Iodine → HCID 24938885, compound

HRID 1989845Notes

Reaction equation

HRID 1989845 reaction equation
[NH2:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[C:3]=1[CH3:9].C(=O)([O-])[O-].[Na+].[Na+].[I:16]I.S([O-])([O-])=O.[Na+].[Na+].S([O-])([O-])=O>C1COCC1.CO>[NH2:1][C:2]1[CH2:7][CH2:6][CH:5]([I:16])[C:4](=[O:8])[C:3]=1[CH3:9]

Participants

8

Reactant 5

HCID 807Iodine2×HCID 1099Sulfite2×HCID 10340Sodium CarbonateHCID 24437Sodium Sulfite2×HCID 14791419HCID 14791419, compound

Product 1

HCID 24938885HCID 24938885, compoundYield 65%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
10 °C

Procedure

50 g (0.4 mol, 1 eq) of 3-amino-2-methyl-2-cyclohexen-1-one and 106 g (1 ml, 2.5 eq) of sodium carbonate are dispensed into the reactor. 480 mL of MeOH is added. The mixture is cooled in an ice bath to 10° C. A solution of iodine in THF, made by dissolving 253 g (1 mol, 2.5 eq) of iodine in 300 ml of THF, is added to above suspension slowly so that the temperature does not exceed 25° C. The resulting dark suspension is stirred for ˜1 h at room temperature and HPLC shows the ending point of reaction (product area percentage at 265 nm was larger than 70%). To the reaction mixture in the ice bath, is added an aqueous saturated solution of sodium sulfite slowly, until the peroxide level is below 3 ppm (by peroxide test strips), and at same time, the sulfite level is below 50 ppm (by sulfite test strips). Approximately 1.5 q of sodium sulfite is used. The suspension is filtered through a celite pad and the pad is washed with 150 mL×3 of THF (washings not optimized). The combined filtrate and washes are concentrated under vacuum until solid crashes out. 250 mL of MTBE is added and the two layer mixture is concentrated again under vacuum until all upper layer evaporates. 250 mL of MTBE and 100 mL of H2O are added and the mixture is stirred at room temperature for 30 minutes. A dark yellow solid crashes out upon stirring and is filtered and washed with water to give 3-amino-6-iodo-2-methyl-2-cyclohexen-1-one 65 g (65% yield).

Workup

  1. additionis added to above suspension slowly so that the temperature
  2. customdoes not exceed 25° C
  3. customthe ending point of reaction (product area percentage at 265 nm was larger than 70%)
  4. filtrationThe suspension is filtered through a celite pad
  5. washthe pad is washed with 150 mL×3 of THF (washings not optimized)
  6. concentrationThe combined filtrate and washes are concentrated under vacuum until solid crashes out
  7. addition250 mL of MTBE is added
  8. concentrationthe two layer mixture is concentrated again under vacuum until all upper layer
  9. customevaporates
  10. addition250 mL of MTBE and 100 mL of H2O are added
  11. stirringthe mixture is stirred at room temperature for 30 minutes
  12. stirringA dark yellow solid crashes out upon stirring
  13. filtrationis filtered
  14. washwashed with water

Sources & evidence

ORD record
ord-cd5646c256194fcba7493585ad046eec
Source dataset
uspto-grants-2010_01
Patent number
US07642381B2

Reaction notes

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