Ferrocenecarboxaldehyde

Ferrocenecarboxaldehyde
Names
	Other names FcCHO, Formylferrocene
Identifiers
CAS Number	12093-10-6 ;
3D model (JSmol)	Interactive image; Interactive image;
ChemSpider	26585886;
ECHA InfoCard	100.031.950
PubChem CID	15184314;
	InChI InChI=1S/C6H5O.C5H5.Fe/c7-5-6-3-1-2-4-6;1-2-4-5-3-1;/h1-5H;1-5H;/q2-1;+2 Key: MQHZGUNMWQBVDK-UHFFFAOYSA-N; InChI=1S/C6H5O.C5H5.Fe/c7-5-6-3-1-2-4-6;1-2-4-5-3-1;/h1-5H;1-5H;/q2-1;+2 Key: MQHZGUNMWQBVDK-UHFFFAOYSA-N;
	SMILES [CH-]1C=CC=C1.C1=C[C-](C=C1)C=O.[Fe+2]; C(=O)[C-]12[Fe+2]3456789([CH]1=[CH]3[CH]4=[CH]52)[CH-]%10[CH]6=[CH]7[CH]8=[CH]9%10;
Properties
Chemical formula	C11H10FeO
Molar mass	214.045 g·mol−1
Appearance	orange solid
Density	1.566 g/cm3
Melting point	118–120 °C (244–248 °F; 391–393 K)
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Ferrocenecarboxaldehyde is the organoiron compound with the formula (C₅H₅)Fe(C₅HCHO). The molecule consists of ferrocene substituted by an formyl group on one of the cyclopentadienyl rings. It is an orange, air-stable solid that is soluble in organic solvents.

Synthesis

Ferrocenecarboxaldehyde is prepared by Vilsmeier-Haack reaction (formylation) using dimethylformamide and phosphorus oxychloride.^[2] Diformylation does not occur readily.^[3]

According to X-ray crystallography ferrocenecarboxaldehyde adopts the expected sandwich structure exhibited by other ferrocenes. The formyl group is coplanar with its attached ring.^[4]

In its IR spectrum, ferrocenecarboxaldehyde is characterized by a low frequency ν_CO band at 1670 cm⁻¹ vs 1704 cm⁻¹ for benzaldehyde.^[3]

Reactions

Ferrocenecarboxaldehyde behaves like other aldehydes in terms of its reactivity, the main difference is that it is electroactive. Its basicity is indicated by the solubility of the compound in hydrochloric acid.^[3]

Ferrocenecarboxaldehyde, owing to the versatility of the formyl group, is a precursor to many ferrocene-modified compounds. With a Wittig reagent, it converts to vinylferrocene and related derivatives.^[5] With primary amines, ferrocenecarboxaldehyde condenses to give imines. The azomethine derivative undergoes 1,3-cycloaddition to C₆₀.^[6]

It can be reduced to the corresponding alcohol with hydride reducing agents.^[7] Asymmetric alkylation gives the chiral α-hydroxyethylferrocene.^[8] Dioxane derivatives, obtainable from 1,3-diols and the aldehyde, sustain ortho lithiation.^[9]

