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Methanol → Methyl 2-((2-chloro-4-(dimethylcarbamoyl)phenyl)(methyl)-carbamoyl)-4,5-dihydrobenzo[b] thieno[2,3-d]oxepine-8-carboxylate

HRID 627938
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 627938
Br[C:2]1[CH:3]=[CH:4][C:5]2[C:11]3[S:12][C:13]([C:15]([N:17]([C:19]4[CH:24]=[CH:23][C:22]([C:25](=[O:29])[N:26]([CH3:28])[CH3:27])=[CH:21][C:20]=4[Cl:30])[CH3:18])=[O:16])=[CH:14][C:10]=3[CH2:9][CH2:8][O:7][C:6]=2[CH:31]=1.[CH3:32][OH:33].CN([CH:37]=[O:38])C>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:30][C:20]1[CH:21]=[C:22]([C:25](=[O:29])[N:26]([CH3:28])[CH3:27])[CH:23]=[CH:24][C:19]=1[N:17]([CH3:18])[C:15]([C:13]1[S:12][C:11]2[C:5]3[CH:4]=[CH:3][C:2]([C:32]([O:38][CH3:37])=[O:33])=[CH:31][C:6]=3[O:7][CH2:8][CH2:9][C:10]=2[CH:14]=1)=[O:16]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 887MethanolHCID 6228DimethylformamideHCID 568341588-bromo-N-(2-chloro-4-(dimethylcarbamoyl)phenyl)-N-methyl-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxamide

Produkt 1

HCID 56834268Methyl 2-((2-chloro-4-(dimethylcarbamoyl)phenyl)(methyl)-carbamoyl)-4,5-dihydrobenzo[b] thieno[2,3-d]oxepine-8-carboxylateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845
palladium(II) acetate
Katalysator
HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Katalysator

Versuchsvorschrift

The mixture of 8-bromo-N-(2-chloro-4-(dimethylcarbamoyl)phenyl)-N-methyl-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxamide (27.0 g, 51.9 mmol), dppf (23.20 g, 41.9 mmol), Pd(OAc)2 (5.8 g, 25.8 mmol), TEA (27 mL), in DMF (270 mL) and MeOH (400 mL) was stirred under CO (50 psi) atmosphere at 70° C. for 2 days. The reaction mixture was filtrated and the filtrate was concentrated. The crude product was purified by silica gel chromatography eluted with Hexanes: EtOAc=1:1 to give methyl 2-((2-chloro-4-(dimethylcarbamoyl)phenyl)(methyl)-carbamoyl)-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-8-carboxylate (23.00 g, 89%). ESI-MS: 499.1. 1H NMR (DMSO-d6, 400 MHz): δ7.74-7.69 (m, 2H, ArH), 7.58-7.47 (m, 4H, ArH), 6.79 (s, 1H, ═CH), 4.23 (t, J=4.8 Hz, 2H, CH2), 3.83 (s, 3H, CH3), 3.31 (s, 3H, CH3), 3.01 (br, 5H, CH2, CH3), 2.94 (s, 3H, CH3).

Aufarbeitung

  1. filtrationThe reaction mixture was filtrated
  2. concentrationthe filtrate was concentrated
  3. customThe crude product was purified by silica gel chromatography
  4. washeluted with Hexanes

Quellen und Nachweise

ORD-Eintrag
ord-c471105527f2483d9ad82b05fdd8170b
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09309265B2

Notizen zur Reaktion

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