A correlative IR, MS, 1H, 13C and 15N NMR and theoretical study of 4-arylthiazol-2(3H)-onesElectronic supplementary information (ESI) available: NMR data, including graphs; Cartesian coordinates for 3a and 4. See http://www.rsc.org/suppdata/p2/b1/b106322g/
Pihlaja, Kalevi; Ovcharenko, Vladimir; Kolehmainen, Erkki; Laihia, Katri; Fabian, Walter M. F.; Dehne, Heinz; Perjéssy, Alexander; Kleist, Marion; Teller, Joachim; Šusteková, Zora; Pihlaja Kalevi; Department of Chemistry, University of Turku; Ovcharenko Vladimir; Department of Chemistry, University of Turku; Kolehmainen Erkki; Department of Chemistry, University of Jyväskylä; Laihia Katri; Department of Chemistry, University of Jyväskylä; Fabian Walter M. F.; Institute of Chemistry, Karl Franzens University; Dehne Heinz; Department of Chemistry, University of Rostock; Perjéssy Alexander; Department of Organic Chemistry and Institute of Chemistry, Faculty of Natural Sciences; Kleist Marion; Department of Chemistry, University of Rostock; Teller Joachim; Micromod Partikeltechnologie GmbH, Friedrich-Barnewitz-Str. 4; Å usteková Zora; Department of Organic Chemistry and Institute of Chemistry, Faculty of Natural Sciences
Журнал:
Journal of the Chemical Society, Perkin Transactions 2
Дата:
2002
Аннотация:
Sixteen 4-arylthiazol-2(3H)-ones (3) were synthesised by cyclisation of α-thiocyanatoacetophenones (1) in acid solution. They appear to prefer greatly the oxo tautomeric forms. In CCl4 solution an equilibrium between the free C.dbd;O bond and a â dimericâ hydrogen-bonded form exists in which the latter predominates. Several IR and NMR (<sup>1</sup>H, <sup>13</sup>C and <sup>15</sup>N) spectral properties are shown to correlate with Hammett Ï -values and/or atomic Mulliken charges and bond orders, the latter being estimated by PM3 or AM1 semiempirical methods. The electron-impact mass spectra were also recorded and the fragmentation mechanisms interpreted in terms of the energetics of the ionic species. In addition, the geometric and electronic properties of 4-phenylthiazol-2(3H)-one (3a) and the related benzothiazol-2(3H)-one (4) based on ab initio HF/6-31 G* calculations are compared with each other.
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