Toluene → HCID 54095494, compound

HRID 1601025Notes

Reaction equation

HRID 1601025 reaction equation
[I:1][C:2]1[C:8]([Br:9])=[CH:7][C:6]([Br:10])=[CH:5][C:3]=1[NH2:4].[CH2:11]([C:18](=O)[C:19]([O-:21])=[O:20])[C:12]1C=CC=C[CH:13]=1.[O-]S([O-])(=O)=O.[Na+].[Na+].[C:30]1([CH3:36])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>>[CH2:36]([O:21][C:19](=[O:20])[CH:18]([NH:4][C:3]1[CH:5]=[C:6]([Br:10])[CH:7]=[C:8]([Br:9])[C:2]=1[I:1])[CH2:11][CH:12]=[CH2:13])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

5

Reactant 4

HCID 1140TolueneHCID 24436Sodium SulfateHCID 45926973-PhenylpyruvateHCID 21831119HCID 21831119, compound

Product 1

HCID 54095494HCID 54095494, compound

Procedure

To a solution of 2-iodo-3,5-dibromoaniline (1.1 g) in dry toluene (20 ml) were added benzylglyoxylate (0.530 g) and Na2SO4 (1 g). The mixture was refluxed overnight. After filtration the resulting solution was concentrated under vacuum to a brown oil, which was then taken up with dry dichloromethane (20 ml). After cooling to -78°, TiCl4 (0.318 ml) was slowly added with a syringe and stirring continued for 5 min. The solution was then allowed to warm to room temperature over 30 min by removing the dry ice/acetone bath, then cooled again to -78° and tributylallyltin (0.98 ml) added. After 1 hour the reaction was stopped by pouring it into a saturated solution of NH4Cl (80 ml). The aqueous phase was extracted with EA (2×100 ml) and the combined organic fractions washed with HCl (3 N, 2×30 ml) and brine (50 ml) and dried. Final purification by column chromatography (CH/EA 8/2) gave the title compound (0.6 g) as a yellow oil.

Workup

  1. temperatureThe mixture was refluxed overnight
  2. filtrationAfter filtration the resulting solution
  3. concentrationwas concentrated under vacuum to a brown oil, which
  4. temperatureAfter cooling to -78°
  5. additionTiCl4 (0.318 ml) was slowly added with a syringe
  6. customby removing the dry ice/acetone bath
  7. temperaturecooled again to -78°
  8. additiontributylallyltin (0.98 ml) added
  9. waitAfter 1 hour the reaction was stopped
  10. additionby pouring it into a saturated solution of NH4Cl (80 ml)
  11. extractionThe aqueous phase was extracted with EA (2×100 ml)
  12. washthe combined organic fractions washed with HCl (3 N, 2×30 ml) and brine (50 ml)
  13. customdried
  14. customFinal purification by column chromatography (CH/EA 8/2)

Sources & evidence

ORD record
ord-a88d48c51dfd4936aca34ad6d1fcbdbf
Source dataset
uspto-grants-1999_11
Patent number
US05977136

Reaction notes

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