Synthesis and Electrochemical Characterization of New Water Soluble Thiophene Derivatives

STELIAN LUPU1*, PAUL CATALIN BALAURE2,*, ION COSTEA2, CECILIA LETE3, MARIANA MARIN3, CRISTIAN ENACHE4 1 Department of Analytical Chemistry and Instrumental Analysis, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 1-3 Polizu Str., 011061, Bucharest, Romania 2 Department of Organic Chemistry, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 1-3 Polizu Str., 011061, Bucharest, Romania 3 Institute of Physical Chemistry Ilie Murgulescu, 202A Splaiul Independentei, 060021, Bucharest, Romania 4 Central Laboratory for Phytosanitary Quarantine, 11 Afumati Str., Bucharest, Romania

The synthesis and the electrochemical characterisation of new water soluble thiophene derivatives are reported. (3-Thenyl)triethylammonium bromide and (3-thenyl)triethylammonium perchlorate were obtained by bromination of 3-methylthiophene and using the corresponding bromoderivative as alkylation agent in reaction with triethylamine in dry benzene. The new thiophene derivatives were characterised by 1H-NMR, 13C-NMR, heteronuclear correlations experiments, and ESI-MS techniques. The electrochemical characterization of the new compounds has been performed in aqueous solution by means of cyclic voltammetry. Keywords: thiophene derivatives, quaternary ammonium salts, cyclic voltammetry

During the last two decades much interest has been devoted to the synthesis and characterization of new organic conducting polymers due to their electronic and electrochemical properties. Organic conducting polymers can be deposited as thin films onto conventional electrode substrates allowing the preparation of new chemically modified electrodes. A large number of conducting polymers has been prepared by using various monomers, such as aniline, pyrrole and thiophene as well as their derivatives [1-5]. Usually the chemical or electrochemical synthesis is carried out in organic media and the resulted polymer is characterised in view of the applications in organic media. The use of solvents is related to safety health and environmental pollution problems and nowadays several procedures are used to reduce their impact on the quality of life and environment. For these reasons new synthetic procedures and new organic conducting polymers have been developed in order to allow the use of friendly environmental and safety compounds. Design of new substances and materials that can be used to prepare modified electrodes suitable for analytical applications in aqueous media is therefore a research area of great interest. Quaternary ammonium salts are among those substances used to achieve this goal. They have been used in order to increase the electrochemical flux of larger redox species such as erythromycin that, otherwise, cannot be detected at a Nafion modified electrode [6, 7]. In above mentioned references a Nafion membrane incorporated with quaternary ammonium bromides, prepared by simple co-casting the quaternary ammonium bromide with a suspension of the perfluorinated sulfonate polymer, was pipetted onto the electrode surface followed by solvent evaporation and a final thermal treatment (annealing) of the modified electrode surface. Quaternary ammonium salts can also be immobilized on silica gel by chemically modifying silica on treatment, for instance, with 3aminopropyltriethoxysilane and alkylation of the terminal amino group [8]. By supporting this material on a mixture of graphite powder with epoxy resin, a potentiometric sensor for perchlorate ions was prepared. Synthesis of new
* email: stelianl@yahoo.com
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thiophene derivatives bearing appropriate moieties that make them water soluble and able to polymerize in aqueous media, by electrochemical or chemical means, giving rise to highly conjugated electroactive polymers suitable for electrochemical sensing of a large scale of analytes is also of major interest [9]. For instance, copolymerization between 3-[N-succinimido (tetraethoxy) oxy]-4-methyl thiophene and 1-methyl-3-[3-(2-ethoxy)-4methylthiophene]imidazolium bromide leads to a water soluble copolymer that was used with good results as biosensor for alkali metals ions and nucleic acids [10, 11]. Other quaternary ammonium salts, such as tetrabutylammonium (3-thienyl)ethoxybutanesulfonate (TEBSTA) and tetrabutylammonium (3,4-ethylenedioxy) methoxybutanesulfonate (EDOTSTBA), contain as their anion a sulfonated thiophene derivative, and can be easily polymerized in water with iron trichloride [12, 13], the resulting conducting polythiophenes being also water soluble. Due to this special property thin films of these polymers have been spray coated on a SnO2 substrate [12]. With respect to this growing interest for new water soluble monomers, we report the synthesis and electrochemical characterization of some new water soluble quaternary ammonium salts containing a 3-thenyl moiety. Experimental part The NMR spectra were recorded on a 200 MHz VARIAN spectrometer, using D2O as a solvent. ESI mass spectra were recorded on a 1200 L/MS/MS VARIAN triple-quadrupol mass spectrometer by flow injection analysis (FIA) technique, using water as a solvent, nitrogen as nebuliser gas, and air as drying gas. (3-Thenyl)triethylammonium bromide (3). To 1.2 g (6.78 mmol) of 3-thenylbromide were added dropwise with cooling and stirring 2 mL of triethylamine. The reaction mixture was stirred for two hours at room temperature and allowed to stay overnight in order to complete the chemical reaction. The resulted precipitate was filtered off with suction and washed well on filter with 10 mL of dry benzene. Yield 1.82g (96%).
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Scheme 1. Synthesis of the quaternary ammonium salts 3 and 4.

