Water → HCID 90135473, compound

HRID 1506795Notes

Reaction equation

HRID 1506795 reaction equation
[CH2:1]([C:3]1([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:12][CH2:11][C:10]2[C:5](=[CH:6][CH:7]=[C:8](B3OC(C)(C)C(C)(C)O3)[CH:9]=2)[C:4]1=[O:22])[CH3:2].Br[C:30]1[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][N:31]=1.C(=O)([O-])[O-].[Cs+].[Cs+].O>C(O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[CH2:1]([C:3]1([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:12][CH2:11][C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:30]3[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][N:31]=3)[CH:9]=2)[C:4]1=[O:22])[CH3:2]

Participants

8

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 782402-Bromo-5-nitropyridineHCID 90135454HCID 90135454, compound

Product 1

HCID 90135473HCID 90135473, compoundYield 66.3%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Pd(PPh3)4 (0.479 g, 0.414 mmol) was added to a solution of 4E (3.2 g, 8.28 mmol), 2-bromo-5-nitropyridine (1.84 g, 9.11 mmol) and cesium carbonate (8.1 g, 24.85 mmol) in a mixture of ethanol (4 mL), water (4 mL) and toluene (80 mL) under argon atmosphere. The resulting mixture was degassed for further 10 min and stirred at 100° C. for 48 h. The solvent was removed under reduced pressure, and the residue was partitioned between ethyl acetate and water. The separated organic layer was treated with saturated NaCl solution, dried over sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The crude product was triturated in ethanol to afford the title compound (2.1 g, 66%) as a solid. 1H NMR (300 MHz, CDCl3): δ 9.52 (d, J=2.7 Hz, 1H), 8.56 (dd, J1=2.1 Hz, J2=8.4 Hz, 1H), 8.21 (d, J=8.4 Hz, 1H), 7.97 (m, 3H), 4.11 (q, J=7.5 Hz, 2H), 3.23-3.12 (m, 1H), 3.06-2.93 (m, 2H), 2.56-2.46 (m, 2H), 2.14-2.07 (m, 1H), 1.85-1.61 (m, 2H), 1.22 (t, J=6.9 Hz, 3H), 0.94 (t, J=7.8 Hz, 3H). ESI-MS m/z=383 (M+H).

Workup

  1. customThe resulting mixture was degassed for further 10 min
  2. customThe solvent was removed under reduced pressure
  3. customthe residue was partitioned between ethyl acetate and water
  4. additionThe separated organic layer was treated with saturated NaCl solution
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe crude product was triturated in ethanol

Sources & evidence

ORD record
ord-75f1e2315244449490ac95b5255e7b51
Source dataset
uspto-grants-2015_12
Patent number
US09221766B2

Reaction notes

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