Water → 4-Benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one

HRID 1687936Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1687936
[CH2:1]([N:8]1[CH2:17][C:16](=[O:18])[C:15]2[C:10](=[CH:11][C:12]([O:19][CH3:20])=[CH:13][CH:14]=2)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N-:21]=[N+]=[N-].[Na+].O.[OH-].[Na+]>CS(O)(=O)=O>[CH2:1]([N:8]1[CH2:9][C:10]2[CH:11]=[C:12]([O:19][CH3:20])[CH:13]=[CH:14][C:15]=2[NH:21][C:16](=[O:18])[CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

6

Edukt 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 33557Sodium AzideHCID 13760255N-benzyl-7-methoxy-1,2-dihydroisoquinolin-4(3H)-one

Produkt 1

HCID 578538974-Benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-oneAusbeute 73 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6395Methanesulfonic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

To a solution of 2-benzyl-7-methoxy-2,3-dihydro-1H-isoquinolin-4-one (7.0 g, 26.2 mmol) in methanesulfonic acid (50 mL) was added sodium azide (3.4 g, 52.4 mmol) portionwise with stirring (Caution: mild exotherm, gas evolution). The mixture was heated to 65° C. for two hours before being cooled to ambient temperature. Water (100 mL) was added, the mixture was cooled in an ice-water bath, and the pH was adjusted to 7-8 (10N NaOH). The gummy precipitate was extracted (DCM), the organic phase was washed with brine, dried over magnesium sulfate, filtered and concentrated. Further purification by flash chromatography over silica gel (DCM/MeOH) gave 4-benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one (5.4 g, 73%) as a tan solid; 1H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 7.33 (m, 5H), 6.97 (d, J=8 Hz, 1H), 6.87 (d, J=8 Hz, 1H), 6.82 (s, 1H), 3.73 (s, 3H), 3.67 (s, 4H), 3.09 (s, 2H); MS (m/e) 283 (M+1); mp 134° C.

Aufarbeitung

  1. temperaturebefore being cooled to ambient temperature
  2. temperaturethe mixture was cooled in an ice-water bath
  3. extractionThe gummy precipitate was extracted (DCM)
  4. washthe organic phase was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customFurther purification by flash chromatography over silica gel (DCM/MeOH)

Quellen und Nachweise

ORD-Eintrag
ord-08e62f45a1f94d408e64d4556da233e1
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148391B2

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