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, 1.05 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 completion 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% hydrochloric acid (100 mL) in water (150 mL). A yellow solid precipitated (nitrostyrene), and this was collected by filtration, washed with water (1.5 L) until the filtrate 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.
2. customA yellow solid precipitated (nitrostyrene)
3. filtrationthis was collected by filtration
4. washwashed with water (1.5 L) until the filtrate
5. customdried
6. customrecrystallized from hot ethanol (3 L)

ORD-Eintrag

ord-1529b65f13ef41f2a9e1dd6cd60996e1

Quelldatensatz

uspto-grants-2005_09

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06946481B1