Electrochemical reduction of α-diketones and α-diimines in the presence of a bielectrophilic substrate: Synthesis of new aza-crown compounds

Article abstract of DOI:10.1149/2.0871702jes

The electrochemical reduction of α-diketones and α-diimines with the tritosylate of diethanolamine produces the corresponding aza crown compounds. This study was conducted using cyclic voltammetry in an aprotic medium and by preparative electrolysis on a stirred mercury pool. The obtained products were fully characterized by spectroscopic IR, NMR and HRMS methods and by elementary analysis.

Full text of DOI:10.1149/2.0871702jes

G36
Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
0013-4651/2017/164(2)/G36/8/$33.00 © The Electrochemical Society
Electrochemical Reduction of α-Diketones and α-Diimines in the
Presence of a Bielectrophilic Substrate: Synthesis of New
Aza-Crown Compounds
Hayet Khemis Medini,a,b Nejib Hussein Mekni,a,c,z Sami Ben Aoun,d and Khaled Boujlelb
aDepartment of Chemistry, Deanship of Educational Services, Taibah University, Al-Munawarah, Saudi Arabia
bLaboratory of Analytic Chemistry and Electrochemistry, Department of Chemistry Faculty of Sciences of Tunis,
University of Tunis El Manar, 2092 Tunis, Tunisia
cLaboratory of Structural Organic Chemistry, Synthesis and Physico-Chemical Studies, Department of Chemistry,
Faculty of Science of Tunis, University of Tunis El Manar, 2092 Tunis, Tunisia
dDepartment of Chemistry, Faculty of Science, Taibah University, Al-Munawarah, Saudi Arabia
The electrochemical reduction of α-diketones and α-diimines with the tritosylate of diethanolamine produces the corresponding
aza crown compounds. This study was conducted using cyclic voltammetry in an aprotic medium and by preparative electrolysis
on a stirred mercury pool. The obtained products were fully characterized by spectroscopic IR, NMR and HRMS methods and by
elementary analysis.
© 2016 The Electrochemical Society. [DOI: 10.1149/2.0871702jes] All rights reserved.
Manuscript submitted October 17, 2016; revised manuscript received December 12, 2016. Published December 22, 2016.
Crown ethers were first introduced by Pedersen in 19671 and con-
As a preparative step for this synthesis, we have performed cyclic
voltammetry measurements on the tritosylate of diethanolamine 2 in
an aprotic solution. The reduction of these compounds takes place
according to two irreversible cathodic peaks, located at close poten-
tials (i.e., ca. −1.57 V and ca. −1.65 V, vs Ag/AgI/I− reference).
(Figure 2)
The first peak can be attributed to the bielectronic cleavage of the
oxygen-sulfur bond, which is weaker than the nitrogen-sulfur bond.
The second peak seems to correspond to a simultaneous break of the
second oxygen-sulfur bond and/or the nitrogen-sulfur bond. It should
be noted here that the behavior of tritosylate of diethnolamine 2 as a
bielectrophile is quite similar to that of p-toluene sulfonamides such
as the previously reported N,N’-ditosylethylene or N,N’,N”-tritosylate
of diethylenetriamine (Scheme 1).19,20
However, the exploration of the cyclic voltammograms in the
electrochemical study of the α-diketones, 1A, and α-diimines, 1B,
shows that the α-diketones are reduced in two mono-electronic peaks,
whereas the α-diimines are reduced in a single peak (Table I).
Raising the voltage sweep rate leads to an increase in the current
peak. Accordingly, the gradient of a plot of the log ip versus log v was
stitute an important variety of macromolecules that have been em-
ployed in a large array of applications.2 These ethers are also used
in supramolecular chemistry3 and have drawn special interest in the
environmental field for complexing heavy metals in water.4 In addi-
tion, the compounds complexing and lipophilic properties5 triggered
their applications as drug and pharmaceutical adjuvants.6 These com-
pounds are also used as catalysts in organic synthesis (18-crown 6).7
The replacement of oxygen atoms by nitrogen atoms improves the
complexing property of crown ethers and affects their selectivity for
metals.8 Consequently, aza-crown ethers constitute an important class
of macrocylic complexing compounds, due to their nitrogen lone pairs
and N–H moieties, rendering them able to complex both cations and
anions, depending on the pH value of the aqueous solution.9 Nitrogen-
oxygen mixed donor macrocycles, such as aza-crown ethers, can form
stable complexes with both alkali and transition metal cations.10
Alternatively, aza-crown ethers also find utility in sensor systems,11
especially as chemosensors,12 in the design of host-guest compounds,
in a wide array of cation detection applicatoins,13 and in ion-selective
membrane electrodes.14
Various synthetic methods of aza-crown ethers were described,15
starting from different reagents16 and using different procedures.17
The alkylation reactions of the radical anions and the electrogenerated
dianions in a weakly acidic medium are widely developed in organic
electrochemistry.18
Previously, we have shown that the electrochemically obtained
dianions, stable in an aprotic medium, can react with reagents having
two electrophilic centers containing two good leaving groups, such
as tosylates, to generate macromolecules.19 In this way the action of
the 1,4-dianions on bis-toluene sulfonates allowed the preparation of
oxa-, oxaza- and aza-crown ethers having one or multiple units of
Z-CH2-CH2.19
As a continuation of this work, in this study, we describe the re-
action of the dianions, obtained by the reduction of α-diketones or
α-diimines, with the tritosylate of diethanolamine to give the corre-
sponding aza-crown ethers, diesters and diamides.
