Hydrochloric Acid → 3-Iodo-1-methanesulfonyl-5-methoxy-benzene

HRID 418077Notes

Reaction equation

HRID 418077 reaction equation
[CH3:1][S:2]([C:5]1(N)[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][CH2:6]1)(=[O:4])=[O:3].Cl.N([O-])=O.[Na+].[I-:19].[K+]>O>[I:19][C:7]1[CH:6]=[C:5]([S:2]([CH3:1])(=[O:4])=[O:3])[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 23668193Sodium NitriteHCID 666496371-Methanesulfonyl-5-methoxy-phenylamine

Product 1

HCID 578630533-Iodo-1-methanesulfonyl-5-methoxy-benzeneYield 70%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of 1-methanesulfonyl-5-methoxy-phenylamine (1.0 g, 4.94 mmol) in water (2.66 mL) was added a concentrated hydrochloric acid (2.21 mL, 29.66 mmol, 36%) at 0° C. To this mixture was added a chilled solution of sodium nitrite (0.622 g, 8.89 mmol) in water (3.78 mL) dropwise with a vigorous stirring. Then, the resulting colored mixture was stirred for 15 min at 0° C., and a cold solution of potassium iodide (1.64 g, 9.88 mmol) in water (3.78 mL) was added carefully. During this addition, a black brown solid was formed and after addition the ice bath was removed, and the reaction mixture was stirred for 2 days at room temperature. Then, the reaction mixture was diluted with water (50 mL) and saturated sodium thiosulfate solution (100 mL). The organic compound was extracted into ethyl acetate (3×50 mL). The combined organic extracts were washed with brine solution (100 mL) and dried over anhydrous magnesium sulfate. The filtration of the drying agent and concentration of the filtrate under reduced pressure gave the crude residue which was purified by using a silica gel column, eluting with 0-35% ethyl acetate in hexanes to obtain 3-iodo-1-methanesulfonyl-5-methoxy-benzene (1.08 g, 70%) as a white solid: ES(+)-HRMS m/e calcd for C8H9IO3S (M+H)+ 312.9390, found 312.9390.

Workup

  1. additionDuring this addition
  2. customa black brown solid was formed
  3. customwas removed
  4. stirringthe reaction mixture was stirred for 2 days at room temperature
  5. additionThen, the reaction mixture was diluted with water (50 mL) and saturated sodium thiosulfate solution (100 mL)
  6. extractionThe organic compound was extracted into ethyl acetate (3×50 mL)
  7. washThe combined organic extracts were washed with brine solution (100 mL)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationThe filtration of the drying agent and concentration of the filtrate under reduced pressure
  10. customgave the crude residue which
  11. customwas purified
  12. washeluting with 0-35% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-63df20b408db48db9d969ec421f4da57
Source dataset
uspto-grants-2012_01
Patent number
US08093253B2

Reaction notes

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