1,2-Ethanediamine, N1,N1,N2-trimethyl- → 4-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-propylbenzaldehyde

HRID 2293588Notes

Reaction equation

HRID 2293588 reaction equation
CN(C)CCNC.[CH2:8]([Li])[CH2:9][CH2:10]C.[Si:13]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[O:26])=[CH:23][CH:22]=1)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]>C1COCC1>[Si:13]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[O:26])=[C:23]([CH2:8][CH2:9][CH3:10])[CH:22]=1)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]

Participants

5

Reactant 3

HCID 673381,2-Ethanediamine, N1,N1,N2-trimethyl-HCID 108791334-{[tert-Butyl(dimethyl)silyl]oxy}benzaldehydeHCID 178418339Butyllithium2×

Product 1

HCID 214769234-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-propylbenzaldehydeYield 13%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-20 °C

Procedure

To a solution of 1.226 g (0.012 mol) of N,N,N'-trimethylethylenediamine in 25 mL of anhydrous THF was added 4.40 mL of a 2.5M solution of n-butyllithium in THF at -20° C. under a nitrogen atmosphere. After 15-20 minutes, 2.501 g (0.010 mol) of the product of Step C dissolved in 5.0 mL of THF was added and the reaction mixture was stirred at -20° C. for an additional 15-20 minutes. Next, 12.0 mL of a 2.5M solution of n-butyllithium in THF was added to the reaction, the cooling bath was removed and the mixture was stirred at room temperature for 3.5 hours. At the end of this period, the reaction mixture was cooled to -40° C. and 5.85 mL of 1-iodopropane was added via syringe. The reaction mixture was then allowed to slowly warm to room temperature and was stirred for 16 hours. The mixture was then partitioned between diethylether and 10% aqueous NaHSO4 and extracted. The organic layer was separated, dried (MgSO4), filtered, and evaporated. The residue was partially purified on a silica gel flash chromatography column eluted with 5% EtOAc-hexane. The semi-purified fractions were combined and evaporated, then rechromatographed on a silica gel flash chromatography column eluted with 50% CHCl3 -hexane. Evaporation of the purified fractions and solvent removal in vacuo afforded 0.386 g (13%) of the title compound.

Workup

  1. additionwas added
  2. customthe cooling bath was removed
  3. stirringthe mixture was stirred at room temperature for 3.5 hours
  4. temperatureAt the end of this period, the reaction mixture was cooled to -40° C.
  5. addition5.85 mL of 1-iodopropane was added via syringe
  6. temperatureto slowly warm to room temperature
  7. stirringwas stirred for 16 hours
  8. customThe mixture was then partitioned between diethylether and 10% aqueous NaHSO4
  9. extractionextracted
  10. customThe organic layer was separated
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. customevaporated
  14. customThe residue was partially purified on a silica gel flash chromatography column
  15. washeluted with 5% EtOAc-hexane
  16. customevaporated
  17. customrechromatographed on a silica gel flash chromatography column
  18. washeluted with 50% CHCl3 -hexane
  19. customEvaporation of the purified fractions and solvent removal in vacuo

Sources & evidence

ORD record
ord-a758fba5f1304a5181a041fd87ad23e8
Source dataset
uspto-grants-1997_11
Patent number
US05686478

Reaction notes

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