Water → HCID 178520603, compound

HRID 917867Notes

Reaction equation

HRID 917867 reaction equation
[CH-:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[CH-:6]1[CH:10]=[CH:9][CH:8]=[CH:7]1.[Fe+2:11].[OH2:12].O=[C:14]1[O:20][C@H:19]([C@H:21]([CH2:23]O)O)[C:17](O)=[C:15]1O.Cl[CH2:26]Cl>FC(F)(F)C(OC(=O)C(F)(F)F)=O.FC(F)(F)C(O)=O>[C-:1]1([C:19]([C-:6]2[CH:10]=[CH:9][CH:8]=[CH:7]2)([CH2:17][CH2:15][CH2:14][OH:20])[CH2:21][CH2:23][CH2:26][OH:12])[CH:5]=[CH:4][CH:3]=[CH:2]1.[CH-:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[Fe+2:11].[CH-:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[Fe+2:11]

Participants

7

Reactant 4

HCID 962WaterHCID 6344DichloromethaneHCID 7611Bis(eta-cyclopentadienyl) ironHCID 54670067L-Ascorbic Acid

Product 1

HCID 178520603HCID 178520603, compoundYield 59%

Reagents, catalysts & solvents 2

HCID 6422Trifluoroacetic acidCatalystHCID 9845Trifluoroacetic anhydrideCatalyst

Procedure

Ten grams of ferrocene and 2.0 g. of I were dissolved in 40 ml of dichloromethane. To this was added a mixture of 6.6 g of trifluoroacetic anhydride and 8.0 g of trifluoroacetic acid as catalyst. The solution was mixed and allowed to stand at 25°C. A nitrogen atmosphere was maintained in the reaction vessel during mixing and during the subsequent reaction. After 16 hours, 100 ml of water was stirred with the brown colored reaction mixture and enough ascorbic acid was added to discharge the green color of the aqueous phase and to turn the organic phase orange in color. The phases were separated and the organic phase was stirred with another 100 ml of water and separated. Dichloromethane was removed from the organic phase under reduced pressure and the residue was dissolved in 100 ml of methanol containing 2 ml of water and 2.0 g of potassium hydroxide. The solution was stirred for 30 minutes and then the methanol and water were removed under reduced pressure. The residue was extracted with (dissolved in) 700 ml of hot ethylene dichloride and filtered. The cooled filtrate was poured onto a dry 36 mm by 240 mm alumina column. Unreacted ferrocene, 5.0 g, was eluted from the column with ethylene dichloride. Using 2% methanol in ethylene dichloride, 5.8 g of a mixture of IV, V and other byproducts were eluted. Recrystallization of this mixture from ethylene dichloride gave 4.6 g (59% yield) of 4,4-diferrocenylheptane-1,7-diol, mp 166°-168°C. Another recrystallization raised the mp to 168°-170°C.

Workup

  1. additionTo this was added
  2. additionThe solution was mixed
  3. customto stand at 25°C
  4. temperatureA nitrogen atmosphere was maintained in the reaction vessel
  5. additionduring mixing and during the subsequent reaction
  6. additionwas added
  7. customThe phases were separated
  8. customseparated
  9. customDichloromethane was removed from the organic phase under reduced pressure
  10. dissolutionthe residue was dissolved in 100 ml of methanol containing 2 ml of water and 2.0 g of potassium hydroxide
  11. stirringThe solution was stirred for 30 minutes
  12. customthe methanol and water were removed under reduced pressure
  13. extractionThe residue was extracted with (dissolved in) 700 ml of hot ethylene dichloride
  14. filtrationfiltered
  15. additionThe cooled filtrate was poured onto a dry 36 mm by 240 mm alumina column
  16. washwas eluted from the column with ethylene dichloride
  17. washwere eluted
  18. customRecrystallization of this mixture from ethylene dichloride

Sources & evidence

ORD record
ord-4b57c92dad8d45a0ac7d587539c0dfe8
Source dataset
uspto-grants-1976_07
Patent number
US03968126

Reaction notes

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