Hydrochloric Acid → 6-Methyl-N4-(4-nitrophenyl)pyrimidine-2,4-diamine

HRID 547526Notes

Reaction equation

HRID 547526 reaction equation
[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)([O-:3])=[O:2].[NH2:11][C:12]1[N:17]=[C:16](Cl)[CH:15]=[C:14]([CH3:19])[N:13]=1.Cl>C(OCCO)C>[CH3:19][C:14]1[N:13]=[C:12]([NH2:11])[N:17]=[C:16]([NH:8][C:7]2[CH:9]=[CH:10][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)[CH:15]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 74754-NitroanilineHCID 218102-Amino-4-chloro-6-methylpyrimidine

Product 1

HCID 597628266-Methyl-N4-(4-nitrophenyl)pyrimidine-2,4-diamineYield 51%

Reagents, catalysts & solvents 1

HCID 8076Glycol monoethyl etherSolvent

Procedure

4-Nitroaniline (B1) [9.22 g, 0.07 mol] and 2-amino-4-chloro-6-methylpyrimidine (E1) (9.30 g, 0.07 mol) were dissolved in 2-ethoxyethanol (330 mL). To the resulting solution were added a few drops of c.HCl, and the resulting mixture was refluxed for 30 min, and then allowed to cool to room temperature overnight. After this time, the reaction mixture was filtered, and the resulting solid was basified by addition of aqueous ammonia solution, and then crystallized from H2O:EtOH to afford amine E2 as an amorphous bright-yellow solid (7.33 g). Concentration of the filtrate, followed by basification and reprecipitation as before, afforded a further quantity (0.78 g, overall yield 51%). 1H NMR [(CD3)2SO]: 2.14 [s, 3H, ArCH3], 6.00 [s, 1H, ArNHAr], 6.37 [s, 2H, ArNH2], 8.00 [ddd, J=10.24, 5.05, 2.96 Hz, 2H, ArH], 8.12 [ddd, J=10.24, 4.95, 2.90 Hz, 2H, ArH], 9.75 [s, 1H, ArH]. LCMS (APCI+): 246 (100%).

Workup

  1. additionTo the resulting solution were added a few drops of c
  2. filtrationAfter this time, the reaction mixture was filtered
  3. additionthe resulting solid was basified by addition of aqueous ammonia solution
  4. customcrystallized from H2O

Sources & evidence

ORD record
ord-9763b27466384b2a84433dd9f7c907f1
Source dataset
uspto-grants-2011_05
Patent number
US07939546B2

Reaction notes

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