Tetradentate diamido-bis-sulfide ligands on the base of o-aminobenzenethiol and their complexation with NiII, CoII, CuII chlorides in DMF solution and on the gold electrode surface

Article abstract of DOI:10.1007/s11172-009-0236-7

A series of cyclic and acyclic diamido-bis-sulfide ligands were synthesized by N-acylation of 1,2-bis(2-aminophenylthio)ethane and 1,4-bis(2- aminophenylthio)butane with acetic, malonic, and 3,3'-dithiodipropionic acid chlorides or esters. The complexation of obtained ligands with CuII, NiII, and CoII salts in solution and on the gold electrode surface was studied. The formation of complexes of these ligands with copper(II) chloride in DMF is irreversible and accompanied by deprotonation of the amide nitrogen atoms.

Full text of DOI:10.1007/s11172-009-0236-7

Russian Chemical Bulletin, International Edition, Vol. 58, No. 8, pp. 1707—1712, August, 2009
1707
Tetradentate diamidoꢀbisꢀsulfide ligands on the base of oꢀaminobenzenethiol
and their complexation with NiII, CoII, CuII chlorides in DMF solution
and on the gold electrode surface
Е. К. Beloglazkina,a А. G. Majouga,a F. S. Moiseev,a V. V. Frolov,b А. А. Moiseeva,a N. V. Zyk,a and M. P. Egorovb
aM. V. Lomonosov Moscow State University, Department of Chemistry,
Build. 3, 1 Leninskie Gory, 119992 Moscow, Russian Federation.
Eꢀmail: bel@org.chem.msu.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation
A series of cyclic and acyclic diamidoꢀbisꢀsulfide ligands were synthesized by Nꢀacylation
of 1,2ꢀbis(2ꢀaminophenylthio)ethane and 1,4ꢀbis(2ꢀaminophenylthio)butane with acetic, malꢀ
onic, and 3,3′ꢀdithiodipropionic acid chlorides or esters. The complexation of obtained ligands
with CuII, NiII, and CoII salts in solution and on the gold electrode surface was studied. The
formation of complexes of these ligands with copper(II) chloride in DMF is irreversible and
accompanied by deprotonation of the amide nitrogen atoms.
Key words: copper(II) complexes, amides, sulfides, N2S2 ligands, electrochemistry.
Transition metal complexes, such as NiII, CuII, and
Scheme 1
CoII complexes, with organic N,Sꢀcontaining ligands are
extensively studied as electroactive catalysts and models
of metalloenzymes.1—3 Lowꢀmolecularꢀweight nickel, coꢀ
balt, and copper copmlexes are used as catalysts of various
organic reactions, including asymmetric synthesis, alkene
epoxidation,4—6 cyclopropanation,7 aziridination,8 sulfide
oxidation,9,10 the Diels—Alder reactions,11 C—H bond
activation,12—14 epoxide ring opening.15—19 Such comꢀ
plexes were studied20 as catalysts for electrochemical reꢀ
duction of organic halides. In recent years, the problem of
Freon utilization21 attracts considerable attention and,
therefore, the possibility of using nickel complexes with
organic N2S2ꢀligands for electrocatalytic reduction of
polyfluorochloroalkanes is of interest.22 Thus, the syntheꢀ
sis of novel N,Sꢀcontaining organic ligands and their comꢀ
plexes with transition metals, as well as studies of their
redox properties seem to be a topical problem.
Macrocyclic diamidoꢀbisꢀsulfides 5 and 6 containing
Results and Discussion
a disulfide fragment were prepared from 3,3´ꢀdithioꢀ
di(propionyl chloride) 7and diamines 1and 2 (see Scheme 3).
Additional disulfide groups were introduced into comꢀ
pounds 5, 6 in order to ensure their chemisorption and of
their complexes on the surface of metal with high thiophiꢀ
licity (e.g., on the gold electrode surface). As a result,
a selfꢀassembled monolayer of an organic compound
forms on the surface.23,24
Acylation of diamines 1 and 2 with acid chlorides and
esters of carboxylic and dicarboxylic acids affords diamidoꢀ
bisꢀsulfide ligands 3—6 (Schemes 1—3).
Resinification occurs in the synthesis of macrocyclic
ligand 4 by acylation with malonyl dichloride. Therefore,
an alternative procedure was used, viz., the reaction of
diamine 1 with dimethyl malonate in diphenyl ether (see
Scheme 2).