Results and Discussion
Analytical study.—The electroreduction curve of the dimethyl-
formamide as aprotic solvent, and tetrabutylammonium hypochlorite
(n-Bu4NClO4) (0.1 M) as supporting electrolyte (blank) show a pick
at −2.5 V (Figure 1). This value is low enough to allow the reduction
of a great number of organic compounds.
Figure 1. Blank curve of analytical solution study (DMF + n-Bu4NClO4)
zE-mail: n.mekni@gmail.com
(0.1 M).
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
G37
peak intensities of 1A, remain practically unchanged (Figures 3b and
4b).
The observed changes in the voltammograms of substrates 1Aa-f
can be explained by the interaction in solution of the dianion 1A2−
with the reactive tritosylate of diethanolamine 2.
The α-diimines, 1B, are reduced in a single bielectronic irreversible
peak (Figure 5, curve a, and Table I) via an ECE mechanism and
behave differently from the α-diketones 1A. This finding can be inter-
preted in terms of the differences in the basicities of the corresponding
radical anions. Indeed, the radical anion B.−, formed by the reduction
of the α-diimines, 1B, was shown to be more basic than that obtained
from the α-diketones 1A.22 Thereby, it can be quickly protonated
from the residual impurities of the solvents,23 giving a neutral radical,
which is more electroactive than the starting substrate.
On the reverse scan, an oxidation peak appears at potentials near
−0.2 V for which the current intensity is less than that of the reduction
peak of the corresponding substrate. This peak disappears completely
in the presence of phenol as a proton donor (Figure 5, curve c) and
corresponds probably to the oxidation of the mono protonated form,
1BH–, of the diimine 1B.
The addition of the tritosylate of diethanolamine 2 to a solution
containing N1,N,21,2-tetraphenylethane−1,2-diimine, 1Ba, decreases
the current intensity of both the reduction and the oxidation peaks
(Figure 6) as a results of the reaction between the reduced form of
diimine 1Ba and the tritosylate of diethanolamine 2.
Therefore, the above analytical study indicates that the α-diketones
1A and the α-diimines 1B are reducible at lower potential than the
tritosylate of diethanolamine 2. The latter contains two good leaving
groups (tosyl) and can be used as a bielectrophilic reagent, whereas
compounds 1A and 1B constitute the binucleophilic source, toward the
produced dianions, leading to the formation of the desired heterocyclic
compounds.
Figure 2. Voltammogram of the tritosylate of diethanolamine 2 (10−3 M) in
DMF-Bu4NClO4 (0.1 M). Stationary mercury electrode. Reference electrode:
Ag/AgI/I− (0.1 M). ν = 10 mV.s−1
.
determined to be ca. 0.5 for all the compounds studied, indicating a
diffusion controlled process.21
For the α-diketones 1A, the first reduction peak is reversible even
at low-scan rates. This peak corresponds to the formation of the anion
radical A−, which, at more negative potential, undergoes a second
electron transfer to form the dianion 1A2− (Figures 3a and 4a).
The reversibility of the second reduction peak is observed only in
the presence of activated alumina as a drying agent, which enables
efficient limiting of the protonation reaction of the dianion 1A2− by
proton impurities.
The quasi-reversible character of the second reduction peak of the
α-diketones, 1A, disappears completely upon addition of a solution
of the tritosylate of diethanolamine 2. However, the reduction current
Organic electrochemical synthesis of aza-crown compounds.—
The reduction of the α-diketones 1A and the α-diimines 1B is realized
in an aprotic solution of the substrate (1A or 1B) and the tritosyle
Scheme 1. Mechanism of reduction of tritosylate of diethanolamine 2.
Table I. Characteristics of the cyclic voltammetric curves of the used α-diketones, 1A, and α-diimines, 1B, (5 × 10−3 M) in DMF, TBAP (0.1 M).
Reference Ag/AgI/I− (0.1 M). ν = 50 mV.s−1
.
