Formaldehyde → 1,1-Dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamate

HRID 1014389Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1014389
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([O:16][CH3:17])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:7]=1.[CH2:18]=O.C[O-].[Na+].[BH4-].[Na+]>CO.C(OCC)(=O)C.C(=O)(O)[O-].[Na+]>[CH3:18][NH:1][C:2]1[CH:3]=[CH:4][C:5]([O:16][CH3:17])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:13])[CH3:14])[CH:7]=1

Komponenten

8

Edukt 4

HCID 712FormaldehydeHCID 4311764Sodium borohydrideHCID 10942334Sodium MethoxideHCID 22344747tert-butyl N-(5-amino-2-methoxyphenyl)carbamate

Produkt 1

HCID 594418351,1-Dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamateAusbeute 104,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 516892Sodium BicarbonateLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A suspension of 1,1-dimethylethyl [5-amino-2-(methyloxy)phenyl]carbamate (1.94 g, 8.14 mmol), paraformaldehyde (1.222 g, 40.7 mmol), and sodium methoxide (2.199 g, 40.7 mmol) in methanol (50 ml) was maintained at 50° C. for 16 hours, cooled, sodium borohydride (0.924 g, 24.42 mmol) was added portionwise, and the solution was re-heated to 50° C. and maintained for an additional 24 hours. The solution was cooled, diluted with ethyl acetate, saturated sodium bicarbonate, and the organic layer was dried over sodium sulfated, filtered, taken to a residue under reduced pressure, and purified by column chromatography to afford 1,1-dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamate (2.15 g, 8.52 mmol, quant. Yield) as a pale yellow oil. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.58 (s, 1 H), 7.10 (d, J=1.6 Hz, 1 H), 6.76 (d, J=8.8 Hz, 1 H), 6.14 (dd, J=8.7, 2.7 Hz, 1H), 5.07-5.31 (m, 1 H), 3.61-3.74 (m, 3 H), 2.60 (d, J=4.4 Hz, 3 H), 1.44 (s, 9 H).

Aufarbeitung

  1. temperaturecooled
  2. temperaturethe solution was re-heated to 50° C.
  3. temperaturemaintained for an additional 24 hours
  4. temperatureThe solution was cooled
  5. dry with materialthe organic layer was dried over sodium
  6. filtrationfiltered
  7. custompurified by column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-86ff43889252450e9139978a77ad0a01
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07981903B2

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