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

HRID 1684033ノート

反応式

HRID 1684033 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 22272175Benzene--water (1/1)溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-678b78fbfdc64de49b7ef8d2f9fff4b7
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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