Artículo

Hoijemberg, P.A.; Karlen, S.D.; Sanramé, C.N.; Aramendía, P.F.; García-Garibay, M.A. "Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state" (2009) Photochemical and Photobiological Sciences. 8(7):961-969
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Abstract:

In this work we study the product distribution in the steady state photolysis of a diazene, (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene, and a ketone, 2,4-bis(biphenyl-4-yl)-2,4-dimethyl-pentan-3-one, in the solid state and in solution. The two compounds yield 1-biphenyl-4-yl-1-methyl-ethyl (BME) radicals upon photolysis. The ketone yields two units of this radical, whereas the diazene yields one BME and one tert-butyl radical. Product analysis of the two compounds in solution makes it possible to differentiate their origin from their corresponding geminate cages, and from the different encounter pairs in the case of the asymmetrically substituted diazene photolysis. In this way we obtain a complete reaction scenery for the diazene, a compound with interesting features as a radical photoinitiator and as a cage effect probe in fluid media. The reaction in cages containing two BME radicals shows a decrease by a factor of 4 in the ratio of combination to disproportionation products upon going from the solid to the liquid phase. On the contrary, the reaction in cages containing a BME and a tert-butyl radical shows a 30-fold increase in combination to disproportionation ratio in liquid compared to the crystal. We analyze the reasons for these differences considering the differences in the reactivity of the radicals and in cage rigidity. © The Royal Society of Chemistry and Owner Societies 2009.

Registro:

Documento: Artículo
Título:Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state
Autor:Hoijemberg, P.A.; Karlen, S.D.; Sanramé, C.N.; Aramendía, P.F.; García-Garibay, M.A.
Filiación:INQUIMAE and Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, UBA, Pabellón 2 Ciudad Universitaria 1428, Buenos Aires, Argentina
Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, United States
Department of Chemistry, Oxford University, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA., United Kingdom
Transform Pharmaceuticals Inc., 29 Hartwell Ave., Lexington, MA 02421, United States
Palabras clave:biphenyl; diamide; ketone derivative; radical; article; chemical reaction kinetics; controlled study; crystal structure; energy; entropy; liquid; photochemistry; photolysis; priority journal; solid state; substitution reaction; temperature
Año:2009
Volumen:8
Número:7
Página de inicio:961
Página de fin:969
DOI: http://dx.doi.org/10.1039/b902272d
Título revista:Photochemical and Photobiological Sciences
Título revista abreviado:Photochem. Photobiol. Sci.
ISSN:1474905X
CODEN:PPSHC
CAS:biphenyl, 92-52-4; diamide, 10465-78-8
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1474905X_v8_n7_p961_Hoijemberg

Referencias:

