HCID 88777142、化合物 → HCID 70617022、化合物

HRID 1657429ノート

反応式

HRID 1657429 の反応式
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

参加物

4

反応物 1

HCID 88777142HCID 88777142、化合物

生成物 1

HCID 70617022HCID 70617022、化合物

試薬・触媒・溶媒 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)触媒HCID 1140Toluene溶媒

実験手順

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.

後処理

  1. temperaturewas refluxed under nitrogen for 5.5 hours
  2. temperatureThe reaction mixture was cooled the rhodium complex
  3. customwas removed by filtration
  4. additionthe filtrate was poured slowly into petroleum ether (250 ml)
  5. additiona mixture of rhodium complex and product
  6. customwas collected
  7. customThe product was purified by chromatography on a silica gel column (250 g)
  8. customFractions of 4.5 ml were collected

出典と根拠

ORDレコード
ord-54618c3115384e8094b69cb6a6c2d3e4
出典データセット
uspto-grants-1976_06
特許番号
US03960853

反応ノート

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