Hydrochloric Acid → Methyl 3-azido-2,6-bis(4-methoxyphenyl)isonicotinate

HRID 2410679Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2410679
[NH2:1][C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=2)=[N:10][C:9]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].Cl.N([O-])=O.[Na+].[N-:33]=[N+:34]=[N-].[Na+]>C(O)C>[N:1]([C:2]1[C:11]([C:12]2[CH:13]=[CH:14][C:15]([O:18][CH3:19])=[CH:16][CH:17]=2)=[N:10][C:9]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])=[N+:33]=[N-:34]

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 66604440Methyl 3-amino-2,6-bis(4-methoxyphenyl)isonicotinate

Produkt 1

HCID 86663006Methyl 3-azido-2,6-bis(4-methoxyphenyl)isonicotinateAusbeute 42 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

Methyl 3-amino-2,6-bis(4-methoxyphenyl)isonicotinate (234 mg, 0.642 mmol) was dissolved with heating in ethanol (8 mL). After cooling to room temperature, 17% aqueous HCl (4 mL) was added and the reaction was cooled in an ice bath. Sodium nitrite (70.9 mg, 1.027 mmol) was added and the solution turned orange-red. After 25 min, sodium azide (66.8 mg, 1.027 mmol) was added and, after a further 20 min, the reaction was removed from the bath and left stirring at room temperature for 1 hr. The reaction was partitioned between ethyl acetate and sufficient saturated aqueous sodium bicarbonate solution to neutralize the acid. The organic phase was separated, washed with brine, and dried with sodium sulfate. Radial silica gel chromatography (step gradient elution with hexane containing 5 to 20% ethyl acetate) afforded methyl 3-azido-2,6-bis(4-methoxyphenyl)isonicotinate (105 mg, 42% yield) as a yellow solid. MS (ESI) m/z 391.1 (M+H). 1H NMR (CDCl3) δ ppm 8.03 (2H, d, J=8.85 Hz), 7.93 (1H, s), 7.83 (2H, d, J=8.85 Hz), 7.02 (2H, d, J=8.85 Hz), 6.98 (2H, d, J=9.16 Hz), 4.03 (3H, s), 3.88 (3H, s), 3.86 (3H, s).

Aufarbeitung

  1. temperaturethe reaction was cooled in an ice bath
  2. customthe reaction was removed from the bath
  3. waitleft
  4. customThe reaction was partitioned between ethyl acetate and sufficient saturated aqueous sodium bicarbonate solution
  5. customThe organic phase was separated
  6. washwashed with brine
  7. dry with materialdried with sodium sulfate
  8. washRadial silica gel chromatography (step gradient elution with hexane containing 5 to 20% ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-c805f52558ea4804a97da46e770068a8
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08815840B2

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