Related compounds

References

^ Sato, Kumiko; Iwai, Makoto; Sano, Hirotoshi; Konno, Michiko (1984). "Plastic Phase of Formylferrocene Studied by X-Ray Diffraction and Mössbauer Spectroscopy". Bulletin of the Chemical Society of Japan. 57 (3): 634–638. doi:10.1246/bcsj.57.634.
^ Graham, P. J.; Lindsey, R. V.; Parshall, G. W.; Peterson, M. L.; Whitman, G. M. (1957). "Some Acyl Ferrocenes and their Reactions". Journal of the American Chemical Society. 79 (13): 3416–3420. doi:10.1021/ja01570a027.
^ ^a ^b ^c Rausch, M. D. (1963). "Metallocene Chemistry—A Decade of Progress". Canadian Journal of Chemistry. 41 (5): 1289–1314. doi:10.1139/v63-182.
^ Lousada, Cláudio M.; Pinto, Susana S.; Canongia Lopes, José N.; Minas Da Piedade, M. Fátima; Diogo, Hermínio P.; Minas Da Piedade, Manuel E. (2008). "Experimental and Molecular Dynamics Simulation Study of the Sublimation and Vaporization Energetics of Iron Metalocenes. Crystal Structures of Fe(η⁵-C₅H₄CH₃)₂and Fe[(η⁵-(C₅H₅)(η⁵-C₅H₄CHO)]". The Journal of Physical Chemistry A. 112 (13): 2977–2987. doi:10.1021/jp7107818. PMID 18331009.
^ Liu WY, Xu QH, Ma YX, Liang YM, Dong NL, Guan DP (2001). "Solvent-free synthesis of ferrocenylethene derivatives". J. Organomet. Chem. 625: 128–132. doi:10.1016/S0022-328X(00)00927-X.
^ Maggini, Michele; Scorrano, Gianfranco; Prato, Maurizio (1993). "Addition of Azomethine Ylides to C₆₀: Synthesis, Characterization, and Functionalization of Fullerene Pyrrolidines". Journal of the American Chemical Society. 115 (21): 9798–9799. doi:10.1021/ja00074a056.
^ Lednicer, Daniel; Mashburn, Jr., T. Arthur; Hauser, Charles R. (1960). "Hydroxymethylferrocene". Organic Syntheses. 40: 52. doi:10.15227/orgsyn.040.0052.
^ Kitamura, Masato; Oka, Hiromasa; Suga, Seiji; Noyori, Ryoji (2002). "Catalytic Enantioselective Addition of Dialkylzincs To Aldehydes Using (2S)-(−)-3-exo-(Dimethylamino)isoborneol: (S)-1-Phenyl-1-propanol". Organic Syntheses. 79: 139. doi:10.15227/orgsyn.079.0139.
^ Riant, Olivier; Samuel, Odile; Flessner, Timo; Taudien, Stephan; Kagan, Henri B. (1997). "An Efficient Asymmetric Synthesis of 2-Substituted Ferrocenecarboxaldehydes". The Journal of Organic Chemistry. 62 (20): 6733–6745. doi:10.1021/jo970075u.

[1] Sato, Kumiko; Iwai, Makoto; Sano, Hirotoshi; Konno, Michiko (1984). "Plastic Phase of Formylferrocene Studied by X-Ray Diffraction and Mössbauer Spectroscopy". Bulletin of the Chemical Society of Japan. 57 (3): 634–638. doi:10.1246/bcsj.57.634.

[2] Graham, P. J.; Lindsey, R. V.; Parshall, G. W.; Peterson, M. L.; Whitman, G. M. (1957). "Some Acyl Ferrocenes and their Reactions". Journal of the American Chemical Society. 79 (13): 3416–3420. doi:10.1021/ja01570a027.

[Rausch-3] Rausch, M. D. (1963). "Metallocene Chemistry—A Decade of Progress". Canadian Journal of Chemistry. 41 (5): 1289–1314. doi:10.1139/v63-182.

[4] Lousada, Cláudio M.; Pinto, Susana S.; Canongia Lopes, José N.; Minas Da Piedade, M. Fátima; Diogo, Hermínio P.; Minas Da Piedade, Manuel E. (2008). "Experimental and Molecular Dynamics Simulation Study of the Sublimation and Vaporization Energetics of Iron Metalocenes. Crystal Structures of Fe(η⁵-C₅H₄CH₃)₂and Fe[(η⁵-(C₅H₅)(η⁵-C₅H₄CHO)]". The Journal of Physical Chemistry A. 112 (13): 2977–2987. doi:10.1021/jp7107818. PMID 18331009.

[5] Liu WY, Xu QH, Ma YX, Liang YM, Dong NL, Guan DP (2001). "Solvent-free synthesis of ferrocenylethene derivatives". J. Organomet. Chem. 625: 128–132. doi:10.1016/S0022-328X(00)00927-X.

[6] Maggini, Michele; Scorrano, Gianfranco; Prato, Maurizio (1993). "Addition of Azomethine Ylides to C₆₀: Synthesis, Characterization, and Functionalization of Fullerene Pyrrolidines". Journal of the American Chemical Society. 115 (21): 9798–9799. doi:10.1021/ja00074a056.

[7] Lednicer, Daniel; Mashburn, Jr., T. Arthur; Hauser, Charles R. (1960). "Hydroxymethylferrocene". Organic Syntheses. 40: 52. doi:10.15227/orgsyn.040.0052.

[8] Kitamura, Masato; Oka, Hiromasa; Suga, Seiji; Noyori, Ryoji (2002). "Catalytic Enantioselective Addition of Dialkylzincs To Aldehydes Using (2S)-(−)-3-exo-(Dimethylamino)isoborneol: (S)-1-Phenyl-1-propanol". Organic Syntheses. 79: 139. doi:10.15227/orgsyn.079.0139.

[9] Riant, Olivier; Samuel, Odile; Flessner, Timo; Taudien, Stephan; Kagan, Henri B. (1997). "An Efficient Asymmetric Synthesis of 2-Substituted Ferrocenecarboxaldehydes". The Journal of Organic Chemistry. 62 (20): 6733–6745. doi:10.1021/jo970075u.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]