Sodium Carbonate → 4-[5-(3-Amino-5-nitrophenyl)-1,3-thiazol-2-yl]-1,4-diazepan-2-one

HRID 1028095Notes

Reaction equation

HRID 1028095 reaction equation
Br[C:2]1[S:6][C:5]([N:7]2[CH2:13][CH2:12][CH2:11][NH:10][C:9](=[O:14])[CH2:8]2)=[N:4][CH:3]=1.[NH2:15][C:16]1[CH:17]=[C:18](B(O)O)[CH:19]=[C:20]([N+:22]([O-:24])=[O:23])[CH:21]=1.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC>[NH2:15][C:16]1[CH:17]=[C:18]([C:2]2[S:6][C:5]([N:7]3[CH2:13][CH2:12][CH2:11][NH:10][C:9](=[O:14])[CH2:8]3)=[N:4][CH:3]=2)[CH:19]=[C:20]([N+:22]([O-:24])=[O:23])[CH:21]=1

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 27378063-Amino-5-nitrobenzeneboronic acidHCID 672367974-(5-Bromo-1,3-thiazol-2-yl)-1,4-diazepan-2-one2×

Product 1

HCID 672367484-[5-(3-Amino-5-nitrophenyl)-1,3-thiazol-2-yl]-1,4-diazepan-2-oneYield 25%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
100 °C

Procedure

4-(5-Bromo-1,3-thiazol-2-yl)-1,4-diazepan-2-one (Step 5 of Intermediate XX, 1.96 g, 7.10 mmol), (3-amino-5-nitrophenyl)boronic acid (1.291 g, 7.10 mmol), tetrakis-(triphenylphosphine)palladium(0) (0.410 g, 0.355 mmol), 1,2-dimethoxyethane (42 mL) and 2M aqueous sodium carbonate (10.65 mL, 21.29 mmol) were successively introduced in a high pressure reaction vessel. The headspace was flushed with nitrogen, the vessel capped and the mixture was stirred at 100° C. for 18 h. The reaction was then cooled to room temperature and 25% aqueous ammonium acetate was added. The aqueous layer was extracted with ethyl acetate (3×). The combined organics were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. Purification via CombiFlash (ethanol/ethyl acetate) afforded 590 mg (1.77 mmol, 25% yield) of 4-[5-(3-amino-5-nitrophenyl)-1,3-thiazol-2-yl]-1,4-diazepan-2-one as a yellow solid. MS APCI: [M+H]+ m/z 334.1.

Workup

  1. customThe headspace was flushed with nitrogen
  2. customthe vessel capped
  3. temperatureThe reaction was then cooled to room temperature
  4. addition25% aqueous ammonium acetate was added
  5. extractionThe aqueous layer was extracted with ethyl acetate (3×)
  6. washThe combined organics were washed with brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customPurification via CombiFlash (ethanol/ethyl acetate)

Sources & evidence

ORD record
ord-1cfd24ec1784499db5e9371e0c09c57b
Source dataset
uspto-grants-2014_05
Patent number
US08735417B2

Reaction notes

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