(ꢀ)-CHERYLLINE AND LATIFINE DIMETHYL ETHER
1593
t, J ¼ 7.6 Hz, Ar-CH-Ar), 6.74–7.26 (7H, m, ArH); 13C NMR (CDCl3) (d ppm); 43.9
(NCH3), 49.4 (ArCHAr), 55.3 (OCH3), 55.81 (OCH3), 55.86 (OCH3), 56.6 (NCH2Ar),
112.1 (CHar), 112.2 (CHar), 114.1 (2ꢂ CHar), 119.8 (Car), 129.0 (2ꢂ CHar),
136.2 (Car), 136.8 (Car), 147.5 (OCar), 148.9 (OCar), 157.9 (OCar).
(ꢀ)-Cherylline Dimethyl Ether (5)
A mixture of 13 (2.0 g, 0.006 mol), formaldehyde (0.64 g, 0.007 mol), and acetic
acid (5 mL) was stirred at 90 ꢁC under an inert atmosphere for 2.0 h. After cooling to
room temperature, the reaction mixture was basified with saturated NaHCO3 sol-
ution. This basified solution was extracted ethyl acetate (3 ꢂ 25 mL), dried, filtered,
and concentrated to obtain 1.1 g of crude product. Purification of crude product by
column chromatography using 1% methanol in dichloromethane as an eluent gave 5
(0.93 g, 45%), as a white solid, mp 90–92 ꢁC (lit.[11] mp 90–92 ꢁC); IR (KBr, cmꢃ1):
1610, 1514; HRMS m=z calculated for C19H23NO3 314.1756 [M þ 1], found
314.175; 1H NMR (CDCl3) (d ppm): 2.41 (3H, s, NCH3), 2.44 (1H, m,
CHꢃHCHꢃN), 2.98 (1H, m, CHꢃHCHꢃN), 3.56 (2H, s (br), ArꢃCH2ꢃN), 3.65
(3H, s, OCH3), 3.80 (3H, s, OCH3), 3.86 (3H, s, OCH3), 4.12 (1H, t, ArꢃCHꢃAr),
6.34 (1H, s, 5-CH), 6.56 (1H, s, 8-CH), 6.84 (2H, d, J ¼ 8.8 Hz, 20-CH), 7.11 (2H, d,
J ¼ 8.8 Hz, 30-CH); 13C NMR (CDCl3) (d ppm); 43.9 (NCH3), 45.9 (ArCHAr), 55.3
(OCH3), 55.81 (OCH3), 55.86 (OCH3), 57.7 (NCH2ꢃ), 61.6 (NCH2Ar), 109.7
(CHar), 112.5 (CHar), 113.9 (2 ꢂ CHar), 127.7 (Car), 129.2 (Car), 130.0 (2 ꢂ CHar),
137.7 (Car), 147.5 (OCar), 147.6 (OCar), 158.0 (OCar).
(ꢀ)-Latifine Dimethyl Ether (6)
A mixture of 8 (2.0 g, 0.006 mol), formaldehyde 37% solution in water (2.81 g,
0.034 mol), and formic acid (6 mL) was stirred at 95 ꢁC under an inert atmosphere for
18.0 h. After cooling to room temperature, the reaction mixture was basified with
50% sodium hydroxide solution. This basified solution was extracted ethyl acetate
(3 ꢂ 25 mL), dried, filtered, and concentrated to obtain 0.9 g of crude product.
Purification of crude product by column chromatography using 1% methanol in
dichloromethane as an eluent gave 6 (1.30 g, 60%) as a white solid, mp 86–88 ꢁC
(lit.[16] mp 86–88 ꢁC); IR (KBr, cmꢃ1): 1620, 1520; HRMS m=z calculated for
C19H23NO3 314.1756 [M þ 1], found 314.1758; 1H NMR (400 MHz, CDCl3) (d
ppm): 2.32 (3H, s, NCH3), 2.70 (2H, d, J ¼ 4.4 Hz, CHꢃCH2ꢃN), 3.20 (3H, s,
OCH3), 3.75 (3H, s, OCH3), 3.79 (3H, s, OCH3), 3.34 and 3.80 (each 1H, d,
J ¼ 14.4 Hz, Ar-HCHꢃN), 4.26 (1H, t, J ¼ 4.4 Hz, ArꢃCHꢃAr), 6.76–6.80 (4H,
m, ArH), 7.11 (2H, d, J ¼ 8.8 Hz, ArH); 13C NMR (400 MHz, CDCl3) (d ppm);
40.5 (ArCHAr), 46.1 (NCH3), 55.1 (OCH3), 55.7 (OCH3), 57.9 (NCH2Ar), 59.4
(NCH2), 61.5 (OCH3), 111.1 (CHar), 113.1 (2 ꢂ CHar), 121.1 (CHar), 128.7 (Car),
129.3 (2 ꢂ CHar), 130.2 (Car), 139.9 (Car), 147.8 (OCar), 151.1 (OCar), 157.6 (OCar).
ACKNOWLEDGMENTS
We are grateful to SVNIT, Surat, and the Indian Institute of Chemical
Technology, Hyderabad, for supporting this work.