Diisopropylamine → HCID 59545179, compound

HRID 886684Notes

Reaction equation

HRID 886684 reaction equation
[C:1](=[O:3])=[O:2].[CH3:4][C:5](C)=O.[CH:8](NC(C)C)(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)([CH2:37][CH:38]([CH3:40])[CH3:39])[CH2:33][CH:34]([CH3:36])[CH3:35])(=O)=O>C1COCC1>[CH2:33]([Si:32]([CH2:37][CH:38]([CH3:40])[CH3:39])([CH2:21][C:20]([O:23][CH2:24][CH3:25])=[O:22])[CH2:8][C:1]([O:3][CH2:4][CH3:5])=[O:2])[CH:34]([CH3:36])[CH3:35]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 8857Ethyl AcetateHCID 18522661Acetone cardiceHCID 86646801HCID 86646801, compoundHCID 178418339Butyllithium

Product 1

HCID 59545179HCID 59545179, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A dry-ice-acetone cooled 500 mL-RB flask is charged with anhydrous THF (90 ml) and diisopropylamine (6.7 g, 0.066 mol). A solution of butyl lithium in hexanes (1.6 M, 48 ml, 0.075 mol) is added over 1 hour. After stirring at −78° C. for an additional 30 minutes, the mixture is warmed to 0° C. and stirred for an hour and at room temperature for 15 minutes. The mixture is cooled again in a dry-ice acetone bath, and anhydrous ethyl acetate (5.28 g, 0.06 mol) is added dropwise over 30 minutes. After the mixture is stirred at −78° C. for 1 hour, diisobutylsilanediyl bis(trifluoromethanesulfonate) (14.4 g, 0.01 mol) is added dropwise over 30 minutes. After about 4 hours, 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 flash column chromatography on silica gel yield 2.6 g (27%) of product as a yellowish oil. 1H NMR (500 MHz, CDCl3, in ppm) δ 4.10 (q, 4H, J=7.0 Hz), 2.03 (s, 4H), 1.82-1.92 (theptat, 2H, J=6.5 Hz, 6.5 Hz), 1.25 (t, 6H, J=7.0 Hz), 0.96 (d, 12H, J=6.5 Hz), 0.75 (d, 4H, J=6.5 Hz).

Workup

  1. temperaturethe mixture is warmed to 0° C.
  2. stirringstirred for an hour and at room temperature for 15 minutes
  3. temperatureThe mixture is cooled again in a dry-ice acetone bath
  4. stirringAfter the mixture is stirred at −78° C. for 1 hour
  5. waitAfter about 4 hours
  6. customthe reaction is quenched with water
  7. additionpoured into ice-water
  8. customThe organic layer is separated
  9. extractionthe aqueous layer is extracted with ether
  10. washThe combined organic solution is washed with brine
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationthe filtrate concentrated
  14. customThe residue is purified by flash column chromatography on silica gel yield 2.6 g (27%) of product as a yellowish oil

Sources & evidence

ORD record
ord-37c662daad7c4603a1101dcacd338178
Source dataset
uspto-grants-2012_08
Patent number
US08247341B2

Reaction notes

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