Synthesis And Properties Of C₂-Symmetric Fused Heterocyclic Compounds Based On Different Cores

Nowadays organic functional materials have attracted numerous attention.The ladder-type acene-fused aromatics as good semiconductor materials due to their optoelectronic properties,have been used in devices such as organic field effect transistors(OFETs)and organic light-emitting diodes(OLEDs).The introduction of heteroatoms such as nitrogen and oxygen into the acene-fused cyclic compounds not only improves their solubility and processability,but also increases the luminescence effect,which enhances the applications in the above mentioned area.In view of the good properties of heterocyclefused aromatics and the prospects of optoelectronic materials,we synthetized a series of heterocyclic acene compounds and evaluated their basic optoelectronic properties.The first part of this dissertation is about the synthesis and properties of 3,3’-dimethoxy-8,8’-disubstituted-8H,8’H-4,4’-dibenzo [f] pyrazolo [3,4-b] quinolones with 2-naphthol as raw material,which was transferred to racemic binaphthol in the presence of ferric chloride hexahydrate,and further nitration was furnished with fuming nitric acid to introduce two nitro groups at the 6,6’-positions.The protection of hydroxyl group was completed with methyl iodide,and the reduction of dinitro groups was reached by Pd/C-hydrazine system.Then it was acylated with acetic anhydride and subsequently ring-closed to the key intermediate 3,3’-dichloro-8,8’-dimethoxy-[7,7’-diphenyl [f] quinolone]-2,2’-diformaldehyde by Meth-Cohn method.Which can be easily get into the cyclized product 3,3’-dimethoxy-8H,8’H-4,4’-dibenzo [f] pyrazole [3,4-b] quinolone by reacting with hydrazine.Finally,a series of 3,3’-dimethoxy-8,8’-disubstituted-8H,8’H-4,4’-dibenzo [f] pyrazole [3,4-b] quinolone derivatives were synthesized by reacting with different alkyl bromides.The second part of this dissertation is about the synthesis and properties of 3,11-diaryl dinaphtho [2,1-b:1’,2’-d] furan.The bromination of 1,1’-bi-2-naphthol led to the formation of 6,6’-dibromo-1,1-bi-2-naphthol,which was cyclized to form the key intermediate 3,11-dibromo dinaphtho [2,1-b:1’,2’-d] furan with p-TsOH as catalyst and PhMe as solvent.Subsequently 15 aryl-substituted dinaphthofuras were obtained by Suzuki coupling between 3,11-dibromo dinaphtho [2,1-b:1’,2’-d] furan and arylboronic acid.Some other 5 compounds were synthesized through coupling of boronic pinacol ester 3,11-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dinaphtho [2,1-b:1’,2’-d] furan and different halides.The third part of this dissertation is the synthesis and properties of 6,12-disubstituted-[2’,1’:2,3]-dibenzofuro [5,4-i] phenanthridines and 6,7-disubstituted dibenzothiadiazole [3,4-f] [2,9] phenanthrolines.The approach of 6,12-disubstituted-[2’,1’:2,3] dibenzofuro [5,4-i] phenanthridines came from above described 3,11-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dinaphtho [2,1-b:1’,2’-d] furan with 2-bromoanilines via Suzuki coupling to afford 2-aminoaryl substituted dinaphthofurans,which were then acylated with acyl chloride followed by Bishler-Napieralski cyclization to obtain the products.The synthesis of 6,7-disubstituted dibenzothiadiazole [3,4-f][2,9] phenanthrolines came with 4,7-dibromobenzo [c] [1,2,5] thiadiazole as key intermediate,which reacted with 2-bromoanilines via Suzuki coupling to afford 2,2’-(benzo [c] [1,2,5] thiadiazole-4,7-diyl)dianiline.The latter was then acylated with acylchloride followed by Bishler-Napiera-lski cyclization to obtain the products.