Compounds 3—6 do not form crystalline complexes
when NiII, CoII, and CuII chlorides are mixed with soluꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1655—1660, August, 2009.
1066ꢀ5285/09/5808ꢀ1707 © 2009 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 8, August, 2009
Beloglazkina et al.
Scheme 2
spectra in addition to new peaks corresponding to the comꢀ
plex compounds. For all the complexes obtained, one
band of the d—d transition at 440—445 nm (ε =
= 680—780 L mol–1 cm–1) is recorded in the visible specꢀ
tral region.
Oxidation of ligands 3—6 (a glassy carbon electrode)
proceeds in one twoꢀelectron step (Table 1). Compounds
3 and 4 are reduced in one step (Fig. 1, а, dashed line),
whereas compounds 5 and 6 are reduced in two steps
(Fig. 1, b, solid line). The semiꢀempirical quantum chemꢀ
ical calculations that we have performed by the РМ3 methꢀ
od25 showed that both HOMO and LUMO of ligands 3
and 4 are predominantly localized on the sulfur atom and
consequently the redox processes should involve the sulꢀ
fide fragments. Indeed, the values of reduction and oxidaꢀ
tion potentials fall in the range of redox potentials which
are typical of alkyl aryl sulfides.26а
Compounds 5 and 6 with a disulfide group differ from
ligands 3 and 4 in the values of redox potentials (see Table 1).
The values of both oxidation and reduction potentials are
more typical of dialkyl disulfides.26b This is in agreement
with the fact that, according to the computational data,
Scheme 3
Table 1. Oxidation (EOx) and reduction potentials (ERed) of
ligands 3—6 and their complexes formed in solution (glassy carꢀ
bon electrode, A) and on the Au electrode surface (relative to
Ag|AgCl|KCl sat., DMF, 0.1 M Bu4NClO4, B)a
Red b
Red c
Ox
Ox c
Compound (type
of experiment)
Ep
E1/2
Ep
E1/2
V
3 (A)
4 (A)
5 (A)
–2.48
–2.68
–2.09
–2.62
–2.41(2)
–2.60
–2.14 (2)
–2.66
1.47 1.46 (2)
1.52 (2)
1.40 1.41 (2)
6 (A)
–2.04
–2.63
–2.10 (2)
–2.66
1.40 1.40 (2)
5 (B)
6 (B)
3 + CuCl2
(A)
4 + CuCl2
(A)
–1.83/0.32
–1.81/0.35
0.36/0.45d
–2.46
0.40/0.56d
–2.46
n = 1 (1, 5), 3 (2, 6)
–0.48 (1)d 1.33 1.32 (2)
–2.23 (2)
–0.52 (1)d 1.33 1.25 (2)
–2.55 (1.9)
tions of ligands (or boiled) in DMF, MeСN, or EtOH.
However, the complex formation is evidenced by the gradꢀ
ual color change during addition of the metal salt to the
ligand solution, as well as by comparing the electronic
absorption spectra and the results of electrochemical studꢀ
ies for ligands 3—6 and their mixtures with NiII, CoII, and
CuII salts in the ratio of 1 : 1 in DMF.
6 + CuCl2
(A)
0.40/0.56
–2.00
–2.70
–0.84
–1.93
—
1.26
—
5 (B) + CuCl2
6 (B) + CuCl2
–0.88
In the electronic absorption spectra of the equimolar
mixtures of 3—6 with CuCl2•6Н2О (10–3 mol L–1, DMF
solutions), the absorption bands of the initial inorganic
salt completely disappeared 30 min after mixing. In the
case of NiCl2•6Н2О and CoCl2•6Н2О, the complexation
reaction in DMF is likely reversible. Even several hours
after mixing the reactants, the absorption bands of the
initial salts were still observed in the electronic absorption
–1.97
a Presented in parentheses is the number of electrons as deterꢀ
mined by comparison with the height of the oneꢀelectone oxidaꢀ
tion wave of ferrocene.
b Ep
is the cathodic peak potential (200 mV s–1)/the reverse
Red
peak potential.
c The halfꢀwave potentials measured by RDE (2800 rpm).
d The initial potential is 0.7 V.

