Dimethylformamide → 9-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carbonyl chloride

HRID 575015Notes

Reaction equation

HRID 575015 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][N:11]3[C:7](=[N:8][C:9]([C:15](O)=[O:16])=[CH:10]3)[C:6]=2[CH:18]=1.C(Cl)(C([Cl:23])=O)=O.CN(C)C=O>C(#N)C.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][N:11]3[C:7](=[N:8][C:9]([C:15]([Cl:23])=[O:16])=[CH:10]3)[C:6]=2[CH:18]=1

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 7174327210-Bromo-5,6-dihydrobenzo[F]imidazo[1,2-D][1,4]oxazepine-2-carboxylic acid

Product 1

HCID 866930509-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carbonyl chlorideYield 94%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Into a 10000-mL 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was placed a solution of 9-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carboxylic acid (450 g, 1.46 mol, 1.00 equiv) in ACN (4500 mL), followed by the addition of (COCl)2 (450 mL) dropwise with stirring at 0° C. over 45 min. To this was added N,N-dimethylformamide (5 mL). The resulting solution was stirred at room temperature for 7 h, diluted with 2000 mL of DCM and concentrated under vacuum to afford 450 g (94%) of 9-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carbonyl chloride as a gray solid.

Workup

  1. customInto a 10000-mL 4-necked round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. stirringThe resulting solution was stirred at room temperature for 7 h
  4. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-478956f1ef89460091dc0076f6dc2410
Source dataset
uspto-grants-2015_05
Patent number
US09034866B2

Reaction notes

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