HCID 88777142、化合物 → HCID 70617022、化合物

HRID 1657423ノート

反応式

HRID 1657423 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
  3. customThe rhodium complex was 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-ebc9d2f869d24e70b504b4fd08b1418f
出典データセット
uspto-grants-1976_06
特許番号
US03960852

反応ノート

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