3-Bromo-5-formylbenzoic acid → 3-Ethyl-5-formylbenzoic acid

HRID 1958803Notes

Reaction equation

HRID 1958803 reaction equation
[CH:1]([C:3]1[CH:4]=[C:5]([CH:9]=[C:10](Br)[CH:11]=1)[C:6]([OH:8])=[O:7])=[O:2].[CH2:13]([Zn]CC)[CH3:14]>O1CCOCC1.C1(C)C=CC=CC=1>[CH:1]([C:3]1[CH:4]=[C:5]([CH:9]=[C:10]([CH2:13][CH3:14])[CH:11]=1)[C:6]([OH:8])=[O:7])=[O:2]

Participants

5

Reactant 2

HCID 223207963-Bromo-5-formylbenzoic acidHCID 178418750HCID 178418750, compound

Product 1

HCID 866505073-Ethyl-5-formylbenzoic acid

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
75 °C

Procedure

Under nitrogen, Pd(dppf) (97 mg, 0.119 mmol) was added to a stirred solution of 3-formyl-5-bromo-benzoic acid (3.00 g, 11.92 mmol) in dioxane (100 mL). Diethyl zinc (14.7 g, 17.9 mmol, as a 15% solution in toluene) was added and the mixture was stirred at 75° C. for 1 h. The reaction was quenched by adding water (5 mL) and the solvent was evaporated to a volume of about 50 mL. The mixture was basified by adding sat. aq. ammonia (1 mL). The mixture was filtered and the filtrate was acidified by adding formic acid (4 mL) before it was separated by prep. HPLC to give the title compound as a colourless resin (1.17 g). LC-MS*: tR=0.44 min, [M−H]−=177.26; 1H NMR (D6-DMSO): δ 1.24 (t, J=7.8 Hz, 3H), 2.77 (q, J=7.5 Hz, 2H), 7.92 (t, J=1.8 Hz), 8.08 (t, J=1.8 Hz, 1H), 8.26 (t, J=1.5 Hz, 1H), 10.06 (s, 1H).

Workup

  1. customThe reaction was quenched
  2. additionby adding water (5 mL)
  3. customthe solvent was evaporated to a volume of about 50 mL
  4. additionby adding sat. aq. ammonia (1 mL)
  5. filtrationThe mixture was filtered
  6. additionby adding formic acid (4 mL) before it
  7. customwas separated by prep

Sources & evidence

ORD record
ord-aec92accb95e453aadc93020a1547137
Source dataset
uspto-grants-2013_04
Patent number
US08410151B2

Reaction notes

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