74，No.

8（2006） 691

― Note ―

Indirect Electroreduction of Imines and Diimines Using a Sacrificial

Sulfur-Graphite Electrode
Ikuichiro IZUMI ＊ a, Mikito YASUZAWAb, and Akira KUNUGIc
a
Department of Chemical Engineering, Nara National College of Technology (Yamatokoriyama, Nara 639-1080,
Japan)
b
Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima
(Minamijosanjima, Tokushima 770-8506, Japan)
c
Emeritus professor, The University of Tokushima (Shinkurachou, Tokushima 770-8501, Japan)

Received January 29, 2006 ; Accepted May 25, 2006

Indirect electroreductions of 4-methyl-4-trichloromethyl-p-quinone-(1)-arylimines using a sacrificial sulfur-graphite

electrode (S-C electrode) caused the elimination of a trichloromethyl group to give the corresponding N-tolylary-
lamines, whose yields increased largely with an increase in temperature and by the addition of benzoic acid as a
proton donor. Similarly, diimines with two trichloromethyl groups underwent the elimination of two
trichloromethyl groups. The above indirect electroreduction using the S-C electrode was undertaken at the low
cathodic overpotential, and gave high product yields compared with the direct electroreduction.

Key Words : Sacrificial Sulfur-graphite Electrode, Indirect Electroreduction, Imines, N-Tolylation of Aromatic
Amines

1 Introduction times from ethyl acetate-methanol, and dried in vacuum

A sacrificial sulfur-graphite electrode (S-C electrode)
has been used for introduction of sulfur atoms into some
organic compounds, since the reactive polysulfide anions
such as S82 − and S62 − can be generated by an electro-
chemical reduction of elemental sulfur (S8).１, ２） This
electrode has been proposed because the solubility of S8
is poor in usual organic solvents and the electrode prepa-
ration is facile.
Preceding work has shown that the direct electrore-
duction of 4-methyl-4-trichloromethyl-p-quinone-(1)-
arylimines (1a - 1c) gives the corresponding N-tolylary-
lamines (2a - 2c), whose yields were strongly dependent
on the kind of electrode materials.３） Such a conversion
of the imine 1 into the amine 2 was called electroreduc-
tive aromatization reaction. The imine 1 is synthesized
by a condensation of 4-methyl-4-trichloromethyl-p-
quinone with arylamines.４） Therefore, this method is a
convenient N-tolylation of aromatic amines.
The present investigation has aimed at the new use of
the sacrificial sulfur-graphite electrode, involving the
indirect electroreduction of 1a - 1c. Furthermore, the
indirect electroreduction of diimines such as 1,1-bis [p-(4-
methyl-4-trichloromethyl-2,5-cyclohexadienone-(1)-
iminyl)phenyl]cyclohexane (1d) and 1,1-bis [p-(4-methyl-4-
trichloromethyl-2,5-cyclohexadienone-(1)-iminyl) phenyl]-
4-methylcyclohexane (1e) is described.
2 Experimental
The anhydrous N,N-dimethylformamide solution was
prepared from the pre-deoxygenated DMF and
tetraethylammonium p-toluenesulfonate (Et4NOTs). The
purification of DMF was accomplished according to the
published method.５） Et4NOTs was recrystallized three
at 80 ℃ for three days.
The imines 1a - 1c were prepared by a condensation of
4-methyl-4-trichloromethyl-p-quinone with arylamines in
the presence of p-toluenesulfonic acid, according to the
published method.４） Similarly, the diimines 1d and 1e
were prepared from N-magnesium bromine salt of 1,1-bis
(4-p-aminophenyl) cyclohexane or 1,1-bis (4-p-amino-
phenyl)-4-methylcyclohexane and 4-methyl-4-trichloro-
methyl-p-quinone.４） The prepared substrates were iden-
tified by their physical properties, NMR and M/S spec-
tra. They showed 1H and 13C NMR, and M/S consistent
with the structures assigned. All NMR spectra were
observed with a EX-400 spectrometer and M/S spectra
were measured with Shimadzu GCMS, QP-1000.
The S-C electrode was prepared by the method similar
to that of Le Guillanton,１） i.e., the mixture of powdered
sulfur and powdered graphite (mass ratio of S : C = 1 : 1)
was introduced in a test tube, and the test tube was
heated in an oil bath at 135 ℃. Once the sulfur had melt-
ed, a platinum wire was plugged in the pasty mixture,
taken out, and cooled at room temperature. Repeating
these processes provided a suitable sized S-C electrode
(ca. 5.0 cm2).
The controlled potential macroelectrolysis was carried
out, using the same experimental setup and procedures
as reported in the previous paper.６） The macroelectrol-
yses of imines 1a - 1c and diimines 1d - 1e finished when
total charges of 5 and 10 F mol − 1, respectively, were
passed. After working-up in the normal manner, the
crude products were separated by means of preparatory
TLC and column chromatography to provide pure prod-
ucts, which were subjected to 1H NMR and 13C NMR,
and M/S for characterization of the products. Each
692 Electrochemistry

