Electrochemical Oxidation of 1,2-Dimethoxybenzene

Synthetic Aspects
Olga P. M6rquez, Jairo M~,rquez, and Reynaldo Ortlz
Laboratory of Electrochemistry, Department of Chemistry, Faculty of Science,
Universidad de Los Andes, Merida 5101-Venezuela

ABSTRACT
Growth of a highly colored insoluble material on a platinum electrode by the oxidative reaction of 1,2-dimethoxyben-
zene (veratrole) in acetonitrile is observed when tetrabutylammonium tetrafluoroborate is used as supporting electrolyte.
The organic yield of the deposit reaches 98% when short-timed electrolyses are performed. The main product has been
characterized by several electrochemical and spectroscopic methods.

Electrochemical oxidation of methoxybenzenes has been magnetic susceptibility measurement system was used. IR
studied since 1964.1 The same year, Eberson 2 and Ross 3pro- were taken using a Perkin Elmer 1725X FTIR. Mass spectra
posed a radical ion as the intermediate species involved. using a HP 5988A mass spectrometer. Scanning electron
Theoretical models were developed in order to explain the microscopy was run on a S-2500 Hitachi equipment.
electrochemical behavior of the substrates. 41~ A rule was Experiments were run at room temperature (18-20~
suggested 14 for the electrochemical reaction of aromatic and concentration of the supporting electrolyte was always
compounds: side chain substitution would follow a mech- 0.1M.
anism via free radical, while ring substitution would be After completion of each electrolysis, excess of support-
explained via a carbonium ion mechanism. Bechgaard and ing electrolyte and other impurities of the deposit on the
Parker 16 synthesized mono-triphenylene, di-triphenylene, working electrode surface were washed off with CH2CI2
and tri-triphenylene cations from the anodic oxidation of and then vacuum dried until constant weight.
1,2-dimethoxybenzene in trifluoroacetic acid (TFA). The
extraordinary stability of organic cationic radicals in TFA Resultsand Discussion
allowed the reaction to be stopped at the radical cation This study has been in progress in our laboratory since
stage, thus enabling the study of the effect of electrochemi- 1984. Samples have been stored and periodically analyzed
cal variables on it. during eight years. Paramagnetic properties, IR, and mass
Ortho-dimethoxybenzene (veratrole) has been re-
ported 17-2~to exhibit two conformational forms at low tem-
peratures: one showing coplanarity of the two methoxy
groups with respect to the aromatic ring and a n o n p l a n a r
conformation. A more recent paper 21 concludes that the
two methoxy groups could be arranged as either the cis-
trans ortho-dimethoxybenzene or the trans-trans ortho-
dimethoxybenzene, both with planar arrangement, with
the trans-trans structure energetically favored from the
steric point of view.
Some authors 22-24have pointed out that, in veratrole, the
two ortho-methoxyl groups interact in a manner which
considerably lowers the energy barrier for conformational
change as compared with the para substituted isomer.
In this paper, synthetic aspects of veratrole oxidation in
acetonitrile with tetrabutylammonium tetrafluoroborate
as supporting electrolyte are discussed. I
I i
Experimental 0.00 a 2.00
Veratrole (Aldrich Chemical Company) was vacuum dis- E.V -I
tilled. Acetonitrile (Baker, HPLC grade) was distilled from
P205, redistilled at a rate of 3 ml per min and stored over
neutral alumina (Wolhem Super). Tetraethyl ammonium ] 100.A
perchlorate (Eastman Kodak) was recrystallized twice
from hot water, filtered, and vacuum dried at 80~ for 48 h.
Tetrabuty]ammonium tetrafluoroborate (Eastman Kodak)
was dissolved in CH2C12 and then washed three times with
distilled water. The organic phase was recovered, filtered,
and poured into diethyl ether. The crystals were vacuum
dried at 80~ for 48 h.
Voltammetric measurements were performed with a 273
Princeton Applied Research (PAR) potentiostat/galvano-
stat coupled to a 286 MBVLSI-168B IBM compatible AT
microcomputer, using a typical voltammetric cell with
platinum wire as the working electrode (0.05 cm 2, geomet-
ric area) surrounded by a platinum coil as counterelec-
0.00 2.00
trode, using a silver/silver nitrate (0.01M) as reference b E.V -I
electrode. Electrolyses were carried out with a BAS 100A
electrochemical analyzer using the same voltammetric cell. Fig. 1. Cyclic voltammetry of 1 mM veratroie in 1M Et4NCJO4. (a)
For magnetic properties measurement, a George Associates CH3CN, (b) 1:1 TFA/CH3CN.
J. Electrochem. Soc., Vol. 140, No. 8, August 1993 9 The Electrochemical Society, Inc. 2163
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 2164 J. Electrochem. Soc., Vol. 140, No. 8, August 1993 @.The Electrochemical Society, Inc.

Iloo, A

{
D.O 2.0
a E.V-I

1.2

I .mA -I

II.I?

