Sodium periodate → HCID 12088010, compound

HRID 1169279Notes

Reaction equation

HRID 1169279 reaction equation
I([O-])(=O)(=O)=[O:2].[Na+].[Cl:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[N:14]1[C:19](=[O:20])[C:18]2[S:21][CH:22]=[CH:23][C:17]=2[N:16]=[C:15]1[CH:24]=CN(C)C>O1CCCC1>[Cl:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[N:14]1[C:19](=[O:20])[C:18]2[S:21][CH:22]=[CH:23][C:17]=2[N:16]=[C:15]1[CH:24]=[O:2]

Participants

4

Reactant 2

HCID 23667635Sodium periodateHCID 86591394HCID 86591394, compound

Product 1

HCID 12088010HCID 12088010, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a well stirred mixture of sodium periodate (9.7 9, 45.3 mmol) in pH 7 buffer (115 mL) and tetrahydrofuran (115 mL) was added 3-(2-chloro-phenyl)-2-(dimethylamino-vinyl)-4-oxo-3,4-dihydro-thieno[3,2-d]pyrimidine (5.0 g, 15.1 mmol) all at once. The mixture warmed slightly to the touch and was stirred for 1 hour at ambient temperature. The reaction was filtered through celite and the pad was washed with ethyl acetate. The phases were separated from the filtrate and the aqueous layer was extracted with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate and concentrated to a yellow oil. The oil was flash chromatographed on silica gel (70 g) with elution proceeding as follows: 50% methylene chloride/hexane (500 mL), unweighed forerun; 50% ethyl acetate/hexane (1000 mL), 4.6 g (100%) of 3-(2-chloro-phenyl)-4-oxo-3,4-dihydro-thieno[3,2-d]pyrimidine-2-carbaldehyde as a foam which was a 2:1 mixture of free aldehyde and hydrate and had: 1H NMR δ 9.56 (s) [CHO], 7.94 and 7.87 (pair of d, J=5.2, 5.4 Hz, respectively, 1H), 7.60-7.30 (m, 5H), 5.30 (dd, J=7, 9.5 Hz) [hydrate methine CH], 4.76 (d, J=9.5 Hz) [hydrate OH], 3.79 (d, J=7 Hz) [hydrate OH]. Note that the doublets at 4.76 and 3.79 ppm are washed out and the dd at 5.30 ppm is converted to a singlet when deuterium oxide is added to the NMR sample.

Workup

  1. temperatureThe mixture warmed slightly to the touch
  2. stirringwas stirred for 1 hour at ambient temperature
  3. filtrationThe reaction was filtered through celite
  4. washthe pad was washed with ethyl acetate
  5. customThe phases were separated from the filtrate
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. washThe combined organic phase was washed with brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated to a yellow oil
  10. customchromatographed on silica gel (70 g) with elution proceeding
  11. additiona 2:1 mixture of free aldehyde and hydrate
  12. washare washed out
  13. additionis added to the NMR sample

Sources & evidence

ORD record
ord-2637f23d59a34f1189c008f05cb2b55f
Source dataset
uspto-grants-2003_09
Patent number
US06627755B1

Reaction notes

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