Azobisisobutyronitrile → HCID 20369550, compound

HRID 616302Notes

Reaction equation

HRID 616302 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH:25]([CH3:27])[CH3:26])[CH2:9][O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH:13]=2)=[CH:4][CH:3]=1.BrN1C(=O)C[CH2:31][C:30]1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.[Cl-].[NH4+]>C(Cl)(Cl)(Cl)Cl.O1CCCC1.O.CCOCC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]([CH:25]([CH3:27])[CH3:26])[CH2:9][O:10][CH:11]([C:30]#[CH:31])[C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH:13]=2)=[CH:6][CH:7]=1

Participants

9

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 25517Ammonium ChlorideHCID 67184N-bromobutanimideHCID 21604654HCID 21604654, compound

Product 1

HCID 20369550HCID 20369550, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

3.8 g of 3-phenoxybenzyl 2-(4-chlorophenyl)-2-isopropylethyl ether, 1.8 g of N-bromosuccinimide and a few crystals of azo-bis-isobutyronitrile were stirred under reflux in 80 ml of carbon tetrachloride for 30 minutes. The mixture was cooled in an ice-bath, filtered and the solvent removed to give a pale orange oil. A solution of the oil in 10 ml of tetrahydrofuran was added over a 20 minute period to a solution of an acetylenic Grignard reagent (prepared by saturating a solution of 2.3 g of ethyl bromide and 0.5 g of magnesium in 35 ml of tetrahydrofuran with acetylene at 15° C) whilst bubbling a slow stream of acetylene through the mixture. The stirring was continued overnight at room temperature under a stream of nitrogen. The black reaction mixture was warmed to 70° C for 30 minutes, cooled and a saturated solution of 20 ml of ammonium chloride added, followed by ether and water. The mixture was filtered through a "Celite" bed to remove the black solid and the organic layer separated, washed successively with ammonium chloride, sodium bicarbonate, sodium hydroxide and dried (MgSO4). Removal of the solvent gave a dark brown oil which was purified by chromatography on silica gel using 1:1 toluene: petroleum ether 60°-80° C as eluent, to give 2.

Workup

  1. temperatureThe mixture was cooled in an ice-bath
  2. filtrationfiltered
  3. customthe solvent removed
  4. customto give a pale orange oil
  5. customprepared
  6. concentrationby saturating a solution of 2.3 g of ethyl bromide and 0.5 g of magnesium in 35 ml of tetrahydrofuran with acetylene at 15° C)
  7. customwhilst bubbling a slow stream of acetylene through the mixture
  8. customThe black reaction mixture
  9. temperaturecooled
  10. filtrationThe mixture was filtered through a "Celite" bed
  11. customto remove the black solid
  12. customthe organic layer separated
  13. washwashed successively with ammonium chloride, sodium bicarbonate, sodium hydroxide
  14. dry with materialdried (MgSO4)
  15. customRemoval of the solvent
  16. customgave a dark brown oil which
  17. customwas purified by chromatography on silica gel using 1:1 toluene
  18. custompetroleum ether 60°-80° C as eluent, to give 2

Sources & evidence

ORD record
ord-decee20e9f5e47f4b08cc9b298eed333
Source dataset
uspto-grants-1978_02
Patent number
US04073812

Reaction notes

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