Acetic Acid → 3-Amino-8-bromo-n,n-diethyl-1,2-dihydro-1-oxobenzo[f]quinazolin-9-sulfonamide

HRID 381570Notes

Reaction equation

HRID 381570 reaction equation
[NH2:1][C:2]1[NH:11][C:10](=[O:12])[C:9]2[C:8]3[CH:13]=[C:14]([S:18]([N:21]([CH2:24][CH3:25])[CH2:22][CH3:23])(=[O:20])=[O:19])[C:15]([Br:17])=[CH:16][C:7]=3[CH2:6][CH2:5][C:4]=2[N:3]=1.BrN1C(=O)CCC1=O.C(O)(=O)C>C(OC(=O)C(C)(C)C)(=O)C(C)(C)C>[NH2:1][C:2]1[NH:11][C:10](=[O:12])[C:9]2[C:8]3[CH:13]=[C:14]([S:18]([N:21]([CH2:24][CH3:25])[CH2:22][CH3:23])(=[O:19])=[O:20])[C:15]([Br:17])=[CH:16][C:7]=3[CH:6]=[CH:5][C:4]=2[N:3]=1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 67184N-bromobutanimideHCID 1358381053-Amino-8-bromo-N,N,-diethyl-5,6-dihydrobenzo[f]quinazolin-1(2H)-one-9-sulfonamide

Product 1

HCID 1358381543-Amino-8-bromo-n,n-diethyl-1,2-dihydro-1-oxobenzo[f]quinazolin-9-sulfonamideYield 33.2%

Reagents, catalysts & solvents 1

HCID 15234Pivalic anhydrideSolvent

Procedure

3-Amino-8-bromo-N,N,-diethyl-5,6-dihydrobenzo[f]quinazolin-1(2H)-one-9-sulfonamide (0.165 g,0.39 mmole) was suspended in pivalic anhydride (5 ml) (Aldrich) and heated under nitrogen until dissolved. The solution was heated under reflux for 10 minutes, cooled, and the pivalic anhydride removed in vacuo. The dried solid was dissolved in benzene (20 ml), pyridine (0.05 ml) added, and the solution heated to boiling under nitrogen. N-Bromosuccinimide (0.07 g, 0.47 mmole) was added, and the mixture refluxed for an additional 6 hours. The reaction mixture was cooled to room temperature, solvent removed in vacuo, and the solid residue crystallized from methanol. The pivalamide (0.105 g) was dissolved in methanol(2 ml), 1N NaOH(4 ml) added, and the solution heated to reflux under nitrogen for 1 hour. The cooled reaction mixture was neutralized with dilute acetic acid, the crystals collected by filtration and suspended in methanol. The collected crystals were dried in vacuo to give 3-amino-8-bromo-N,N-diethyl-1,2-dihydro-1-oxobenzo[f]quinazolin-9-sulfonamide (0.055 g, 33%). Mp>250° C. 1H NMR (DMSO-d6, 200 MHz) δ: 1.10 (t, J=7 Hz, 6H, ethyl CH3), 3.38 (q, J=7 Hz, 4H, ethyl CH2), 6.78 (br s, 2H, NH2), 7.47 (d, J=9 Hz, 1H, Ar), 8.09 (d, J=9 Hz, 1H, Ar), 8.40 (s, 1H, Ar), 10.30 (s, 1H, Ar), 11.32 (br s 1H, NH). Anal Calculated for C16H17BrN4O3S: C,45.19; H,4.03; Br,18.79; N,13.17; S,7.54. Found: C,45.10; H,4.03; Br,18.74; N,13.07; S,7.56.

Workup

  1. temperatureheated under nitrogen
  2. dissolutionuntil dissolved
  3. temperatureThe solution was heated
  4. temperatureunder reflux for 10 minutes
  5. temperaturecooled
  6. customthe pivalic anhydride removed in vacuo
  7. dissolutionThe dried solid was dissolved in benzene (20 ml)
  8. additionpyridine (0.05 ml) added
  9. temperaturethe solution heated
  10. temperaturethe mixture refluxed for an additional 6 hours
  11. customsolvent removed in vacuo
  12. customthe solid residue crystallized from methanol
  13. dissolutionThe pivalamide (0.105 g) was dissolved in methanol(2 ml)
  14. addition1N NaOH(4 ml) added
  15. temperaturethe solution heated
  16. temperatureto reflux under nitrogen for 1 hour
  17. customThe cooled reaction mixture
  18. filtrationthe crystals collected by filtration
  19. customThe collected crystals were dried in vacuo

Sources & evidence

ORD record
ord-02da0b286db54fc18b60b6e0534ff6e1
Source dataset
uspto-grants-2001_10
Patent number
US06306865B1

Reaction notes

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