product showed 1H and 13C NMR, and M/S consistent direct electrolysis, because the electroreduction was con-
with the assigned structure. ducted at the lower cathodic overpotential.
Although it is difficult to elucidate the effects of a pro-
3 Results and Discussion ton donor, N-tolylarylamines 2a - 2c would form accord-
A series of the controlled potential macroelectrolyses ing to Scheme 3. That is, polysulfide dianions generated
of the substrates 1a - 1e using the S-C electrode were by the electrode reductions would attack a carbon of a
performed in DMF containing 0.1 mol dm − 3 Et4NOTs at trichloromethyl group, to produce the intermediate anion
− 0.50 V vs. Ag/AgI corresponding to the first reduction A. Release of dichlorocarbene from A and protonation
potential of S8. At this potential, 1a - 1e do not directly
undergo an electrochemical reduction since the sub-
strates 1a - 1e exhibited the reduction waves with half-
wave potentials of − 1.24 to − 1.28 V vs. Ag/AgI.
The results are summarized in Table 1. The imines
1a - 1c underwent the elimination of a trichloromethyl
group to give the corresponding N-tolylarylamines 2a -
2c, as shown in Scheme 1. The diimines 1d and 1e pro-
vided 1,1-bis[4-N-p-tolylaminophenyl]cyclohexane (3d) and
1,1-bis[4-N-p-tolylaminophenyl]-4-methylcyclohexane (3e)
by the elimination of two trichloromethyl groups togeth-
er with 1-[4-N-p-tolylaminophenyl]-1-[p-(4-methyl-4-
trichloromethyl-2,5-cyclohexadienone-(1)-iminyl) phenyl]
cyclohexane (4d) and 1-[4-N-p-tolylaminophenyl]-1-[p-(4- Scheme 1
methyl-4-trichloromethyl-2,5-cyclohexadienone-(1)-
iminyl)phenyl]-4-methylcyclohexane (4e) as by-products
(see Scheme 2).
As shown on Table 1, an increase in temperature of
the reduction of 1a using the S-C electrode (30 to 60 ℃)
resulted in a large increase in the product yield of 2a
with or without adding benzoic acid as a proton donor.
Furthermore, the yield of the unreacted 1a decreased.
On the influence of the proton donor on the product
yield, product yields of 2a - 2c increased by the addition
of benzoic acid and yields of the unreacted 1a - 1c
decreased. As described above, the imines 1a - 1c are
synthesized by the condensation of 4-methyl-4-
trichloromethyl-p-quinone with arylamines.４） Therefore,
this indirect electrolysis using the S-C electrode is more
convenient N-tolylation of aromatic amines than the
Scheme 2

Table 1 Macroelectrolyses of 1a-1e using the S-C

electrode at − 0.50 V vs. Ag/AgI in DMF containing 0.1
mol dm − 3 Et4NOTs at 60 ℃.
Proton donor Charge
Run Substrate Yield (%)
(equiv.) (F/mol)
1 2 3 4
a)
1 1a None 5.0 42 18 − −
2 1aa) PhCOOH (4) 5.0 22 34 − −
3 1a None 5.0 23 58 − −
4 1a PhCOOH (4) 5.0 22 78 − −
5 1b None 5.0 33 41 − −
6 1b PhCOOH (4) 5.0 2 88 − −
7 1c None 5.0 38 34 − −
8 1c PhCOOH (4) 5.0 20 71 − −
9 1d PhCOOH (4) 10.0 3 − 75 18
10 1e PhCOOH (4) 10.0 1 − 77 15 Scheme 3 Proposed reaction mechanism for formation of
a)
30 ℃ 2.
74，No. 8（2006）
would give the product 2. Although the fate of the inter-
mediate A was not ascertained, the similar dichlorocar-
bene has been proposed in the non-electrochemical elimi-
nation of the dichloromethy group of 4-dichloromethyl-4-
methyl-2,5-cyclohexadiene-1-one.６）
The synthesis of 3d from 1d is particularly interesting
by reason that further tolylation of 3d by p-iodotoluene
led to the formation of 1,1-bis(4-N,N-di-p-toly-
laminophenyl) cyclohexane, which has been successfully
used as the hole-conduction and the injection-agent in
the organic diode.７） The synthesis of 3e from 1e, as well
as the synthesis of 3d, will be interesting. The indirect
electrolyses of 1d and 1e using the S-C electrode in the
presence of benzoic acid provided 3d and 3e in high
yields of 75-77%, whereas the direct electrolyses at differ-
ent graphite felt cathodes have showed low yields of 47-
56 ％ (see Table 4 in Ref. 3).
In conclusion, the S-C electrode was found to be useful
693
for N-tolylation of aromatic amines from the standpoint
of lower cathodic overpotential and higher product
yields.
References
1）G. Le Guillanton, Sulfur Reports, 12, 405 (1992).
2）A. Kunugi, K. Kuwamura, M. Inoue, Y. Kawamura, and
K. Abe, Electrochim. Acta, 41, 1987 (1996).
3）A. Kunugi, M. Yasuzawa, H. Matsui, and K. Abe, J.
Appl. Electrochem., 27, 1390 (1997).
4）K. Abe and M. Takahashi, Synthesis, 939 (1990).
5）D. W. Leedy and D. L. Muck, J. Am. Chem. Soc., 93, 4264
(1971).
6）A. Kunugi, Md. A. Jabbar, K. Mori, and H. Uno,
Electrochim. Acta, 44, 4583 (1999).
7）K. Nagarajan and A. Venkateswarlu, Tetrahedron Lett.,
293 (1967).
8）C. W. Tang and S. A. Van Slyke, Appl. Phys. Lett., 51,
913 (1987).