p-Toluenesulfonic acid → Ethyl 1-((6-hydroxynaphthalen-2-yl)methyl)piperidine-4-carboxylate

HRID 525428

Reaktionsgleichung

Reaktionsgleichung von HRID 525428
[OH:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([CH:12]=O)[CH:6]=[CH:5]2.[NH:14]1[CH2:19][CH2:18][CH:17]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:16][CH2:15]1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].CC1C=CC(S(O)(=O)=O)=CC=1>>[OH:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([CH2:12][N:14]1[CH2:19][CH2:18][CH:17]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:16][CH2:15]1)[CH:6]=[CH:5]2

Komponenten

5

Edukt 4

HCID 6101p-Toluenesulfonic acidHCID 70770Ethyl 4-piperidinecarboxylateHCID 27641106-Hydroxy-2-naphthaldehydeHCID 5049666Sodium triacetoxyborohydride

Produkt 1

HCID 68279222Ethyl 1-((6-hydroxynaphthalen-2-yl)methyl)piperidine-4-carboxylateAusbeute 45,6 %

Versuchsvorschrift

A mixture of 4 Å molecular sieves, 6-hydroxy-2-naphthaldehyde (1.0 g, 5.81 mmol), ethyl piperidine-4-carboxylate (0.91 g, 5.81 mmol), NaBH(OAc)3 (3.76 g, 17.43 mmol) and TsOH (0.1 g, 0.581 mmol) was stirred at rt for 2 h and then quenched with water (5 mL). The mixture was extracted with DCM (20 mL*2). The combined organics were washed with saturated brine (20 mL*3) and then concentrated. The white precipitates were filtered and dissolved in water (10 mL) and EtOAc (10 mL), NaHCO3 was added to adjust pH=8-9. The mixture was extracted with EtOAc (20 mL*2). The combined organics were washed with saturated brine (20 ml*2), dried over Na2SO4, concentrated and recystallized with EtOAc to give ethyl 1-((6-hydroxynaphthalen-2-yl)methyl)piperidine-4-carboxylate as a white solid (0.83 g, yield: 41%), ESI-MS: 314.1 (M+H)+. 1H NMR (400 MHz, DMSO-d6) δ: 9.65 (s, 1H), 7.71 (d, J=8.8 Hz, 1H), 7.61-7.63 (m, 2H), 7.32-7.35 (m, 1H), 7.03-7.08 (m, 2H), 4.02-4.03 (q, J=7.2 Hz, 2H), 3.52 (s, 2H), 2.72-2.75 (m, 2H), 2.25-2.32 (m, 2H), 1.98-2.03 (m, 1H), 1.77-1.79 (m, 2H), 1.51-1.61 (m, 2H), 1.17 (t, J=7.2 Hz, 3H).

Aufarbeitung

  1. customquenched with water (5 mL)
  2. extractionThe mixture was extracted with DCM (20 mL*2)
  3. washThe combined organics were washed with saturated brine (20 mL*3)
  4. concentrationconcentrated
  5. customThe white precipitates
  6. filtrationwere filtered
  7. dissolutiondissolved in water (10 mL)
  8. additionEtOAc (10 mL), NaHCO3 was added
  9. extractionThe mixture was extracted with EtOAc (20 mL*2)
  10. washThe combined organics were washed with saturated brine (20 ml*2)
  11. dry with materialdried over Na2SO4
  12. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-e5485f2607c2412e8a3f8e69ae21c4f5
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09340527B2

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