布朗斯特酸催化的碳碳键和碳氮键的形成反应的研究
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摘要
C-C键和C-N键的形成反应在现代有机合成领域具有非常重要的地位。传统的方法,往往需要在C-C、C-N键形成时使用昂贵的金属催化剂,或者需要多步转化,生成大量的副产物,不符合现代“绿色化学”对环境友好性和原子经济性的要求。因此,研究新的C-C、C-N键形成反应催化剂成为当前化学工作者关注的焦点之一。本论文主要研究了布朗斯特酸催化下的C-C键和C-N键的形成反应。包括以下四个部分：
一、首次研究了采用HBF4为催化剂,在微波加热的反应条件下催化1,3-二羰基化合物和醇的烷基化反应。实验结果表明：通过微波加热,只需要5分钟,对一系列反应底物都获得很好的反应收率。
二、在传统加热和微波加热两种加热方式下,研究了H2SO4催化下1,3-二羰基化合物和醇的烷基化反应。实验结果表明：传统加热和微波加热对该反应具有相似的反应结果。在传统加热和微波加热条件下,对于一系列的反应底物,仅经过5分钟,都得到了很好的反应收率。
三、本论文首次将三氟甲磺酸(TfOH)吸附在硅胶上,成功地制备了硅胶负载的三氟甲磺酸(TfOH-SiO2),该催化剂能够在无溶剂或硝基甲烷为溶剂的条件下,实现一系列1,3-二羰基化合物和醇的烷基化反应。并且TfOH-SiO2可以方便地回收和循环使用,该催化剂循环使用5次后还能保持很好的催化效果。
四、在磺酰胺类化合物对烯烃的加成反应中,本论文首次研究了通过加入硅胶简便地实现TfOH催化剂的回收和循环使用。实验结果表明：含适量水的硅胶吸附的TfOH可以重复使用5次,而催化反应的活性与收率基本不变。另外,在磺酰胺类化合物对烯烃的加成反应中,该催化剂对一系列底物都获得了较好的反应收率。
The construction of C-C bonds and C-N bonds is one of the most important areas in modern organic chemistry. The traditional methods to achieve these transformations usually need expensive metal catalysts or tedious steps, which are against the demands of enviromental benignity and atom economy in "green chemistry". In this thesis, we report our investigations of C-C and C-N bond formation reactions with Br(?)nsted acids as the catalysts. This thesis consists of four parts.
Part 1:The microwave-assisted addition ofβ-dicarbonyl compounds to secondary alcohols has been achieved efficiently for the first time, using very cheap fluoroboric acid as the catalyst. For various P-dicarbonyl compounds and a series of secondary alcohols, the direct additions give high yields only after 5 minutes of microwave irradiation.
Part 2:Under the conventional heating condition or the microwave-assisted condition, the reactions ofβ-dicarbonyl compounds and alcohols with sulfuric acid as the catalysts demonstrated similar reaction results. For various P-dicarbonyl compounds and a series of alcohols, the catalystic reactions under conventional thermal condition and microwave irradiation condition all gave high yields only after 5 minutes.
Part 3:The new silica gel supported triflic acid was readily prepared via simple absorption of TfOH onto silica gel. This solid acid was applied as an efficient catalyst for the heterogeneous addition of variousβ-dicarbonyl compounds to a series of alcohols and alkenes, which afforded good to excellent yields under solvent-free conditions or in nitromethane. Moreover, this silica gel supported catalyst can be readily recovered and reused up to 5 runs with almost maintained reactivity and yields.
Part 4:In the hydroamination of alkene with sulfonamide, the readily recovery and efficient reusability of the catalyst, triflic acid, have been achieved successfully through simply adding wet silica gel as the adsorbent. This silica gel absorbed TfOH can be readily recovered and reused up to 5 runs with almost maintained reactivity and yields. Moreover, for a series of alkenes and various sulfonamides, the hydroaminations catalyzed by this silica gel absorbed TfOH afforded moderate to excellent yields.
一、首次研究了采用HBF4为催化剂,在微波加热的反应条件下催化1,3-二羰基化合物和醇的烷基化反应。实验结果表明：通过微波加热,只需要5分钟,对一系列反应底物都获得很好的反应收率。
二、在传统加热和微波加热两种加热方式下,研究了H2SO4催化下1,3-二羰基化合物和醇的烷基化反应。实验结果表明：传统加热和微波加热对该反应具有相似的反应结果。在传统加热和微波加热条件下,对于一系列的反应底物,仅经过5分钟,都得到了很好的反应收率。
三、本论文首次将三氟甲磺酸(TfOH)吸附在硅胶上,成功地制备了硅胶负载的三氟甲磺酸(TfOH-SiO2),该催化剂能够在无溶剂或硝基甲烷为溶剂的条件下,实现一系列1,3-二羰基化合物和醇的烷基化反应。并且TfOH-SiO2可以方便地回收和循环使用,该催化剂循环使用5次后还能保持很好的催化效果。
四、在磺酰胺类化合物对烯烃的加成反应中,本论文首次研究了通过加入硅胶简便地实现TfOH催化剂的回收和循环使用。实验结果表明：含适量水的硅胶吸附的TfOH可以重复使用5次,而催化反应的活性与收率基本不变。另外,在磺酰胺类化合物对烯烃的加成反应中,该催化剂对一系列底物都获得了较好的反应收率。
The construction of C-C bonds and C-N bonds is one of the most important areas in modern organic chemistry. The traditional methods to achieve these transformations usually need expensive metal catalysts or tedious steps, which are against the demands of enviromental benignity and atom economy in "green chemistry". In this thesis, we report our investigations of C-C and C-N bond formation reactions with Br(?)nsted acids as the catalysts. This thesis consists of four parts.
Part 1:The microwave-assisted addition ofβ-dicarbonyl compounds to secondary alcohols has been achieved efficiently for the first time, using very cheap fluoroboric acid as the catalyst. For various P-dicarbonyl compounds and a series of secondary alcohols, the direct additions give high yields only after 5 minutes of microwave irradiation.
Part 2:Under the conventional heating condition or the microwave-assisted condition, the reactions ofβ-dicarbonyl compounds and alcohols with sulfuric acid as the catalysts demonstrated similar reaction results. For various P-dicarbonyl compounds and a series of alcohols, the catalystic reactions under conventional thermal condition and microwave irradiation condition all gave high yields only after 5 minutes.
Part 3:The new silica gel supported triflic acid was readily prepared via simple absorption of TfOH onto silica gel. This solid acid was applied as an efficient catalyst for the heterogeneous addition of variousβ-dicarbonyl compounds to a series of alcohols and alkenes, which afforded good to excellent yields under solvent-free conditions or in nitromethane. Moreover, this silica gel supported catalyst can be readily recovered and reused up to 5 runs with almost maintained reactivity and yields.
Part 4:In the hydroamination of alkene with sulfonamide, the readily recovery and efficient reusability of the catalyst, triflic acid, have been achieved successfully through simply adding wet silica gel as the adsorbent. This silica gel absorbed TfOH can be readily recovered and reused up to 5 runs with almost maintained reactivity and yields. Moreover, for a series of alkenes and various sulfonamides, the hydroaminations catalyzed by this silica gel absorbed TfOH afforded moderate to excellent yields.
引文
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