RSC Advances
Paper
15.4 Hz), 5.67 (1H, s), 3.69 (8H, m), 3.26–3.15 (1H, m), 2.77 (1H, MHz, CDCl3) d 200.05, 174.28, 172.59, 169.27, 135.57, 132.23,
d, J ¼ 13.6 Hz), 2.33 (1H, s), 2.29 (1H, d, J ¼ 12.0 Hz), 2.06–1.94 130.41, 129.02 (2C), 128.57, 128.36 (2C), 127.64, 78.72, 61.77,
(3H, m), 1.85 (1H, d, J ¼ 13.1 Hz), 1.68–1.61 (5H, m), 1.47–1.41 54.93, 48.10, 45.26, 43.92 (2C), 43.82 (2C), 43.27, 39.10 (2C),
(5H, m), 1.36 (3H, s), 1.32 (1H, s), 1.24 (3H, s), 1.19 (1H, d, J ¼ 37.69, 37.06, 33.12, 32.79, 31.77 (2C), 28.37, 28.07, 27.26, 27.03,
12.8 Hz), 1.12 (3H, s), 1.11 (3H, s), 1.05 (1H, s), 1.00 (3H, s), 0.97– 26.69, 26.39, 23.12 (2C), 18.66, 17.46, 16.34, 16.20, 15.56; HRMS
0.92 (1H, m), 0.81 (3H, s), 0.80 (3H, s), 0.69 (1H, d, J ¼ 11.4 Hz); (ESI): m/z calcd for C44H63N2O4 [M + H]+ 683.4788, found
13C NMR (101 MHz, CDCl3) d 200.01, 174.32, 169.22, 165.07, 683.4813.
141.68, 138.49, 128.61, 127.93 (2C), 127.85, 125.78 (2C, q, J ¼ 4.0
(E)-1-(4-(3b-Hydroxy-11-oxo-18b-olean-12-en-30-carbonyl)
Hz), 123.83 (d, J ¼ 272.7 Hz), 119.09, 78.73, 61.81, 54.97, 48.13, piperazin-1-yl)-3-phenylpropyl-1-one (4i). White solid; mp 134.8–
45.28, 43.98 (2C), 43.87 (2C), 43.30, 39.16, 39.12, 37.71, 37.11, 136.1 ꢀC; yield 63%; 1H NMR (400 MHz, CDCl3) d 7.27 (2H, d, J ¼
33.13, 32.83, 31.80 (2C), 28.39, 28.09, 27.30, 27.03, 26.74, 26.41, 7.0 Hz), 7.20 (3H, d, J ¼ 7.1 Hz), 5.64 (1H, s), 3.60–3.34 (8H, m),
23.14 (2C), 18.69, 17.49, 16.35, 15.56; HRMS (ESI): m/z calcd for 3.22–3.18 (1H, m), 3.10–3.02 (1H, m), 2.96 (2H, t, J ¼ 7.6 Hz),
C
44H60F3N2O4 [M + H]+ 737.4505, found 737.4526.
2.76 (1H, d, J ¼ 13.5 Hz), 2.62 (2H, t, J ¼ 7.6 Hz), 2.31 (1H, s),
2.25 (1H, d, J ¼ 12.2 Hz), 2.07–1.91 (3H, m), 1.86–1.77 (1H, m),
(E)-1-(4-(3b-Hydroxy-11-oxo-18b-olean-12-en-30-carbonyl)
piperazin-1-yl)-3-(4-(methoxy)phenyl)-2-propen-1-one (4f). White 1.64–1.56 (5H, m), 1.46–1.37 (5H, m), 1.34 (3H, s), 1.19 (3H, s),
solid; mp 1172.3–174.2 ꢀC; yield 80%; 1H NMR (400 MHz, 1.15 (1H, s), 1.11 (3H, s), 1.09 (3H, s), 1.02 (1H, s), 0.98 (3H, s),
CDCl3) d 7.66 (1H, d, J ¼ 15.3 Hz), 7.48 (2H, d, J ¼ 8.7 Hz), 6.90 0.94 (1H, d, J ¼ 12.5 Hz), 0.78 (6H, s), 0.68 (1H, d, J ¼ 11.5 Hz);
(2H, d, J ¼ 8.7 Hz), 6.72 (1H, d, J ¼ 15.4 Hz), 5.69 (1H, s), 3.83 13C NMR (101 MHz, CDCl3) d 200.00, 174.14, 170.89, 169.25,
