Water → HCID 68817206, compound

HRID 733297Notes

Reaction equation

HRID 733297 reaction equation
[Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](/[CH:15]=[CH:16]/[C:17](=[O:26])[CH:18]([CH3:25])[C:19](=[O:24])[C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:11][C:10]=1[O:27][CH3:28])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].[CH3:31]I.O>C1COCC1.C(Cl)Cl>[Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](/[CH:15]=[CH:16]/[C:17](=[O:26])[C:18]([CH3:31])([CH3:25])[C:19](=[O:24])[C:20]([CH3:21])([CH3:23])[CH3:22])=[CH:11][C:10]=1[O:27][CH3:28])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 68815305HCID 68815305, compound

Product 1

HCID 68817206HCID 68817206, compoundYield 48%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirring solution of (E)-1-(4-tert-butyldimethylsilyloxy-3-methoxyphenyl)-4,6,6-trimethylhept-1-ene-3,5-dione (540 mg, 1.33 mmol) in THF (10 ml) under N2 was added sodium hydride (64 mg (of 60%), 1.60 mmol) and stirred for a further 45 min at room temperature. A solution of methyl iodide (0.1 ml, 1.60 mmol) in THF (1 ml) was added and the mixture heated at reflux for 5 h. Water (25 ml) was added to the cooled mixture followed by DCM (25 ml). The organic layer was separated, washed with water (25 ml), dried (MgSO4(anh)), filtered and concentrated. The residue was purified by column chromatography on silica using dichloromethane as eluent to give (E)-1-(4-tert-butyldimethylsilyloxy-3-methoxyphenyl)-4,4,6,6-tetramethylhept-1-ene-3,5-dione (266 mg, 48%) as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 0.17 (6H, s, Si(CH3)2), 0.99 (9H, s, SiC(CH3)3), 1.18 (9H, s, C(CH3)3), 1.41 (6H, s, 2×C(CH3)), 3.83 (3H, s, OCH3), 6.54 (1H, d, J=15.6 Hz, vinyl CH), 6.84 (1H, d, J=8.0 Hz, ArH), 6.98 (1H, d, J=2.0 Hz, ArH), 7.06 (1H, dd, J=8.0, 2.0 Hz, ArH), 7.66 (1H, d, J=15.6 Hz, vinyl CH) ppm.

Workup

  1. temperaturethe mixture heated
  2. temperatureat reflux for 5 h
  3. customThe organic layer was separated
  4. washwashed with water (25 ml)
  5. dry with materialdried (MgSO4(anh))
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica

Sources & evidence

ORD record
ord-c8017fe8357c4974b68e824b9d46f68a
Source dataset
uspto-grants-2009_09
Patent number
US07589123B2

Reaction notes

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