Potassium Carbonate → 9-[(2-pyridyl)methyl]-5-carbomethoxy-1,2-dihydrocarbazol-4(3H)-one

HRID 51435

Reaction equation

HRID 51435 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][CH:15]=[C:14]2[C:6]=1[C:7]1[C:8](=[O:18])[CH2:9][CH2:10][CH2:11][C:12]=1[NH:13]2)([O:3][CH3:4])=[O:2].C(=O)([O-])[O-].[K+].[K+].Cl.[N:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[CH2:32]Cl>[I-].[Na+]>[N:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[CH2:32][N:13]1[C:12]2[CH2:11][CH2:10][CH2:9][C:8](=[O:18])[C:7]=2[C:6]2[C:14]1=[CH:15][CH:16]=[CH:17][C:5]=2[C:1]([O:3][CH3:4])=[O:2]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 23392Picolyl chloride hydrochlorideHCID 11368514methyl 4-oxo-2,3,4,9-tetrahydro-1H-carbazole-5-carboxylate

Product 1

HCID 227385139-[(2-pyridyl)methyl]-5-carbomethoxy-1,2-dihydrocarbazol-4(3H)-oneYield 82.4%

Reagents, catalysts & solvents 1

HCID 5238Sodium IodideCatalyst

Procedure

A 0° C. suspension of 5-carbomethoxy-1,2-dihydro-9H-carbazol-4(3H)-one (1.50 g, 6.17 mmol), potassium carbonate (2.60 g, 18.8 mmol), and catalytic amount of sodium iodide (ca. 10 mg), was treated with 2-picolyl chloride hydrochloride (1.10 g, 6.70 mmol). The cold bath was removed and the reaction stirred at ambient temperature 72 hours. The reaction was poured into H2O (100 mL) and the mixture extracted four times with ethyl acetate. The combined organic layers were washed four times with H2O, once with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (elution with 70% then 80% then 85% EtOAc in hexanes) to afford 1.70 g (82%) of the 9-[(2-pyridyl)methyl]-5-carbomethoxy-1,2-dihydrocarbazol-4(3H)-one as an oil which solidified on standing. 1H NMR (CDCl3) δ8.52 (br s, 1H), 7.54-7.47 (m, 1H), 7.34-7.26 (m, 2H), 7.18-7.11 (m, 2H), 6.67 (d, J=7.8 Hz, 1H) 5.34 (s, 2H), 3.99 (s, 3H), 2.87 (t, 2H, J=6.0 Hz), 2.50 (t, 2H, J=6.3 Hz), and 2.20-2.13 (m, 2H). IR (CDCl3, cm−1) 3010, 2953, 1725, 1654, 1463, 1446, 1288 and 1121. MS (ES) m/e 335 (M+1).

Workup

  1. customThe cold bath was removed
  2. additionThe reaction was poured into H2O (100 mL)
  3. extractionthe mixture extracted four times with ethyl acetate
  4. washThe combined organic layers were washed four times with H2O
  5. dry with materialonce with saturated brine, dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel (
  9. washelution with 70%

Sources & evidence

ORD record
ord-b1f560c1f41940afbcee640b9bc7f113
Source dataset
uspto-grants-2004_03
Patent number
US06713645B1

Linked notes

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