Diisopropylamine → HCID 59438430, compound

HRID 2177482Notes

Reaction equation

HRID 2177482 reaction equation
C(NC(C)C)(C)C.[Li]CCCC.[CH3:13][N:14]1[CH2:19][C:18]([N+:26]([O-:28])=[O:27])([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH2:17][CH2:16][C:15]1=[O:29].C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:40])(=O)=O)=CC=1>C1COCC1.CCCCCC>[F:40][CH:16]1[CH2:17][C:18]([N+:26]([O-:28])=[O:27])([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH2:19][N:14]([CH3:13])[C:15]1=[O:29]

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 588007N-FluorobenzenesulfonimideHCID 59438516HCID 59438516, compoundHCID 178418339Butyllithium

Product 1

HCID 59438430HCID 59438430, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 78.4 ul (0.555 mmol) diisopropylamine in 2 ml THF were added 347 ul (0.555 mmol) of a 1.6M n-BuLi solution in hexane at −5° C. The solution was stirred for 15 minutes at 0° C. and then cooled to −70° C. A solution of 100 mg (0.427 mmol) rac-1-methyl-5-nitro-5-phenyl-piperidin-2-one in 1 ml THF was added dropwise. The brown solution was stirred at −70° C. for 45 minutes. A solution of 180 mg (0.555 mmol) N-fluorobenzenesulphonimide in 1 ml THF was added dropwise. The mixture was stirred at −70° C. for 1.5 hour, quenched with 2 ml of a 20% NH4Cl solution and allowed to warm to room temperature. Water and ethyl acetate were added. The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude oil was purified on silica gel (Eluent: Heptane/ethyl acetate 0 to 100%) to provide 58 mg (54%) of the title compound as a light yellow solid. MS (m/e): 253.2 (M+H).

Workup

  1. temperaturecooled to −70° C
  2. stirringThe brown solution was stirred at −70° C. for 45 minutes
  3. stirringThe mixture was stirred at −70° C. for 1.5 hour
  4. customquenched with 2 ml of a 20% NH4Cl solution
  5. temperatureto warm to room temperature
  6. additionWater and ethyl acetate were added
  7. extractionThe aqueous layer was extracted twice with ethyl acetate
  8. dry with materialThe combined organic layers were dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe crude oil was purified on silica gel (Eluent: Heptane/ethyl acetate 0 to 100%)

Sources & evidence

ORD record
ord-eaad55ce081a4affb711ba6e7b1757dc
Source dataset
uspto-grants-2015_06
Patent number
US09067911B2

Reaction notes

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