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Abstract

Photochemical Study of the Reactions of the 2-Naphtoxide Ion with Haloadamantanes

Departamento de Química. Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria. (5000) Córdoba, Argentina
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Authors to whom correspondence should be addressed.
Molecules 2000, 5(3), 455-456; https://doi.org/10.3390/50300455
Published: 22 March 2000

Abstract

:
The fluorescent excited state of 2-naphtoxide ion is quenched by haloadamantanes (X-Ada) as electron acceptors according to an electron-transfer mechanism. This mechanism is proposed on the basis of:1) decreasing quenching rate constant as the reduction potential of X-Ada is made more negative and 2) the analysis of reaction products.

Introduction

It is known that the 2-naphtoxide ion reacts with a variety of aryl halides under photostimulation in liquid ammonia yielding 1-aryl-2-naphtoxides as substitution products.[1] It was proposed that these reactions occur by the SRN1 mechanism, and involve the participation of radicals and radical anions as intermediates. However, no quantitative photochemical studies of these reactions have been performed. Considering that the photophysics of 2-naphtoxide ion was determined by Soumillion and coworkers, [2] we undertook a systematic study of the photoinduced reaction of this ion with haloadamantanes.

Results and Discussion

The deactivation of the singlet excited state of 2-naphtoxide ion by haloadamantanes, X-Ada, was studied in dimethylsulfoxide (DMSO) by fluorescence stationary techniques. The results obtained from the inhibition of the fluorescence of 2-naphtoxide ion by 1-iodo, 1-bromo and 1-chloroadamantane showed Stern-Volmer linear plots. The quenching rate constants from these plots show a good correlation with the reduction potentials of the adamantyl halides. (Table 1).
Figure 1. Quenching of 2-naphtoxide ion by 1-Iodoadamantane.
Figure 1. Quenching of 2-naphtoxide ion by 1-Iodoadamantane.
Molecules 05 00455 g001
1-Iodoadamantane quenches the fluorescence of 2-naphtoxide ion with a rate constant near the diffusion limit (kdiff for DMSO = 3,3x109 M-1s-1) [4] . A plot of the logarithm of the rate constants vs. the change in free energy follows a typical behavior for an electron transfer reaction. From the photochemical study we performed a detailed analysis of the reaction products. Thus, the photoinduced reaction of 2-naphtoxide ion with 1-iodoadamantane in DMSO rendered a mixture of adamantane (coming from the reduction of the adamantyl radical intermediate), substitution products (which arise from the addition of the adamantyl radical to the 3, 6 and 8 positions of the ion) as well as 1adamantanol and minor amounts of 1-adamantyl-2-naphthylether.

References and Notes

  1. Pierini, A. B.; Baumgartner, M. T.; Rossi, R. A. J. Org. Chem. 1991, 56, 580.
  2. Soumillion, J.; Vandereecken, P.; Van Der Auweraer, M.; De Schryver, F. C.; Schanck, A. J. Am. Chem. Soc. 1989, 111, 2217.
  3. Adcock, W.; Clark, C. I.; Houmam, A.; Krstic, A. R.; Pinson, J.; Savéant, J.-M.; Taylor, D. K.; Taylor, J. F. J. Am. Chem. Soc. 1994, 116, 4653.
  4. Murov, S. L.; Carmichael, I.; Hug, G. L. Handbook of Photochemistry, 2nd Edition; Marcel Dekker, Inc.: New York, 1993. [Google Scholar]
Table 1. Fluorescence quenching of the 2-naphtoxide ion by X-Ada.
Table 1. Fluorescence quenching of the 2-naphtoxide ion by X-Ada.
X-Ada (Q)kSVkq (109 M-1s-1)log kqEred [3]
1-Iodoadamantane1035.79.8-2,20
1-Bromoadamantane2.20.128.1-2,54
1-Chloroadamantane0.810.0457.65-2,64

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MDPI and ACS Style

Argüello, J.E.; Puiatti, M.; Peñéñory, A.B. Photochemical Study of the Reactions of the 2-Naphtoxide Ion with Haloadamantanes. Molecules 2000, 5, 455-456. https://doi.org/10.3390/50300455

AMA Style

Argüello JE, Puiatti M, Peñéñory AB. Photochemical Study of the Reactions of the 2-Naphtoxide Ion with Haloadamantanes. Molecules. 2000; 5(3):455-456. https://doi.org/10.3390/50300455

Chicago/Turabian Style

Argüello, Juan E., Marcelo Puiatti, and Alicia B. Peñéñory. 2000. "Photochemical Study of the Reactions of the 2-Naphtoxide Ion with Haloadamantanes" Molecules 5, no. 3: 455-456. https://doi.org/10.3390/50300455

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