(3-Thenyl)triethylammonium perchlorate (4). 50 mg (0.181 mmol) of (3-Thenyl)triethylammonium bromide (3) were dissolved in 10 mL aqueous acetonitrile (volumetric ratio 1:1) and a solution of 37.52 mg (0.181 mmol) of silver perchlorate in 5 mL of doubly distilled water was added dropwise with magnetical stirring. Yellow silver bromide precipitates and it is filtered off with suction. The filtrate yields after removal of the solvent under reduced pressure 51mg (95%) of perchlorate 4. Electrochemical measurements were performed using an undivided cell with three electrodes. The working electrode was a platinum disk (diameter = 3 mm) and the counter electrode was a platinum wire. All potentials were referred to the Ag/AgCl electrode. The electrochemical measurements were carried out by using a potentiostat/ galvanostat AUTOLAB 302 N (Ecochemie) connected to a PC running the software GPES. Prior to each measurement, the working electrode was polished with 1, 0.3 and 0.05 m aluminium oxide powder. All measurements were performed at ambient temperature. The solutions were bubbled with high purity argon and a flow of argon was maintained over the solution during the electrochemical experiments. Results and discussions Organic synthesis and characterisation. Two new quaternary ammonium salts containing a 3thenyl radical were prepared by the procedure depicted in scheme 1. (3-Thenyl)triethylammonium bromide (3) was obtained in a two steps synthesis starting with 3-methylthiophene (1), which was first brominated in the side chain using Nbromosuccinimide as bromination reagent [14, 15] and benzoyl peroxide as promoter. The reaction was carried out in dry benzene at reflux. After removal of the solvent under reduced pressure, the crude reaction product was purified by further vacuum distillation (3mm Hg) collecting the fraction between 80-82oC [16]. 3-Thenyl bromide (2) was used as alkylating agent and by treatment with triethylamine the desired water soluble quaternary ammonium salt 3 was obtained. Substitution of bromide for perchlorate anion on treatment with silver perchlorate leads to the quaternary ammonium salt 4.

The synthesis of (3-thenyl)triethylammonium perchlorate (4) was performed in aqueous acetonitrile because as compared to the corresponding bromide 3, perchlorate 4 is less water soluble. The reaction products 3 and 4 were characterized by 1 H-NMR, 13 C-NMR, heteronuclear correlation, and electrospray ionization (ESI) mass spectrometr y techniques. Tables 1 and 2 present the recorded 1H-NMR and, respectively, 13C-NMR spectra of the organic cation in compounds 3 and 4 confirming its structure.

The splitting patterns and the coupling constants are consistent with the structure of (3-thenyl)triethylammonium cation. The data of a heteronuclear correlation experiment, more specific HMQC, also confirm the correct attributions of signals in table 2. Heteronuclear Multiple Quantum Coherence (HMQC) is a 2-dimensional inverse H, C correlation that allows for the determination of carbon to hydrogen connectivity. HMQC is selective for direct C H coupling (1JCH). Thus, HMQC indicates that the hydrogen atoms giving rise to the triplet centred at 1.375 ppm are attached to the carbon atom at 7.02 ppm. Since the triplet at 1.375 ppm in the 1H-NMR spectrum is undoubtedly assigned to the methyl group denoted as Hg, it means that the signal at 7.02 ppm in the 13C-NMR spectrum belongs to Cg. Similarly, the quartet centred at 3.1725 ppm in the 1HNMR spectrum (Hf) is correlated with the carbon at 52.20 ppm (Cf) in the 13C-NMR spectrum, while the singlet at 4.400 ppm (He) is attached to the carbon Ce at 54.21 ppm. Since the quaternary carbon atom (Cb) at 127.23 ppm has no H attached it has no match in the HMQC experiment. Finally, the doublet of doublets centred at 7.7025 ppm (Ha) is correlated with the signal at 131.17 ppm (Ca), the doublet of doublets centred at 7.548 ppm (Hd) matches the carbon signal at 127.69 ppm (Cd), while the doublet of doublets at 7.2085 ppm (Hc) is attached to the carbon at 129.49 ppm (Cc).

