Water → HCID 54435300, compound

HRID 2119103Notes

Reaction equation

HRID 2119103 reaction equation
[CH3:1][O:2][C:3](=[O:17])[CH:4](P(OCC)(OCC)=O)[CH2:5][CH:6]([CH3:8])[CH3:7].[H-].[Na+].[CH:20](=O)[CH:21]([CH3:23])[CH3:22].O>O1CCCC1.CCOCC>[CH3:1][O:2][C:3](=[O:17])[C:4]([CH2:5][CH:6]([CH3:7])[CH3:8])=[CH:20][CH:21]([CH3:23])[CH3:22]

Participants

7

Reactant 4

HCID 962WaterHCID 6561IsobutyraldehydeHCID 24758Sodium hydrideHCID 13653348HCID 13653348, compound

Product 1

HCID 54435300HCID 54435300, compoundYield 64.5%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

4-Methyl-2-(diethylphosphono)pentanoic acid methyl ester (28 g, 0.1M) prepared as in Example (1) in dry tetrahydrofuran (200 ml) was stirred under nitrogen whilst sodium hydride (2.2 g, 80% dispersion in oil; 0.11M) was added portion wise at 23° C. The reaction was stirred for 30 minutes and isobutyraldehyde (72 g, 1M) added with cooling to maintain the temperature below 30° C. The reaction was stirred for 16 h at 20° C. and water (20 ml) added. The organic phase was diluted with ether and then washed successively with aqueous sodium hydrogen carbonate, water and aqueous citric acid (1M), dried over sodium sulphate and concentrated in vacuo. Vacuum distillation of the resulting oil afforded E and Z 2-(2-methylpropyl)-4-methyl-pent-2-enoic acid methyl ester (12.5 g) b.p. 60°-70° C. at 0.5 mm Hg as a colourless oil δ(CDCl3) 0.86 and 0.88 (6H, each d, each J=7 Hz CH2CH(CH3)2); 1.0-1.02 (6H, each d, each J=7 Hz, CHCH(CH3)2); 1.6-1.85 (1H, m, CH2CH) and 2.1 and 2.2 (2H, each d, each J=7 Hz, CH2) 2.55 and 2.75 (1H, each m, C=CHCH); 3.74 (3H, s, OCH3); 5.58 and 6.59 (1H, each d, each J=9 Hz, C=CH).

Workup

  1. additionwas added portion wise at 23° C
  2. temperaturewith cooling
  3. temperatureto maintain the temperature below 30° C
  4. stirringThe reaction was stirred for 16 h at 20° C.
  5. washwashed successively with aqueous sodium hydrogen carbonate, water and aqueous citric acid (1M)
  6. dry with materialdried over sodium sulphate
  7. concentrationconcentrated in vacuo
  8. distillationVacuum distillation of the resulting oil

Sources & evidence

ORD record
ord-9e95ac16c06849bda5d12b236b72136e
Source dataset
uspto-grants-1987_07
Patent number
US04681966

Reaction notes

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