Tridentate phosphine ligand, catalyst, preparation method and application thereof
A technology of tridentate phosphine ligands and catalysts, applied in the application of catalysts in catalytic hydrogenation reactions, in the field of tridentate phosphine ligands and catalysts made of them, can solve the problems of weak catalytic activity of metal complexes, and achieve good Effects of Reactivity and Selectivity
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Embodiment 1
[0027] Follow the steps below to synthesize the tridentate phosphine ligand
[0028]
[0029] 2-Iodobromobenzene (24.1g, 85.3mmol), diphenylphosphine (15.9g, 85.3mmol), triethylamine (101g, 100mmol) and a catalytic amount of Pd (PPh 3 ) 4 (513.0 mg, 0.45 mmol) was dissolved in 15 mL of toluene to give a clear, bright yellow solution. The solution was stirred and heated at 80° C. for 16 hours in a sealed reactor, and triethylammonium iodide was precipitated. The resulting orange solution was dried under vacuum at 50 °C, extracted into diethyl ether (400 mL), filtered through a pad of silica gel to give a clear pale yellow solution, volatiles were removed in vacuo to give a milky white powder (27.6 g, 95%). The characterization data matched those previously reported for this compound.
[0030] (2-Bromophenyl)diphenylphosphine (1.71 g, 5 mmol) was dissolved in 20 mL of ether and cooled to -40°C. A hexane solution of n-butyllithium (3.75 mL, 6 mmol) was added dropwise to th...
Embodiment 2
[0036] Catalyst 2 was synthesized according to the following steps
[0037]
[0038] Ligand 1 (0.57g, 1mmol) and RuHCl(CO)(PPh 3 ) 3 (952 mg, 1 mmol) was added to toluene (10 mL), and the mixture was heated to reflux for 5 hours. After cooling to room temperature, diethyl ether (10 mL) was added and stirred for 5 minutes, the reaction mixture was filtered and washed with diethyl ether (5 mL, 3 times). The off-white solid was judged as two compounds by TLC, and the mixture was separated by column chromatography (dichloromethane / methanol, 50:1 to 20:1). Less polar compounds were detected by HRMS (m / z 997.0997 ([M] + ), calcdfor C 55 h 44 ClO 2 P 4 Ru + : 997.1018) identified as RuCl (CO) (PPh 3 ), probably because the raw material RuCl 2 (CO)(PPh 3 ) 3 Contains impurities. The more polar compound was identified as Catalyst 2 (light gray solid, 0.46 g, 46% yield).
[0039] 1 H NMR (400MHz, CDCl 3 ):δ=8.26-8.50(m,2H),7.29-7.38(m,2H),6.91-7.23(m,21H),6.55-6.87(m,...
Embodiment 3
[0045] In an argon glove box, add the required amount of catalyst 2 (0.005 mol%), substrate (5 mmol), and solvent (1.5 mL) to a 5 mL vial equipped with a magnetic stir bar, and transfer the mixture to a contamination-free autoclave , then use H 2 (10atm) Pressurization / exhaust three cycles for ventilation. then use H 2 (50 atmospheres) pressurized and mixed with H 2 The source was disconnected, and the autoclave was placed in an oil bath preheated to the required temperature. After 20 hours of reaction, the autoclave was cooled in an ice bath, and hydrogen gas was slowly released. The product 4a was obtained by passing through a silica gel column, and the product 4a was monitored by gas chromatography. and the ratio of 5a. The results obtained are shown in the table below:
[0046]
[0047]
[0048] s / c is the ratio of substrate to catalyst, s / c multiplied by the yield is the conversion number.
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