Complexes of diamidoꢀbisꢀsulfides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 8, August, 2009
1709
а
I/μA
these ligands, the abnormally strong influence of the elecꢀ
trode nature on the reduction potential is observed (see
Table 1, Fig. 1, b). It was for disulfides that a similar fact
has been noted previously,26c it has been rationalized by
specific interaction of the disulfide group with the electrode
surface. Thus, one can infer that the reduction of moleꢀ
cules 5 and 6 proceeds initially at the difulside fragment.
The investigation of ligands 5 and 6 on an Au electrode
revealed an additional, as compared with a glassy carbon
and Pt electrodes, cathodic peak at Ерс ≈ –0.9 V, which
corresponds to the reduction of the fragment Au—S
(Au—S—R + e– → Au0 + R—S–)27—29 and suggests
chemisorption of a ligand on the electrode surface to form
gold thiolate (Fig. 1, с, dashed line).
–20
0
20
1.0
0
–1.0
–2.0
E/V
The CV curves obtained in a pure solvent (i.e., ligandꢀ
free) with an Au electrode that has been immersed into a soꢀ
lution of a ligand (5 or 6) for 30 min and then rinsed
multiply with DMF reveal the same peaks as those obserꢀ
ved in the CV curves obtained for ligand solutions. This fact
also confirms the ligand chemisorption on the Au elecꢀ
trode surface to form the Au—S bond (see Table 1, Fig. 1, с).
In a study of interaction of ligands 3—6 with
CuCl2•6Н2О, NiCl2•6Н2О, and CoCl2•6Н2О in DMF
in an electrochemical cell, the irreversible complexation
was observed only for copper(II) chloride. The completion
of complex formation (∼30 min, the ligand and salt conꢀ
centrations are each 10–3 mol L–1) is evidenced by the
change in the solution color and the disappearance of the
peaks of the initial inorganic salt in the voltammogram. At
the same time, according to the electrochemical data (see
discussion below), it its the metal that is initially reduced
in the complexes with the composition Cu(L – 2 Н)2
(L = 3, 4, 5, or 6), which have been formed in solution. In
the first step, singleꢀelectron quasireversible reduction at
the copper atom occurs at Ерс ≈ 0.4 V (Scheme 4).
b
I/μA
–40
–20
0
20
1.0
0
–1.0
–2.0
E/V
c
I/μA
–12
–8
–4
0
Scheme 4
4
II
I
Cu (L – 2 Н)2
[Cu (L – 2 Н)2]
8
L = 3—6
12
The intermediate [Cu(L – 2 Н)2] formed upon reducꢀ
tion on a glassy carbon electrode is stable in the CVA time
scale. The peak of oxidative desorption of the copper metꢀ
al from the electrode on the reverse scan of the CV curve is
absent even after achieving the potential Ерс = –2.0 V (see
Table 1, Fig. 1, а). At the same time, on the metal elecꢀ
trodes (on Pt to a lesser degree and on Au to a greater
degree), an intermediate resulting from complex reducꢀ
tion undergoes disproportionation into a CuII compound
and a complex containing Cu0. The latter is decomposed
releasing the copper metal and, additionally, it is visually
observed that copper is deposited on the electrode surface
1.0
0
–1.0
–2.0 E/V
Fig. 1. Cyclic voltammograms (glassy carbon electrode, DMF,
0.1 M Bu4NClO4): (а) ligand 3 (dashed line) and the complex of
3 with Cu2+ formed in solution (solid line) at the concentration
10–3 mol L–1; (b) ligand 6 on a Auꢀ and glassy carbon elecꢀ
trodes (dashed and solid lines, respectively) at the concentration
5•10–4 mol L–1; (с) monolayers of ligand 6 on a Au electrode
(dashed line) and of the complex of ligand 6 with Cu2+ (solid line).
both HOMO and LUMO of macrocycles 5 and 6 are localꢀ
ized on the sulfur atoms of the disulfide fragment. For

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Beloglazkina et al.
Scheme 5
L = 3—6
as a black powder (see Refs 30, 31). We have noted32 such
a phenomenon for copper(II) salts and coordination comꢀ
pounds; in particular, the reduction product of copper(II)
chloride is not disproportionated on a glass carbon elecꢀ
trode in DMF, but it is disproportionated upon reduction
on a Ptꢀ and Auꢀelectrodes to release copper metal.
The second cathodic peak in the CV curve (see Fig. 1, а,
solid line) corresponds to reduction of the ligand fragment
of the complex.
ions in the CV curves of the adsorbed complexes with
ligands 5 and 6 (see Table 1, Fig. 1, с).