First peak
Second peak
Substrate
Ep1/V
Ip1/μA
Ep2/V
Ip2/μA
Benzil
1Aa
1Ab
1Ac
1Ad
1Ae
1Af
1Ba
1Bb
1Bc
−0.75
−0.30
−0.20
−0.35
−0.15
−0.10
−1.00
−1.05
−0.98
6.6
5.0
4.0
6.5
4.7
6.0
6.6
8.0
9.5
−1.50
−1.30
−0.75
−0.70
−0.45
−1.00
−
5.6
5.0
3.2
5.8
4.5
5.4
−
Acenaphthylene-1,2-dione
Phenanthrene-9,10-dione
(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione
Naphthalene-1,2-dione
Naphthalene-1,4-dione
N1,N2,1,2-tetraphenylethane-1,2-diimine
(1S,4S)-1,7,7-trimethyl-N2,N3-diphenylbicyclo[2.2.1]heptane-2,3-diimine
N1,N2-diphenylacenaphthylene-1,2-diimine
−
−
−
−
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

G38
Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
Figure 3. Cyclic voltammetric curves of: (a) Benzil 1Aa (10−3 M). (b) Benzil 1Aa after addition of the tritosylate of diethanolamine 2 (10−3 M) in 0.1 M
DMF-Bu4NClO4. Stationary mercury electrode. Reference electrode: Ag/AgI/I− (0.1 M). ν = 10 mV.s−1
.
of diethanolamine 2. The reaction is undertaken on a stirred mercury
pool in an electrolysis cell, at potentials corresponding to the first
reduction peak of the α-diketone 1A or the α-diimine 1B (Table I), to
produce the corresponding binucleophilic species and to avoid their
second reduction, (leading to non nucleophilic species), as well as
the reduction of the tritosylate of diethanolamine 2 (-111.57 V). The
choice of the working potential is very interesting in a such synthetic
method, because it allows to select the desired species and to control
their formation, which is not possible with ordinary organic synthetic
reactions. This reduction reverses the reaction side by generation of
binucleophilic groups (C-O− and C-N−) from the corresponding elec-
trophiles (C=O and C=N).
For substrates 1Ab-d and 1Bb-c, the reaction yields the corre-
sponding diesters 3Ab-d or diamides 3Bb-c as aza-crown products.
The formation of such compounds can be explained by the presence of
the oxygen, as impurities in the solution introduced by the continuous
nitrogen bubbling (less than 0.3%) disturb the reaction results. The
bubbling of nitrogen is necessary to avoid the protonation of the anion
radicals issue from the simultaneous reduction of the substrate.
In fact, the imposed potential of the working electrode allows the
simultaneous formation of the radical anions A.− (or B.−) and the
superoxide ion O2−. Under these conditions, a radical duplication
reaction of the two electrogenerated radical anions can give rise to an
unstable cyclic peroxydic intermediate (Scheme 2), which evolves by
cleavage of the central C-C bond allowing the bidentate dicarboxylate
(Scheme 2) or diamidate (Scheme 3) diions. The reaction with the
tritosylate of diethanolamine 2, affords the corresponding aza-crown
diesters or diamides, respectively.
The products shown in Tables II and III have different and variable
structures, confirming the reaction of the tritosylate of diethanolamine
2 as a bielectrophile with the dianion as a binuclephile, to yield the
corresponding heterocyclic aza-crown compounds 3 (except for com-
pounds 1Aa and 1Ba) with a variable amount of the imposed charge,
Note that the formation of this type of peroxide intermediate
through the reaction of substituted olefins with electron withdrawing
exceeding 2 F.mol−1
.
Figure 4. Cyclic voltammetric curves of: (a) Naphthalene-1,4-dione 1Af (10−3 M). (b) Naphthalene-1,4-dione after addition of the tritosylate of diethanolamine
2 (10−3 M) in 0.1 M DMF-Bu4NClO4. Stationary mercury electrode. Reference electrode: Ag/AgI/I− (0.1 M). ν = 10 mV.s−1
.
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
G39
−.
occurred between the superoxide ion O2 and the α-dikotones 1A,19
regenerating the molecular oxygen.
The continuous bubbling of nitrogen gas allows us to compensate
for the oxygen consumed by the reaction, showing that the traces of
oxygen result in products 3 in good yields.
For the reactant 1Aa, the cleavage of the central C-C bond leads
to two carboxylate species that react by nucleophilic attacks on both
O-tosylate groups of the tritosylate of diethanolamine 2, yielding the
symmetric acyclic diester 3Aa (Scheme 4). However, the obtained
product from the split of the acyclic dimine 1Ba is not a sufficiently
strong nucleophile to react with substrate 2, instead easily capturing
a proton, to afford the corresponding amide 3Ba. (Scheme 4)
The experimental results shown in Tables II and III indicate that
only the naphthalene-1,2-dinone 1Ae and the naphthalene-1,4-dinone
1Af yield aza-crown ethers, 3Ae and 3Af, respectively (Scheme 5).
