Potassium Carbonate → Tert-butyl 4-(4-amino-3-nitrophenoxy)picolinate

HRID 13446

Reaktionsgleichung

Reaktionsgleichung von HRID 13446
C[Si]([N-][Si](C)(C)C)(C)C.[K+].[NH2:11][C:12]1[CH:17]=[CH:16][C:15]([OH:18])=[CH:14][C:13]=1[N+:19]([O-:21])=[O:20].Cl[C:23]1[CH:28]=[CH:27][N:26]=[C:25]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH:24]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[NH2:11][C:12]1[CH:17]=[CH:16][C:15]([O:18][C:23]2[CH:28]=[CH:27][N:26]=[C:25]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH:24]=2)=[CH:14][C:13]=1[N+:19]([O-:21])=[O:20]

Komponenten

6

Edukt 4

HCID 11430Potassium CarbonateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 37588824-Amino-3-NitrophenolHCID 11806045tert-Butyl 4-chloropicolinate

Produkt 1

HCID 22041090Tert-butyl 4-(4-amino-3-nitrophenoxy)picolinate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Solid anhydrous white powdered KHMDS (2 eq) was suspended in a solution of dimethylformamide. Red crystalline 4-amino-3-nitrophenol (1 eq) was charged to the rapidly stirring solution under an inert atmosphere and the heterogeneous solution was allowed to stir for 2 hours. Then a dimethylformamide solution of tert-butyl 4-chloropyridine-2-carboxylate (1 eq) was added dropwise. Anhydrous powdered potassium carbonate (1.2 eq) was charged to the reaction as an acid scavenger. The purple colored viscous mixture was heated to 80° C. for 12-15 hours until when it was determined to be complete by HPLC. The reaction was evaporated under reduced pressure and diluted with excess ethyl acetate and water. An extraction of the aqueous layer was made with ethyl acetate. The organic layers were combined and washed 4 times with water followed by brine. The organic layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure. The crude material was purified by flash silica gel chromatography using an eluent of 1:1 mixture of hexanes to ethyl acetate to give the desired product. MS: MH+=332.

Aufarbeitung

  1. customThe reaction was evaporated under reduced pressure
  2. additiondiluted with excess ethyl acetate and water
  3. extractionAn extraction of the aqueous layer
  4. washwashed 4 times with water
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. customevaporated under reduced pressure
  7. customThe crude material was purified by flash silica gel chromatography
  8. additionan eluent of 1:1 mixture of hexanes to ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-00d13c5c1a234708ab4cef80b7b55f27
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07728010B2

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