Stannane, tributyl[5-(1,3-dioxolan-2-yl)-2-furanyl]- → 4-(4-Benzyloxyanilino)-6-(5-formylfuran-2-yl) pyrido[3,4-d]pyrimidine

HRID 6830Notes

Reaction equation

HRID 6830 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]2[C:17]3[CH:25]=[C:24](Cl)[N:23]=[CH:22][C:18]=3[N:19]=[CH:20][N:21]=2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O:27]1CCO[CH:28]1[C:32]1[O:36][C:35]([Sn](CCCC)(CCCC)CCCC)=[CH:34][CH:33]=1>Cl>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]2[C:17]3[CH:25]=[C:24]([C:35]4[O:36][C:32]([CH:28]=[O:27])=[CH:33][CH:34]=4)[N:23]=[CH:22][C:18]=3[N:19]=[CH:20][N:21]=2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 10960952Stannane, tributyl[5-(1,3-dioxolan-2-yl)-2-furanyl]-HCID 219521684-(4-Benzyloxyanilino)6-chloropyrido[3,4-d]pyrimidine

Product 1

HCID 219520464-(4-Benzyloxyanilino)-6-(5-formylfuran-2-yl) pyrido[3,4-d]pyrimidineYield 52%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

(4-Benzyloxyphenyl)-(6-chloro-pyrido[3,4-d]pyrimidin-4-yl)-amine (4.0 g, 11.0 mmol), 5-(1,3-dioxolan-2-yl)-2-(tributylstannyl)furan (J. Chem. Soc., Chem. Commun., (1988), 560) (6.0 g, 14.0 mmol) were reacted together in a procedure analogous to Procedure B above for 20 hrs. The reaction mixture was allowed to cool, 1N HCl (50 ml) added and stirred at room temperature for 15 minutes. The reaction was filtered and the residue washed with dioxane (20 ml) and 2N HCl (20 ml). The combined filtrate and washings were stirred at room temperature for a further hour. The dioxane was removed under vacuum, the reaction diluted with water and the solid which precipitated was collected by filtration, and washed with water, iso-hexane and acetone. This precipitate was converted to the free base by partitioning into a mixture of triethylamine, ethyl acetate and water. The organic phase was washed with water, dried (magnesium sulphate) and the solvent removed under vacuum. The residue was triturated with iso-hexane/ethyl acetate to give the product (2.41 g, 52%) as a yellow solid; δH [2H6]-DMSO 10.60 (1H, b, NH), 9.83 (1H, s, CHO), 9.30 (1H, s, 2-H), 9.08 (1H, s, 5-H or 8-H), 8.76 (1H, s, 5-H or 8-H), 7.89 (1H, d, furan-H), 7.82 (2H, d, 2′-H, 6′-H), 7.65–7.42 (6H, m, 5×Ph-H, furan-H), 7.21 (2H, d, 3′-H, 5′-H), 5.26 (2H, s, OCH2); m/z (M+1)+423.

Workup

  1. temperatureto cool
  2. filtrationThe reaction was filtered
  3. washthe residue washed with dioxane (20 ml) and 2N HCl (20 ml)
  4. stirringThe combined filtrate and washings were stirred at room temperature for a further hour
  5. customThe dioxane was removed under vacuum
  6. additionthe reaction diluted with water
  7. customthe solid which precipitated
  8. filtrationwas collected by filtration
  9. washwashed with water, iso-hexane and acetone
  10. customby partitioning into a mixture of triethylamine, ethyl acetate and water
  11. washThe organic phase was washed with water
  12. dry with materialdried (magnesium sulphate)
  13. customthe solvent removed under vacuum
  14. customThe residue was triturated with iso-hexane/ethyl acetate

Sources & evidence

ORD record
ord-8d8f1c75637248039f15ee802bde1ef1
Source dataset
uspto-grants-2006_08
Patent number
US07084147B2

Reaction notes

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