Nitrogen → 9-Bromo-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-2-carboxamide

HRID 1498115Notes

Reaction equation

HRID 1498115 reaction equation
[Br:1][C:2]1[CH:16]=[CH:15][C:5]2[C:6]3[N:10]([CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1)[CH:9]=[C:8](I)[N:7]=3.N#N.C[Si](C)(C)N[Si](C)(C)C.C[N:29](C)[CH:30]=[O:31]>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>[Br:1][C:2]1[CH:16]=[CH:15][C:5]2[C:6]3[N:10]([CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1)[CH:9]=[C:8]([C:30]([NH2:29])=[O:31])[N:7]=3

Participants

6

Reactant 4

HCID 947NitrogenHCID 6228DimethylformamideHCID 13838HexamethyldisilazaneHCID 582048589-Bromo-2-iodo-5,6-dihydroimidazo[1,2-d][1,4]benzoxazepine

Product 1

HCID 582046299-Bromo-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-2-carboxamideYield 76%

Reagents, catalysts & solvents 1

HCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
70 °C

Procedure

Alternatively, a solution of 8-Bromo-2-iodo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene (10.00 g, 0.02558 mol) in N,N-Dimethylformamide (250 mL) was thoroughly degassed with N2. Bis(triphenylphosphine)palladium(II) chloride (0.807 g, 0.00115 mol) was added followed by Hexamethyldisilazane (21.58 mL, 0.1023 mol). The solution was flushed with CO for 2 minutes and then sealed with a CO balloon attached. The reaction was heated to 70° C. for 2.5 hours. Methylene chloride and saturated NH4Cl were added and the mixture was extracted 4 times with methylene chloride. The organic phases were combined, dried with MgSO4 and concentrated. A small amount of isopropanol was added and the mixture was triturated overnight. The mixture was filtered to yield 5.97 g (76% yield) of 8-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carboxylic acid amide as a fine brown powder. MS(ESI+) 308.0/310.0

Workup

  1. customThe solution was flushed with CO for 2 minutes
  2. customsealed with a CO balloon
  3. additionMethylene chloride and saturated NH4Cl were added
  4. extractionthe mixture was extracted 4 times with methylene chloride
  5. dry with materialdried with MgSO4
  6. concentrationconcentrated
  7. additionA small amount of isopropanol was added
  8. customthe mixture was triturated overnight
  9. filtrationThe mixture was filtered

Sources & evidence

ORD record
ord-713d1b7f79564d998be6cb5833072c35
Source dataset
uspto-grants-2015_12
Patent number
US09198918B2

Reaction notes

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