯甲烷溶液和三氯化铁饱和溶液依次浸渍后经分离、干燥，制得Fe3O4@C@Fe（Ⅲ）催化剂，将其用于HMF参与的Ferrier重排反应合成2,3‑不饱和氧糖苷。本发明与现有技术相比具有工艺简单、操作方便、收率高、生产成本低、反应条件温和、可循环使用等优点，较好的解决了催化剂重金属残留，反应局限在乙酰基保护的葡萄糖烯而其它糖烯底物则很少的等问题，是一种绿色环保、经济高效且很有应用前景的2,3‑不饱和氧糖苷制备新方法。
Description
技术领域
本发明涉及生物医药中间体合成技术领域，具体地说是一种磁性核壳材料催化剂的制备方法及其在5-羟甲基糠醛(HMF)进行糖环修饰合成2,3-不饱和氧糖苷的应用。
背景技术
2,3-不饱和糖苷是在合成一些具有生物活性的分子时常见的中间体，其吡喃环中的双键可以通过氢化、环氧化、二羟基化或氨基羟化反应进行转化。Ferrier重排反应则是一种合成2,3-不饱和糖苷的高效途径。用于Ferrier重排反应的各类催化剂，如作为质子酸的H3PO4，作为路易斯酸的FeCl3、InCl3、ZnBr2等，以及作为氧化剂的K5CoW12O40·3H2O等，这些传统的催化剂多具有一定的局限性和缺点，例如:催化剂易存在重金属残留问题、反应局限在乙酰基保护的葡萄糖烯而其它糖烯底物很少、反应时间长等(AM Gómez.,F,Lobo.,Curiel.,JC,López.Eur.J.Org.Chem.2013,7221-7262)。糖类在高温条件下会聚合成多环芳烃结构，可以在纳米粒子外面形成碳壳。在碳壳上可以再通过一些反应修饰我们所需要的活性官能团如羟基、磺酸基等(Atsushi,T.,Masakazu,T.,Mai,O.,et al.Nature.2005,438.)，从而得到新型的纳米核壳材料。
5-羟甲基糠醛(HMF)，作为一种多功能的重要中间体，可以用于合成一系列具有呋喃环结构的化合物。在生物应用领域，HMF拥有良好的生物活性，是中药山茱萸和熟地黄中治疗贫血和糖尿病的有效成分(Rosatella,A.A.,Simeonov,S.P.,Frade,R.F.M.,Afonso,C.A.M.Green Chem.2011,754)，对其进行修饰改造是现代药物化学的研究重点。
综上所述，现有技术的2,3-不饱和糖苷的合成工艺复杂、反应时间长，催化剂易存在重金属残留等问题，反应局限在乙酰基保护的葡萄糖烯而其它糖烯底物则很少，且催化剂不能回收利用，不符合绿色化学的原子经济性的要求。基于这样的考虑，研制一种高效、可循环利用的核壳材料催化剂(Fe3O4@C@Fe(Ⅲ))，可以有效地催化Ferrier重排反应。
发明内容
本发明的目的是针对现有技术的不足而提供的一种磁性核壳材料催化剂的制备方法及其应用，采用纳米Fe3O4为核壳材料与葡萄糖混合，高温反应后将其依次在氯磺酸/二氯甲烷溶液和三氯化铁/二氯甲烷溶的溶液中浸渍，得到的磁性催化剂Fe3O4@C@Fe(Ⅲ)用于5-羟甲基糠醛(HMF)参与的Ferrier重排反应，进行糖环修饰合成2,3-不饱和氧糖苷，制备工艺简单，操作方便，反应条件温和、速度快，易于回收利用，较好的解决了催化剂重金属残留，反应局限在乙酰基保护的葡萄糖烯而其它糖烯底物则很少的等问题，且催化剂可循环使用，是一种绿色环保、经济高效且很有应用前景的2,3-不饱和氧糖苷制备新方法。
实现本发明目的的具体技术方案是：一种磁性核壳材料催化剂制备方法，其特点是以葡萄糖和Fe3O4为原料制备核壳材料，将其置于氯磺酸/二氯甲烷溶液(0.2～0.5mL/50mL)中浸渍4～48h，洗涤干燥后置于三氯化铁饱和溶液中浸渍2～48h，然后用二氯甲烷洗涤、磁力分离、干燥后为催化剂Fe3O4@C@Fe(Ⅲ)。
所述三氯化铁饱和溶液的溶剂为乙醇或二氯甲烷，其溶质为三氯化铁或六水合三氯化铁。
所述于氯磺酸/二氯甲烷溶液中浸渍时间优选10～12h。
