AUTHOR=Prinčič Griša Grigorij , Maselj Nik , Goreshnik Evgeny , Iskra Jernej 

TITLE=Oxidation of Iodine to Dihaloiodate(I) Salts of Amines With Hydrogen Peroxides and Their Crystal Structures

JOURNAL=Frontiers in Chemistry

VOLUME=10

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.912383

DOI=10.3389/fchem.2022.912383

ISSN=2296-2646

ABSTRACT=<p>Herein we report a general preparation of dihaloiodate salts of heterocyclic amines (tertiary and quaternary) with sterically accessible and hindered nitrogen atom. A number of such compounds were prepared from preformed HICl<sub>2</sub> or HIBr<sub>2</sub> formed <italic>in situ</italic> by the reaction of corresponding hydrogen halide, iodine and H<sub>2</sub>O<sub>2</sub>. The salts of 1,4-diazabicyclo[2.2.2]octane (DABCO) and its methylated derivatives, 1,3,5,7-tetraazaadamantane (HMTA), diazabicycloundecene (DBU) and 2,4,6-tri-<italic>tert</italic>-butylpyridine (TBP) were obtained in excellent yields and their structure was determined by NMR and Raman spectroscopy and single crystal X-ray diffraction. Non-hindered bases such as DABCO, HMTA and DBU formed IX<sub>2</sub><sup>−</sup> salts, which further decomposed to complexes with interhalogen compounds due to formation of N…X halogen bonds. The dihaloiodiate(I) salts of sterically hindered 2,4,6-tri-<italic>tert</italic>-butylpyridine were stable. Its dichlorobromate(I) salt was also prepared <italic>via</italic> a different synthetic method using <italic>N</italic>-chlorosuccinimide as oxidant.</p>