Cesium carbonate → HCID 58425627, compound

HRID 1966441Notes

Reaction equation

HRID 1966441 reaction equation
BrC1C=CC([N+]([O-])=O)=C(F)C=1.C(O)C.CNC.Br[C:19]1[CH:20]=[CH:21][C:22]([N+:28]([O-:30])=[O:29])=[C:23]([N:25]([CH3:27])[CH3:26])[CH:24]=1.[C:31]([N:39]1[CH2:44][CH2:43][NH:42][CH2:41][CH2:40]1)(=[O:38])[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.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.C(=O)([O-])[O-].[Cs+].[Cs+]>CN1C(=O)CCC1.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].C(OCC)(=O)C.O>[CH3:26][N:25]([CH3:27])[C:23]1[CH:24]=[C:19]([N:42]2[CH2:43][CH2:44][N:39]([C:31]([C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)=[O:38])[CH2:40][CH2:41]2)[CH:20]=[CH:21][C:22]=1[N+:28]([O-:30])=[O:29]

Participants

11

Reactant 6

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 7626541-BenzoylpiperazineHCID 27833624-Bromo-2-fluoro-1-nitrobenzeneHCID 22184060Dimethylamine ethanolHCID 67183248HCID 67183248, compound

Product 1

HCID 58425627HCID 58425627, compoundYield 21.2%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent2×

Procedure

A solution of 4-bromo-2-fluoro-1-nitrobenzene (1.0 g, 4.5 mmol) and 2.0 M dimethylamine ethanol solution (6.9 ml, 13.6 mmol) in 20 ml NMP was stirred at room temperature for 16 hours. The solution was added 200 ml water. The solids (1.03 g, 90%) were filtered dried under high vacuum. A solution of 5-bromo-N,N-dimethyl-2-nitrobenzenamine (0.2 g, 0.8 mmol), benzoyl piperazine (0.19 g, 1.0 mml), Tris(dibenzylideneacetone)dipalladium (9 mg), BINAP (38 mg) and cesium carbonate (0.24 g, 1.2 mmol) in 20 ml NMP was stirred at 100° C. under argon atmosphere for 16 hours. The reaction was cooled to room temperature before filtration. (4-(3-(dimethylamino)-4-nitrophenyl)piperazin-1-yl)(phenyl)methanone (0.06 g, 20%) was obtained after flash column chromatograph (50% ethyl acetate in hexanes). 1H NMR (500 MHz, CDCl3) δ (ppm) 2.93 (s, 6H), 3.40-3.57 (m, 8H), 6.26 (d, J=2.6 Hz, 1H), 6.35 (dd, J=2.6, 9.6 Hz, 1H), 7.48 (m, 5H), 7.98 (d, J=9.6 Hz, 1H).

Workup

  1. filtrationThe solids (1.03 g, 90%) were filtered
  2. customdried under high vacuum

Sources & evidence

ORD record
ord-5fac743b4a204abe8499bf548bf76517
Source dataset
uspto-grants-2013_04
Patent number
US08420640B2

Reaction notes

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