1,4-Dioxane → Methyl 4-bromo-7,7-dimethyl-9-oxo-5,6,7,8,9,10-hexahydroacridine-1-carboxylate

HRID 521399

反応式

HRID 521399 の反応式
O[C:2]1[CH2:7][CH2:6][C:5]([CH3:9])([CH3:8])[CH2:4][C:3]=1[C:10]([O:12]C)=O.[NH2:14][C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][C:24]=1[Br:25])[C:18]([O:20][CH3:21])=[O:19].O1CCOCC1>O>[Br:25][C:24]1[C:15]2[NH:14][C:2]3[CH2:7][CH2:6][C:5]([CH3:8])([CH3:9])[CH2:4][C:3]=3[C:10](=[O:12])[C:16]=2[C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:22][CH:23]=1

参加物

5

反応物 3

HCID 312751,4-DioxaneHCID 3928639Methyl 3-amino-4-bromobenzoateHCID 54676124Methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate

生成物 1

HCID 89655891Methyl 4-bromo-7,7-dimethyl-9-oxo-5,6,7,8,9,10-hexahydroacridine-1-carboxylate収率 27%

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
130 °C

実験手順

A mixture of methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate (26 g, 0.141 mol), methyl 3-amino-4-bromobenzoate (25 g, 0.109 mol), polyphosphoric acid (220 g) and dioxane (220 mL) was heated at 130° C. for 5 hours. After cooling, the mixture was diluted with water. The resulting precipitate was collected by filtration and dried. The solid was suspended in methanol (400 mL), and TMSCl (90 mL) was added. The mixture was stirred at reflux for 5 hours, concentrated and treated with water (80 mL), extracted with ethyl acetate (250 mL). The organic layer was separated, concentrated and recrystallized with methanol to afford desired compound (10.6 g, 27%). 1H NMR (DMSO-d6) δ 10.32 (s, 1H), 7.98 (d, 1H, J=7.2 Hz), 7.10 (d, 1H, J=7.2 Hz), 3.80 (s, 3H), 2.90 (t, 2H, J=6.6 Hz), 2.22 (s, 2H), 1.56 (t, 2H, J=6.6 Hz), and 0.97 (s, 6H). MS (ESI) m/e [M+1]+364.

後処理

  1. temperatureAfter cooling
  2. filtrationThe resulting precipitate was collected by filtration
  3. customdried
  4. additionTMSCl (90 mL) was added
  5. temperatureat reflux for 5 hours
  6. concentrationconcentrated
  7. additiontreated with water (80 mL)
  8. extractionextracted with ethyl acetate (250 mL)
  9. customThe organic layer was separated
  10. concentrationconcentrated
  11. customrecrystallized with methanol

出典と根拠

ORDレコード
ord-63c433ca5a9c4c4d9a7a233410442823
出典データセット
uspto-grants-2016_05
特許番号
US09328111B2

関連ノート

読み込み中…