Nitric Acid → 4-Iodo-3-nitrothioanisole

HRID 2089267Notes

Reaction equation

HRID 2089267 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH3:9])=[CH:4][CH:3]=1.COS(OC)(=O)=O.[N+:17]([O-])([OH:19])=[O:18]>S(=O)(=O)(O)O>[I:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH3:9])=[CH:4][C:3]=1[N+:17]([O-:19])=[O:18]

Participants

5

Reactant 3

HCID 944Nitric Acid2×HCID 6497Dimethyl SulfateHCID 27593741-Iodo-4-(methylsulfanyl)benzene

Product 1

HCID 597545804-Iodo-3-nitrothioanisoleYield 80%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
90 °C

Procedure

A flask was charged with 10 g of 4-iodothioanisole and 5.5 mL of dimethylsulfate and warmed to ca. 90° C. for 10 min. The resulting solution was dissolved in conc. sulfuric acid (30 mL) and cooled to ca. 0-4° C., whereupon it was treated, with extreme caution, slowly with conc. HNO3 (ca. 2 mL) while maintaining the reaction temperature below 4° C. After stirring it for ca. 10 min, the reaction mixture was stirred at ca. 90° C. for ca. 3 d. The reaction was monitored with HPLC, TLC, and LC-MS, and if needed, smaller portions of nitric acid were added to the reaction mixture to force it to completion. Use of fuming sulfuric acid is also helpful. After the complete consumption of the aromatic starting material, the reaction mixture was cooled, poured over crushed ice, treated with 30% aq. perchloric acid at 4° C. The light colored precipitate was filtered, washed thoroughly with water, and dried under vacuum. The perchlorate salt was stirred with saturated aq. NaCl solution at 95° C. for 3-6 h. Upon cooling to room temperature, the precipitate was filtered, washed thoroughly with water to get rid of any inorganic salts, and dried under vacuum to obtain 4-iodo-3-nitrothioanisole in >80% yield.

Workup

  1. temperaturecooled to ca. 0-4° C., whereupon it
  2. temperaturewhile maintaining the reaction temperature below 4° C
  3. stirringthe reaction mixture was stirred at ca. 90° C. for ca. 3 d
  4. customAfter the complete consumption of the
  5. temperaturethe reaction mixture was cooled
  6. additionpoured
  7. customover crushed ice
  8. additiontreated with 30% aq. perchloric acid at 4° C
  9. filtrationThe light colored precipitate was filtered
  10. washwashed thoroughly with water
  11. customdried under vacuum
  12. stirringThe perchlorate salt was stirred with saturated aq. NaCl solution at 95° C. for 3-6 h
  13. temperatureUpon cooling to room temperature
  14. filtrationthe precipitate was filtered
  15. washwashed thoroughly with water
  16. customto get rid of any inorganic salts
  17. customdried under vacuum

Sources & evidence

ORD record
ord-122290786c8149acbb0e9815bd9073bc
Source dataset
uspto-grants-2013_05
Patent number
US08436031B2

Reaction notes

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