Iodine → HCID 44544524, compound

HRID 2387287Notes

Reaction equation

HRID 2387287 reaction equation
[C:1]([O:5][C:6](=[O:17])[NH:7][C:8]1[CH:9]=[N:10][C:11]([S:14][CH2:15][CH3:16])=[CH:12][CH:13]=1)([CH3:4])([CH3:3])[CH3:2].CN(C)CCN(C)C.C([Li])CCC.[I:31]I>C(OCC)C>[C:1]([O:5][C:6](=[O:17])[NH:7][C:8]1[CH:9]=[N:10][C:11]([S:14][CH2:15][CH3:16])=[CH:12][C:13]=1[I:31])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 807IodineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 44544523HCID 44544523, compoundHCID 178418339Butyllithium

Product 1

HCID 44544524HCID 44544524, compoundYield 67.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-78 °C

Procedure

To (6-ethylsulfanylpyridin-3-yl)carbamic acid tert-butyl ester (27.6 g; 0.108 mol) and N,N,N′,N′-tetramethylethylenediamine (27 mL; 0.180 mol) in 300 mL diethyl ether at −78° C. was added dropwise n-butyllithium (100 mL of a 2.5 M solution in hexanes; 0.25 mol). The mixture was stirred mechanically for 15 minutes, warmed to 0° C.-5° C., stirred for 3 hours, cooled to −78° C. and iodine (60.6 g; 0.239 mol) in 300 mL of diethyl ether was added dropwise. The mixture was slowly warmed to room temperature, stirred overnight, and quenched with aqueous ammonium chloride and diethyl ether. The organic layer was washed with aqueous sodium metabisulfite, water, and brine, and dried over magnesium sulfate (MgSO4). Removal of the volatiles in vacuo provided a residue which was purified by CombiFlash chromatography using ethyl acetate and hexanes as the eluent. The product-rich fractions were concentrated in vacuo to provide (6-ethylsulfanyl-4-iodopyridin-3-yl)carbamic acid tert-butyl ester (27.7 g; 67%), MS (ES+) m/z 381 [M+H]+.

Workup

  1. temperaturewarmed to 0° C.-5° C.
  2. stirringstirred for 3 hours
  3. temperatureThe mixture was slowly warmed to room temperature
  4. stirringstirred overnight
  5. customquenched with aqueous ammonium chloride and diethyl ether
  6. washThe organic layer was washed with aqueous sodium metabisulfite, water, and brine
  7. dry with materialdried over magnesium sulfate (MgSO4)
  8. customRemoval of the volatiles in vacuo
  9. customprovided a residue which
  10. customwas purified by CombiFlash chromatography
  11. concentrationThe product-rich fractions were concentrated in vacuo

Sources & evidence

ORD record
ord-f4de69e5fcda446e9a31616d57f157da
Source dataset
uspto-grants-2012_09
Patent number
US08268859B2

Reaction notes

Loading…