Dimethylformamide → 10-Bromoanthracene-9-carbaldehyde

HRID 1381769Notes

Reaction equation

HRID 1381769 reaction equation
Br[C:2]1[C:3]2[C:8]([C:9]([Br:16])=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2.[Li]CCCC.CN([CH:25]=[O:26])C>>[Br:16][C:9]1[C:8]2[C:3](=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:2]([CH:25]=[O:26])=[C:15]2[C:10]=1[CH:11]=[CH:12][CH:13]=[CH:14]2

Participants

4

Reactant 3

HCID 6228DimethylformamideHCID 682269,10-DibromoanthraceneHCID 178418339Butyllithium

Product 1

HCID 60074310-Bromoanthracene-9-carbaldehydeYield 76%

Procedure

This material was made from 9,10-dibromoanthracene (Eastman, 20 g, 60 mmol) by the procedure of R. Kuhn and H. Fischer, Chem. Ber. 94 3060 (1961) with some modifications. In this procedure, the reaction mixture was cooled to -78° before the n-BuLi (Aldrich) was added. The resulting mixture was warmed to RT over 1 h and then refluxed until the crystalline starting material disappeared. The mixture was then cooled to -78° again before the DMF was added (in one portion). The flask was warmed to RT and then quenched with 1M HBr (200 mL). The two-phase system was then extracted with CH2Cl2 (3×500 mL). The extracts were combined, dried (MgSO4), filtered, and the solvent removed to give the crude material. This was purified by preparative HPLC using PhCH3 as the eluting solvent to give 13.06 g (76%) of 10-bromo-9-anthracenecarbaldehyde mp 215°-216.5°, (lit. mp 218°, P. Kuhn and H. Fischer, Chem. Ber. 94 3060 (1961)), (C, H, Br).

Workup

  1. additionwas added
  2. temperaturerefluxed until the
  3. additionwas added (in one portion)
  4. temperatureThe flask was warmed to RT
  5. customquenched with 1M HBr (200 mL)
  6. extractionThe two-phase system was then extracted with CH2Cl2 (3×500 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customthe solvent removed
  10. customto give the crude material
  11. customThis was purified by preparative HPLC

Sources & evidence

ORD record
ord-7c04b1a8be254daaaaa7264ebf19e7fc
Source dataset
uspto-grants-1989_02
Patent number
US04803221

Reaction notes

Loading…