Acetic Acid → N-(10-amino-9-bromo-1,2-dihydro-1-oxobenzo[f]quinazolin-3-yl)pivalamide

HRID 381556Notes

Reaction equation

HRID 381556 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH:14]=[CH:13][C:12]3[N:11]=[C:10]([NH:15][C:16](=[O:21])[C:17]([CH3:20])([CH3:19])[CH3:18])[NH:9][C:8](=[O:22])[C:7]=3[C:6]=2[C:23]=1[N+:24]([O-])=O.C(O)(=O)C.C(Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>C(O)C.[Fe].O>[NH2:24][C:23]1[C:6]2[C:7]3[C:8](=[O:22])[NH:9][C:10]([NH:15][C:16](=[O:21])[C:17]([CH3:19])([CH3:20])[CH3:18])=[N:11][C:12]=3[CH:13]=[CH:14][C:5]=2[CH:4]=[CH:3][C:2]=1[Br:1]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 6212ChloroformHCID 516892Sodium BicarbonateHCID 135838163N-(9-bromo-1,2-dihydro-10-nitro-1-oxobenzo[f]quinazolin-3-yl)pivalamide

Product 1

HCID 135838115N-(10-amino-9-bromo-1,2-dihydro-1-oxobenzo[f]quinazolin-3-yl)pivalamide

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A mixture of N-(9-bromo-1,2-dihydro-10-nitro-1-oxobenzo[f]quinazolin-3-yl)pivalamide (0.8 g, 1.9 mmoles) and iron powder (0.44 g, 7.8 mmoles) in ethanol:glacial acetic acid/1:1 (25 ml) was stirred and heated to reflux under a nitrogen atmosphere for 3 hours. The reaction mixture was poured into chloroform:water/2:1 (150 ml) and neutralized by addition of solid sodium bicarbonate. The chloroform layer was separated, and the aqueous phase was washed twice with chloroform (50 ml each). Combined chloroform layers were dried over sodium sulfate, filtered and evaporated under reduced pressure. The crude product was purified on a silica gel column eluting with chloroform to give N-(10-amino-9-bromo-1,2-dihydro-1-oxobenzo[f]quinazolin-3-yl)pivalamide as a bright yellow solid. (0.66 g, 89%) 1H NMR(DMSO-d6, 200 MHz) δ: 1.27(s, 9H, t-butyl); 6.51(s, 2H, NH2); 7.22(d, J=8.4 Hz, 1H, Ar); 7.51(br d, J=9 Hz, 1H, Ar); 7.72(d, J=8.4 Hz, 1H, Ar); 8.12(d, J=9.0 Hz, 1H, Ar); 11.40(br s, 1H, NH); 12.45(br s, 1H, NH).

Workup

  1. temperatureheated
  2. temperatureto reflux under a nitrogen atmosphere for 3 hours
  3. customThe chloroform layer was separated
  4. washthe aqueous phase was washed twice with chloroform (50 ml each)
  5. dry with materialCombined chloroform layers were dried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe crude product was purified on a silica gel column
  9. washeluting with chloroform

Sources & evidence

ORD record
ord-fe01c9dbaf604e78af4bacd8d5b2d7b1
Source dataset
uspto-grants-2001_10
Patent number
US06306865B1

Reaction notes

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