Dimethylformamide → 2-Fluoro-3-(1-dodecynyl)benzaldehyde

HRID 977549Notes

Reaction equation

HRID 977549 reaction equation
[C:1]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[F:19])#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C([Li])(CC)C.CN(C)[CH:27]=[O:28]>O1CCCC1.C(OCC)(=O)C>[F:19][C:14]1[C:13]([C:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])=[CH:18][CH:17]=[CH:16][C:15]=1[CH:27]=[O:28]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 183730582-(1-Dodecynyl)fluorobenzeneHCID 178418400CID 53628100

Product 1

HCID 183730612-Fluoro-3-(1-dodecynyl)benzaldehydeYield 91%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 7.00 g (27.0 mmol) of 2-(1-dodecynyl)fluorobenzene in tetrahydrofuran (60 ml) at -78° C. was added slowly sec-butyllithium (1.3M, cyclohexane) (21 ml). The mixture was stirred at -78° C. for 30 min, and dimethylformamide (2.8 ml) was added dropwise. The mixture was stirred for 5 min at -78° C. and allowed to warm to room temperature. The mixture was diluted with ethyl acetate and washed with water. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated in vacuo. The residue was flash chromatographed on silica gel (eluted with ethyl acetate/heptane/:1:10). The appropriate fractions were collected and evaporated. The residue was chromatographed a second time over silica gel (eluted with dichloromethane) to afford 7.10 g (91%) of product.

Workup

  1. stirringThe mixture was stirred for 5 min at -78° C.
  2. temperatureto warm to room temperature
  3. washwashed with water
  4. customThe organic phase was separated
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated in vacuo
  8. customchromatographed on silica gel (eluted with ethyl acetate/heptane/:1:10)
  9. customThe appropriate fractions were collected
  10. customevaporated
  11. customThe residue was chromatographed a second time over silica gel (eluted with dichloromethane)

Sources & evidence

ORD record
ord-68fb3fe274c2475e8c0439251425b79f
Source dataset
uspto-grants-1997_03
Patent number
US05614631

Reaction notes

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