Carbon Dioxide → 4-Bromo-1-naphthoic acid

HRID 1669738Notes

Reaction equation

HRID 1669738 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([Br:12])=[CH:4][CH:3]=1.[Mg].II.[C:16](=[O:18])=[O:17].Cl>C1COCC1.O>[Br:12][C:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:2]([C:16]([OH:18])=[O:17])=[CH:3][CH:4]=1

Participants

8

Reactant 5

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 807IodineHCID 665211,4-DibromonaphthaleneHCID 5462224Magnesium

Product 1

HCID 2825914-Bromo-1-naphthoic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
70 °C

Procedure

A solution of 1,4-dibromonaphthalene (100 g) in THF (500 ml) is added to magnesium (8.49 g) and iodine (trace) in THF (200 ml) over about 2 h and heated at 65-75° C. for up to 7 h (typically 3-4 h) to prepare a solution of the Grignard reagent. The solution is cooled to 0-10° C. and carbon dioxide gas is passed through the solution for 10-16 h. Water (100 ml) is added slowly, and after stirring for about 30 min at 0-10° C., is acidified (typically to pH 2-3) with hydrochloric acid. The THF layer is separated off, and concentrated. The residue is added to aqueous sodium carbonate (20%, 500 ml) and washed with toluene (2×200 ml). The aqueous solution is treated with hydrochloric acid (typically to pH 2-3). The product is filtered off, washed with water, and dried under vacuum at about 90-100° C. for about 12 h (dry weight 60 g).

Workup

  1. temperatureThe solution is cooled to 0-10° C.
  2. customThe THF layer is separated off
  3. concentrationconcentrated
  4. additionThe residue is added to aqueous sodium carbonate (20%, 500 ml)
  5. washwashed with toluene (2×200 ml)
  6. additionThe aqueous solution is treated with hydrochloric acid (typically to pH 2-3)
  7. filtrationThe product is filtered off
  8. washwashed with water
  9. customdried under vacuum at about 90-100° C. for about 12 h
  10. custom(dry weight 60 g)

Sources & evidence

ORD record
ord-c5c4713ed9184965a7e91bf667733e02
Source dataset
uspto-grants-2011_08
Patent number
US07989629B2

Reaction notes

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