Method for preparing caffeic acid ester derivatives
A technology of caffeic acid and derivatives, which is applied in the field of medicine and chemical industry, can solve the problems of cumbersome feeding or reaction operation, difficulty in product separation and purification, and weak generality of the method, and is beneficial to laboratory synthesis and large-scale production application, reaction Universal and easy-to-control effects
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Embodiment 1
[0040] Preparation of Caffeic Acid Phenylethyl Ester
[0041]
[0042] Mix 1.0 g (1.0 equivalent) of caffeic acid, 678 mg (1.0 equivalent) of phenylethyl alcohol, 1 mol% trifluoromethanesulfonate with 125 mL of solvent, place in a hot bath at 120°C and stir for 40 minutes, remove the hot bath, and wait After reaching room temperature, wash with 30 mL of pure water and 30 mL of 2% wt sodium bicarbonate solution, and dry over anhydrous sodium sulfate. Add 0.5 g of activated carbon, stir at 80° C. for 30 minutes, filter, and concentrate to obtain a crude product.
[0043] The crude product was subjected to column chromatography to obtain a white solid product (758 mg, 48.0%). Mp128‐130℃; IR(KBr)ν max 3480,3328,1683,1601,1362,1301,1279,1182cm ‐1 ; 1 H NMR (400MHz, DMSO‐d 6 )δ H 7.46 (1H, d, J = 16Hz, C H =CHCO),7.34‐7.18(5H,m,CH 2 CH 2 C 6 h 5 ), 7.05 (1H, s, 2‐ArH), 6.99 (1H, d, J=8.0Hz, 6‐ArH), 6.77 (1H, d, J=8.0Hz, 5‐ArH), 6.24 (1H, d , J=16Hz, CH=C H CO),4.32(2H,...
Embodiment 2
[0045] Preparation of Caffeic Acid Phenylpropanol Ester
[0046]
[0047] Operation steps with reference to embodiment 1.
[0048] The crude product obtained in this example was subjected to column chromatography to obtain a white solid product (787mg, 47.5%). Mp122‐124℃; IR(KBr)ν max 3495,3338,1683,1638,1602,1278,1184cm ‐1 ; 1 H NMR (400MHz, DMSO‐d 6 )δ H 7.47 (1H, d, J = 16Hz, C H =CHCO),7.32‐7.13(5H,m,CH 2 CH 2 CH 2 C 6 H 5 ), 7.07 (1H, s, 2‐ArH), 7.01 (1H, d, J=8.0Hz, 6‐ArH), 6.78 (1H, d, J=8.0Hz, 5‐ArH), 6.27 (1H,d , J=16Hz, CH=C H CO),4.10(2H,t,J=6.8Hz,OC H 2 ),2.67(2H,t,J=7.6Hz,C H 2 C 6 h 5 ),1.93(2H,m,CH 2 C H 2 CH 2 ) ppm; 13 C NMR (100MHz, DMSO‐d 6 )δ C HRMS‐ESI C 18 h 18 o 4 Measurement [M‐H] ‐ 297.1127, measured 297.1135.
Embodiment 3
[0050] Preparation of phenylethyl cinnamate
[0051]
[0052] Mix 1.0 g (1.0 equivalent) of cinnamic acid, 824 mg of phenylethyl alcohol (1.0 equivalent), 1.66 mol% trifluoromethanesulfonate with 100 mL of solvent, stir in a hot bath at 120 ° C, and reflux for 2 hours and 4 hours, respectively. Add 1.66 mol% trifluoromethanesulfonate (a total of 5 mol% trifluoromethanesulfonate was added) at the time of 1 hour, and then remove the hot bath after reflux for 2 hours. After cooling to room temperature, add 30mL pure water and 30mL 2% carbonic Washed with sodium hydrogen solution, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product.
[0053] The crude product was crystallized in petroleum ether to obtain a white solid product (1630mg, 95.8%). Mp50‐52℃; 1 H NMR (400MHz, CDCl 3 )δ7.74‐7.68(2H,m,2,6‐ArH),7.64(1H,d,J=16Hz,C H = CHCO), 7.42 (3H, m, 3, 4, 5‐ArH), 7.35‐7.19 (5H, m, 2', 3', 4', 5', 6'‐ArH), 6.62 (1H, d , J=16Hz, CH=C H CO),4.36(2H,t,J=...
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