Artículo
Estruch, G.A.; Aramendía, P.F. "Photoisomerization of alfa calcidol by a sensitized quantum chain reaction" (2012) Photochemistry and Photobiology. 88(4):769-773
Consulte la política de Acceso Abierto del editor
Abstract:
The production of vitamin D3 is a pharmaceutically relevant process, producing high added-value products. Precursors are extracts from vegetal origin but bearing mainly an E geometry in the 5,6 double bond. The synthesis of vitamin D3 (5-E-α-calcidol) with the correct Z stereochemistry in the 5,6 double bond from the E isomer using anthracene and triethylamine (TEA) as the sensitizer system was studied from the kinetic and mechanistic point of view. The sensitized isomerization of E-calcidol by irradiation of anthracene takes place only in deoxygenated solution and yields the Z isomer in ca 5% yield in the photostationary state. When TEA is added to the system, the E-Z reaction is not inhibited by oxygen any more, the quantum yield of photoisomerization to the Z isomer grows linearly with the concentration of E-calcidol, while conversions higher than 95% to the Z isomer are reached in the photostationary state and E-Z quantum yields as high as 45 at [E-calcidol] = 25 mm are reached. If TEA is replaced by 1,4-diazabicyclo[2.2.2]octane, the reaction rate drops to one-third at the same amine concentration. The observations can be explained by a quantum chain reaction mechanism. The high conversion achieved eliminates the need of isomer separation. © 2012 Wiley Periodicals, Inc.
Registro:
| Documento: | Artículo |
| Título: | Photoisomerization of alfa calcidol by a sensitized quantum chain reaction |
| Autor: | Estruch, G.A.; Aramendía, P.F. |
| Filiación: | Departamento de Química Inorgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellõn 2, 1428 Ciudad de Buenos Aires, Argentina |
| Palabras clave: | 1,4 diazabicyclo[2.2.2]octane; anthracene; anthracene derivative; colecalciferol; ethylamine; oxygen; piperazine derivative; triethylamine; chemical structure; chemistry; conference paper; high performance liquid chromatography; isomerism; kinetics; photochemistry; quantum theory; solution and solubility; spectroscopy; synthesis; thermodynamics; ultraviolet radiation; Anthracenes; Cholecalciferol; Chromatography, High Pressure Liquid; Ethylamines; Isomerism; Kinetics; Models, Molecular; Oxygen; Photochemical Processes; Piperazines; Quantum Theory; Solutions; Spectrum Analysis; Thermodynamics; Ultraviolet Rays |
| Año: | 2012 |
| Volumen: | 88 |
| Número: | 4 |
| Página de inicio: | 769 |
| Página de fin: | 773 |
| DOI: | http://dx.doi.org/10.1111/j.1751-1097.2011.01054.x |
| Título revista: | Photochemistry and Photobiology |
| Título revista abreviado: | Photochem. Photobiol. |
| ISSN: | 00318655 |
| CODEN: | PHCBA |
| CAS: | 1,4 diazabicyclo[2.2.2]octane, 280-57-9; anthracene, 120-12-7; colecalciferol, 1406-16-2, 67-97-0; ethylamine, 75-04-7; oxygen, 7782-44-7; triethylamine, 121-44-8; Anthracenes; Cholecalciferol, 67-97-0; Ethylamines; Oxygen, 7782-44-7; Piperazines; Solutions; anthracene, EH46A1TLD7; triethylamine, VOU728O6AY; triethylenediamine, 280-57-9 |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00318655_v88_n4_p769_Estruch |
Referencias:
- Kimlin, M.G., Geographic location and vitamin D synthesis (2008) Mol. Asp. Med., 29, pp. 453-461
- Moon, S.J., Fryer, A.A., Strange, R.C., Ultraviolet radiation, Vitamin D and risk of prostate cancer and other diseases (2005) Photochem. Photobiol., 81, pp. 1252-1260
- Lehmann, B., The Vitamin D3 pathway in human skin and its role for regulation of biological processes (2005) Photochem. Photobiol., 81, pp. 1246-1251
- Holick, M.F., MacLaughlin, J.A., Clark, M.B., Photosynthesis of previtamin D3 in human skin and the physiologic consequences (1980) Science, 210, pp. 203-205
- Braun, A.M., Maurettte, M.-T., Oliveros, E., (1986) Technologie Photochimique, pp. 483-505. , pp. Presses Polytechniques Romandes, Lausanne, Switzerland, Chapter 12
