Cesium carbonate → HCID 69269583, compound

HRID 1181964Notes

Reaction equation

HRID 1181964 reaction equation
[CH3:1][O:2][C:3]([C:5]1(Br)[CH:14]=[C:13]([O:15][CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:24][CH3:25])[CH:11]=2)[NH:6]1)=[O:4].[CH3:27][N:28]1[CH2:34][CH2:33][CH2:32][NH:31][CH2:30][CH2:29]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+]>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[CH:14]=[C:13]([O:15][CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[C:12]2[C:7](=[C:8]([N:31]3[CH2:32][CH2:33][CH2:34][N:28]([CH3:27])[CH2:29][CH2:30]3)[CH:9]=[C:10]([O:24][CH3:25])[CH:11]=2)[N:6]=1)=[O:4]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 2283491-MethylhomopiperazineHCID 634876Binap, (A+-)-HCID 69269824HCID 69269824, compound

Product 1

HCID 69269583HCID 69269583, compoundYield 92.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a clear, light brown solution of 2-bromo-6-methoxy-4-(2-trimethylsilanyl-ethoxymethoxy)-quinoline-2-carboxylic acid methyl ester (1.01 g, 2.28 mmol), N-methylhomopiperazine (0.32 mL, 2.57 mmol), and 4 Å sieves in 30 mL anhydrous toluene was added Pd2 (dba)2 (43.8 mg, 0.048 mmol) and BINAP (169.8 mg, 0.27 mmol). The resulting wine colored solution was treated with cesium carbonate (1.124 g, 3.45 mmol). The reaction mixture was heated at reflux under nitrogen for 21 hours. The pea green reaction mixture was cooled to room temperature and concentrated. The crude mixture was purified by flash chromatography on silica gel using a gradient of 95:5 to 40:60 methylene chloride:methanol to afford the desired product as a yellow foam (1.004 g, 92%). 1H NMR (300 MHz, DMSO, d6) δ 7.67 (s, 1 H, ArH3), 6.94 (d, 1 H, Jm=2.4 Hz, ArH5), 6.66 (d, 1 H, Jm=2.4 Hz, ArH7), 5.60 (s, 2 H, OCH2O), 3.94 (s, 3 H, CO2CH3), 3.88 (s, 3 H, OCH3), 3.82 (t, 2 H, J=8.0 Hz, OCH2CH2Si), 3.75 (bs, 4 H, ArNCH2CH2CH2NCH3 & ArNCH2CH2N—CH3), 3.45 (bs, 2 H, ArNCH2CH2NCH3), 3.31 (bs, 2 H, ArNCH2CH2CH2NCH3), 2.83 (s, 3 H, NCH3), 2.28 (bs, 2 H ArNCH2CH2 CH2NCH3), 0.92 (t, 2 H, J=8.0 Hz, OCH2CH2Si), −0.04 (s, 9 H, Si(CH3)3; Mass Spec.: calc. for [C24H37N3O5Si+H]+ Theor. m/z=476; Obs. 476.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux under nitrogen for 21 hours
  3. concentrationconcentrated
  4. customThe crude mixture was purified by flash chromatography on silica gel using a gradient of 95:5 to 40:60 methylene chloride

Sources & evidence

ORD record
ord-0d4f414618f24f4ca24386f4b47cff37
Source dataset
uspto-grants-2007_10
Patent number
US07285662B2

Reaction notes

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