JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
New b-Methoxyacrylate Analogues
by chromatography on a silica gel column using a mixture
of n-hexane and ethyl acetate (3:1) to afford the title com-
pound 6 (5.2 g, 80%) as a yellow solid. 1H NMR (DMSO-
d6) d 3.49 (s, 3H, CO2CH3), 3.72 (s, 3H, =CH-OCH3), 7.10
(s, 1H, CH-Py), 7.30 (m, 3H, 3,4,5-ArH), 7.42 (m, 1H, 6-
ArH), 7.54 (s, 1H, =CH-OCH3), 8.64 (s, 1H, CH-Py); MS
m/z (ESI): 321 (M+H)+.
CO2CH3), 3.73 (s, 3H, =CH-OCH3), 6.46 (s, 1H, CH-Py),
7.26 (d, J = 8.0 Hz, 1H, 3-ArH), 7.29 (m, J = 8.0 Hz, 2H,
5,6-ArH), 7.40 (m, 1H, 4-ArH), 7.44 (d, J = 8.0 Hz, 2H,
2¢,6¢-ArH), 7.55 (s, 1H, =CH-OCH3), 7.83 (d, J = 8.0 Hz,
2H, 3¢,5¢-ArH), 8.41 (s, 1H, CH-Py); m/z (ESI): 447
(M+H)+; 469 (M+Na)+; Anal. calcd for C22H17F3N2O5
(446.1): C, 59.20; H, 3.84; N, 6.28; Found: C, 59.04; H,
3.96; N, 6.21.
Data for 1e. 1H NMR (DMSO-d6) d 1.05-1.08 (t, 3H,
-CH2CH3), 3.49 (s, 3H, =CH-OCH3), 3.54 (s, 2H, -CH2-),
3.73 (s, 3H, CO2CH3), 3.95 (q, 2H, -CH2CH3), 6.23 (s, 1H,
CH-Py), 7.16 (d, J = 8.0 Hz, 1H, 6¢-ArH), 7.23 (d, J = 8.0
Hz, 1H, 3-ArH), 7.26 (m, 3H, 3¢,4¢,5-ArH), 7.38 (m, 3H,
5¢,4,6-ArH), 7.54 (s, 1H, =CH-OCH3), 8.35 (s, 1H, CH-
Py); MS m/z (EI): 465.2 (M+H)+; 487.2 (M+Na)+; Anal.
calcd for C25H24N2O7 (464.2): C, 64.65; H, 5.21; N, 6.03;
Found: C, 64.51; H, 5.06; N, 5.87.
General procedures for the preparation of target
compounds 1a-1m
A solution of 6 (1 mmol), 1,4-diazabicyclo[2.2.2]oc-
tane (0.1 mmol), anhydrous potassium carbonate (1.5
mmol) and RXH (1 mmol) in dry DMF (10 mL) was stirred
under the protection of nitrogen at 80 oC for 2 h. The mix-
ture was poured into cool H2O (40 mL) and was extracted
with dichloromethane (3 × 20 mL), followed by drying
with anhydrous sodium sulfate. The solvent was removed
from the filtrate in vacuo, the residue was purified by chro-
matography on a silica gel column to afford the target com-
pounds.
Data for 1a. 1H NMR (CD3OD) d 3.58 (s, 3H, =CH-
OCH3), 3.75 (s, 3H, CO2CH3), 3.94 (s, 3H, -OCH3), 5.95 (s,
1H, CH-Py), 7.16 (d, J = 8.0 Hz, 1H, 3-ArH), 7.29 (m, J =
8.0 Hz, 2H, 5,6-ArH), 7.28 (m, 1H, 4-ArH), 7.50 (s, 1H,
=CH-OCH3), 8.36 (s, 1H, CH-Py); MS m/z (ESI): 317
(M+H)+; 339 (M+Na)+; Anal. calcd for C16H16N2O5
(316.10): C, 60.75; H, 5.10; N, 8.86; Found: C, 60.56; H,
5.32; N, 8.71.
Data for 1b. 1H NMR (CDCl3) d 2.12 (s, 3H, CH3),
2.35 (s, 3H, CH3), 3.62 (s, 3H, =CH-OCH3), 3.77 (s, 3H,
CO2CH3), 6.20 (s, 1H, CH-Py), 6.88 (s, 1H, 6¢-ArH), 7.02
(d, J = 8.0 Hz, 1H, 4¢-ArH), 7.17 (d, J = 8.0 Hz, 1H,
3-ArH), 7.22 (d, J = 8.0 Hz, 1H, 3¢-ArH), 7.33 (m, 2H,
4,5-ArH), 7.41 (d, J = 8.0 Hz, 1H, 6-ArH), 7.49 (s, 1H,
=CH-OCH3), 8.44 (s, 1H, CH-Py); MS m/z (ESI): 407
(M+H)+; 429 (M+Na)+; Anal. calcd for C23H22N2O5
(406.15): C, 67.97; H, 5.46; N, 6.89; Found: C, 67.83; H,
5.62; N, 6.77.
