Transcript (5-Ethoxycarbonylmethylidene-4-oxothiazolidine

(5-ETHOXYCARBONYLMETHYLIDENE-4OXOTHIAZOLIDINE-2-ILYDENE)-1-PHENYLETANONE
IN APROTIC MEDIA:
PHYSICAL CHEMISTRY 2010
ELECTROCHEMICAL AND SPECTRAL STUDY
Isidora Cekić-Lasković 1,2, Dragica Minić 1,2, Rade Marković2,3, Elena Volanschi4
1Faculty of Physical Chemistry, Studentski trg 12, Beograd, University of Belgrade, Serbia,
2Center for Chemistry ICTM, P.O. Box 473, 11001 Belgrade,
3Faculty of Chemistry, University of Belgrade, Studentski trg 16, 11001 Belgrade and
4Faculty of Chemistry, University of Bucharest, Romania
ABSTRACT
Push-pull alkenes, consisting of one or two electron-donating groups (EDG) at the terminus of the C=C bond and one or two electron-withdrawing groups
(EWG) at the other terminus, have been widely studied on the account of their low rotational barrier around the C-C double bond. This is attributed to the high
degree of polarization, or in valence-bond language, to the importance of zwitterionic limiting forms of the push-pull alkenes as convenient description of their
ground states. Previous electrochemical studies of selected 5-substituted 2-alkylidene-4-oxothiazolidines, as a typical representatives of push-pull alkenes, in aprotic
polar solvents gave valuable insight on electrochemical behavior of these compounds. The aim of the present work is to study (5-etoxycarbonylmethylidene-4oxotiazolidine-2-ylidene)-1-phenylethanone (1), synthesized as mixture of (2E,5Z)- and (2Z,5Z)-1 isomers (molar ratio 90/10%), in order to assess the role of the C-C
double bond at C(5) position, as well as EWG substituent on the electrochemical behaviour of selected 4-oxothiazolidines in terms of the reduction mechanism and
the reactivity of the intermediate species. The comparison between experimental data and theoretical curves, calculated by means of the DigiSim software, indicates
an ECECE reaction sequence as a major reaction pathway. It consists of monoelectronic reduction of the investigated compound to the anion radical (E), followed
by deprotonation of the substrate by the anion radical to form the anion (C) and reduction of the anion to dianion radical (E). The dianion radical of predominant
isomer (2E,5Z)-1 obtained at the second reduction step is observed by both, optical and EPR spectra.
ylidene)-1-phenylethanone in DMSO
Elucidation of the reduction mechanism
Determination of the reaction intermediate species
 Investigation of the influence of the C(5)=C(5') bond, as well as electron withdrawing substituent on the
electrochemical behaviour of selected 4-oxothiazolidines
15
Va
5
H
1
-5
-20
-100
-40
-60
-2
20
|c
IIc
il,IIc / Acm
j / A/cm 2
10
0
-10
-160
-50
-180
-1,8
-1,6
-1,4
-1,2
-1,0
-0,8
-0,6
-0,4
-0,2
0,0
E / V vs Ag/Ag
0,0
E / V vs Ag/Ag
0,2
0,4
0,8
-200
-1,8
1,2
-1,5
2
3
4
5
(1)
6
7
0,0
8
1/2
-0,6
-0,3
0,0
350
0,3
(a)
 / rpm
+
Fig. 1. Cyclic voltammogram of compound 1 (c = 4·10-3 M) starting Fig. 2. RDE curves of the cathodic waves of 1 solution (c = 4 mM)
with reduction, in 0.1 M TBAHFP/DMSO, in the range -1.6 to 1.25 V, in 0.1 M TBAHFP/DMSO at rotating rates 100-3500 rpm; insert:
v = 0.1 Vs-1; insert: potential range -1.6 to 0.1 V, different scan rates plot of the limit current density in function of the square root of the
rotation rate
400
450
500
 / nm
280
550
(b)
0
0
-5
-5
j /Acm
-2
5
-10
320
360
400
440
480
520
 / nm
Fig. 4. (a) Absorption spectra registered on electrochemical reduction of compound 1 in 0.1 M TBAHFP/DMSO at
the potential in between the first and second reduction wave, (curves 1-7)
(b) UV-Vis spectra of 1 at cTBOH/cSubstrate molar ratios from 0:1 to 1.5:1 (curves 1-16)
H
H
5
0,4
0,0
1/2
-0,9
(16)
0,2
 / (rot/s)
-1,2
0,6
0,1
1
=3500rpm
0,2
+
-0,4
(1)
-100
-40
IIc
(7)
0,3
-140
-30
-0,8
-80
-120
-150
-20
Ic
Absorbance
30
-1,2
(16)
Absorbance
-2
0.1V/s
0.5V/s
1V/s
40
-15
1,0
0,8
0
-10
(1)
0,4
IIIa
IIa
(1)
(7)
0,5
-50
j / Acm
2
N
H
SPECTROELECTROCHEMICAL RESULTS AND
THEORETICAL CALCULATIONS in DMSO
=100rpm
IVa
j / A/cm
O
2'
0
10
-2
5
O
• Pt working electrode and Pt counter electrode
• Ag/Ag+ reference electrode
• Solvent: DMSO
 Numerical simulation, accomplished by the software DigiSim 3.03 Bioanalytical Systems Inc.
