Cesium carbonate → Ethyl [(1-isopropyl-4,4,7-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)amino)benzoate

HRID 365520Notes

Reaction equation

HRID 365520 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH:13]([N:16]1[C:25]2[C:20](=[CH:21][C:22]([NH2:27])=[C:23]([CH3:26])[CH:24]=2)[C:19]([CH3:29])([CH3:28])[CH2:18][CH2:17]1)([CH3:15])[CH3:14].C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH:13]([N:16]1[C:25]2[C:20](=[CH:21][C:22]([NH:27][C:11]3[CH:12]=[CH:2][CH:3]=[CH:4][C:5]=3[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[C:23]([CH3:26])[CH:24]=2)[C:19]([CH3:29])([CH3:28])[CH2:18][CH2:17]1)([CH3:15])[CH3:14]

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 22043Ethyl 4-bromobenzoateHCID 23291943(1-Isopropyl-4,4,7-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)amine2×

Product 1

HCID 86755923Ethyl [(1-isopropyl-4,4,7-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)amino)benzoateYield 56%

Reagents, catalysts & solvents 4

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of ethyl 4-bromobenzoate (0.98 g, 4.3 mmol) and (1-isopropyl-4,4,7-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)amine (Compound 19, 0.69 g, 3.0 mmol) in 15.0 mL of toluene stirring under argon was added cesium carbonate (1.84 g, 5.6 mmol), tris(dibenzylideneacetone)dipalladium(0) (35 mg, 0.04 mmol) and BINAP (68 mg, 0.11 mmol) consecutively. The reaction mixture was then heated at 100° C. for 48 hours. The reaction mixture was then cooled to room temperature, diluted with water and extracted with ethyl ether (2×). The combined organic extracts were washed with brine and dried (MgSO4). The filtered solution was concentrated under reduced pressure and the crude product was purified by silica gel chromatography (10% ethyl acetate in hexanes) to give the title compound (0.63 g, 56% 2 steps) as an orange solid.

Workup

  1. temperatureThe reaction mixture was then cooled to room temperature
  2. extractionextracted with ethyl ether (2×)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried (MgSO4)
  5. concentrationThe filtered solution was concentrated under reduced pressure
  6. customthe crude product was purified by silica gel chromatography (10% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-fd87b0850c4042ada6b5d59bc012f156
Source dataset
uspto-grants-2000_10
Patent number
US06127382

Reaction notes

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