Water → tert-butyl (4-fluoro-3-(2-(methylsulfinyl)-7-oxopyrido[2,3-d]pyrimidin-8(7H)-yl)phenyl)carbamate

HRID 527404Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 527404
[F:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][C:3]=1[N:16]1[C:21]2[N:22]=[C:23]([S:26][CH3:27])[N:24]=[CH:25][C:20]=2[CH:19]=[CH:18][C:17]1=[O:28].C1C=C(Cl)C=C(C(OO)=[O:37])C=1.O.C([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][C:3]=1[N:16]1[C:21]2[N:22]=[C:23]([S:26]([CH3:27])=[O:37])[N:24]=[CH:25][C:20]=2[CH:19]=[CH:18][C:17]1=[O:28]

Komponenten

6

Edukt 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 70297m-Chloroperbenzoic acidHCID 86732014tert-butyl (4-fluoro-3-(2-(methylthio)-7-oxopyrido[2,3-d]pyrimidin-8(7H)-yl)phenyl)carbamate

Produkt 1

HCID 86732015tert-butyl (4-fluoro-3-(2-(methylsulfinyl)-7-oxopyrido[2,3-d]pyrimidin-8(7H)-yl)phenyl)carbamateAusbeute 131,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

At 0° C., a suspension of tert-butyl (4-fluoro-3-(2-(methylthio)-7-oxopyrido[2,3-d]pyrimidin-8(7H)-yl)phenyl)carbamate (59) (270 mg, 0.67 mmol) in DCM (10 mL) was treated with MCPBA (77 wt. %, 161 mg, 0.72 mmol) in one portion and stirred at 0° C. for 1 h. The reaction mixture was diluted with DCM (50 mL), and treated with ice and water (30 mL) followed by 10% Na2CO3 (ca. 10 mL). The DCM layer was separated and the aqueous layer was extracted with an additional amount of DCM (2×50 mL), dried over Na2SO4 and concentrated to give crude tert-butyl (4-fluoro-3-(2-(methylsulfinyl)-7-oxopyrido[2,3-d]pyrimidin-8(7H)-yl)phenyl)carbamate (60) (369 mg) as a light yellow solid. m/z (ESI, +ve ion) 440.9 (M+Na)+. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.63 (1H, br. s.), 8.24 (1H, d, J=9.6 Hz), 7.68 (1H, d, J=3.5 Hz), 7.44-7.52 (1H, m), 7.33-7.41 (1H, m), 6.95-7.01 (1H, m), 5.76 (1H, s), 2.72-2.78 (3H, m), 1.47 (9H, s). 19F NMR (376 MHz, DMSO-d6) δ ppm-129.58 (1F, s).

Aufarbeitung

  1. customThe DCM layer was separated
  2. extractionthe aqueous layer was extracted with an additional amount of DCM (2×50 mL)
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-c3aeb60e221a4aaa8353b17b32e01f59
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09346801B2

Notizen zur Reaktion

Wird geladen…