【作者】 白林；

【导师】 王进贤；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2004， 博士

【摘要】 芳基硼酸及其衍生物与卤代芳烃在过渡金属催化下的交叉偶联反应，Suzuki偶联反应，由于硼化合物的高稳定性、低毒性和反应条件温和、可容忍多种活性官能团、受空间位阻影响不大、产率高等优越性而成为普遍适用的形成C-C键的重要方法，被广泛应用于药物、除草剂、天然产物、导电聚合物、液晶材料等领域。近年来，随着绿色化学的兴起和发展，环境友好-经济性已成为技术创新的主要推动力，同时对绿色有机合成提出了严峻的挑战和发展机遇。改进合成技术、缩短反应时间、降低能耗，制备稳定性好、可循环使用的载体催化剂替代均相催化剂，利用经济易得的四苯硼钠替代芳基硼酸反应，在环境友好溶剂中进行反应是本文研究的主要内容。 利用有机合成新技术，从制备二苯基膦锂开始，首次在超声辐射下合成了不同交联度、不同磷钯比的氯甲基聚苯乙烯载体钯（Ⅱ）催化剂。常规催化反应实验显示，催化剂中Pd／P比越高其催化活性也越高，当Pd／P比接近1时，载体钯催化剂在Suzuki偶联反应中活性最高。与均相催化剂相比，其催化活性与Pd（PPh₃）₄和PdCl₂（PPh₃）₂相当，但载体催化剂可循环使用，经连续循环5次试验，催化活性略有降低。经XPS测定载体催化剂中的活性态是金属Pd（0），与均相催化剂一样，在反应中经历了氧化加成和还原消除的催化循环过程，不同于均相催化剂的是载体催化剂中坚实的聚合物母体阻止了金属微晶的聚集而始终保持高活性。与常规方法相比，超声法制备时间短、微球不易破碎、载体催化剂中磷和钯的含量高，是一种简便、高效的制备方法。载体催化剂克服了均相催化剂的缺点，可回收和循环利用，避免了贵金属的流失，降低了反应成本，符合绿色化学的发展观。 首次将载体钯（Ⅱ）催化剂应用于微波促进的芳基硼酸、四苯硼钠与溴代芳烃发生的Suzuki偶联反应中，高效地合成了30种含不同官能团的二芳基化合物。苯-水、甲苯-水是较佳的溶剂，且溶剂的沸点越高，在微波中的反应效率也愈高。在微波场中载体催化剂稳定，催化剂经连续循环5次试验，催化活性略有降低。微波促进聚合物载体钯催化的反应节能、操作简便、反应时间短，为二芳基化合物摘要的合成提供了一条新的途径。 出人意料的是，在微波辐射下实现了聚合物载体把（11）催化的无溶剂Suzuki偶联反应。不使用有机溶剂，避免了有机溶剂的易燃、易挥发等不安全因素及对人体健康和环境造成的危害，同时也降低了反应成本。使用微波技术提高了反应速率，大大缩短了反应时间，使反应从数小时变为几分钟，也节省了能源。载体催化剂经简单的处理后可连续循环使用，催化活性没有明显降低。微波促进无溶剂条件下的 Suzuki偶联反应，反应时间短、收率高、后处理简单，是一种快捷、简便的绿色‘合成方法，也是合成二芳基化合物的较佳方法。 水是价廉易得、安全可靠的绿色溶剂，微波是一种环境友好的加热替代技术，本论文将微波技术与水作溶剂二者结合起来，在一个相对一简单的微波回流反应系统中实现了环境友好的Suzuki偶联反应。以及CO3为碱，rrBAB为相转移催化剂，在均相催化剂PdC12（P Ph3）:催化下澳代芳烃与芳基硼酸高效偶联，合成了30种含不同官能团的二芳基化合物，反应时一间由常规条件的6h缩短为10 min。 在微波促进水溶液中进行的澳代芳烃与芳基硼酸偶联反应研究的基础上，实现了四苯硼钠与溟代芳烃的原子经济偶联。在Pd（OAc）:和TBAB协同催化下，以NaZCO:为碱，四苯硼钠与带吸电子官能团的溟代芳烃发生偶联，四苯硼钠中的四个苯基全部参与了反应。高效地合成了带各种不同宫能团的二芳基化合物，扩大了取代基的应用范围，并总结出其原子经济反应规律。四苯硼钠是一种价廉、无毒、商品化的试剂，是替代单芳基硼酸在环境友好溶剂中实现芳化反应的最佳试剂。 微波促进水溶液中进行的Suzuki偶联反应是一种与环境友好的绿色化学反应，以四苯硼钠替代芳基硼酸在水溶液中与澳代芳烃发生偶联反应，符合绿色化学的原子经济性。与常规反应条件相比，微波反应能耗低、操作简便、反应时间短、收率高，具有潜在的应用前景。更多还原

