Calcium Carbonate → 4-Amino-5-fluoro-7-iodo-1,3-benzodioxole

HRID 1785098Notes

Reaction equation

HRID 1785098 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:5]2[O:6][CH2:7][O:8][C:4]=2[C:3]=1[NH2:11].[I:12](Cl)(=O)=O.I(Cl)(=O)=O.C([N+](C)(C)C)C1C=CC=CC=1.C(=O)([O-])[O-].[Ca+2]>ClCCl.CO>[NH2:11][C:3]1[C:4]2[O:8][CH2:7][O:6][C:5]=2[C:9]([I:12])=[CH:10][C:2]=1[F:1]

Participants

6

Reactant 3

HCID 10112Calcium CarbonateHCID 179805645-Fluoro-2H-1,3-benzodioxol-4-amineHCID 56924451Trimethylbenzylammonium Dichloroiodate

Product 1

HCID 688813424-Amino-5-fluoro-7-iodo-1,3-benzodioxoleYield 57.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

5-Fluoro-1,3-benzodioxol-4-amine (1.1 g, 7.10 mmol), benzyltrimethylammonium dichloroiodate (2.7 g, 7.76 mmol) and calcium carbonate (0.92 g, 9.2 mmol) in a mixture of dichloromethane (10 ml) and methanol (5 ml) were stirred at room temperature for 3 hr. The mixture was filtered through Celite and then evaporated to a dark brown solid. The residue was purified by column chromatography on silica using a 1:1 mixture of methyl tert-butyl ether and iso-hexane as eluent to give 4-amino-5-fluoro-7-iodo-1,3-benzodioxole (1.14 g, 57%) as a pale brown solid; NMR Spectrum: (CDCl3) 3.61 (s, 2H), 6.00 (s, 2H), 6.81 (d, 1H).

Workup

  1. filtrationThe mixture was filtered through Celite
  2. customevaporated to a dark brown solid
  3. customThe residue was purified by column chromatography on silica using
  4. additiona 1:1 mixture of methyl tert-butyl ether and iso-hexane as eluent

Sources & evidence

ORD record
ord-a0bb6e202603404c829e87cd57f5bc37
Source dataset
uspto-grants-2009_03
Patent number
US07504408B2

Reaction notes

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