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Issue 2, 2016
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Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate

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Abstract

The reaction of neat 3-chloroaniline with neat S[double bond, length as m-dash]C[double bond, length as m-dash]N–P(O)(OPh)2 leads to a new N-phosphorylated thiourea, 3-ClC6H4NHC(S)NHP(O)(OPh)2 (1). The same reaction in non-dried CH2Cl2 or C6H6 leads to the salt-like compounds [3-ClC6H4NH3]+[NCS] (2) and [3-ClC6H4NH3]+[P(O)2(OPh)2]·0.5C6H6 (3·0.5C6H6), respectively, while using non-dried acetone yields 1-(3-chlorophenyl)-4,4,6-trimethyl-3,4-dihydropyrimidine-2(1H)-thione (4). Dissolution of 1 in non-dried CH2Cl2, C6H6 or Me2C[double bond, length as m-dash]O leads to the direct formation of 2, 3·0.5C6H6 and 4, respectively. It was established that thione 4 is most likely formed through the thiourea 1-assisted aldol condensation of acetone leading to mesityl oxide. In turn the latter ketone interacts with 1 followed by its hydrolysis leading to 4. Compounds 1–4 have been characterized by NMR spectroscopy and elemental analysis and their molecular structures were elucidated by X-ray diffraction. Hirshfeld surface analysis showed that the structures of both 1 and 4 are mainly characterized by H⋯H, H⋯C, H⋯Cl and H⋯S contacts as well as by H⋯O in the structure of 1. The enrichment ratio, derived as the decomposition of the crystal contact surface between pairs of interacting chemical species, for 1 was found, as expected for the polar contacts, which are generally hydrogen bonds, to be significantly larger than unity for the contacts of the type H⋯O and H⋯S. A much larger than unity value was found for the enrichment ratio of the C⋯C contacts in the structure of 1, which is due to extensive π⋯π stacking in the crystal packing. The enrichment ratio for 4 was found to be larger than unity for the contacts of the type H⋯C and, but with a lesser degree, H⋯Cl and H⋯S.

Graphical abstract: Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate

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Publication details

The article was received on 23 Sep 2015, accepted on 09 Nov 2015 and first published on 16 Nov 2015


Article type: Paper
DOI: 10.1039/C5NJ02588E
Author version available: Download Author version (PDF)
Citation: New J. Chem., 2016,40, 1230-1236
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    Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate

    M. G. Babashkina, K. Robeyns, Y. Filinchuk and D. A. Safin, New J. Chem., 2016, 40, 1230
    DOI: 10.1039/C5NJ02588E

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