0.0 1.6
b E.V -1

Fig. 2. Cyclic voltammetry of 1 mM veratrole: (a) in 0.1M CH3CN/

Bu4NBF4, (bl effect of repetitive potential sweeps.

spectra r e m a i n e d unchanged, indicating the high stability

of the final solid.
Cyclic voltammetry.--Anodic oxidation of veratrole in
acetonitrile/tetraethylammonium perchlorate produces a
single peak at +1.066 V vs. Ag/Ag § When trifluoroacetic
acid (TFA) is added to the anolyte, the peak is shifted to-
wards +0.987 V and two additional peaks are observed at
+1.200 and +1.640 V (Fig. i). In both cases, at the first wave
potential, a red species is observed diffusing from the elec-
trode surface to the bulk solution. In the presence of TFA,
oxidation is slightly favored and the intermediate lifetime
is long enough to al]ow further oxidation. Figure 2a shows
the cyclic voltammogram of veratrole in CH3CN/tetra-
butylammonium tetrafluoroborate; two oxidation peaks at
+1.086 V, +1.557 V, and a weak wave at +1.829 V~ against
Ag/Ag + are, respectively, observed. Addition of TFA does
not considerably affect this system. When repetitive
voltammograms are monitored (Fig. 2b), an oxidation pre-
peak develops at +0.750 V with a reverse reduction wave at
+0.625 V. Linearity of a plot of the peak current against
potential sweep rate (Fig. 3) suggests the adsorption of an
electroactive monolayer. As cycling over the whole poten-
tial range continues, a green deposit grows on the electrode
surface under mixed control. The formation of the green
deposit is highly influenced by the nature of the supporting
electrolyte. There is a proposed interaction between the
radical cation (assumed as the red species) and the anion of
the supporting electrolyte. In the case of tetraethylammo-
nium perchlorate, diffusion of the intermediate species to
Fig. 4. Scanning electron micrographs (SEM) of the veratrole oxida-
tion product scraped off from the eledTode surface.
the bulk solution occurs, and no deposit is observed, even
though it is observed under the microscope. Tetrabutylam-
monium tetrafluoroborate, however, produces a possible
doping effect, and a green material initially grows like ran-
domly oriented interbred rods as shown in Fig. 4. This mor-
phology has been studied for several compounds 2s but its
origin is not yet clear.
Preparative coulometry.--Controlled potential cou-
lometry at the first wave potential shows that the amount
of deposited material is limited by adherence of the mate-
rial to the platinum surface: after a certain electrolysis
time, the thick layer sloughs off when deposited on a
smooth platinum surface and thereafter the weight of the
covered electrode remains constant (Fig. 5). 140 mg of
product are deposited per square centimeter of electrode
geometrical area. Organic yield is 98% as referred to vera-
trole when a series of short electrolyses are performed. The
unreaeted amount of ortho dimethoxybenzene was deter-
mined by quantitative cyclic voltammetry of the anolyte.
-i
M .m,

i O _ _ O - - --O-- O -- ~ - - O - - -O--
6
I.pA -I /

20 /

/
/
r
l
d
0
i I I I I I
I I I ] I I
1O 20 30
40 60
.mv-ls t . m i n -I

Fig. 3. Prepeak current v s . potential sweep rate for the anodic Fig. 5. Controlled potential coulometry. Mass of material deposited
oxidation of veratrole in CH3CN/Bu4NBF4. v s . electrolysis time (E = 1.60 V).

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 J. Electrochem. Soc., Vol. 140, No. 8, August 1993 9 The Electrochemical Society, Inc. 2165
100

I,
(408) (393)

