Thionyl Chloride → HCID 19050680, compound

HRID 863746Notes

Reaction equation

HRID 863746 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[C:9](=[O:10])[O:8][C:7]2(O)[C:12]1[N:17]=[C:16]([O:18][CH3:19])[CH:15]=[C:14]([O:20][CH3:21])[N:13]=1.O=S(Cl)[Cl:25]>CN(C=O)C.C(Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[C:9](=[O:10])[O:8][C:7]2([C:12]1[N:17]=[C:16]([O:18][CH3:19])[CH:15]=[C:14]([O:20][CH3:21])[N:13]=1)[Cl:25]

Participants

5

Reactant 2

HCID 24386Thionyl ChlorideHCID 19050642HCID 19050642, compound

Product 1

HCID 19050680HCID 19050680, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of 0.7 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml of CCl4, 2 ml of SOCl2 and 4 drops of DMF are refluxed at 60° for 11/2 hrs. The mixture is then cooled, excess SOCl2 and CCl4 removed on a rotovaporator. The residue is diluted with 20 ml of CH2Cl2 and added to a stirred mixture of 10 ml of methanol and 2 ml of diethylamine. After 21/2 hrs the mixture is stripped on a rotovaporator to remove excess CH2Cl2 and methanol and the residue partitioned between CH2Cl2 (50 ml) and water (50 ml). The organic phase is separated, concentrated and the gummy residue flash chromatographed over silica gel using 80/20 hexane/ethyl acetate (500 ml), 60/40 hexane/ethyl acetate (500 ml) (28 fractions×50 ml). Fractions 18 to 20 yielded title compound a) and fractions 11 to 16 the compound b).

Workup

  1. temperatureare refluxed at 60° for 11/2 hrs
  2. temperatureThe mixture is then cooled
  3. customexcess SOCl2 and CCl4 removed on a rotovaporator
  4. additionThe residue is diluted with 20 ml of CH2Cl2
  5. additionadded to a stirred mixture of 10 ml of methanol and 2 ml of diethylamine
  6. custom2 hrs
  7. customto remove excess CH2Cl2 and methanol
  8. customthe residue partitioned between CH2Cl2 (50 ml) and water (50 ml)
  9. customThe organic phase is separated
  10. concentrationconcentrated
  11. customthe gummy residue flash chromatographed over silica gel using 80/20 hexane/ethyl acetate (500 ml), 60/40 hexane/ethyl acetate (500 ml) (28 fractions×50 ml)

Sources & evidence

ORD record
ord-d7a5a945ffa84764b97dcd5f59d77039
Source dataset
uspto-grants-1996_10
Patent number
US05561101

Reaction notes

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