Artículo
Völker, E.; O'Connell, M.; Negri, R.M.; Aramendía, P.F. "Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates)" (2001) Helvetica Chimica Acta. 84(9):2751-2764
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Abstract:
The thermal back-isomerization of spiro[indole-naphtho-oxazine] 1 and spiro[indole-phenanthro-oxazine] 2 was studied in a series of primary alcohols, nitriles, and poly(methylmethacrylate), poly(ethylmethacrylate), and poly(isobutyl methacrylate) films by laser-flash photolysis in the temperature range of 0-70°. The decay is monoexponential in fluid solution, but deviates strongly from this behavior in polymeric environments even above the glass transition temperature of the polymers (Tg). In liquids, a very small solvent effect is observed on the isomerization rate constants (kiso) for 1, which is attributed mostly to the solvent viscosity η. The values of kiso for 2 show influence of solvent viscosity and polarity, which were studied by application of a semiempirical relationship that accounts for non-Markovian processes. The decay kinetics in polymers was described by a Gaussian distribution of the activation energy and by a kinetic model that takes into account the simultaneous relaxation of the probe and the environment. For 1 and 2, the rate constant at the center of the Gaussian distribution is very similar to the first-order rate constant in nonpolar solvents. The Gaussian width of the distribution (σ) decreases with temperature and is very similar in all polymers under Tg, and, above Tg, σ decreases more abruptly. We make comparisons of the parameters derived from analysis of both 1 and 2 in polymers, as well as of their behaviors in solution and in polymers.
Registro:
| Documento: | Artículo |
| Título: | Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates) |
| Autor: | Völker, E.; O'Connell, M.; Negri, R.M.; Aramendía, P.F. |
| Filiación: | INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina |
| Palabras clave: | Activation energy; Derivatives; Glass transition; Organic compounds; Photolysis; Polarization; Polymers; Viscosity; Thermal back-isomerization; Isomerization; alcohol; naphthol derivative; nitrile; oxazine derivative; phenanthroline derivative; poly(ethyl methacrylate); poly(isobutyl methacrylate); poly(methyl methacrylate); polymethacrylic acid; solvent; spiro compound; spiro(indolenaphthooxazine); spiro(indolephenanthrooxazine); unclassified drug; article; isomerism; phase transition; photolysis; polymerization; temperature dependence; thermal analysis; viscosity |
| Año: | 2001 |
| Volumen: | 84 |
| Número: | 9 |
| Página de inicio: | 2751 |
| Página de fin: | 2764 |
| DOI: | http://dx.doi.org/10.1002/1522-2675(20010919)84:9<2751::AID-HLCA2751>3.0.CO;2-H |
| Título revista: | Helvetica Chimica Acta |
| Título revista abreviado: | Helv. Chim. Acta |
| ISSN: | 0018019X |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0018019X_v84_n9_p2751_Volker |
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Citas:
---------- APA ----------
Völker, E., O'Connell, M., Negri, R.M. & Aramendía, P.F. (2001) . Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates). Helvetica Chimica Acta, 84(9), 2751-2764.http://dx.doi.org/10.1002/1522-2675(20010919)84:9<2751::AID-HLCA2751>3.0.CO;2-H
---------- CHICAGO ----------
Völker, E., O'Connell, M., Negri, R.M., Aramendía, P.F. "Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates)" . Helvetica Chimica Acta 84, no. 9 (2001) : 2751-2764.http://dx.doi.org/10.1002/1522-2675(20010919)84:9<2751::AID-HLCA2751>3.0.CO;2-H
---------- MLA ----------
Völker, E., O'Connell, M., Negri, R.M., Aramendía, P.F. "Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates)" . Helvetica Chimica Acta, vol. 84, no. 9, 2001, pp. 2751-2764.http://dx.doi.org/10.1002/1522-2675(20010919)84:9<2751::AID-HLCA2751>3.0.CO;2-H
---------- VANCOUVER ----------
Völker, E., O'Connell, M., Negri, R.M., Aramendía, P.F. Thermal back-isomerization of spirocyclic naphtho-oxazine and phenanthro-oxazine derivatives in alcohols, nitriles, and poly(alkyl methacrylates). Helv. Chim. Acta. 2001;84(9):2751-2764.http://dx.doi.org/10.1002/1522-2675(20010919)84:9<2751::AID-HLCA2751>3.0.CO;2-H
