Hydrochloric Acid → HCID 178440842, compound

HRID 915719Notes

Reaction equation

HRID 915719 reaction equation
ClC(Cl)C.[C:5]([C:9]1[C:10]([C:22]([CH3:25])([CH3:24])[CH3:23])=[C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])[C-:12]([C:14]([CH3:17])([CH3:16])[CH3:15])[CH:13]=1)([CH3:8])([CH3:7])[CH3:6].[CH-:26]1[CH:30]=[CH:29][CH:28]=[CH:27]1.[Fe+2:31].[Br:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][C:38](Cl)=O.[Al+3].[Cl-].[Cl-].[Cl-].Cl.CC[O:48]CC>[Zn].O>[Br:32][CH2:33][CH2:34][CH2:35][CH2:36][C:37](=[O:48])[CH2:38][C-:13]1[C:12]([C:14]([CH3:17])([CH3:16])[CH3:15])=[C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:10]([C:22]([CH3:25])([CH3:24])[CH3:23])=[C:9]1[C:5]([CH3:8])([CH3:7])[CH3:6].[CH-:26]1[CH:30]=[CH:29][CH:28]=[CH:27]1.[Fe+2:31]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 3283Diethyl Ether2×HCID 63651,1-DichloroethaneHCID 898486-Bromohexanoyl chlorideHCID 6451240Aluminum(III) Chloride2×HCID 129652319HCID 129652319, compound

Product 1

HCID 178440842HCID 178440842, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 962WaterSolvent

Procedure

First, a nitrogen purged flask was charged with 350 ml of dichloroethane, 50.0 g (122 mmol) of tetra-tert-butylferrocene (prepared according to T. Leigh, J. Am. Chem. Soc. 1964, 3294–3302), and 19.3 ml (126 mmol) of 6-bromohexanoyl chloride. Second, the solution was cooled to 0 degrees centigrade, whereupon 13.3 g (100 mmol) of AlCl3 was charged into the reaction vessel in 3 equal portions at two hour intervals. It will be understood that the freshness and/or purity of the AlCl3 can impact the degree of substitution of, for example, tert-butyl groups on a cyclopentadienyl ligand. Third, the reaction mixture was then slowly poured into 300 ml of agitating H2O. Fourth, the organic-aqueous mixture was charged with a sufficient quantity of diethyl ether so that an organic layer was appreciably formed on top of the aqueous layer. Fifth, 50 ml of concentrated hydrochloric acid (HCl) was charged into the vessel. Sixth, approximately 2–5 g of zinc dust was charged into the vessel to reduce any ferrocinium species present in the aqueous layer to the ether soluble ferrocene. Once the layers were clearly defined, they were separated and the aqueous layer was extracted with 200 ml of diethyl ether (Et2O). The two organic portions were combined and washed with NaHCO3 and brine. Next the organic solution was dried over MgSO4. The organic solution was then decanted from the MgSO4 and filtered. Next, the solvent was removed by rotary evaporation to yield a red oil. The red oil was applied to a vacuum assisted silica gel column and washed with hexane to remove any residual ferrocene. The product was eluted with Et2O. Upon solvent removal and cooling in a freezer, 64.29 g of 6-bromo-1-(tetra-tert-butylferrocenyl)-2-hexanone was isolated as a red solid.

Workup

  1. additionwas charged into the reaction vessel in 3 equal portions at two hour intervals
  2. customwas appreciably formed on top of the aqueous layer
  3. customthey were separated
  4. extractionthe aqueous layer was extracted with 200 ml of diethyl ether (Et2O)
  5. washwashed with NaHCO3 and brine
  6. dry with materialNext the organic solution was dried over MgSO4
  7. customThe organic solution was then decanted from the MgSO4
  8. filtrationfiltered
  9. customNext, the solvent was removed by rotary evaporation
  10. customto yield a red oil
  11. washwashed with hexane
  12. customto remove any residual ferrocene
  13. washThe product was eluted with Et2O
  14. customUpon solvent removal
  15. temperaturecooling in a freezer

Sources & evidence

ORD record
ord-1c231b6d36b24a88bea98199900a16d3
Source dataset
uspto-grants-2007_09
Patent number
US07265888B2

Reaction notes

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