tert-butyl N-(4-aminobutyl)carbamate → {4-[(3-Methyl-pyridin-2-ylmethyl)-amino]-butyl}-carbamic acid tert-butyl ester

HRID 250934

反応式

HRID 250934 の反応式
[CH3:1][C:2]1[C:3]([CH:8]=O)=[N:4][CH:5]=[CH:6][CH:7]=1.[C:10]([O:14][C:15](=[O:22])[NH:16][CH2:17][CH2:18][CH2:19][CH2:20][NH2:21])([CH3:13])([CH3:12])[CH3:11].[BH4-].[Na+]>CO>[C:10]([O:14][C:15](=[O:22])[NH:16][CH2:17][CH2:18][CH2:19][CH2:20][NH:21][CH2:8][C:3]1[C:2]([CH3:1])=[CH:7][CH:6]=[CH:5][N:4]=1)([CH3:13])([CH3:11])[CH3:12]

参加物

5

反応物 3

HCID 4351tert-butyl N-(4-aminobutyl)carbamateHCID 15018743-Methylpyridine-2-carboxaldehydeHCID 4311764Sodium borohydride

生成物 1

HCID 58997087{4-[(3-Methyl-pyridin-2-ylmethyl)-amino]-butyl}-carbamic acid tert-butyl ester収率 87%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒2 回

実験手順

Using General Procedure B, 3-methyl-pyridine-2-carbaldehyde (2.87 g, 23.7 mmol) in dry MeOH (10 mL) was added to a solution (4-amino-butyl)-carbamic acid tert-butyl ester (4.47 g, 23.7 mmol) (Krapcho, A. et al. Synth. Commun. 1990, 20, 2559-2564) in dry MeOH (50 mL) and warmed to 50° C. under N2 for 17 h. The mixture was cooled to ambient temperature and NaBH4 (1.35 g, 35.7 mmol) was added, resulting in bubbling. The mixture was stirred for 90 min. under N2 when the bubbling subsided. A solution of saturated NaHCO3 (50 mL) and CH2Cl2 (150 mL) were added to the MeOH solution and the layers were separated. The aqueous layer was extracted with CH2Cl2 (3×100 mL), dried over Na2SO4 and concentrated in vacuo. Purification by column chromatography on silica gel (130 g) with CH2Cl2/MeOH (96:4) to CH2Cl2/MeOH/NH4OH (88:8:4) afforded the title compound (6.05 g, 87%) as an orange oil which solidified on standing. 1H NMR (CDCl3) δ 1.35-1.50 (m, 4H), 1.43 (s, 9H), 2.05 (bs, 1H), 2.30 (s, 3H), 2.72 (t, 2H, J=6.5 Hz), 3.00-3.20 (m, 2H), 3.86 (s, 2H), 4.76 (bs, 1H), 7.07 (dd, 1H, 7.5, 4.5 Hz), 7.42 (d, 1H, J=7.5 Hz), 8.38 (d, 1H, J=4.5 Hz); 13C NMR (CDCl3) δ 18.06, 27.45, 27.89, 28.43, 40.48, 49.54, 52.18, 78.89, 121.78, 130.84, 137.52, 146.41, 156.03, 157.25; ES-MS m/z 194 (M+H). Anal Calcd. For C16H27N3O2.0.2(H2O): C, 64.70; H, 9.30; N, 14.15. Found: C, 65.07; H, 9.35; N, 14.29.

後処理

  1. customresulting
  2. customin bubbling
  3. additionA solution of saturated NaHCO3 (50 mL) and CH2Cl2 (150 mL) were added to the MeOH solution
  4. customthe layers were separated
  5. extractionThe aqueous layer was extracted with CH2Cl2 (3×100 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated in vacuo
  8. customPurification by column chromatography on silica gel (130 g) with CH2Cl2/MeOH (96:4) to CH2Cl2/MeOH/NH4OH (88:8:4)

出典と根拠

ORDレコード
ord-96b84b36703c460a9f324d5cfaadeb9c
出典データセット
uspto-grants-2011_01
特許番号
US07863293B2

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