HCID 88777142, Verbindung → HCID 70617022, Verbindung

HRID 1578875Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1578875
C([C:3]1[CH:8]([C:9]([O:11][CH:12]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:10])[N:7]2[C:25](=[O:36])[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C@H:6]2[S:5][CH:4]=1)=O>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh].C1(C)C=CC=CC=1>[CH:12]([O:11][C:9]([C:8]1[N:7]2[C:25](=[O:36])[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C@H:6]2[S:5][CH2:4][CH:3]=1)=[O:10])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Komponenten

4

Edukt 1

HCID 88777142HCID 88777142, Verbindung

Produkt 1

HCID 70617022HCID 70617022, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)KatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

A mixture of the benzhydryl ester from Example 28 (2.5 g. 4.79 mmol). tris-(triphenylphosphine)chlororhodium (3.5 g. 4.79 mmol) and dry toluene (75 ml) was refluxed under nitrogen for 5.5 hours. The reaction mixture was cooled, the rhodium complex was removed by filtration and the filtrate was poured slowly into petroleum ether (250 ml) with stirring. The precipitated solid, which was a mixture of rhodium complex and product, was collected. The product was purified by chromatography on a silica gel column (250 g) using 99:0.5 chloroform:ethyl acetate as eluent. Fractions of 4.5 ml were collected; fractions 1-47 discarded, 48-66 contained bis-(triphenylphosphine)carbonylchlororhodium, and 67-198 contained the product. NMR data indicated the product after chromatography to be the Δ3 isomer instead of the Δ2 isomer. A decoupling experiment showed the 2-methylene group at 3.3 ppm. to be coupled with the 3-proton at 6.6 ppm.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled
  2. customthe rhodium complex was removed by filtration
  3. additionthe filtrate was poured slowly into petroleum ether (250 ml)
  4. additiona mixture of rhodium complex and product
  5. customwas collected
  6. customThe product was purified by chromatography on a silica gel column (250 g)
  7. customFractions of 4.5 ml were collected

Quellen und Nachweise

ORD-Eintrag
ord-e8b21e310985454a9056d37647fd829c
Quelldatensatz
uspto-grants-1976_02
Patentnummer
US03939266

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