Boron trifluoride etherate → cis-7-chloro-1,2,2a,3,4,9-hexahydro-8-methyl-9bH-cyclobuta[a]carbazole-9b-acetic acid ethyl ester

HRID 477585

Reaktionsgleichung

Reaktionsgleichung von HRID 477585
[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C@@:6]12[CH2:13][CH2:12][C@@H:11]1[CH2:10][CH2:9][CH2:8][C:7]2=O)[CH3:2].[Cl:16][C:17]1[C:18]([CH3:25])=[C:19]([NH:23]N)[CH:20]=[CH:21][CH:22]=1.B(F)(F)F.CCOCC>C1(C)C=CC=CC=1.O.C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C@:6]12[CH2:13][CH2:12][C@H:11]1[CH2:10][CH2:9][C:8]1[C:20]3[C:19]([NH:23][C:7]=12)=[C:18]([CH3:25])[C:17]([Cl:16])=[CH:22][CH:21]=3)[CH3:2]

Komponenten

7

Edukt 3

HCID 8000Boron trifluoride etherateHCID 702863(3-Chloro-2-methylphenyl)hydrazineHCID 53960823cis-2-Oxobicyclo[4.2.0]octane-1-acetic acid ethyl ester

Produkt 1

HCID 86742522cis-7-chloro-1,2,2a,3,4,9-hexahydro-8-methyl-9bH-cyclobuta[a]carbazole-9b-acetic acid ethyl esterAusbeute 45 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 962WaterLösungsmittel2×HCID 1140TolueneLösungsmittel

Versuchsvorschrift

cis-2-Oxobicyclo[4.2.0]octane-1-acetic acid ethyl ester (3.7 g, 18.87 mmol) prepared by the process of Ziegler et al, J. Am. Chem. Soc., 104, 7181 (1982) and 3-chloro-2-methylphenylhydrazine (2.95 g, 18.87 mmol) were dissolved in 50 mL of toluene and refluxed under nitrogen with azeotropic removal of water for 48 hours. The toluene was removed and 13 mL of acetic acid and 2.78 mL (22.64 mmol) of borontrifluoride etherate was added to the residue. The reaction mixture was then allowed to reflux under nitrogen for 30 minutes. The reaction mixture was then poured into 50 mL of water and extracted with 4×30 mL of ether. The combined organic layers were washed with 4×30 mL of 1N HCl, 1×30 mL of 1N NaOH, and 1×30 mL of brine. The ether layers were dried over MgSO4 and concentrated in vacuo affording 5.7 g of crude product. Flash chromatography (70 mm column, 5% ethyl acetate/petroleum ether eluant) afforded 2.7 g (45%) of cis-7-chloro-1,2,2a,3,4,9-hexahydro-8-methyl-9bH-cyclobuta[a]carbazole-9b-acetic acid ethyl ester.

Aufarbeitung

  1. customThe toluene was removed
  2. temperatureto reflux under nitrogen for 30 minutes
  3. extractionextracted with 4×30 mL of ether
  4. washThe combined organic layers were washed with 4×30 mL of 1N HCl, 1×30 mL of 1N NaOH, and 1×30 mL of brine
  5. dry with materialThe ether layers were dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customaffording 5.7 g of crude product

Quellen und Nachweise

ORD-Eintrag
ord-93e3f5d377604d00ab19df0fcc273996
Quelldatensatz
uspto-grants-1989_12
Patentnummer
US04888431

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