Dimethyl Sulfide → (E,E)-Farnesyl chloride

HRID 22199Notes

Reaction equation

HRID 22199 reaction equation
[Cl:1]N1C(=O)CCC1=O.CSC.[CH3:12][C:13]([CH2:17][CH2:18][CH:19]=[C:20]([CH3:28])[CH2:21][CH2:22][CH:23]=[C:24]([CH3:27])[CH2:25][CH3:26])=[CH:14]CO>ClCCl>[Cl:1][CH2:26]/[CH:25]=[C:24](\[CH3:27])/[CH2:23][CH2:22]/[CH:21]=[C:20](\[CH3:28])/[CH2:19][CH2:18][CH:17]=[C:13]([CH3:14])[CH3:12]

Participants

5

Reactant 3

HCID 1068Dimethyl SulfideHCID 31398ChlorosuccinimideHCID 53916694HCID 53916694, compound

Product 1

HCID 6003397(E,E)-Farnesyl chlorideYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

(Note: all temperatures indicated are for the contents of the reaction flask). To a stirred solution of 299 mg (2.24 mmol) of N-chlorosuccinimide in 15 mL of dichloromethane at -30° C. under argon was added 0.18 mL (2.45 mmol) of distilled dimethyl sulfide over 5 minutes. After 10 minutes at -30° C., the reaction was allowed to warm to 0° C. for 10 minutes, followed by cooling to -40° C. A solution of 441.4 mg (1.99 mmol) of 3,7,11-trimethyl-2,6,10-tridecatrien-1-ol in 5 mL of dichloromethane was added dropwise over 10 minutes. The reaction was allowed to warm gradually to 0° C. over 1 hour, and then maintained for 1 hour. After quenching with cold water, the mixture was extracted with hexane and the hexane extract was washed with cold water and cold brine, dried (MgSO4) and evaporated to afford 483 mg of a crude product. Rapid flash chromatography on 20 g of silica gel eluted with 3:97 ethyl acetate:petroleum ether provided 406.5 mg (85%) of a colorless liquid. 13C NMR indicated that this material contained a trace (3%) impurity.

Workup

  1. temperatureby cooling to -40° C
  2. temperatureto warm gradually to 0° C. over 1 hour
  3. temperaturemaintained for 1 hour
  4. customAfter quenching with cold water
  5. extractionthe mixture was extracted with hexane
  6. extractionthe hexane extract
  7. washwas washed with cold water and cold brine
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customto afford 483 mg of a crude product
  11. washRapid flash chromatography on 20 g of silica gel eluted with 3:97 ethyl acetate

Sources & evidence

ORD record
ord-1aeb0e8232fd4fddae696d18baf2db6c
Source dataset
uspto-grants-1995_06
Patent number
US05428028

Reaction notes

Loading…