Scheme 6
It is known that two types of compounds can be proꢀ
duced upon complexation of the amideꢀtype ligands with
the transition metal salts: the complexes with the metal
ion coordinated by the neutral amide ligand33—35 or
complexes with the covalent nitrogen—metal bond that
is formed upon deprotonation of the amide nitrogen
atom.36,37 In the case of the studied ligands, complexes of
type I or II must be produced, respectively (Scheme 5).
The results of the electrochemical study of the copꢀ
per(II) complexes with ligands 3—6 in DMF and on the
Au electrode surface allow one to assume that the studied
ligands are deprotonated during the complex formation
and thereby the coordination compounds with the comꢀ
position Cu(L – 2 Н) are formed (see Scheme 5, type II).
For the preparation of monolayers of the Сu2+ comꢀ
plexes with ligands 5 and 6 (Scheme 6), the Au electrode
with ligand adsorbed on its surface (vide supra) was imꢀ
mersed into a solution of CuCl2•6Н2О for 1 h and then
washed with solvent to remove the excess of the inorganic
salt. When the voltammograms were recorded in the saltꢀ
free solution, only the peaks of copperꢀcontaining comꢀ
plex were observed in CV. The ligand deprotonation durꢀ
ing the formation of the coordination compounds follows
from the absence of the oxidation peaks of the chloride
For the copper(II) chloride complexes with ligands 3
and 4 that have been synthesized in DMF solution the
observed CV curves are similar to those of the complexes
with ligands 5 and 6, which were obtained on the surface.
For this reason, one can conclude that the copper(II) coꢀ
ordination compounds formed in solution and on the elecꢀ
trode surface have similar structures. In the CV curves,
after completion of the complexation, no oxidation peaks
of the chloride ions of the initial salt are observed in soluꢀ
tion in the region of ~1.1—1.2 V.38
In the anodic potential region, the oxidation wave at
1.26—1.46 V is also recorded for the complexes of ligands
3—6. At the same time, in the preparation of complexes in
the solutions containing ligand and copper(II) chloride in
a ratio of 1 : 2 and 1 : 3, an additional peak at 1.18 V
remains in the anodic potential region, which corresponds
to the oxidation reaction Cl– → 0.5 Cl2.

Complexes of diamidoꢀbisꢀsulfides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 8, August, 2009
1711
pared as described above was immersed into a solution of
CuCl2•6H2O in DMF (10–2 mol L–1) for 1 h and then washed
once again with DMF and dried in air. Afterwards, the electroꢀ
chemical curves were recorded in pure supporting electrolyte.
Synthesis of α,ωꢀbis(2ꢀaminophenylthio)alkanes (general proꢀ
cedure). In a 500 mL threeꢀnecked flask equipped with a reflux
condenser, a dropping funnel, and a stirring bar, EtOH (100 mL)
was placed and sodium metal was dissolved in EtOH. оꢀAminoꢀ
benzenethiol was added to the resulting solution. A solution of
α,ωꢀdibromoalkane in EtOH (50 mL) was then added under
reflux. The reaction mixture was stirred for 7 h under reflux,
cooled and quenched with water (150 mL). The precipitate that
formed was filtered off and recrystallized from EtOH.
1,2ꢀBis(2ꢀaminophenylthio)ethane (1) was prepared from soꢀ
dium (1.84 g, (80 mmol), оꢀaminobenzenethiol (8.51 mL, 10.0 g,
80 mmol), and 1,2ꢀdibromoethane (3.46 mL, 7.52 g, 40 mmol).
The yield was 8.12 g (74%), m.p. 76—78 °С (cf. Ref. 39: m.p.
76—78 °С). 1H NMR (CDCl3, δ): 7.35 (dd, 2 Н, Н(5), J1 = 7.6 Hz,
J2 = 1.3 Hz); 7.15 (td, 2 Н, Н(2), J1 = 7.4 Hz, J2 = 1.6 Hz); 6.71
(m, 4 Н, Н(3), Н(4)); 4.28 (br.s, 4 Н, NH2); 2.89 (s, 4 Н,
СН2S). IR, ν/cm—1: 3330 (NH).
