Ammonium Hydroxide → benzyl N-(2-methyl-5,6-dihydro-4H-imidazo[1,2-a][1]benzazepin-4-yl)carbamate

HRID 2068541Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2068541
[CH2:1]([N:5]1[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[CH2:9][CH2:8][C@@H:7]([NH:16][C:17](=[O:26])[O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:6]1=O)[C:2]([CH3:4])=O.C([O-])(=O)C.[NH4+:32].[OH-].[NH4+]>C(O)(=O)C>[NH3:5].[CH3:4][C:2]1[N:32]=[C:6]2[CH:7]([NH:16][C:17](=[O:26])[O:18][CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH2:8][CH2:9][C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[N:5]2[CH:1]=1

Komponenten

6

Edukt 3

HCID 14923Ammonium HydroxideHCID 517165Ammonium AcetateHCID 58304091Benzyl N-[(3R)-1-acetonyl-2-oxo-4,5-dihydro-3H-1-benzazepin-3-yl]carbamate

Produkt 2

HCID 222AmmoniaAusbeute 10 %HCID 58304090benzyl N-(2-methyl-5,6-dihydro-4H-imidazo[1,2-a][1]benzazepin-4-yl)carbamateAusbeute 63,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

Combine benzyl N-[(3R)-1-acetonyl-2-oxo-4,5-dihydro-3H-1-benzazepin-3-yl]carbamate (0.7 g, 1.91 mmol) with ammonium acetate (2.94 g, 38.2 mmol) in acetic acid (20.0 mL) and heat at 115° C. for 24 hours, and then stir the mixture at ambient temperature for approximately 16 hours. Pour the reaction mixture into ice-water, basify it with ammonium hydroxide (28-30%), and extract with dichloromethane. Wash with water and brine, dry over sodium sulfate, and concentrate the organic layer under reduced pressure. Purify the residue by flash chromatography (10% ethyl acetate/hexane to 50% ethyl acetate/hexane), then an SCX column (methanol, then 10% 2N ammonia in methanol/CH2Cl2) to give the title compound (0.21 g, 32%) as a white solid: MS (m/z): 348 (M+1). (Based on the final compounds made from this intermediate, the title compound is partially racemized.)

Aufarbeitung

  1. extractionextract with dichloromethane
  2. washWash with water and brine
  3. dry with materialdry over sodium sulfate
  4. concentrationconcentrate the organic layer under reduced pressure
  5. customPurify the residue by flash chromatography (10% ethyl acetate/hexane to 50% ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-b7240dbb2a704e9a878529f6f707fa05
Quelldatensatz
uspto-grants-2012_10
Patentnummer
US08299061B2

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