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

HRID 521406

反応式

HRID 521406 の反応式
O=[C:2]1[CH2:7][CH2:6][CH2:5][CH2:4][CH:3]1[C:8](OC)=[O:9].[NH2:12][C:13]1[CH:14]=[C:15]([CH:20]=[CH:21][C:22]=1[CH3:23])[C:16]([O:18][CH3:19])=[O:17].O1CCOCC1>O>[CH3:23][C:22]1[C:13]2[NH:12][C:2]3[CH2:7][CH2:6][CH2:5][CH2:4][C:3]=3[C:8](=[O:9])[C:14]=2[C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:20][CH:21]=1

参加物

5

反応物 3

HCID 312751,4-DioxaneHCID 170489Cyclohexanecarboxylic acid, 2-oxo-, methyl esterHCID 337778Methyl 3-amino-4-methylbenzoate

生成物 1

HCID 89669513Methyl 4-methyl-9-oxo-5,6,7,8,9,10-hexahydroacridine-1-carboxylate収率 31.7%

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-oxocyclohexanecarboxylate (1.0 g, 6.4 mmol), methyl 3-amino-4-methylbenzoate (1.06 g, 6.4 mmol), polyphosphoric acid (4 mL) and dioxane (6 mL) was heated at 130° C. for 2 hours. After cooling to room temperature, the mixture was diluted with water (100 mL) and the resulting precipitate was collected by filtration and dried. The solid was suspended in methanol (100 mL) and SOCl2 (10 mL) was added. The mixture was stirred at reflux for 5 hours, concentrated and treated with water (80 mL), extracted with ethyl acetate (3×80 mL). The organic layer was separated, concentrated to give the crude product. Then the mixture was purified by chromatography column on silica gel (eluted with CH2Cl2/MeOH) to afford crude product, and the final product (0.55 g) was obtained from recrystallization using MeOH as solvent. 1H NMR (DMSO-d6) δ 10.3 (s, 1H), 7.41 (d, 1H, J=7.8 Hz), 6.99 (d, 1H, J=7.8 Hz), 3.73 (s, 3H), 2.78-2.81 (m, 2H), 2.50 (s, 3H), 2.35-2.37 (m, 2H), and 1.64-1.73 (m, 4H). MS (ESI) m/e [M+1]+272.0.

後処理

  1. temperatureAfter cooling to room temperature
  2. filtrationthe resulting precipitate was collected by filtration
  3. customdried
  4. additionSOCl2 (10 mL) was added
  5. temperatureat reflux for 5 hours
  6. concentrationconcentrated
  7. additiontreated with water (80 mL)
  8. extractionextracted with ethyl acetate (3×80 mL)
  9. customThe organic layer was separated
  10. concentrationconcentrated
  11. customto give the crude product
  12. customThen the mixture was purified by chromatography column on silica gel (eluted with CH2Cl2/MeOH)
  13. customto afford crude product

出典と根拠

ORDレコード
ord-40aa67c6e29f42c98fda582dab79a74b
出典データセット
uspto-grants-2016_05
特許番号
US09328111B2

関連ノート

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