Ammonium formate → Methyl 5,6,7,8-tetrahydro-2,7-naphthyridine-4-carboxylate

HRID 338768ノート

反応式

HRID 338768 の反応式
[CH3:1][O:2][C:3]([C:5]1[C:14]2[CH2:13][CH2:12][N:11](CC3C=CC=CC=3)[CH2:10][C:9]=2[CH:8]=[N:7][CH:6]=1)=[O:4].C([O-])=O.[NH4+]>CO.[Pd]>[CH3:1][O:2][C:3]([C:5]1[C:14]2[CH2:13][CH2:12][NH:11][CH2:10][C:9]=2[CH:8]=[N:7][CH:6]=1)=[O:4]

参加物

5

反応物 2

HCID 2723923Ammonium formateHCID 866958797-Benzyl-5,6,7,8-tetrahydro-[2,7]naphthyridine-4-carboxylic acid methyl ester

生成物 1

HCID 84663902Methyl 5,6,7,8-tetrahydro-2,7-naphthyridine-4-carboxylate収率 79.4%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 887Methanol溶媒

実験手順

In a 2 L 3-necked flask equipped with a mechanical stirrer and condenser was placed 7-benzyl-5,6,7,8-tetrahydro-[2,7]naphthyridine-4-carboxylic acid methyl ester (11.28 g, 0.04) in methanol (500 mL). To this solution was added ammonium formate (37.8 g, 0.6 mol) and 10% Pd/C (11 g, 50% water wet). The resulting mixture was stirred and heated to reflux for 15 min. The reaction mixture was filtered through glass microfiber filter paper. The catalyst on filter paper was washed with hot methanol (200 mL). The filtrate was concentrated under reduced pressure to give a solid residue. The residue was purified by flash chromatography over silica gel (120 g) with anhydrous sodium sulfate (15 g) on top packed with hexane. The column was eluted with 100 mL portions of dichloromethane for fractions 1-4, 5% of (10% ammonia in methanol) in dichloromethane for fractions 6-9, and 10% of (10% ammonia in methanol) in dichloromethane for fractions 10-18. All fractions checked by TLC [10% of (10% ammonia in methanol) in dichloromethane]. The product was eluted in fractions 11-16 to give the title compound (6.1 g, 79%) as a light yellow solid. 1H NMR 60 MHz, (CDCl3), δ 8.8 (s, 1H), 8.2 (s, 1H), 4.0 (s, 2H), 3.8 (s, 3H), 3.0 (s, 4H), 1.7 (s, 1H).

後処理

  1. customIn a 2 L 3-necked flask equipped with a mechanical stirrer and condenser
  2. temperatureheated
  3. temperatureto reflux for 15 min
  4. filtrationThe reaction mixture was filtered through glass microfiber
  5. filtrationfilter paper
  6. filtrationThe catalyst on filter paper
  7. washwas washed with hot methanol (200 mL)
  8. concentrationThe filtrate was concentrated under reduced pressure
  9. customto give a solid residue
  10. customThe residue was purified by flash chromatography over silica gel (120 g) with anhydrous sodium sulfate (15 g) on top
  11. washThe column was eluted with 100 mL portions of dichloromethane for fractions 1-4, 5% of (10% ammonia in methanol) in dichloromethane for fractions 6-9, and 10% of (10% ammonia in methanol) in dichloromethane for fractions 10-18
  12. washThe product was eluted in fractions 11-16

出典と根拠

ORDレコード
ord-848843ff50774837bcba4ef1f8f3dc6c
出典データセット
uspto-grants-2014_11
特許番号
US08889870B2

反応ノート

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