CN105348428B - 一种交联型聚合催化剂的制备方法及其应用 - Google Patents
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Abstract
本发明公开了一种交联型聚合催化剂的制备方法及其应用,其特点是采用金鸡纳碱与乙烯基苯的衍生物合成分子中带有乙烯基苯的中间化合物,然后与交联剂二乙烯基苯在引发剂的作用下聚合形成聚合物催化剂,该催化剂用于β‑羰基酯与氯代试剂的不对称α‑氯代催化反应,催化活性高,催化剂易分离和循环使用。本发明与现有技术相比具有制备简单,操作容易,后处理容易,原料利用率高,优化反应条件,降低反应要求,尤其使用在β‑羰基酯的不同碳上构建手性中心得到的化合物,在药物化学以及医药中间体化合物的研究中具有重要的现实意义。
Description
技术领域
本发明涉及催化剂及有机催化应用技术领域,具体地说是一种交联型聚合催化剂的制备方法及其应用。
背景技术
自金鸡纳碱被研究者运用在有机催化反应中起,此类有机小分子就被开发并应用在不同类型的反应中。从催化剂的类型来看,可以分为均相催化剂和非均相催化剂,而非均相的催化剂大都是将有效的均相催化剂固载在固体材料上,如SBA-15、FDU等介孔或其他材料。但是催化剂的固载量总是有限的,催化剂的催化性能也不可能完全保持不变,改变催化剂的固载类型,也是优化反应的一条途径。多相催化剂与传统的均相催化剂相比,催化性能上可能无法完全与之媲美,但是也有许多均相催化剂所没有的优点,比如,用量少,浪费小,污染少,可重复使用等等,绿色化学也越来越受到人们的重视。
现有技术的多相固载型催化剂固载量低,收率不高,存在着催化剂容易失活,催化剂用量大,产品分离困难,不能回收与循环使用,而且污染环境,制备成本高。
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交联型聚合催化剂的制备方法及其应用,采用对金鸡纳碱9-位羟基的修饰构造出乙烯基苯衍生物,在自由基引发剂的作用下进一步与二乙烯基苯反应得到聚合型催化剂,交联聚合物制备简单,操作容易,再结合多相催化剂的诸多优点,将小分子有机催化剂与交联剂聚合,形成聚合型多相催化剂运用在不对称反应中,合成路线短,后处理容易,原料利用率高,大大提高了催化剂的稳定性,拓展催化剂的运用范围,优化反应条件,降低反应要求。
实现本发明目的的具体技术方案是:一种交联型聚合催化剂的制备方法,其特点是该方法按下述结构反应式进行:
第一步:将对乙烯基苯甲酸和4-二甲氨基吡啶溶于二氯甲烷,然后分别加入1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和奎尼丁,在常温下进行12~24h的酯化反应,反应结束后旋干溶剂,由二氯甲烷和蒸馏水进行分液,分液后的水相用二氯甲烷萃取,合并有机相后用饱和食盐水萃取,萃取的有机相经干燥、过滤、浓缩和硅胶柱层析得淡黄色油状化合物为催化剂前体;所述乙烯基苯甲酸与4-二甲氨基吡啶、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、奎尼丁和二氯甲烷的摩尔比为1:0.3~0.5:1.2~2.5:1.0~1.3:50~180;所述1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDCI)分三次加入,每次间隔10~15分钟。
第二步:将上述催化剂前体与二乙烯基苯和偶氮二异丁腈按1:1~4:0.01~0.15的摩尔比混合,在氩气保护下加入甲醇并在65~85℃温度下回流12~24h进行交联聚合反应,反应结束后滤出的固体分别用丙酮、乙腈和DMF浸没,洗涤后得产物为交联型聚合金鸡纳碱衍生物催化剂,所述催化剂前体与甲醇的摩尔比为1:25~125。
一种交联型聚合催化剂的应用,其特点是该催化剂用于β-羰基酯与氯代试剂按下述反应结构式进行不对称α-氯代催化反应:
所述不对称α-氯代催化反应为β-羰基酯与催化剂和碳酸氢钠按摩尔比为1:0.03~0.15:1.0~1.8混合后溶于乙酸乙酯中,在25~-40℃温度下搅拌10分钟后加入氯代试剂进行不对称α-氯代催化反应,反应结束后滤出催化剂并用蒸馏水分液,分液后的水相用乙醚萃取,合并有机相后用饱和食盐水萃取,萃取的有机相经干燥、过滤、浓缩和硅胶柱层析得产物为α-氯代β-羰基酯;所述β-羰基酯与乙酸乙酯的摩尔比为1:50~100。
