Ethyl Acetate → HCID 22052089, compound

HRID 1831532Notes

Reaction equation

HRID 1831532 reaction equation
[CH2:1]([O:8][C:9]1[C:14]([N+:15]([O-:17])=[O:16])=[C:13](Cl)[CH:12]=[CH:11][N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])([O-])=O.[Na+].[Na+].[CH3:25][O:26][C:27]1[CH:32]=[CH:31][C:30](B(O)O)=[C:29]([CH3:36])[CH:28]=1.CCOC(C)=O>C(O)C.C1(C)C=CC=CC=1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH2:1]([O:8][CH:9]1[CH:14]([N+:15]([O-:17])=[O:16])[C:13]([C:30]2[CH:31]=[CH:32][C:27]([O:26][CH3:25])=[CH:28][C:29]=2[CH3:36])=[CH:12][CH:11]=[N:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 2773486(4-Methoxy-2-methylphenyl)boronic acidHCID 220520652-(Benzyloxy)-4-chloro-3-nitropyridine

Product 1

HCID 22052089HCID 22052089, compoundYield 78%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a solution of 2-benzyloxy-4-chloro-3-nitro-pyridine (Wilde, et al. WO 99/01454, which is incorporated herein by reference) (0.98 g, 3.7 mmol) in ethanol (10 mL) and toluene (40 mL), was added Na2CO3 (4.6 mL, 2M), 4-methoxy-2-methylphenyl boronic acid (1.0 g, 5.6 mmol), and Pd(PPh3)2Cl2 (0.156 g, 0.22 mmol) and the mixture was heated at reflux for 5 h. The reaction was cooled and poured into EtOAc and H2O (500 mL). The EtOAc layer was washed with H2O, brine, dried Na2SO4, filtered and concentrated in vacuo. Purification using flash chromatography (10% EtOAc/hexane) gave 1.01 g (78%) of 2-benzyloxy-4-(4-methoxy-2-methyl-phenyl)-3-nitro-2,3-dihydro-pyridine as a viscous oil; MS(AP) m/z 351.6 [(M+H)+, 100], 392.0 [(M+H+CH3CN)+, 35]. The purified intermediate was used in the following step.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 5 h
  3. temperatureThe reaction was cooled
  4. washThe EtOAc layer was washed with H2O, brine, dried Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification

Sources & evidence

ORD record
ord-39fa361049cf48e78d54ec6f0c32a526
Source dataset
uspto-grants-2006_06
Patent number
US07067658B2

Reaction notes

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