  • Engel, P.S., Ying, Y.M., He, S.L., An aliphatic bifunctional free radical initiator. Synthesis of a block copolymer from an azoperester by sequential thermal and photochemical initiation (2003) Macromolecules, 36, pp. 3821-3825
  • Rabek, J.F., (1987) Mechanisms of Photophysical Processes and Photochemical Reactions in Polymers, , Wiley & Sons, New York
  • Engel, P.S., Mechanism of the thermal and photochemical decomposition of azoalkanes (1980) Chem. Rev., 80, pp. 99-150
  • Adam, W., Oppenlander, T., 185 nm Photochemistry of olefins, strained hydrocarbons, and azoalkanes in solution (1986) Angew. Chem., Int. Ed. Engl., 25, pp. 661-672
  • Fogel, L.D., Steel, C., Photochemistry of azoisopropane (1976) J. Am. Chem. Soc., 98, pp. 4859-4867
  • Gould, I.R., Zimmt, M.B., Turro, N.J., Baretz, B.H., Lehr, G.F., Dynamics of radical pair reactions in micelles (1985) J. Am. Chem. Soc., 107, pp. 4607-4612
  • Diau, E.W.G., Zewail, A.H., Femtochemistry of trans-azomethane: A combined experimental and theoretical study (2003) ChemPhysChem, 4, pp. 445-456
  • O'Shea, K.E., Combes, J.R., Fox, M.A., Johnston, K.P., Photolysis of dibenzylketones in supercritical ethane and carbon-dioxide (1991) Photochem. Photobiol., 54, pp. 571-576
  • Turro, N.J., García Garibay, M.A., Thinking topologically about photochemistry (1991) Photochemistry in Organized and Constrained Media, pp. 39-77. , ed. V. Ramamurthy, VCH Publishers, New York. Ch. 2
  • Claridge, R.F.C., Fischer, H., Self-termination and electronic spectra of substituted benzyl radicals in solution (1983) J. Phys. Chem., 87, pp. 1960-1967
  • Jaffe, A.B., Skinner, K.J., McBride, J.M., Solvent steric effects. II. Free-radical, chemistry of azobisisobutyronitrile and azobis-3-cyano-3-pentane in viscous and crystalline media (1972) J. Am. Chem. Soc., 94, pp. 8510-8515
  • Jaffe, A.B., Malament, D.S., Slisz, E.P., McBride, J.M., Solvent steric effects. III. Molecular, and crystal structures of azobisisobutyronitrile and azobis-3-cyano-3-pentane. Structural deuterium isotope effect (1972) J. Am. Chem. Soc., 94, pp. 8515-8521
  • Skinner, K.J., Blaskiewicz, R.J., McBride, J.M., Solid-state photolysis of azobis-3-phenyl-3-pentane. Crystal-lattice control of the stereochemistry of radical disproportionation (1972) Isr. J. Chem., 10, pp. 457-470
  • Danek, S.K., Kelly, D.P., Serelis, A.K., A stereospecific synthesis of azo nitriles (1987) J. Org. Chem., 52, pp. 2911-2919
  • Engel, P.S., Pan, L., Ying, Y.M., Alemany, L.B., Thermolysis of free-radical initiators: Tert-butylazocumene and its 1,3-and 1,4-bisazo and 1,3,5-trisazo analogues (2001) J. Am. Chem. Soc., 123, pp. 3706-3715
  • Ciganek, E., Tertiary carbinamines by addition of organocerium reagents to nitriles and ketimines (1992) J. Org. Chem., 57, pp. 4521-4527
  • Bundes, D., (1975), German Patent 2401819; Bhandari, S., Ray, S., A novel synthesis of bisbenzyl ketones by DCC induced condensation of phenylacetic acid (1998) Synth. Commun., 28, pp. 765-771
  • Sauriat-Dorizon, H., Maris, T., Wuest, J.D., Enright, G.D., Molecular tectonics. Construction of porous hydrogen-bonded networks from bisketals of pentaerythritol (2003) Journal of Organic Chemistry, 68 (2), pp. 240-246. , DOI 10.1021/jo026267t
  • Stille, J.K., Noren, G.K., Catenation and kinetics of the Diels-Alder step-growth reaction in the synthesis of phenylated polyphenylenes (1972) Macromolecules, 5, pp. 49-55
  • Millard, A.A., Rathke, M.W., Procedure for permethylation of ketones using potassium hydride and methyl-iodide (1978) J. Org. Chem., 43, pp. 1834-1835
  • Grovenstein, E., Lu, P.C., Carbanions.21. Reactions of 2-p-biphenylylalkyl and 3-p-biphenylylalkyl chlorides with alkali-metals - Preparation of labile spiro anions (1982) J. Org. Chem., 47, pp. 2928-2939
  • Gauglitz, G., Azobenzene as a convenient actinometer for determination of quantum yields of photoreactions (1976) J. Photochem., 5, pp. 41-47
  • Gauglitz, G., Hubig, S., Azobenzene as a convenient actinometer - Evaluation values for UV mercury lines and for the N<inf>2</inf> laser line (1981) J. Photochem., 15, pp. 255-257
  • Gauglitz, G., Hubig, S., Chemical actinometry in the UV by azobenzene in concentrated solution - A convenient method (1985) J. Photochem., 30, pp. 121-125
  • Kuhn, H.J., Braslavsky, S.E., Schmidt, R., Chemical actinometry (2004) Pure Appl. Chem., 76, pp. 2105-2146
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Pople, J.A., (1998) GAUSSIAN 98 (Revision A.7), , Gaussian, Inc., Pittsburgh, PA
  • Resendiz, M.J.E., García-Garibay, M.A., Hammett analysis of photodecarbonylation in crystalline 1,3-diarylacetones (2005) Org. Lett., 7, pp. 371-374
  • Skinner, K.J., Hochster, H.S., McBride, J.M., O- and p-Semibenzene dimers of benzylic radicals. Autoxidation of quinoid dimers (1974) J. Am. Chem. Soc., 96, pp. 4301-4306
  • Nelsen, S.F., Bartlett, P.D., Azocumene. I. Preparation, and decomposition of azocumene. Unsymmetrical coupling products of the cumyl radical (1966) J. Am. Chem. Soc., 88, pp. 137-143
  • Boate, D.R., Scaiano, J.C., Transient phenomena in the photochemistry of trans-azocumene (1989) Tetrahedron Lett., 30, pp. 4633-4636
  • Gould, I.R., Baretz, B.H., Turro, N.J., Primary processes in the type i photocleavage of dibenzyl ketones. A pulsed laser and photochemically induced dynamic nuclear polarization study (1987) J. Phys. Chem., 91, pp. 925-929
  • Sheldon, R.A., Kochi, J.K., Pair production and cage reactions of alkyl radicals in solution (1970) J. Am. Chem. Soc., 92, pp. 4395-4404
  • Schuh, H.H., Fischer, H., The kinetics of the bimolecular self-reaction of t-butyl radicals in solution. II. Disproportionation/combination ratios (1978) Helv. Chim. Acta, 61, pp. 2463-2481

Citas:

---------- APA ----------
Hoijemberg, P.A., Karlen, S.D., Sanramé, C.N., Aramendía, P.F. & García-Garibay, M.A. (2009) . Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state. Photochemical and Photobiological Sciences, 8(7), 961-969.
http://dx.doi.org/10.1039/b902272d
---------- CHICAGO ----------
Hoijemberg, P.A., Karlen, S.D., Sanramé, C.N., Aramendía, P.F., García-Garibay, M.A. "Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state" . Photochemical and Photobiological Sciences 8, no. 7 (2009) : 961-969.
http://dx.doi.org/10.1039/b902272d
---------- MLA ----------
Hoijemberg, P.A., Karlen, S.D., Sanramé, C.N., Aramendía, P.F., García-Garibay, M.A. "Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state" . Photochemical and Photobiological Sciences, vol. 8, no. 7, 2009, pp. 961-969.
http://dx.doi.org/10.1039/b902272d
---------- VANCOUVER ----------
Hoijemberg, P.A., Karlen, S.D., Sanramé, C.N., Aramendía, P.F., García-Garibay, M.A. Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state. Photochem. Photobiol. Sci. 2009;8(7):961-969.
http://dx.doi.org/10.1039/b902272d