Hydrochloric Acid → 2-Bromo-6-fluorobenzaldehyde

HRID 2410072Notes

Reaction equation

HRID 2410072 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[CH:3]=1.C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.Cl.C1C[O:33][CH2:32]C1>O.C(OC)(C)(C)C.C(O)(=O)C.CN(C=O)C>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[CH:32]=[O:33]

Participants

11

Reactant 6

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 8028TetrahydrofuranHCID 140821-Bromo-3-fluorobenzeneHCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Product 1

HCID 224739772-Bromo-6-fluorobenzaldehyde

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

1-Bromo-3-fluorobenzene (17.3 g, 0.1 M) was added over 5 minutes to a solution of lithium diisopropylamide (prepared from the addition of 40 mL of 2.5 N butyllithium in hexanes to 11.5 g of 0.1 M diisopropylamine) in THF at a temperature between −70 and −75° C. The mixture was stirred cold for 1 hour after which DMF (8 mL) was added over 10 minutes. The mixture was stirred cold for an additional 40 minutes followed by the addition of acetic acid (26 g). The mixture was allowed to warm to ambient temperature, transferred into a mixture of 200 mL methyl tert-butyl ether, 200 mL water and 150 mL hydrochloric acid (˜4 N). The organic layer was separated and concentrated under reduced pressure to provide the title compound. 1H-NMR (CDCl3) δ 10.36 (s, 1H), 7.49 (dt, 1H), 7.40(dt, 1H), 7.15 (tdd, 1H).

Workup

  1. additionwas added over 10 minutes
  2. customThe organic layer was separated
  3. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-751a0eb72fee49498d199c6b881c2c7d
Source dataset
uspto-grants-2014_08
Patent number
US08815930B2

Reaction notes

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