Iodine → HCID 9904119, compound

HRID 1595278Notes

Reaction equation

HRID 1595278 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:11](=[O:17])[O:12][CH2:13][CH:14]([CH3:16])[CH3:15])=[CH:6][CH:5]=1)(=O)[CH3:2].[NH2:18][C:19]([NH2:21])=[S:20].II>C(O)(C)C.CCOC(C)=O>[NH2:21][C:19]1[S:20][CH:2]=[C:1]([C:4]2[CH:9]=[CH:8][C:7]([NH:10][C:11](=[O:17])[O:12][CH2:13][CH:14]([CH3:16])[CH3:15])=[CH:6][CH:5]=2)[N:18]=1

Participants

6

Reactant 3

HCID 807IodineHCID 2723790ThioureaHCID 12553762HCID 12553762, compound

Product 1

HCID 9904119HCID 9904119, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the product of the preceding section (a) (19 g, 80.75 mmol) in isopropanol (120 mL) was added thiourea (24.6 g, 323 mmol) and iodine (20.5 g, 161.5 mmol). The resulting mixture was heated at reflux for 7 h, then diluted with EtOAc, washed serially with H2O and saturated aqueous NaHCO3. The resulting solution was then treated with 4N aqueous HCl and Et2O and stirred vigorously. The precipitate was filtered and washed with Et2O. The collected solid was then treated with saturated aqueous NaHCO3 and extracted serially with EtOAc and CH2Cl2. The combined organic extracts were washed with H2O and brine, then dried (MgSO4) and concentrated under reduced pressure to yield 2-methylpropyl N-{4-(2-amino-4-thiazolyl)-phenyl}carbamate (12 g, 51% yield) as a pale yellow solid: 1H NMR (400 MHz, DMSO-d6) δ9.63 (s, 1H), 7.70 (d, 2H, J=8.9 Hz), 7.46 (d, 2H, J=8.7 Hz), 6.99 (s, 2H), 6.84 (s, 1H), 3.88 (d, 2H, J=6.9 Hz), 1.95 (m, 1H), 0.99 (d, 6H, J=6.9 Hz); MS (FAB) m/z 292 (MH)+. This product was used as such in the next reaction (section (c)).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 7 h
  3. washwashed serially with H2O and saturated aqueous NaHCO3
  4. additionThe resulting solution was then treated with 4N aqueous HCl and Et2O
  5. filtrationThe precipitate was filtered
  6. washwashed with Et2O
  7. additionThe collected solid was then treated with saturated aqueous NaHCO3
  8. extractionextracted serially with EtOAc and CH2Cl2
  9. washThe combined organic extracts were washed with H2O and brine
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-12325b1053b34f26b454f1a5138c93a7
Source dataset
uspto-grants-2001_09
Patent number
US06288091B1

Reaction notes

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