Phosphorus oxychloride → HCID 178435384, compound

HRID 1934416Notes

Reaction equation

HRID 1934416 reaction equation
[CH3:1][C:2]1[NH:7][C:6]2[NH:8][C:9]([CH2:11][CH3:12])=[CH:10][C:5]=2[C:4](=O)[N:3]=1.P(Cl)(Cl)([Cl:16])=O>>[CH3:1][C:2]1[NH:7][C:6]2=[N:8][C:9]([CH2:11][CH3:12])=[CH:10][C:5]2=[C:4]([Cl:16])[N:3]=1

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 178435420HCID 178435420, compound

Product 1

HCID 178435384HCID 178435384, compoundYield 86%

Procedure

A solution of 3.50 g (19.8 mmol) of 1,7-dihydro-2-methyl-6-ethyl-4H-pyrrolo[2,3-d]pyrimidin-4-one in 180 mL of phosphorous oxychloride was heated to reflux for 4 hours. The reaction was cooled to ambient temperature and concentrated under vacuum. The residue was dissolved in 100 mL of methylene chloride and poured onto 100 g of ice. The mixture was neutralized to pH 7 by the addition of powdered potassium carbonate. After an additional 200 mL of methylene chloride and 200 mL of water were added, some solids remained and were removed by filtration. The solids were shown to be desired product by thin layer chromatography (silica, 19:1 methylene chloride-methanol). The solids were combined with the organic phase and concentrated to 4.0 g of brown residue. The residue was purified by flash chromatography (200 g of silica, 19:1 methylene chloride-methanol) to provide 3.32 g (86%) of 2-methyl-4-chloro-6-ethyl-1H-pyrrolo[2,3-d]pyrimidine as an off-white solid. nmr (500 MHz, dmso-d6) δ1.25 (t, J=7.5 Hz, 3H), 2.56 (s, 3H), 2.73 (q, J=-7.5 Hz, 2H), 6.21 (s, 1H), 12.15 (s, 1H)

Workup

  1. temperatureto reflux for 4 hours
  2. concentrationconcentrated under vacuum
  3. dissolutionThe residue was dissolved in 100 mL of methylene chloride
  4. additionpoured onto 100 g of ice
  5. additionThe mixture was neutralized to pH 7 by the addition of powdered potassium carbonate
  6. additionAfter an additional 200 mL of methylene chloride and 200 mL of water were added
  7. customwere removed by filtration
  8. concentrationconcentrated to 4.0 g of brown residue
  9. customThe residue was purified by flash chromatography (200 g of silica, 19:1 methylene chloride-methanol)

Sources & evidence

ORD record
ord-4eff291b33f3450c9131a6d1fdfd2870
Source dataset
uspto-grants-2002_05
Patent number
US06384041B1

Reaction notes

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