Diisopropylamine → HCID 58136634, compound

HRID 877213Notes

Reaction equation

HRID 877213 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][CH:14]([CH3:19])[C:15]([O:17][CH3:18])=[O:16].Br[CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([N+:28]([O-:30])=[O:29])[CH:23]=1.[Cl-].[NH4+]>C1COCC1.CCCCCC.C(OCC)(=O)C.C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:13][C:14]([CH3:19])([CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([N+:28]([O-:30])=[O:29])[CH:23]=1)[C:15]([O:17][CH3:18])=[O:16]

Participants

10

Reactant 5

HCID 7912DiisopropylamineHCID 11039Methyl isobutyrateHCID 25517Ammonium ChlorideHCID 77568Benzene, 1-(bromomethyl)-3-nitro-HCID 178418339Butyllithium

Product 1

HCID 58136634HCID 58136634, compound

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 21584019Toluene ethylacetateSolvent

Conditions

Temperature
-78 °C

Procedure

Under argon, 11.7 ml (83.32 mmol) of diisopropylamine were dissolved in 200 ml of THF and cooled to −78° C. 33.3 ml (83.32 mmol) of a 2.5 M solution of n-butyllithium in hexane were added dropwise to this solution. The reaction solution was then warmed to −10° C. and stirred at this temperature for 10 min. The reaction solution was then once more cooled to −78° C., and 8.4 ml (72.9 mmol) of methyl 2-methylpropanoate were added slowly. The mixture was then stirred at −78° C. for 30 min. 15 g (69.4 mmol) of 1-(bromomethyl)-3-nitrobenzene, dissolved in 150 ml of THF, were then slowly added dropwise. After the addition had ended, the solution was slowly warmed to room temperature and stirred overnight. After TLC check (mobile phase: toluene/ethyl acetate 10:1), saturated ammonium chloride solution was added and the reaction mixture was taken up in ethyl acetate. The aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. The crude product was purified chromatographically on silica gel (mobile phase toluene/ethyl acetate 20:1). This gave 12.2 g (51.4 mmol, 74% of theory) of the title compound.

Workup

  1. temperatureThe reaction solution was then warmed to −10° C.
  2. temperatureThe reaction solution was then once more cooled to −78° C.
  3. stirringThe mixture was then stirred at −78° C. for 30 min
  4. additionwere then slowly added dropwise
  5. additionAfter the addition
  6. temperaturethe solution was slowly warmed to room temperature
  7. stirringstirred overnight
  8. extractionThe aqueous phase was extracted three times with ethyl acetate
  9. dry with materialThe combined organic phases were dried over sodium sulfate
  10. filtrationAfter filtration
  11. customthe solvent was removed under reduced pressure
  12. customThe crude product was purified chromatographically on silica gel (mobile phase toluene/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-c61a2500752641ccac7043efb87d3651
Source dataset
uspto-grants-2015_03
Patent number
US08987256B2

Reaction notes

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