CN1171893C - 微囊包封的路易斯酸 - Google Patents

微囊包封的路易斯酸 Download PDF

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CN1171893C
CN1171893C CNB998039349A CN99803934A CN1171893C CN 1171893 C CN1171893 C CN 1171893C CN B998039349 A CNB998039349 A CN B998039349A CN 99803934 A CN99803934 A CN 99803934A CN 1171893 C CN1171893 C CN 1171893C
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lewis acid
microencapsulation
yield
catalyzer
reaction
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CN1292792A (zh
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小林修
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Abstract

本发明提供一种微囊包封的路易斯酸，其特征在于，路易斯酸是通过配价键载在有机聚合物形成的微胶囊上，作为一种新的载在聚合物上路易斯酸，以便克服常规的载在聚合物上的催化剂的技术性限制，另外，解决了在反应体系的制备、与反应产物的分离、和具有大的工业价值的路易氏酸催化剂的回收中所伴随的问题。

Description

微囊包封的路易斯酸
发明领域
本发明涉及微囊包封的路易斯酸，其中路易斯酸被限制在聚合物凝胶的网络中。该微囊包封的路易斯酸处于这样的状态，其中路易斯酸固定在聚合物胶囊的表面或内部，并被限制在确定的室中以作为有机合成的催化剂。
发明背景
载在有机聚合物上的催化剂的研制至今仍是有机合成的一个很重要的题目。其原因是，载在有机聚合物上的催化剂在制备和与反应产物的分离方面都是非常经济的，并且其工业用途也是所希望的。而且，虽然迄今为止已经报道了某些载在聚合物上的催化剂，但是与无载体催化剂相比这样的催化剂的活性是低的，并且高活性的载在有机聚合物上的催化剂是很难制得的。
另一方面，注意力应放在路易斯酸上，因为其特有的催化活性和反应选择性，另外，路易斯酸在模塑(molder)条件下促进了催化反应，因此，认为路易斯酸在工业上是非常有用的。然而，路易斯酸在水溶液中分解，因此难以回收和再循环，并且这些事实是载在聚合物上的路易斯酸催化剂所共有的。例如，虽然载在交联有机聚合物上的氯化铝催化剂是已知的，并且在使用一次之后可容易地从反应体系回收，但是使用两次或更多次之后就难以从反应体系回收催化剂，而使其不可能再循环。
因此，常规路易斯酸催化剂在反应体系的制备、与反应产物的分离，以及其回收和再循环方面并不一定是容易的。载在有机聚合物上的催化剂也难以回收和再循环，从而使它的应用是不经济的。
因此，本发明的目的是克服载在聚合物上的常规催化剂在技术上的限制，另外，解决了在反应体系的制备、与反应产物的分离、和关于具有大的工业有用性的路易氏酸催化剂的回收中所伴随的问题，从而提供了新的载在聚合物上的微囊包封的路易斯酸和它们所形成的催化剂。
发明概述
作为第一发明本发明提供了微囊包封的路易斯酸，其特征在于路易斯酸通过配价键载在有机物聚合物形成的微胶囊上。
与第一发明有关，作为第二发明本发明还提供了微囊包封的路易斯酸颗粒或其聚集体；作为第三发明提供了微囊包封的路易斯酸，其中有机聚合物实质上是通过加成聚合制备的非交联聚合物；作为第四发明提供了微囊包封的路易斯酸，其中有机聚合物实质上是含有芳香环的非交联聚合物；作为第五发明提供了微囊包封的路易斯酸，其中有机聚合物实质上是含有苯环的非交联聚合物；作为第六发明提供了微囊包封的路易斯酸，其中有机聚合物实质上是在侧链上含有芳香环的非交联聚合物；作为第七发明提供了微囊包封的路易斯酸，其中有机聚合物实质上是在侧链上含有苯环的非交联聚合物；作为第八发明提供了微囊包封的路易斯酸，其中路易斯酸是稀土金属的三氟甲烷磺酸盐。
作为第九发明本发明进一步提供了路易氏酸催化剂，其特征在于该催化剂是由上述第一至第八发明的微囊包封的路易斯酸形成的。
