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Hydrochloric Acid → (4-Iodophenyl)-3-methoxy-1-(4-methoxyphenyl)-1,4,5,6-tetrahydro-7h-pyrazolo[3,4-c]pyridin-7-one

HRID 892293
ノート
印刷プレビュー

反応式

HRID 892293 の反応式
Cl[C:2](Cl)(Cl)[C:3](Cl)=O.I[C:9]1[CH:14]=[CH:13][C:12]([N:15]2CCC=C(N3CCOCC3)[C:16]2=[O:27])=C[CH:10]=1.Cl.[CH3:29][O:30][C:31]1[CH:36]=[CH:35][C:34]([NH:37][NH2:38])=[CH:33][CH:32]=1.Cl.[H-].[Na+].[CH3:42][I:43].[CH2:44]1[CH2:48][O:47][CH2:46][CH2:45]1>CN(C1C=CN=CC=1)C.C(Cl)Cl.CN(C=O)C.C(N(CC)CC)C>[I:43][C:42]1[CH:10]=[CH:9][C:14]([CH:13]2[CH2:12][NH:15][C:16](=[O:27])[C:45]3[N:37]([C:34]4[CH:35]=[CH:36][C:31]([O:30][CH3:29])=[CH:32][CH:33]=4)[N:38]=[C:48]([O:47][CH3:46])[C:44]2=3)=[CH:3][CH:2]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

12

反応物 7

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 6420Trichloroacetyl chlorideHCID 8028TetrahydrofuranHCID 24758Sodium hydrideHCID 27239044-Methoxyphenylhydrazine hydrochlorideHCID 222404531-(4-Iodophenyl)-3-morpholino-5,6-dihydropyridin-2(1H)-one

生成物

1
HCID 22240487(4-Iodophenyl)-3-methoxy-1-(4-methoxyphenyl)-1,4,5,6-tetrahydro-7h-pyrazolo[3,4-c]pyridin-7-one収率 91%

試薬・触媒・溶媒 4

HCID 142844-(Dimethylamino)pyridine触媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒HCID 8471Triethylamine溶媒

