Hydrogen Bromide → 3-[(3-Chlorophenyl)thio]piperidine hydrobromide

HRID 236091

反応式

HRID 236091 の反応式
ClC1C=C(S)C=CC=1.C(=O)([O-])[O-].[Na+].[Na+].[Cl:15][C:16]1[CH:17]=[C:18]([S:22][CH:23]2[CH2:28][CH2:27][CH2:26][N:25](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:24]2)[CH:19]=[CH:20][CH:21]=1.C1(O)C=CC=CC=1.[BrH:46]>CN(C)C=O>[BrH:46].[Cl:15][C:16]1[CH:17]=[C:18]([S:22][CH:23]2[CH2:28][CH2:27][CH2:26][NH:25][CH2:24]2)[CH:19]=[CH:20][CH:21]=1

参加物

7

反応物 5

HCID 260Hydrogen BromideHCID 996PhenolHCID 10340Sodium CarbonateHCID 162573-ChlorothiophenolHCID 202178253-[(3-Chlorophenyl)thio]-1-[(4-methylphenyl)sulfonyl]piperidine

生成物 1

HCID 202180083-[(3-Chlorophenyl)thio]piperidine hydrobromide

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

A mixture of 25.2 g (0.175 mole) of m-chlorothiophenol, 48.26 g (0.118 mole) of 1-[(4-methylphenyl)sulfonyl]-3-piperidinol-4-methylphenylsulfonate ester and 56 g of sodium carbonate in 300 ml of dimethylformamide was heated at 100° C. for 22 hr. The mixture was cooled and quenched in excess 1M sodium hydroxide solution. The aqueous mixture was extracted with several portions of methylene chloride and the combined methylene chloride extracts were extracted with several portions of 1N sodium hydroxide solution and dried over magnesium sulfate. The solvent was removed in vacuo to give an oil which was shown by NMR, mass spectrum and TLC to be 3-[(3-chlorophenyl)thio]-1-[(4-methylphenyl)sulfonyl]piperidine. A mixture of the oil and excess phenol in 200 ml of 48% hydrobromic acid was refluxed for 1 hr and quenched in an ice-water mix. The mixture was made basic with sodium hydroxide and extracted with several portions of methylene chloride. The combined methylene chloride extracts were extracted with several portions of 1M sulfuric acid and the methylene chloride layer discarded. The combined acidic extracts were made basic with sodium hydroxide and the basic solution was extracted with several portions of methylene chloride. The aqueous layer was discarded. The combined methylene chloride extract was dried over magnesium sulfate and methylene chloride was removed in vacuo to give an oil, the free base of the title compound. The free base was reacted with hydrogen bromide using the solvent pair isopropanol-isopropyl ether for crystallization and recrystallization to obtain the hydrobromide salt, m.p. 117.5°-120° C.

後処理

  1. temperatureThe mixture was cooled
  2. customquenched in excess 1M sodium hydroxide solution
  3. extractionThe aqueous mixture was extracted with several portions of methylene chloride
  4. extractionthe combined methylene chloride extracts were extracted with several portions of 1N sodium hydroxide solution
  5. dry with materialdried over magnesium sulfate
  6. customThe solvent was removed in vacuo
  7. customto give an oil which
  8. temperaturewas refluxed for 1 hr
  9. customquenched in an ice-water
  10. additionmix
  11. extractionextracted with several portions of methylene chloride
  12. extractionThe combined methylene chloride extracts were extracted with several portions of 1M sulfuric acid
  13. extractionthe basic solution was extracted with several portions of methylene chloride
  14. extractionThe combined methylene chloride extract
  15. dry with materialwas dried over magnesium sulfate and methylene chloride
  16. customwas removed in vacuo
  17. customto give an oil

出典と根拠

ORDレコード
ord-a1d6088af74849b18c710c0dac1551e5
出典データセット
uspto-grants-1987_02
特許番号
US04642348

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