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Data for 1f. H NMR (CDCl3) d 3.61 (s, 3H, =CH-
OCH3), 3.76 (s, 3H, CO2CH3), 6.31 (s, 1H, CH-Py), 7.21
(d, 1H, J = 8.0 Hz, 3-ArH), 7.32 (m, 2H, 4,5-ArH), 7.40 (d,
J = 8.0 Hz, 1H, 6-ArH), 7.42 (m, 2H, 2¢,6¢-ArH), 7.46 (s,
1H, =CH-OCH3), 7.64 (d, J = 8.0 Hz, 2H, 3¢,5¢-ArH), 7.72
(s, 1H, CH-Im), 8.14 (s, 1H, CH-Im), 8.50 (s, 1H, CH-Py);
MS m/z (ESI): 479 (M+H)+; Anal. calcd for C24H19ClN4O5
(478.10): C, 60.19; H, 4.00; N, 7.40; Found: C, 60.02; H,
4.21; N, 7.22.
Data for 1g. 1H NMR (DMSO-d6) d 2.34 (s, 3H, CH3),
3.41 (s, 3H, =CH-OCH3), 3.67 (s, 3H, CO2CH3), 6.01 (s,
1H, CH-Py), 7.16 (d, 1H, J = 8.0 Hz, 3-ArH), 7.22 (m, 2H,
5,3¢-ArH), 7.32 (m, 2H, 4,4¢-ArH), 7.46 (m, 3H, 6,5¢-ArH
and =CH-OCH3), 7.59 (d, J = 8.0 Hz, 1H, 6¢-ArH), 8.49 (s,
1H, CH-Py); MS m/z (ESI): 409 (M+H)+; Anal. calcd for
C22H20N2O4S(408.1): C, 64.69; H, 4.94; N, 6.86; Found: C,
64.54; H, 5.06; N, 6.81.
Data for 1h.1H NMR (DMSO-d6) d 2.34 (s, 3H, CH3),
3.42 (s, 3H, =CH-OCH3), 3.68 (s, 3H, CO2CH3), 6.11 (s,
1H, CH-Py), 7.16 (d, 1H, J = 8.0 Hz, 3-ArH), 7.24 (m, 2H,
5,4¢-ArH), 7.33 (m, 2H, 4,5¢-ArH), 7.41 (d, 2H, 6,6¢-ArH),
7.44 (s, 1H, 2¢-ArH), 7.48 (s, 1H, =CH-OCH3), 8.50 (s, 1H,
CH-Py); MS m/z (ESI): 409 (M+H)+, 431 (M+Na)+; Anal.
calcd for C22H20N2O4S (408.1): C, 64.69; H, 4.94; N, 6.86;
Found: C, 64.59; H, 5.02; N, 6.77.
Data for 1i. 1H NMR (DMSO-d6) d 2.37 (s, 3H, CH3),
3.42 (s, 3H, =CH-OCH3), 3.68 (s, 3H, CO2CH3), 6.08 (s,
1H, CH-Py), 7.15 (d, 1H, J = 8.0 Hz, 3-ArH), 7.22 (d, 2H,
3¢,4¢-ArH), 7.34 (m, 3H, 4,5,6-ArH), 7.41 (d, 2H, 6,6¢-
ArH), 7.50 (s, 1H, =CH-OCH3), 8.49 (s, 1H, CH-Py); MS
1
Data for 1c. H NMR (DMSO-d6) d 3.50 (s, 3H,
CO2CH3), 3.74 (s, 3H, =CH-OCH3), 6.41 (s, 1H, CH-Py),
7.25 (d,1H, 3-ArH), 7.29 (m, J = 8.0 Hz, 2H, 5,6¢-ArH),
7.40 (m, 1H, 4-ArH), 7.53 (s, 1H, 2¢-ArH), 7.55 (s, 1H,
=CH-OCH3), 7.64 (d, J = 8.0 Hz, 1H, 6-ArH), 7.68 (d, J =
8.0 Hz, 1H, 4¢-ArH), 7.71 (m, J = 8.0 Hz, 1H, 5¢-ArH), 8.41
(s, 1H, CH-Py); m/z (ESI): 447 (M+H)+; 469 (M+Na)+;
Anal. calcd for C22H17F3N2O5 (446.11): C, 59.20; H, 3.84;
N, 6.28; Found: C, 59.07; H, 4.02; N, 6.17.
1
Data for 1d. H NMR (DMSO-d6) d 3.49 (s, 3H,
J. Chin. Chem. Soc. 2013, 60, 27-34
© 2013 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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