Ammonium Chloride → (4-Aminomethyl-3-methyl-phenyl)-(3,6-dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulen-9-yl)-methanone

HRID 220958

Reaktionsgleichung

Reaktionsgleichung von HRID 220958
[CH3:1][N:2]1[C:11]2[NH:10][C:9]3[CH:12]=[C:13]([CH3:16])[CH:14]=[CH:15][C:8]=3[N:7]([C:17]([C:19]3[CH:26]=[CH:25][C:22]([C:23]#[N:24])=[C:21]([CH3:27])[CH:20]=3)=[O:18])[CH2:6][C:5]=2[CH:4]=[N:3]1.CC1C=C2N=C3C(=NC(NC3=O)=O)N(C[C@H](O)[C@H](O)[C@H](O)CO)C2=CC=1C.N1CCCC(=O)C2C=CC=CC1=2.[BH4-].[Na+].[NH4+].[Cl-]>CO.O.O.O.O.O.O.[Co](Cl)Cl>[NH2:24][CH2:23][C:22]1[CH:25]=[CH:26][C:19]([C:17]([N:7]2[CH2:6][C:5]3[CH:4]=[N:3][N:2]([CH3:1])[C:11]=3[NH:10][C:9]3[CH:12]=[C:13]([CH3:16])[CH:14]=[CH:15][C:8]2=3)=[O:18])=[CH:20][C:21]=1[CH3:27]

Komponenten

8

Edukt 5

HCID 25517Ammonium ChlorideHCID 2947881,2,3,4-Tetrahydro-benzo(b)azepin-5-oneHCID 493570RiboflavinHCID 4311764Sodium borohydrideHCID 1357360404-(3,6-Dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-2-methyl-benzonitrile

Produkt 1

HCID 135736053(4-Aminomethyl-3-methyl-phenyl)-(3,6-dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulen-9-yl)-methanoneAusbeute 35 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 517166Dichlorocobalt hexahydrateKatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

A solution of 4-(3,6-dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-2-methyl-benzonitrile from Example E101.1 (1.42 g, 4.0 mmol) in methanol (50 ml) at 0° C. was treated with cobalt(II) chloride hexahydrate (1.90 g, 8.0 mmol). The mixture was stirred for 15 min at room temperature then sodium borohydride (1.51 g, 40.0 mmol) was added portionwise. The reaction mixture was stirred for 2 h then saturated NH4Cl was added. The mixture was stirred for 30 min then the solid was filtered off through Celite® filter agent and the filtrate concentrated in vacuo. The residue was re-dissolved in EtOAc and saturated NaHCO3. The layers were partitioned and the aqueous layer was extracted further with chloroform. Organics were combined, dried and concentrated in vacuo. The residue was purified by flash chromatography on silica gel through an isolute (eluant; 1% 35% ammonia:9% methanol:90% dichloro-methane) to yield the title compound (511 mg, 35%).

Aufarbeitung

  1. stirringThe reaction mixture was stirred for 2 h
  2. stirringThe mixture was stirred for 30 min
  3. filtrationthe solid was filtered off through Celite®
  4. filtrationfilter agent
  5. concentrationthe filtrate concentrated in vacuo
  6. dissolutionThe residue was re-dissolved in EtOAc
  7. customThe layers were partitioned
  8. extractionthe aqueous layer was extracted further with chloroform
  9. customdried
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by flash chromatography on silica gel through an isolute (eluant; 1% 35% ammonia:9% methanol:90% dichloro-methane)

Quellen und Nachweise

ORD-Eintrag
ord-a43f03a49b7c473382257548c67b4054
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08202858B2

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