Trifluoroacetic anhydride → 2,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone

HRID 1040739Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1040739
[CH3:1][O:2][C:3]1[CH:13]=[CH:12][C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1.[F:14][C:15]([F:26])([F:25])[C:16](O[C:19](=[O:24])[C:20]([F:23])([F:22])[F:21])=[O:17].[N+:27]([O-:30])([O-:29])=[O:28].[K+]>C(#N)C>[F:14][C:15]([F:26])([F:25])[C:16]([N:9]1[CH2:10][CH2:11][C:5]2[CH:4]=[C:3]([O:2][CH3:1])[C:13]([N+:27]([O-:29])=[O:28])=[CH:12][C:6]=2[CH2:7][CH2:8]1)=[O:17].[F:23][C:20]([F:21])([F:22])[C:19]([N:9]1[CH2:10][CH2:11][C:5]2[C:4]([N+:27]([O-:30])=[O:28])=[C:3]([O:2][CH3:1])[CH:13]=[CH:12][C:6]=2[CH2:7][CH2:8]1)=[O:24]

Komponenten

6

Edukt 3

HCID 9845Trifluoroacetic anhydrideHCID 24434Potassium NitrateHCID 138533487-Methoxy-2,3,4,5-tetrahydro-1h-3-benzazepine

Produkt 2

HCID 866338662,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanoneAusbeute 38 %HCID 866338672,2,2-Trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanoneAusbeute 25 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

Into a 1-neck round-bottom flask 7-methoxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (17.00 g, 0.096 mol) was dissolved in acetonitrile (100 mL). Trifluoroacetic anhydride (47.4 mL, 0.34 mol) was added at −20° C. After 10 minutes potassium nitrate (9.7 g, 0.096 mol) was added at the same temperature, and the reaction mixture was stirred for 1.5 hours. The reaction was quenched by addition of diluted NaHCO3, and allowed to warm to room temperature. Partition between saturated aqueous Na2CO3 and dichloromethane, extraction, drying (MgSO4), filtration, and concentration, provided the crude product. Flash chromatography separation on SiO2 with dichloromethane (100%) provided 2,2,2-trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone (11.5 g, 38%) and 2,2,2-trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone (7.5 g, 25%). 2,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone: 1H-NMR (CDCl3; amide rotamers observed) δ 7.72 (1H), 6.89 (1H), 3.95 (3H), 3.65-3.85 (4H), 2.95-3.07 (4H); LC/MS (ESI+): 319.20 (M+H). 2,2,2-Trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone: 1H-NMR (CDCl3; amide rotamers observed) δ 7.24 (1H), 6.85 (1H), 3.88 (s, 3H), 3.65-3.81 (4H), 2.80-3.05 (4H).

Aufarbeitung

  1. customThe reaction was quenched by addition of diluted NaHCO3
  2. customPartition between saturated aqueous Na2CO3 and dichloromethane, extraction
  3. customdrying
  4. filtration(MgSO4), filtration, and concentration
  5. customprovided the crude product
  6. customFlash chromatography separation on SiO2 with dichloromethane (100%)

Quellen und Nachweise

ORD-Eintrag
ord-bfe89bf7038847d68cbc80de01e8769b
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08552186B2

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