Iodine chloride → TERT-BUTYL 2-IODOTHIOPHEN-3-YLCARBAMATE

HRID 2098172Notes

Reaction equation

HRID 2098172 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:13]=[CH:12][S:11][CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC([O-])=O.[Na+].[I:19]Cl>C(O)(=O)C>[I:19][C:10]1[S:11][CH:12]=[CH:13][C:9]=1[NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7]

Participants

5

Reactant 3

HCID 24640Iodine chlorideHCID 517045Sodium AcetateHCID 736476tert-Butyl thiophen-3-ylcarbamate

Product 1

HCID 11034707TERT-BUTYL 2-IODOTHIOPHEN-3-YLCARBAMATEYield 81%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

A vial was charged with 199 mg (1.0 mmol) 3-(tert-butoxycarbonylamino)thiophene, 164 mg (2.0 mmol) NaOAc, 4.0 mL HOAc, and a stir bar. The mixture was stirred at room temperature, giving a homogeneous solution “A”. A second vial was charged with 162 mg (1.0 mmol) iodine monochloride and 2.0 mL glacial acetic acid. The second mixture was swirled at room temperature. This second homogeneous solution “B” was added to solution “A” dropwise over three minutes. A white solid began to precipitate immediately. After the addition, the mixture was allowed to stand overnight, at which time the white solid had separated from the brown supernatant. With stirring, 200 uL sat. Na2S2O3/H2O was added, decolorizing the mixture from brown to yellow. 10 mL water was added, and then the mixture was evaporated, affording a semi-solid light brown residue. The residue was partitioned between EtOAc and H2O, and the separated EtOAc phase was washed (sat. NaHCO3, then sat. NaCl). The EtOAc phase was filtered, and concentrated to give 262 mg (81%) of the title compound as light brown crystals. 1H NMR (CDCl3, 300 MHz) δ 7.49 (bs, 1H), 7.45 (d, J=5.4 Hz, 1H), 6.50 (bs, 1H), 1.54 (s, 9H). Method [5]: rt=1.40 min; m/z=269.9 (MH+ minus isobutylene).

Workup

  1. customgiving a homogeneous solution “A”
  2. customwas swirled at room temperature
  3. additionThis second homogeneous solution “B” was added to solution “A” dropwise over three minutes
  4. customto precipitate immediately
  5. additionAfter the addition
  6. customthe white solid had separated from the brown supernatant
  7. stirringWith stirring
  8. addition200 uL sat. Na2S2O3/H2O was added
  9. addition10 mL water was added
  10. customthe mixture was evaporated
  11. customaffording a semi-solid light brown residue
  12. customThe residue was partitioned between EtOAc and H2O
  13. washthe separated EtOAc phase was washed (sat. NaHCO3
  14. filtrationThe EtOAc phase was filtered
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-7b66c6dd736c4db1a3c20877c741e119
Source dataset
uspto-grants-2013_05
Patent number
US08450363B2

Reaction notes

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