N-bromobutanimide → HCID 86738627, compound

HRID 2198542Notes

Reaction equation

HRID 2198542 reaction equation
BrN1C(=O)CCC1=O.[C:9]([OH:12])(=[O:11])[CH3:10].[C:13]([OH:16])(=[O:15])[CH3:14].[C:17]([OH:20])(=[O:19])[CH3:18].[F:21][C:22]([F:56])([F:55])[C:23](O)([CH2:28][CH2:29][CH2:30][C@H:31]([C@@H:33]1[C@:51]2([CH3:52])[C@H:36]([C@H:37]3[C@H:48]([CH2:49][CH2:50]2)[C@:46]2([CH3:47])[C:40]([CH2:41][C@H:42]([CH2:44][C@@H:45]2O)O)=[CH:39][CH2:38]3)[CH2:35][CH2:34]1)[CH3:32])[C:24]([F:27])([F:26])[F:25]>C(Cl)(Cl)(Cl)Cl>[F:21][C:22]([F:55])([F:56])[C:23]([O:19][C:17](=[O:20])[CH3:18])([CH2:28][CH2:29][CH2:30][C@H:31]([C@@H:33]1[C@:51]2([CH3:52])[C@H:36]([C:37]3[C@H:48]([CH2:49][CH2:50]2)[C@:46]2([CH3:47])[C:40]([CH2:41][C@@H:42]([O:15][C:13](=[O:16])[CH3:14])[CH2:44][C@@H:45]2[O:11][C:9](=[O:12])[CH3:10])=[CH:39][CH:38]=3)[CH2:35][CH2:34]1)[CH3:32])[C:24]([F:25])([F:27])[F:26]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 86738626HCID 86738626, compound

Product 1

HCID 86738627HCID 86738627, compoundYield 27.3%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

N-bromosuccinimide (14 mg) was added to a refluxing solution of 35 mg of triacetate (6) in 2 ml of CCl4 and the reaction mixture was refluxed further under argon atmosphere. After cooling in an ice-water bath, the resulting precipitate was filtered off. The filtrate was evaporated to dryness below 40° C. The residue is xylene (1 ml) was added dropwise to a refluxing solution of xylene (1.5 ml) and s-collidine (0.5 ml) and refluxing was continued under argon atmosphere for 20 min. The reaction mixture was extracted with AcOEt, washed with 2 N-HCl, sat. NaHCO3, brine and the solution was dried over MgSO4. After removal of the solvent, the residue was treated with a catalytic amount of pTsOH in acetone (10 ml) at room temperature for 16 hr under argon in the dark. The mixture was extracted with AcOEt and the extract was washed with sat. NaHCO3 and brine, and then dried over MgSO4. Removal of the solvent gave a crude 5,7-diene, which was purified by preparative TLC developed twice with a solvent of n-hexane-AcOEt (10:1). The band of Rf value 0.26 was scraped off and eluted with AcOEt. Removal of the solvent gave 8.8 mg (25%) of the product (7); UV(EtOH)λmax, 294, 282, 272 nm.

Workup

  1. temperaturethe reaction mixture was refluxed further under argon atmosphere
  2. temperatureAfter cooling in an ice-water bath
  3. filtrationthe resulting precipitate was filtered off
  4. customThe filtrate was evaporated to dryness below 40° C
  5. additionwas added dropwise to a refluxing solution of xylene (1.5 ml) and s-collidine (0.5 ml)
  6. temperaturerefluxing
  7. extractionThe reaction mixture was extracted with AcOEt
  8. washwashed with 2 N-HCl, sat. NaHCO3, brine
  9. dry with materialthe solution was dried over MgSO4
  10. customAfter removal of the solvent
  11. additionthe residue was treated with a catalytic amount of pTsOH in acetone (10 ml) at room temperature for 16 hr under argon in the dark
  12. extractionThe mixture was extracted with AcOEt
  13. washthe extract was washed with sat. NaHCO3 and brine
  14. dry with materialdried over MgSO4
  15. customRemoval of the solvent
  16. customgave a crude 5,7-diene, which
  17. customwas purified by preparative TLC
  18. washeluted with AcOEt
  19. customRemoval of the solvent

Sources & evidence

ORD record
ord-6961f89132b849509a9da39e147e538f
Source dataset
uspto-grants-1982_11
Patent number
US04358406

Reaction notes

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