ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Pyrylium Compounds. XXV. Quantum Chemical Calculations Concerning the Valence Isomerization of 2-Amino-2H-pyran and -thiopyranThe equilibrium 2-amino-2H-pyran 6 ⇌ 5-amino-2,4-dien-1-one 7 was investigated using the semi-empirical MINDO/3 and MNDO methods. In accordance with experimental findings for the substituted derivatives 1/2a-d, the introduction of a methyl group into the position 3 of 6 or the exchange of oxygen by sulfur shifts the equilibrium towards the cyclic structures 8 and 10, respectively. Polar solvents, the influence of which was estimated applying the reaction field approach as well as the solvaton theory, and entropy effects are calculated to favour the ring-open valence isomer 7. These results also correspond to experimental results.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19843260614
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