此外，作为第十发明本发明提供了制备微囊包封的路易斯酸的方法，其特征在于路易斯酸是通过配价键载在通过微囊法由有机聚合物同时形成的微胶囊上，和作为第十一发明提供了制备微囊包封的路易斯酸的方法，其中该微囊法是相分离方法。
在根据本发明的通过配价键载在有机聚合物上的微囊包封的路易斯酸中，该路易斯酸是置于胶囊的表面上，并在一定条件下暴露于聚合物，其中该酸是被限制的并包围在胶囊内部的复杂室中，从而作为催化剂参加反应。
附图简述
图1是显示实施例15中反应活性对比的附图。
发明详述
本发明具有上述特性。其次，实施方案举例说明如下。
迄今为止已经报导了一些载在聚合物上的路易斯酸的例子(Neckers，D.C.，等人，美国化学协会期刊，94，9284(1972)；Drago，R.S.，等人，美国化学协会期刊，110，3311(1988)；Clark，J.H.，等人，化学协会期刊，化学通讯，1995，2037；等等)。此外，该发明人还报导了一些例子(Kobayashi，S.，等人，有机化学期刊，61，2256(1996)；和Kobayashi，S.，等人，美国化学协会期刊，118，8977(1996))。
然而，这些载在聚合物上的路易斯酸的缺点是与无载体路易斯酸相比仅具有低的催化活性。
有机聚合物形成的微胶囊还描述在日本专利公开号296855/1994中。然而，该微胶囊具有的破裂性质使其不可能再循环，并且仅仅是物理上的包含路易斯酸。
另一方面，其中上述路易斯酸是通过配价键载在有机聚合物上的微囊包封的路易斯酸在其制备和调节中是容易的，它意外地显示出高的催化活性，该微囊包封的路易斯酸可以从反应产物分离和收回用于再循环，并且可用于各种有机合成反应。这些微囊包封的路易斯酸实质上不同于常规的有机聚合物载体路易斯酸。
至今有机聚合物形成的微胶囊在药物领域是已知的。本发明首次提出路易斯酸的微囊法及其用作催化剂。
本发明的微囊包封的路易斯酸可以以粒径为微米-毫微米级的细粒或聚集体的形式提供。路易斯酸是通过配价键载在有机聚合物形成的胶囊上，并置于其颗粒或聚集体的表面上，或者在路易斯酸是被限制的和包封在胶囊内部的复杂室中的条件下暴露于和置于聚合物上。在该聚集体中，发现包封的路易斯酸还在颗粒彼此接触的条件下被暴露。在这些条件下，该路易斯酸法表现和显示出稳定作用和与无载体路易斯酸相比更高的催化活性。
交联和非交联有机聚合物都能够用作有机聚合物只要该聚合物可以进行微囊包封，但实质上非交联聚合物是优选的。通过加成聚合形成的聚合物是更合适的。更具体的是，该聚合物实质上是含有芳香环，希望是苯环的非交联聚合物，包括聚苯乙烯，苯乙烯/丙烯腈共聚物，和苯乙烯/MMA共聚物。
在通过配价键载在由含有苯环的有机聚合物形成的微胶囊上的路易斯酸中，认为路易斯酸和苯环的π-电子之间的相互作用产生了有效的催化作用。
实质上非交联聚合物是指不通过使用交联剂进行交联反应的聚合物，这并非意谓着排除其中在聚合物制备期间产生少量交联结构的聚合物。也就是说，该聚合物需要含有对溶剂是不必要的实质上未交联的聚合物凝胶。
在含有芳香环的有机聚合物中，在分子结构中的芳香环可以是形成聚合物主链的那些或者是存在于侧链中的那些。从路易斯酸和苯环的π电子之间的相互作用的观点来看，例如在聚苯乙烯或苯乙烯和另一个单体的共聚物或嵌段共聚物的情况下，更优选的是通过加成聚合形成的和含有侧链上的苯环的有机聚合物。
含有芳香环的有机聚合物可以具有许多种分子结构，例如聚烯烃结构、聚酯结构、聚醚结构和聚酰胺结构，只要该聚合物在结构中含有芳香环。或者各种单体的共聚物也可以包括在其中。虽然该聚合物的分子量没有特别限制，但是通常可用的聚合物的重均分子量为约10,000-约2,000,000。
可用各种方法将路易斯酸载在这些有机聚合物形成的微胶囊上。界面聚合作用，相分离(凝聚)，和界面沉淀是已知的简单方法。在本发明中，优选使用相分离(凝聚)。
本发明的路易斯酸形成的微囊包封的路易斯酸是定义为电子对接受体的那些，并且各种路易斯酸都是可用的。虽然也可以使用已知的路易斯酸比如AlCl3或BF3，但是优选用于本发明的路易斯酸的例子包括钪(Sc)、钇(Y)和镧系元素(Ln)的稀土金属的有机金属化合物，例如稀土金属的三氟甲烷磺酸盐，例如三氟甲烷磺酸钪(三氟酸(triflate)钪)，三氟酸钇，三氟酸镧系元素(Ln＝La，Ce，Pr，Nd，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，和Lu)。尤其是，本发明人发现的钪化合物在水相中是稳定的，并且是优选的例子。其中，典型的路易斯酸是三氟酸钪(Sc(OTf)3]。
