Triacetoxyperiodinane → 6,11-Dihydro-5H-dipyrido[2,3-b:3',4'-f]azepin-5-one

HRID 75208

Reaction equation

HRID 75208 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[N:23]1[C:28]2[NH:29][C:30]3[CH:38]=[CH:37][N:36]=[CH:35][C:31]=3[CH2:32][CH:33]([OH:34])[C:27]=2[CH:26]=[CH:25][CH:24]=1.S(=O)(=O)(O)[O-].[Na+]>ClCCl.O.C(=O)(O)[O-].[Na+]>[N:23]1[C:28]2[NH:29][C:30]3[CH:38]=[CH:37][N:36]=[CH:35][C:31]=3[CH2:32][C:33](=[O:34])[C:27]=2[CH:26]=[CH:25][CH:24]=1

Participants

7

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 516919Sodium BisulfateHCID 668863896,11-Dihydro-5H-dipyrido[2,3-b:3',4'-f]azepin-5-ol

Product 1

HCID 668868736,11-Dihydro-5H-dipyrido[2,3-b:3',4'-f]azepin-5-oneYield 90%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

Dess-Martin periodinane (0.810 g, 1.91 mmol) was added to a solution of 6,11-dihydro-5H-dipyrido[2,3-b:3′,4′-f]azepin-5-ol (0.370 g, 1.74 mmol, Intermediate D-5) in dichloromethane (30 mL) under an atmosphere of nitrogen and stirred for 1 h. The yellow mixture was poured into a solution of sodium bisulfate in water and stirred for 5 minutes. The mixture was then diluted with dichloromethane and sodium bicarbonate was added to adjust the pH to 8-9. The mixture was extracted three times with dichloromethane and the combined extracts were dried over sodium sulfate, filtered, and concentrated. The crude product residue was adsorbed onto silica gel and chromatographed on a silica gel column eluting with 10% methanol/dichloromethane to provide the desired product as a light tan solid (330 mg, 90%). 1H NMR (DMSO-d6): δ 10.55 (s, 1H), 8.51 (dd, 1H), 8.42 (s, 1H), 8.35 (d, 1H), 8.18 (dd, 1H), 7.33 (d, 1H), 7.06 (dd, 1H), 3.82 (s, 2H). LC/MS: 212 (M+H)+.

Workup

  1. stirringstirred for 5 minutes
  2. additionwas added
  3. extractionThe mixture was extracted three times with dichloromethane
  4. dry with materialthe combined extracts were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customchromatographed on a silica gel column
  8. washeluting with 10% methanol/dichloromethane

Sources & evidence

ORD record
ord-4cc63b5c2c2540fda0eedca268d15367
Source dataset
uspto-grants-2014_09
Patent number
US08835423B2

Linked notes

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