Ethyl Acetate → 2-(Bromomethyl)quinoline

A magnetically stirred solution of 2-bromomethyl-7-chloroquinoline (1.0 g, 3.91 mmol) and triethyl phosphite (0.74 g, 4.45 mmol) in dry toluene (10.0 ml) was heated under reflux for 24 h. The cooled solution was adsorbed onto a quantity of silica (ca. 5.0 g) and column chromatography (ethyl acetate--light petroleum (b.p. 40°-60° C.), 1:4) provided unreacted 2-bromomethylquinoline (0.12 g, 0.469 mmol--12%) as brown crystals. Further elution (ethyl acetate) secured the title compound (0.88 g, 72%) as a yellow / brown oil. Distilled at 240° C. at 0.05 mmHg using a Kugelrohr short-path distillation apparatus as a bright yellow oil which crystallised on standing (m.p. 33°-37° C.); (Found: C, 53.17; H, 5.40; N; 4.31; Cl, 11.22. C14H17ClNO3P requires C, 53.6; H, 5.46; N, 4.46; Cl, 11.3%); νmax (thin film)/cm-1 3060.5, 2981.5, 1612.5, 1598.5, 1559.5. δH (270 MHz) 1.27 (6H, t, 2×CH2CH3, 3J=6.9 Hz); 3.60 (2H, d, CH2P, 2J=22.4 Hz); 4.11 (4H, m, 2×CH2CH3); 7.47 (1H, dd, 3-H, Jo =7.0, 4J3H,P =0.8 Hz); 7.51 (1H, dd, 6-H, Jo =8.4, Jm =1.5 Hz); 7.72 (1H, d, 5-H, Jo =8.9 Hz); 8.05 (1H, d, 8-H, Jm =1.7 Hz); 8.06 (1H, d, 4-H, Jo =8.3 Hz). δC (67.8 MHz) 16.15 (CH2CH3, d, 3JC,P =6.1 Hz); 37.0 (CH2P, d, 1JC,P =134.3 Hz); 62.3 (CH2CH3, d, 2JC,P =6.1 Hz); 122.3 (3-C, d, 3JC,P =2.5 Hz), 125.1 (4a-C), 135.3 (7-C), 136.2 (4-C); 147.9 (8a-C), 154.3 (2-C, d, 2JC,P =8.6 Hz). Remaining signals fall in the narrow range 127.1-128.6 ppm; m/z 315.3, 313.2 (7.52, 22.18, M+), 277.3 (2.21), 242.1, 240.1 (1.79, 5.13), 193.1 (6.84), 179.1, 177.1 (33.1, 100), 142.2 (3.65), 109.1 (4.57).

1. temperatureunder reflux for 24 h

ORD record

ord-d63bd18df747491c947072d5990e4ac7

Source dataset

uspto-grants-1998_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05807866