2-Methylpentane → ethyl 4-bromo-1-(5-chloro-2-nitrobenzyl)-1H-pyrrole-2-carboxylate

HRID 1877788

Reaktionsgleichung

Reaktionsgleichung von HRID 1877788
[H-].[Na+].CCCC(C)C.[Br:9][C:10]1[CH:11]=[C:12]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[NH:13][CH:14]=1.Br[CH2:21][C:22]1[CH:27]=[C:26]([Cl:28])[CH:25]=[CH:24][C:23]=1[N+:29]([O-:31])=[O:30]>CN(C)C(=O)C>[Br:9][C:10]1[CH:11]=[C:12]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[N:13]([CH2:21][C:22]2[CH:27]=[C:26]([Cl:28])[CH:25]=[CH:24][C:23]=2[N+:29]([O-:31])=[O:30])[CH:14]=1

Komponenten

6

Edukt 4

HCID 78922-MethylpentaneHCID 24758Sodium hydrideHCID 5324607Ethyl 4-bromopyrrole-2-carboxylateHCID 124231272-(Bromomethyl)-4-chloro-1-nitrobenzene

Produkt 1

HCID 68156115ethyl 4-bromo-1-(5-chloro-2-nitrobenzyl)-1H-pyrrole-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 31374DimethylacetamideLösungsmittel

Versuchsvorschrift

Wash 60% mineral oil suspended sodium hydride (1.2 equiv; 1.1 g, 27.52 mmoles) with a small amount of iso-hexane (×2). Suspend in N,N-dimethylacetamide (15 mL) and chill in an ice-bath. Add ethyl 4-bromo-1H-pyrrole-2-carboxylate (5.0 g, 22.93 mmoles) portionwise over 15 minutes allowing gas evolution to subside between additions. Stir at room temperature for 15 minutes to give a brown solution. Add 2-(bromomethyl)-4-chloro-1-nitro-benzene (1.15 equiv; 6.61 g, 26.37 mmoles) in portions over 15 minutes and stir the resulting purple solution at room temperature for 2.5 h. Cool in an ice-bath and quench with water (10 mL). Partition between 1M hydrochloric acid (100 mL) and EtOAc (300 mL). Wash the organic layer with water (2×100 mL) then brine. Dry over Na2SO4 and decolorize with activated charcoal. Filter through celite and evaporate to give ethyl 4-bromo-1-(5-chloro-2-nitrobenzyl)-1H-pyrrole-2-carboxylate as a an orange oil (9.1 g, quantitative). 1H-NMR (CDCl3) δ: 8.12 (1H, d), 7.40 (1H, dd), 7.07 (1H, d), 6.92 (1H, d), 6.53 (1H, d), 5.87 (2H, s), 4.17 (2H, q), 1.25 (3H, t).

Aufarbeitung

  1. washWash 60% mineral oil
  2. temperaturechill in an ice-bath
  3. customto give a brown solution
  4. stirringstir the resulting purple solution at room temperature for 2.5 h
  5. temperatureCool in an ice-bath
  6. customquench with water (10 mL)
  7. customPartition between 1M hydrochloric acid (100 mL) and EtOAc (300 mL)
  8. washWash the organic layer with water (2×100 mL)
  9. dry with materialDry over Na2SO4
  10. filtrationFilter through celite
  11. customevaporate

Quellen und Nachweise

ORD-Eintrag
ord-7e8e6cc5c9a74d26bd4884f7ea7f919d
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08314092B2

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