Aniline → 4-Anilino-2,5-dichloropyrimidine

HRID 480015Notes

Reaction equation

HRID 480015 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[C:5]([Cl:9])=[CH:4][N:3]=1.[NH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C(N(CC)C(C)C)(C)C>C(O)CCC>[NH:10]([C:6]1[C:5]([Cl:9])=[CH:4][N:3]=[C:2]([Cl:1])[N:7]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 6115AnilineHCID 81531DiisopropylethylamineHCID 2372592,4,5-Trichloropyrimidine

Product 1

HCID 187680474-Anilino-2,5-dichloropyrimidine

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Procedure

A solution of 2,4,5-trichloropyrimidine (Method 3; 5.5 g, 30.0 mmol), aniline (2.79 g, 30.0 mmol) and N,N-diisopropylethylamine (3.87 g, 30.0 mmol) in n-butanol (75 ml) was heated under reflux for 4 hours. Volatile material was removed by evaporation and the residue was dissolved in DCM (100 ml). The solution was washed with water (3×100 ml) and saturated sodium chloride solution (100 ml) and dried. Volatile material was removed by evaporation and the residue was purified by column chromatography on silica gel, eluting with 15% ethyl acetate/isohexane, to give the product as an oil which solidified on standing (3.94 g, 54%). NMR: 7.2 (t, 1H), 7.4 (t, 2H), 7.6 (d, 2H), 8.4 (s, 1H), 9.45 (br s, 1H); MS (MH+): 240, 242, 244.

Workup

  1. temperatureunder reflux for 4 hours
  2. customVolatile material was removed by evaporation
  3. dissolutionthe residue was dissolved in DCM (100 ml)
  4. washThe solution was washed with water (3×100 ml) and saturated sodium chloride solution (100 ml)
  5. customdried
  6. customVolatile material was removed by evaporation
  7. customthe residue was purified by column chromatography on silica gel
  8. washeluting with 15% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-255e95f1f4734a1f9bf21843ae19c96f
Source dataset
uspto-grants-2003_11
Patent number
US06649608B2

Reaction notes

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