Indeed, compounds 1Ae and 1Af having quinoidal structures are more
easily reducible than molecular oxygen.26 Therefore, at the potential
of electrolysis, the superoxide ion is not electrogenerated and the
reaction does not take place.
In an attempt to improve the yields of the cyclic products, we
thought to use alkaline salts as an electrolytic support instead of
tetrabutylammonium perchlorate in order to promote the formation
of macroheterocycles by complexation of the alkaline ion as reported
in the literature.27
Therefore, the obtained voltammogram represented in Figure 7b
shows, for example, that Benzil 1Aa is reduced into the corresponding
bielectronic product in the presence of lithium perchlorate as a sup-
porting electrolyte. However, the preparative electrolysis in solutions
containing the α-diketones, 1A, and the tritosylate of diethanolamine 2
does not afford the expected product but instead gives the correspond-
ing α-hydroxyketone (Scheme 6). This finding is probably observed
due to the formation of the ion pair O−, Li+ with a significant covalent
character,28 inhibiting the nucleophilic properties of the oxyanion.
Figure 5. Cyclic voltammetric curves of: (a) N1,N,21,2-tetraphenylethane-
1,2-diimine 1Ba (10−3 M). (b) N1,N,21,2-tetraphenylethane-1,2-diimine 1Ba
(10−3 M) + 5 μL of phenol (5 × 10−2 M). (c): N1,N,21,2-tetraphenylethane-
1,2-diimine 1Ba (10−3 M) + 15 μL of phenol (5 × 10−2 M) in 0.1 M DMF-
Bu4NClO4. Stationary mercury electrode. Reference electrode: Ag/AgI/I−
(0.1 M). ν = 10 mV.s−1
.
groups in the presence of the potassium superoxide was previously
reported by Hoz.24 In addition, we have previously show that the
cyclic diesters are not formed upon addition of an oxygen trap to the
medium.25
In order to explain how the concentration of O2 is sufficient to
transform 0.5 g of the starting material into the products, 3Aa-d and
3Ba-c, it was previously established that a redox catalytic process
Conclusions
The electrochemical reduction of certain bifunctional α-diketones,
1A, and α-diimines, 1B, in the absence of a proton donor produces the
2−
corresponding dianions 1AO2 (or 1BO22−) after the dimerization
of the two anion radicals 1A−. (or 1B−.) and O2−.. The nucleophilic-
ity of the dianions was explored during the synthesis of macrocyclic
aza-crown compounds by performing electrolyses in the presence of
a bielectrophile, the tritosylate of diethanolamine 2. The choice of
the tritosylate of diethanolamine 2 as the bielectrophilic reagent is
based on its unreactivity at the reduction potential of the α-diketones,
and the α-diimines, enabling the nucleophilic substitution. Certain
α-diketones, such as 1Ab, 1Ac and the 1Ad, yield the correspond-
ing cyclic diesters through a mechanism of formation involving the
reduced form of the dissolved oxygen. The same phenomenon was
observed with the α-diimine analogs, giving the corresponding macro-
cyclic aza-crown diamide. However, the electrochemical reduction of
substrates 1Ae and 1Af is easier than the reduction of oxygen and
yields the corresponding aza-crown ethers.
Experimental.—Melting points were determined with an Elec-
1
trothermal 9100 apparatus. H and 13C NMR spectra were recorded
using a Bruker Advance 300 MHz spectrometer in CDCl3 with tetram-
ethylsilane as the internal standard. IR spectra were performed in
chloroform using a Bruker Alpha ATR spectrometer. HRMS spectra
were collected on an AH MS-50 spectrometer in electronic mode at an
ionization potential of 70 eV. Anhydrous DMF (10 ppm, anhydroscan)
was purchased from Labscan and dried over activated alumina. All
chemicals were purchased from Sigma-Aldrich and were used without
further purification.
Figure 6. Cyclic voltammetric curves of: (a) N1,N,21,2-tetraphenylethane-
1,2-diimine 1Ba (10−3 M). (b) N1,N,21,2-tetraphenylethane-1,2-diimine 1Ba
(10−3 M) + tritosylate of diethanolamine 2 (10−3 M). (c) N1,N,21,2-
Electrochemical.—Cyclic voltammetry measurements were per-
formed using a PAR scanning potentiostat model 362. The cell was
a three-electrode type with a mercury pool as working electrode (12
cm3 surface), the counter electrode was a polished platinum wire,
tetraphenylethane-1,2-diimine 1Ba (10−3 M)
+
the tritosylate of di-
ethanolamine 2 (2×10−3 M) in 0.1 M DMF-Bu4NClO4. Stationary mercury
electrode. Reference electrode: Ag/AgI/I− (0.1 M). ν = 10 mV.s−1
.
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

G40
Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
Table II. Electrolysis of α-diketones, 1A, in the presence of the tritosylate of diethanolamine 2 in a solution of DMF-Bu4NClO4, (0.1 M). Working
electrode: mercury pool (A = 12 cm2). Reference electrode Ag/AgI/I− (0.1 M).
