Aniline → N-(1-Boc-piperidin-3-ylmethyl)aniline

HRID 479784ノート

反応式

HRID 479784 の反応式
[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([CH:14]=O)[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[BH3-]C#N.[Na+]>CO.COC(OC)OC>[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([CH2:14][NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

参加物

6

反応物 3

HCID 6115AnilineHCID 5003444Sodium cyanoborohydrideHCID 99644481-Boc-piperidine-3-carboxaldehyde

生成物 1

HCID 12972131N-(1-Boc-piperidin-3-ylmethyl)aniline収率 79%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 9005Trimethyl orthoformate溶媒

実験手順

To a solution of N-Boc-piperidin-3-yl-formaldehyde 3 (5.20 g, 24.4 mmol) in 50 mL of dry methanol and 50 mL of trimethylorthoformate was added aniline (2.50 g, 1.1 eq.), and the mixture was stirred at room temperature for 30 minutes. NaBH3CN (95%, 1.84 g, 1.1 eq.) was introduced in one portion, and the mixture was stirred at room temperature overnight. The mixture was quenched with 30 mL of aqueous potassium carbonate (sat.), then extracted with ethyl acetate (3×100 mL). The extracts were combined and washed with aqueous NaHCO3 (sat., 2×50 mL), brine (50 mL), and dried over anhydrous sodium sulfate. After the solvent was removed, the remaining oily residue was purified by a flash column chromatography (silica gel, hexane:ethyl acetate (1:1) to afford N-(1-Boc-piperidin-3-ylmethyl)-aniline 4 as white solid (5.60 g, 79%). IR (film, cm−1) 3520, 3263, 3004, 2976, 2932, 2854, 1688, 1589, 1521, 1482, 1422, 1365, 1267, 1243, 1175, 1150, 794, 709; 1H NMR (CDCl3, ppm) 7.20 (t, 2H, J=7.8 Hz), 6.72 (t, 1H, J=6.8 Hz), 6.63 (d, 2H, J=8.3 Hz), 4.00-3.78 (m, 3H), 3.07-2.70 (m, 4H), 2.00-1.20 (m, 5H), 1.48 (s, overlap, 9H).

後処理

  1. stirringthe mixture was stirred at room temperature overnight
  2. customThe mixture was quenched with 30 mL of aqueous potassium carbonate (sat.)
  3. extractionextracted with ethyl acetate (3×100 mL)
  4. washwashed with aqueous NaHCO3 (sat., 2×50 mL), brine (50 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. customAfter the solvent was removed
  7. customthe remaining oily residue was purified by a flash column chromatography (silica gel, hexane:ethyl acetate (1:1)

出典と根拠

ORDレコード
ord-5d6f55b461e94c8682b8177bdfe3dd03
出典データセット
uspto-grants-2003_11
特許番号
US06645980B1

反応ノート

読み込み中…