Hydrochloric Acid → tert-Butyl (1-(5-oxo-4-(m-tolylamino)-6,7-dihydro-5H-pyrrolo[3,4-d]pyrimidin-2-yl)piperidin-2-yl)methylcarbamate

HRID 516011ノート

反応式

HRID 516011 の反応式
[C:1]([O:5][C:6]([NH:8][CH2:9][CH:10]1[CH2:15][CH2:14][CH2:13][CH2:12][N:11]1[C:16]1[N:21]=[C:20]([C:22]#[N:23])[C:19]([C:24](OC)=[O:25])=[C:18]([NH:28][C:29]2[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=2)[N:17]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Cl>[Pd].CCO>[O:25]=[C:24]1[C:19]2[C:18]([NH:28][C:29]3[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=3)=[N:17][C:16]([N:11]3[CH2:12][CH2:13][CH2:14][CH2:15][CH:10]3[CH2:9][NH:8][C:6](=[O:7])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[N:21][C:20]=2[CH2:22][NH:23]1

参加物

5

反応物 2

HCID 313Hydrochloric AcidHCID 67238205Methyl 2-(2-((tert-butoxycarbonylamino)methyl)piperidin-1-yl)-4-cyano-6-(m-tolylamino)pyrimidine-5-carboxylate

生成物 1

HCID 86654716tert-Butyl (1-(5-oxo-4-(m-tolylamino)-6,7-dihydro-5H-pyrrolo[3,4-d]pyrimidin-2-yl)piperidin-2-yl)methylcarbamate収率 73.1%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 702Ethanol溶媒

実験手順

A mixture of methyl 2-(2-((tert-butoxycarbonylamino)methyl)piperidin-1-yl)-4-cyano-6-(m-tolylamino)pyrimidine-5-carboxylate (310.1 mg, 0.645 mmol), palladium on carbon (72.4 mg, 0.680 mmol) in EtOH (8 mL), and 1N HCl (4 mL) was stirred at RT for 16 h. The mixture was filtered to remove the catalyst. The filtrate was treated with saturated aq NaHCO3 (20 mL) for 3 h. The mixture was concentrated under reduced pressure and the residue was extracted with EtOAc (2×40 mL). The organic layers were washed with saturated aq NaHCO3 (20 mL), water (20 mL), and brine (20 mL), were dried over anhydrous Na2SO4, and then filtered through SiO2. The filtrate was concentrated under reduced pressure to give the title compound as a colorless solid (213.4 mg, 73%). 1H-NMR (DMSO-d6) δ ppm 1.28 (s, 9H), 1.35 (br s, 1H), 1.49-1.56 (m, 2H), 1.67-1.69 (m, 3H), 2.31 (s, 3H), 3.06 (br s, 1H), 3.24 (br s, 2H), 4.16 (s, 2H), 4.67 (br s, 1H), 5.08 (br s, 1H), 6.77 (br s, 1H), 6.87 (d, 1H, J=7.0 Hz), 7.23-7.25 (m, 1H), 7.53 (br s, 2h), 8.07 (s, 1H), 8.55 (s, 1H). [M+H] calc'd for C24H33N6O3, 453; found, 453.5.

後処理

  1. filtrationThe mixture was filtered
  2. customto remove the catalyst
  3. additionThe filtrate was treated with saturated aq NaHCO3 (20 mL) for 3 h
  4. concentrationThe mixture was concentrated under reduced pressure
  5. extractionthe residue was extracted with EtOAc (2×40 mL)
  6. washThe organic layers were washed with saturated aq NaHCO3 (20 mL), water (20 mL), and brine (20 mL)
  7. dry with materialwere dried over anhydrous Na2SO4
  8. filtrationfiltered through SiO2
  9. concentrationThe filtrate was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-202bcbe7278f459ea3c943030ce6a58d
出典データセット
uspto-grants-2015_08
特許番号
US09108970B2

反応ノート

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