Dimethylformamide → HCID 86736281, compound

HRID 1390189Notes

Reaction equation

HRID 1390189 reaction equation
C([Li])CCC.[Br-].[CH3:7][CH:8]([CH3:15])[CH2:9][CH2:10][P+](C)(C)C.[Cl:16][CH2:17][CH2:18][C@H:19]([CH3:22])[CH:20]=O.CN(C)C=O>CCOCC>[Cl:16][CH2:17][CH2:18][C@H:19]([CH3:22])/[CH:20]=[CH:10]\[CH2:9][CH:8]([CH3:15])[CH3:7]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 12365953HCID 12365953, compoundHCID 20558511HCID 20558511, compoundHCID 178418339Butyllithium

Product 1

HCID 86736281HCID 86736281, compoundYield 53%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

23.5 ml of n-butyllithium (about 2-M in n-hexane) are added dropwise under argon to a suspension of 20.4 g of 3-methylbutyl-trimethylphosphonium bromide in 80 ml of dry ether, a reaction temperature of about 20° being adhered to by slight cooling. Thereafter, the mixture is stirred at room temperature for a further 2 hours. The mixture is cooled to -10° and a solution of 5.4 g of (S)-4-chloro-2-methylbutyraldehyde in 5 ml of dry ether is added thereto. The separated precipitate is stirred for one hour without cooling bath, whereupon 100 ml of dimethylformamide are added dropwise at room temperature. The mixture is stirred at room temperature for 16 hours, hydrolysed on ice and extracted with ether. The ether phase is washed with water, dried and concentrated under reduced pressure. The residue is purified by adsorption on silicagel as well as on neutral aluminium oxide of the activities III and II (elution agent: n-hexane). After distillation under reduced pressure (13 mm Torr/90°), there are obtained 4.13 g (53%) of (S)-cis-1-chloro-3,7-dimethyl-4-octene. [α]D20 = -32.6° (2.15% in chloroform).

Workup

  1. customa reaction temperature of about 20°
  2. temperatureThe mixture is cooled to -10°
  3. stirringThe separated precipitate is stirred for one hour
  4. temperaturewithout cooling bath
  5. stirringThe mixture is stirred at room temperature for 16 hours, hydrolysed on ice
  6. extractionextracted with ether
  7. washThe ether phase is washed with water
  8. customdried
  9. concentrationconcentrated under reduced pressure
  10. customThe residue is purified by adsorption on silicagel as well as on neutral aluminium oxide of the activities III and II (elution agent: n-hexane)
  11. distillationAfter distillation under reduced pressure (13 mm Torr/90°), there

Sources & evidence

ORD record
ord-e95ce3bf654c4ff588d8d9b238645809
Source dataset
uspto-grants-1979_02
Patent number
US04138289

Reaction notes

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