Ammonia → 1,8-Dichloroanthracene

HRID 2273587

Reaction equation

HRID 2273587 reaction equation
[Cl:1][C:2]1[C:15]2[C:14](=O)[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][C:12]=3[Cl:17])[C:7](=O)[C:6]=2[CH:5]=[CH:4][CH:3]=1.N>[Zn]>[Cl:1][C:2]1[C:15]2[C:6](=[CH:7][C:8]3[C:13]([CH:14]=2)=[C:12]([Cl:17])[CH:11]=[CH:10][CH:9]=3)[CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 222AmmoniaHCID 67081,8-Dichloroanthraquinone

Product 1

HCID 6188901,8-DichloroanthraceneYield 62%

Reagents, catalysts & solvents 1

HCID 23994ZincCatalyst

Conditions

Temperature
100 °C

Procedure

A suspension of 1,8-dichloroanthraquinone 1 (10.0 g, 36.1 mmol) and Zinc dust (50.0 g, 765 mmol) in 200 ml of aqueous 28% NH3 was stirred for 3 h at 100° C. After cooling to room temperature, the resulting solid was separated by suction filtration. A CH2Cl2 solution of the resulting crude solid was combined with the CH2Cl2 extract of the supernatant liquid, and the mixture was dried over MgSO4 and concentrated under vacuo. The residual crude solid was dissolved in a mixture of 500 ml of isopropanol and 50 ml of 12 M HCl. After the resulting solution had been refluxed for 3 h, it was concentrated and partitioned between CH2Cl2 and 5% NaHCO3. The organic layer was collected and dried over MgSO4. The solvent was evaporated, and the crude solid product was recrystallized from a CH2Cl2-hexane mixture. The collected product was allowed to dry in the air for 24 h to provide 5.5 g (62%) of 1,8-dichloroanthracene 2 as yellow needles: mp 153° C. IR (KBr): ν=1617, 1547, 1438, 1300, 1210, 953, 872, 775, 720, 678; 1H NMR (CDCl3, 400 MHz) δ=7.25-7.88 (m; 6H, ArH), 8.36 (s; 1H, ArH-10), 9.16 (s; 1H, ArH-9); 13C NMR (CDCl3, 400 MHz) δ=120.99, 125.68, 126.04, 127.33, 127.61, 132.63; MS (EI) m/z (%)=246 (100) [M+], 248 (65); HRMS (EI) Calcd. For C14H8Cl2 [M+] 246.0003, Found 246.0001.

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe resulting solid was separated by suction filtration
  3. extractionextract of the supernatant liquid
  4. dry with materialthe mixture was dried over MgSO4
  5. concentrationconcentrated under vacuo
  6. dissolutionThe residual crude solid was dissolved in a mixture of 500 ml of isopropanol and 50 ml of 12 M HCl
  7. temperatureAfter the resulting solution had been refluxed for 3 h
  8. concentrationit was concentrated
  9. custompartitioned between CH2Cl2 and 5% NaHCO3
  10. customThe organic layer was collected
  11. dry with materialdried over MgSO4
  12. customThe solvent was evaporated
  13. customthe crude solid product was recrystallized from a CH2Cl2-hexane mixture
  14. customto dry in the air for 24 h

Sources & evidence

ORD record
ord-b4ae0e2020a7427da6538868d5aa9b34
Source dataset
uspto-grants-2015_09
Patent number
US09125866B1

Linked notes

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