Sodium hydride → HCID 20571279, compound

HRID 1577624Notes

Reaction equation

HRID 1577624 reaction equation
[C:1]1([NH2:15])[N:2]=[C:3]([NH2:14])[N:4]=[C:5]2[C:10]=1[C:9]1[CH:11]=[CH:12][NH:13][C:8]=1[CH:7]=[CH:6]2.[H-].[Na+].[CH3:18][C:19]1[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][C:20]=1[S:26](Cl)(=[O:28])=[O:27]>CN(C)C=O>[CH3:18][C:19]1[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][C:20]=1[S:26]([N:13]1[C:8]2[CH:7]=[CH:6][C:5]3[C:10](=[C:1]([NH2:15])[N:2]=[C:3]([NH2:14])[N:4]=3)[C:9]=2[CH:11]=[CH:12]1)(=[O:27])=[O:28]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 87910Benzenesulfonyl chloride, 2,5-dimethyl-HCID 178508668HCID 178508668, compound

Product 1

HCID 20571279HCID 20571279, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 11.97 g. 7H-pyrrolo[3,2-f]quinazoline-1,3-diamine, as prepared in Example 1, in 750 ml. dry dimethylformamide is stirred under nitrogen as 3.18 g. of ca. 50% sodium hydride-mineral oil is added carefully. After stirring for 1.5 hours and chilling with an ice-water bath, a solution of 13.51 g. 2,5-dimethylbenzenesulfonyl chloride in 50 ml. dry dimethylformamide is added dropwise to the chilled stirring suspension. Stirring is continued for 4 hours, while the reaction slowly warms to ambient temperature, and is quenched with 30 ml. isopropanol. After removal of solvent (in vacuo), the residue is stirred thoroughly with excess aqueous potassium carbonate solution and filtered. The solids are collected, washed well with water, rinsed with hexane, and dried. The crude product is dissolved in 2.5 liters of boiling methanol, treated with charcoal, and filtered through Celite. The filtrate is concentrated to ca. 1 liter and chilled. The crystalline solid is collected and again recrystallized from methanol and dried to afford 9.68 g. of the title compound, m.p. 271.5°-272.5° C., NMR (d DMSO): δ2.35 (singlet, 5--CH3), 2.39 (singlet, 2--CH3), 5.93 (singlet, 3--NH2), 6.88 (singlet, 1--NH2), 7.16 (doublet, J=9 cps, 5H), 7.48 (doublet, J=31/2 cps, 9H), 8.9 (doublet, J=31/2 cps, 8H) p.p.m.; λmax95%EtOH 242 shoulder (ε28,300), 257 (ε31,700), 288 shoulder (ε12,500), 350 (ε4,900) nm; λmin95%EtOH 320 (ε2,700) nm.

Workup

  1. temperaturechilling with an ice-water bath
  2. stirringstirring suspension
  3. stirringStirring
  4. customis continued for 4 hours, while the reaction
  5. customslowly warms to ambient temperature
  6. customis quenched with 30 ml
  7. customAfter removal of solvent (in vacuo)
  8. stirringthe residue is stirred thoroughly with excess aqueous potassium carbonate solution
  9. filtrationfiltered
  10. customThe solids are collected
  11. washwashed well with water
  12. washrinsed with hexane
  13. customdried
  14. dissolutionThe crude product is dissolved in 2.5 liters of boiling methanol
  15. additiontreated with charcoal
  16. filtrationfiltered through Celite
  17. concentrationThe filtrate is concentrated to ca. 1 liter
  18. temperaturechilled
  19. customThe crystalline solid is collected
  20. customagain recrystallized from methanol
  21. customdried
  22. customto afford 9.68 g

Sources & evidence

ORD record
ord-ecbfd2a6c30e4c21ac1925d558ffe4fc
Source dataset
uspto-grants-1981_09
Patent number
US04288595

Reaction notes

Loading…