Table 1 H-NMR SPECTRUM OF (3-THENYL)TRIETHYLAMMONIUM CATION (5)

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Table 2 C-NMR SPECTRUM OF (3-THENYL)TRIETHYLAMMONIUM CATION (5)

Scheme 2 Fragmentation pattern for (3-thenyl)triethylammonium cation

The ESI mass spectrometry data are consistent with the structures of compounds 3 and 4. Operation in the positive mode reveals the molecular mass of (3thenyl)triethylammonium cation, m/z =198. In a fragmentation experiment along with the molecular mass peak, m/z =198, two other peaks, i. e., m/z = 97 and m/z = 59 appear. A fragmentation pattern consistent with these peaks is depicted in scheme 2. The peak at m/z = 97 is obviously due to loss of neutral triethylamine from cation 5 . Further elimination of cyclopropenyl carbene gives rise to protonated propargylthiol, which is responsible for the other peak observed in the fragmentation experiment. As expected, operating in the negative mode two peaks at m/z = 79 and m/z = 81 in a ratio 1:1 appear in the mass spectrum of bromide 3 corresponding to the two naturally occurring isotopes of bromine. In the case of perchlorate 4, operation in the negative mode reveals two peaks at m/ z = 99 and m/z = 101 in a ratio of 3 : 1. Electrochemical characterisation. The electrochemical behaviour of the new water soluble thiophene derivatives 3 and 4 has been studied in aqueous solution by using cyclic voltammetry. Figure 1 shows the cyclic voltammograms of (3-thenyl)triethylammonium bromide recorded at platinum electrode in 0.1 M KClO4 aqueous solution at a scan rate of 50 mV/s for different concentrations. The electrode potential was swept between 0.0 and 1.3 V, when a redox wave has been observed at about 0.95 V. A peak to peak potential separation of 100 mV has been measured. Both the anodic and cathodic peak currents increase with the concentration of the thiophene derivative 3. The oxidation of the thiophene derivative 3 occurs at the potential value 1.01 V, which is higher than that observed for the electrochemical polymerization of 3,4-ethylenedioxythiophene in aqueous solution [17]. Despite of the presence of a well defined redox wave, no electrochemical polymerization takes place. These results demonstrate that the water soluble thiophene derivative 3 can not be used for the electrochemical generation of thin polymeric films unto electrode surface. Based on these results and taking into account the electrochemical behaviour of 3,4- ethylenedioxythiophene, it is worth to compare the electrochemical behaviour of
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thiophene derivative 3 with that of bromide ions at various concentrations. Figure 2 reports the cyclic voltammograms of 1 mM and 5 mM (3-thenyl)triethylammonium bromide overlayed with those of 1 mM and 5 mM potassium bromide. The voltammograms show that the values of the anodic and cathodic peak potentials for these species are quite similar, which suggests that the thiophene derivative 3 is not electroactive.

Fig,1. Cyclic voltammograms of 1mM (b) and 5mM (3thenyl)triethylammonium bromide (c) in 0.1 M KClO4. Cyclic voltammogram of 0.1 M KClO4 at platinum electrode (a). Potential scan rate: 50 mV/s

Fig, 2. Cyclic voltammograms of 1mM (dotted line), 5mM (3-thenyl)triethylammonium bromide (thin solid line), 1mM (thick solid line) and 5mM (trash line) KBr, respectively, in 0.1 M KClO4 on platinum electrode. Potential scan rate: 50 mV/s REV. CHIM. (Bucureti) 60 Nr.3 2009

