Dimethylformamide → HCID 22715028, compound

HRID 352033Notes

Reaction equation

HRID 352033 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[C:10]([C:11]([CH3:18])([CH3:17])[CH2:12][O:13][CH2:14][O:15][CH3:16])=[CH:9][C:8](Br)=[CH:7][C:6]=1[C:20]([CH3:23])([CH3:22])[CH3:21].[Li]C(C)(C)C.CN([CH:32]=[O:33])C.[Cl-].[NH4+]>C1COCC1>[C:20]([C:6]1[CH:7]=[C:8]([CH:9]=[C:10]([C:11]([CH3:18])([CH3:17])[CH2:12][O:13][CH2:14][O:15][CH3:16])[C:5]=1[O:4][CH2:3][O:2][CH3:1])[CH:32]=[O:33])([CH3:23])([CH3:22])[CH3:21]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 22973407HCID 22973407, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 22715028HCID 22715028, compoundYield 83.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 48 (925 mg, 2.38 mmol) in THF (20 ml) was cooled to −50° C., and t-BuLi (1.7 M in pentane, 3.08 ml, 5.24 mmol) was dropwise added to the solution while maintaining the temperature below −40° C. After completion of the addition, the mixture was stirred at this temperature, and DMF (0.12 ml) in THF (5 ml) was added. The mixture was warmed slowly to room temperature. Aqueous solution of saturated ammonium chloride (50 ml) was added, and the mixture was extracted with ethyl acetate (50 ml). The organic layer was washed with saturated brine (50 ml), and after dryness, the solvent was removed in vacuo. The residue was purified by column chromatography to yield 669 mg (83.1%) of 49 as colorless oil. 1H NMR (CDCl3) δ: 1.47 (9H, s, tBu), 1.48 (6H, s, 2×CH3), 3.29, 3.66 (each 3H, s, CH3), 3.84 (2H, s, CH2), 4.60, 4.95 (each 2H, s, CH2), 7.81 (1H, d, J=2.2 Hz, Ar—H), 7.84 (1H, d, J=2.2 Hz, Ar—H), 9.92 (1H, s, CHO).

Workup

  1. temperaturewhile maintaining the temperature below −40° C
  2. additionAfter completion of the addition
  3. additionwas added
  4. extractionthe mixture was extracted with ethyl acetate (50 ml)
  5. washThe organic layer was washed with saturated brine (50 ml)
  6. customafter dryness, the solvent was removed in vacuo
  7. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-c1ed41e5709e4cb4abfc53072dd01404
Source dataset
uspto-grants-2004_06
Patent number
US06743923B2

Reaction notes

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