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

HRID 564765Notes

Reaction equation

HRID 564765 reaction equation
[CH2:1]([O:8][C:9]1[CH:26]=[CH:25][C:12]([NH:13][C:14]2[C:15]3[CH:23]=[C:22](Cl)[N:21]=[CH:20][C:16]=3[N:17]=[CH:18][N:19]=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:33][C:34]([Sn](CCCC)(CCCC)CCCC)=[CH:35][CH:36]=1>Cl>[CH2:1]([O:8][C:9]1[CH:26]=[CH:25][C:12]([NH:13][C:14]2[C:15]3[CH:23]=[C:22]([C:34]4[O:33][C:32]([CH:28]=[O:27])=[CH:36][CH:35]=4)[N:21]=[CH:20][C:16]=3[N:17]=[CH:18][N:19]=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-(4-Benzyloxyanilino)-6-chloropyrido[3,4-d]pyrimidine (4.0 g, 110 mmol), 2-(1,3-dioxolan-2-yl)-5-(tributylstannyl)furan (J. Chem. Soc., Chem Commun., (1988), 560) (6.0 g, 14.0 mmol) were reacted together according to Procedure B for 20 hrs. The reaction mixture was allowed to cool, 1N HCl (50 ml) added and stirred at RT 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 RT 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, 5x 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 RT 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-0aefde0a0cc84a9b801f61e2926414ec
Source dataset
uspto-grants-2001_01
Patent number
US06169091A

Reaction notes

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