N,N-Dimethylaniline → HCID 479082, compound

HRID 127026Notes

Reaction equation

HRID 127026 reaction equation
CN(C)C1C=CC=CC=1.[NH2:10][C:11]1[N:16]=[C:15](O)[C:14]([CH2:18][C:19]2[CH:24]=[C:23]([O:25][CH3:26])[C:22]([C:27]([CH3:29])=[CH2:28])=[C:21]([O:30][CH3:31])[CH:20]=2)=[C:13]([NH2:32])[N:12]=1.P(Cl)(Cl)(Cl)=O>>[NH2:10][C:11]1[N:12]=[C:13]([NH2:32])[C:14]([CH2:18][C:19]2[CH:20]=[C:21]([O:30][CH3:31])[C:22]([C:27]([CH3:29])=[CH2:28])=[C:23]([O:25][CH3:26])[CH:24]=2)=[CH:15][N:16]=1

Participants

4

Reactant 3

HCID 949N,N-DimethylanilineHCID 24813Phosphorus oxychlorideHCID 178439675HCID 178439675, compound

Product 1

HCID 479082HCID 479082, compound

Procedure

0.65 G. of dimethylaniline was added dropwise while stirring to a suspension of 0.8 g. of 2,6-diamino-5-(3,5-dimethoxy-4-isopropenylbenzyl)-4-pyrimidinol in 6.5 g. of phosphorus oxychloride. The mixture was boiled for 4 hours while stirring and then about half of the phosphorus oxychloride was distilled under reduced pressure. About 10 g. of ice were added to the residue. The suspension was left to stand at room temperature for 2 days, adjusted to pH 10 with concentrated ammonia solution and the precipitate was filtered under suction 2 hours later. The precipitate was freed from dimethylaniline by steam distillation. After cooling the aqueous suspension, the resulting crude 2,6-diamino-4-chloro-5-(3,5-dimethoxy-4-isopropenylbenzyl)-pyrimidine was chromatographed on silica gel with benzene/methanol (9:1, v/v) and, after evaporation of the solvents, recrystallized from methanol. Yield: 0.27 g. (32%); melting point 199°-200° C.

Workup

  1. stirringwhile stirring
  2. distillationabout half of the phosphorus oxychloride was distilled under reduced pressure
  3. additionof ice were added to the residue
  4. waitThe suspension was left
  5. waitto stand at room temperature for 2 days
  6. filtrationthe precipitate was filtered under suction 2 hours later
  7. distillationThe precipitate was freed from dimethylaniline by steam distillation
  8. temperatureAfter cooling the aqueous suspension
  9. customthe resulting crude 2,6-diamino-4-chloro-5-(3,5-dimethoxy-4-isopropenylbenzyl)-pyrimidine was chromatographed on silica gel with benzene/methanol (9:1
  10. customv/v) and, after evaporation of the solvents
  11. customrecrystallized from methanol

Sources & evidence

ORD record
ord-e9b6f90ef1ba48bdafc67d6f508842eb
Source dataset
uspto-grants-1981_03
Patent number
US04254286

Reaction notes

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