Benzenamine hydrochloride (1:1) → 8-Nitro-10-azaacephenanthrene

HRID 36625

Reaktionsgleichung

Reaktionsgleichung von HRID 36625
[NH2:1][C:2]1[C:12]2[C:13]3[C:5]([CH2:6][CH2:7][C:8]=3[CH:9]=[CH:10][CH:11]=2)=[CH:4][CH:3]=1.[CH:14](/[O-])=[C:15](\[N+:18]([O-:20])=[O:19])/[CH:16]=O.O.[Na+].Cl.NC1C=CC=CC=1.P(Cl)(Cl)(Cl)=O.[OH-].[Na+]>C(O)(=O)C>[N+:18]([C:15]1[CH:14]=[C:3]2[C:2](=[N:1][CH:16]=1)[C:12]1=[C:13]3[C:5]([CH2:6][CH2:7][C:8]3=[CH:9][CH:10]=[CH:11]1)=[CH:4]2)([O-:20])=[O:19]

Komponenten

7

Edukt 5

HCID 8870Benzenamine hydrochloride (1:1)HCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 625475-AminoacenaphtheneHCID 12244252sodium N-oxido-1,3-dioxopropanimine oxide hydrate

Produkt 1

HCID 233640248-Nitro-10-azaacephenanthrene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

A mixture of 5-aminoacenaphthene (Grabe, C. Liebigs Ann. der Chemie 1903, 327, 77) (5.0 g, 29.5 mmol) and sodium nitromalondialdehyde monohydrate (Fanta, P. E. Org. Syntheses Coll. vol. 4 1963, 844) (5.51 g, 35 mmol) in acetic acid (140 mL) was stirred for 1 h at room temperature and aniline hydrochloride (5.21 g, 40.2 mmol) was added. This mixture was stirred for 10 min and heated at reflux for 2 h. Phosphorous oxychloride (3 mL, 32.2 mmol) was added and heating was continued for 3 h. The resulting mixture was cooled to room temperature and poured into ice/water (200 mL). The aqueous mixture was neutralized with 2M sodium hydroxide solution and extracted with dichloromethane. The extracts were dried over sodium sulfate and condensed to dryness. The condensed product was purified using flash chromatography (20% hexane/dichloromethane, silica gel) to obtain a fluffy, bright yellow solid, 3.20 g (43%): MS m/e 251 (M+H +); 1H NMR (CD2C12, 300 MHz) δ 3.48-3.55 (m, 4H), 7.56 (s, 1H), 7.68 (d, J=7.0 Hz, 1H), 7.77 (t, J=7.8 Hz, 1H), 8.79 (d, J=8.1 Hz, 1H), 8.94 (d, J=2.5 Hz, 1H), 9.65 (d, J=2.5 Hz, 1H).

Aufarbeitung

  1. stirringThis mixture was stirred for 10 min
  2. temperatureheated
  3. temperatureat reflux for 2 h
  4. temperatureheating
  5. waitwas continued for 3 h
  6. temperatureThe resulting mixture was cooled to room temperature
  7. extractionextracted with dichloromethane
  8. dry with materialThe extracts were dried over sodium sulfate and condensed to dryness
  9. customThe condensed product was purified
  10. customto obtain a fluffy, bright yellow solid, 3.20 g (43%)

Quellen und Nachweise

ORD-Eintrag
ord-1e8427f94cd94078aa77583ff7c2032f
Quelldatensatz
uspto-grants-1995_05
Patentnummer
US05416089

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