含膦酸根等水溶性膦配体及其钯配合物的合成、表征和催化羰基化反应
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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[Ph_2P(CH_2OH)_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：(Ph_2PCH_2)_2N(CH_2CH_2NH)_nCH_2CH_2PO_3Na_2(n=0，1)；(Ph_2PCH_2)_2N(CH_2CH_2O)_nCH_2CH_2NHCH_2CH_2PO_3Na_2(n=1，2，3)；(Ph_2PCH_2)(HOCH_2CH_2)NCH_2CH_2PO_3Na_2；(Ph_2PCH_2)(HOCH_2CH_2)NCH_2CH_2N(CH_2PPh_2)CH_2CH_2PO_3Na_2；HO_3SCH_2CH_2N(CH_2PPh_2)CH_2CH_2SO_3H；HO_3SCH_2CH_2N(CH_2PPh_2)CH_2CH_2N(CH_2PPh_2)CH_2CH_2SO_3H；Ph_2PCH_2N(CH_2CH_2)_2N(CH_2PPh_2)；Ph_2PCH_2N(CH_2CH_2)_2O。上述膦配体与H_2PdCl_4在氮气保护下正丁醇中回流3～4h制备得到PPh_2／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、~(13)CNMR、~(31)P 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。
Synthesis, characterization and catalytic carbonyl-
ation reactions of Phosphine Hands containing
phosphonate and their palladium complexes
Specialty: Organic Chemistry Dr. Candidate: Ma xuebing Instructor: Prof. Fu Xiangkai
Carbonylation 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 pa
lladium complexes had been characterized by element analysis, IR, UV, MS,1H NMR, 13C NMR, 31P NMR, XPS and UV. Water solubility experimental showed that the
solubility 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 seve
ral times.
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。
Synthesis, characterization and catalytic carbonyl-
ation reactions of Phosphine Hands containing
phosphonate and their palladium complexes
Specialty: Organic Chemistry Dr. Candidate: Ma xuebing Instructor: Prof. Fu Xiangkai
Carbonylation 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 pa
lladium complexes had been characterized by element analysis, IR, UV, MS,1H NMR, 13C NMR, 31P NMR, XPS and UV. Water solubility experimental showed that the
solubility 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 seve
ral times.
引文
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7 陈华，黎耀忠，李东文，程缚明，黄裕林，李贤均．水溶性膦配体的合成方法．分子催化．1999，13(2)：151～160
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2 Wiebus E, Cornils B. Water-soluble catalysts improve hydroformylation of olefins.Hrdrocarbon Processing. 1996, 63～66
3 郑晓来，王艳华，左焕培．水溶性膦配体的合成进展．分子催化．1996，10(1)：70～80
4 郑晓来，蒋景阳，王兵，金子林．两相催化—均相催化多相化新进展．化学进展．1997，9(2)：111～122
5 方志平．水溶性过渡金属络合物及其催化性能的研究进展．石油化工．1997，26(7)：479～486
6 陈华，黎耀忠，李东文，程缚明，李贤均．水溶性均相络合催化研究进展 化学进展．1998，10(2)：146～157
7 陈华，黎耀忠，李东文，程缚明，黄裕林，李贤均．水溶性膦配体的合成方法．分子催化．1999，13(2)：151～160
8 Joo F, Katho A. J Mol Catal. A: Chemical. 1997, 116:3-26
9 Wan K T, Davis M E. Nature. 1994, 370:449～450
10 Brown J M, Davis S G. Nature. 1994, 370:418～419
11 燕远勇，左焕培，金子林．分子催化，1994，8(2)：147～151
12 Wang Yanhua, Jin zilin.Thermoregulated phase transfer ligand and catalysis.Ⅱ Thermoregulated phase transfer catalysis for hydroformylation of l-hexene. 催化学报. 1996, 17(4):275～276
13 Horvath I T, Rabai J. Science. 1994, 266:72～74
14 Lecomte L, Sinou D. Phsphines sulfonees asymmetriques V. Cinetique de sulfonation of phosphines. Phosphorus Sulfur and Silicon. 1990, 53:239～251
15 Lensink C, de Vries J D. Inproving enatioselectivity by using a monosulfonated diphosphine as ligands for homogeneous imine hydrogenation. Tetrahedron:Asymmetry. 1992, 3:235～238
16 陈华，刘海超，黎耀忠等．水溶性铑-膦配合物的结构及性能表征．分子催化．1994，8(2)：124～130
17 Herrmann W A, Kohlpaintner C W, Manetsberger R B et al, Water soluble metal complexes and catalysts. Part 7． New efficient water-soluble catalysts for two-phase olefin hydriformylation: BINAS-Na, a superlative in propene hydroformylation. J Mol Catal A: Chemical. 1995, 97: 65-72
18 Herrmann W A, Kohlpaintner C W, Bahrmann H. DE-B, 4040314． 1990
19 Herrmann W A, Kohlpaintner C W, Bahrmann H, et al. i Mo! Catal. 1992,73:191
20 Herrmann W A, Albanese G P, Manetsberger R B rt al. New process for the sukfonation of phosphine ligands for catalysts. Angew Chem Int Ed Engl. 1995, 34 (7) : 811-813
21 Bahrmann H, Lapper P, Herrmann W A et al. Process for the preparation of sulfonated arylphosphines. US 5451698． 1995
22 Verspui G, Panadogianakis G, Sheldon R A. Catalytic conversions in water. Part 9． High Activity of Pd/dpppr-s/Bronsted acid system in the alternating copolymerization of ethene and carbon monoxide. Chem Commun. 1998, 401-402
23 Bartik T, Bartik B, Hanson B E et al. Water-soluble electron-donating phosphines: sulfonation of tris (ω-phenylalkyI)phosphines. Organometallics. 1993, 12: 164-170
24 Hanson B E, Bartik T, Bartik B. Two-phase hydroformylation of octene-1 with Rhodium complexes of P[C6H4(CH2) mC6H4-p-SO3Na]3 (m=3,6) . Rate and selectivity enchancement with surface-active phosphines. Organometallics. 1994, 13: 3761-3763
25 Bartik T, Ding H, Bartik B, Hanson B E. Sulfur-active phosphines for catalysis under two-phase reaction condition. P (menthyl) [(CH2) gC6H4-p-SO3Na]2 and the hydroformylation of styrene. J Mol Catal A: Chemical. 1995, 98: 117-122
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