Pivalic acid → 4-Methoxycarbonylmethyl-4-(3'-methoxyphenyl)-1-methyl-3-methylene-2-piperidone

HRID 67798

Reaktionsgleichung

Reaktionsgleichung von HRID 67798
O[CH2:2][C:3]1[C:4](=[O:18])[N:5]([CH3:17])[CH2:6][CH2:7][C:8]=1[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH3:16])[CH:10]=1.[C:19](OC)([O:23]C)([O:21][CH3:22])[CH3:20].C(O)(=O)C(C)(C)C>COCCOCCOC>[CH3:22][O:21][C:19]([CH2:20][C:8]1([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH3:16])[CH:10]=2)[CH2:7][CH2:6][N:5]([CH3:17])[C:4](=[O:18])[C:3]1=[CH2:2])=[O:23]

Komponenten

5

Edukt 3

HCID 6417Pivalic acidHCID 15050Trimethyl orthoacetateHCID 131079803-Hydroxymethyl-4-(3'-methoxyphenyl)-1-methyl-5,6-dihydro-2-pyridone

Produkt 1

HCID 129475534-Methoxycarbonylmethyl-4-(3'-methoxyphenyl)-1-methyl-3-methylene-2-piperidone

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8150DiglymeLösungsmittel

Versuchsvorschrift

The allylic alcohol 27 of Example 9 (1.22 g, 4.96 mmol), trimethyl orthoacetate (5.52 g, 46 mmol), and pivalic acid (25 mg, 0.50 mmol) were placed in diglyme (25 mL) and refluxed at 155°-160° C. (internal) with fractionation to remove CH3OH. after 18 h the solvents were evaporated and the residue distilled [bp 175°-185° C. (0.15 mm)] to return 1.21 g (80%) of methyl ester 28. Upon standing the ester crystallized: mp 85°-86° C.; NMR δ7.30 (m, 1H), 6.86 (m, 4H), 6.65 (s, 1H), 5.57 (s, 1H), 3.76 (s, 3H), 3.47 (s 3H), 3.17 (m, 3H), 2.87 (s, 4H), 2.53 (m, 2H); IR 1733, 1653, 1595 cm-1 ; mass spectrum m/e (rel intensity) 303 (38), 230 (100). Anal. Calcd for C17H21NO4 : C, 67.3; H, 7.0; N, 4.6. Found: C, 67.2; H, 7.0; N, 4.6.

Aufarbeitung

  1. temperaturerefluxed at 155°-160° C. (internal) with fractionation
  2. customto remove CH3OH
  3. customafter 18 h the solvents were evaporated
  4. distillationthe residue distilled [bp 175°-185° C. (0.15 mm)]
  5. customcrystallized

Quellen und Nachweise

ORD-Eintrag
ord-1c22feec8e68477d9dec17d225a43063
Quelldatensatz
uspto-grants-1982_08
Patentnummer
US04346224

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