Water → cycloheptanone O-(4-nitro-phenyl)-oxime

HRID 1819842Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1819842
CC(C)([O-])C.[K+].[C:7]1(=[N:14][OH:15])[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.Cl[C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][CH:18]=1.O>CN(C=O)C>[N+:23]([C:20]1[CH:21]=[CH:22][C:17]([O:15][N:14]=[C:7]2[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]2)=[CH:18][CH:19]=1)([O-:25])=[O:24]

Komponenten

6

Edukt 4

HCID 962WaterHCID 74741-Chloro-4-nitrobenzeneHCID 137457Cycloheptanone OximeHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 57890302cycloheptanone O-(4-nitro-phenyl)-oximeAusbeute 80,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Versuchsvorschrift

Potassium t-butoxide (19 g, 1600 mmol) was added in portions to a cooled (2° C.) solution of cycloheptanone oxime (19 g, 150 mmol) in DMF (150 mL). The cooled reaction mixture was stirred for 40 minutes and then 1-chloro-4-nitrobenzene (25 g, 160 mmol) in DMF (50 mL) was added over 5 minutes. The reaction mixture was stirred at ˜10° C. for 30 minutes and then allowed to warm to room temperature and stirred for an additional 2 hours, and then stood at ambient temperature for 16 hours. The reaction mixture poured into water (1600 mL) with stirring. The mixture was stirred for an additional 20 minutes and then allowed to stand at room temperature for 5 hours. The precipitate was collected by filtration and washed with water. Recrystallization of the crude material from hexane provided cycloheptanone O-(4-nitro-phenyl)-oxime (30 g). Cycloheptanone O-(4-nitro-phenyl)-oxime (12 g, 50 mmol) was dissolved in warm isopropanol (120 mL) and 12 N hydrochloric acid (17 mL) was added. The reaction mixture was heated to reflux for 4 hours and then cooled in an ice bath. The solid was collected by filtration, washed with water and cold isopropanol, and dried in an oven to give 2-nitro-7,8,9,10-tetrahydro-6H-benzo[b]-cyclohepta[d]furan (7.8 g, 34 mmol). A mixture of 2-nitro-7,8,9,10-tetrahydro-6H-benzo[b]-cyclohepta[d]furan (5.8 g, 25 mmol) and Raney nickel (-5.6 g wet weight) in ethanol (270 mL) was hydrogenated at 50 PSI on a Parr shaker overnight. The mixture was filtered through Celite® and the filtrate was concentrated. The crude solid was purified by flash column chromatography (gradient elution with 15-25% ethyl acetate-hexanes) to give 7,8,9,10-tetrahydro-6H-benzo[b]-cyclohepta[d]furan-2-ylamine (4.6 g). Mp 98-99° C.

Aufarbeitung

  1. customThe cooled reaction mixture
  2. stirringThe reaction mixture was stirred at ˜10° C. for 30 minutes
  3. stirringstirred for an additional 2 hours
  4. waitstood at ambient temperature for 16 hours
  5. stirringwith stirring
  6. stirringThe mixture was stirred for an additional 20 minutes
  7. waitto stand at room temperature for 5 hours
  8. filtrationThe precipitate was collected by filtration
  9. washwashed with water
  10. customRecrystallization of the crude material from hexane

Quellen und Nachweise

ORD-Eintrag
ord-27424dc7f94c4ab5a1e36f3f630ae401
Quelldatensatz
uspto-grants-2009_10
Patentnummer
US07601856B2

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