Potassium Iodide → 5-Bromo-2-cyclopropyliodobenzene

HRID 40476

Reaction equation

HRID 40476 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:9]2[CH2:11][CH2:10]2)=[C:6]([CH:8]=1)N.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.N([O-])=O.[Na+].[I-:28].[K+].C(=O)(O)[O-].[Na+].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>C(#N)C.O.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:9]2[CH2:11][CH2:10]2)=[C:6]([I:28])[CH:8]=1

Participants

10

Reactant 6

HCID 4875Potassium IodideHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 656671Sodium PyrosulfiteHCID 47122485-Bromo-2-cyclopropylanilineHCID 23668193Sodium Nitrite

Product 1

HCID 580615715-Bromo-2-cyclopropyliodobenzene

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-Bromo-2-cyclopropylaniline (4.74 g) is added to a solution of para-toluene sulfonic acid monohydrate (12.2 g, 0.064 mol) in acetonitrile (130 ml), followed by stirring for 10 minutes at room temperature. The suspension is then cooled to 10° C. and a mixed solution of sodium nitrite (8.9 g, 0.054 mol) and potassium iodide (3.1 g, 0.044 mol) in water (16 ml) is added dropwise over 30 minutes. Once the addition is complete the reaction mixture is allowed to stir at 10° C. for 20 minutes and then at room temperature for 4 hours. The reaction mixture is basified to pH 9-10 with aqueous sodium bicarbonate, followed by addition of ethyl acetate and 10% aqueous sodium metabisulphite. The phases are separated and the aqueous layer is extracted again with ethyl acetate (×2). Organics are combined, washed with brine, dried over magnesium sulfate then concentrated in vacuo to give the crude product which is purified by flash column chromatography on silica gel (isohexane eluant) to afford 5-bromo-2-cyclopropyliodobenzene as a colourless oil.

Workup

  1. temperatureThe suspension is then cooled to 10° C.
  2. additionOnce the addition
  3. stirringto stir at 10° C. for 20 minutes
  4. waitat room temperature for 4 hours
  5. customThe phases are separated
  6. extractionthe aqueous layer is extracted again with ethyl acetate (×2)
  7. washwashed with brine
  8. dry with materialdried over magnesium sulfate
  9. concentrationthen concentrated in vacuo
  10. customto give the crude product which
  11. customis purified by flash column chromatography on silica gel (isohexane eluant)

Sources & evidence

ORD record
ord-dca1166a6f994406a6bc161350a955b5
Source dataset
uspto-grants-2013_09
Patent number
US08530388B2

Linked notes

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