Water → HCID 178440841, compound

HRID 915720Notes

Reaction equation

HRID 915720 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].[H-].[H-].[H-].[H-].[Li+].[Al+3].[Br:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16](=O)[CH2:17][C-:18]1[C:22]([C:23]([CH3:26])([CH3:25])[CH3:24])=[C:21]([C:27]([CH3:30])([CH3:29])[CH3:28])[C:20]([C:31]([CH3:34])([CH3:33])[CH3:32])=[C:19]1[C:35]([CH3:38])([CH3:37])[CH3:36].[CH-:40]1[CH:44]=[CH:43][CH:42]=[CH:41]1.[Fe+2:45].O>CCOCC.CCCCCC>[Br:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C-:18]1[C:19]([C:35]([CH3:36])([CH3:37])[CH3:38])=[C:20]([C:31]([CH3:34])([CH3:33])[CH3:32])[C:21]([C:27]([CH3:30])([CH3:29])[CH3:28])=[C:22]1[C:23]([CH3:26])([CH3:25])[CH3:24].[CH-:40]1[CH:44]=[CH:43][CH:42]=[CH:41]1.[Fe+2:45]

Participants

7

Reactant 4

HCID 962WaterHCID 6451240Aluminum(III) ChlorideHCID 21226445Aluminium lithium hydrideHCID 178440842HCID 178440842, compound

Product 1

HCID 178440841HCID 178440841, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

First, 2.27 g (17.02 mmol) of AlCl3 was dissolved in 200 ml of dry Et2O in a Schlenk flask under controlled, positive nitrogen pressure. Second, the solution was cooled to 0 degrees centigrade and 17.0 g (17.0 mmol) of 1.0M LiAlH4 was charged into the flask via syringe. The resulting suspension was warmed to room temperature and agitated for approximately 15 minutes. Next, 10.00 g (17.02 mmol) of the above prepared 6-bromo-1-(tetra-tert-butylferrocenyl)-2-hexanone was slowly added to the suspension. Once the addition of the ketonic product was complete, the solution was heated to reflux for approximately 3 hours, after which time the solution was cooled to room temperature. The reaction was then quenched by slowly adding H2O to the solution. When no further exothermic reaction was observed, 250 ml of H2O was added to dilute the solution. The solution was then transferred to a separatory funnel, whereupon the organic layer was collected and the aqueous layer was extracted with 100 ml of Et2O. The organic portions were combined and then washed with NaHCO3 and brine. Next, the solution was dried over MgSO4. The solution was then decanted from the drying agent and filtered. Next, the solvent was removed via rotary evaporation yielding a yellow-orange oil. The oil was dissolved in a small amount of hexane, applied to a vacuum assisted gel column, and eluted with more hexane. Upon solvent removal, 8.73 g of 6-bromo-1-(tetra-tert-butylferrocenyl)hexane was isolated as a yellow-orange solid.

Workup

  1. temperatureSecond, the solution was cooled to 0 degrees centigrade
  2. additionwas slowly added to the suspension
  3. additionOnce the addition of the ketonic product
  4. temperaturethe solution was heated
  5. temperatureto reflux for approximately 3 hours
  6. temperatureafter which time the solution was cooled to room temperature
  7. customThe reaction was then quenched by slowly adding H2O to the solution
  8. customWhen no further exothermic reaction
  9. additionto dilute the solution
  10. customThe solution was then transferred to a separatory funnel, whereupon the organic layer
  11. customwas collected
  12. extractionthe aqueous layer was extracted with 100 ml of Et2O
  13. washwashed with NaHCO3 and brine
  14. dry with materialNext, the solution was dried over MgSO4
  15. customThe solution was then decanted from the drying agent
  16. filtrationfiltered
  17. customNext, the solvent was removed via rotary evaporation
  18. customyielding a yellow-orange oil
  19. washeluted with more hexane
  20. customUpon solvent removal

Sources & evidence

ORD record
ord-31693b383171496eabe780b94dffecd9
Source dataset
uspto-grants-2007_09
Patent number
US07265888B2

Reaction notes

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