Acetone → HCID 86693331, compound

HRID 575460Notes

Reaction equation

HRID 575460 reaction equation
Br[C:2]1(Br)[CH2:8][O:7][C:6]2[CH:9]=[CH:10][C:11]([I:13])=[CH:12][C:5]=2[N:4]2[N:14]=[C:15]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH:16]=[C:3]12.CC(C)=[O:25]>O.[N+]([O-])([O-])=O.[Ag+]>[I:13][C:11]1[CH:10]=[CH:9][C:6]2[O:7][CH2:8][C:2](=[O:25])[C:3]3[N:4]([N:14]=[C:15]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH:16]=3)[C:5]=2[CH:12]=1

Participants

5

Reactant 2

HCID 180AcetoneHCID 86693523HCID 86693523, compound

Product 1

HCID 86693331HCID 86693331, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent

Procedure

A solution of ethyl 4,4-dibromo-9-iodo-4,5-dihydrobenzo[b]pyrazolo[1,5-d][1,4]oxazepine-2-carboxylate (0.93 g, 1.71 mmol) in acetone (40 ml) and water (10 ml) was treated with silver(I) nitrate (0.78 g, 4.59 mmol) and then stirred at room temperature for 2 hours. The solids were removed by filtration through celite and carefully washed with acetone (3×50 ml). The filtrate and washings were combined and concentrated in vacuo before the residue was distributed between ethyl acetate (300 ml) and brine (100 ml). The organic layer was separated, dried over MgSO4, filtered and concentrated. The residue was purified by FCC (silica, 0-20% ethyl acetate in heptane) to give 0.54 g (79%) of the title compound as crystalline solid. 1H-NMR (500 MHz, CDCl3) 8 ppm 1.45 (3H, t, J=7.10 Hz), 4.48 (2H, q, J=7.17 Hz), 4.78 (2H, s), 7.06 (1H, d, J=8.39 Hz), 7.67 (1H, s), 7.70 (1H, dd, J=8.54, 2.14 Hz), 8.44 (1H, d, J=2.14 Hz); M+1=399.

Workup

  1. customThe solids were removed by filtration through celite
  2. washcarefully washed with acetone (3×50 ml)
  3. concentrationconcentrated in vacuo before the residue
  4. customThe organic layer was separated
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by FCC (silica, 0-20% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-df67028e511c43beb423c1fe41a6f2b1
Source dataset
uspto-grants-2015_05
Patent number
US09034866B2

Reaction notes

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