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

HRID 1684025Notes

Reaction equation

HRID 1684025 reaction equation
[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]

Participants

9

Reactant 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

Product 1

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

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 887MethanolSolventHCID 21226206Ethyl acetate hexaneSolventHCID 22272175Benzene--water (1/1)Solvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-806d3f8fcfb94e118b63ecb87732b8c6
Source dataset
uspto-grants-1997_06
Patent number
US05639782

Reaction notes

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