Acetic Acid → (3R,4R)-4-(4-Bromo-2-nitro-phenylamino)-1-methyl-piperidin-3-ol

HRID 1670632ノート

反応式

HRID 1670632 の反応式
C=O.Cl.[Br:4][C:5]1[CH:10]=[CH:9][C:8]([NH:11][C@@H:12]2[CH2:17][CH2:16][NH:15][CH2:14][C@H:13]2[OH:18])=[C:7]([N+:19]([O-:21])=[O:20])[CH:6]=1.[C:22](O)(=O)C.C([BH3-])#N.[Na+]>O>[Br:4][C:5]1[CH:10]=[CH:9][C:8]([NH:11][C@@H:12]2[CH2:17][CH2:16][N:15]([CH3:22])[CH2:14][C@H:13]2[OH:18])=[C:7]([N+:19]([O-:21])=[O:20])[CH:6]=1

参加物

6

反応物 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 67334527HCID 67334527、化合物

生成物 1

HCID 67334708(3R,4R)-4-(4-Bromo-2-nitro-phenylamino)-1-methyl-piperidin-3-ol収率 97%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

Add formaldehyde (20.5 mL, 37-41% aqueous solution) to a solution of (3R,4R)-4-(4-bromo-2-nitro-phenylamino)-piperidin-3-ol.hydrochloride salt (0.0.024 mol, 8.68 g) and acetic acid (10.2 mL) in water (42 mL) and stir the reaction mixture at room temperature for 30 min. Add sodium cyanoborohydride (0.073 mol, 4.6 g) and stir the reaction mixture for 3 h. Quench the reaction mixture with sodium bicarbonate solution and extract with dichloromethane. Dry the organic layer over anhydrous sodium sulfate, filter, and concentrate to obtain the title compound (7.8 g, 97%). 1H NMR (400 MHz, CDCl3) δ 1.63-1.71 (m, 1H), 2.16-2.21 (m, 2H), 2.33 (s, 3H), 2.35-2.38 (m, 1H), 2.60 (br s, 1H), 2.80 (d, 1H), 3.54-3.56 (m, 1H), 3.75-3.79 (m, 1H), 6.92 (d, 1H), 7.48 (dd, 1H), 8.14 (d, 1H), 8.30 (d, 1H).

後処理

  1. customQuench the reaction mixture with sodium bicarbonate solution
  2. extractionextract with dichloromethane
  3. dry with materialDry the organic layer over anhydrous sodium sulfate
  4. filtrationfilter
  5. concentrationconcentrate

出典と根拠

ORDレコード
ord-6eb42c0856d049e1bdb7fea96cfa16ea
出典データセット
uspto-grants-2011_08
特許番号
US07994164B2

反応ノート

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