- Kubodera, N., Pharmaceutical studies on vitamin D derivatives and practical syntheses of six commercially available vitamin D derivatives that contribute to current clinical practice (2010) Heterocycles, 80, pp. 83-98
- Moriarty, R.M., Albinescu, D., Synthesis of 1a-Hydroxyvitamin D5 using a modified two wavelength photolysis for vitamin D formation (2005) J. Org. Chem., 70, pp. 7624-7628
- Calverley, M.J., Synthesis of mc 903, a biologically active vitamin D metabolite analogue (1987) Tetrahedron, 43, pp. 4609-4619
- Hyndman, H.L., Monroe, B.M., Hammond, G.S., Mechanisms of photochemical reactions in solution. LX. Photochemical isomerization of 2,4-hexadiene via a quantum-chain mechanism (1969) J. Am. Chem. Soc., 91, pp. 2852-2859
- Saltiel, J., Townsend, D.E., Sykes, A., The quantum chain process in the sensitized cis-trans photoisomerization of 1,3-dienes (1973) J. Am. Chem. Soc., 95, pp. 5968-5973
- Ganapathy, S., Trehan, A., Liu, R.S.H., Photoisomerization of 7-cis-retinal. The concentration effect (1990) J. Chem. Soc. Chem. Commun., pp. 199-200
- Ganapathy, S., Liu, R.S.H., Photoisomerization of polyenes. 30. Quantum chain processes in photoisomerization of the all-trans, 7-cis, and 11-cis isomers of retinal (1992) J. Am. Chem. Soc., 114, pp. 3459-3464
- Hentz, R.R., Shima, K., Burton, M., High-energy induced isomerization of stilbene in benzene solution (1967) J. Phys. Chem., 71, pp. 461-462
- Dainton, F.S., Peng, C.T., Salmon, G.A., Transient species in the radiolysis of solutions of stilbene (1968) J. Phys. Chem., 72, pp. 3801-3807
- Mizuno, K., Ichinose, N., Otsuji, Y., Photochemistry of 9,10-dicyanoanthracene-1,2-diarylcyclopropane systems. Photocycloaddition and photoisomerization (1992) J. Org. Chem., 57, pp. 1855-1860
- Mizuno, K., Nire, K., Sugita, H., Maeda, H., A novelcis-trans photoisomerization of vinylidenecyclopropanes via an electron-transfer chain process (2001) Tetrahedron Lett., 42, pp. 2689-2692
- Takagi, K., Aoshima, K., Sawaki, Y., Iwamura, H., Electron-relay chain mechanism in the sensitized photoisomerization of stilbazole salts in aqueous anionic micelles (1985) J. Am. Chem. Soc., 107, pp. 47-52
- Arai, T., Tokumaru, K., Photochemical one-way adiabatic isomerization of aromatic olefins (1993) Chem. Rev., 93, pp. 23-39
- Arai, T., Photochemical cis-trans isomerization in the triplet state (1999) Molecular and Supramolecular Photochemistry. Vol. 3. Organic Molecular Photochemistry, pp. 131-167. , In (Edited by V. Ramamurthy and K. S. Schanze), pp. Marcel Dekker, New York
- Daraio, M.E., Volker, A., Aramendía, P.F., San Román, E., Reaction of zinc phtalocyanine excited states with amines in cationic micelles (1996) Langmuir, 12, pp. 2932-2938
- Brink, M., Jonson, H., Sundahl, M., Catalysis of triplet state cis-trans isomerizations making a quantum chain process more efficient (1998) J. Photochem. Photobiol. A: Chem., 112, pp. 149-153
Citas:
---------- APA ----------
Estruch, G.A. & Aramendía, P.F. (2012) . Photoisomerization of alfa calcidol by a sensitized quantum chain reaction. Photochemistry and Photobiology, 88(4), 769-773.http://dx.doi.org/10.1111/j.1751-1097.2011.01054.x
---------- CHICAGO ----------
Estruch, G.A., Aramendía, P.F. "Photoisomerization of alfa calcidol by a sensitized quantum chain reaction" . Photochemistry and Photobiology 88, no. 4 (2012) : 769-773.http://dx.doi.org/10.1111/j.1751-1097.2011.01054.x
---------- MLA ----------
Estruch, G.A., Aramendía, P.F. "Photoisomerization of alfa calcidol by a sensitized quantum chain reaction" . Photochemistry and Photobiology, vol. 88, no. 4, 2012, pp. 769-773.http://dx.doi.org/10.1111/j.1751-1097.2011.01054.x
---------- VANCOUVER ----------
Estruch, G.A., Aramendía, P.F. Photoisomerization of alfa calcidol by a sensitized quantum chain reaction. Photochem. Photobiol. 2012;88(4):769-773.http://dx.doi.org/10.1111/j.1751-1097.2011.01054.x
