Hydrochloric Acid → 4-(4-chlorophenyl)sulfonyl-4-(2,5-difluorophenyl)cyclohexan-1-one

HRID 1178863ノート

反応式

HRID 1178863 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]([C:13]2[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=2[F:20])=[CH2:12])(=[O:10])=[O:9])=[CH:4][CH:3]=1.C[Si](C)(C)[O:23][C:24]([CH:26]=[CH2:27])=[CH2:25].Cl>C1COCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]2([C:13]3[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=3[F:20])[CH2:27][CH2:26][C:24](=[O:23])[CH2:25][CH2:12]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 5546572-(Trimethylsiloxy)-1,3-butadieneHCID 11529749HCID 11529749、化合物

生成物 1

HCID 104301374-(4-chlorophenyl)sulfonyl-4-(2,5-difluorophenyl)cyclohexan-1-one収率 90%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
130 °C

実験手順

A solution of 2-[1-[(4-chlorophenyl)sulfonyl]ethenyl]-1,4-difluorobenzene (Example 3) (100 g, 0.32 mol) in xylenes (500 ml) was azeotropically distilled at 38° C., 20 mmHg, until 300 mL solvent had been removed. 2-Trimethylsilyloxybutadiene (90.4 g, 0.64 mol) was then added under a nitrogen atmosphere and the mixture heated to 130° C. After the reaction was completed, the mixture was distilled in vacuo to remove residual diene, whilst maintaining a constant volume by the addition of xylenes (400 mL). The mixture was cooled to 50° C. and THF (500 mL) and 3M HCl (424 mL, 1.27 mol) were added. After the hydrolysis was complete, the layers were separated. The organic layer was washed with water (300 mL) and then concentrated by atmospheric distillation until 350 mL of solvent had been removed. The solution was allowed to cool until crystallisation started, heptane (600 mL) was added and the resulting mixture cooled to ambient. The solids were filtered and washed sequentially with heptane:xylenes (3:1, 200 ml) and then heptane (200 ml). Drying overnight in vacuo at 40° C. furnished 4-[(4-chlorophenyl)sulfonyl]-4-(2,5-difluorophenyl)cyclohexanone (110 g, 90% yield). 1H NMR CDCl3 7.43-7.37 (4H, m), 7.22-7.1 (2H, m), 6.97-6.9 (1H, m), 3.05-2.98 (4H, m) and 2.61-2.53 (4H, m).

後処理

  1. custom20 mmHg, until 300 mL solvent had been removed
  2. distillationthe mixture was distilled in vacuo
  3. customto remove residual diene
  4. temperaturewhilst maintaining a constant volume
  5. additionby the addition of xylenes (400 mL)
  6. temperatureThe mixture was cooled to 50° C.
  7. customthe layers were separated
  8. washThe organic layer was washed with water (300 mL)
  9. concentrationconcentrated by atmospheric distillation until 350 mL of solvent
  10. customhad been removed
  11. temperatureto cool until crystallisation
  12. additionheptane (600 mL) was added
  13. temperaturethe resulting mixture cooled
  14. filtrationThe solids were filtered
  15. washwashed sequentially with heptane:xylenes (3:1, 200 ml)
  16. customDrying overnight in vacuo at 40° C.

出典と根拠

ORDレコード
ord-b65674fdbe4540e2b87df497a59bd12c
出典データセット
uspto-grants-2007_10
特許番号
US07276637B2

反応ノート

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