Dimethylformamide → 9-Chloro-5,6-dihydrobenzo[f][1,2,4]triazolo[1,5-d][1,4]oxazepine-2-carboxamide

HRID 1498302Notes

Reaction equation

HRID 1498302 reaction equation
[Cl:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]([N:11]=[C:12]([C:14](O)=[O:15])[N:13]=3)[CH2:8][CH2:9][O:10][C:4]=2[CH:3]=1.C[N:20](C)C=O.F[P-](F)(F)(F)(F)F.C[N+](C)=C(N(C)C)ON1C2N=CC=CC=2N=N1.ClC1C=CC2N=NN(O)C=2C=1.[NH4+].[Cl-].C(N(CC)C(C)C)(C)C>>[Cl:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]([N:11]=[C:12]([C:14]([NH2:20])=[O:15])[N:13]=3)[CH2:8][CH2:9][O:10][C:4]=2[CH:3]=1

Participants

7

Reactant 6

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 2327116-Chloro-1-hydroxy-1H-benzotriazoleHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 582045869-Chloro-5,6-dihydrobenzo[f][1,2,4]triazolo[1,5-d][1,4]oxazepine-2-carboxylic acid

Product 1

HCID 582043089-Chloro-5,6-dihydrobenzo[f][1,2,4]triazolo[1,5-d][1,4]oxazepine-2-carboxamideYield 5.3%

Procedure

To 9-Chloro-5,6-dihydrobenzo[f][1,2,4]triazolo[1,5-d][1,4]oxazepine-2-carboxylic acid (0.137 g, 0.515 mmol) in N,N-dimethylformamide (1.20 mL, 15.4 mmol) was added N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate (0.587 g, 1.54 mmol) and 6-chloro-1-hydroxybenzotriazole (0.262 g, 1.54 mmol). The mixture was stirred vigorously, and NH4Cl (0.220 g, 4.12 mmol) was added. After 10 minutes, N,N-diisopropylethylamine (0.359 mL, 2.06 mmol) was added. The reaction was stirred at room temperature for 3 hours. Then, the reaction was concentrated, taken to dryness, and washed with water. The crude product was purified by a silica gel plug, eluting with DCM/MeOH, and then by reverse phase HPLC to give 9-Chloro-5,6-dihydrobenzo[f][1,2,4]triazolo[1,5-d][1,4]oxazepine-2-carboxamide (5.3% yield)

Workup

  1. stirringThe reaction was stirred at room temperature for 3 hours
  2. concentrationThen, the reaction was concentrated
  3. washwashed with water
  4. customThe crude product was purified by a silica gel plug
  5. washeluting with DCM/MeOH

Sources & evidence

ORD record
ord-5bcf1b8aba4148cda8ea30f56f9b4b84
Source dataset
uspto-grants-2015_12
Patent number
US09198918B2

Reaction notes

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