Diisopropylamine → HCID 58288342, compound

HRID 1476079Notes

Reaction equation

HRID 1476079 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20][C:21]([O:23][CH3:24])=[O:22])=[CH:16][CH:15]=1.[C:25]1(=[O:30])[CH2:29][CH2:28][CH:27]=[CH:26]1.[Cl-].[NH4+]>C1COCC1.CCCCCC.C(OCC)(=O)C.C1CCCCC1.C(OCC)(=O)C>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([CH:20]([CH:27]2[CH2:28][CH2:29][C:25](=[O:30])[CH2:26]2)[C:21]([O:23][CH3:24])=[O:22])=[CH:18][CH:19]=1

Participants

10

Reactant 5

HCID 7912DiisopropylamineHCID 135882-Cyclopenten-1-oneHCID 25517Ammonium ChlorideHCID 104196Methyl 4-chlorophenylacetateHCID 178418339Butyllithium

Product 1

HCID 58288342HCID 58288342, compound

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 21867204Cyclohexane ethylacetateSolvent

Conditions

Temperature
-30 °C

Procedure

Under argon, 14.8 ml (105.6 mmol) of diisopropylamine were initially charged in 150 ml of THF, the mixture was cooled to −30° C. and 42.3 ml (105.75 mmol) of a 2.5 M solution of n-butyllithium in hexane were added slowly. The reaction solution was then warmed to −20° C., 15 g (81.25 mmol) of methyl (4-chlorophenyl)acetate, dissolved in 90 ml of THF, were added slowly and the mixture was stirred at this temperature for 2 h. The reaction solution was then cooled to −78° C., and 7.2 ml (86.1 mmol) of 2-cyclopentene-1-one, dissolved in 60 ml of THF, were added slowly. After the addition had ended, the solution was stirred at this temperature for 1 h. After TLC check (mobile phase cyclohexane/ethyl acetate 9:1), saturated ammonium chloride solution was added and the mixture was taken up in ethyl acetate. The aqueous phase was extracted twice with ethyl acetate. The combined organic phases were dried over magnesium sulphate. After filtration, the solvent was removed under reduced pressure. The crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 4:1). This gave 15.65 g (58.67 mmol, 72% of theory) of the title compound as a yellowish oil.

Workup

  1. temperatureThe reaction solution was then warmed to −20° C.
  2. additionwere added slowly
  3. temperatureThe reaction solution was then cooled to −78° C.
  4. additionwere added slowly
  5. additionAfter the addition
  6. stirringthe solution was stirred at this temperature for 1 h
  7. extractionThe aqueous phase was extracted twice with ethyl acetate
  8. dry with materialThe combined organic phases were dried over magnesium sulphate
  9. filtrationAfter filtration
  10. customthe solvent was removed under reduced pressure
  11. customThe crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 4:1)

Sources & evidence

ORD record
ord-97b5e309f3cd4ef5995c3342fd633745
Source dataset
uspto-grants-2015_04
Patent number
US09018414B2

Reaction notes

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