 UV-Vis absorption spectroscopy
 EPR spectroscopy
 Semiempirical calculation (PM3 method, HyperChem-7)
ELECTROCHEMICAL RESULTS
j /Acm
1
S
 Cyclic and linear voltammetry with stationary and rotating disc electrode (RDE)
 Electrochemical and spectral investigation of the reduction of (5-etoxycarbonylmethylidene-4-oxotiazolidine-2-
-1,6
5'
MATERIALS AND METHODS
OBJECTIVES
-20
CO2Et
1cm = 0,778G
1cm = 0,778mT
-10
-15
-15
(a)
(b)
-20
-20
-1,6
-1,2
-0,8
E / V vs Ag/Ag
-0,4
0,0
+
-1,6
-1,2
-0,8
E / V vs Ag/Ag
-0,4
0,0
+
Fig. 5. EPR spectrum obtained by in situ electrochemical reduction of 1 in 0.1 M TBAHFP/DMSO at the potential of
the second wave on the voltammogram (a) experimental; (b) simulated spectrum
Fig. 3. (a) Experimental and (b) simulated cyclic voltammogram curves of 1 in 0,1 M TBAHPF/DMSO, in the potential range -1.6 to
0.1 V, c = 4·10-3 M, v = 0.1 Vs-1, room temperature
Proposed reduction mechanism:
(E)
(C)
(E)
(C)
(E)
(2E,5Z) -1 + eˉ  (2E,5Z)ˉ˙-1
Eo = -0.75 V, α = 0.5, ks = 1ּ10-5 cms-1
(2E,5Z)ˉ˙-1 + (2E,5Z)-1  (2E,5Z)˙-1 + (2E,5Z)ˉ-1 Keq = 160, kf = 106 M-1s-1
(2E,5Z)--1+ eˉ  (2E,5Z)2ˉ˙-1
Eo = -1.3 V, α = 0.5, ks = 0.05 cms-1
(2E,5Z)2ˉ˙-1  (2Z,5Z)2ˉ˙-1
Keq = 5, kf = 0.2 M-1s-1
(2E,5Z)˙-1 , (2E,5Z)ˉ-1 → Pox + eˉ Eo = +0.65 V, α = 0.5, ks = 1ּ10-4 cms-1
Fig. 6. SOMO at the optimized geometry of dianion radical (2E,5Z)2ˉ-1 in DMSO
CONCLUSION
The electrochemical results point to an ECECE reaction sequence. Unlike the previously studied related compound (5-etoxycarbonylmethylidene-4-oxothiazolidine-2-ylidene)-N phenylethanamide, where the chemical
step following the first ET is E/Z isomerisation, the chemical step in this case is a rapid proton transfer between the electrogenerated base (EGB) anion radical and the substrate i.e. a self-protonation reaction. The proposed
ECECE sequence is supported by DigiSim simulations, EPR and UV-Vis spectroelectrochemistry in absence and presence of exogeneous base, which outline the role of the anion radical as EGB. Gas phase and solvent
dependent semi-empirical PM3-MO calculations allow the characterization of all intermediate species evidenced by experimental data, in terms of their electronic structure and reactivity.