Cesium carbonate → HCID 59442054, compound

HRID 1014176Notes

Reaction equation

HRID 1014176 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[CH3:13][CH:14]([N:16]1[CH2:21][CH2:20][NH:19][CH2:18][CH2:17]1)[CH3:15].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.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].O.C(OCC)(=O)C>[CH3:13][CH:14]([N:16]1[CH2:21][CH2:20][N:19]([C:2]2[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=2)[CH:7]=[O:8])[CH2:18][CH2:17]1)[CH3:15]

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 780131-IsopropylpiperazineHCID 811235-Chloro-2-nitrobenzaldehydeHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Product 1

HCID 59442054HCID 59442054, compoundYield 10%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To 5-chloro-2-nitrobenzaldehyde (10.0 g, 54.0 mmol, Aldrich) in dioxane (300 mL) was added 1-(1-methylethyl)piperazine (13.8 g, 108.0 mmol, Aldrich), XANTPHOS (3.1 g, 5.4 mmol, Aldrich), and Cs2CO3 (35.2 g, 108.0 mmol, Aldrich). The mixture was bubbled with N2 for 15 min prior to the addition of Pd2(dba)3 (2.5 g, 2.7 mmol, Aldrich). The reaction was stirred at 100° C. for 5 h. Ethyl acetate (150 mL) was used to dilute the reaction mixture, followed by the addition of water (100 mL). After partitioning, extraction with Ethyl acetate (2×75 mL), drying (Na2SO4), concentration, and silica gel chromatography afforded 5-[4-(1-methylethyl)-1-piperazinyl]-2-nitrobenzaldehyde (1.5 g, 10% yield). 1H NMR (400 MHz, CDCl3) δ ppm 1.08 (d, J=6.6 Hz, 6 H), 2.62-2.69 (m, 4 H), 2.70-2.79 (m, 1 H), 3.46-3.51 (m, 4 H), 6.93 (dd, J=9.2, 2.9 Hz, 1 H), 7.13 (d, J=2.9 Hz, 1 H), 8.09-8.12 (m, 1 H), 10.53 (s, 1 H).

Workup

  1. customThe mixture was bubbled with N2 for 15 min
  2. additionto dilute the reaction mixture
  3. customAfter partitioning
  4. extractionextraction with Ethyl acetate (2×75 mL)
  5. customdrying
  6. concentration(Na2SO4), concentration, and silica gel chromatography

Sources & evidence

ORD record
ord-b47074bddbb349f489e2c0d936bc59c2
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

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