Water → HCID 68281244, compound

HRID 1475908Notes

Reaction equation

HRID 1475908 reaction equation
[NH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][C:2]1=[O:11].[H-].[Na+].Cl[C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:16].O>O1CCCC1.CN(C1C=CN=CC=1)C.CCCCCC.C(OCC)(=O)C>[O:11]=[C:2]1[CH2:3][CH2:4][C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[N:1]1[C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:16]

Participants

8

Reactant 4

HCID 962WaterHCID 10387Benzyl chloroformateHCID 24758Sodium hydrideHCID 64796Hydrocarbostyril

Product 1

HCID 68281244HCID 68281244, compoundYield 76%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolventHCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
0 °C

Procedure

A reactor was charged with 1.5 g (10 mmol) of 3,4-dihydroquinolin-2(1H)-one and 77 mL of tetrahydrofuran as a solvent. After cooling the mixture to 0° C., 0.8 g (20 mmol) of sodium hydride was added dropwise to the mixture. The mixture was stirred for 30 minutes, and held at 0° C., followed by the addition of 5.12 g (30 mmol) of benzyl chloroformate (acyl chloride (RCl)) and 0.24 g (2 mmol) of N,N-dimethyl-4-aminopyridine (DMAP). After adjusting the temperature of the reaction system to room temperature (about 20° C.), the mixture was reacted for 12 hours with stirring. After cooling the mixture including the reaction product to 0° C., water was added dropwise to the mixture, followed by extraction with ethyl acetate. After the addition of excess anhydrous magnesium sulfate to the resulting organic layer, the solvent was evaporated under reduced pressure to obtain a concentrate including a crude product. The concentrate was subjected to silica gel flash column chromatography (eluant: hexane/ethyl acetate=1/1) to obtain benzyl 2-oxo-3,4-dihydroquinoline-1(2H)-carboxylate (yellow oily product) represented by the following formula (ai2) having a Cbz group (PhCH2OCO—) as a protecting group (yield: 76%). The analysis data for the resulting compound (ai2) is shown below.

Workup

  1. customheld at 0° C.
  2. customto room temperature
  3. custom(about 20° C.)
  4. customthe mixture was reacted for 12 hours
  5. stirringwith stirring
  6. temperatureAfter cooling the mixture
  7. customto 0° C.
  8. extractionfollowed by extraction with ethyl acetate
  9. additionAfter the addition of excess anhydrous magnesium sulfate to the resulting organic layer
  10. customthe solvent was evaporated under reduced pressure
  11. customto obtain a concentrate

Sources & evidence

ORD record
ord-2f107b484c5e49ae934f2b60d5c95292
Source dataset
uspto-grants-2015_04
Patent number
US09018394B2

Reaction notes

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