Hydrochloric Acid → 3,4-Methylenedioxy-beta-nitrostyrene

Temperatur

12.5 °C

To a stirred solution of piperonal (75 g, 500 mmol) in methanol (120 mL) at 10° C. was added nitromethane (27.1 mL, 500 mmol, 1 eq)followed by the dropwise addition of sodium hydroxide (21 g, 525 mmol, 1 eq) in sufficient water to achieve a total volume of 50 mL while maintaining the temperature between 10-15° C. The reaction mixture became cloudy, turning to a thick paste. The mixture was stirred for 30 minutes upon complention of the addition, and the mixture was then diluted with ice-water (˜350 mL) maintaining the temperature below 5° C. until solution was achieved. The resultant solution was poured in a narrow stream (such that it just failed to break into drops (into a rapidly stirred solution of 36% hydrochoric acid )100 mL) in water (150 mL). A yellow solid preciptated (nitrostyrene), and this was collected by filtration, washed with water (1.5 L) until the filrate was neutral. The filter cake was air dried and then recrystallized from hot ethanol (3 L) to yield E-2-(3,4-methylenedioxy)-nitrostyrene as yellow needles (53 g, 55%). 1H NMR (300 MHz, CDCl3) δ 7.94 (1H, d, J=13.5 Hz), 7.47 (1H, d, J=13.5 Hz), 7.09 (1H, dd, J=7.5 & 2 Hz), 7.01 (1H, d, J=2 Hz), 6.87 (1H, d, J=7.5 Hz), 6.06 (2H, s). MS (DCl/NH3) m/e 194 (M+H)+, 211 (M+H+NH3)+.

1. temperaturemaintaining the temperature below 5° C. until solution
2. filtrationA yellow solid preciptated (nitrostyrene), and this was collected by filtration
3. washwashed with water (1.5 L) until the filrate
4. customdried
5. customrecrystallized from hot ethanol (3 L)

ORD-Eintrag

ord-1659ab1e03524a3aa8e6e5f67e4887cd

Quelldatensatz

uspto-grants-2002_04

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06380241B1