JFC_Accepted_Manuscript_May_2019.pdf (1.45 MB)
NMR spectral analysis of second-order 19F-19F, 19F-1H and 13C-19F coupling constants in pentafluorobenzene and tetrafluoro-4-(morpholino)pyridine using ANATOLIA
journal contribution
posted on 2019-05-24, 12:19 authored by Mark Edgar, Fatemeh Zeinali, Mariam Mojally, Charlotte Hughes, Shahzad Riaz, George WeaverGeorge WeaverA new and simple to use line-shape analysis method ANATOLIA (ANAlysis of TOtal
LIneshApe) optimised all and 19F19F and 19F1H coupling constants in pentafluorobenzene
(AA’BB’C’H) within 10 seconds. This free and open-source NMR analysis method, which works within the Bruker Topspin-4 software and can import Bruker/JEOL/Varian data, was
able to accommodate grossly inaccurate input coupling constants to provide an accurate
result even for the second-order interactions 4
JAA’ and 4
JBB’. The 13C spectrum and the 19F13C-satellites share the same coupling values, but required manual intervention to achieve
an acceptable fit, especially for the 19FBB’-
13C-satellites which are deceptively simple but
have significant second-order effects and display Δδ 19FB –
19FB’ of ~100 Hz.
A real-world analysis of a new compound, that has potential anti-cancer drug activity,
tetrafluoro-4-(morpholino)pyridine molecule, is shown for the first time. The 19F spectrum
consists of a spin-system of 8 coupling nuclei (AA’BB’-H4) which was analysed within 20
seconds. The 13C satellites in the 19F spectrum consist of 9-spins (AA’BB’-
13C-H4) and the
carbon spectrum shows a series of 13C isotopomer multiplets consisting of 5 coupling nuclei
(
13C-AA’BB’) was optimised in less than a minute using a laptop computer.
Ab initio structure optimisations were carried out using B3LYP/6-31G*, and chemical shifts
and coupling constants were calculated with the basis-set B3LYP/6-311++G**. Fluorine and
carbon chemical shifts were in reasonable agreement with experimental values, and n
JFF and
2-4
JCF couplings were close to the experimental values, such that these were reasonable
starting values for the ANATOLIA optimisation.
History
School
- Science
Department
- Chemistry
Published in
Journal of Fluorine ChemistryVolume
224Pages
35 - 44Citation
EDGAR, M. ... et al., 2019. NMR spectral analysis of second-order 19F-19F, 19F-1H and 13C-19F coupling constants in pentafluorobenzene and tetrafluoro-4-(morpholino)pyridine using ANATOLIA. Journal of Fluorine Chemistry, 224, pp. 35 - 44.Publisher
© Elsevier BVVersion
- AM (Accepted Manuscript)
Publisher statement
This paper was accepted for publication in the journal Journal of Fluorine Chemistry and the definitive published version is available at https://doi.org/10.1016/j.jfluchem.2019.04.018.Acceptance date
2019-04-25Publication date
2019-05-08ISSN
0022-1139Publisher version
Language
- en