Acetic Anhydride → 5-fluoro-4-formyl-1-tosyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid

HRID 1968256Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1968256
[Cl-].[Li+].[CH:3]([O-:5])=[O:4].[Li+].[F:7][C:8]1[CH:13]=[N:12][C:11]2[N:14]([S:18]([C:21]3[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=3)(=[O:20])=[O:19])[CH:15]=[C:16](I)[C:10]=2[C:9]=1[CH:28]=[O:29].C(OC(=O)C)(=O)C.C(N(C(C)C)C(C)C)C>CO.C(Cl)Cl.C(O[Pd]OC(=O)C)(=O)C.CN(C=O)C>[F:7][C:8]1[C:9]([CH:28]=[O:29])=[C:10]2[C:16]([C:3]([OH:5])=[O:4])=[CH:15][N:14]([S:18]([C:21]3[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=3)(=[O:20])=[O:19])[C:11]2=[N:12][CH:13]=1

Komponenten

9

Edukt 5

HCID 7918Acetic AnhydrideHCID 81531DiisopropylethylamineHCID 433294Lithium ChlorideHCID 23680280Lithium formateHCID 582934925-fluoro-3-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde

Produkt 1

HCID 582934835-fluoro-4-formyl-1-tosyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acidAusbeute 85,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 21226129Dichloromethane methanolLösungsmittel

Reaktionsbedingungen

Temperatur
56 °C

Versuchsvorschrift

Lithium chloride (0.472 g, 11.14 mmol) and lithium formate (0.579 g, 11.14 mmol) were combined in a sealable dried tube. DMF (10 mL), 5-fluoro-3-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde (1.650 g, 3.71 mmol), acetic anhydride (0.702 mL, 7.43 mmol) and diacetoxypalladium (0.083 g, 0.371 mmol) were added. N-Ethyl-N-isopropylpropan-2-amine (1.294 mL, 7.43 mmol) was added and the mixture was sealed and heated at 56° C. for 3 h. The reaction mixture was taken up in MeOH/DCM (20%) and filtered. The yellow solution was concentrated and the residue was dissolved in MeOH/DCM (10%) and washed with aqueous HCl (0.1N). The aqueous phase was extracted two more times. The organics were combined, dried over MgSO4 and concentrated to an orange oil, which was triturated in ether (300 mL). The precipitate was filtered and dried in vacuo to afford the title compound as light yellow solid (1.15 g, 77%). 1H NMR (400 MHz, DMSO-d6) δ 2.37 (s, 3H) 7.47 (d, J=8.08 Hz, 2H) 8.10 (d, J=8.10 Hz, 2H) 8.54-8.65 (m, 2H) 10.60 (s, 1H) 13.45 (br. s., 1H). [M+H] calc'd for C15H10FIN2O3S, 363; found, 363.4.

Aufarbeitung

  1. customthe mixture was sealed
  2. filtrationfiltered
  3. concentrationThe yellow solution was concentrated
  4. dissolutionthe residue was dissolved in MeOH/DCM (10%)
  5. washwashed with aqueous HCl (0.1N)
  6. extractionThe aqueous phase was extracted two more times
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated to an orange oil, which
  9. customwas triturated in ether (300 mL)
  10. filtrationThe precipitate was filtered
  11. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-9ba2ba35006c4f50b86368766dd1a945
Quelldatensatz
uspto-grants-2013_04
Patentnummer
US08420816B2

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