Substrate
Electrolysis potential (V)
Charge consumed (F.mol−1
)
Product 3
Yield (%)
1Aa
1Ab
−0.75
3.20
3Aa
3Ab
60
−0.75
2.20
95
1Ac
1Ad
−0.50
−0.60
2.10
2.40
3Ac
3Ad
48
77
1Ae
1Af
−0.40
−0.35
2.00
1.97
3Ae
3Af
30
25
Table III. Electrolysis of α-diimines, 1B, in the presence of the tritosylate of diethanolamine 2 in a solution of DMF-Bu4NClO4, (0.1 M). Working
electrode: mercury pool (A = 12 cm2). Reference electrode Ag/AgI/I− (0.1 M).
Substrate
Electrolysis potential (V)
Charge consumed (F.mol−1
)
Product 3
Y (%)
1Ba
1Bb
−0.95
3.50
Ph-NHCO-Ph
3Ba
3Bb
100
−1.05
−0.95
3.10
2.40
35
20
1Bc
3Bc
1 mm diameter. The solvent-supporting was a solution of tetrabuty-
lammonium perchlorate 0.1 mol.L−1 in DMF. The reference electrode,
consisting of the system Ag/AgI/I− (0.1 M), was maintained near the
mercury surface.
Preparative electrolyses were carried out at room temperature
(25◦C) in a conventional three compartment U-cell with a central com-
partment, between the analyte and the catholyte. Mercury was used
as a cathode and platinum as an anode. The solvent-supporting was
a solution of tetrabutylammonium perchlorate 0.1 mol.L−1 in DMF.
The current generator (Tacussel model PJT 35-2) was coupled with
an integrator (Tacussel model IG5) for coulometric measurements.
Electroorganic synthesis of aza-crown esters 3A and diamides
3B.—In a typical preparative electrolysis, the three compartments of
the electrochemical cell were filled with a solution of tetrabutylam-
monium perchlorate (0.1 M) in DMF. In the cathodic compartment
0.4 to 0.5 g of the substrate were added and the electrolysis started
by fixing the working corresponding potential for each substrate after
degassing the solution. The solution was purged continuously with
nitrogen gas and magnetically stirred.
When the value of the current reached 0.1% of its initial value, the
electrolysis was stopped. The catholyte was filled with an aqueous
solution of sodium hydrogenocarbonate NaHCO3 to a low basic pH
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
G41
Scheme 2. Mechanism of formation of aza-crown diesters 3Ab.
Scheme 3. Mechanism of formation of the diamide aza-crown diamide 3Bc.
Scheme 4. Mechanism of cleavage of the C-C bond of the α-diketone 1Aa, and the α-diimine 1Ba, followed by the formation of the amide 3Aa and the amide
3Ba.
Scheme 5. Electrochemical reduction of substrate 1Ae and the formation of aza-crown ether 3Ae.
obtained after evaporation of the solvent was purified by chromatog-
raphy on a silica gel 60 column, using petroleum ether/ethyl acetate
(70/30) as eluent. All products were characterized by 1H and 13C NMR
spectroscopy, IR spectroscopy, EI mass spectrometry and elemental
analysis.
2,2’-(tosylazanediyl)bis(ethane-2,1-diyl) dibenzoate 3Aa.—Mp
Scheme 6. The ion pair O−, Li+ evolution.
1
(◦C) = 71◦C; IR νC = O = 1719 cm−1; H NMR (CDCl3), δ (ppm):
2.34 (s., 3H, CH3), 3.66 (t., 4H, 2CH2-N), 4.51 (t., 4H, 2CH2-
O), 7.10-7.90 (m., 14H, CHar); 13C (CDCl3), δ (ppm): 21.4 (1C,
medium. The solution was extracted three times with diethyl ether,
washed with distilled water, and dried on MgSO4. The crude product
CH3-), 47.5 (2C, 2CH2-N), 62.8 (2C, 2CH2-O), 127.0, 128.0, 129.4,
129.5, 129.7, 133.1, 136.2, & 143.6 (18C, Car), 166.1 (2C, CO); m/z:
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

G42
Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
Figure 7. Cyclic voltammetry on a stationary mercury electrode; Reference electrode: Ag/AgI/I− (0.1 M); ν = 10 mV.s−1 of: (a) Benzil 1Aa (10−3 M) in 0.1 M
DMF-Bu4NClO4; (b) Benzil 1Aa (10−3 M) in 0.1 M DMF-LiClO4.
[M+H]+ = 468.2 (55%), [M+Na]+ = 490.2, [M+K]+ = 506.0, 364.3
(100%), 149.0 (52.5%), 105 (15%); HRMS: Calcd. 467.14026, Found:
467.14011; Anal. Calcd. for C25H25NO6S: C 64.22%, H 5.39%, N
3.00%, Found: C 64.08%, H 5.33%, N 2.93%.
