Water → HCID 58203878, compound

HRID 707821Notes

Reaction equation

HRID 707821 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]=[C:8]([C:14]([NH2:16])=O)[S:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1.P(Cl)(Cl)(Cl)=O.O>N1C=CC=CC=1>[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]=[C:8]([C:14]#[N:16])[S:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 962WaterHCID 24813Phosphorus oxychlorideHCID 670505308-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid amide

Product 1

HCID 58203878HCID 58203878, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
-30 °C

Procedure

To a suspension of 8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid amide 25 (11.44 g, 35.2 mmol) in pyridine (115 mL) at −30° C. was added phosphorus oxychloride (8.4 mL, 91 mmol) dropwise over 10 minutes. The mixture was stirred at −30° C. for 1 hour then allowed to warm to RT and stirred for 2 hours. The mixture was poured into water, stirred for 10 minutes and the solid was collected by filtration. The solid was dissolved in EtOAc and washed with copper sulfate solution. The organic layer was passed through a silica pad eluting with EtOAc and the solvent was removed in vacuo to afford 8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carbonitrile (7.78 g, 72%). 1H NMR δ (ppm) (DMSO-d6): 8.25 (1H, d, J=8.61 Hz), 7.38 (1H, dd, J=8.68, 2.23 Hz), 7.32-7.30 (1H, m), 4.39 (2H, t, J=5.01 Hz), 3.50-3.44 (2H, m)

Workup

  1. temperatureto warm to RT
  2. stirringstirred for 2 hours
  3. stirringstirred for 10 minutes
  4. filtrationthe solid was collected by filtration
  5. dissolutionThe solid was dissolved in EtOAc
  6. washwashed with copper sulfate solution
  7. washeluting with EtOAc
  8. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-1da9e80cd3894c3b80a8d6fbab17c41e
Source dataset
uspto-grants-2015_11
Patent number
US09175009B2

Reaction notes

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