Calcium Carbonate → 2-Iodo-4-(1H-1,2,4-triazol-1-yl)aniline

HRID 1919600Notes

Reaction equation

HRID 1919600 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[N:11][CH:10]=[N:9]2)=[CH:4][CH:3]=1.C([O-])([O-])=O.[Ca+2].[I:18]Cl>CO.O>[I:18][C:3]1[CH:4]=[C:5]([N:8]2[CH:12]=[N:11][CH:10]=[N:9]2)[CH:6]=[CH:7][C:2]=1[NH2:1]

Participants

6

Reactant 3

HCID 10112Calcium CarbonateHCID 24640Iodine chlorideHCID 7358264-(1,2,4-Triazol-1-yl)aniline

Product 1

HCID 671861892-Iodo-4-(1H-1,2,4-triazol-1-yl)anilineYield 67.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent

Procedure

To a stirred solution of 1-(4-aminophenyl)-1,2,4-triazole (1.0 g, 6.25 mmol) in MeOH (10 mL) and water (10 mL) was added CaCO3 (1.2 g, 12.0 mmol), followed by a solution of iodine monochloride (1.2 g, 7.38 mmol) in MeOH (10 mL). The reaction mixture was stirred at r.t. for 1.5 h, and then partitioned between EtOAc (100 mL) and aqueous sat. Na2S2O3 (100 mL). The organic fraction was separated, washed with aqueous sat. Na2S2O3 (100 mL), then water (100 mL), brine (50 mL), dried (Na2SO4), filtered and concentrated in vacuo. Purification by column chromatography (SiO2, 0-100% EtOAc/hexanes) gave the title compound (1.2 g, 67%). LCMS (ES+) 286.9 (M+H)+, RT 2.78 minutes (Method 4).

Workup

  1. custompartitioned between EtOAc (100 mL) and aqueous sat. Na2S2O3 (100 mL)
  2. customThe organic fraction was separated
  3. washwashed with aqueous sat. Na2S2O3 (100 mL)
  4. dry with materialwater (100 mL), brine (50 mL), dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by column chromatography (SiO2, 0-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-257380dbf3ab4a628db073dbc92e4b07
Source dataset
uspto-grants-2012_05
Patent number
US08168634B2

Reaction notes

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