4-tosyl-3,4,5,6-tetrahydro-2H-naphtho[2,1-b][1,4,7]dioxazonine
3Ae.—Mp (◦C) = 148◦C; IR νC = C = 1666 cm−1; 1H NMR (CDCl3),
δ (ppm): 2.39 (s., 3H, CH3-), 3.55 (t., 4H, 2CH2-N), 4.42 (t., 4H,
2CH2-O), 7.16-7.89 (m., 10H, 10 CHar); 13C (CDCl3), δ (ppm): 21.1
(1C, CH3), 45.1 (2C, 2CH2-N), 69.5 (2C, 2CH2-O), 117.8, 122.2,
124.8, 126.2, 126.9, 128.3, 128.7, 128.8, 130.0, 132.1, 138.7, 141.0,
143.3 & 146.4 (16C, 10Car); HRMS: Calcd. 383.11913, Found:
383.11881; Anal. Calcd. for C21H21NO4S: C 65.78%, H 5.52%, N
3.65%, Found: C 65.69%, H 5.45%, N 3.47%.
5-tosyl-4,5,6,7-tetrahydro-1H-naphtho[1,8-
ij][1,7,4]dioxaazacyclododecine-1,9(3H)-dione 3Ab.—Mp (◦C)
= 191◦C; IR νC = O = 1724 cm−1; 1H NMR (CDCl3), δ (ppm): 2.41
(s., 3H), 3.66 (t., 4H, 2CH2-N), 4.57 (t., 4H, 2CH2-O), 7.28-8.03
(m., 10H, CHar); 13C (CDCl3), δ (ppm): 21.5 (1C, CH3-), 49.6 (2C,
2CH2-N), 65.3 (2C, CH2-O), 125.2, 127.4, 127.5, 129.6, 129.8,
132.6, 134.2, 135.1, & 143.9 (16C, 16Car), 170.0 (1C, C = O);
m/z: [M+H]+ = 440.0 (100%), [M+K]+ = 478.0 (55%), 346.0
(20%), 239.7 (15%), 141.0 (15%), 105.0 (5%), 441.0 (20%), 442.0
(10%); HRMS: Calcd. 439.10896, Found: 439.10881; Anal. Calcd.
for C23H21NO6S: C 62.86%, H 4.81%, N 3.19%, Found: C 62.77%,
H 4.74%, N 3.14%.
5-tosyl-1,4,5,6,7,9-hexahydro-3H-1,9-
ethenobenzo[i][1,7]dioxa[4]azacycloundecine
3Af.—Mp
(◦C)
= 136◦C; IR νC = C = 1498 cm−1; 1H NMR (CDCl3), δ (ppm): 2.35
(m., 3H, CH3-), 3.48 (t., 4H, 2CH2-N), 3.58 (t., 4H, 2CH2-O), 5.35
& 6.12 (d.m., 2H, 2CH = ), 7.29-7.89 (m., 8H, 8CHar); 13C (CDCl3),
δ (ppm): 21.1 (1C, CH3), 47.7 (2C, 2CH2-N), 67.2 (2C, 2CH2-O),
75.3 (2C, 2CH-O), 126.6, 128.8, 130.0, 136.2, 138.7 & 141.0 (12C,
12Car), 129.8 (2C, 2CH = ); HRMS: Calcd. 383.11913, Found:
383.11902; Anal. Calcd. for C21H21NO4S: C 65.78%, H 5.52%, N
3.65%, Found: C 65.68%, H 5.47%, N 3.58%.
9-tosyl-8,9,10,11-tetrahydro-5H-dibenzo[i,
k][1,7,4]dioxaazacyclotridecine-5,13(7H)-dione 3Ac.—IR νC = O
=
1
N-phenylbenzamide 3Ba.—Mp (◦C) = 163◦C; IR νC = C = 1530
1722 cm−1; H NMR (CDCl3), δ (ppm): 2.40 (s., 3H, CH3-), 3.55
1
cm−1, νC = O = 1600 cm−1, νN-H = 3340 cm−1; H NMR (CDCl3),
(t., 4H, 2CH2-N), 4.40 (t., 4H, 2CH2-O), 7.15-7.81 (m., 12Har); 13
C
δ (ppm): 7.12-7.87 (m., 10H, 10CHar), 13C (CDCl3), δ (ppm): 122.5,
124.9, 128.2, 128.6, 129.0, 131.7, 135.0 & 136.7 (12C, 12Car), 167.6
(1C, 1CON); HRMS: Calcd. 197.08406, Found: 197.08384; Anal.
Calcd. for C13H11NO: C 65.78%, H 5.52%, N 3.65%, Found: C
65.69%, H 5.47%, N 3.59%.
