Phenyl isocyanate → HCID 67928930, compound

HRID 982282Notes

Reaction equation

HRID 982282 reaction equation
[C:1]1([N:7]=[C:8]=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:10]([C:14]1[CH:19]=[CH:18][C:17]([C:20]2[O:21][CH:22]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH:23]([OH:26])[CH2:24][N:25]=2)=[CH:16][CH:15]=1)([CH3:13])([CH3:12])[CH3:11]>O1CCCC1>[C:10]([C:14]1[CH:15]=[CH:16][C:17]([C:20]2[O:21][CH:22]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH:23]([O:26][C:8](=[O:9])[NH:7][C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[CH2:24][N:25]=2)=[CH:18][CH:19]=1)([CH3:13])([CH3:11])[CH3:12]

Participants

4

Reactant 2

HCID 7672Phenyl isocyanateHCID 67928885HCID 67928885, compound

Product 1

HCID 67928930HCID 67928930, compoundYield 31.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Phenyl isocyanate (2 g) is added at a temperature in the region of 20° C. to a solution, maintained under an argon atmosphere, of (5RS, 6SR)-2-(4-tert-butylphenyl)-6-phenyl-5,6-dihydro-4H-1,3-oxazin-5-ol (3.2 g) in anhydrous tetrahydrofuran (35 cc). The solution obtained is heated to 50° C. for 5 hours and then concentrated to dryness under reduced pressure (2.7 kPa). The solid obtained is purified by chromatography on silica (0.063-0.2 mm; 200 g) contained in a column 3.5 cm in diameter, collecting 20-cc fractions. Fractions 22 to 29, eluted with a mixture of cyclohexane and ethyl acetate (7:3 by volume), are concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. The solid obtained is again purified by chromatography on silica (0.063-0.2 mm; 200 g) contained in a column 2.5 cm in diameter, collecting 10-cc fractions. Fractions 19 to 25, eluted with a mixture of dichloromethane and methanol (98:2 by volume), are concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. After recrystallization in ethyl acetate, (5RS, 6SR)-2-(4-tert-butylphenyl)-6-phenyl-5-phenylcarbamoyloxy-5,6-dihydro-4H-1,3-oxazine (1.4 g), m.p. 80° C., is obtained.

Workup

  1. customThe solution obtained
  2. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  3. customThe solid obtained
  4. customis purified by chromatography on silica (0.063-0.2 mm; 200 g)
  5. customcollecting 20-cc fractions
  6. washFractions 22 to 29, eluted with a mixture of cyclohexane and ethyl acetate (7:3 by volume)
  7. concentrationare concentrated to dryness under reduced pressure (2.7 kPa) at 40° C
  8. customThe solid obtained
  9. customis again purified by chromatography on silica (0.063-0.2 mm; 200 g)
  10. customcollecting 10-cc fractions
  11. washFractions 19 to 25, eluted with a mixture of dichloromethane and methanol (98:2 by volume)
  12. concentrationare concentrated to dryness under reduced pressure (2.7 kPa) at 40° C
  13. customAfter recrystallization in ethyl acetate

Sources & evidence

ORD record
ord-9398242f42cc42ee968d61ffdc5da6bc
Source dataset
uspto-grants-1991_02
Patent number
US04994569

Reaction notes

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