Iodine → 1,3-difluoro-2-iodo-4-nitrobenzene

HRID 523115Notes

Reaction equation

HRID 523115 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[Mg+2].[Cl-].[Cl-].[I:15]I>C1COCC1.[NH4+].[Cl-].[O-]S([O-])(=S)=O.[Na+].[Na+]>[F:8][C:6]1[CH:5]=[CH:4][C:3]([N+:9]([O-:11])=[O:10])=[C:2]([F:1])[C:7]=1[I:15]

Participants

7

Reactant 3

HCID 807IodineHCID 679672,4-DifluoronitrobenzeneHCID 5360315Magnesium Chloride

Product 1

HCID 582416821,3-difluoro-2-iodo-4-nitrobenzeneYield 74%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 24477Sodium ThiosulfateSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
25 °C

Procedure

A dry, argon-filled Schlenk tube with a magnetic stirrer bar and septum is initially charged with 2,4-difluoro-1-nitrobenzene (159 mg, 1 mmol) in anhydrous THF (2 ml). After adding (TMP)2Zn.MgCl2 (3.00 ml, 1.2 mmol) at 25° C., the mixture is stirred for 30 min, then a solution of iodine (381 mg, 1.5 mmol) in anhydrous THF (2 ml) is added dropwise and the mixture is stirred at 25° C. overnight. For workup, the mixture is diluted with aqueous sat. NH4Cl solution (30 ml) and aqueous sat. Na2S2O3 solution (30 ml) and extracted with ethyl acetate (3×30 ml). After the combined organic phases have been dried over Na2SO4, the solvent has been distilled off and purification has been effected by column chromatography on silica gel (heptane:ethyl acetate), the desired compound (210 mg, 74% of theory) was obtained as a colourless crystalline product.

Workup

  1. additionA dry, argon-filled Schlenk tube with a magnetic stirrer bar
  2. additionAfter adding (TMP)2Zn
  3. extractionextracted with ethyl acetate (3×30 ml)
  4. dry with materialAfter the combined organic phases have been dried over Na2SO4
  5. distillationthe solvent has been distilled off
  6. custompurification

Sources & evidence

ORD record
ord-1e41b501b1714f38a57af74cf980f595
Source dataset
uspto-grants-2016_05
Patent number
US09334292B2

Reaction notes

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