载在有机聚合物形成的微胶囊上的路易斯酸的量没有特别的限制，可以根据所用的路易斯酸、所用的有机聚合物、所用的微囊包封的路易斯酸的应用目的和使用来选择。例如，当使用重均分子量为约10,000-约2,000,000的上述聚合物时，路易斯酸与有机聚合物的重量比通常是1∶100或更多，标准的是优选1∶3或更少至1∶50或更多。
在本发明中，上述微囊包封的路易斯酸用作各种有机合成反应的催化剂。
微囊包封的路易斯酸可以在间歇式反应体系和流动反应体系的实施方案中用作催化剂，例如用于各种有机合成反应例如亚氨基醛醇缩合，曼尼期型反应，醛醇缩合反应，迈克尔加成反应，和Friedel-Crafts反应。另外，发现本发明的催化剂具有高的反应活性，并与单个的无载体路易斯酸相比产生高的反应产率(选择性)。证实了从反应混合物回收的微囊包封的路易斯酸在再循环时也显示出高的反应活性的非常有效的作用。
当然，当通过分离从反应产物回收微囊包封的路易斯酸时，可非常容易地以固体(颗粒)的形式回收。
实施例
通过下列实施例更详细地举例说明本发明的实施方案，但这些实施例并不解释为限制本发明。
实施例1
根据下列方法制备本发明的微囊包封的路易斯酸。在该方法中采用相分离(凝聚)微囊包封方法。
首先，在40℃的温度下将1.000克重均分子量为280,000的聚苯乙烯溶于20毫升环己烷中，随后将0.200克三氟酸钪[Sc(OTf)3]加到所产生的溶液中。
在上述温度下搅拌分离开的得到的混合物1小时，并逐渐冷却至0℃。相分离(凝聚)形成了聚苯乙烯覆盖三氟酸钪的状态。加入30毫升己烷以硬化微胶囊的的颗粒壁。
进一步搅拌1小时后，用乙腈洗涤微胶囊颗粒产物几次，然后在50℃下干燥。
在上述方法中回收0.08克三氟酸钪，证实有0.120克三氟酸钪载在微胶囊上。
微囊包封的路易斯酸的总重量为1.167克(含乙腈)。
它的红外吸收光谱(KBr)示于下列表1。
                        表1
胶囊的重量是1.167克，其含有乙腈，IR(KBr)3062，3030(vCH)，1946，1873，1805(δCH)，1601，1493(苯环)。1255(VasSO2)，1029(VsSO2)，756(vC-S)，696(vS-O)cm-1.Cf.Sc(OTf)3：1259(vasSO2)，1032(vsSO2)，769(vC-S)，647(vS-O)cm-1；聚苯乙烯：3062，3026(vCH)，1944，1873，1803(δCH)，1600，1491(苯环)cm-1。
严格地说，根据扫描电子显微镜(SEM)和钪能量色散X射线(EDX)图不能识别微胶囊结构。然而，证实了细粒是处于紧紧聚集的状态，三氟酸钪分布在聚合物微胶囊的表面上。
实施例2
实施例1制备的微囊包封的路易斯酸用作催化剂，如表2所示进行亚氨基-醛醇缩合反应。
使用含有0.120克三氟酸钪[MC Sc(OTf)3]的微胶囊颗粒产物，经过流动过程通过乙腈溶剂循环塔在室温下进行反应3小时。
即，将1.167克上述[MC Sc(OTf)3]作为催化剂放入塔(1.6×15厘米)中，然后加入10毫升乙腈。加入在5毫升丙酮中的0.50毫摩尔醛亚胺和0.60毫摩尔烯醇酸(enolate)甲硅烷基酯的混合物，在室温下循环该溶液3小时。
回收溶液并在真空下浓缩。用色谱法在硅胶上提纯得到的粗产物。
回收微囊包封的路易斯酸[MC Sc(OTf)3]并再循环使用7次。反应的收率也包含在表2。
                              表2
Figure C9980393400091
应用a    1     2     3     4    5     6     7
收率％    90    90    88    89   89    88    90
a回收的催化剂继续使用(应用2，3，4....)
证实了以很高的收率制备了作为反应产物的甲酰胺基化合物，另外，催化剂的再循环没有引起收率的降低。
这表明本发明的催化剂产生了出乎意料的很有效的作用。
实施例3
类似于实施例2，进行曼尼期(Mannich)型反应，其中使用表3所示的3种原料。
类似于实施例2，如表3所示得到了高产率。另外，也证实了催化剂的再循环没有引起收率的降低。
