论文总字数：29574字

摘 要

联苯类化合物是许多化合物的基本构成单元，是有机合成中重要的组成部分，在医药中间体、天然产品和功能材料中有着重要的应用。Suzuki-Miyaura交叉偶联反应是合成联苯类化合物最重要的方法，高活性非均相纳米催化剂的发展得到了广泛的关注。本文测试了具有高热稳定性、高比表面积的共聚材料Ph负载纳米钯催化剂。在传统的Suzuki-Miyaura偶联反应中，金属钯催化剂不易回收利用，并且使用有机溶剂。论文设计合成了一种高活性的纳米钯催化剂催化Suzuki-Miyaura交叉偶联反应，这种非均相催化剂表现出很高的反应活性。主要研究内容如下：

1、催化剂钯@ PhPad2的准备是在CP耦合和催化剂进行合成的。1,2,4,5-四溴苯（0.591g，1.5mmol），二-1-金刚烷基（0.151g，0.5mmol），醋酸钯（9.0mg，0.04mmol），1,1'-二异丙基膦-二茂铁（9.0mg，0.022mmol）和叔丁醇钠（67mg，0.7mmol）合并于一个Schlenk管用2ml甲苯中并加热至110℃，在氩气下搅拌24小时。将冷却的反应混合物中加入DMF（30mg），苯-1,4-二硼酸（0.463g，2.8mmol）和K ₂ CO ₃（2.0M，5.0mL）中。将混合物脱气3次并用氩气吹扫并加热至120℃为在搅拌另外20小时。之后将反应混合物冷却至室温后，将沉淀物过滤并用水和DMF洗涤。干燥的催化剂贮存在氩气氛和命名为钯@ PhPad2.

2、本文研究了催化剂Pd/Ph催化15种芳基溴化物和苯硼酸的Suzuki-Miyaura偶联反应。结果表明联苯类化合物都能得到很高的收率，用简单的过滤方法就能回收Pd/Ph，并且催化剂Pd/PIC可以重复使用十次而活性不降低。我们考察了温度、时间、溶剂、碱、相转移剂的量和催化剂的量对反应的影响，优化了实验条件，得到了芳基溴化物和苯硼酸Suzuki-Miyaura交叉偶联反应的最优条件是：水作溶剂、碳酸钠作碱(2.0当量)、四丁基溴化铵作相转移剂(1.0当量)、在100℃时，加入0.01 mol％的Pd/(Ph)，空气下反应2小时。

3、本文研究了催化剂Pd/PIC催化7种芳基氯化物和苯硼酸的Suzuki-Miyaura偶联反应。带有吸电子基团的氯化物用O.01 mo1％．1.0 mo1％的Pd/Ph，在120℃下，反应10小时就能得到较高产率的联苯类产品。反应体系应用范围广泛，对很多官能团具有耐受性，例如含有-CN、-N0₂、-CHO、-COCH₃、-COOCH₃等官能团的氯化物都能和苯硼酸顺利地反应得到相应的联苯产品。催化剂Pd/Ph在该体系中，也能重复利用，产率没有大的改变。我们优化了温度、时间、碱和催化剂的量，得出的最优条件是：水作溶剂，氢氧化钠(2.0当量)，四丁基溴化铵(1.0当量)，在120℃时，加入1.0 mo1％的Pd/(Ph)，空气下反应10小时完成芳基溴化物和苯硼酸的Suzuki-Miyaura偶联反应。

关键词：Suzuki-Miyaura 交叉偶联 钯 芳基溴化物 芳基氯化物

ABSTRACT

Biaryl is basic structural motif in chemical products，and the formations of biaryl conpounds are widely used in the processes of pharmaceuticals，natural product and functional materials．The Suzuki-Miyaura CROSS-coupling reaction is the most important method for the synthesis of biaryl compounds，and the development of highly active heterogeneous

nanocatalysts is highly desirable．Here，a porous ionic copolymer(PIC)was designed and synthesized with high thermal stability and large surface area．For the traditional Suzuki—Miyaura cross-coupling reaction，palladium catalysts used are difficult to be recycled and organic solvents were used．We designed and synthesized an highly efficient nano-palladium catalyst for the Suzuki-Miyaura cross-coupling reaction，the catalyst was a heterogeneous catalyst for the coupling reaction with high activity．

