Hexachloroethane → (Z)-3-chloro-6,6-dimethyl-2-hepten-4-yn-1-ol

HRID 580008Notes

Reaction equation

HRID 580008 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C[O-].[Na+].[CH3:10][C:11]([CH3:19])([CH3:18])[C:12]#[C:13][C:14]#[C:15][CH2:16][OH:17].C(OCC)(=O)C.[Cl:26]C(Cl)(Cl)C(Cl)(Cl)Cl>O1CCCC1>[Cl:26]/[C:14](/[C:13]#[C:12][C:11]([CH3:19])([CH3:18])[CH3:10])=[CH:15]\[CH2:16][OH:17]

Participants

7

Reactant 5

HCID 6214Hexachloroethane2×HCID 8857Ethyl AcetateHCID 99893222,4-Heptadiyn-1-ol, 6,6-dimethyl-HCID 10942334Sodium MethoxideHCID 21226445Aluminium lithium hydride

Product 1

HCID 15611167(Z)-3-chloro-6,6-dimethyl-2-hepten-4-yn-1-olYield 41%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of lithium aluminum hydride (11.4 mmol; 1M solution in tetrahydrofuran, (hereafter THF) was added to a stirred suspension of sodium methoxide (1.23 g, 22.8 mmol) in 18 ml of dry THF and the mixture was stirred at room temperature for 1/2 hour. 6,6-Dimethyl-2,4-heptadiyn-1-ol (777 mg, 5.71 mmol) was added and the mixture stirred at room temperature overnight. The mixture was cooled to 0° C. and dry ethyl acetate (1.0 g, 11.4 mmole) was added dropwise. Hexachloroethane (4.05 g, 17.13 mmole) was then added and the mixture was allowed to warm to room temperature. After 4.5 hours, additional hexachloroethane (1.35 g, 5.71 mmol) was added to the reaction mixture which was then stirred for 68 hours. The mixture was partitioned between ether and dilute aqueous hydrochloric acid, and the aqueous layer was extracted 3 times with ether. The combined ethereal extract was washed with water an brine, dried over anhydrous sodium sulfate and concentrated in vacuo to afford 3.43 g of crude product. This mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95. Combination and concentration of the appropriate fractions afforded 404 mg of the desired (Z)-3-chloro-6,6-dimethyl- 2-hepten-4-yn-1-ol.

Workup

  1. stirringthe mixture stirred at room temperature overnight
  2. temperatureThe mixture was cooled to 0° C.
  3. temperatureto warm to room temperature
  4. waitAfter 4.5 hours
  5. stirringwas then stirred for 68 hours
  6. customThe mixture was partitioned between ether and dilute aqueous hydrochloric acid
  7. extractionthe aqueous layer was extracted 3 times with ether
  8. extractionThe combined ethereal extract
  9. washwas washed with water an brine
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated in vacuo
  12. customto afford 3.43 g of crude product
  13. customThis mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95

Sources & evidence

ORD record
ord-c5ea2e744d2b4feca245d8ce84fed59f
Source dataset
uspto-grants-1988_06
Patent number
US04751245

Reaction notes

Loading…