The Catalytic Application Of Water-Soluble Cyclopalladated Ferrocenylimine In Suzuki Cross-Coupling Reaction

In this thesis, a series of water-soluble cyclopalladated ferrocenylimine which bearing hydrophilic functional group (-COONa,-SO3sNa) were designed and prep-ared. These catalysts could effectively catalyze Suzuki cross-coupling reaction of aryl bromide and phenylboronic acid in water or in ethanol aqueous. Then we study the effect of reaction atmosphere on these catalysts’activity. Finally, the recycle of catalyst C2DNa could be realized in ethanol aqueous solution under air in room temperature, and it could be used for6times in which a significant loss of reaction activity was not been observed.1. Synthesis and characterization of water-soluble cyclopalladated ferrocenyl-imineSix water-soluble ferrocenylimine (L1DH, L1JH, L1DNa, L1JNa, L2DNa, and L2JNa) were synthesized by the reaction of ferrocenecarboxaldehyde with correspo-nding phenylamine which bearing hydrophilic functional group (-COOH,-COONa,-SO3Na) such as P-aminobenzoic acid,m-aminobenzoic acid,p-phenylcarboxylic sodium salt,m-phenylcarboxylic sodiumsalt,p-phenylsulfonic sodium salt, m-phen-ylsulfonic sodium salt. Furthermore, these water-soluble ferrocenylimine were characterized by IR, MS, and1H NMR.Four new water-soluble cyclopalladated ferrocenylimine complexes (CiDNa, C1JNa, C2DNa, and C2JNa) were synthesized by the reaction of corresponding fer-rocenylimine (L1DNa, L1JNa, L2DNa, and L2JNa) with PdCL2, and NaOAc and were characterized by IR, MS,1H NMR and Elemental Analysis.2. Water-soluble cyclopalladated ferrocenylimine complexes for Suzuki coupling reaction in waterUnder the optimized reaction conditions (C2DNa0.5mol%, NaOH2equiv., PEG20001equiv.,60℃), the Suzuki coupling reaction of4-bromotoluene with phenylb-oronic acid could be finished in4hours and the isolated yield of target product could up to99%. The Suzuki coupling reaction between a variety of aryl bromide and phe-nylboronic acid could be efficiently catalyzed with catalytic system of c2dDNa-H2O-PEG2000which also be applied to some heterocyclic compounds.3. Water-soluble cyclopalladated ferrocenylimine complexes for Suzuki coup-ling reaction in ethanol aqueous solutionUnder the optimized reaction conditions (C2DNa0.1mol%, NaOH2equiv., H2O:C2H5OH=l:2, r.t), the Suzuki coupling reaction of4-bromotoluene with phen-ylboronic acid could be finished in1hours and the isolated yield of target product could up to99%. The catalytic system of C2DNa-H2O-C2H5OH could be applied to variety of aryl bromide and some heterocyclic compounds, just as the system of C2DNa-H2O-PEG2000. Moreover, the catalysts recycling could be achieved. 4. Effect of reaction atmosphere on the Suzuki reactionWe study the effect of reaction atmosphere on the reaction activity of these catalysts on the Suzuki reaction of3-bromoanisole with phenylboronic acid. The reaction activity under air was better than that under N2, which may be caused by the oxygen of the air which play a positive role in promoting the reaction activity of catalysts on the Suzuki coupling reaction in aqueous solution.