Study On The Reaction Of Benzyne With Fluorene Derivatives

As a highly reactive intermediate for electron deficient,benzyne is widely used in organic synthesis.Based on their specific structural properties,benzyne can participate as a dienophile in the pericyclic reaction,insertion-cyclization,and multi-component coupling reactions for the purpose of rapidly constructing various carbocyclic and heterocyclic rings.Fluorene and its derivatives are by-products derived from coal tar.Its rigid fused ring structure makes hydrazine derivatives exhibit many unique photoelectric properties and biological activities,and has potential applications in many fields such as optoelectronic materials and medicine.Polycyclic aromatic hydrocarbons and functionalized spiro polycyclic aromatic hydrocarbons are important structural skeletons in many optoelectronic materials,so how to construct such structures efficiently has urgent application requirements and important significance.1.Synthesis of benzo[b]fluoranthene and its derivatives.The Diels-Alder reaction of the phenylene formed in situ by the diene and the fluoride ion under the action of the ruthenium-based phenylene group produces a Diels-Alder reaction,and the obtained cycloaddition product is further dehydrogenated under the action of manganese dioxide to obtain the target product.Through a large number of conditions screening,25 kinds of benzo[b]fluoranthene and its derivatives were synthesized with a yield of 35%-87%,and a possible reaction mechanism was proposed.2.Synthesis of a fluorene-substituted spirocyclic acridine derivative.The aza-diene formed by the ruthenium-based skeleton reacts with the phenylene formed by the Kobayashi phenylene precursor under the action of fluoride ion,and the spirocyclic acridine derivative is obtained. 15 kinds of snails are synthesized through a large number of conditions screening.The cyclic acridine derivative and its derivative have a yield of between 38% and 79%.The reaction mechanism of the reaction was investigated,and the mechanism hypothesis of [2+2] cycloaddition reopening was proposed.In summary,through the study of phenylene and anthracene derivatives,a new way to synthesize benzo[b]fluoranthene and its derivatives was explored,and a new method for synthesizing spiro acridine derivatives was discovered,which enriched and improved benzene.The application of alkyne in organic synthesis has opened up the use of antimony derivatives in the field of optoelectronic materials.