                         表3
第一应用，90％收率；第二应用，96％收率；第三应用，93％收率
实施例4
在实施例1中制备的微囊包封的路易斯酸[MC Sc(OTf)3]用作催化剂，并在表4中所示的间歇式系统中进行醛醇缩合反应。反应时间是6小时。
表4显示以高于90％的收率制备了羟基羰基化合物，甚至在催化剂通过再循环使用3次之后仍保持95％的极高收率。
                        表4
Figure C9980393400101
第一应用，92％收率；第二应用，97％收率；第三应用，95％收率
实施例5
类似于实施例4，根据表5所示的间歇式系统进行迈克尔加成反应。
如表5所示，证实了虽然催化剂进行了再循环，但使用本发明的微囊包封的路易斯酸催化剂可以保持高的反应收率。
                        表5
Figure C9980393400102
第一应用，92％收率；第二应用，97％收率；第三应用，95％收率
实施例6
类似于实施例4，如表6所示进行弗里德尔-克拉夫茨(Friedel-Crafts)酰化反应。
在LiClO4共同存在下在50℃温度下在硝基甲烷中进行该反应6小时。
如表6所示，证实了甚至在催化剂通过再循环使用3次之后，仍得到了81％的收率并保持高的收率。
                        表6
Figure C9980393400103
第一应用，76％收率；第二应用，76％收率；第三应用，81％收率
实施例7
如表7所示，进行醛类的的烯丙基化反应。根据下列方法通过间歇式系统进行该反应。
即，实施例1制备的1.167克含0.120克三氟酸钪的微囊包封的路易斯酸[MC Sc(OTf)3]用作催化剂，在室温下将在5毫升乙睛中的0.50毫摩尔的醛和0.30毫摩尔的四烯丙基锡的混合物与催化剂混合。
在相同的温度下搅拌得到的混合物2小时。过滤后，在真空下浓缩滤液，通过色谱法在硅胶上提纯产生的粗产物。
通过再循环使用催化剂3次。反应收率显示在表7中。
                            表7
           应用a                      收率％
           1                           92
           2                           91
           3                           90
证实了虽然进行了重复再循环，但仍保持高于90％的收率。
实施例8
类似于实施例7，如表8所示，进行醛的氰化反应。
该实施例证实了虽然经过再循环本发明的催化剂仍保持高收率。
                            表8
Figure C9980393400112
          应用                        收率％
          1                           79
          2                           78
          3                           74
实施例9
类似于实施例7，如表9所示，进行狄尔斯-阿尔德(Diels-Alder)反应。
我们发现载在本发明聚合物上的催化剂具有极好的催化活性，并在再循环中显示出保持高活性。
                            表9
           应用                        收率％
           1                           77
           2                           79
           3                           80
实施例10
类似于实施例2，如表10所示，进行氮杂Diels-Alder(AzaDiels-Alder)反应。
发现催化剂的再循环保持了高收率。
                            表10
          应用                        收率％
          1                           80
          2                           78