【Abstract】 The palladium-catalyzed cross-coupling of aryl halides with boronic acids in presence of base, a Suzuki type reaction, is one of the most versatile and utilized reactions for the selective construction of carbon-carbon bonds, in particular for the formation of biaryls. In recent years, developments for the Suzuki reaction have received much recent attention that involve the catalysts, solvents, bases, reaction conditions and synthetic technique, which permit the use of organoboron compounds that are thermally stable and inert to water and oxygen. The low toxicity, stability and ease of handling of boronic acids have made them among the most popular intermediates for cross coupling reaction with variety of substrates. As the biaryl motif is found in a range of Pharmaceuticals, herbicides, and natural products as well as in conducting polymers and liquid crystalline materials. The destination of this dissertation is to develop Suzuki cross-coupling reaction in green chemistry and some possibilities for improvements especially in areas of solvent replacement, catalysis recycling, reaction times reducing, energy saving, and synthetic technique improving.The polymer-supported palladium(.II) is first prepared in the presence of ultrasound. The preparation of polymer-supported catalyst using ultrasound is certainly direct, rapid, and highly efficient. The polymer-supported palladium(II) with a Pd/P ratio of 1/1 gives very high activity in the Suzuki coupling of phenylboronic acid with aryl bromide. A comparative study shows that this catalyst is considerably more efficient than Pd(PPh3)4 or PdCl2(PPh3)2. XPS studies have been used to determine that the active state of the catalyst is metallic palladium. The polymeric catalyst can be easily separated from a reaction mixture and reused more than 5 times with no decrease in activity. This suggests that a comparatively stable palladium phosphine complex is the reacting species in this special case.It is possible to prepare biaryls in good yield very rapidly from aryl bromides andarylboronic acids or sodium tetraphenylborate using toluene-H2O or benzene-H2O as a solvent and polymer-supported palladium( II ) as catalyst. The reaction can be performed equally well using microwave and conventional heating, showing that these conditions probably no nonthermal microwave effects are associated with the impressive speed of the reaction.The development of a no solvent, microwave-promoted Suzuki coupling reaction utilizing a readily recyclable polymer-supported palladium catalyst offers numerous benefits. These include the straightforward recovery of both product and catalyst, conservation of energy through the use of microwave irradiation, simple commercial scale up, and low waste protocols due to the absence of solvents. The new reaction is convenient, environmentally friendly, and generates good yields of the coupled products. The use of microwave irradiation accelerates the reaction, decreasing reaction times from hours to minutes.Water is an inexpensive and nontoxic reaction medium for the microwave-promoted Suzuki cross coupling of arylboronic acids with aryl halides. This environmentally friendly microwave protocol offers convenient operation and synthesis of variety of substituted biaryls in good yield very rapidly employing PdCl2(PPh3)2 as catalyst and potassium carbonate as the base.A rapid, efficient, and atom economical cross-coupling reaction of sodium tetraphenylborate with aryl bromides using Pd(OAc)2 as a catalyst in water under microwave irradiation conditions gives polyfunctional biaryls in high yield. According to the stoichiometry and the yields, it would appear that the four phenyl groups of the sodium tetraphenylborate are available for phenylation. The effects of the structure of functional groups in aryl bomides, including some heterocyclized species on the reaction have been investigated. The commercially available and non-toxic sodium tetraphenylborate can be used in water for a rapid and efficient phenylation of aryl bromides that c更多还原