Sodium hydride → Bis(1,1-dimethylethyl) {3-[(3-bromo-5-chlorophenyl)oxy]-2-fluoro-4-nitrophenyl}propanedioate

HRID 1874932Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1874932
[H-].[Na+].[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH2:4][C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].[Br:18][C:19]1[CH:20]=[C:21]([O:26][C:27]2[C:32]([F:33])=[C:31](F)[CH:30]=[CH:29][C:28]=2[N+:35]([O-:37])=[O:36])[CH:22]=[C:23]([Cl:25])[CH:24]=1.OS([O-])(=O)=O.[Na+]>C1COCC1>[Br:18][C:19]1[CH:20]=[C:21]([O:26][C:27]2[C:32]([F:33])=[C:31]([CH:4]([C:5]([O:7][C:8]([CH3:9])([CH3:10])[CH3:11])=[O:6])[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH:30]=[CH:29][C:28]=2[N+:35]([O-:37])=[O:36])[CH:22]=[C:23]([Cl:25])[CH:24]=1

Komponenten

6

Edukt 4

HCID 24758Sodium hydrideHCID 68324Di-tert-butyl malonateHCID 516919Sodium BisulfateHCID 684866412-[(3-Bromo-5-chlorophenyl)oxy]-3,4-difluoro-1-nitrobenzene

Produkt 1

HCID 68487247Bis(1,1-dimethylethyl) {3-[(3-bromo-5-chlorophenyl)oxy]-2-fluoro-4-nitrophenyl}propanedioate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Sodium hydride (60% dispersion in oil, 3.95 g, 98.6 mmol) was added to anhydrous THF (100 mL) and cooled to 0° C. under nitrogen. A solution of di-tert-butyl malonate (9.79 g, 45.3 mmol) in THF (20 mL) was added dropwise and the reaction mixture was stirred 30 min. A solution of 2-[(3-bromo-5-chlorophenyl)oxy]-3,4-difluoro-1-nitrobenzene (15.0 g, 41.1 mmol) was added dropwise in THF (50 mL) was added dropwise, the reaction was allowed to warm to RT and stirred for 90 min. The reaction was cooled to 0° C., a solution of saturated aqueous NaHSO4 (200 mL) was added and the aqueous mixture was extracted with EtOAc (3×100 mL). The organic extracts were combined, dried over Na2SO4, filtered and evaporated to afford the title compound a brown solid. 1H NMR (400 MHz, DMSO-d6): δ ppm 8.05 (d, 1H), 7.58 (d, 1H), 7.48 (s, 1H), 7.20 (s, 1H), 7.12 (s, 1H), 3.82-3.80 (m, 1H), 1.35 (s, 18H).

Aufarbeitung

  1. additionwas added dropwise
  2. temperatureto warm to RT
  3. stirringstirred for 90 min
  4. temperatureThe reaction was cooled to 0° C.
  5. extractionthe aqueous mixture was extracted with EtOAc (3×100 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-a40882cfe4ac4839aff1536e5ce2b5bf
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08304419B2

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