Dichloromethane → 2-Chloroanthracene

HRID 862717

Reaktionsgleichung

Reaktionsgleichung von HRID 862717
[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[C:12](=O)[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5](=O)[C:4]=2[CH:3]=1.C(Cl)Cl.C1C2C(=O)C3C(=CC=CC=3)C(=O)C=2C=CC=1.C1C2C(=CC3C(C=2)=CC=CC=3)C=CC=1>[OH-].[NH4+].O.[Zn]>[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[CH:5][C:6]3[C:11]([CH:12]=2)=[CH:10][CH:9]=[CH:8][CH:7]=3)[CH:3]=1

Komponenten

8

Edukt 4

HCID 6344Dichloromethane2×HCID 6780AnthraquinoneHCID 8418AnthraceneHCID 85532-Chloroanthraquinone

Produkt 1

HCID 283082-ChloroanthraceneAusbeute 14,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23994ZincKatalysator2×HCID 962WaterLösungsmittelHCID 14923Ammonium HydroxideLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

A stirred suspension of 2-chloroanthraquinone (1260 g, 5.19 moles) in concentrated ammonium hydroxide (7.5 L) and water (2.5 L) was warmed to 40° C. Zinc dust (845 g, 12.93 moles) was added in one portion, changing the color to deep red. The mixture was stirred for 45 min at 50° C., then cautiously treated with a second portion of zinc dust (845 g). After the addition, the stirred mixture was heated gradually over 3 h to 90° C., then maintained at 90°-95° C. for 2 h (red color dissipated). TLC analysis [silica gel/hexane:methylene chloride (3:1)] showed complete conversion of the anthraquinone (Rf =0.35) to the desired anthracene (Rf =0.80). The reaction mixture was stirred overnight as it cooled to room temperature. The cooled mixture was treated with methylene chloride (4 L), stirred for 2 h, then filtered through Celite to remove the excess zinc. The filter cake was washed with methylene chloride (6×1 L). The methylene chloride layer was separated from the aqueous, then treated with 6N hydrochloric acid (3 L) and stirred for 2 h. A first crop of 2-chloroanthracene was collected by filtration and washed with water (4×1 L). Vacuum drying afforded a light yellow crystalline product weighing 804.6 g (mp 220°-221° C.). The methylene chloride portion of the filtrate was concentrated in vacuo to 10% of its original volume. This produced an additional 158.5 g of the desired compound for a total yield of 963.1 g (87.2%). 1H NMR (CDCl3): δ8.39 (s, 1H), 8.30 (s,1H), 7.96 (s, 4H), 7.49 (s, 2H), 7.36 (d, J=8.7 Hz, 1H).

Aufarbeitung

  1. additionAfter the addition
  2. temperaturethe stirred mixture was heated gradually over 3 h to 90° C.
  3. temperaturemaintained at 90°-95° C. for 2 h (red color dissipated)
  4. stirringThe reaction mixture was stirred overnight as it
  5. temperaturecooled to room temperature
  6. stirringstirred for 2 h
  7. filtrationfiltered through Celite
  8. customto remove the excess zinc
  9. washThe filter cake was washed with methylene chloride (6×1 L)
  10. customThe methylene chloride layer was separated from the aqueous,
  11. additionthen treated with 6N hydrochloric acid (3 L)
  12. stirringstirred for 2 h
  13. filtrationA first crop of 2-chloroanthracene was collected by filtration
  14. washwashed with water (4×1 L)
  15. customVacuum drying
  16. customafforded a light yellow crystalline product
  17. concentrationThe methylene chloride portion of the filtrate was concentrated in vacuo to 10% of its original volume

Quellen und Nachweise

ORD-Eintrag
ord-ecb916794e4748148a669cd0aa128684
Quelldatensatz
uspto-grants-1998_02
Patentnummer
US05719166

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