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

HRID 521406

반응식

HRID 521406 반응식
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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 962Water용매

반응 조건

온도
130 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-40aa67c6e29f42c98fda582dab79a74b
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09328111B2

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