所述三氯化铁饱和溶液优选溶剂为二氯甲烷。
一种磁性核壳材料催化剂的应用，其特点是以5-羟甲基糠醛(HMF)为受体，以保护基的糖烯为给体，二氯甲烷、二氯乙烷、乙腈或四氢呋喃为溶剂，在催化剂Fe3O4@C@Fe(Ⅲ)的催化作用下，按下述反应方程式进行2,3-不饱和氧糖苷合成的Ferrier重排反应：
所述重排反应温度为0～70℃，反应时间为8～210min，反应结束后经磁性分离、提纯，得产物为2,3-不饱和氧糖苷，所述给体与受体、催化剂和溶剂的摩尔体积比为1mol:0.5～1.5mol:0.05～0.5mol:2L；所述保护基为乙酰基、苯甲酰基或苄基；所述糖烯为葡萄糖烯、木糖烯、鼠李糖烯或乳糖烯。
所述溶剂优选二氯乙烷；所述反应温度优选30～60℃；所述给体与受体的摩尔比优选1:1.2～1.5；所述给体与催化剂的摩尔比优选1:0.1～0.3；所述催化剂循环使用四次后，反应时间增长、产率基本不变。
本发明与现有技术相比具有工艺简单、操作方便、收率高、生产成本低、反应条件温和、可循环使用等优点，较好的解决了催化剂重金属残留，反应局限在乙酰基保护的葡萄糖烯而其它糖烯底物则很少的等问题，是一种绿色环保、经济高效且很有应用前景的2,3-不饱和氧糖苷制备新方法。
具体实施方式
本发明将D-葡萄糖、蔗糖或淀粉和Fe3O4混匀，加入去离子水置于反应釜中高温反应，磁力分离、洗涤干燥后置于氯磺酸/二氯甲烷溶液中浸渍，然后磁力分离、洗涤，干燥后置于三氯化铁/二氯甲烷饱和溶液中浸渍，磁力分离即可得到催化剂Fe3O4@C@Fe(Ⅲ)。
将保护基糖烯和5-羟甲基糠醛溶于有机溶剂，在催化剂Fe3O4@C@Fe(Ⅲ)下进行Ferrier重排反应，制备的2,3-不饱和氧糖苷按下述反应结构式进行：
以下将通过具体的实施例对本发明做进一步的阐述：
实施例1
1)称取5g(0.028mol)D-葡萄糖与500mg(0.002mol)Fe3O4混合均匀，加入60mL去离子水置于反应釜中，在180℃温度下反应6h，反应物用去离子水(5mL)、二氯甲烷(5mL)各洗涤两次后磁力分离和干燥，制得365mg产物为Fe3O4@C。
2)称取100mg上述制备的Fe3O4@C于氯磺酸/二氯甲烷溶液(0.3mL/50mL)中浸渍12h，用二氯甲烷(5mL)洗涤两次后磁力分离，干燥后将其置于三氯化铁/二氯甲烷饱和溶液(20mL)中浸渍24h，然后用二氯甲烷(5mL)洗涤两次，磁力分离和干燥后，得产物为催化剂Fe3O4@C@Fe(Ⅲ)。
实施例2
称取27.2mg(0.1mmol)全乙酰化葡萄糖烯(0.1mmol)、15.1mg(0.12mmol)5-羟甲基糠醛(HMF)和5mg(0.01mmol)实施例1制备的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(10min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物27.8mg为2,3-不饱和葡萄糖苷，其产率为82.3％。
对上述所得产物进行1H NMR分析，确认为目标产物，其结构表征数据如下：
1H NMR(500MHz,CDCl3)δ9.63(s,1H),7.22(d,J＝3.4Hz,1H),6.56(d,J＝3.4Hz,1H),5.93(d,J＝10.1Hz,1H),5.86–5.83(m,1H),5.35(dd,J＝9.2,0.7Hz,1H),5.16(s,1H),4.79(d,J＝13.3Hz,1H),4.66(d,J＝13.2Hz,1H),4.26(dd,J＝12.1,5.2Hz,1H),4.18(dd,J＝12.1,2.2Hz,1H),4.15–4.10(m,1H),2.11(s,3H),2.09(s,3H)。
实施例3
