Cyclic supported catalysts
A compound and oxidation state technology, applied in physical/chemical process catalysts, catalytic reactions, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as poor performance
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Embodiment 1
[0351] Example 1: Preparation of Chlorinated Precursors
[0352] Preparation of calixarene 2:
[0353] Benzyloxyphenol 1 (200 g, 1 mol), paraformaldehyde (78.7 g) and xylene (2 L) were loaded and the medium was placed under argon. t-BuOK (7,39 g, 65.9 mmol) was loaded and vacuum-argon cycled. The mixture was refluxed for 8 hours with vigorous stirring and the water formed was collected with a Dean-Stark water separator. The mixture was cooled to room temperature, and xylene was evaporated under reduced pressure. The solid residue was heated at 45°C in 3L tetrahydrofuran (THF) with vigorous stirring, filtered and rinsed with 500ml THF. The filter cake was placed in 2.5 L THF and dispersed at 45°C for 30 minutes with vigorous stirring. 1 L THF was evaporated and a THF / HCl (33%) (200 / 50ml) solution was added. The mixture was stirred at room temperature for 30 minutes, filtered and rinsed with 250ml THF. The product was allowed to dry overnight in air and then for a few ho...
Embodiment 2
[0356] Embodiment 2: Preparation of phosphorus ligand
[0357] Phospholigand 4
[0358] Calixarene 3 (10 g, 4, 13 mmol) was loaded into the reactor, dried under vacuum for 30 minutes, then THF (17 ml) was added under argon. The solution was cooled to -20°C, and potassium diphenylphosphate (KPPh 2 ) (70.2 ml, 0.5 M in THF, 35.1 mmol) solution. The solution was stirred at room temperature for 4 hours, then dichloromethane (DCM) (20ml) was added. The mixture was filtered through celite and rinsed with DCM. The filtrate was evaporated to dryness, the residue was triturated with ether and filtered. The filter cake was triturated with pentane and filtered. The product was vacuum-dried to obtain 14.2 g of a pale yellow product (yield: 95%). 1 H NMR (CDCl 3 , ppm): 7.39to 7.33(m, 40H), 7.26to 7.23(m, 40H), 7.00(s, 30H), 6.45(s, 16H), 4.43(s, 16H), 3.88(s, 16H), 3.60(m,16H), 2.09 to 1,97(m,16H), 1,78(m,16H), 1,57(m,16H). 31 PNMR (CDCl 3 ,ppm): -16.33(s).
Embodiment 3
[0359] Embodiment 3: the preparation of imidazolium salt (precursor of heterocyclic N-carbene ligand)
[0360] Ligand IMes.HCI 5:
[0361] Load calixarene 3 (10.1 g, 4.2 mmol) and mesylimidazole (25 g, 134.2 mmol). The reactor was placed under argon atmosphere, then anhydrous DMF (200ml) was added. Vacuum / Argon was applied 3 times and the mixture was heated at 100 °C with stirring for 7-9 days (reaction monitored by NMR). DMF was evaporated and the product was dissolved in DCM (200ml) and precipitated with ether (300ml). The resulting brown solid was washed with ether (300ml), triturated with ether (100ml) and filtered. 15.5 g of a brown solid were obtained (yield = 97%). 1 H NMR(DMSO-d6,ppm):10.04(s,8H),8.21(s,8H),7.95(s,16H),7.06(s,56H),6.48(s,16H),4.61(s,16H ),4.39(s,16H),3.89(s,16H),3.71(s,16H),2.89(s,32H),2.73(s,32H),2.28(s,24H),2.03(s,16H) ,1.66(s,48H),1.65(s,16H). m / z (ESI, positive ion mode): 942.49[M+4Na + ] / 4 (calculated value=942.50) 1268.31[M+3Na + ] / 3 (...
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