Iodine → HCID 19866639, compound

HRID 1199459Notes

Reaction equation

HRID 1199459 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[S:10][CH3:11].[Mg].II.[CH3:15][O:16][C:17]1[CH:22]=[CH:21][N:20]=[CH:19][CH:18]=1.C1(OC(Cl)=O)C=CC=CC=1>O1CCCC1>[CH3:15][O:16][C:17]1[CH:22]=[CH:21][N:20]=[C:19]([C:2]2[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=2[S:10][CH3:11])[CH:18]=1

Participants

7

Reactant 5

HCID 807IodineHCID 15891Phenyl chloroformateHCID 692784-MethoxypyridineHCID 5462224MagnesiumHCID 109224181-bromo-4-methoxy-2-(methylsulfanyl)benzene

Product 1

HCID 19866639HCID 19866639, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A Grignard reagent was prepared from the product of step (d) above (12.3 g), magnesium (1.28 g) and iodine (1 crystal) in dry tetrahydrofuran (150 ml). 4-Methoxypyridine (5.76 g) was dissolved in dry tetrahydrofuran (300 ml) and stirred under nitrogen. The solution was cooled to -70°and treated with the above Grignard solution in one portion. After stirring for 10 minutes phenylchloroformate (6.6 ml) was added dropwise. After stirring at -70°for 30 minutes the mixture was allowed to warm up to room temperature. After stirring for 90 minutes the mixture was poured onto water and extracted with ether. The ether was washed with water and brine then dried and evaporated. The residue was taken up in toluene (250 ml) and stirred at room temperature. A solution of 3,4,5,6-tetrachloro-1,2-benzoquinone (13.0 g) in acetic acid (120 ml) was added dropwise. When addition was complete the mixture was stirred for a further 18 hours. The mixture was ice cooled and treated with a cold solution of sodium hydroxide (700 ml of 10%). After stirring for 10 minutes the mixture was filtered and separated. The aqueous filtrates were extracted with ether and the combined organic filtrates were extracted with dilute hydrochloric acid. The extracts were combined and basified with sodium hydroxide solution. The mixture was extracted with ether and the combined extracts washed with brine then dried and evaporated. Flash chromatography (1:1 ethyl acetate/petroleum ether) produced the subtitle compound as a clear oil 5.4 g. NMR (CDCl3) d 8.50 (d,1 H), 7.39 (d,1H), 7.60 (d,1H), 6.85 (d,1H), 6.77 (m,2H), 3.88 (s,3H), 3.86 (s,3H), 2.40 (s,3H).

Workup

  1. temperatureThe solution was cooled to
  2. addition-70°and treated with the above Grignard solution in one portion
  3. additionwas added dropwise
  4. stirringAfter stirring at -70°for 30 minutes the mixture
  5. stirringAfter stirring for 90 minutes the mixture
  6. additionwas poured onto water
  7. extractionextracted with ether
  8. washThe ether was washed with water and brine
  9. customthen dried
  10. customevaporated
  11. stirringstirred at room temperature
  12. additionA solution of 3,4,5,6-tetrachloro-1,2-benzoquinone (13.0 g) in acetic acid (120 ml) was added dropwise
  13. additionWhen addition
  14. stirringwas stirred for a further 18 hours
  15. temperaturecooled
  16. additiontreated with a cold solution of sodium hydroxide (700 ml of 10%)
  17. stirringAfter stirring for 10 minutes the mixture
  18. filtrationwas filtered
  19. customseparated
  20. extractionThe aqueous filtrates were extracted with ether
  21. extractionthe combined organic filtrates were extracted with dilute hydrochloric acid
  22. extractionThe mixture was extracted with ether
  23. washthe combined extracts washed with brine
  24. customthen dried
  25. customevaporated

Sources & evidence

ORD record
ord-89fe9a39ba32497eb13cc24efe4c264d
Source dataset
uspto-grants-1990_02
Patent number
US04900751

Reaction notes

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