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Daylight LED promotes photochemical ring contraction of 2-amine-4H-pyran-3-carbonitriles with consequent loss of their antifungal activity

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Abstract

The initial objective of our work was to synthesize a series of 2-amino-4H-pyran-3-carbonitriles to be tested for their antifungal activities against economically relevant phytopathogenic fungi. Fourteen compounds were prepared in up to 94% yield and shown percentages of Botrytis cinerea inhibition above 70%. Despite the promising biological results, we observed that stock solutions prepared for biological tests showed color changing when kept for a few days on the laboratory bench, under room conditions, illuminated by common LED daylight tubes (4500–6000 k). This prompted us to investigate the possible photo-induced degradation of our compounds. FT-IR ATR experiments evidenced variations in the expected bands for functional of -amino-4H-pyran-3-carbonitriles stored under LED daylight. Following, HPLC–UV analysis showed reductions in the intensity of chromatographic peaks of 2-amino-4H-pyran-3-carbonitriles, and but not for solutions kept in the dark. A solution of (E)-2-amino-8-(4-nitrobenzylidene)-4-(4-nitrophenyl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile underwent 84.4% of conversion after 72 h of exposure to continuous LED daylight in a BOD chamber, and the reaction product was isolated in 36% yield and characterized as (E)-7-cyano-5-(4-nitrobenzylidene)-8-(4-nitrophenyl)bicyclo[4.2.0]oct-1(6)-ene-7-carboxamide (7*). Despite freshly prepared solutions of 2-amino-4H-pyran-3-carbonitriles produced antifungal activities, these solutions lost biological activity when left on the bench for a week. Besides, compound 7* formed from photo-induced degradation of 7 also showed no antifungal activity. With this, we hope to bring two contributions: (1) production of cyclobutenes through photochemical reactions of 2-amino-4H-pyran-3-carbonitriles can be carried out through exposure to simple white LED daylight; (2) biological applications of such 2-amino-4H-pyran-3-carbonitriles may be impaired by their poor photostability.

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Acknowledgements

We thanks the Brazilian agencies FAPEMIG (Fundação de Amparo a Pesquisa do Estado de Minas Gerais), CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), and FINEP (Financiadora de Estudos e Projetos) for financial support.

Funding

This work was supported by the following Brazilian agencies: Conselho Nacional de Pesquisa e Desenvolvimento (CNPq) (Grant nos. 459271/2014-8 and 438712/2018-8) and Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) (Grant no. APQ-02789-14, APQ-01577-17).

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Authors and Affiliations

  1. Department of Chemistry, Universidade Federal de Viçosa, Av PH Rolfs sn, Viçosa, MG, 36.570-900, Brazil

    Ueveton Pimentel da Silva, Bianca Lana de Sousa & Eduardo Vinícius Vieira Varejão

  2. Department of Phytopathology, Universidade Federal de Viçosa, Av PH Rolfs sn, Viçosa, MG, 36.570-900, Brazil

    Bruno Wesley Ferreira & Robert Weingart Barreto

  3. Department of Chemistry, Universidade Federal de Juiz de Fora, Rua José Lourenço Kelmer sn, Juiz de Fora, MG, 36.036-900, Brazil

    Giovanni Wilson Amarante

  4. Institute of Chemistry, Universidade Federal de Goiás, Av Esperança, sn, Samambaia, Goiânia, 74.690-900, Brazil

    Rodolfo Rodrigues da Silva & Boniek Gontijo Vaz

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  1. Ueveton Pimentel da Silva
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  2. Bianca Lana de Sousa
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Correspondence to Eduardo Vinícius Vieira Varejão.

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da Silva, U.P., de Sousa, B.L., Ferreira, B.W. et al. Daylight LED promotes photochemical ring contraction of 2-amine-4H-pyran-3-carbonitriles with consequent loss of their antifungal activity. Photochem Photobiol Sci 20, 1309–1321 (2021). https://doi.org/10.1007/s43630-021-00108-9

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