Hydrochloric Acid → Hydantoin, 3-allyl-2-thioxo-

HRID 2075296Notes

Reaction equation

HRID 2075296 reaction equation
[NH2:1][CH2:2][C:3]([OH:5])=O.C(N(CC)CC)C.[CH2:13]([N:16]=[C:17]=[S:18])[CH:14]=[CH2:15].Cl>O.N1C=CC=CC=1>[CH2:13]([N:16]1[C:3](=[O:5])[CH2:2][NH:1][C:17]1=[S:18])[CH:14]=[CH2:15]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 750GlycineHCID 5971Allyl IsothiocyanateHCID 8471Triethylamine

Product 1

HCID 3032418Hydantoin, 3-allyl-2-thioxo-Yield 71%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent

Conditions

Temperature
55 °C

Procedure

Glycine (30 g, 0.40 mol), triethylamine (44 g, 0.44 mol), pyridine (100 mL), and water (100 mL) were mixed in a flask equipped with a magnetic stirrer and a temperature controller. Allyl isothiocyanate (44 g, 0.44 mol) was added, and the temperature was raised to 55° C. (the mixture became homogeneous at ca. 30°). When the mixture reached this temperature, it was allowed to cool to room temperature. The mixture was extracted with 3×200 mL of toluene to remove the pyridine and excess isothiocyanate and was then treated with 66 mL (0.8 mol) of concentrated hydrochloric acid. The mixture was heated at 90° C. for 2.5 hr and was then stirred rapidly while it cooled to room temperature. A solid mass of crystals formed instantaneously when the solution was seeded with a fragment of a crystal of authentic product. After the suspension stood at room temperature overnight, the product was collected and pressed with rubber dam. The filter cake was washed with 3×60 mL of water (the filter cake was pressed with rubber dam after each wash). After the material had dried to constant weight in a hood draft, it weighed 49 g (71% yield). NMR (CD3OD) δ 4.9-6.1 (m, 3H), 4.6 (s, 1H), 4.3 (d, 2H), 4.0 (s, 2H). HPLC analysis showed no other components at several wavelengths.

Workup

  1. customequipped with a magnetic stirrer
  2. custombecame homogeneous at ca. 30°
  3. temperatureto cool to room temperature
  4. extractionThe mixture was extracted with 3×200 mL of toluene
  5. customto remove the pyridine and excess isothiocyanate
  6. temperatureThe mixture was heated at 90° C. for 2.5 hr
  7. temperaturecooled to room temperature
  8. customA solid mass of crystals formed instantaneously when the solution
  9. customthe product was collected
  10. washThe filter cake was washed with 3×60 mL of water (the filter cake
  11. washeach wash)
  12. customAfter the material had dried to constant weight in a hood draft, it

Sources & evidence

ORD record
ord-d9eecbb9ce54405c83dbd9ac584a0fb0
Source dataset
uspto-grants-2011_04
Patent number
US07919630B2

Reaction notes

Loading…