Abstract
The chemistry and the regioselectivity of alcoholysis, aminolysis, and hydrolysis of symmetrical trimethinecyanine carbenium ions in 4-[3-(2,2-diorganyl-6-phenyl-4H-1,3-dioxen-4-ylidene) prop-1-enyl]-2,2-diorganyl-6-phenyl-1,3-dioxenium perchlorates (4a,b) were investigated. The structures of trimethinecyanine 4,5:4′,5′-bisannelated at the methine chain (3) and of a product of the reaction of nonannelated trimethinecyanine with the methoxide anion were established by X-ray diffraction analysis,1H NMR spectroscopy, and quantum-chemical calculations (PM3). The nucleophile attacks the mesomeric π-conjugated system of the trimethinecyanine cation selectivily at the C(6) atom of one of the dioxenium fragrments, the second dioxenium ring being deactivated. Alcoholysis affords products of addition of the methoxy group to trimethinecyamines. In the course of aminolysis and hydrolysis, the dioxenium ring that is subjected to the attack eliminates acetone to form 1,3-dioxenylidenepropenylic derivatives of 1,3-enaminoketones and 1,3-ketoenols, respectively.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 521–529, March. 1999.
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Arseniev, V.G., Olekhnovich, E.P., Borbulevych, O.Y. et al. Reactions of trimethinecyanines of the 1,3-dioxenium series with nucleophiles. The structures of the parent carbocation and of a product of its reaction with methanol. Russ Chem Bull 48, 516–524 (1999). https://doi.org/10.1007/BF02496173
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DOI: https://doi.org/10.1007/BF02496173
Key words
- 2,2-dimethyl-6-[3-2,2-dimethyl-6-phenyl-4H-1,3-dioxen-4-ylidene) prop-1-enyl]-4-methoxy-4-phenyl-4H-1,3-dioxene
- 4-methoxy-4-phenyl-2-[3-(4-phenyl-1,5-dioxaspiro[5.5]undec-3-en-2-ylidene)prop-1-enyl]-1,5-dioxaspiro[5.5]undec-2-ene
- 1-amino-6-(2,2-dimethyl-6-phenyl-4H-1,3-dioxen-4-ylidene)-1-phenylhexa-1,4-dien-3-one
- 6-(2,2-dimethyl-6-phenyl-4H-1,3-dioxen-4-ylidene)-1-morpholino-1-phenylhexa-1,4-dien-3-one
- 6-(2,2-dimethyl-6-phenyl-4H-1,4-dioxen-4-ylidene)-1-hydroxy-1-phenylhexa-1,4-dien-3-one
- X-ray diffraction study, molecular structure