(3H, s), 3.68 (8H, m), 3.26–3.16 (1H, m), 2.78 (1H, d, J ¼ 13.4 Hz), 140.85, 128.49 (2C), 128.38 (2C), 128.36, 126.24, 78.62, 61.71,
2.32 (2H, d, J ¼ 13.2 Hz), 2.08–1.98 (3H, m), 1.86–1.81 (1H, m), 54.86, 47.99, 45.41, 45.20, 43.82 (2C), 43.75 (2C), 43.20, 41.56,
1.65–1.57 (5H, m), 1.47–1.42 (4H, m), 1.36 (3H, s), 1.31 (1H, s), 39.05, 37.62, 37.00, 34.85, 32.96, 32.73, 31.69, 31.39, 28.32,
1.24 (3H, s), 1.18 (2H, d, J ¼ 16.1 Hz),1.13 (3H, s), 1.12 (3H, s), 28.03, 27.20, 26.93, 26.62, 26.32, 23.08 (2C), 18.60, 17.40, 16.30,
1.04 (1H, s), 1.00 (3H, s), 0.96 (1H, d, J ¼ 14.9 Hz), 0.82 (3H, s), 15.54; HRMS (ESI): m/z calcd for C43H63N2O4 [M + H]+ 671.4788,
0.80 (3H, s), 0.69 (1H, d, J ¼ 11.4 Hz); 13C NMR (101 MHz, found 671.4811.
CDCl3) d 200.06, 174.27, 169.14, 165.85, 160.92, 143.28, 129.45
4.1.3 General procedure for the synthesis of 6a–6i. Anhy-
(2C), 128.60, 127.72, 114.23 (2C), 113.85, 78.76, 61.79, 55.36, drous methanol (1 mL, 25 mmol) was added slowly into the
54.93, 48.05, 45.27, 43.96 (2C), 43.91 (2C), 43.28, 39.12 (2C), solution of cinnamic acid chloride (prepared as described
37.73, 37.08, 33.00, 32.81, 31.78 (2C), 28.40, 28.08, 27.29, 27.06, above) in dry dichloromethane (10 mL) and reacted at room
26.71, 26.39, 23.16 (2C), 18.68, 17.48, 16.37, 15.57; HRMS (ESI): temperature for 0.5 h. Then the solvent was evaporated in vacuo
m/z calcd for C44H63N2O5 [M + H]+ 699.4737, found 699.4765.
(E)-1-(4-(3b-Hydroxy-11-oxo-18b-olean-12-en-30-carbonyl)
to give the crude product, which was not puried for further
reaction. The product was dissolved in ethylenediamine and
piperazin-1-yl)-3-(3,4,5-(trimethoxy)phenyl)-2-propen-1-one (4g). reacted under reux for 2 h. Aer the reaction was nished, the
White solid; mp 1163.2–164.8 ꢀC; yield 63%; 1H NMR (400 MHz, solution was extracted with ethyl acetate (3ꢂ) and washed by
CDCl3) d 7.62 (1H, d, J ¼ 15.3 Hz), 6.72 (3H, d, J ¼ 17.7 Hz), 5.68 saturated brine (3ꢂ). The organic layer was dried over anhy-
(1H, s), 3.90 (6H, s), 3.88 (3H, s), 3.70 (8H, m), 3.22 (1H, m), 2.78 drous magnesium sulphate, ltered and evaporated. Purica-
(1H, d, J ¼ 13.2 Hz), 2.34 (1H, s), 2.29 (1H, d, J ¼ 16.0 Hz), 2.10– tion was performed using column chromatography
1.98 (3H, m), 1.87–1.82 (1H, m), 1.71–1.60 (5H, m), 1.48–1.41 (dichloromethane/methanol
(5H, m), 1.37 (3H, s), 1.25 (3H, s), 1.20 (2H, d, J ¼ 15.3 Hz), 1.13 product 6a–6i.
