Pyridine → (S)-cyclopropyl(2-methyl-6-(4-nitro-1H-pyrazol-1-yl)-5-phenoxy-3,4-dihydroquinolin-1(2H)-yl)methanone

HRID 1051713Notes

Reaction equation

HRID 1051713 reaction equation
[CH:1]1([C:4]([N:6]2[C:15]3[C:10](=[C:11]([O:25][C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[C:12](B4OC(C)(C)C(C)(C)O4)=[CH:13][CH:14]=3)[CH2:9][CH2:8][C@@H:7]2[CH3:32])=[O:5])[CH2:3][CH2:2]1.[N+:33]([C:36]1[CH:37]=[N:38][NH:39][CH:40]=1)([O-:35])=[O:34].N1C=CC=CC=1>C([O-])(=O)C.[Cu+2].C([O-])(=O)C.CN(C)C=O>[CH:1]1([C:4]([N:6]2[C:15]3[C:10](=[C:11]([O:25][C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[C:12]([N:38]4[CH:37]=[C:36]([N+:33]([O-:35])=[O:34])[CH:40]=[N:39]4)=[CH:13][CH:14]=3)[CH2:9][CH2:8][C@@H:7]2[CH3:32])=[O:5])[CH2:3][CH2:2]1

Participants

6

Reactant 3

HCID 1049PyridineHCID 163764-nitro-1H-pyrazoleHCID 123908387(5)-cyclopropyl(2-methyl-5-phenoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydroquinolin-1(2H)-yl)methanone

Product 1

HCID 118076030(S)-cyclopropyl(2-methyl-6-(4-nitro-1H-pyrazol-1-yl)-5-phenoxy-3,4-dihydroquinolin-1(2H)-yl)methanoneYield 26.1%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A 100-mL round-bottom flask equipped with a balloon filled with air was charged with (5)-cyclopropyl(2-methyl-5-phenoxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydroquinolin-1(2H)-yl)methanone (0.240 g, 0.55 mmol), 4-nitro-1H-pyrazole (0.188 g, 1.66 mmol), copper (II) acetate (0.301 g, 1.66 mmol), pyridine (0.2 mL), and N,N-dimethylformamide (5 mL), and the resulting mixture stirred overnight at 90° C. The reaction mixture was cooled to room temperature and filtered through a pad of Celite. The filtrate was concentrated, and the residue was purified by preparative thin layer chromatography (eluting with 1:3, ethyl acetate/petroleum ether) to afford (S)-cyclopropyl(2-methyl-6-(4-nitro-1H-pyrazol-1-yl)-5-phenoxy-3,4-dihydroquinolin-1(2H)-yl)methanone (0.060 g, 26%) as yellow oil. MS (ESI, pos. ion) m/z 419 [M+H]+.

Workup

  1. customA 100-mL round-bottom flask equipped with a balloon
  2. additionfilled with air
  3. temperatureThe reaction mixture was cooled to room temperature
  4. filtrationfiltered through a pad of Celite
  5. concentrationThe filtrate was concentrated
  6. customthe residue was purified by preparative thin layer chromatography (eluting with 1:3, ethyl acetate/petroleum ether)

Sources & evidence

ORD record
ord-04402c8a6a1c4d8e8bd6a6b6d506b941
Source dataset
uspto-grants-2016_07
Patent number
US09388161B2

Reaction notes

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