3,4,5-Trimethoxybenzaldehyde → trans-2,4-Bis-(3,4,5-trimethoxyphenyl)-1,3-dithiolane

HRID 1684025ノート

反応式

HRID 1684025 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:13]([SH:16])[CH2:14][SH:15])[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].[CH3:17][O:18][C:19]1[CH:20]=[C:21]([CH:24]=[C:25]([O:29][CH3:30])[C:26]=1[O:27][CH3:28])[CH:22]=O.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C12(CS(O)(=O)=O)C(C)(C)C(CC1)CC2=O>CCCCCC.C(OCC)(=O)C.CO.C1C=CC=CC=1.O.C1C=CC=CC=1>[CH3:30][O:29][C:25]1[CH:24]=[C:21]([C@H:22]2[S:16][C@H:13]([C:5]3[CH:6]=[C:7]([O:11][CH3:12])[C:8]([O:9][CH3:10])=[C:3]([O:2][CH3:1])[CH:4]=3)[CH2:14][S:15]2)[CH:20]=[C:19]([O:18][CH3:17])[C:26]=1[O:27][CH3:28]

参加物

9

反応物 4

HCID 68583,4,5-TrimethoxybenzaldehydeHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 190417461-(3,4,5-Trimethoxyphenyl)-1,2-ethanedithiol

生成物 1

HCID 9954830trans-2,4-Bis-(3,4,5-trimethoxyphenyl)-1,3-dithiolane

試薬・触媒・溶媒 4

HCID 241Benzene溶媒HCID 887Methanol溶媒HCID 21226206Ethyl acetate hexane溶媒HCID 22272175Benzene--water (1/1)溶媒

実験手順

1-(3,4,5-trimethoxyphenyl)-1,2-ethanedithiol (38) (0.56 g, 2.15 mmole), 3,4,5-trimethoxybenzaldehyde (24) (0.35 g, 1.78 mmole) and 0.178 g of pyridinium paratoluene sulfonate are added to 40 ml dry benzene and refluxed with Dean-Stark removal of the benzene-water azeotrope for 24 hours. The benzene is removed in vacuo, and the remaining oil redissolved in ethyl acetate. The organic layer is washed with H2O and was dried over MgSO4, filtered, and evaporated in vacuo to a white foam which is purified by flash column chromatography using 1:1 hexane/ethyl acetate as eluent (0.630 g, 81%). The trans isomer is isolated from the 1:1 mixture of diastereomers after three recrystallizations from methanol (25 mg). If the above reaction is performed under reduced pressure (aspirator) at 45° C. for 2.5 hours using camphor sulfonic acid as the catalyst, the product mixture contains a 3:1 cis/trans ratio of diastereomers. The cis diastereomer is isolated from this product mixture by recrystallization from either methanol or hexane/ethyl acetate.

後処理

  1. customThe benzene is removed in vacuo
  2. dissolutionthe remaining oil redissolved in ethyl acetate
  3. washThe organic layer is washed with H2O
  4. dry with materialwas dried over MgSO4
  5. filtrationfiltered
  6. customevaporated in vacuo to a white foam which
  7. customis purified by flash column chromatography
  8. customThe trans isomer is isolated from the 1:1 mixture of diastereomers
  9. customafter three recrystallizations from methanol (25 mg)
  10. customIf the above reaction

出典と根拠

ORDレコード
ord-806d3f8fcfb94e118b63ecb87732b8c6
出典データセット
uspto-grants-1997_06
特許番号
US05639782

反応ノート

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