Acetic Acid → N-{[7-(Methylsulfonyl)-4H-1,3-benzodioxin-2-YL]methyl}propan-1-amine

HRID 452395ノート

反応式

HRID 452395 の反応式
[CH2:1]([N:8]([CH2:12][CH:13]1[O:18][C:17]2[CH:19]=[C:20]([S:23]([CH3:26])(=[O:25])=[O:24])[CH:21]=[CH:22][C:16]=2[CH2:15][O:14]1)CCC)[C:2]1C=CC=C[CH:3]=1.CC(O)=O>[Pd].CCO>[CH3:26][S:23]([C:20]1[CH:21]=[CH:22][C:16]2[CH2:15][O:14][CH:13]([CH2:12][NH:8][CH2:1][CH2:2][CH3:3])[O:18][C:17]=2[CH:19]=1)(=[O:24])=[O:25]

参加物

5

反応物 2

HCID 176Acetic AcidHCID 67155851(+)-N-benzyl-N-{[7-(methylsulfonyl)-4H-1,3-benzodioxin-2-yl]methyl}propan-1-amine

生成物 1

HCID 44481357N-{[7-(Methylsulfonyl)-4H-1,3-benzodioxin-2-YL]methyl}propan-1-amine収率 71%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 702Ethanol溶媒

実験手順

(−)-N-benzyl-N-{[7-(methylsulfonyl)-4H-1,3-benzodioxin-2-yl]methyl}propan-1-amine (0.25 g, 0.67 mmol), palladium on carbon (10%, 30 mg), concentrated AcOH (0.1 ml) and EtOH (15 ml) was hydrogenated at 40 psi for 1 h. The reaction mixture was filtered through a pad of celite and the filtrate was evaporated to dryness. The crude product was dissolved in EtOAc (100 ml) and basified with Na2CO3 (10%, 50 ml). The layers were separated and the aqueous layer was extracted with EtOAc (2×75 ml). The combined organic layers were collected, dried (Na2SO4), filtered and evaporated to dryness (0.32 g). Purification by flash chromatography (EtOAc/MeOH 10:1) afforded the pure title compound (0.13 g, 71%, >95% e.e.). The amine was converted into the hydrochloric acid salt and crystallized from EtOH/MeOH/DEE. M.p. 235° C. [α]DMeOH=−80°. 1H-NMR (400 MHz, MeOH): δ 7.49 (1H, dd, J1 8.0 Hz J2 2.0 Hz), δ 7.41 (1H, d, 2.0 Hz), δ 7.30 (1H, d, J 8 Hz), δ 5.25 (1H, t, J 5.2 Hz), δ 5.02 (2H, dd, J1 50 Hz, J2 16 Hz), δ 3.1 (3H, s), δ 2.97 (2H, m), δ 2.65 (2H, t, J 7.2 Hz), δ 1.56 (2H, m), δ 0.95 (3H, t, J 7.6 Hz).

後処理

  1. filtrationThe reaction mixture was filtered through a pad of celite
  2. customthe filtrate was evaporated to dryness
  3. dissolutionThe crude product was dissolved in EtOAc (100 ml)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc (2×75 ml)
  6. customThe combined organic layers were collected
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customevaporated to dryness (0.32 g)
  10. customPurification by flash chromatography (EtOAc/MeOH 10:1)

出典と根拠

ORDレコード
ord-28c4a9eb38f54b558a96d0e756e289be
出典データセット
uspto-grants-2013_07
特許番号
US08492372B2

反応ノート

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