          3                           78
实施例11
类似于实施例2，如表11所示，进行氰化反应。
发现催化剂的再循环保持了与使用未用过的催化剂相同水平的高收率。
                         表11
Figure C9980393400131
          应用                        收率％
          1                           77
          2                           77
          3                           76
实施例12
类似于实施例11，如表12所示，进行氰化反应，其中使用3种原料。
催化剂的再循环得到的收率高于使用未用过的催化剂所得到的收率。
                         表12
         应用                        收率％
         1                           70
         2                           71
         3                           75
实施例13
类似于实施例2，如表13所示，进行烯丙基化反应。
该实施例证实了虽然经过再循环但该催化剂能够保持高的反应收率。
                          表13
Figure C9980393400141
          应用a                      收率％
          1                           85
          2                           87
          3                           83
实施例14
类似于实施例2，如表14所示，进行喹啉稠合。
该实施例证实了虽然经过再循环但该催化剂能够保持高的反应收率。
                        表14
         应用                        收率％
         1                           68
         2                           69
         3                           69
实施例15
在实施例2的亚氨基-醛醇缩合反应中，比较本发明的微囊包封的路易斯酸[MC Sc(OTf)3]和无载体催化剂Sc(OTf)3的催化活性。
在分别的催化剂中Sc(OTf)3的量都为0.120克。
反应时间和收率之间的关系显示在图1中。图1显示了与无载体催化剂Sc(OTf)3(图中的B)相比，本发明的催化剂(图中的A)具有高的活性，并且能更迅速地进行亚氨基-醛醇缩合反应。
如详细所示，在本发明中，将在各种有机合成反应中用作催化剂的路易斯酸通过配价键载在聚合物上发挥了非常有效的作用，该催化剂的制备、回收和再循环是容易的，催化剂的活性是高的，并且在再循环中也保持高的活性。

Claims (8)

1.一种微囊包封的路易斯酸，其特征在于，路易斯酸通过配价键载在由通过加成聚合形成的实质上非交联聚合物制成的微胶囊上。
2.根据权利要求1的微囊包封的路易斯酸，其中实质上非交联聚合物包含芳香环。
3.根据权利要求2的微囊包封的路易斯酸，其中实质上非交联聚合物包含苯环。
4.根据权利要求2的微囊包封的路易斯酸，其中实质上非交联聚合物包含在侧链上的芳香环。
5.根据权利要求4的微囊包封的路易斯酸，其中实质上非交联聚合物包含在侧链上的苯环。
6.根据权利要求1-4之任一项的微囊包封的路易斯酸，其中路易斯酸是稀土金属的三氟甲烷磺酸盐。
7.一种制备微囊包封的路易斯酸的方法，其包括在路易酸的金属原子和实质上非交联聚合物的芳香环之间形成配价键；和通过微囊包封方法形成微胶囊。
8.根据权利要求7的方法，其中微囊包封方法是相分离方法。
CNB998039349A 1998-02-13 1999-02-12 微囊包封的路易斯酸 Expired - Lifetime CN1171893C (zh)

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