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

HRID 479784

Reaktionsgleichung

Reaktionsgleichung von HRID 479784
[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]

Komponenten

6

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 9005Trimethyl orthoformateLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-5d6f55b461e94c8682b8177bdfe3dd03
Quelldatensatz
uspto-grants-2003_11
Patentnummer
US06645980B1

Verknüpfte Notizen

Wird geladen…