Sodium Hydroxide → 7-Methoxy-9-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine

HRID 1686912Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1686912
[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.FC(F)(F)C([NH-])=O.N1C2C=CC=CC=2C=CC=C1.[N+:32]([O-:35])([O-:34])=[O:33].[K+].[OH-].[Na+]>C(#N)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O>[CH3:1][O:2][C:3]1[C:13]([N+:32]([O-:34])=[O:33])=[CH:12][C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1.[CH3:1][O:2][C:3]1[CH:13]=[C:12]([N+:32]([O-:35])=[O:33])[C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1

Komponenten

9

Edukt 5

HCID 14798Sodium HydroxideHCID 24434Potassium NitrateHCID 138533487-Methoxy-2,3,4,5-tetrahydro-1h-3-benzazepineHCID 155596581H-1-BenzazepineHCID 178514236HCID 178514236, Verbindung

Produkt 2

HCID 672642267-Methoxy-9-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepineHCID 672643517-Methoxy-8-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6342AcetonitrileLösungsmittelHCID 9845Trifluoroacetic anhydrideLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

7-Methoxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (750 mg/4.2 mmol) was dissolved in a mixture of dry acetonitrile (3 mL) and trifluoroacetic anhydride (3 mL) and cooled to 0° C. (ice bath). The trifluoroacetyl amide of the benzazepine forms immediately (observed by HPLC). Potassium nitrate (450 mg/4.2 mmol) was added in one portion and the mixture allowed to warm to room temperature. After one hour the reaction was complete (HPLC); 33% sodium hydroxide (1 mL) was added via pipette (exotherm) and the mixture stirred for an additional two hours (to hydrolyze the TFA amide). The resulting mixture was partitioned between water (20 mL) and methylene chloride (20 mL). The aqueous layer was extracted with an additional portion of methylene chloride (20 mL) and the combined organics were dried over magnesium sulfate, filtered and concentrated to afford a 1.7:1 ratio of 7-Methoxy-8-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine and 7-Methoxy-9-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a yellow oil (770 mg/82%). The material was used without further purification. 1H NMR (400 MHz, CDCl3) major isomer: δ 7.66 (s, 1H), 6.82 (s 1H); minor isomer: 7.14 (d, J=8.3 Hz, 1H), 6.76 (d, J=8.3 Hz, 1H).

Aufarbeitung

  1. temperatureto warm to room temperature
  2. customThe resulting mixture was partitioned between water (20 mL) and methylene chloride (20 mL)
  3. extractionThe aqueous layer was extracted with an additional portion of methylene chloride (20 mL)
  4. dry with materialthe combined organics were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-7991309e17f14feb8a7e81fd33ccafe5
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148391B2

Notizen zur Reaktion

Wird geladen…