Benzene → trans-2-(4-Hydroxy-3-methoxy-5-nitrophenyl)-4-(3,4,5-trimethoxyphenyl)-1,3-dithiolane

HRID 1684033Notes

Reaction equation

HRID 1684033 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:15]([SH:18])[CH2:16][SH:17])[CH:6]=[C:7]([O:13][CH3:14])[C:8]=1[O:9][CH2:10]OC.[N+:19]([C:22]1[C:23]([OH:32])=[C:24]([O:30][CH3:31])[CH:25]=[C:26]([CH:29]=1)[CH:27]=O)([O-:21])=[O:20].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C1C=CC=CC=1>C1C=CC=CC=1.O>[OH:32][C:23]1[C:22]([N+:19]([O-:21])=[O:20])=[CH:29][C:26]([C@H:27]2[S:18][C@H:15]([C:5]3[CH:6]=[C:7]([O:13][CH3:14])[C:8]([O:9][CH3:10])=[C:3]([O:2][CH3:1])[CH:4]=3)[CH2:16][S:17]2)=[CH:25][C:24]=1[O:30][CH3:31]

Participants

6

Reactant 4

HCID 241BenzeneHCID 811345-NitrovanillinHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 190418081-(3,5-Dimethoxy-4-methoxymethoxyphenyl)-1,2-ethanedithiol

Product 1

HCID 86749583trans-2-(4-Hydroxy-3-methoxy-5-nitrophenyl)-4-(3,4,5-trimethoxyphenyl)-1,3-dithiolane

Reagents, catalysts & solvents 1

HCID 22272175Benzene--water (1/1)Solvent

Procedure

1-(3,4,5-trimethoxyphenyl)-1,2-ethanedithiol (39) (FIG. 19) (25.4 g,97.7 mmole), 5-nitrovanillin (16.73 g, 84.9 mmole), pyridinium para-toluenesulfonate (PPTS) (8.52 g, 33.9 mmole) and 100 ml dry benzene were refluxed under an argon atmosphere with Dean-Stark removal of the benzene-water azeotrope for 12 hours. The reaction was cooled to room temperature and the precipitated PPTS removed by vacuum filtration. Hexane (100 ml) was added to the filtrate and the precipitate collected by vacuum filtration. The yellow solid was washed with cold water, followed by minimal cold methanol and finally cold diethyl ether to leave 28.62 g of a 1:1.3 cis/trans ratio of product. Six recrystallizations from ethyl acetate/hexane gives 4.3 g of pure trans diastereomer. An additional 2.4 g trans product can be obtained by repeating the above crystallization process from the material remaining in the mother liquors. Once 6.7 g of trans product was isolated,0.315 g of cis diastereomer was isolated by recrystallizing the combined mother liquors from above.

Workup

  1. customthe precipitated PPTS removed by vacuum filtration
  2. additionHexane (100 ml) was added to the filtrate
  3. filtrationthe precipitate collected by vacuum filtration
  4. washThe yellow solid was washed with cold water
  5. customto leave 28.62 g of a 1:1.3 cis/trans ratio of product
  6. customSix recrystallizations from ethyl acetate/hexane
  7. customgives 4.3 g of pure trans diastereomer
  8. customAn additional 2.4 g trans product can be obtained
  9. customOnce 6.7 g of trans product was isolated
  10. custom0.315 g of cis diastereomer was isolated
  11. customby recrystallizing the combined mother liquors from above

Sources & evidence

ORD record
ord-678b78fbfdc64de49b7ef8d2f9fff4b7
Source dataset
uspto-grants-1997_06
Patent number
US05639782

Reaction notes

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