The Synthesis Of Benzophenanthrene By Palladium-catalyzed Suzuki-Heck-coupled Tandem Reaction Of Dibromobiphenyl And Arylboronic Acid

With the rapid development of science and technology, people have an increasing strong demand for functional organic materials, a kind of important ?-conjugate functional organic materialspolycyclic aromatic hydrocarbons (PAHs) received more and more people's attention. Studies on polycylic aromatic hydrocarbons have always been a hot research topic in theoretical chemistry, organic synthesis and material science. Development of a high efficient synthesis methods of polycyclic aromatic hydrocarbons is very important for improvement of performance and the design of novel organic functional materials. Triphenylene and its derivatives is a kind of very typical PAHs, discotic liquid crystal material, a kind of ?-conjugated functional materials, has a skeleton formed by triphenylene.Triphenylene are also exhibited excellent light emission characteristics, superconductivity and pharmaceutically active cancer.Because of the widely used of triphenylene in material fields, more and more organic scientist focus on the high efficient synthesis methods of triphenylene.Traditional constructions of triphenylene derivatives mainly rely on polymeriton of arynes,the reaction of the organometallic reagents with halogenated hydrocarbons as well as double couplings between 1,4-dimetallic reagents and dihaloarenes.The triphenylene can be obtained in the high yields and environmentally friendly with the method of Polymeriton of arynes, but the aryne intermediate is very active and the reaction process is difficult to control; For example, when the Reactant was the Arylalkynyl with a functional group, we often cannot get the only product but the isomerized triphenylene derivatives. Organometallic reagents tend to have good activity, so the method with the reaction of the organometallic reagents with halogenated hydrocarbons can get the triphenylene with a excellent yields. However, this method has a great disadvantage, that is the organometallic reagents is highly toxic and environmentally unfriendly. Double couplings between 1,4-dimetallic reagents and dihaloarenesofen get the triphenylene yield on the middle but 1,4-dimetallic reagents difficult to prepare, expensive and hard to keep. Other method such as 2-phenyl-biphenyl and its derivatives via the intramolecular cyclization to made the tirphenylene.This method had the low yield and the tough conditions.Our group developed a new method through the Suzuki-Heck type coupling with 2,2'- dibromo biphenyl and arylboronic acid to synthesize triphenylene.This article is about a new method through the Suzuki-Heck type coupling with 2,2'-dibromo biphenyl and arylboronic acid to synthesize triphenylene. After a lot of our experimentalresearch, we found the optimal conditionto synthesize triphenylene through the Suzuki-Heck coupling with 2,2'-dibromo biphenyl and arylboronic acid.The thesis comprises three capters.The first chapter introduces the mechanism, the synthetic applications and the latest developments of C-C cross-coupling reaction, mainly introduced the Suzuki and the Heck reactions;the synthesis of current research of triphenylene and the thesis's purpose and meaning.The second chapter is about the synthesize of 8 kind of arylboronic acid?2 kind of dibromo biphenyl and 6 kind of palladium catalyst.In chapter three, we take the reaction between 2,2'- dibromo biphenyl and 4-nitro arylboronic acid as templates, select the optimal reaction conditions. On this basis, using 2,2'-dibromo biphenyl and 2,2'-dibromo-4,4',5,5'-tetramethyl biphenyl as the substrate with a number of arylboronic acid and its derivatives to synthesize the triphenylene and its derivatives in moderate to good yields.Our method has many advantages such as good yields, environmental friendly, easy to operation and cheap.