称取32.4mg(0.1mmol)全苯甲酰化木糖烯、15.1mg(0.12mmol)5-羟甲基糠醛(HMF)和5mg(0.01mmol)实施例1制备的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(8min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物31.5mg为2,3-不饱和木糖苷，其产率为81.0％。
对上述所得产物进行1H NMR分析，确认为目标产物，其结构表征数据如下：
1H NMR(500MHz,CDCl3)δ9.64(s,1H),8.05(dd,J＝16.4,8.2Hz,2H),7.56(d,J＝7.4Hz,1H),7.44(t,J＝7.5Hz,2H),7.22(s,1H),6.57(s,1H),6.30–6.18(m,1H),6.10(dd,J＝13.4,10.8Hz,1H),5.25–5.19(m,1H),5.15(d,J＝24.3Hz,1H),4.81(dd,J＝13.3,8.2Hz,1H),4.67(d,J＝13.2Hz,1H),4.27(d,J＝12.9Hz,1H),4.01(d,J＝12.7Hz,1H)。
实施例4
称取21.4mg(0.1mmol)全乙酰化鼠李糖烯、15.1mg(0.12mmol)HMF和5mg(0.01mmol)实施例1制备的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(10min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物24.2mg为2,3-不饱和鼠李糖苷，其产率为86.5％。滤液浓缩提纯后得到的产物24.2mg，产率86.5％。
对上述所得产物进行1H NMR分析，确认为目标产物，其结构表征数据如下：
1H NMR(500MHz,CDCl3)δ9.63(s,1H),7.21(s,1H),6.54(s,1H),5.85(dd,J＝40.3,9.9Hz,2H),5.07(d,J＝12.2Hz,2H),4.76(d,J＝13.4Hz,1H),4.65(d,J＝13.2Hz,1H),4.02–3.93(m,1H),2.08(s,3H),1.20(d,J＝5.9Hz,3H)。
实施例5
称取49.8mg(0.1mmol)全乙酰化乳糖烯、15.1mg(0.12mmol)HMF和5mg(0.01mmol)实施例1制备的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(2h)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物44.1mg为2,3-不饱和乳糖苷，其产率为78.2％。
对上述所得产物进行1H NMR分析，确认为目标产物，其结构表征数据如下：
1H NMR(500MHz,CDCl3)δ9.62(s,1H),7.21(d,J＝3.3Hz,1H),6.54(d,J＝3.5Hz,1H),6.15(d,J＝10.3Hz,1H),5.76(d,J＝9.9Hz,1H),5.39(d,J＝2.8Hz,1H),5.21(dd,J＝9.8,8.4Hz,1H),5.10(s,1H),5.00(dd,J＝10.4,3.3Hz,1H),4.76(d,J＝13.6Hz,1H),4.63(d,J＝13.5Hz,1H),4.57(d,J＝8.0Hz,1H),4.28(d,J＝11.7Hz,1H),4.21–4.16(m,2H),4.10(dd,J＝11.3,6.6Hz,2H),4.04(dd,J＝8.1,4.2Hz,1H),3.95–3.90(m,1H),2.16(s,3H),2.13(s,3H),2.08(s,3H),2.05(s,3H),1.98(s,3H)。
