Diisopropylamine → HCID 67958273, compound

HRID 1475672Notes

Reaction equation

HRID 1475672 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[CH:13]1([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:16][CH2:15][CH2:14]1.[Br:24][C:25]1[CH:26]=[C:27]([CH:30]=[CH:31][C:32]=1[Cl:33])[CH:28]=[O:29].[Cl-].[NH4+]>CCCCCC.C1COCC1>[Br:24][C:25]1[CH:26]=[C:27]([CH:28]([OH:29])[C:13]2([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:14][CH2:15][CH2:16]2)[CH:30]=[CH:31][C:32]=1[Cl:33]

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 140498093-Bromo-4-chlorobenzaldehydeHCID 15444481HCID 15444481, compoundHCID 178418339Butyllithium

Product 1

HCID 67958273HCID 67958273, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

21.65 ml (54.12 mmol) of a 2.5 M solution of n-butyllithium in hexane were added dropwise to a solution, cooled to from −20° C. to −30° C., of 7.6 ml (54.12 mmol) of diisopropylamine in 30 ml of abs. THF. After the addition had ended, the mixture was stirred at from −20° C. to −30° C. for another 30 min. The mixture was then cooled to −78° C., and a solution of 6.2 g (39.7 mmol) of tert-butyl cyclobutanecarboxylate in 10 ml of abs. THF was added dropwise at this temperature. After 4 h at −78° C., a solution of 7.9 g (36.1 mmol) of 3-bromo-4-chlorobenzaldehyde in 10 ml of abs. THF was then added. The reaction mixture was slowly warmed to RT overnight, saturated aqueous ammonium chloride solution was then added and the mixture was extracted with ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated under reduced pressure. The crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 50:1→10:1). This gave 7.77 g of the target compound (56% of theory).

Workup

  1. additionAfter the addition
  2. waitAfter 4 h at −78° C.
  3. temperatureThe reaction mixture was slowly warmed to RT overnight
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe organic phase was dried over magnesium sulphate
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 50:1→10:1)

Sources & evidence

ORD record
ord-6e6d5ce8b1a34658abb69b2afcf74150
Source dataset
uspto-grants-2015_04
Patent number
US09018258B2

Reaction notes

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