Water → HCID 178440841, compound

HRID 1582494Notes

Reaction equation

HRID 1582494 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].[Br:5][CH2:6][CH2:7][CH2:8][CH2:9][C:10](=O)[CH2:11][C-:12]1[C:16]([C:17]([CH3:20])([CH3:19])[CH3:18])=[C:15]([C:21]([CH3:24])([CH3:23])[CH3:22])[C:14]([C:25]([CH3:28])([CH3:27])[CH3:26])=[C:13]1[C:29]([CH3:32])([CH3:31])[CH3:30].[CH-:34]1[CH:38]=[CH:37][CH:36]=[CH:35]1.[Fe+2:39].O>CCOCC.CCCCCC>[Br:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C-:12]1[C:13]([C:29]([CH3:30])([CH3:31])[CH3:32])=[C:14]([C:25]([CH3:28])([CH3:27])[CH3:26])[C:15]([C:21]([CH3:24])([CH3:23])[CH3:22])=[C:16]1[C:17]([CH3:20])([CH3:19])[CH3:18].[CH-:34]1[CH:38]=[CH:37][CH:36]=[CH:35]1.[Fe+2:39]

Participants

6

Reactant 3

HCID 962WaterHCID 6451240Aluminum(III) ChlorideHCID 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 10 M 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 MgSO. 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. addition17.0 g (17.0 mmol) of 10 M LIAlH4 was charged into the flask via syringe
  3. additionwas slowly added to the suspension
  4. additionOnce the addition of the ketonic product
  5. temperaturethe solution was heated
  6. temperatureto reflux for approximately 3 hours
  7. temperatureafter which time the solution was cooled to room temperature
  8. customThe reaction was then quenched by slowly adding H2O to the solution
  9. customWhen no further exothermic reaction
  10. additionto dilute the solution
  11. customThe solution was then transferred to a separatory funnel, whereupon the organic layer
  12. customwas collected
  13. extractionthe aqueous layer was extracted with 100 ml of Et2O
  14. washwashed with NaHCO3 and brine
  15. dry with materialNext, the solution was dried over MgSO
  16. customThe solution was then decanted from the drying agent
  17. filtrationfiltered
  18. customNext, the solvent was removed via rotary evaporation
  19. customyielding a yellow orange oil
  20. washeluted with more hexane
  21. customUpon solvent removal

Sources & evidence

ORD record
ord-56b61aeaccb84d749f87fce63a987146
Source dataset
uspto-grants-2004_05
Patent number
US06735011B2

Reaction notes

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