Ammonium Chloride → 1-Chloro-4-iodo-2-vinylbenzene

HRID 602059Notes

Reaction equation

HRID 602059 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[K+].[Cl:11][C:12]1[CH:19]=[CH:18][C:17]([I:20])=[CH:16][C:13]=1[CH:14]=O.[NH4+].[Cl-]>C1COCC1>[Cl:11][C:12]1[CH:19]=[CH:18][C:17]([I:20])=[CH:16][C:13]=1[CH:14]=[CH2:1]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 221152692-Chloro-5-iodobenzaldehyde

Product 1

HCID 574706061-Chloro-4-iodo-2-vinylbenzeneYield 73.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Ph3PMeBr (9.10 g, 25.47 mmol) was added to anhydrous THF (34 mL) under N2 and then cooled to −78° C. KHMDS (1 M solution, 25.47 mL, 25.47 mmol) was slowly added to the solution and the resultant solution was stirred at −78° C. for 1 h. 2-chloro-5-iodobenzaldehyde (4.86 g, 22.14 mmol) in THF (10 mL) was then slowly added and the resultant solution allowed to warm slowly to room temperature overnight. After 16 h, saturated aqueous NH4Cl was added and the crude product extracted with EtOAc (3×). The combined organic extracts were dried (Na2SO4), concentrated, and purified by Biotage chromatography (0%-20% EtOAc/hexanes) to afford 4.32 g of product as an oil that solidifies (90%). 1H NMR (400 MHz, chloroform-d) δ ppm 7.87 (d, J=2.27 Hz, 1 H) 7.50 (dd, J=8.34, 2.27 Hz, 1 H) 7.09 (d, J=8.34 Hz, 1 H) 6.99 (dd, J=17.56, 10.99 Hz, 1 H) 5.74 (d, J=17.43 Hz, 1 H) 5.43 (d, J=11.12 Hz, 1 H).

Workup

  1. temperatureto warm slowly to room temperature overnight
  2. extractionthe crude product extracted with EtOAc (3×)
  3. dry with materialThe combined organic extracts were dried (Na2SO4)
  4. concentrationconcentrated
  5. custompurified by Biotage chromatography (0%-20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-59ba57e0f4e24ab2b56e33c4ec965aea
Source dataset
uspto-grants-2011_03
Patent number
US07902394B2

Reaction notes

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