本发明与现有技术相比具有催化活性高,催化剂易分离回收和再次循环使用的优点,交联聚合物制备简单,操作容易,结合多相催化剂的诸多优点,将小分子有机催化剂与交联剂聚合,形成聚合型多相催化剂运用在不对称反应中,合成路线短,后处理容易,原料利用率高,大大提高了催化剂的稳定性,拓展催化剂的运用范围,优化反应条件,降低反应要求,尤其使用在β-羰基酯的不同碳上构建手性中心得到的化合物,在药物化学以及医药中间体化合物的研究中具有重要的现实意义。
具体实施方式
通过以下具体实施例对本发明作进一步的详细说明。
实施例1
第一步:称取2.04g对乙烯基苯甲酸与0.52g4-二甲氨基吡啶(DMAP)溶于20ml二氯甲烷,然后分三次加入6.6g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDCI),每次间隔15分钟,最后加入5.36g奎尼丁(Cinchonidine)固体,在常温下进行12h的酯化反应,反应结束后旋干溶剂,加20ml二氯甲烷和等体积的蒸馏水分液,分液后的水相用40ml二氯甲烷分两次萃取,合并有机相后用30ml饱和食盐水萃取一次,萃取的有机相用无水硫酸钠干燥后,经过滤、浓缩和硅胶柱层析(EA:PE=1:5)得淡黄色油状化合物为催化剂前体,其产率为86%。
第二步:称取0.91g上述制备的催化剂前体与0.52g二乙烯基苯和0.043g偶氮二异丁腈(AIBN)混合,在氩气保护下加入3ml甲醇并在70℃温度下回流12h进行交联聚合反应,反应结束后滤出的固体分别用丙酮、乙腈和DMF浸没,洗涤后得产物为交联型聚合金鸡纳碱衍生物催化剂,其产率为75%。
实施例2
称取0.015g(5mol%)上述制备的催化剂与0.076gβ-酮酯(methyl1-oxo-2,3-dihydro-1H-indene-2-carboxylate)和和0.034g碳酸氢钠溶于4ml乙酸乙酯中,在-40℃下搅拌10分钟后加入0.150g氯代试剂(5,7,7-trichloroquinolin-8(7H)-one)进行下述反应结构式的不对称α-氯代催化反应:
反应完毕后滤出催化剂,加10ml蒸馏水分液,分液后的水相用等体积乙醚萃取两次,合并有机相后用饱和食盐水萃取一次,萃取的有机相经干燥、过滤、浓缩和硅胶柱层析得产物为α-氯代β-酮酯,并用高效液相色谱仪测定其对映选择性。
以上各实施例只是对本发明做进一步说明,并非用以限制本发明专利,凡为本发明等效实施,均应包含于本发明专利的权利要求范围之内。
Claims (2)
1.一种交联型聚合催化剂的制备方法,其特征在于该方法按下述反应结构式进行:
第一步:将对乙烯基苯甲酸和4-二甲氨基吡啶溶于二氯甲烷,然后分别加入1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和奎尼丁,在常温下进行12~24h的酯化反应,反应结束后旋干溶剂,由二氯甲烷和蒸馏水进行分液,分液后的水相用二氯甲烷萃取,合并有机相后用饱和食盐水萃取,萃取的有机相经干燥、过滤、浓缩和硅胶柱层析得淡黄色油状化合物为催化剂前体;所述乙烯基苯甲酸与4-二甲氨基吡啶、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、奎尼丁和二氯甲烷的摩尔比为1:0.3~0.5:1.2~2.5:1.0~1.3:50~180;所述1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐分三次加入,每次间隔10~15分钟;
第二步:将上述催化剂前体与二乙烯基苯和偶氮二异丁腈按1:1~4:0.01~0.15的摩尔比混合,在氩气保护下加入甲醇并在65~85℃温度下回流12~24h进行交联聚合反应,反应结束后滤出的固体分别用丙酮、乙腈和DMF浸没,洗涤后得产物为交联型聚合金鸡纳碱衍生物催化剂,所述催化剂前体与甲醇的摩尔比为1:25~125。
2.一种权利要求1所述方法制备的交联型聚合催化剂的应用,其特征在于该催化剂用于β-羰基酯与氯代试剂按下述反应结构式进行不对称α-氯代催化反应:
所述不对称α-氯代催化反应为β-羰基酯与催化剂和碳酸氢钠按摩尔比为1:0.03~0.15:1~1.8混合后溶于乙酸乙酯中,在25~-40℃温度下搅拌10分钟后加入氯代试剂进行不对称α-氯代催化反应,反应结束后滤出催化剂并用蒸馏水分液,分液后的水相用乙醚萃取,合并有机相后用饱和食盐水萃取,萃取的有机相经干燥、过滤、浓缩和硅胶柱层析得产物为α-氯代β-羰基酯;所述β-羰基酯与乙酸乙酯的摩尔比为1:50~100。
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