Author
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SVENDSEN, SKYLER - Concordia College |
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Hakk, Heldur |
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Submitted to: American Chemical Society
Publication Type: Abstract Only Publication Acceptance Date: 2/26/2015 Publication Date: 3/23/2015 Citation: Svendsen, S.A., Hakk, H. 2015. Spectral characterization of steroids following fluorination by Selectfluor. 249th American Chemical Society National Meeting. p. 159. Interpretive Summary: Estrogens are eliminated from nearly all animals in large quantities, and when released into the environment they are recognized as endocrine disrupting compounds, particularly to aquatic organisms. Tracing the movement of estrogens from animal waste to impacted waters is complicated by historical estrogen burdens, as well as their introduction through wildlife. Tracer studies can be conveniently performed with radiochemicals; however, these are not suitable for field-scale research. Stable fluorine isotope analogs of environmental contaminants may prove a fruitful method to study the movement of not only estrogens but all steroids in the environment. Therefore, the aim of this project was to synthesize a series of fluorinated steroids, whose physicochemical similarity with the native steroids would be evaluated in soil batch and column studies, and then ultimately used in tracer studies at the field level. Selectfluor was chosen as the fluorinating agent, mild conditions were selected, and 17ß-estradiol was used as a model compound to investigate whether fluorination of steroids is feasible. Full characterization of product by 1H- and 13C-NMR will be presented, as well as available mass spectra. The effect of varying the synthetic conditions was also investigated. The methods were also applied to various other estrogens (estrone), androgens (testosterone and androstene-3,17-dione), progestins (progesterone), as well as cortisol and cholesterol, whose spectral data will also be presented. In general, under the mildest conditions selected, monofluorination at the C-9 position was achieved, and discussion will be provided on how higher degrees of fluorination can be achieved, and which steroids are resistant to fluorination under the selected conditions. Technical Abstract: Estrogens are eliminated from nearly all animals in large quantities, and when released into the environment they are recognized as endocrine disrupting compounds, particularly to aquatic organisms. Tracing the movement of estrogens from animal waste to impacted waters is complicated by historical estrogen burdens, as well as their introduction through wildlife. Tracer studies can be conveniently performed with radiochemicals; however, these are not suitable for field-scale research. Stable fluorine isotope analogs of environmental contaminants may prove a fruitful method to study the movement of not only estrogens but all steroids in the environment. Therefore, the aim of this project was to synthesize a series of fluorinated steroids, whose physicochemical similarity with the native steroids would be evaluated in soil batch and column studies, and then ultimately used in tracer studies at the field level. Selectfluor was chosen as the fluorinating agent, mild conditions were selected, and 17ß-estradiol was used as a model compound to investigate whether fluorination of steroids is feasible. Full characterization of product by 1H- and 13C-NMR will be presented, as well as available mass spectra. The effect of varying the synthetic conditions was also investigated. The methods were also applied to various other estrogens (estrone), androgens (testosterone and androstene-3,17-dione), progestins (progesterone), as well as cortisol and cholesterol, whose spectral data will also be presented. In general, under the mildest conditions selected, monofluorination at the C-9 position was achieved, and discussion will be provided on how higher degrees of fluorination can be achieved, and which steroids are resistant to fluorination under the selected conditions. |