(CDCl3), δ (ppm): 21.5 (1C, 1CH3-), 48.6 (2C, 2CH2-N), 65.6 (2C,
2CH2-O), 127.2, 127.4, 128.8, 129.9, 130.5, 131.0, 135.8, 141.3
& 143.8 (18C, 18CHar), 167.5 (2C, 2CO); m/z: [M+H]+ = 466.2
(100%), [M+K]+ = 504.0, [M+H]+ = 488.3 (30%), [M+H]+
=
483.3 (100%), HRMS: Calcd. 465.12461, Found: 465.12447; Anal.
Calcd. for C25H23NO6S: C 64.50%, H 4.98%, N 3.01%, Found: C
64.42%, H 4.89%, N 2.93%.
(1S,11S)-1,14,14-trimethyl-3,9-diphenyl-6-tosyl-3,6,9-
triazabicyclo[9.2.1]tetradecane-2,10-dione 3Bb.—Mp (◦C)
=
42◦C; IR νC = O = 1743 cm−1
;
1H NMR (CDCl3), δ (ppm): 0.99
(1S,11S)-1,14,14-trimethyl-6-tosyl-3,9-dioxa-6-
azabicyclo[9.2.1]tetradecane-2,10-dione 3Ad.—IR νC = O
(s., 6H, 2CH3), 1.15 (s., 3H, CH3-), 1.71 & 1.96 (d.m., 2H, 1CH2),
1.74 & 3.12 (d.m., 2H, 1CH2), 2.36 (s., 3H, CH3-), 2.41 (t., 1H,
CH), 3.54 (m., 4H, 2CH2-N), 3.65 & 3.73 (d.m., 4H, 2CH2-NCO),
7.18-7.90 (m., 14H, CHar); 13C (CDCl3), δ (ppm): 18.1 (1C, CH3-),
21.6 (1C, CH3-Car), 22.7 (2C, 2CH3), 23.0 (1C, 1CH2-), 33.1 (1C,
1CH2), 45.3 (2C, 2CH2-N), 46.6 and 47.9 (2C, 1CH2-NCO), 47.8
(1C, 1C), 51.9 (1C, 1C), 59.7 (1C, C), 126.9, 127.2, 128.2, 129.6,
129.7, 129.8, 129.9, 130.9, 134.4 (14C, 15HCar), 135.7 (1C, 1Car-S),
143.8 (1C, 1Car-CH3), 144.2 & 144.8 (2C, 2Car-N), 177.5 & 181.3
(2C, 2CON); HRMS: Calcd. 573.26613, Found: 573.26605; Anal.
Calcd. for C33H39N3O4S: C 69.08%, H 6.85%, N 7.32%, Found: C
68.99%, H 6.80%, N 7.27%.
=
1728 cm−1; 1H NMR (CDCl3), δ (ppm): 0.96 (s., 6H, 2CH3), 1.21 (s.,
3H, 1CH3), 2.42 (s., 3H, 1CH3), 1.70-1.95 & 2.88 (m., 4H, 2CH2),
2.14 (m., 1H, 1CH), 3.53 (t., 4H, 2CH2-N), 4.22 (t., 4H, 2CH2-O),
7.23-7.75 (m., 4H, 4CHar); 13C (CDCl3), δ (ppm): 21.3 (1C, 1CH3),
22.15 (1C, 1CH3), 23.5 (2C, 2CH3), 25.4 (1C, 1CH2), 32.6 (1C,
1CH2), 45.7 (2C, 2CH2-N), 45.9 (1C, 1C), 51.3 (1C, C), 57.6 (1C,
C), 60.3 & 60.9 (2C, 2CH2-O), 128.8, 130.0, 138.7 & 141.0 (6C,
6Car), 173.8 & 174.8 (2C, 2CO); HRMS: Calcd. 423.17156, Found:
423.17161; Anal. Calcd. for C21H29NO6S: C 59.55%, H 6.90%, N
3.31%, Found: C 59.51%, H 6.84%, N 3.28%.
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

Journal of The Electrochemical Society, 164 (2) G36-G43 (2017)
G43
2,8-diphenyl-5-tosyl-3,4,5,6,7,8-hexahydro-1H-naphtho[1,8-
8. K. Ozpinar, P. Deveci, M. Kilinc, E. Ozcan, B. D. Karaman, H. Karaarslan, B. Taner,
and Z. Kilic, J. Incl. Phenom. Macrocycl. Chem., 82(3), 407 (2015).
9. E. Kleinpeter and A. Holzberger, Tetrahedron, 62(43), 10237 (2006).
10. J. M. Caridade Costa, B. Jeyashri, and D. Bethell, J. Electroanal. Chem., 351(1-2),
259 (1993).
