Org. Synth. 1960, 40, 45
DOI: 10.15227/orgsyn.040.0045
FERROCENYLACETONITRILE
[Iron, [(cyanomethyl)cyclopentadienyl]cyclopentadienyl]
Submitted by Daniel Lednicer and Charles R. Hauser
1.
Checked by B. C. McKusick and R. D. Vest.
1. Procedure
Caution! This preparation should be carried out in a hood since trimethylamine is evolved.
A solution of
57 g. (0.88 mole) of potassium cyanide in 570 ml. of water is placed in a
1-l. three-necked flask equipped with a
stirrer and a
reflux condenser.
Fifty-eight grams (0.15 mole) of N,N-dimethylaminomethylferrocene methiodide2 is added and the mixture is heated to boiling with good stirring. As the mixture is brought to boiling, the solid goes into solution. Within a few minutes of the onset of boiling, evolution of
trimethylamine begins and a steam-volatile oil starts to separate from the solution. The reaction mixture is boiled vigorously with stirring for 2 hours and then is allowed to cool to room temperature. During the cooling the oil that has separated solidifies.
The solid is separated by filtration and the filtrate is extracted with three 150-ml. portions of ether. (Caution! Gloves should be worn when handling this solution because of the large amount of cyanide it contains.) The solid is dissolved in ether and this solution is combined with the extracts. The combined ethereal solutions are washed with water and dried over 5 g. of sodium sulfate. Removal of the solvent by distillation leaves crude ferrocenylacetonitrile as a solid or as an oil that crystallizes on being scratched. The nitrile is dissolved in about 200 ml. of boiling technical grade hexane. The hot solution is decanted from a small amount of insoluble black tar and is cooled to room temperature. Ferrocenylacetonitrile is deposited as bright yellow crystals, m.p. 79–82° (Note 1). The yield of the nitrile is 24–26 g. (71–77%) (Note 2).
2. Notes
1.
The pure nitrile melts at
81–83° after further recrystallization from
hexane.
32.
The yield is directly dependent on the quality of the methiodide employed. Yields as high as
95% have been obtained.
3
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3. Discussion
This method is that described by Lednicer, Lindsay, and Hauser.
3 No other procedure appears to have been employed to prepare this compound.
Essentially the present procedure converted
1-methylgramine to
1-methyl-3-indoleacetonitrile,
4 but it failed to convert
benzyldimethylphenylammonium chloride to
phenylacetonitrile.
5
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
N,N-Dimethylaminomethylferrocene methiodide
Ferrocenylacetonitrile
ether (60-29-7)
sodium sulfate (7757-82-6)
potassium cyanide (151-50-8)
phenylacetonitrile (140-29-4)
Trimethylamine (75-50-3)
hexane (110-54-3)
1-methylgramine
1-methyl-3-indoleacetonitrile
benzyldimethylphenylammonium chloride
Iron, [(cyanomethyl)cyclopentadienyl]cyclopentadienyl
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