-OCH3 L (365)
J,(-OH 3 )
3000 20'00 1500 1000 400
~.cm

334)
s (35o)
i -co

~
-CH 3

~ -OCH3 + -cH2 ) +
-co

(3071 (276) -Ca 2 -C

]000
' 2000
' 1500
' ' I0'00 50

~.cm

Fi~. 6. FTIRspectra of (a, top) veratrole and (b, bottom) electrolysis

product.
(2041
* OCH 3

nature of the sample. Paramagnetism is confirmed by

solid-state room temperature electron spin resonance
(ESR) which produces a strong singlet with g = 2.0032,
without hyperfine structure, indicative of one localized
3300 free electron without interaction with the nuclear spin of
the protons (Fig. 7). Quantification of spins number gives
~.ie3~7o4CH~
2.4 x 1019 spins, g 1, which is lower than the expected value
I' hexamethoxy-triphenylene cation radicals (1.47 x 1021
spins, g-l), probably due to coupling of some adjoining free
electrons, suggesting a possible alignment of several
Fig. 7. Room temperature solid-state ESR spectrum of veratrole trimeric units, one on top of the other.
oxidation product. High-field solid-state 13C NMR spectrum is shown in
Fig. 8. Although paramagnetic species usually show broad
nuclear magnetic resonance (NMR) spectra, a solid-state
signal is sharper than that in solution because the relax-
Analysis.--Fourier transform infrared (FTIR) spec-
ation time is shorter in solid state. A high-field instrument
troscpic analysis of veratrole (Fig. 6a) shows the following
allowed us to adjust the magnetic field to minimize broad-
main bands: (3064-3001) cm-i: aromatic C-H bonds vibra-
ening of the signal. On the other hand, dilution of spins also
tions; 2954 cm-l: aliphatic C - - H bonds stretching vibra- minimizes broadening effect. Since there is not coupling
tions; 2830 cm-l: C - - H bond stretching vibrations of
methoxy groups; (2047-1593) cm-l: overtones and combi-
nation bands indicating ring substitution; (1505-1461)
cm-l: aromatic C=C bonds stretching vibrations; (1255-
1230) cm-l: absm~otion bands due to the Cr~ng--(O--C)ether
stretching vibrations; 746 cm 1: strong absorption band
due to ring ortho-substitution.
The oxidation product exhibits an IR spectrum with a
few differences (Fig. 6b): those bands corresponding to aro- OCH3
matic absorptions are weaker, suggesting the presence of
fused rings. The disappearance of the 746 cm -1 band possi-
bly indicates that sole 1,2-ring substitution has disap- tc.s

peared, although methoxy groups are kept. The presence of

a band at 835 cm -1, represents a C - - H bond out of plane
vibration of tetra substituted aromatic rings. A new strong
signal at 1050 cm -I partially represents the absorption
band corresponding to species BF4. From these data, it is =c-o
inferred that several units of veratrole have been fused to-
=ic-o
gether and associated with the anion BF4. = c-o = . :c ~ zc<

Mass spectrometry of the product gives m/e fractions of

408,393,365,350,334,307,276,234, and 204 u.m.a., which
I i I
agree with chemical scheme I. 150 1110 50 0 PP.
250 200
Room temperature magnetic susceptibility measure-
ment, run at a magnetic field of 2000 gauss, produces a Fig. 8. High performance solid-state 13 C NMR spectrum of veratrole
positive value of the field gradient due to the paramagnetic oxidation product.

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 2166 J. Electrochem. Soc., Vol. 140, No. 8, August 1993 9 The Electrochemical Society, Inc.
Table I. Elemental analysis of veratrole oxidation product
obtained from acetonitrile/tetrabutylammonium
tetrafluoroborate on platinum electrode.
Calculated % Experimental %
C 58.21 56.78
H 4.88 5.29
O 19.38 2t.06
BF~ 17.53 16.87
with the protons, the observance of a sharp NMR is not
surprising. NMR spectrum assignment matches with the
results obtained by mass and IR spectroscopy.
Direct quantitative determination of B F J c a t i o n radical
ratio was not possible because the available method in-
volves digestion and chelation of the sample followed b y
spectroscopic measurement, b u t the strong dark color of
the sample did not allow us the colorimetric performance.
However, FTIR spectra reveal, qualitatively, the presence of
BF~ in the structure, and elemental analysis of the product
(Table I), suggests one BF~ unit for each hexamethoxy
triphenylene cation radical.
Conclusions
These experiments indicate that the first stage of the an-
odic oxidation of veratrole in acetonitrile involves three
units of veratrole for each net electron transferred to pro-
duce the hexamethoxy-triphenylene cation radical (chemi-
cal scheme II) This species, in the presence of tetraethylam-
monium perchlorate, possibly undergoes chemical
reactions in the bulk solution to yield soluble products
which have not been analyzed in the present study. Tetra-
butylammonium tetrafluoroborate, however, associates
with (II) to grow on the electrode surface. Morphology of
the deposit and mechanism of nucleation and growth is
now in progress. Sc,E,E ]l
0CH3
CH30 ~0
CH3
0CH~
(r)
Assumption of hexamethoxytriphenylene cation radical
(red) as the intermediate species is supported by the results
reported by Parker and eoworkers. 1~The use of a different
solvent and dryness of the medium enabled us to observe a
further reaction which is the electrodeposition of the green
material.
Summarizing, we have isolated a new material with con-
duetive properties in solution. The deposit behaves as an
electrode in several electrolytic media (evaluation of its
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response as an electrode is also in progress). Aging of the
product has been monitored during eight years and no
chemical change has been observed. We were able to quan-
tify the organic yield related to the starting material (98%).
These results offer us an interesting subject that has ori-
ented our efforts towards understanding this phenomenon,
the properties, and possible applications of the material.
On the other hand, it also shows the importance of the
contribution of electrochemistry in the field of new materi-
als and electrocatalysis.
Acknowledgments
This work has been supported by CDCHT (Universidad
de Los Andes), and CONICIT (Venezuela).
Manuscript submitted April 15, 1992; revised manuscript
received May i0, 1993.
Universidad de Los Andes assisted in meeting the publi-
cation costs of this article.
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