Reacción #6043

Ecuación de reacción

ethoxycarbonyl-3-methylenecyclobutane

lithium aluminum hydride

diethyl ether

H2O

NaOH

H2O

→

title compound

Rendimiento 71.0%

1,2-bis(hydroxymethyl)-3-methylenecyclobutane

Rendimiento 71.0%

Condiciones de reacción

Tratamiento posterior

1. 1
   OtroThe resulting white solid was removed by filtration
2. 2
   Lavadowashed thoroughly with diethyl ether

Procedimiento

To a stirred solution of 40.0 g (0.188 mol) of 1,2-bis(ethoxycarbonyl-3-methylenecyclobutane (Cripps, H. N.; Williams, J. K.; Sharkey, W. H. J. Am. Chem. Soc. 1959, 81, 2723-2728) in 1.4 L of diethyl ether at 0° C. was added 14.4 g (0.379 mol) of lithium aluminum hydride in small portions. After 2 h at 0° C., 14.4 mL of H2O, 14.4 mL of 15% aq. NaOH, and then 44.0 mL of H2O were added sequentially. The resulting white solid was removed by filtration and washed thoroughly with diethyl ether. Concentration of the combined filtrates under reduced pressure afforded 17.1 g (71%) of the title compound as an oil, judged to be 95% pure by NMR: Rf 0.27 (silica gel, 1:1/acetone:hexane); IR (CDCl3) cm-1; 1H NMR (CDCl3) 1.66 (bs, 1H, OH), 2.24-2.41 (m, 2H), 2.44 (bs, 1H, OH), 2.57-2.71 (m, 1H), 2.87-2.96 (m, 1 H), 3.54, 3.58 (2 dd, 2H, J=J'=12 Hz, CH2O), 3.79, 3.84 (2 dd, 2H, J=10.5 Hz, J'=4.5 Hz, CH2O), 4.78, 4.82 (2 ddd, 2H, J=J'=J"=2.5 Hz, C=CH2); 13C NMR (CDCl3, CDCl3 =77.00 ppm)146.21, 105.39, 66.13, 63.74, 51.70, 38.67, 31.86; DCI- NH3MS, m/z 129 (M+1)+, 146 (M+NH4+)+.

Fuente