Iodine → 5-Bromo-1,3-diethyl-2-iodobenzene

HRID 735603

Reaction equation

HRID 735603 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([CH2:9][CH3:10])[C:5](N)=[C:4]([CH2:11][CH3:12])[CH:3]=1.[I:13]I.C(ON=O)(C)(C)C.[O-]S([O-])=O.[Na+].[Na+]>C(#N)C>[Br:1][C:2]1[CH:8]=[C:7]([CH2:9][CH3:10])[C:5]([I:13])=[C:4]([CH2:11][CH3:12])[CH:3]=1

Participants

6

Reactant 4

HCID 807IodineHCID 10906Tert-Butyl nitriteHCID 24437Sodium SulfiteHCID 6114524-Bromo-2,6-diethylaniline

Product 1

HCID 448911015-Bromo-1,3-diethyl-2-iodobenzeneYield 13%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

A solution of 4-bromo-2,6-diethylaniline (10 g, 44 mmol) in acetonitrile (20 mL) was added dropwise to a solution of I2 (33.4 g, 131.6 mmol), tert-butylnitrite (7.4 mL, 65.8 mmol) in acetonitrile (80 mL), never allowing the internal temperature to exceed 30° C. After stirring 4 h at ambient temperature, Na2SO3 (100 mL, saturated aqueous) was added and stirred for 1 h. The mixture was extracted with hexanes (3×200 mL). The organics were combined, washed with brine, dried over Na2SO4 and concentrated. The crude oil was purified by flash chromatography (100% hexanes) to afford 37A (1.9 g, 13%) as a red oil. 1H NMR (400 MHz, CDCl3) δ ppm 1.20 (t, J=7.45 Hz, 6 H) 2.77 (q, J=7.58 Hz, 4 H) 7.18 (s, 2 H).

Workup

  1. customto exceed 30° C
  2. stirringstirred for 1 h
  3. extractionThe mixture was extracted with hexanes (3×200 mL)
  4. washwashed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe crude oil was purified by flash chromatography (100% hexanes)

Sources & evidence

ORD record
ord-a56b6e009e0a4f4cb338fe58ef63f838
Source dataset
uspto-grants-2009_09
Patent number
US07592331B2

Linked notes

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