HCID 10597031, compound → HCID 10548794, compound

HRID 363506Notes

Reaction equation

HRID 363506 reaction equation
[CH3:1]C(C)([O-])C.[K+].O=[C:8]([CH2:28][CH2:29][C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH2:9][CH2:10][C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[O:12]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1C=CC=CC=1.C1COCC1>[CH2:33]([O:32][C:30]([CH2:29][CH2:28][C:8](=[CH2:1])[CH2:9][CH2:10][C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])=[O:12])=[O:31])[CH3:34]

Participants

6

Reactant 2

HCID 10597031HCID 10597031, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 10548794HCID 10548794, compoundYield 156.5%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Potassium t-butoxide (0.195 g, 1.73 mmol) was added to a stirred suspension of methyl triphenylphosphonium bromide (0.618 g, 1.73 mmol) in dry benzene (8 mL), which was maintained under argon at room temperature. After stirring for 30 min, the reaction mixture was cooled to 0° C. and a solution of ketone 3.17 (0.46 g, 1.16 mmol) in dry THF was added rapidly. The reaction mixture was quenched after 30-60 minutes at 0° C. with brine (~10 mL), extracted with EtOAc (3×20 mL), and the combined organic layer was washed with water (1×10 mL) and dried (Na2SO4). The residue obtained after concentration was purified by flash column chromatography over silica gel using hexane:EtOAc (95:5) giving 3.18 as a liquid (0.72g, 71.5%); IR (neat) 1738 (C=O) and 1647 cm-1 ; 1H NMR (CDCl3) δ 0.85(distorted t, 3H, CH3 (CH2)13), 1.20-1.40 (m, 25 H, CH3 (CH2)11CH2CH2OCO, CH3CH2OCO), 1.60 (m, 2 H, CH3 (CH2)11CH2CH2OCO), 2.35 (m, 4 H, OCCH2CH2 (C=CH2)CH2CH2CO), 2.45 (m, 4 H, OCCH2CH2 (C=CH2)CH2CH2CO), 4.00-4.15 (m, 4H, CH3 (CH2)11CH2CH2OCO, CH3CH2O), 4.75 (s, 2 H, =CH2); 13C NMR (CDCl3) δ 14.09, 14.20, 22.66, 25.89, 28.60, 29.23, 29.33, 29.50, 29.56, 29.62, 31.00, 31.03, 31.89, 32.64, 60.35, 64.61, 109.75, 146.37, 173.08, 173.181. Anal. Calcd for C24H44O4 : C, 72.67; H, 11.19. Found: C, 72.63; H, 11.23.

Workup

  1. temperaturethe reaction mixture was cooled to 0° C.
  2. customThe reaction mixture was quenched after 30-60 minutes at 0° C. with brine (~10 mL)
  3. extractionextracted with EtOAc (3×20 mL)
  4. washthe combined organic layer was washed with water (1×10 mL)
  5. dry with materialdried (Na2SO4)
  6. customThe residue obtained
  7. concentrationafter concentration
  8. customwas purified by flash column chromatography over silica gel

Sources & evidence

ORD record
ord-63a4c9ebb20b4e0b83ee8e88a4b2b9ab
Source dataset
uspto-grants-1999_02
Patent number
US05874464

Reaction notes

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