References
1. MAKOWSKI, O., KOWALEWSKA, B., SZYMANSKA, D., STROKA, J., MIECZNIKOWSKI, K., PALYS, B., MALIK, M. A., KULESZA, P. J., Electrochim. Acta, 53, 2007, p. 1235 2. SOMANI, P., RADHAKRISHNAN, S., Mater. Chem. Phys., 76, 2002, p. 15 3. LUPU, S., MIHAILCIUC, C., PIGANI, L., SEEBER, R., TOTIR, N., ZANARDI, C., Electrochem. Commun., 4, 2002, p. 753 4. KULESZA, P. J., MIECZNIKOWSKI, K., MALIK, M. A., GALKOWSKI, M., CHOJAK, M., CABAN, K., WIECKOWSKI, A., Electrochim. Acta, 46, 2001, p. 4065. 5.LISOWSKA-OLEKSIAK, A., NOWAK, A. P., JASULAITIENE, V., Electrochem. Commun., 8, 2006, p. 107 6. THOMAS, T. J., PONNUSAMY, K. E., CHANG, N. M., GALMORE, K., MINTEER, S. D., J. Membr. Sci., 213, 2003, p. 55 7. SCHRENK, M. J., VILLIGRAM, R. E., TORRENCE, N. J., BRANCATO, S. J., MINTEER, S. D., J. Membr. Sci., 205, 2002, 3. 8. DE CAMPOS, E. A., DA SILVA ALFAYA, A. A., FERRARI, R. T., COSTA, C. M. M., J. Colloid Interface Sci., 240, 2001, p. 97 9. VIINIKANOJA, A., AREVA, S., KOCHAROVA, N., RITALO, T., VUORINEN, M., SAVUNEN, A., KANKARE, J., LUKKARI, J., Langmuir 22 (14), 2006, p. 6078 10. BRA-ABREM, M., HO, H-A., LECLERC, M., Tetrahedron, 60 , 2004, p. 11169 11. HO, H-A., BOISSINOT, M., BERGERON, M. G., CORBEIL, G., DOR, K., BOUDREAU, D., LECLERC, M., Angew. Chem. Int. Ed., 41, 2002, p. 1548 12. STEPHAN, O., SCHOTTLAND, P., LE GALL, P. Y., CHEVROT, C., MARIET, C., CARRIER, M., J. Electroanal. Chem., 443, 1998, p. 217 13. TRAN-VAN, F., CARRIER, M., CHEVROT, C., Synth. Met., 142, 2004, p. 251 14. RAJAGOPAL, R., SIDDIQUI, S. A., DANIEL, T., LAHOTI, R. J., SRINIVASAN, K. V., J. Mol. Cat. A, 210, 2004, p. 165 15. SALAHELDIN, A. M., OLIVEIRA-CAMPOS, A. M. F., RODRIGUES, L. M., Tetrahedron Lett., 48, 2007, 8819. 16. CAMPAIGNE, E., TULLAR, B. F., Org. Synth., Coll., 4, 1963, p. 921 17. SAKMECHE, N., AARON, J. J., AEIYACH, S., L ACAZE, P. C., Electrochim. Acta, 45, 2000, p. 1921 18. TOTIR, N.D., LUPU, S., UNGUREANU, E.M., IFTIMIE, N., Rev. Chim. (Bucuresti) (English Edition), 2(1-2), 2001, p. 23 Manuscript received: 25.02.2008

Fig, 3. Cyclic voltammogram of 500 L of saturated solution of (3-thenyl)triethylammonium perchlorate in 0.1 M KClO4 on platinum electrode. Potential scan rate: 50 mV/s

For this reason, the counter ion bromide was replaced by perchlorate ion as described in the experimental section. The electrochemical behaviour of (3-thenyl) triethylammonium perchlorate was investigated in aqueous solution containing 0.1 M KClO4. Figure 3 shows the cyclic voltammogram of 500 L of saturated solution of (3thenyl)triethylammonium perchlorate in 0.1 M KClO4 on platinum electrode at 50 mV/s. In this case an anodic peak potential around 0.82 V could be observed. This electrochemical behaviour is quite different than that reported for thiophene derivatives in aqueous solution. Further studies are necessary in order to clarify the electrochemical behaviour of both organic cation and counter anions. These studies will provide new data and further develloping our previous results concerning the use of modified electrodes in aqueous solutions for electrochemical sensing [18]. Conclusions In this work the synthesis and the characterization of new water soluble thiophene derivatives have been reported. The NMR and mass spectra results clearly sustain the chemical structures of the newly synthesised compounds. The obtained results suggest that further studies are required in order to design new chemical structures characterized by improved electrochemical properties.
Acknowledgments. We thank Professor Dr. Renato Seeber and Dr. Chiara Zanardi from the Department of Chemistry, University of Modena and Reggio Emilia, Italy, for the NMR measurements.

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