Water → HCID 59142168, compound

HRID 2234753Notes

Reaction equation

HRID 2234753 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][O:8][P:9]([CH2:13][C:14]([C:16]1([C:19](=O)[CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:18][CH2:17]1)=[O:15])([O:11][CH3:12])=[O:10].[NH4+].[Cl-].O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH3:7][O:8][P:9]([CH2:13][C:14]([C:16]1([C:19](=[CH2:1])[CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:18][CH2:17]1)=[O:15])([O:11][CH3:12])=[O:10]

Participants

7

Reactant 4

HCID 962WaterHCID 25517Ammonium ChlorideHCID 23665647Potassium tert-butoxide2×HCID 59142172HCID 59142172, compound2×

Product 1

HCID 59142168HCID 59142168, compoundYield 68%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

To a vigorously stirred suspension of methyltriphenylphosphonium bromide (942 mg; 2.64 mmol) in tetrahydrofuran (6 ml) 1M solution of potassium tert-butoxide in tetrahydrofuran (2.64 ml; 2.64 mmol) was added dropwise at 0° C. To the next flask with a solution of 20 (255 mg; 0.88 mmol) in tetrahydrofuran (1.1 ml) 1M solution of potassium tert-butoxide (0.88 ml; 0.88 mmol) was added. After 20 min. both mixtures were warmed to room temperature and cooled again to 0° C. after 30 min. The solution of enolate of 20 was transferred via cannula to the stirred solution of ylide. After 1 h the mixture was warmed up to room temperature and stirred for next 4 h. Then saturated aqueous solution of NH4Cl (8 ml) and water (30 ml) was added and the mixture was extracted with diethyl ether (3×100 ml). Organic phase was dried over anhydrous MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography (2-15% acetone/benzene) to give 172 mg (0.60 mmol; 68% yield) of 6. 1H NMR (400 MHz, CDCl3) δ 0.89 (3H, t, J=6.9 Hz), 1.00 (2H, m), 1.27-1.35 (4H, m), 1.40 (2H, m), 1.48 (2H, m), 2.09 (2H, t, J=7.8 Hz), 3.78 (2H, d, JH-P=21.7 Hz), 3.78 (6H, d, JH-P=11.2 Hz), 5.14 (2H, m); 13C NMR (101 MHz, CDCl3) δ 14.0, 17.2, 22.5, 27.3, 31.7, 36.0, 37.0 (d, JC-P=135 Hz), 52.9 (d, JC-P=6.5 Hz), 115.4, 147.7, 201.8 (d, JC-P=7.0 Hz).

Workup

  1. additionwas added dropwise at 0° C
  2. temperaturecooled again to 0° C. after 30 min
  3. temperatureAfter 1 h the mixture was warmed up to room temperature
  4. extractionthe mixture was extracted with diethyl ether (3×100 ml)
  5. dry with materialOrganic phase was dried over anhydrous MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography (2-15% acetone/benzene)
  8. customto give 172 mg (0.60 mmol; 68% yield) of 6

Sources & evidence

ORD record
ord-a5761043b09042e5b6e9171973f9b3d8
Source dataset
uspto-grants-2010_05
Patent number
US07713953B2

Reaction notes

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