¼
50/1) to give the desired
1
(3H, s), 1.12 (3H, s), 1.05 (1H, s), 1.00 (3H, s), 0.96 (1H, d, J ¼ 10.7
N-(2-Aminoethyl)cinnamamide (6a). Yellow oil; yield 52%; H
Hz), 0.82 (3H, s), 0.81 (3H, s), 0.70 (1H, d, J ¼ 11.1 Hz); 13C NMR NMR (500 MHz, d6-DMSO) d 8.12 (1H, s), 7.55 (2H, d, J ¼ 7.1 Hz),
(101 MHz, CDCl3) d 200.06, 174.30, 169.28, 165.68, 153.42 (2C), 7.42–7.34 (4H, m), 6.63 (1H, d, J ¼ 15.8 Hz), 3.19 (2H, dd, J ¼
143.64, 139.84, 130.54, 128.60, 115.65, 105.15 (2C), 78.73, 61.81, 12.2, 6.2 Hz), 2.65 (2H, t, J ¼ 6.4 Hz), 1.22 (1H, s); LC-MS: [M +
60.94, 56.23 (2C), 54.96, 48.14, 45.28, 43.98 (2C), 43.85 (2C), H]+ 191.1.
43.30, 39.15, 39.11, 37.71, 37.10, 33.14, 32.82, 31.79 (2C), 28.39,
(E)-N-(2-Aminoethyl)-3-(4-uorophenyl)acrylamide (6b). Yellow
28.08, 27.29, 27.03, 26.74, 26.41, 23.14 (2C), 18.69, 17.48, 16.35, oil; yield 61%; 1H NMR (500 MHz, d6-DMSO) d 8.52 (1H, t, J ¼ 5.5
15.55; HRMS (ESI): m/z calcd for C46H67N2O7 [M + H]+ 759.4948, Hz), 7.64 (2H, dd, J ¼ 8.7, 5.6 Hz), 7.47 (1H, d, J ¼ 15.9 Hz), 7.26
found 759.4978.
(2H, t, J ¼ 8.8 Hz), 6.60 (1H, d, J ¼ 15.9 Hz), 3.42 (2H, dd, J ¼
12.1, 6.1 Hz), 2.90 (2H, t, J ¼ 6.2 Hz), 1.23 (2H, s); LC-MS: [M +
(E)-1-(4-(3b-Hydroxy-11-oxo-18b-olean-12-en-30-carbonyl)
piperazin-1-yl)-2-methyl-3-phenyl-2-propen-1-one (4h). White H]+ 209.1.
solid; mp 1145.3–146.6 ꢀC; yield 80%; 1H NMR (400 MHz,
(E)-N-(2-Aminoethyl)-3-(4-chlorophenyl)acrylamide (6c). Yellow
CDCl3) d; 7.40–7.29 (5H, m), 6.56 (1H, s), 5.68 (1H, s), 3.69–3.62 oil; yield 51%; 1H NMR (500 MHz, d6-DMSO) d 8.16 (1H, t, J ¼ 5.4
(8H, m), 3.21 (1H, dd, J ¼ 10.2, 5.1 Hz), 2.78 (1H, d, J ¼ 13.3 Hz), Hz), 7.58 (2H, d, J ¼ 8.5 Hz), 7.46 (2H, d, J ¼ 8.5 Hz), 7.40 (1H, d,
2.33 (1H, s), 2.29 (1H, d, J ¼ 11.5 Hz), 2.11 (3H, s), 2.05–1.96 (3H, J ¼ 15.8 Hz), 6.63 (1H, d, J ¼ 15.8 Hz), 3.21 (2H, dd, J ¼ 12.2, 6.2
m), 1.87–1.80 (1H, m), 1.69–1.59 (6H, m), 1.48–1.38 (5H, m), Hz), 2.67 (2H, t, J ¼ 6.4 Hz), 1.22 (2H, s); LC-MS: [M + H]+ 225.2.
1.36 (3H, s), 1.24 (3H, s), 1.19 (1H, d, J ¼ 13.9 Hz), 1.13 (3H, s),
(E)-N-(2-Aminoethyl)-3-(p-tolyl)acrylamide (6d). Yellow oil;
1.11 (3H, s), 1.05 (1H, s), 1.00 (3H, s), 0.95 (1H, d, J ¼ 14.3 Hz), yield 56%; H NMR (500 MHz, d6-DMSO) d 8.08 (1H, t, J ¼ 5.3
1
0.81 (3H, s), 0.80 (3H, s), 0.69 (1H, d, J ¼ 11.1 Hz); 13C NMR (101 Hz), 7.43 (2H, d, J ¼ 8.0 Hz), 7.36 (1H, d, J ¼ 15.8 Hz), 7.21 (2H,
27300 | RSC Adv., 2019, 9, 27294–27304
This journal is © The Royal Society of Chemistry 2019