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Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid
Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates promoted by trifluoromethanosulfonic acid afforded diethyl 1-(pyrene-1-carbothioamido)alkylphosphonates in 83–94% yield. These compounds were transformed, in 87–94% yield, into the corresponding diethyl 1-(pyrene...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Beilstein-Institut
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4685883/ https://www.ncbi.nlm.nih.gov/pubmed/26734093 http://dx.doi.org/10.3762/bjoc.11.266 |
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author | Wrona-Piotrowicz, Anna Zakrzewski, Janusz Gajda, Anna Gajda, Tadeusz Makal, Anna Brosseau, Arnaud Métivier, Rémi |
author_facet | Wrona-Piotrowicz, Anna Zakrzewski, Janusz Gajda, Anna Gajda, Tadeusz Makal, Anna Brosseau, Arnaud Métivier, Rémi |
author_sort | Wrona-Piotrowicz, Anna |
collection | PubMed |
description | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates promoted by trifluoromethanosulfonic acid afforded diethyl 1-(pyrene-1-carbothioamido)alkylphosphonates in 83–94% yield. These compounds were transformed, in 87–94% yield, into the corresponding diethyl 1-(pyrene-1-carboxamido)alkylphosphonates by treatment with Oxone(®). 1-(Pyrene-1-carboxamido)methylphosphonic acid was obtained in a 87% yield by treating the corresponding diethyl phosphonate with Me(3)Si-Br in methanol. All of the synthesized amidophosphonates were emissive in solution and in the solid state. The presence of a phosphonato group brought about an approximately two-fold increase in solution fluorescence quantum yield in comparison with that of a model N-alkyl pyrene-1-carboxamide. This effect was tentatively explained by stiffening of the amidophosphonate lateral chain which was caused by the interaction (intramolecular hydrogen bond) of phosphonate and amide groups. The synthesized phosphonic acid was soluble in a biological aqueous buffer (PBS, 0.01 M, pH 7.35) and was strongly emissive under these conditions (λ(em) = 383, 400 nm, τ = 18.7 ns, Φ(F) > 0.98). Solid-state emission of diethyl 1-(pyrene-1-carboxamido)methylphosphonate (λ(max) = 485 nm; Φ(F) = 0.25) was assigned to π–π aggregates, the presence of which was revealed by single-crystal X-ray diffraction analysis. |
format | Online Article Text |
id | pubmed-4685883 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-46858832016-01-05 Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid Wrona-Piotrowicz, Anna Zakrzewski, Janusz Gajda, Anna Gajda, Tadeusz Makal, Anna Brosseau, Arnaud Métivier, Rémi Beilstein J Org Chem Full Research Paper Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates promoted by trifluoromethanosulfonic acid afforded diethyl 1-(pyrene-1-carbothioamido)alkylphosphonates in 83–94% yield. These compounds were transformed, in 87–94% yield, into the corresponding diethyl 1-(pyrene-1-carboxamido)alkylphosphonates by treatment with Oxone(®). 1-(Pyrene-1-carboxamido)methylphosphonic acid was obtained in a 87% yield by treating the corresponding diethyl phosphonate with Me(3)Si-Br in methanol. All of the synthesized amidophosphonates were emissive in solution and in the solid state. The presence of a phosphonato group brought about an approximately two-fold increase in solution fluorescence quantum yield in comparison with that of a model N-alkyl pyrene-1-carboxamide. This effect was tentatively explained by stiffening of the amidophosphonate lateral chain which was caused by the interaction (intramolecular hydrogen bond) of phosphonate and amide groups. The synthesized phosphonic acid was soluble in a biological aqueous buffer (PBS, 0.01 M, pH 7.35) and was strongly emissive under these conditions (λ(em) = 383, 400 nm, τ = 18.7 ns, Φ(F) > 0.98). Solid-state emission of diethyl 1-(pyrene-1-carboxamido)methylphosphonate (λ(max) = 485 nm; Φ(F) = 0.25) was assigned to π–π aggregates, the presence of which was revealed by single-crystal X-ray diffraction analysis. Beilstein-Institut 2015-12-04 /pmc/articles/PMC4685883/ /pubmed/26734093 http://dx.doi.org/10.3762/bjoc.11.266 Text en Copyright © 2015, Wrona-Piotrowicz et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms) |
spellingShingle | Full Research Paper Wrona-Piotrowicz, Anna Zakrzewski, Janusz Gajda, Anna Gajda, Tadeusz Makal, Anna Brosseau, Arnaud Métivier, Rémi Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title_full | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title_fullStr | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title_full_unstemmed | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title_short | Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
title_sort | friedel–crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4685883/ https://www.ncbi.nlm.nih.gov/pubmed/26734093 http://dx.doi.org/10.3762/bjoc.11.266 |
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