Iodine → HCID 57776262, compound

HRID 1094671Notes

Reaction equation

HRID 1094671 reaction equation
[CH3:1][N:2]([CH3:20])[P:3]([O:8][C:9]1[CH:10]=[C:11]([CH:17]=[CH:18][CH:19]=1)[C:12]([O:14][CH2:15][CH3:16])=[O:13])([N:5]([CH3:7])[CH3:6])=[O:4].[I:21]I>C1COCC1>[CH3:20][N:2]([CH3:1])[P:3]([O:8][C:9]1[C:10]([I:21])=[C:11]([CH:17]=[CH:18][CH:19]=1)[C:12]([O:14][CH2:15][CH3:16])=[O:13])([N:5]([CH3:6])[CH3:7])=[O:4]

Participants

4

Reactant 2

HCID 807IodineHCID 329909HCID 329909, compound

Product 1

HCID 57776262HCID 57776262, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A dry and nitrogen-flushed 25-ml Schlenk flask, equipped with a magnetic stirring bar and a septum, was charged ethyl 3-{[bis(dimethylamino)phosphoryl]oxy}benzoate 44 (300 mg, 1.00 mmol) in dry THF (3 ml). After cooling to 0° C., a freshly prepared (TMP)Mg(Bt).2LiCl solution (4.33 ml, 0.3 M in THF, 1.3 mmol) was added dropwise and the reaction mixture was stirred at the same temperature. The completion of the metalation (10 min) was checked by GC-analysis of reaction aliquots quenched with a solution of I2 in dry THF. Iodine (508 mg, 2.0 mmol) dissolved in dry THF (2 ml) was then added at 0° C. and the resulting mixture warmed to room temperature. After stirring for 1 hour, the reaction mixture was quenched with sat. aq. Na2S2O3, extracted with ether (3×20 ml) and dried over Na2SO4. After filtration, the solvent was removed in vacuo. Purification by flash-chromatography using ethyl acetate as eluent furnished ethyl 3-{[bis(dimethylamino)phosphoryl]oxy}-2-iodobenzoate 44a (332 mg, 78%) as a yellow oil.

Workup

  1. customA dry
  2. customnitrogen-flushed 25-ml Schlenk flask
  3. customequipped with a magnetic stirring bar
  4. customThe completion of the metalation (10 min) was checked by GC-analysis of reaction aliquots
  5. customquenched with a solution of I2 in dry THF
  6. additionwas then added at 0° C.
  7. temperaturethe resulting mixture warmed to room temperature
  8. stirringAfter stirring for 1 hour
  9. customthe reaction mixture was quenched with sat. aq. Na2S2O3
  10. extractionextracted with ether (3×20 ml)
  11. dry with materialdried over Na2SO4
  12. filtrationAfter filtration
  13. customthe solvent was removed in vacuo
  14. customPurification by flash-chromatography

Sources & evidence

ORD record
ord-906f897796724eefa3b99219e6bb65f4
Source dataset
uspto-grants-2012_03
Patent number
US08134005B2

Reaction notes

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