Hydrochloric Acid → 7-tert-butyl-2,3-dihydro-3,3-dimethylbenzothiophene

HRID 2257256ノート

反応式

HRID 2257256 の反応式
[CH:1]([S:5][C:6]1[C:11]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:10][CH:9]=[CH:8][C:7]=1Br)=[C:2]([CH3:4])[CH3:3].[PH2](O)=O.C(N(CC)CC)C.Cl>O1CCOCC1.[Cl-].[Na+].O>[CH3:3][C:2]1([CH3:4])[CH2:1][S:5][C:6]2[C:11]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:10][CH:9]=[CH:8][C:7]1=2

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 4124402Phosphinic AcidHCID 22905880HCID 22905880、化合物

生成物 1

HCID 107041827-tert-butyl-2,3-dihydro-3,3-dimethylbenzothiophene

試薬・触媒・溶媒 2

HCID 312751,4-Dioxane溶媒2 回HCID 57417360Sodium chloride; water溶媒

反応条件

温度
24 °C

実験手順

A solution of 2-bromo-6-tert-butylphenyl isobutenyl thioether (600 mg, 2.07 mmol), 90% hypophosphorous acid (4.4 g, 60 mmol), and triethylamine (8.4 mL, 60 mmol) in dioxane (30 mL) is deoxygenated by bubbling with N2 for 20 min. The solution is then heated under N2 to reflux, and a solution of azo-bis-isobutyrylnitrile (205 mg, 1.04 mmol) in deoxygenated dioxane (2 mL) is added in 0.2-mL portions over 3 h. The reaction is allowed to cool to 24° C., and 1N HCl (40 mL) and brine (30 mL) are added. The mixture is extracted with Et2O (3×50 mL), and the ethereal layers are back extracted with 1N NaOH (40 mL). The organic phase is dried (MgSO4), filtered and evaporated to a yellow oil. Kugelrohr distillation provides 3,3-dimethyl-7-tert-butyl-2,3-dihydrobenzo[b]thiophene as a colorless oil.

後処理

  1. customby bubbling with N2 for 20 min
  2. temperatureThe solution is then heated under N2
  3. temperatureto reflux
  4. extractionThe mixture is extracted with Et2O (3×50 mL)
  5. extractionthe ethereal layers are back extracted with 1N NaOH (40 mL)
  6. dry with materialThe organic phase is dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated to a yellow oil
  9. distillationKugelrohr distillation

出典と根拠

ORDレコード
ord-1a64a750e14c4f85a7ec3b51ea3c9542
出典データセット
uspto-grants-1997_08
特許番号
US05656661

反応ノート

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