Transition-Metal-Catalyzed Cross-Dehydrogenative Coupling Reaction And Synthesis, Characterization Of BTA-based Functional Copolymers

From the view of synthetic chemistry, the discovery of new reactivities improve atom economy of existing processes or introduce highly effective methods to construct complex molecules is one of the long-standing goals of synthetic chemists. Synthesis of functional polymers in order to develop renewable energies is one of the long-standing goals of synthetic chemists.This dissertation was divided into two parts. In the first section, the studies focused on transition-metal-catalyzed C-H activation methods for the synthesis of amination and Phosphonation. And in the second part, the paper mainly studied on the design, synthesis and properties of based on BTA-based D-π-A Type Copolymers.1A highly regioselective sp3C-H amination of tertiary amides based on Fe(II) complex catalystsWhen FeCl2is used as catalyst, tert-butyl hydroperoxide (TBHP) as oxidant, and n-decane as solvent, both aryl amides and aryl sulfonamides can react with N-substituted tert-amides to obtain the desired amination products. With respect to amide derivatives, both aryl amides and aryl sulfonamides can react with N-substituted tert-amides. It is found that amides involving electron-donating groups have higher reactivity than those containing electron-deficient groups. We also find that the tertiary amides, such as N-substituted cycloamides show better reaction activities than N-substituted piperidin-2-one, moderate yields could be afforded using N-ethylpyrrolidin-2-ones as material. When1-benzylpyrrolidin-2-one,1-cyclohexylpyrrolidin-2-one were chosen as substrates, only trace products were obtained owing to steric hindrance. A free radical reaction process would be involved for this reaction. It also offers a facile method for construction of C-N bonds.2A Silver-Catalyzed Highly Regioselective Phosphonation of Arenes Bearing an Electron-Withdrawing GroupWhen Ag (I) compounds were chosen as catalysts, K2S2O8as oxidant and CH3CN/H2O (v:v=1:1) as solvent, the substrates bearing different N-alkyl substituent amides such as N-branched amides, cycloalkanes substituent amides were efficiently coupled to afford the expected products in high yields under the standard condition. As for aryl substituted N,N-diethylbenzamides, electron-rich group as well as most of electron-withdrawing ones on the aromatic rings were compatible in the C-P coupling reaction. N, M-dialkylbenzenesulfonamides also successfully underwent the cross-dehydrogenative-coupling (CDC) reactions with dialkyl phosphites and highly regioselective C-P bond formation was achieved with moderate to good yields. Under the identical reaction condition, both M-phenylacetamide and nitrobenzene could react with diethyl phosphonate, providing the corresponding phosphonation in moderate yields. A free radical reaction process would be involved. This facile method offers a broad scope of the construction of C-P bonds.3Synthesis and Characterization of BTA-based D-π-A Type CopolymersD-π-A type copolymers of P1, P2, P3and P4were synthesized via Sonogashira cross-coupling reaction of M1with M2, M3, M4and M5by using Pd(PPh3)4as a catalyst in DMF/NEt3at80℃for48h under N2, respectively. These resulting D-π-A conjugated copolymers show fluorescence emission in the range of473-568nm, The newly synthesized polymers are readily soluble in common organic solvents. the curves of TGA indicate that the polymers have relatively high thermal stability without5%weight loss before320℃, which can provide desirable thermal property for practical applications. The emissive wavelengths of four polymers are observed at505,473,568,528nm for P1, P2, P3and P4, respectively. The calculation results of model compounds show Model-3<Model-4<ModeL-1＜Model-2in HOMO-LUMO gap, which are excellently identical to the order of the absorption maxima of UV-vis absorption in the order of P3> P4> P1>P2.