Formaldehyde → 1-Hydroxymethyl-2-dimethylaminomethyl ferrocene

HRID 1724100Notes

Reaction equation

HRID 1724100 reaction equation
C([Li])CCC.[CH3:6][N:7]([CH2:9][C-:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1)[CH3:8].[CH-:15]1[CH:19]=[CH:18][CH:17]=[CH:16]1.[Fe+2:20].[CH2:21]=[O:22]>C(OCC)C>[OH:22][CH2:21][C-:11]1[CH:12]=[CH:13][CH:14]=[C:10]1[CH2:9][N:7]([CH3:8])[CH3:6].[CH-:15]1[CH:19]=[CH:18][CH:17]=[CH:16]1.[Fe+2:20]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 15764045cyclopenta-1,3-diene;1-cyclopenta-2,4-dien-1-yl-N,N-dimethylmethanamine;iron(2+)HCID 178418339Butyllithium

Product 1

HCID 1317272671-Hydroxymethyl-2-dimethylaminomethyl ferrocene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

n-Butyl lithium (Aldrich, 1.6 molar in diethyl ether, 5.14 ml, 8.24 mmol) is added to a solution of 1-dimethylaminomethyl ferrocene (Aldrich, 1.0 g, 4.12 mmol) in diethyl ether (20 mL) under argon. The reaction is stirred for 3 hours and developes a reddish colour. The solution is then cooled in a dry ice/acetone bath, calcined paraformaldehyde (0.247 g, 2 times excess) added and the resultant mixture stirred overnight at room temperature. The reaction is then quenched with water, extracted with diethyl ether, dried over MgSO4, and filtered over celite. The solvent is removed in vacuo to yield crude title compound. The crude product is applied to a neutral alumina column, which is eluted with petrol/diethyl ether (9:1 ratio) to remove the starting material, 1-dimethylaminomethyl ferrocene. The column is then eluted with substantially pure ethyl acetate to elute the title compound. The ethyl acetate is removed in vacuo, to yield the title compound as an orange oil/crystalline mass.

Workup

  1. temperatureThe solution is then cooled in a dry ice/acetone bath
  2. customThe reaction is then quenched with water
  3. extractionextracted with diethyl ether
  4. dry with materialdried over MgSO4
  5. filtrationfiltered over celite
  6. customThe solvent is removed in vacuo
  7. customto yield crude title compound
  8. washis eluted with petrol/diethyl ether (9:1 ratio)
  9. customto remove the starting material, 1-dimethylaminomethyl ferrocene
  10. washThe column is then eluted with substantially pure ethyl acetate
  11. washto elute the title compound
  12. customThe ethyl acetate is removed in vacuo

Sources & evidence

ORD record
ord-20f2172b2a484c0da73bbf5a0f77af6e
Source dataset
uspto-grants-2009_02
Patent number
US07485739B2

Reaction notes

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