HCID 10975430, compound → HCID 21538704, compound

HRID 1076868Notes

Reaction equation

HRID 1076868 reaction equation
C([Li])CCC.[CH2:6]([CH2:9]/[C:10](/[O:17]CC)=[CH:11]/[C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]#[CH:8].[Cl:20][CH:21]([CH2:24][CH3:25])[CH:22]=[O:23].P(O)(O)([O-])=O.[Na+]>CCCCCC.O1CCCC1.O>[O:17]=[C:10]([CH2:9][CH2:6][C:7]#[C:8][CH:22]([OH:23])[CH:21]([Cl:20])[CH2:24][CH3:25])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

8

Reactant 4

HCID 10975430HCID 10975430, compoundHCID 23672064Monosodium phosphateHCID 86733439HCID 86733439, compoundHCID 178418339Butyllithium

Product 1

HCID 21538704HCID 21538704, compoundYield 41.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-60 °C

Procedure

42.2 ml of 1.4 N butyl lithium in hexane were added with stirring to a solution of 10 g of ethyl γ-propargyl-β-ethoxy-crotonate in 75 ml of tetrahydrofuran cooled to -60°C and after holding the mixture at the said temperature for 2 hours, 6.5 g of α-chlorobutyraldehyde were added thereto. The mixture was held at -60°C for 1 hour and after raising the temperature to 0°C a mixture of 90 g of monosodium phosphate in 110 ml of water was added thereto. The mixture was decanted and the aqueous phase was extracted with ethyl acetate. The extracts were washed with a saturated sodium bicarbonate solution, then with water, was dried and evaporated to dryness. The oil residue was mixed with stirring with 120 ml of ethanol and 60 ml of 2 N hydrochloric acid for 16 hours and was then poured into water. The mixture was extracted with methylene chloride and the extracts were washed with water, dried and evaporated to dryness. The oily residue was chromatographed over silica and was eluted with a 3-1 cyclohexane-ethyl acetate mixture to obtain 5.8 g of ethyl 3-oxo-8-hydroxy -9-chloro-6-undecynoate with a refractive index of nD22 = 1.4855.

Workup

  1. customfor 2 hours
  2. temperatureafter raising the temperature to 0°C
  3. additionwas added
  4. customThe mixture was decanted
  5. extractionthe aqueous phase was extracted with ethyl acetate
  6. washThe extracts were washed with a saturated sodium bicarbonate solution
  7. dry with materialwith water, was dried
  8. customevaporated to dryness
  9. additionThe oil residue was mixed
  10. additionwas then poured into water
  11. extractionThe mixture was extracted with methylene chloride
  12. washthe extracts were washed with water
  13. customdried
  14. customevaporated to dryness
  15. customThe oily residue was chromatographed over silica
  16. washwas eluted with a 3-1 cyclohexane-ethyl acetate mixture

Sources & evidence

ORD record
ord-d254f7fcf9814c37ae90a2d310c20a99
Source dataset
uspto-grants-1976_05
Patent number
US03958005

Reaction notes

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