Dimethylformamide → 10-Bromoanthracene-9-carbaldehyde

HRID 926434Notes

Reaction equation

HRID 926434 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.C(Cl)Cl.CCCCCC>C1COCC1>[Br:16][C:9]1[C:10]2[C:15]([C:2]([CH:25]=[O:26])=[C:3]3[C:8]=1[CH:7]=[CH:6][CH:5]=[CH:4]3)=[CH:14][CH:13]=[CH:12][CH:11]=2

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 682269,10-DibromoanthraceneHCID 21226440Methylenechloride HexaneHCID 178418339Butyllithium

Product 1

HCID 60074310-Bromoanthracene-9-carbaldehydeYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To the yellow suspension of 9,10-Dibromoanthracene (2 g, 5.95 mmol) in THF (20 mL) at −90° C., n-BuLi (2.88 mL, 7.18 mmol, 2.5 M in hexane) was added dropwise. Orange solution was observed after 45 min additional stirring. Anhydrous DMF (0.92 mL, 11.9 mmol) was added to the orange solution. The reaction mixture was slowly warmed to room temp and stirred overnight. The reaction mixture was quenched with H2O and extracted with CH2Cl2. The organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL). The CH2Cl2 layer was separated, dried over anhydrous Na2SO4, filtered and removed in vacuo to give yellow solid. The crude product was purified by column chromatography using 30% CH2Cl2/hexane to give 6 in 68% yield. R1=0.3 (30% CH2Cl2/hexane; 1H NMR (CDCl3) δ 11.39 (s, 1H), 8.77-8.82 (d, 2H), 8.55-8.60 (d, 2H), 7.56-7.67 (m, 4H). (Ref. de Montigny, Frederic; Argouarch, Gilles; Lapinte, Claude. New route to unsymmetrical 9,10-disubstituted ethynylanthracene derivatives. Synthesis, 2006, 2, 293-298.)

Workup

  1. customThe reaction mixture was quenched with H2O
  2. extractionextracted with CH2Cl2
  3. washThe organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL)
  4. customThe CH2Cl2 layer was separated
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. customremoved in vacuo
  8. customto give yellow solid
  9. customThe crude product was purified by column chromatography
  10. customto give 6 in 68% yield

Sources & evidence

ORD record
ord-0e68ae1be2f640abb6e953a79c19e569
Source dataset
uspto-grants-2016_03
Patent number
US09285320B2

Reaction notes

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