Propanal → 2,4-Dimethyl-6-oxo-1-propylamino-1,6-dihydro-pyridine-3-carboxylic acid methyl ester

HRID 222792

反応式

HRID 222792 の反応式
[CH3:1][O:2][C:3]([C:5]1[C:10]([CH3:11])=[CH:9][C:8](=[O:12])[N:7]([NH2:13])[C:6]=1[CH3:14])=[O:4].[CH:15](=O)[CH2:16][CH3:17].[BH4-].[Na+]>CO>[CH3:1][O:2][C:3]([C:5]1[C:10]([CH3:11])=[CH:9][C:8](=[O:12])[N:7]([NH:13][CH2:15][CH2:16][CH3:17])[C:6]=1[CH3:14])=[O:4]

参加物

5

反応物 3

HCID 527PropanalHCID 4311764Sodium borohydrideHCID 583074511-Amino-2,4-dimethyl-6-oxo-1,6-dihydro-pyridine-3-carboxylic acid methyl ester

生成物 1

HCID 583074682,4-Dimethyl-6-oxo-1-propylamino-1,6-dihydro-pyridine-3-carboxylic acid methyl ester

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

A mixture of 1-amino-2,4-dimethyl-6-oxo-1,6-dihydro-pyridine-3-carboxylic acid methyl ester (2.8 g, 14 mmol), propionaldehyde (5.1 mL, 71 mmol) and molecular sieves (size 4 Å, 5 g) in methanol (50 mL) was stirred overnight at room temperature. The solution was cooled to 5° C. and sodium tetrahydroborate (2.2 g, 57 mmol) was added in small portions. It was stirred for 1 hour at 5° C., then filtered and evaporated. The residue was partitioned between water (100 mL) and ethyl acetate (3×100 mL). The combined organic solution was dried (MgSO4) and evaporated. The residue was treated with hot n-heptane, cooled to 10° C. and the unreacted starting material was removed by filtration. The heptane solution was purified by flash chromatography to give the title compound. LC-MS (m/z) 239.1 (MH+); tR=1.20 (method C). 1H NMR (600 MHz, CDCl3): 1.01 (t, J=7.4 Hz, 3H, Me of Pr), 1.61 (sextet, J=7.3 Hz, 2H, CH2 of Pr), 2.19 (d, J=0.9 Hz, 3H, Me), 2.53 (s, 3H, Me), 2.56-3.1 (very br. coalescing d, 2H, CH2N), 3.87 (s, 3H, OMe), 5.92 (t, J=7.3 Hz, 1H, NH), 6.35 (s, 1H, C5-H).

後処理

  1. temperatureThe solution was cooled to 5° C.
  2. stirringIt was stirred for 1 hour at 5° C.
  3. filtrationfiltered
  4. customevaporated
  5. customThe residue was partitioned between water (100 mL) and ethyl acetate (3×100 mL)
  6. dry with materialThe combined organic solution was dried (MgSO4)
  7. customevaporated
  8. additionThe residue was treated with hot n-heptane
  9. temperaturecooled to 10° C.
  10. customwas removed by filtration
  11. customThe heptane solution was purified by flash chromatography

出典と根拠

ORDレコード
ord-5e5aeba34dbc4dfd8837d7d1745debe1
出典データセット
uspto-grants-2012_06
特許番号
US08207347B2

関連ノート

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