Calcium Carbonate → 7-Iodo-1,3-benzodioxol-4-amine

HRID 988117Notes

Reaction equation

HRID 988117 reaction equation
C([O-])([O-])=O.[Ca+2].[O:6]1[C:10]2[CH:11]=[CH:12][CH:13]=[C:14]([NH2:15])[C:9]=2[O:8][CH2:7]1.[I:16](Cl)(=O)=O.I(Cl)(=O)=O.C[N+](C)(C)CC1C=CC=CC=1>C(Cl)Cl.CO.O>[I:16][C:11]1[C:10]2[O:6][CH2:7][O:8][C:9]=2[C:14]([NH2:15])=[CH:13][CH:12]=1

Participants

7

Reactant 3

HCID 10112Calcium CarbonateHCID 103131651,3-Benzodioxol-4-amineHCID 56924451Trimethylbenzylammonium Dichloroiodate

Product 1

HCID 226627507-Iodo-1,3-benzodioxol-4-amineYield 62.4%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

CaCO3 (3.9 g) was added to a mixture of 1,3-benzodioxol-4-amine (4.11 g) in DCM (40 ml) and CH3OH (20 ml). This mixture was stirred at room temperature. N,N,N-trimethyl benzenemethanaminium dichloroiodate (11.5 g) was added portionwise at room temperature. The resulting reaction mixture was stirred for 15 minutes at room temperature. The mixture was diluted with water. The layers were separated. The aqueous phase was extracted with DCM. The combined organic layers were washed with water, dried, filtered and the solvent evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/hexane 80/20). The pure fractions were collected and the solvent was evaporated. The residue was crystallized from DIPE. The precipitate was filtered off and dried, yielding 3.5 g (46.9%) of 7-iodo-1,3-benzodioxol-4-amine (intermediate 2-a).

Workup

  1. customThe resulting reaction mixture
  2. stirringwas stirred for 15 minutes at room temperature
  3. customThe layers were separated
  4. extractionThe aqueous phase was extracted with DCM
  5. washThe combined organic layers were washed with water
  6. customdried
  7. filtrationfiltered
  8. customthe solvent evaporated
  9. customThe residue was purified by column chromatography over silica gel (eluent: CH2Cl2/hexane 80/20)
  10. customThe pure fractions were collected
  11. customthe solvent was evaporated
  12. customThe residue was crystallized from DIPE
  13. filtrationThe precipitate was filtered off
  14. customdried

Sources & evidence

ORD record
ord-a088a0df8cf54be0b172ded045e77ff7
Source dataset
uspto-grants-2003_10
Patent number
US06635643B2

Reaction notes

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