实施例6(催化剂的第一次循环使用)
称取27.2mg(0.1mmol)乙酰化葡萄糖烯、15.1mg(0.12mmol)HMF和5mg(0.01mmol)回收利用的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(25min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物27.5mg为2,3-不饱和葡萄糖苷，其产率为81.4％。所述回收利用的催化剂是将实施例1中磁力分离出的催化剂经DCE(2mL)洗涤、干燥后回收的催化剂。
实施例7(催化剂的第二次循环使用)
称取27.2mg(0.1mmol)乙酰化葡萄糖烯、15.1mg(0.12mmol)HMF和5mg(0.01mmol)回收利用的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(40min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物27.8mg为2,3-不饱和葡萄糖苷，其产率为82.3％。所述催化剂是将实施例6中磁力分离出的催化剂经DCE(2mL)洗涤、干燥后回收的催化剂。
实施例8(催化剂第三次循环使用)
称取27.2mg(0.1mmol)乙酰化葡萄糖烯、15.1mg(0.12mmol)HMF和5mg(0.01mmol)回收利用的催化剂Fe3O4@C@Fe(Ⅲ)混匀，加入DCE(2mL)溶解均匀后在40℃温度下进行Ferrier重排反应，TLC点板(PE:EA＝1:1)监测反应完全(60min)，磁力分离出催化剂，其滤液经浓缩、提纯后得产物27.6mg为2,3-不饱和葡萄糖苷，其产率为81.7％。所述催化剂是将实施例7中磁力分离出的催化剂经经二氯乙烷淋洗、干燥，再生的催化剂经3次循环使用，仍可保持较好的催化效果。
通过上述催化剂的回收利用活性实验，催化剂循环使用四次后，其反应时间虽然有所增长，但产率基本不变，说明回收使用的催化剂仍有较好的催化活性。以上只是对本发明作进一步地说明，并非用于限制本专利，凡为本专利等效实施，均应包含于本专利的权利要求范围之内。
Claims (4)
1.一种磁性核壳材料催化剂制备方法，其特征在于将纳米Fe3O4与葡萄糖、蔗糖或淀粉按1：10～20重量比混合，在100～200℃温度下反应4～8h，然后用去离子水和二氯甲烷洗涤后进行分离和干燥，得产物为Fe3O4@C，将其置于氯磺酸/二氯甲烷溶液中浸渍4～48h后用二氯甲烷洗涤，磁力分离干燥后置于三氯化铁饱和溶液中，浸渍2～48h后用二氯甲烷洗涤，磁力分离、干燥后为催化剂Fe3O4@C@Fe(Ⅲ)。
2.根据权利要求1所述磁性核壳材料催化剂制备方法，其特征在于氯磺酸/二氯甲烷溶液的配比为0.2～0.5mL/50mL。
3.根据权利要求1所述磁性核壳材料催化剂制备方法，其特征在于所述三氯化铁饱和溶液的溶剂为乙醇或二氯甲烷，其溶质为三氯化铁或六水合三氯化铁。
4.一种权利要求1所述磁性核壳材料催化剂制备方法制备的催化剂的应用，其特征在于将保护基糖烯和5-羟甲基糠醛溶于有机溶剂，在催化剂Fe3O4@C@Fe(Ⅲ)的催化作用下，按下述反应结构式进行2,3-不饱和氧糖苷合成制备的Ferrier重排反应：
所述重排反应温度为0～70℃，反应时间为8～210min，反应结束后经磁性分离、提纯，得产物为2,3-不饱和氧糖苷，所述给体与受体、催化剂和有机溶剂的摩尔体积比为1mol:0.5～1.5mol:0.05～0.5mol:2L；所述保护基为乙酰基、苯甲酰基或苄基；所述糖烯为葡萄糖烯、木糖烯、鼠李糖烯或乳糖烯；所述有机溶剂为二氯甲烷、二氯乙烷、乙腈或四氢呋喃。
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