Dimethylformamide → 3-{[tert-Butyl(dimethyl)silyl]oxy}-5-ethyl-2-fluorobenzaldehyde

HRID 1161496Notes

Reaction equation

HRID 1161496 reaction equation
[C:1]([Si:5]([O:8][C:9]1[CH:14]=[C:13]([CH2:15][CH3:16])[CH:12]=[CH:11][C:10]=1[F:17])([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C([Li])(CC)C.CN([CH:26]=[O:27])C.[Cl-].[NH4+]>C1COCC1.C(OCC)C>[Si:5]([O:8][C:9]1[C:10]([F:17])=[C:11]([CH:12]=[C:13]([CH2:15][CH3:16])[CH:14]=1)[CH:26]=[O:27])([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:7])[CH3:6]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 59838026tert-Butyl(5-ethyl-2-fluorophenoxy)dimethylsilaneHCID 178418400CID 53628100

Product 1

HCID 598380723-{[tert-Butyl(dimethyl)silyl]oxy}-5-ethyl-2-fluorobenzaldehyde

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 12.7 g of t-butyl-(5-ethyl-2-fluorophenoxy)dimethylsilane and 7.5 g of N,N,N′N′-tetramethylethylenediamine in 250 ml of THF was cooled to −75° C. under a nitrogen atmosphere, and then 55.6 ml of s-butyllithium (0.99 M, cyclohexane solution) was added and the mixture was stirred for 2 hours. After adding 7.74 ml of DMF and stirring at −75° C. for 1 hour, the temperature was allowed to rise to room temperature. Next, 500 ml of diethyl ether and 500 ml of a 5% aqueous ammonium chloride were added to the reaction mixture, the organic layer was washed twice with 500 ml of water and once with 500 ml of saturated aqueous sodium chloride in that order, and the aqueous layer was extracted with 100 ml of diethyl ether. The organic layers were combined and dried over anhydrous magnesium sulfate, the desiccating agent was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-heptane) to give the title compound (12.6 g) as a white solid.

Workup

  1. stirringstirring at −75° C. for 1 hour
  2. customto rise to room temperature
  3. washthe organic layer was washed twice with 500 ml of water and once with 500 ml of saturated aqueous sodium chloride in that order
  4. extractionthe aqueous layer was extracted with 100 ml of diethyl ether
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationthe desiccating agent was filtered off
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (ethyl acetate-heptane)

Sources & evidence

ORD record
ord-96cc24fd88b7466dbc0dcb9ba7b0fd3d
Source dataset
uspto-grants-2010_10
Patent number
US07816522B2

Reaction notes

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