反应详情

The method of Example 1 was substantially repeated, except that a shorter vigreux head (15 cm) was used, with trans-4,7-octadien-1-ol (18.53 g, 0.146 mol), methyl methacrylate (58.8 g, 0.59 mol), phenothiazine (0.5 g), and tetraisopropyl titanate (1.0 mL). When the head temperature rose to 96° C. (pot 117° C.), the methyl methacrylate was removed at 70 mm and the product was distilled to give 24.8 g (87% yield) of clear, colorless liquid trans-4,7-octadienyl methacrylate, bp 64°-65° C./0.2 mm. IR (film): ν 2950, 1712, 1629, 1445, 1311, 1287, 1156, 964, 933, 907, 810 cm-1. UV (isooctane): end absorption. 220 MHz 1H NMR: δ 6.06 (1H, bs, methacrylate vinyl), 5.76 (1H, m, --HC=CH2), 5.50 (1H, m, methacrylate vinyl), 5.41 (2H, m, --HC=CH--), 5.02-4.92 (2H, m, --HC=CH2), 4.11 (2H, t, J=6, OCH2 --), 2.72 (2H, m, doubly allylic CH2), 2.10 (2H, m, allylic CH2), 1.95 (3H, m, allylic CH3), and 1.73 (2H, pentet, J=6, OCH2CH2CH2). 22.63 MHz 13C NMR: δ 167.2, 137.1, 136.7, 130.2, 128.9, 124.9, 115.0, 64.1, 36.8, 29.1, 28.6, 18.3.

1. customrose to 96° C.
2. custom(pot 117° C.)
3. customthe methyl methacrylate was removed at 70 mm
4. distillationthe product was distilled