3-Hydroxy-2,2-dimethylpropionaldehyde → Ethyl trans-4,4-dimethyl-5-hydroxypent-2-enoate

HRID 1595040Notes

Reaction equation

HRID 1595040 reaction equation
[CH3:1][C:2]([CH3:7])([CH2:5]O)[CH:3]=[O:4].[C:8]([CH:13]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:10][CH2:11][CH3:12])=[O:9]>ClCCl>[CH3:7][C:2]([CH3:1])([CH2:3][OH:4])/[CH:5]=[CH:13]/[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

4

Reactant 2

HCID 116993-Hydroxy-2,2-dimethylpropionaldehydeHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester

Product 1

HCID 10942910Ethyl trans-4,4-dimethyl-5-hydroxypent-2-enoateYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 2,2-dimethyl-3-hydroxypropanal (22 g, 0.22 mol) and (carboethoxymethylene)triphenylphosphorane (75 g, 0.22 mol) in dry dichloromethane (150 ml) was refluxed for 46 h. The solvent was then evaporated and the crude product was distilled at 15 Torr through a very short column. The distillate was separated into two fractions by redistillation through a 40-cm Widmer column. The first fraction gave 22.3 g (60%) of ethyl trans-4,4-dimethyl-5-hydroxypent-2-enoate, b.p. 133 136° C./15 Torr, nD23 1.4641. 1H NMR (CDCl3): (=1.10 [s, 6H, C(CH3)2], 1.25 (t, 3H, CH3CH2), 3.40 (s, 2H, CH2), 3.80 (br. s, 1H, OH), 4.15 (q, 2H, CH2CH3), 5.80 (d, 1H, J=16 Hz, 3-H). Anal. Calad. for C9H16O3: C, 62.76; H, 9.36. Found: C, 62.92; H 9.50.

Workup

  1. customThe solvent was then evaporated
  2. distillationthe crude product was distilled at 15 Torr through a very short column
  3. customThe distillate was separated into two fractions by redistillation through a 40-cm Widmer column

Sources & evidence

ORD record
ord-1ed51f6637754309ab4e052536d2dad1
Source dataset
uspto-grants-2001_09
Patent number
US06284903B1

Reaction notes

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