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Complementary host behaviour of trans-cyclohexane-1,4-diamine derivatives during recrystallization processes from mixed anilines

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Abstract

trans-N,N′-Bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine (1,4-DAX) and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine (1,4-DAT) proved to be highly effective host compounds for the enclathration of aniline (ANI), N-methylaniline (NMA) and N,N-dimethylaniline (DMA) guest solvents: only DMA was not included and only when using 1,4-DAT. When the host compounds were recrystallized from mixtures of these guests, it was revealed that host selectivities were in the order NMA > ANI > DMA and NMA > DMA > ANI for 1,4-DAX and 1,4-DAT, respectively. Single crystal diffraction experiments were employed to identify the host⋯guest interactions responsible for guest retention in these complexes, while thermal analyses proved futile for the determination of their relative thermal stabilities since most of them displayed poor stability even at room temperature. The selectivity data presented here complement the results obtained when the host compounds employed were 1,2-DAX and 1,2-DAT, as per a previous submission, where DMA was significantly preferred. Since NMA and DMA may be prepared from ANI, the resultant products often have one or more of these anilines present as impurities. This work therefore demonstrates that by utilizing the appropriate host compound, these solvents may be purified through host‒guest chemistry principles.

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Acknowledgements

Financial support is acknowledged from the Nelson Mandela University and the National Research Foundation (NRF).

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Authors and Affiliations

  1. Department of Chemistry, Nelson Mandela University, PO Box 77000, Port Elizabeth, 6031, South Africa

    Benita Barton, Daniel V. Jooste & Eric C. Hosten

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  1. Benita Barton
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  2. Daniel V. Jooste
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  3. Eric C. Hosten
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Correspondence to Benita Barton.

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10847_2020_998_MOESM1_ESM.docx

Supplementary file Crystallographic data for the novel complexes were deposited at the Cambridge Crystallographic Data Centre, where SCXRD analyses were possible {CCDC- 1987923 (1,4-DAX•DMA), 1987924 [1,4-DAT•2(ANI)] and 1987925 (1,4-DAT•NMA)}. These data may be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Overlaid thermal traces (DSC, TG and DTG) of each of the complexes of 1,4-DAX and 1,4-DAT are provided in Figures 1Sa‒c and 2Sa and b, respectively. (DOCX 203 kb)

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Barton, B., Jooste, D.V. & Hosten, E.C. Complementary host behaviour of trans-cyclohexane-1,4-diamine derivatives during recrystallization processes from mixed anilines. J Incl Phenom Macrocycl Chem 99, 33–42 (2021). https://doi.org/10.1007/s10847-020-00998-9

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