Synthesis, Characterization And Catalytic Carbonylation Reactions Of Phosphine Liands Containing Phosphonate And Their Palladium Complexes

Synthesis, characterization and catalytic carbonyl-ation reactions of Phosphine Hands containingphosphonate and their palladium complexesSpecialty: Organic Chemistry Dr. Candidate: Ma xuebing Instructor: Prof. Fu XiangkaiCarbonylation reaction in biphase system is the important atomic economic reaction in the field of green chemistry. In this thesis, by Mannich-type reaction using amine compounds containing sulfonate, phosphonate and alcohol groups with bis(hydroxymethyl)diphenylphosphonium chloride [Ph2P(CH2OH)2]+Cl- under mild condition, eleven water-soluble and two amphiphilic phosphine ligands had been synthesized for the first time. Their basic structures of the phosphine ligands are (Ph2PCH2)2N(CH2CH2 NH)nCH2CH2PO3Na2 (n=0,1); (Ph2PCH2)2N(CH2CH2O)n CH2CH2NHCH2CH2PO3Na2 (n=1,2,3); (Ph2PCH2)(HOCH2CH2)NCH2CH2PO3Na2; (Ph2PCH2)(HOCH2CH2)NCH2CH2N(CH2 PPh2)CH2CH2PO3Na2; HO3SCH2CH2N (CH2PPh2)CH2CH2SO3H ; HO3SCH2CH2N(CH2PPh2)CH2CH2N(CH2PPh2)CH2 CH2SO3H;Ph2PCH2N(CH2CH2)2N(CH2 PPh2), Ph2PCH2N(CH2CH2)2O. Their palladium complexes with molar ratio -PPh2/Pd=4:l, 2:1 or 1:1 had also been prepared by reaction the phosphine ligands metioned above with H2PdCl4 in n-butanol to reflux for 3~4 h under N2. The phosphine ligands and their palladium complexes had been characterized by element analysis, IR, UV, MS,1H NMR, 13C NMR, 31P NMR, XPS and UV. Water solubility experimental showed that thesolubility of phosphines in water only containing phosphonic acid group was 0.16~0.29 g/mL; After introduction of ethoxylated group, the solubility of phosphines in water was significantly improved. The distribution coefficient D for ethoxylated phosphines containing phosphonic acid group in water/ organic phase system is near 100% at pH >12.0. The phosphines containing sulfonate group possess the best solubility in water, their solubility in water were about 0.36~0.40 g/mL. The different structures of phosphine complexes between PPh2/Pd= 4:1 and PPh2/Pd= 2:1 were demonstrated by IR and 31P NMR. XPS data revealed that the coordination bonds were formed among phosphorous, some oxygen and nitrogen which meet steric structure and palladium atoms in the palladium complexes. Good catalytic activities of the phosphine palladium complexes were observed in carbonylation of benzyl chloride with atmospheric CO. In some reactions the yield of phenylacetic acid was 91% and the catalyst could be reused repeatedly in several times.