Nitric Acid → 5-[(4-Methyl-8-nitroquinolin-6-yl)methyl]pyrimidine-2,4-diamine

HRID 279980Notes

Reaction equation

HRID 279980 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([CH2:9][C:10]2[CH:11]=[C:12]3[C:17](=[CH:18][CH:19]=2)[N:16]=[CH:15][CH:14]=[C:13]3[CH3:20])=[CH:4][N:3]=1.[N+:21]([O-])([OH:23])=[O:22].[OH-].[NH4+]>S(=O)(=O)(O)O>[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([CH2:9][C:10]2[CH:11]=[C:12]3[C:17](=[C:18]([N+:21]([O-:23])=[O:22])[CH:19]=2)[N:16]=[CH:15][CH:14]=[C:13]3[CH3:20])=[CH:4][N:3]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14923Ammonium HydroxideHCID 233230585-[(4-Methylquinolin-6-yl)methyl]pyrimidine-2,4-diamine

Product 1

HCID 233230505-[(4-Methyl-8-nitroquinolin-6-yl)methyl]pyrimidine-2,4-diamineYield 53.2%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

The product of Example 11 (0.53 g, 2 mmol) was dissolved in 7 ml of concentrated sulfuric acid, and chilled to 0°. Then 0.3 ml (6.4 mmol) of fuming nitric acid (d=1.5) in 0.5 ml of concentrated sulfuric acid was added dropwise to the solution. The reaction was stirred at 0°-5° for 30 minutes, then at 25° for 1 hour. It was then poured onto 50 ml of ice and neutralised to pH 9 with concentrated ammonium hydroxide. The precipitate which formed was filtered and dried, and then purified on a silica gel column which was eluted with methylene chloride:methanol/12:1, giving 0.33 g (53%) of the title compound, which melted at 256°-258° after recrystallisation from beta methoxyethanol:water/2:1. NMR (Me2SO-d6) δ 2.72 (s, 3, Me), 3.90 (s, 2, CH2), 5.77 (br s, 2, NH2), 6.24 (br s, 2, NH2), 7.55 (d, 1, pyridine-beta H, J=4.1), 7.71 (s, 1, pyrimidine-H6), 8.05 (d, 1, ArH5, J=1.8), 8.28 (d, 1, ArH7, J=1.6), 8.81 (d, 1, pyridine-alpha H, J=4.4). Anal. Calcd. for C15H14N6O2 0.5H2O: C, 56.42; H, 4.73; N, 26.32. Found: C, 56.34; H, 4.82; N, 26.21.

Workup

  1. temperaturechilled to 0°
  2. waitat 25° for 1 hour
  3. customThe precipitate which formed
  4. filtrationwas filtered
  5. customdried
  6. custompurified on a silica gel column which
  7. washwas eluted with methylene chloride

Sources & evidence

ORD record
ord-516a38bff61240eba2f4eb3db23bae8d
Source dataset
uspto-grants-1986_05
Patent number
US04587341

Reaction notes

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