実験手順

Part A. To a solution of 1.91 g of DMAP in 10 mL of methylene chloride was added 1.45 mL of trichloroacetyl chloride at 0° C. After stirring at rt for 30 min, 1.0 g of 1-(4-iodophenyl)-3-(4-morpholinyl)-5,6-dihydro-2(1H)-pyridinone was added. The reaction mixture was refluxed overnight, then quenched with water, extracted with ether. The organic layers were dried over Na2SO4 and concentrated to dryness to provide the crude product that was used in the next step without further purification. Part B. The crude material from above in a mixture of 20 mL of ether, 1 mL of water and 1 mL of conc. HCl was heated to reflux (oil bath 65° C.) for 3 h. The mixture was then allowed to cool to rt and filtered to collect the product as a solid (0.97 g, 81% in 2 steps). 1H NMR (DMSO-d6, 300 MHz) δ 7.79 (2H, d, J=8.7 Hz), 7.25 (2H, d, J=8.7 Hz), 3.89 (2H, t, J=6.2 Hz), 2.92 (2H, t, J=6.2 Hz) ppm. Part C. A mixture of the “trione” made above (0.5 g, 1.09 mmol), p-methoxyphenylhyrazine HCl salt (0.152 g, 1.09 mmol) in 20 mL of THF was treated with 0.30 mL of triethylamine at rt overnight. To the reaction mixture was added 20 mL of 1N HCl. The resulting mixture was refluxed for 2 h. After cooling to rt, the compound was collected by filtration (0.42 g, 84%). 1H NMR (DMSO-d6, 300 MHz) δ 8.78 (1H, s), 8.26 (2H, m), 7.92 (2H, m), 7.72 (2H, m), 7.46 (2H, m), 4.59 (2H, m) 4.09 (3H, s), 3.42 (2H, m) ppm. LRMS (AP+) 462 (M++1). Part D. To a solution of the hydroxy compound (1.78 g, 3.86 mmol) in 20 mL of DMF was added sodium hydride (232 mg, 60%, 5.79 mmol) at 0° C. The mixture was stirred at rt for 30 min. To the reaction mixture was added MeI (0.36 mL, 5.79 mmol). The reaction was stirred at rt overnight, then quenched with water, extracted with ether. The organic layers were dried over Na2SO4, concentrated to dry. The residue was purified by column chromatography to yield -(4-iodophenyl)-3-methoxy-1-(4-methoxyphenyl)-1,4,5,6-tetrahydro-7H-pyrazolo[3,4-c]pyridin-7-one (1.67 g, 91%). 1H NMR (DMSO-d6, 300 MHz) δ 7.67 (2H, d, J=8.8 Hz), 7.43 (2H, d, J=9.1 Hz), 7.07 (2H, d, J=8.8 Hz), 6.90 (2H, d, J=9.1 Hz), 4.02 (5H, m, with a three proton singlet), 3.80 (3H, s), 2.90 (2H, d, J=6.6 Hz) ppm. Part E. An oven-dried flask was charged with 0.28 g of 6-(4-iodophenyl)-3-methoxy-1-(4-methoxyphenyl)-1,4,5,6-tetrahydro-7H-pyrazolo[3,4-c]pyridin-7-one, 90 mg of δ-valerolactam, and 70 mg of anhydrous (powdered) potassium carbonate. The solids were dissolved in 3 mL of degassed DMSO, after which 20 mg of copper (I) iodide was added. The flask was fitted with a reflux condenser and heated to 120° C. while stirring for 12 h. The reaction was cooled to rt, then quenched by the addition of water. Product was extracted into ethyl acetate, which was then dried over Na2SO4 and concentrated to yield a yellow solid. The residue was purified by HPLC to yield 50 mg of the title compound as a TFA salt (15% yield). 1H NMR (MeOH-d4, 300 MHz) δ 7.38 (2H, d, J=1.5 Hz), 7.35 (2H, d, J=1.5 Hz), 7.28 (2H, d, J=10 Hz), 6.92 (2H, d, J=10 Hz), 4.06 (2H, t, J=7.0 Hz), 3.96 (3H, s), 3.79 (3H, s), 3.64 (2H, t, J=5.9 Hz), 2.89 (3H, t, J=7.0), 2.49 (3H, t, J=5.9 Hz), 1.94 (4H, m) ppm.

後処理

  1. temperatureThe reaction mixture was refluxed overnight
  2. customquenched with water
  3. extractionextracted with ether
  4. dry with materialThe organic layers were dried over Na2SO4
  5. concentrationconcentrated to dryness
  6. customto provide the crude product that
  7. customwas used in the next step without further purification
  8. additionThe crude material from above in a mixture of 20 mL of ether, 1 mL of water and 1 mL of conc. HCl
  9. temperaturewas heated
  10. temperatureto reflux (oil bath 65° C.) for 3 h
  11. temperatureto cool to rt
  12. filtrationfiltered
  13. customto collect the product as a solid (0.97 g, 81% in 2 steps)
  14. additionA mixture of the “trione”
  15. temperatureThe resulting mixture was refluxed for 2 h
  16. temperatureAfter cooling to rt
  17. filtrationthe compound was collected by filtration (0.42 g, 84%)
  18. stirringThe mixture was stirred at rt for 30 min
  19. stirringThe reaction was stirred at rt overnight
  20. customquenched with water
  21. extractionextracted with ether
  22. dry with materialThe organic layers were dried over Na2SO4
  23. concentrationconcentrated
  24. customto dry
  25. customThe residue was purified by column chromatography

出典と根拠

ORDレコード
ord-cbcd5050808344ae8f0d7e167a222dd3
出典データセット
uspto-grants-2006_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07005435B2

反応ノート

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