Phosphorus oxychloride → HCID 9925643, compound

HRID 1591418Notes

Reaction equation

HRID 1591418 reaction equation
[Cl:1][C:2]1[N:3]=[C:4]([NH:12][C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])[NH:5][C:6](=O)[C:7]=1[N+:8]([O-:10])=[O:9].P(Cl)(Cl)([Cl:20])=O>C(N(CC)C1C=CC=CC=1)C>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6]([Cl:20])[N:5]=[C:4]([NH:12][C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])[N:3]=1

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 135532690HCID 135532690, compound

Product 1

HCID 9925643HCID 9925643, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 7061N,N-DiethylanilineCatalyst

Procedure

The title compound of Example 23 (10.0 g, 38.37 mmol) was heated to reflux in phosphorus oxychloride (200 ml) and N,N-diethylaniline (3-4 drops) for 5 hours under nitrogen. The solution was then cooled to room temperature, concentrated to dryness, and the syrup was dissolved in cold (~ -10° C.) methylene chloride (200 ml). The organic layer was treated with saturated aqueous sodium bicarbonate (100 ml) with vigorous stirring, and the temperature was kept below 5° C. as solid sodium bicarbonate was added portionwise to elevate the pH to between 5 and 7. The layers were separated and the aqueous phase was extracted with methylene chloride. The combined organic layers were filtered over phase-separator paper, concentrated and dried under vacuum to give the title compound (7.71 g, 72%) as a yellow-white solid sufficiently pure to employ in the next step. Recrystallisation of the solid from hexane/methylene chloride provided an analytical sample, m.p. 166°-169° C.; 'H-NMR (DMSO-d6) δ 1.09 (d, J=6.9 Hz, 6H, (CH3)2CH), 2.79 m, J=6.9 Hz, 1H, (CH3)2CH), 11.61 (s, 1H).

Workup

  1. concentrationconcentrated to dryness
  2. dissolutionthe syrup was dissolved in cold (~ -10° C.) methylene chloride (200 ml)
  3. additionThe organic layer was treated with saturated aqueous sodium bicarbonate (100 ml) with vigorous stirring
  4. customwas kept below 5° C. as solid sodium bicarbonate
  5. additionwas added portionwise
  6. customThe layers were separated
  7. extractionthe aqueous phase was extracted with methylene chloride
  8. filtrationThe combined organic layers were filtered over phase-separator paper
  9. concentrationconcentrated
  10. customdried under vacuum

Sources & evidence

ORD record
ord-31479497dec24408945b290f31f1a4f7
Source dataset
uspto-grants-1993_04
Patent number
US05206435

Reaction notes

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