Diisopropylamine → HCID 59545180, compound

HRID 886680Notes

Reaction equation

HRID 886680 reaction equation
[C:1](=[O:3])=[O:2].[CH3:4][C:5](C)=O.C(N[CH:12]([CH3:14])[CH3:13])(C)C.C([Li])CCC.[C:20]([O:23][CH2:24][CH3:25])(=[O:22])[CH3:21].FC(F)(F)S(O[Si:32](OS(C(F)(F)F)(=O)=O)([CH:36]([CH3:38])[CH3:37])[CH:33](C)C)(=O)=O>C1COCC1>[CH:36]([Si:32]([CH:12]([CH3:13])[CH3:14])([CH2:21][C:20]([O:23][CH2:24][CH3:25])=[O:22])[CH2:33][C:1]([O:3][CH2:4][CH3:5])=[O:2])([CH3:38])[CH3:37]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 8857Ethyl AcetateHCID 4457970Diisopropylsilyl bis(trifluoromethanesulfonate)HCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 1

HCID 59545180HCID 59545180, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A dry-ice-acetone cooled 250 mL-RB flask is charged with anhydrous THF (30 ml) and diisopropylamine (2.2 g, 0.022 mol). A solution of butyl lithium in hexanes (1.6 M, 16 ml, 0.025 mol) is added over 30 minutes. After stirring at −78° C. for an additional 30 minutes, the mixture is warmed up to 0° C. and stirred for an hour. The mixture is cooled again in a dry-ice-acetone bath, and anhydrous ethyl acetate (1.76 g, 0.02 mol) is added dropwise over 30 minutes. After the mixture is stirred at −78° C. for 30 minutes, diisopropylsilanediyl bis(trifluoromethanesulfonate) (4.12 g, 0.01 mol) is added dropwise over 10 minutes. The reaction is quenched with water, and poured into ice-water. The organic layer is separated, and the aqueous layer is extracted with ether. The combined organic solution is washed with brine, dried over sodium sulfate, filtered, and the filtrate concentrated. The residue is purified by distillation in a Kugelrohr to yield 1.15 g (40%) of product as a yellowish oil. 1H NMR (500 MHz, CDCl3, in ppm) δ 4.09 (q, 4H, J=7.0 Hz), 1.99 (s, 4H), 1.24 (t, 6H, J=7.0 Hz), 1.12 (heptet, 2H, J=6.5 Hz), 1.06 (d, 12H, J=6.5 Hz).

Workup

  1. temperaturethe mixture is warmed up to 0° C.
  2. stirringstirred for an hour
  3. temperatureThe mixture is cooled again in a dry-ice-acetone bath
  4. stirringAfter the mixture is stirred at −78° C. for 30 minutes
  5. customThe reaction is quenched with water
  6. additionpoured into ice-water
  7. customThe organic layer is separated
  8. extractionthe aqueous layer is extracted with ether
  9. washThe combined organic solution is washed with brine
  10. dry with materialdried over sodium sulfate
  11. filtrationfiltered
  12. concentrationthe filtrate concentrated
  13. distillationThe residue is purified by distillation in a Kugelrohr

Sources & evidence

ORD record
ord-88be32551958462f9e1b0d4e993cad77
Source dataset
uspto-grants-2012_08
Patent number
US08247341B2

Reaction notes

Loading…