1,3-Dibromo-5,5-dimethylhydantoin → HCID 54401871, compound

HRID 596568Notes

Reaction equation

HRID 596568 reaction equation
[C:1]([O:4][C@@H:5]1[C@@:29]2([CH3:30])[C:9](=[CH:10][CH2:11][C@@H:12]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:31])[C@H:13]3[CH2:14][CH2:15][C@@H:16]2[C@H:17]([CH3:24])[CH2:18][CH2:19][CH2:20][CH:21]([CH3:23])[CH3:22])[CH2:8][C@@H:7]([O:32][C:33](=[O:35])[CH3:34])[C@@H:6]1[O:36][C:37](=[O:39])[CH3:38])(=[O:3])[CH3:2].BrN1C(C)(C)C(=O)N(Br)C1=O>C1C=CC=CC=1>[C:1]([O:4][C@@H:5]1[C@@:29]2([CH3:30])[C:9](=[CH:10][CH:11]=[C:12]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:31])[C@H:13]3[CH2:14][CH2:15][C@@H:16]2[C@H:17]([CH3:24])[CH2:18][CH2:19][CH2:20][CH:21]([CH3:23])[CH3:22])[CH2:8][C@@H:7]([O:32][C:33](=[O:35])[CH3:34])[C@@H:6]1[O:36][C:37](=[O:39])[CH3:38])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 13178929HCID 13178929, compound

Product 1

HCID 54401871HCID 54401871, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
70 °C

Procedure

1α,2α,3β-Triacetoxy-cholesta-5-ene (300 mg) was dissolved in a mixture of petroleum benzine (5 ml) and benzene (5 ml). To the solution was added 1,3-dibromo-5,5-dimethyl hydantoin (95 mg) and the resulting solution was heated on water bath at 70° C for 20 minutes. After cooling the solution, precipitated crystals was filtrated off and the filtrate was concentrated under reduced pressure to dryness. The resulting bromide (3 ml) as crude product was dissolved in xylene. A mixture of trimethyl phosphite (1 ml) and xylene (3 ml) was added dropwise to the solution while refluxing it mildly in an argon stream. After continuously refluxing for 2 hours, the solvent was distilled off. The resulting 1α,2α,3β-triacetoxy-cholesta-5,7-diene was dissolved in diethyl ether (10 ml) and to the solution was added slowly 4-phenyl-1,2,4-triazoline-3,5-dione. About 25 mg of triazoline was required. After continuously stirring the mixture for 1 hour, diethyl ether was distilled off and then the residue was subjected to column chromatography with the use of alumina column and a solvent (diethyl ether : hexane = 1 : 1) to obtain 1,4-addition product of 1α,2α,3β-triacetoxy-cholesta-5,7-diene as oil represented by the formula ##STR6## wherein Ac is an acetyl.

Workup

  1. temperatureAfter cooling the solution
  2. customprecipitated crystals
  3. filtrationwas filtrated off
  4. concentrationthe filtrate was concentrated under reduced pressure to dryness
  5. dissolutionThe resulting bromide (3 ml) as crude product was dissolved in xylene
  6. additionA mixture of trimethyl phosphite (1 ml) and xylene (3 ml)
  7. additionwas added dropwise to the solution
  8. temperaturewhile refluxing it mildly in an argon stream
  9. temperatureAfter continuously refluxing for 2 hours
  10. distillationthe solvent was distilled off
  11. dissolutionThe resulting 1α,2α,3β-triacetoxy-cholesta-5,7-diene was dissolved in diethyl ether (10 ml) and to the solution
  12. additionwas added slowly 4-phenyl-1,2,4-triazoline-3,5-dione
  13. distillationdiethyl ether was distilled off

Sources & evidence

ORD record
ord-c4336767cba844689fe19779d0294297
Source dataset
uspto-grants-1977_03
Patent number
US04011250

Reaction notes

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