tert-Butyl acetate → benzyl 3-(1-(tert-butoxy)-2-methoxy-2-oxoethyl)-2-methyl-4-(p-tolyl)-7,8-dihydro-1,6-naphthyridine-6(5H)-carboxylate

HRID 470928

反応式

HRID 470928 の反応式
[OH:1][CH:2]([C:7]1[C:8]([CH3:34])=[N:9][C:10]2[CH2:11][CH2:12][N:13]([C:24]([O:26][CH2:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)=[O:25])[CH2:14][C:15]=2[C:16]=1[C:17]1[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=1)[C:3]([O:5][CH3:6])=[O:4].C(O[C:39]([CH3:42])([CH3:41])[CH3:40])(=O)C>C(Cl)Cl>[C:39]([O:1][CH:2]([C:7]1[C:8]([CH3:34])=[N:9][C:10]2[CH2:11][CH2:12][N:13]([C:24]([O:26][CH2:27][C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)=[O:25])[CH2:14][C:15]=2[C:16]=1[C:17]1[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=1)[C:3]([O:5][CH3:6])=[O:4])([CH3:42])([CH3:41])[CH3:40]

参加物

4

反応物 2

HCID 10908tert-Butyl acetateHCID 86692201benzyl 3-(1-hydroxy-2-methoxy-2-oxoethyl)-2-methyl-4-(p-tolyl)-7,8-dihydro-1,6-naphthyridine-6(5H)-carboxylate2 回

生成物 1

HCID 86692202benzyl 3-(1-(tert-butoxy)-2-methoxy-2-oxoethyl)-2-methyl-4-(p-tolyl)-7,8-dihydro-1,6-naphthyridine-6(5H)-carboxylate収率 73.5%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of benzyl 3-(1-hydroxy-2-methoxy-2-oxoethyl)-2-methyl-4-(p-tolyl)-7,8-dihydro-1,6-naphthyridine-6(5H)-carboxylate (intermediate 11) (0.10 g, 0.217 mmol) in CH2Cl2 (3 ml) was added tert-butyl acetate (2.05 ml, 15.2 mmol) followed by HClO4 (0.056 ml, 0.651 mmol). The flask was sealed and stirred at room temperature for 2.5 h. The reaction was quenched with sat'd aq NaHCO3 (gas evolution). The organic phase was dried (Na2SO4), filtered and concentrated. The residue was purified by flash column chromatography (Biotage; 0%-30% EtOAc/hexanes). The product-containing fractions were combined and concentrated to give benzyl 3-(1-(tert-butoxy)-2-methoxy-2-oxoethyl)-2-methyl-4-(p-tolyl)-7,8-dihydro-1,6-naphthyridine-6(5H)-carboxylate (82.4 mg, 72% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ ppm 7.01-7.78 (m, 9H), 5.13 (s, 2H), 4.97 (s, 1H), 4.29-4.32 (m, 1H), 4.05-4.10 (m, 1H), 3.78-3.81 (m, 2H), 3.71 (s, 3H), 3.06 (bs, 2H), 2.64 (s, 3H), 2.45 (s, 3H) 0.99 (s, 9H). LCMS (M+H) calcd for C31H37N2O5: 517.27. found: 517.4.

後処理

  1. customThe flask was sealed
  2. customThe reaction was quenched with sat'd aq NaHCO3 (gas evolution)
  3. dry with materialThe organic phase was dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography (Biotage; 0%-30% EtOAc/hexanes)
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-e1e2dac7a9684574be810775688814bb
出典データセット
uspto-grants-2014_01
特許番号
US08629276B2

関連ノート

読み込み中…