Iodine → (4-Iodo-pyridin-3-YL)-carbamic acid tert-butyl ester

HRID 890194Notes

Reaction equation

HRID 890194 reaction equation
[Li+].CCC[CH2-].[N:6]1[CH:11]=[CH:10][CH:9]=[C:8]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[CH:7]=1.CN(C)CCN(C)C.[I:28]I>C(OCC)C.O>[I:28][C:9]1[CH:10]=[CH:11][N:6]=[CH:7][C:8]=1[NH:12][C:13](=[O:19])[O:14][C:15]([CH3:16])([CH3:18])[CH3:17]

Participants

7

Reactant 4

HCID 807IodineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 61028n-Butyl lithiumHCID 109323213-(Boc-amino)pyridine

Product 1

HCID 15366413(4-Iodo-pyridin-3-YL)-carbamic acid tert-butyl esterYield 61.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-20 °C

Procedure

N-Butyllithium (1.6M hexane solution 400 mL, 0.64 mol) was added to a solution of tert-butyl N-(3-pyridyl)carbamate (51.8 g, 0.27 mol) and tetramethylethylenediamine (96.6 mL, 0.64 ml) in diethyl ether (1.5 L) at −78° C., followed by stirring at −20° C. for 2.5 hr. After cooling to −78° C. again, a solution of iodine (94.8 g, 0.37 mol) in diethyl ether (200 mL) was added and stirred for one day while raising a temperature to room temperature. Water was added, extracted with diethyl ether, and the organic layer was washed with hypo-water and brine, dried over anhydrous magnesium sulfate and evaporated. The resulting crystals were washed with hexane, to give the title compound (53.0 g) as white crystals.

Workup

  1. temperatureAfter cooling to −78° C. again
  2. stirringstirred for one day
  3. temperaturewhile raising a temperature to room temperature
  4. extractionextracted with diethyl ether
  5. washthe organic layer was washed with hypo-water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customevaporated
  8. washThe resulting crystals were washed with hexane

Sources & evidence

ORD record
ord-6f676df94e5946cf89a8b5a5e16dccd7
Source dataset
uspto-grants-2006_02
Patent number
US06995163B2

Reaction notes

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