【作者】 马学兵；

【导师】 傅相锴；

【作者基本信息】 四川大学 ， 有机化学， 2002， 博士

【摘要】 两相催化体系的羰基化反应是一类重要的绿色化学“原子经济型”反应。本文用季鳞盐[Ph₂P（CH₂OH）₂]⁺C1^-与含膦酸根、羟基和磺酸根的有机胺类化合物的类mannich反应，首次在较温和的反应条件下合成了含膦酸根等极性基团的新型水溶性膦配体十一个和两个含氮两亲膦配体，其基本结构为：（Ph₂PCH₂）₂N（CH₂CH₂NH）_nCH₂CH₂PO₃Na₂（n=0，1）；（Ph₂PCH₂）₂N（CH₂CH₂O）_nCH₂CH₂NHCH₂CH₂PO₃Na₂（n=1，2，3）；（Ph₂PCH₂）（HOCH₂CH₂）NCH₂CH₂PO₃Na₂；（Ph₂PCH₂）（HOCH₂CH₂）NCH₂CH₂N（CH₂PPh₂）CH₂CH₂PO₃Na₂；HO₃SCH₂CH₂N（CH₂PPh₂）CH₂CH₂SO₃H；HO₃SCH₂CH₂N（CH₂PPh₂）CH₂CH₂N（CH₂PPh₂）CH₂CH₂SO₃H；Ph₂PCH₂N（CH₂CH₂）₂N（CH₂PPh₂）；Ph₂PCH₂N（CH₂CH₂）₂O。上述膦配体与H₂PdCl₄在氮气保护下正丁醇中回流3～4h制备得到PPh₂／Pd摩尔比为4：1、2：1和1：1的钯配合物。用元素分析、红外光谱、紫外光谱、质谱、¹HNMR、¹³CNMR、³¹P NMR、XPS和UV等对膦配体及其钯配合物的结构进行了表征。水溶性实验表明，仅含膦酸根的膦配体在水中溶解度约为0.16～0.29g／mL；引入乙氧基后，膦配体的水溶性有明显的改善。在pH＞12时，膦配体在水／有机相两相体系中水相的分布系数D己近100％：磺酸型磷配体的水溶性最强，约为0．360．物g／mL。红外光谱和 uP NMR表明 PPh。／Pd摩尔比为 4：l和 2：l的铅配合物有不同的配位结构。XP S数据说明，－PPhZ基团中的磷原于与过渡金属钮之间形成配位键，满足一定空间结构的氧和氮原子也参与配位键的形成。这些铝配合物催化节基氯的常压毅基化反应有较好的催化活性，有些反应中苯乙酸的产率可达gi％，可重复使用，是一类环境友好的新型绿色催化剂。更多还原

【Abstract】 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.更多还原