The detailed research contents are as follows：

1、The preparation of the catalyst Pd@PhPad₂. The C-P coupling and the catalysts were synthesized 1,2,4,5-Tetrabromobenzene (0.591 g, 1.5 mmol), di-1-adamantylphosphine (0.151 g, 0.5 mmol), Pd(OAc)₂ (9.0 mg, 0.04 mmol), 1,1’-bis(diisopropyl phosphino)ferrocene (dippf, 9.0 mg, 0.022 mmol) and NaOtBu (67 mg, 0.7 mmol) were combined in a schlenk tube with 2 mL of toluene and heated to 110 ℃ with stirring for 24 h under argon. The cooled reaction mixture was then added DMF (30 mL), benzene-1,4-diboronic acid (0.463 g, 2.8 mmol) and K₂CO₃ (2.0 M, 5.0 mL). The mixture was degassed 3 times and purged with argon and heated to 120 ^oC for another 20 h with stirring. After the reaction mixture cooled down to room temperature, the precipitate was filtrated and washed with water and DMF. The dried catalyst was stored in argon atmosphere and named as Pd@PhPad_2.

2、The Pd／PlC catalyst was used for the Suzuki-Miyaura cross·coupling reactions of aryl bromides with phenylboronic acid．The results showed that the yields of biaryl compounds were obtained in high yields．The Pd／PIC can be separated easily by filtration after one cycle of the reaction，and the Pd／PIC nanocatalyst was recyclable(at least 1 0 times)without loss of efficiency．The reaction temperature，solvent，reaction time，bases，phase transfer agent and the catalyst loading，were investigated and the optimized reaction conditions were achieved for the Suzuki-Miyaura cross-coupling reactions of aryl bromides with phenylboronic acid．The optimized reaction conditions are as following：Pd／PIC(0．01 m01％)，water,Na2C03(2．0 equiv．)，tetrabutylammonium bromide(1．0 equiv．)，at 1 000C，under air for 2 h，the Suzuki-Miyaura reactions of aryl bromides and phenylboronic acid．

3、The Pd／PIC catalysts were also used for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides with phenylboronic acid．The coupling reaction of electron poor aryl chlorides afforded the corresponding biphenyl compounds in excellent yields at 120℃ in 10 hours with 0.01mmol％Pd loadings．The protocol was widely applicable．and aryl chlorides with functional groups，including methoxyl，nitriles，nitro，aldehydes，ketones and ester groups，were coupled with phenylboronic acid smoothly to obtain corresponding biphenyl compounds．The Pd／PIC was recyclable also without loss of efficiency for the coupling reactions of aryl chlorides with phenylboronic acid．The reactionconditions such as reaction temperature，reaction time，bases，and the amount of catalyst，were optimized for the coupling reactions of aryl chlorides with phenylboronic acid，the optimized reaction conditions

were as following：Pd／PIC(1．0 mol％)，NaOH(2．0 equiv．)，TBAB(1．0 equiv．)，water,at 120℃ underairfor 12 h．

KEYWORDS：Suzuki··Miyaura；Cross·-coupling；Palladium；Aryl bromides；Aryl chlorides

目录

摘要 I

ABSTRACT III

第一章综述 1

1.1 Suzuki-Miyaura反应研究进展 1

1.1.1 Suzuki-Miyaura反应简介 1

1.1.2均相体系钯催化Suzuki-Miyaura反应 1

1.1.3非均相体系钯催化Suzuki-Miyaura反应 2

1.2 非均相催化体系催化Suzuki-Miyaura反应存在的问题 2

1.3本文研究的目的和内容 2

第二章 催化剂的制备 4

2.1实验部分 4

2.1.1实验仪器 4

2.1.2实验试剂 4

2.2制备过程 5

2.2.1催化剂Pd@PhPad₂的制备 5

第三章Pd／Ph催化芳基溴化物Suzuki-Miyaura反应 6

3.1引言 6

3.2实验部分 6

3.2.1实验仪器 6

3.2.3实验步骤 7

3.3反应条件优化 8

3.3.1温度选择 8

3.3.2溶剂选择 8

3.3.3碱及其用量选择 9

3.3.4催化剂用量选择 10

3.3.5相转移剂及其用量选择 10

3.4反应应用范围和限制 11

3.5反应产物的核磁数据 13

3.6小结 16

第四章Pd/PIC催化芳基氯化物Suzuki-Miyaura偶联反应 17

4.1 引言 17

4.2 实验部分 17

4.2.1实验仪器 17

4.2.2 实验试剂 18

4.2.3 实验步骤 18

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