Iodine → HCID 43140395, compound

HRID 1802333Notes

Reaction equation

HRID 1802333 reaction equation
II.[Mg].Br[C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:6]=1[CH3:12].[C:13](Cl)(=[O:17])[C:14](Cl)=[O:15].C1C[O:22]CC1>BrC1C=C(C)C=CC=1C>[CH3:12][C:6]1[CH:7]=[CH:8][C:9]([CH3:11])=[CH:10][C:5]=1[C:13](=[O:17])[C:14]([OH:22])=[O:15]

Participants

7

Reactant 5

HCID 807IodineHCID 8028Tetrahydrofuran2×HCID 11121Benzene, 2-bromo-1,4-dimethyl-HCID 65578Oxalyl chlorideHCID 5462224Magnesium

Product 1

HCID 43140395HCID 43140395, compound

Reagents, catalysts & solvents 1

HCID 11121Benzene, 2-bromo-1,4-dimethyl-Catalyst

Conditions

Temperature
-65 °C

Procedure

Two drops of 2-bromo-1,4-dimethylbenzene and an iodine crystal were add to magnesium turnings (1.7 g, 70.8 mmol). After heating to initiate the reaction, tetrahydrofuran (50 mL) was added, and then 2-bromo-1,4-dimethylbenzene (10 g, 54.1 mmol) was added dropwise the reaction mixture. The reaction was heated at reflux for an additional 1.5 h after the addition was complete, and then cooled to −65° C. and a solution of oxalyl chloride (5.2 mL, 7.6 g, 60 mmol) in THF (60 mL) was added dropwise. After 1 h the reaction mixture was warmed to 0° C., quenched with saturated aqueous ammonium chloride, poured into water and extracted with ethyl acetate (3×). The combined organic extracts were washed with saturated aqueous sodium chloride, dried (MgSO4) and concentrated under reduced pressure. The crude mixture was taken up in ethyl acetate and extracted two times with sodium hydroxide (1 N). The combined aqueous layers were adjusted to pH 3 with HCl (1 N) and extracted with ethyl acetate (3×). The combined organic extracts were dried (MgSO4) and concentrated under reduced pressure to provide the title compound as a tan solid (4.49 g).

Workup

  1. temperatureAfter heating
  2. additionwas added
  3. temperatureThe reaction was heated
  4. temperatureat reflux for an additional 1.5 h
  5. additionafter the addition
  6. temperatureAfter 1 h the reaction mixture was warmed to 0° C.
  7. customquenched with saturated aqueous ammonium chloride
  8. additionpoured into water
  9. extractionextracted with ethyl acetate (3×)
  10. washThe combined organic extracts were washed with saturated aqueous sodium chloride
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated under reduced pressure
  13. extractionextracted two times with sodium hydroxide (1 N)
  14. extractionextracted with ethyl acetate (3×)
  15. dry with materialThe combined organic extracts were dried (MgSO4)
  16. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3afa4f6ba43d4cf5b8a22f7824e05bc8
Source dataset
uspto-grants-2013_01
Patent number
US08349870B2

Reaction notes

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