11. A. Yari and F. Papi, Sensor. Actuat. B Chem., 138(2), 467 (2009).
12. T. Yu, J. Meng, Y. Zhao, H. Zhang, X. Han, and D. Fan, Spectrochim. Acta Mol.
Biomol. Spectrosc., 78(1), 396 (2011).
ij][1,4,7]triazacyclododecine-1,9(2H)-dione 3Bc.—Mp (◦C)
=
115◦C; IR νC = O = 1709 cm−1; 1H NMR (CDCl3), δ (ppm): 2.40 (s.,
3H, 1CH3), 3.1 (t., 4H, 2CH2-N), 3.8 (t., 4H, 2CH2-O), 7.18-8.50
(m., 14H, 14Har); 13C (CDCl3), δ (ppm): 21.5 (1C, 1CH3-), 42.0
(2C, 2CH2-N), 46.0 (2C, 2CH2-NTs), 122.6 (2C, 2HCar), 126.3
(2C, 2HCar), 127.9 (2C, 2HCar), 128.5 (2C, 2HCar), 128.6 (2C,
2HCar), 130.0 (2C, 2HCar), 131.5 (2C, 2Car), 132.3 (2C, 2HCar),
134.3 (1C, 1Car), 135.5 (1C, 1Car), 136.7 (1C, 1Car-S), 143.6 (2C,
2N-Car), 143.9, (1C, 2Car-CH3), 164.3 (2C, 2CON); HRMS: Calcd.
589.20353, Found: 589.20348; Anal. Calcd. for C35H31N3O4S: C
71.29%, H 5.30%, N 7.13%, Found: C 71.18%, H 5.19%, N 7.08%.
13. P. Deveci, B. Taner, Z. Kilic, A. O. Solak, U. Arslan, and E. Ozcan, Polyhedron,
30(10), 1726 (2011).
14. V. K. Gupta, A. K. Singh, and N. Mergu, Analytica Chimica Acta, 749, 44 (2012).
15. J. B. Smith and A. J. M. Miller, Organomet., 34(19), 4669 (2015).
16. J. E. Richman and T. J. Atkins, J. Am. Chem. Soc., 96(7), 2268 (1974).
17. K. J. Sabah and R. Hashim, Tetrahedron Lett., 54(12), 1534 (2013).
18. T. Troll, H. Leffler, and W. Elbe, Electrochim. Acta, 24(9), 969 (1979).
19. L. Feriani, R. Kossai, and K. Boujlel, Electrochim. Acta., 36(5-6), 783 (1991).
20. R. Kossai, J. Simonet, and G. Dauphin, Tetrahedron Lett., 21(37), 3575 (1980).
21. A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamental and applica-
tions, Wiley, New York (1980).
References
1. C. J. Pedersen, J. Am. Chem. Soc., 89(26), 7017 (1967).
2. H. Alper and D. E. Laycock, Synthesis, (10), 799 (1980).
22. S. M. Kobelev, A. D. Averin, A. K. Buryak, F. Denat, R. Guilard, and I.P. Beletskaya,
Macroheterocycles, 7(1), 28 (2014).
3. H. G. Guo, J. Wu, H. Y. Niu, D. C. Wang, F. Zhang, and G. R. Qu, Bioorg. Med.
Chem. Lett., 20(10), 3098 (2010).
4. H. Li, N. Ma, W. Meng, J. Gallucci, Y. Qiu, S. Li, Q. Zhao, J. Zhang, J.C. Zhao, and
X. Chen, J. Am. Chem. Soc., 137(38), 12406 (2015).
5. S. Levai, T. Nemeth, T. Fodi, J. Kupai, T. Toth, P. Huszthy, and G. T. Balogh, J.
Pharm. Biomed. Anal., 115, 192 (2015).
6. Q. Zhao, Y.N. Wang, and B. Wang, Jpn. J. Clin. Oncol., 43(2), 200 (2013).
7. R. Rishikesan, K. Prabakaran, R. Murugesan, R. Venkataraman, P. K. Ranjith,
S. Arvind, and S. Thennarasu, J. Heterocyclic Chem., 52(5), 1321 (2015).
23. Z. Zheng, Z. Yu, M. Yang, F. Jin, Q. Zhang, H. Zhou, J. Wu, and Y. Tian, J. Org.
Chem., 78(7), 3222 (2013).
24. A. A. Frimer, I. Rosenthal, and S. Hoz, Tetrahedron Lett., 18(52), 4631 (1977).
25. K. Boujlel and J. Simonet, Tetrahedron Lett., 20(12), 1063 (1979).
26. A. J. Fry and R. G. Reed, J. Am. Chem. Soc., 93(2), 553 (1971).
27. F. L. Cook, T. C. Caruso, M. P. Byrne, C. W. Bowers, D. H. Speck, and C. L. Liotta,
Tetrahedron Lett., 15(46), 4029 (1974).
28. A. Lasia and M. K. Kalinowski, J. Electroanal. Chem. Interfacial, Electrochem.,
36(2), 511 (1972).
Downloaded on 2017-01-09 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).