A kind of mn(Ⅲ)-salen catalyst and its preparation method and application
A -salen, catalyst technology, applied in the field of catalysts, can solve the problems of difficult synthesis, harsh reaction conditions, and high preparation costs, and achieve the effects of simple post-treatment process, less catalyst dosage, and simple preparation method
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[0035] A kind of preparation method of Mn (Ⅲ)-Salen catalyst, comprises the following steps:
[0036] 1) Add 5-bromo-3-tert-butylsalicylaldehyde, pyridine-4-boronic acid, palladium salt, inorganic base and 70~200mL solvent a to a 500mL three-necked flask in sequence, at 60~100℃, inert gas protection After reaction for 12~24h; after the reaction is completed, cool to room temperature, and use 10~50mLCH 2 Cl 2 Extract 3 to 5 times, combine the lower layer extracts, add anhydrous Na to the lower layer extracts 2 SO 4 or anhydrous MgSO 4 Stir for 10~30min, stand still for 3~5min and then filter with suction. After the filtrate is concentrated to 2~5mL at 25~40℃, perform column chromatography with 300~500 mesh silica gel to obtain compound A; the chemical structure of compound A is as follows :
[0037] ;
[0038] 2) Add compound A, ethylenediamine and 70~150mL solvent b to a 250mL three-necked flask in sequence, and react at 70~100°C for 12~24h under the protection of an ine...
Embodiment 1
[0051] Example 1. Synthesis of Compound A (4-(4-pyridine)-3-tert-butyl salicylaldehyde)
[0052] Mix 160mL of dioxane and 40mL of water to make solvent a; add 5g, 25mmol of 5-bromo-3-tert-butyl salicylaldehyde, 3.69g, 30mmol of pyridine-4-boronic acid in sequence to a 500mL three-necked flask , 1.16g, 1mmol of Pd(PPh 3 ) 4 , 8.29g, 60mmol of K 2 CO 3 and 70mL solvent a, reacted at 85°C for 12h under the protection of inert gas nitrogen; after the reaction was completed, cool to room temperature, and 2 Cl 2 Extract 3 times, combine the lower layer extracts, add anhydrous Na to the lower layer extracts 2 SO 4 Stir for 10 minutes, stand still for 3 minutes and then filter with suction. After the filtrate was concentrated to 2 mL at 40 ° C, column chromatography was performed with 300-500 mesh silica gel, and the eluent was ethyl acetate / n-hexane = 1:20, and 4.22 g was isolated , A light yellow solid with a purity of 99.5%. 1 HNMR (CD 3 Cl, 400MHz) δ (ppm): 1.50 [s, 9H, C...
Embodiment 2
[0053] Example 2. Synthesis of Compound A (4-(4-pyridine)-3-tert-butyl salicylaldehyde)
[0054] Mix 160mL tetrahydrofuran with 40mL water to make solvent a; add 5g, 25mmol of 5-bromo-3-tert-butyl salicylaldehyde, 3.69g, 30mmol of pyridine-4-boronic acid, 0.816g, 1mmol of Pd(dppf) 2 Cl 2 , 6.63g, 60mmol of Na 2 CO 3 and 100mL solvent a, react at 60°C under the protection of inert gas helium for 16h; after the reaction is completed, cool to room temperature, 2 Cl 2 Extract 2 times, combine the lower layer extracts, add anhydrous Na to the lower layer extracts 2 SO 4 Stir for 20 minutes, let it stand for 4 minutes, and filter it with a Buchner funnel. Concentrate the filtrate to 5 mL at 25°C, and perform column chromatography with 300-500 mesh silica gel. The eluent is ethyl acetate / n-hexane=1:20, 3.58 g of a pale yellow solid with a purity of 99.5% were isolated. 1 HNMR (CD 3 Cl, 400MHz) δ (ppm): 1.50 [s, 9H, C (CH 3 ) 3 ], 7.50(d, J=6Hz, 2H), 7.72(s, 1H), 7.83(s, 1H...
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