Methyl iodide → HCID 68817969, compound

HRID 733293Notes

Reaction equation

HRID 733293 reaction equation
[Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15](=[O:37])[CH2:16][C:17](=[O:36])/[CH:18]=[CH:19]/[C:20]2[CH:25]=[CH:24][C:23]([O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])=[C:22]([O:34][CH3:35])[CH:21]=2)=[CH:11][C:10]=1[O:38][CH3:39])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Na].[CH3:41]I>C(OCC)C>[Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15](=[O:37])[CH:16]([CH3:41])[C:17](=[O:36])[CH:18]=[CH:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][Si:27]([C:30]([CH3:31])([CH3:32])[CH3:33])([CH3:28])[CH3:29])=[C:22]([O:34][CH3:35])[CH:21]=2)=[CH:11][C:10]=1[O:38][CH3:39])([C:4]([CH3:5])([CH3:7])[CH3:6])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 5360545SodiumHCID 68815481HCID 68815481, compound

Product 1

HCID 68817969HCID 68817969, compoundYield 66.7%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of (E)-1,5-bis(4-tert-butyldimethylsilyloxy-3-methoxyphenyl)-pent-4-ene-1,3-dione (459 mg, 0.80 mmol) in anhydrous diethyl ether (8 ml) was added sodium (20 mg, 0.88 mmol). The mixture was stirred for 18 h, when all the sodium had been consumed, forming a yellow solid. The diethyl ether was removed under vacuum, and the yellow oily solid was dissolved in acetone (8 ml). Methyl iodide (45 μl, 0.72 mmol) was added to this mixture and stirred overnight at room temperature. The acetone was removed under vacuum, and the residue was taken up in ethyl acetate, washed with water, dried (MgSO4 (anh)), filtered and concentrated in vacuo. The residue was purified on silica gel column using dichloromethane/petroleum ether (1:1 to 1:0) to give 1,5-bis(4-tert-butyldimethylsilyloxy-3-methoxyphenyl)-2-methylpent-4-ene-1,3-dione (281 mg, 60%) as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 0.16 (6H, s, 2×CH3), 0.18 (6H, s, 2×CH3), 0.99 (18H, br s, 2×(CH3)3)), 1.54 (3H, d, J=7.0 Hz, CH3), 3.83 (3H, s, OCH3), 3.85 (3H, s, OCH3), 4.66 (1H, q, J=7.0 Hz, H-2), 6.69 (1H, d, J=16 Hz, H-4), 6.83 (1H, d, J=8.4 Hz, H-5′), 6.87 (1H, d, J=8.4 Hz, H-5′), 7.00 (1H, d, J=2.0 Hz, H-2′), 7.03 (1H, dd, J=8.4, 2.0 Hz, H-6′), 7.53-7.58 (2H, m, ArH), 7.60 (1H, d, J=16.0 Hz, H-5) ppm.

Workup

  1. customwhen all the sodium had been consumed
  2. customforming a yellow solid
  3. customThe diethyl ether was removed under vacuum
  4. dissolutionthe yellow oily solid was dissolved in acetone (8 ml)
  5. stirringstirred overnight at room temperature
  6. customThe acetone was removed under vacuum
  7. washwashed with water
  8. dry with materialdried (MgSO4 (anh))
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified on silica gel column

Sources & evidence

ORD record
ord-f341e47c5444436aa5d09945c63edfc8
Source dataset
uspto-grants-2009_09
Patent number
US07589123B2

Reaction notes

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