Sodium hydride → 3-Amino-1-cyclopropyl-6-fluoro-2,4-dioxo-1,2,3,4-tetrahydro-pyrido[2,3-d]pyrimidine-7-thiosulfonic acid

HRID 10326

Reaction equation

HRID 10326 reaction equation
[CH:1]1([N:4]2[C:9]3[N:10]=[C:11]([S:15](=[S:18])([OH:17])=[O:16])[C:12]([F:14])=[CH:13][C:8]=3[C:7](=[O:19])[NH:6][C:5]2=[O:20])[CH2:3][CH2:2]1.[H-].[Na+].[N+:23](C1C=C([N+]([O-])=O)C=CC=1NO)([O-])=O>CN(C)C=O.O1CCOCC1>[NH2:23][N:6]1[C:7](=[O:19])[C:8]2[CH:13]=[C:12]([F:14])[C:11]([S:15](=[S:18])([OH:17])=[O:16])=[N:10][C:9]=2[N:4]([CH:1]2[CH2:3][CH2:2]2)[C:5]1=[O:20]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 5743493N-Hydroxy-2,4-dinitrobenzenamineHCID 219793641-Cyclopropyl-6-fluoro-2,4-dioxo-1,2,3,4-tetrahydro-pyrido[2,3-d]pyrimidine-7-thiosulfonic acid

Product 1

HCID 219790013-Amino-1-cyclopropyl-6-fluoro-2,4-dioxo-1,2,3,4-tetrahydro-pyrido[2,3-d]pyrimidine-7-thiosulfonic acidYield 76.7%

Reagents, catalysts & solvents 1

HCID 217120691,4-dioxane N,N-dimethylformamideSolvent

Procedure

A solution of 0.47 g (1.57 mmol) of 1-cyclopropyl-6-fluoro-2,4-dioxo-1,2,3,4-tetrahydro-pyrido[2,3-d]pyrimidine-7-thiosulfonic acid (Example 35) in 20 mL of dimethylformamide/dioxane (1:1) is treated portionwise with 0.08 g (2.0 mmol) of 60% sodium hydride/mineral oil. The reaction is stirred at room temperature for 1 hour and 0.32 g (1.6 mmol) of 2,4-dinitrophenylhydroxylamine is added all at once. After stirring at room temperature overnight, the dioxane is removed in vacuo and the residue is diluted to 100 mL with ice and water and stirred at 5° C. for 1 hour. The aqueous solution is extracted with ethyl acetate (3×50 mL) with the combined organic layers being washed with water, dried (MgSO4), filtered and evaporated in vacuo to give 0.4 g of the title compound, mp 167–169° C.

Workup

  1. stirringAfter stirring at room temperature overnight
  2. customthe dioxane is removed in vacuo
  3. additionthe residue is diluted to 100 mL with ice and water
  4. stirringstirred at 5° C. for 1 hour
  5. extractionThe aqueous solution is extracted with ethyl acetate (3×50 mL) with the combined organic layers
  6. washbeing washed with water
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customevaporated in vacuo

Sources & evidence

ORD record
ord-4df6972c6e4c48278a3fccf487f8d5a4
Source dataset
uspto-grants-2006_08
Patent number
US07094780B1

Linked notes

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