Water → HCID 11053183, compound

HRID 322621Notes

Reaction equation

HRID 322621 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH2:7]([O:14][CH2:15][CH2:16][CH:17]([CH2:23][CH:24]=[CH2:25])[C:18](OCC)=[O:19])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.O.[OH-].[Na+]>CCOCC>[CH2:7]([O:14][CH2:15][CH2:16][CH:17]([CH2:23][CH:24]=[CH2:25])[CH2:18][OH:19])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 962Water2×HCID 14798Sodium HydroxideHCID 21226445Aluminium lithium hydrideHCID 22011261HCID 22011261, compound

Product 1

HCID 11053183HCID 11053183, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A 1 M solution of lithium aluminium hydride (122 mL, 122 mmol) was added via cannula to a stirred solution of crude ester 11 (44 g), prepared according to Example 10, in dry ether (150 mL). The mixture was stirred for 2 h at room temperature under nitrogen, cooled to 0° C. and water (9 mL) was added dropwise with stirring, followed by 15% NaOH (9 mL) and water (27 mL), which was added dropwise at 0° C. to produce a white precipitate. The precipitate was filtered and washed with ether (2×50 mL). The filtrate was dried over MgSO4. The residue, obtained upon concentration, was subjected to column chromatography on silica gel. Contaminant benzyloxy-2-ethoxy ethanol (12.4 g) was first eluted with ether/hexane (2:1) while the alcohol 12(24 g, 59% based on diethyl allylmalonate) was eluted with 2% methanol in ether. IR (KBr) νmax 3404, 3071, 3033, 2930, 2868, 1640, 1498, 1454, 1361, 1202, 1100, 1042, 996, 916, 838, 697 cm−1; 1HNMR (CDCl3) δ 1.63-1.73 (m, 3 H), 2.02-2.15 (m, 2 H), 2.84 (t, J=5.8 Hz, 1 H), 3.45-3.58 (m, 4 H), 4.49 (s, 2 H), 5.00-5.03 (m, 2 H), 5.70-5.85 (m, 1 H), 7.26-7.35 (m, 5 H); 13CNMR (CDCl3) δ 31.65, 3620, 3891, 53.36, 65.58, 68.66, 73.13, 116.28, 127.69, 127.71, 128.39, 136.75, 137.88: mass spectrum (EI), m/z (rel intensity) 263 (M++1.10), 203 (1.5), 185 (2.3), 181 (3.5), 143 (2.5), 129 (5), 111 (6), 108 (6), 107 (22), 95 (5), 93 (6), 92 (12), 91 (100), 81 (16), 79 (10), 77 (5), 67 (10), 65 (13).

Workup

  1. customprepared
  2. temperaturecooled to 0° C.
  3. stirringwith stirring
  4. additionwas added dropwise at 0° C.
  5. customto produce a white precipitate
  6. filtrationThe precipitate was filtered
  7. washwashed with ether (2×50 mL)
  8. dry with materialThe filtrate was dried over MgSO4
  9. customThe residue, obtained upon concentration
  10. washContaminant benzyloxy-2-ethoxy ethanol (12.4 g) was first eluted with ether/hexane (2:1) while the alcohol 12(24 g, 59% based on diethyl allylmalonate)
  11. washwas eluted with 2% methanol in ether

Sources & evidence

ORD record
ord-1aafbc550c4e44e1bf1ac76886b7e7e0
Source dataset
uspto-grants-2001_04
Patent number
US06211360B1

Reaction notes

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