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

HRID 465743Notes

Reaction equation

HRID 465743 reaction equation
C([O:3][C:4]([CH:6]1[CH2:9][C:8](=[CH2:10])[CH:7]1[C:11](OCC)=[O:12])=O)C.[H-].[Al+3].[Li+].[H-].[H-].[H-].O.[OH-].[Na+]>C(OCC)C>[OH:3][CH2:4][CH:6]1[CH2:9][C:8](=[CH2:10])[CH:7]1[CH2:11][OH:12]

Participants

6

Reactant 4

HCID 962Water2×HCID 14798Sodium HydroxideHCID 19794286HCID 19794286, compoundHCID 21226445Aluminium lithium hydride

Product 1

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

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

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

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

Sources & evidence

ORD record
ord-2bc1e0900d524c8ab0f2f1b7a0397dbd
Source dataset
uspto-grants-1992_10
Patent number
US05153352

Reaction notes

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