Sodium bis(trimethylsilyl)amide → HCID 392891, compound

HRID 413928

Reaction equation

HRID 413928 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[Br-].[CH2:12]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].[I:37][C:38]1[CH:39]=[C:40]([CH:56]=[C:57]([C:61]([O:63][CH3:64])=[O:62])[C:58]=1[O:59][CH3:60])[C:41]([C:43]1[CH:48]=[C:47]([C:49]([O:51][CH3:52])=[O:50])[C:46]([O:53][CH3:54])=[C:45]([I:55])[CH:44]=1)=O>C1COCC1>[CH3:12][CH2:13][CH2:14][CH2:15][CH2:16][CH:17]=[C:41]([C:43]1[CH:44]=[C:45]([I:55])[C:46]([O:53][CH3:54])=[C:47]([C:49]([O:51][CH3:52])=[O:50])[CH:48]=1)[C:40]1[CH:39]=[C:38]([I:37])[C:58]([O:59][CH3:60])=[C:57]([C:61]([O:63][CH3:64])=[O:62])[CH:56]=1

Participants

5

Reactant 3

HCID 2724254Sodium bis(trimethylsilyl)amideHCID 2724569Phosphonium, hexyltriphenyl-, bromide (1:1)HCID 10841416HCID 10841416, compound

Product 1

HCID 392891HCID 392891, compoundYield 9.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

NaN(TMS)2 (1 mL, 1 mmol) was added to an ice cold suspension of hexyltriphenylphosphonium bromide (0.427 g, 1 mmol) in THF (20 mL) and the solution was stirred for 30 min at 0° C. A solution of the benzophenone 39 (0.2 g, 0.33 mmol) in THF (5 mL) was added to the preformed ylide and the solution was stirred at rt overnight. The mixture was partitioned between 1 N HCl (100 mL) and ethyl acetate (100 mL). The organic layer was evaporated and flash chromatographed on SiO2 (230-400 mesh, 50.0 g), eluting with hexanes-ethyl acetate (5:1). The fractions which contained the product were pooled, evaporated, and chromatographed on silica gel (230-400 mesh, 20 g), eluting with hexanes-ethyl acetate (5:1), to give the product 40 (0.022 g, 9%) as an oil: 1H NMR (CDCl3, 300 MHz) δ 7.69 (s, 2H), 7.54 (d, J=2.0 Hz, 1H), 7.52 (d, J=2 Hz, 1H), 6.01 (t, J=7.6 Hz, 1H), 3.93 (s, 3H), 3.89 (s, 3H), 3.88 (s, 3H), 3.85 (s, 3H), 2.05 (q, J=7.3 Hz, 2H), 1.42 (m, 2H), 1.25 (m, 2H), 0.85 (t, J=6.7 Hz, 3H); IR (neat) 2953, 2929, 1742, 1738, 1731, 1713 cm−1; HRFABMS calcd for C25H28I2O6 m/z 677.9975 (M+). Found: m/z 677.9954. Anal. (C25H28I2O60.5EtOAc), C, H.

Workup

  1. stirringthe solution was stirred at rt overnight
  2. customThe mixture was partitioned between 1 N HCl (100 mL) and ethyl acetate (100 mL)
  3. customThe organic layer was evaporated
  4. customflash chromatographed on SiO2 (230-400 mesh, 50.0 g)
  5. washeluting with hexanes-ethyl acetate (5:1)
  6. customevaporated
  7. customchromatographed on silica gel (230-400 mesh, 20 g)
  8. washeluting with hexanes-ethyl acetate (5:1)

Sources & evidence

ORD record
ord-350efe5fa38247c1a0512957dd14db9e
Source dataset
uspto-grants-2003_05
Patent number
US06569897B1

Linked notes

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