Citric Acid → 2-(N-methylcarbamoyl)-5-tert-butyl-3-nitropyrrole

HRID 1698916Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1698916
[C:1]([C:5]1[NH:9][C:8]([C:10]([OH:12])=O)=[C:7]([N+:13]([O-:15])=[O:14])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:16][N:17]1CCOCC1.CN.CCN=C=NCCCN(C)C.Cl.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O.CN(C=O)C.C1COCC1>[CH3:16][NH:17][C:10]([C:8]1[NH:9][C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])=[CH:6][C:7]=1[N+:13]([O-:15])=[O:14])=[O:12]

Komponenten

9

Edukt 5

HCID 311Citric AcidHCID 6329MethylamineHCID 79724-MethylmorpholineHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 183223915-tert-butyl-3-nitro-1H-pyrrole-2-carboxylic acid

Produkt 1

HCID 183223572-(N-methylcarbamoyl)-5-tert-butyl-3-nitropyrroleAusbeute 66 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 5-tert-butyl-3-nitropyrrole-2-carboxylic acid (2.01 g, 9.5 mmol) in a solution of anh. THF and anh. DMF (3:1, 100 mL) at 0° C. was added N-methylmorpholine (2.1 mL, 19 mmol, 2.0 equiv), followed by methylamine (2M in THF, 5.93 mL, 11.1 mmol, 1.25 equiv) and EDCI.HCl (2.85 g, 14.9 mmol, 1.57 equiv). The resulting mixture was allowed to warm to room temp. and stirred at that temp. overnight. The reaction mixture was diluted with H2O (100 mL), then made acidic with a 10% citric acid solution, and extracted with EtOAc (2×50 mL). The combined organic layers were washed with a saturated NaCl solution, dried (MgSO4), and concentrated in vacuo. The residue was purified by flash chromatography (15% CH2Cl2/hex) to give 2-(N-methylcarbamoyl)-5-tert-butyl-3-nitropyrrole (1.40 g, 66%) as a yellow solid: 1H NMR (DMSO-d6) δ1.29 (s, 9H), 2.76 (d, J=4.4 Hz, 3H), 6.36 (d, 2.9 Hz, 1H), 8.59-8.60 (m, 1H), 12.19 (br s, 1H).

Aufarbeitung

  1. temperatureto warm to room temp.
  2. customovernight
  3. extractionextracted with EtOAc (2×50 mL)
  4. washThe combined organic layers were washed with a saturated NaCl solution
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography (15% CH2Cl2/hex)

Quellen und Nachweise

ORD-Eintrag
ord-fb12816f606f4e58a10b3791ec1f35e0
Quelldatensatz
uspto-grants-2002_02
Patentnummer
US06344476B1

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