Skip to main content
SpringerLink
Log in

Electron transfer reactions of 1-phenyl-4-vinylpyrazole mediated by cerium(IV) ammonium nitrate

Elektrontransfer-Reaktionen von 1-Phenyl-4-vinylpyrazol mittels Cer(IV)-Ammonnitrat

  • Organische Chemie Und Biochemie
  • Published:
Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Summary

The title compound is converted into the cyclic ethers5 and the alcohol6 upon treatment with ceric ammonium nitrate in acetone. Using methanol as a solvent the dimethoxy derivative9 and the nitrate ester10 are formed. No cross cycloaddition is observed in the presence of olefins such as ethyl vinyl ether,DMAD, or indene; however, with cyclopentadiene as co-reagent a mixture of the exo-endo Diels-Alder adducts14 involving the vinylic system of 1 as 2π component is obtained. The results are rationalized through the interrnediacy of the radical cation1 ·+, generated by single electron transfer (SET) from the neutral precursor1 to Ce(IV).

Zusammenfassung

Die Titelverbindung wurde mittels Cer(IV)-Ammonnitrat in Aceton in die cyclischen Ether5 und den Alkohol6 umgewandelt. Mit Methanol als Lösungsmittel wurde das Dimethoxyderivat9 und der Nitratester10 gebildet. Bei Anwesenheit von Olefinen wie etwa Ethylvinylether,DMAD oder Inden wurden keine Cross-Cycloadditionen beobachtet. Hingegen wurde mit Cyclopentadien als Mitreagens eine Mischung vonexo-endo-Diels-Alder-Produkten14 erhalten, wobei das vinylische System von1 als 2π-Komponente fungiert. Die Ergebnisse werden mittels eines intermediär auftretenden Radikalkation1 ·+ als Produkt eines Einelektronentransfers (SET) des neutralen Vorläufers1 zu Ce(IV) rationalisiert.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Abarca B., Jones R. A., Medio M., Sepúlveda J., Dawes H. M., Hursthouse M. B. (1985) J. Chem. Research (S): 84

  2. Medio M., Sepúlveda J. (1986) Tetrahedron42: 6683

    Google Scholar 

  3. Jones R. A., Abarca B., Sepúlveda J., Quilez J., King T. J. (1984) J. Chem. Soc. Perkin Trans. I: 1423

  4. Sepúlveda J., Medio M. (1985) Tetrahedron Lett.26: 6357

    Google Scholar 

  5. Bauld N. L., Bellville D. J., Hiam B. H., Lorenz K. T., Pavon R. A., Reynolds D. W., Wirth D. D., Chion H. S., Marsh B. K. (1987) Acc. Chem. Res.20: 371

    Google Scholar 

  6. Bauld N. L. (1989) Tetrahedron45: 5307

    Google Scholar 

  7. Spectral data for6 Ir: broad band 3600−3300 cm−1.1H-NMR: 7.8−7.0 (m, aromatic H), 6.6 (dd,J=9 and 3 Hz, CH2−CH=CH), 5.6 (ddd,J=9, 6, and 3 Hz, CH2 CH=CH), 4.3 (dd,J=6 and 2 Hz, CH-O), 2.8−2.6 (m+m, CH2); MS: 338 (M-18, 92), 194 (17), 104 (16), 77 (100), 51 (72)

  8. Eberson L. (1987) Electron Transfer Reactions in Organic Chemistry. Springer-Verlag, Berlin

    Google Scholar 

  9. Dobson P., Norman J. A., Thomas B. (1986) J. Chem. Soc. Perkin Trans. I1986: 1209

    Google Scholar 

  10. Baciocchi E., Rol C., Sebastian G. V. (1988) Gazz. Chim. Ital.1988: 285

    Google Scholar 

  11. Baciocchi E., Giaco T., Murgia S. M., Sebastian G. V. (1988) Tetrahedron44: 6651

    Google Scholar 

  12. Finar I. L., Lord G. H. (1959) J. Chem. Soc.1959: 1819

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Departmento de Química Orgánica, Facultad de Farmacia, E-46100, Burjassot, Valencia, Spain

    M. Pitarch-Vinuesa, M. Medio-Simón & J. Sepúlveda-Arques

  2. Departmento de Química e Instituto de Tecnología Química UPV-CSIC, Universidad Politécnica de Valencia, E-46071, Valencia, Spain

    M. A. Miranda

Authors
  1. M. Pitarch-Vinuesa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. A. Miranda
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Medio-Simón
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. Sepúlveda-Arques
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pitarch-Vinuesa, M., Miranda, M.A., Medio-Simón, M. et al. Electron transfer reactions of 1-phenyl-4-vinylpyrazole mediated by cerium(IV) ammonium nitrate. Monatsh Chem 124, 959–964 (1993). https://doi.org/10.1007/BF00816419

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00816419

Keywords

Search

Navigation