Water → 1,2-Bis(hydroxymethyl)-3-methylenecyclobutane

HRID 5947Notes

Reaction equation

C(O[C:4]([CH:6]1[CH2:9][C:8](=[CH2:10])[CH2:7]1)=[O:5])C.[H-].[Al+3].[Li+].[H-].[H-].[H-].O.[OH-].[Na+].[CH2:20]([O:22]CC)C>>[OH:5][CH2:4][CH:6]1[CH2:7][C:8](=[CH2:10])[CH:9]1[CH2:20][OH:22]

Participants

Reactant 5

HCID 962Water2×

HCID 3283Diethyl Ether

HCID 14798Sodium Hydroxide

HCID 18706839Ethyl 3-methylidenecyclobutane-1-carboxylate

HCID 21226445Aluminium lithium hydride

Product 1

HCID 197942951,2-Bis(hydroxymethyl)-3-methylenecyclobutaneYield 71%

Procedure

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+)+.

Workup

customThe resulting white solid was removed by filtration
washwashed thoroughly with diethyl ether

Sources & evidence

ORD record: ord-19ddf36048d248e6b3036838b58d5b45
Source dataset: uspto-grants-1993_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05246931

Reaction notes

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