Methanol → 1-Aminomethyl-5,6-dihydroxy-3-phenyl-3,4-dihydronaphthalene Hydrobromide

HRID 54124ノート

反応式

HRID 54124 の反応式
Cl.[NH2:2][CH2:3][C:4]1[C:13]2[C:8](=[C:9]([O:16]C)[C:10]([O:14]C)=[CH:11][CH:12]=2)[CH2:7][CH:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:5]=1.B(Br)(Br)[Br:25].CO>C(Cl)Cl>[BrH:25].[NH2:2][CH2:3][C:4]1[C:13]2[C:8](=[C:9]([OH:16])[C:10]([OH:14])=[CH:11][CH:12]=2)[CH2:7][CH:6]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:5]=1

参加物

5

反応物 3

HCID 887MethanolHCID 25134Boron tribromideHCID 19961156HCID 19961156、化合物

生成物 1

HCID 199611231-Aminomethyl-5,6-dihydroxy-3-phenyl-3,4-dihydronaphthalene Hydrobromide収率 45%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

1-Aminomethyl-5,6-dimethoxy-3-phenyl-3,4-dihydronaphthalene hydrochloride (6.0 g, 20.2 mmol), from Step 2, was suspended in 200 mL of methylene chloride and boron tribromide (90.5 mL of 1M solution of BBr3 in methylene chloride) was added dropwise while the reaction mixture was being cooled (to -78° C.) in a dry ice/acetone bath. The reaction mixture was warmed to 0° C. and stirred for 0.5 h, then again cooled to -78° C. in a dry ice/acetone bath. Methanol (50 mL) was added dropwise to the reaction mixture, which was allowed to warm to ambient temperature then concentrated in vacuo. Methanol was added to the residue and the solution was reconcentrated. This residue was dissolved in a small amount of methanol and the methanol solution was added to 700 mL of diethyl ether. The precipitate which formed was filtered, washed with diethyl ether and recrystallized from methanol/ether to give 2.5 g (45% yield) of the title compound, m.p. 223°-225° C. 1H NMR (d6 -DMSO) δ: 2.68 (dd, 1H), 3.09 (dd, 1H), 3.6-3.7 (m, 1H), 3.9 (s, 2H), 5.97 (d, 1H), 6.69 (m, 2H), 7.2-7.35 (m, 5H), 8.1 (br s, 3H), 8.4 (s, 1H), 9.5 (s, 1H).

後処理

  1. temperatureThe reaction mixture was warmed to 0° C.
  2. temperatureagain cooled to -78° C. in a dry ice/acetone bath
  3. temperatureto warm to ambient temperature
  4. concentrationthen concentrated in vacuo
  5. additionMethanol was added to the residue
  6. dissolutionThis residue was dissolved in a small amount of methanol
  7. additionthe methanol solution was added to 700 mL of diethyl ether
  8. customThe precipitate which formed
  9. filtrationwas filtered
  10. washwashed with diethyl ether
  11. customrecrystallized from methanol/ether

出典と根拠

ORDレコード
ord-ae28b7eab5bc4a70853ee2e28a234ca6
出典データセット
uspto-grants-1997_04
特許番号
US05621133

反応ノート

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