Formaldehyde → HCID 11740318, Verbindung

HRID 1270460Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1270460
[NH2:1][C:2]1[CH:24]=[CH:23][C:5]([O:6][C@H:7]2[CH2:12][CH2:11][CH2:10][N:9]([CH2:13][C:14]3[CH:22]=[CH:21][C:17]4[O:18][CH2:19][O:20][C:16]=4[CH:15]=3)[CH2:8]2)=[CH:4][CH:3]=1.[NH4+:25].[OH-].[CH2:27]=O.[CH:29]([CH:31]=O)=O>CO.C1COCC1.O>[N:1]1([C:2]2[CH:3]=[CH:4][C:5]([O:6][C@H:7]3[CH2:12][CH2:11][CH2:10][N:9]([CH2:13][C:14]4[CH:22]=[CH:21][C:17]5[O:18][CH2:19][O:20][C:16]=5[CH:15]=4)[CH2:8]3)=[CH:23][CH:24]=2)[CH:31]=[CH:29][N:25]=[CH:27]1

Komponenten

8

Edukt 4

HCID 712FormaldehydeHCID 7860GlyoxalHCID 14923Ammonium HydroxideHCID 69352678HCID 69352678, Verbindung

Produkt 1

HCID 11740318HCID 11740318, VerbindungAusbeute 72,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittel2×HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

Solution A was prepared by adding (3S)-3-(4-aminophenoxy)-1-[(1,3-benzodioxol-5-yl)methyl]piperidine (4.4 g, 13.5 mmol) and NH4OH (1.2 mL, 15 mmol) in methanol, and diluting with methanol to 10 mL. Solution B was prepared by adding formaldehyde (1.01 mL, 13.5 mmol) and 40% solution glyoxal, and then diluting with THF to 10 mL. Solution A and solution B were added simultaneously to water (6.0 mL, pre-heated to 65° C.) with stirring over a 30 min period. The resulting mixture was then heated to 65° C. for 2 hours. After removal of the solvent in vacuo, the residual oil was dissolved in CH2Cl2 (100 mL), washed with water (50 mL×3), brine (50 mL), and dried (NaSO4). Purification by column chromatography (ethyl acetate/methanol 100:1) afforded (3S)-3-[4-(imidazol-1-yl)phenoxy]-1-[(1,3-benzodioxol-5-yl)methyl]piperidine (3.7 g, 72.5% yield), NMR: (DMSO-d6) 9.1 (s, 1), 7.90 (t, 1), 7.65–7.62 (m, 2), 7.56 t, 1), 7.32 (d, 1), 7.24–7.21 (m, 2), 7.10 (d, 1), 6.98 (d, 1), 5.98 (d, 2), 5.00 (m, 1), 4.28 (d, 1), 4.18 (d, 1), 3.40 (d, 1), 3.12 (m, 1), 3.09–2.98 (m, 2), 2.05–1.88 (m, 3), 1.72 (m, 1) ppm.

Aufarbeitung

  1. customSolution A was prepared
  2. customAfter removal of the solvent in vacuo
  3. dissolutionthe residual oil was dissolved in CH2Cl2 (100 mL)
  4. washwashed with water (50 mL×3), brine (50 mL)
  5. dry with materialdried (NaSO4)
  6. customPurification by column chromatography (ethyl acetate/methanol 100:1)

Quellen und Nachweise

ORD-Eintrag
ord-71819b0840cd44f18e7609b763193e25
Quelldatensatz
uspto-grants-2007_04
Patentnummer
US07202263B2

Notizen zur Reaktion

Wird geladen…