Synthesis, spectroscopic, structural and electrochemical studies of carboxyl substituted 1,4-naphthoquinones

被引:24
作者
Boudalis, Athanassios K. [1 ]
Policand, Xavier [1 ]
Sournia-Saquet, Alix [1 ]
Donnadieu, Bruno [1 ]
Tuchagues, Jean-Pierre [1 ]
机构
[1] CNRS, Chim Coordinat Lab, UPR 8241, F-31077 Toulouse, France
关键词
carboxyl substituted quinones; ester derivatives of carboxyl substituted quinones; spectroscopic and electrochemical studies; stabilization of electrogenerated semiquinones; intermolecular self-protonation; single-crystal X-ray structures;
D O I
10.1016/j.ica.2007.02.027
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Two carboxyl substituted quinones and their ethyl esters were prepared by alkylation of 2-methyl-1,4-naphthoquinone (MNQ), also known as menadione or vitamin K-3. All products were characterized by spectroscopic (H-1 NMR, C-13 NMR, IR) and electrochemical (cyclic voltammetry) methods, and the crystal structure of the two carboxylic derivatives was also determined. Both carboxyl substituted quinones crystallize in the P (1) over bar system as hydrogen bonded dimers. In MeCN, the cyclic voltammograms of the ester derivatives present two reversible one-electron redox waves very similar to those of the parent quinone, MNQ. However, in the same solvent, the corresponding carboxyl substituted quinones show one cathodic and one anodic additional irreversible waves at more positive potentials and a decrease in current intensity of the two quinone reduction waves accompanied by loss of the quasi-reversible character of the second wave. These results show that the presence of the carboxylic substituent does not greatly modify the redox behaviour of the quinone, except for a small anodic shift of the potentials, but the associated presence of H+ ions in solution causes an important perturbation to the system, stabilizing the electrogenerated semiquinones by intermolecular self-protonation and/or hydrogen bonding. (C) 2007 Elsevier B. V. All rights reserved.
引用
收藏
页码:1681 / 1688
页数:8
相关论文
共 45 条
[1]   STRUCTURE OF THE REACTION CENTER FROM RHODOBACTER-SPHAEROIDES R-26 - PROTEIN COFACTOR (QUINONES AND FE-2+) INTERACTIONS .5. [J].
ALLEN, JP ;
FEHER, G ;
YEATES, TO ;
KOMIYA, H ;
REES, DC .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1988, 85 (22) :8487-8491
[2]   STRUCTURE OF THE REACTION CENTER FROM RHODOBACTER-SPHAEROIDES R-26 - THE COFACTORS .1. [J].
ALLEN, JP ;
FEHER, G ;
YEATES, TO ;
KOMIYA, H ;
REES, DC .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1987, 84 (16) :5730-5734
[3]   COMPLETION AND REFINEMENT OF CRYSTAL-STRUCTURES WITH SIR92 [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, C ;
GUAGLIARDI, A .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1993, 26 (pt 3) :343-350
[4]   SIR97:: a new tool for crystal structure determination and refinement [J].
Altomare, A ;
Burla, MC ;
Camalli, M ;
Cascarano, GL ;
Giacovazzo, C ;
Guagliardi, A ;
Moliterni, AGG ;
Polidori, G ;
Spagna, R .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 :115-119
[5]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[6]  
[Anonymous], 1999, J. Appl. Crystallogr, DOI [DOI 10.1107/S0021889899006020, 10.1107/S0021889899006020]
[7]  
[Anonymous], 1998, SHELX97 INCLUDES SHE
[8]   THE INVENTION OF RADICAL REACTIONS .19. THE SYNTHESIS OF VERY HINDERED QUINONES [J].
BARTON, DHR ;
SAS, W .
TETRAHEDRON, 1990, 46 (10) :3419-3430
[9]  
CASSOUX P, 1994, ACTUAL CHIM, V1, P49
[10]  
Clayton R.K., 1980, Photosynthesis: physical mechanisms and chemical patterns