Synthesis And Research Of Chiral Biaromatic/Heteroaromatic Compounds Based On Binaphthalene

Naphthalene ring compounds are the simplest of polycyclic aromatic hydrocarbons?PAHs?,and they are also the basic units and starting materials for the construction of complex PAHs.The PAHs,such as chrysene,picene and so on,owing large?-conjugated structures and strong intermolecular?-?stacking,leading to good photoelectric properties.They are often used as the active materials of organic electronic devices,and have potential applications in the fields of chiral recognition,OLEDs,OFETs and other materials.Therefore,the development of conjugated organic functional molecules based on binaphthyl and its derivatives is of great significance.Focused on the main structure of binaphthyl,a series of?-extended conjugated organic functional molecules including 1,1'-binaphthyl,1,2'-binaphthyl and 2,2'-binaphthyl were synthesized.Numerous high atomic efficiency and high efficiency reaction systems for the synthesis of biaromatic and heteroaromatic hydrocarbons have been developed.Besides,the related photoelectric properties and theoretical calculation of the target molecules were conducted.Thus,the range of substrates for organic photoelectric functional materials was extended in our work.First part mainly introduced the synthesis and study of 1,1'-bichrysene-2,2'-diols and thiophene analogs.Starting from commercial BINOLs,it was functionalized as the dibromide in order to avoid any uncertainty in subsequent steps.6,6'-dibromo-2,2'-dimethoxy-1,1'-binaphthalenes[?S?-/?R?-/rac-2]were thus obtained by bromination of?S?-/?R?-/rac-BINOL,followed by protection of the hydroxy groups with MeI in the presence of K₂CO₃ in acetone.The palladium-catalyzed borylation of?S?-/?R?-/rac-2with bis?pinacolato?diboron was employed to afford the key intermediates,6,6'-diboro-2,2'-dimethoxy-1,1'-binaphthalenes[?S?-/?R?-/rac-3].Then two Suzuki couplings with2-bromobenzaldehyde or 2-bromo-3-thiophenecarbaldehyde were performed to obtain two aldehyde intermediates?S?-/?R?-/rac-4 or-8.Next,the Wittig olefinations were applied to?S?-/?R?-/rac-4 or-8 with?methoxymethyl?triphenylphosphonium chloride as the ylide precursor to construct two diene ether intermediates?S?-/?R?-/rac-5 and-9,which were treated with TfOH to form?S?-/?R?-/rac-6 and-10 via dehydrative cycloaromatization.Finally,deprotection with BBr₃ was accomplished in dichloromethane at low temperature to afford?S?-/?R?-/rac-1,1'-bichrysene-2,2'-diols[?S?-/?R?-/rac-7]and?S?-/?R?-/rac-6,6'-biphenanthro[1,2-b]thiophene-7,7'-diols[?S?-/?R?-/rac-11].In this part,we firstly reported the synthesis of 1,1'-bichrysene-2,2'-diols and 6,6'-biphenanthro-[1,2-b]-thiophene-7,7'-diols.While expanding the?-electron system and introducing heteroatoms,the original twisted structure of 1,1'-binaphthylene was maintained.The product not only had unique fluorescence performance,but also had improved solubility and stability.The method of synchronously constructing the chrysene ring on both sides also provided innovative ideas for the synthesis of other chrysene derivatives.In the second part,the synthesis and research of benzo[c]naphthalene[2,1-p]chrysene were established.Based on the previous part,this part designed a method to synthesize benzo[c]naphthalene[2,1-p]chrysene using trienyl ether intermediates as cyclic precursors,which successfully extended and applied the synthesis idea of C₂symmetrical system to C₃ symmetrical system.The selective synthesis of benzo[c]naphthalene[2,1-p]chrysene was realized.This method started from 1,3,5-tribromobenzene,which was cheap and easy to get,with key steps including two-step Suzuki couplings and acid-mediated cyclization.The third part mainly reported the synthesis and study of picene[13,14-c][1,2,5]thiadiazole.Starting from 2-hydroxy-1-naphthaldehyde,which was cheap and easy to get,the hydroxyl group was activated by trifluoromethanesulfonic anhydride.Then palladium-catalyzed coupling with bis?pinacolato?diboron was employed to afford 2,2'-binaphthyl-1,1'-dicaldehyde?compound 17?.The key intermediate picene-13,14-diketone?compound 18?was synthesized by intramolecular benzoin condensation reaction of compound 17 with thiazolium salt using a DBU/DMF system at room temperature in good yields.Then it reacted with hydroxylamine hydrochloride to form oxime,followed by reduction with stannous chloride to obtain the corresponding cyclic precursor picene-13,14-diamine?compound 20?.Finally,it was treated with thionyl chloride to form picene[13,14-c][1,2,5]thiadiazole via dehydrative cycloaromatization,thus extending the heterocyclic benzo derivative chemistry.Finally,the theoretical calculation results of all above target molecules were compared.The effects of?-conjugation degree and heteroaryl doping on the photoelectric properties and stability of the compounds were studied from the structure of these compounds.The related theoretical basis was further improved,which laid the foundation for the design and synthesis of the related molecules and their applications in the corresponding field of materials.Centered on the binaphthyl,our work has established a novel high-efficiency synthesis to prepare a series of?-extended polycyclic conjugation systems,including1,1'-bichrysene-2,2'-diols and thiophene analogs,benzo[c]naphthalene[2,1-p]chrysene,and picene[13,14-c][1,2,5]thiadiazole.These methods started from cheap and available substituted naphthalene materials.The related research on the structure of binaphthalene was improved,and the substrate range of conjugated organic functional materials was expanded.