Ethyl Acetate → HCID 135730621, compound

HRID 354194Notes

Reaction equation

HRID 354194 reaction equation
[Br:1][C:2]1[N:3]([CH3:24])[N:4]=[C:5]2[C:10](=[O:11])[NH:9][C:8]([C:12]3[C:13]([O:21][CH2:22][CH3:23])=[N:14][CH:15]=[C:16]([N+:18]([O-])=O)[CH:17]=3)=[N:7][C:6]=12.C(OCC)(=O)C>Cl.C(O)(=O)C.[Cl-].[Cl-].[Cl-].[Ti+3]>[Br:1][C:2]1[N:3]([CH3:24])[N:4]=[C:5]2[C:10](=[O:11])[NH:9][C:8]([C:12]3[C:13]([O:21][CH2:22][CH3:23])=[N:14][CH:15]=[C:16]([NH2:18])[CH:17]=3)=[N:7][C:6]=12

Participants

6

Reactant 2

HCID 8857Ethyl AcetateHCID 135730604HCID 135730604, compound

Product 1

HCID 135730621HCID 135730621, compoundYield 42.3%

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalystHCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolvent

Procedure

Titanium trichloride (20.93 g, 140 mL of a 15% solution in hydrochloric acid) was added to a solution of 3-bromo-5-(2-ethoxy-5-nitropyridin-3-yl)-2-methyl-2,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one (Example 53) (7.66 g, 19.4 mmol) in acetic acid (100 mL). After 2 h the acetic acid was evaporated and azeotroped with toluene. The residue was partitioned between sodium bicarbonate solution and dichloromethane and the titanium salts filtered to aid separation of the aqueous and organic phases. The aqueous layer was saturated with sodium chloride and re-extracted with dichloromethane. The organics were dried (MgSO4) and concentrated to give a solid. Trituration with ethyl acetate gave 3 g of pure product.

Workup

  1. customAfter 2 h the acetic acid was evaporated
  2. customazeotroped with toluene
  3. customThe residue was partitioned between sodium bicarbonate solution and dichloromethane
  4. filtrationthe titanium salts filtered
  5. customseparation of the aqueous and organic phases
  6. extractionre-extracted with dichloromethane
  7. dry with materialThe organics were dried (MgSO4)
  8. concentrationconcentrated
  9. customto give a solid

Sources & evidence

ORD record
ord-0b9fbc22d4664aaf89acddc903800f9c
Source dataset
uspto-grants-2004_06
Patent number
US06756373B1

Reaction notes

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