In the reaction of ligands 3—6 with NiCl2•6Н2О and
CoCl2•6Н2О in DMF, the complex compounds are also
formed, but, in contrast to CuCl2•6Н2О, the complexaꢀ
tion reaction is apparantely reversible. Even several hours
after mixing the reactants, the peaks of the initial salt and
ligand are still observed in CV in addition to the new
peaks related to the coordination compounds formed. The
following data are in favor of complex formation: (1) the
peak of desorption of the zerovalent nickel or cobalt obꢀ
served in the reverse scan after the first twoꢀelectron caꢀ
thodic peak (Ерс = –1.25 V) is less intensive than that of
the corresponding salts; (2) the values of reduction potenꢀ
tials related to NiII → Ni0 and СоII → Со0 transitions are
somewhat (by ~0.10—0.15 V) different from the values of
the reduction potentials of the initial salts.
Thus, we have synthesized a series of novel cyclic and
acyclic diamidoꢀbisꢀsulfide ligands by Nꢀacylation reacꢀ
tion of α,ωꢀbis(2ꢀaminophenylthio)alkanes. The results
of the electrochemical studies support deprotonation of
the amide ligands during the formation of their complexes
with copper(II) chloride.
1,4ꢀBis(2ꢀaminophenylthio)butane (2) was prepared analoꢀ
gously in the form of an oil from sodium (0.92 g, 0.04 mol),
оꢀaminobenzenethiol (5.00 g, 0.04 mol) and 1,4ꢀdibromobutane.
The yield was 4.84 g (80%). 1H NMR (CDCl3, δ): 7.36 (dd, 2 Н
arom., J1 = 7.7 Hz, J2 = 1.5 Hz); 7.13 (ddd, 2 Н arom., J1 = 7.7 Hz,
J2 = 7.7 Hz, J3 = 1.5 Hz); 6.74 (m, 2 Н arom.), 6.70 (m, 2 Н
arom.), 4.31 (br.s, 4 Н, 2 NH2); 2.73 (m, 4 Н, 2 СН2S); 1.68
(m, 4 Н, 2 SCH2CH2).
Experimental
1
Н NMR spectra were recorded on a Bruker Avance 400
instrument (400 MHz). IR spectra were recorded on a URꢀ20
instrument in Nujol.
1,4ꢀBis(2ꢀacetylamidophenylthio)ethane (3). In a beaker
equipped with a stirring bar, compound 1 (1.00 g, 3.62 mmol)
was dissolved in benzene (40 mL) and acetic anhydride (0.74 g,
7.20 mmol) was added. The reaction mixture was stirred for
30 min. The precipitate that formed was filtered off, twice washed
with benzene, and dried in air. The yield was 1.147 g (88%), m.p.
A PIꢀ50ꢀ1.1 potentiostat connected to a PRꢀ8 programmer
was used for electrochemical study. The working electrodes
were a glassy carbon (d = 2 mm), a platinum disk (d = 3 mm),
and a gold disk (d = 2 mm). The supproting electrolyte was
a 0.1 М Bu4NClO4 solution in DMF, the reference electrode
was Ag/AgCl/KCl(sat.), and the auxiliary electrode was a platꢀ
inum plate. The surface of the working electrodes was polished
with alumina powder having a particle size less than 10 μm
(Sigma—Aldrich). The potential sweep rate in the CV and
RDE studies were 200 and 20 mV s–1, respectively. The potenꢀ
tials are given with allowance for the iR compensation. The
number of electrons transferred in redox processes was deterꢀ
mined by comparing the limiting wave current in the RDE
experiments with the current of oneꢀelectron oxidation of ferꢀ
rocene at the concentration equal to that of the compound
under study. All measurements were carried out under dry arꢀ
gon. The samples were dissolved in the preꢀdeareated solvent.
DMF (pure grade) was purified by stirring with freshly calcined
K2CO3 for 4 days followed by successive vacuum distillation
over P2O5 and anhydrous CuSO4.
1
204—206 °С. H NMR (DMSOꢀd6, δ): 9.33 (s, 2 Н, NH); 7.56
(d, 2 Н, Н(3), J = 7.6 Hz); 7.34 (d, 2 Н, Н(6), J = 7.6 Hz); 7.25
(t, 2 Н, Н(5), J = 7.8 Hz); 7.14 (t, 2 Н, Н(4), J = 7.4 Hz); 3.00
(s, 4 Н, СН2S); 2.06 (s, 6 Н, СОСН3). IR, ν/cm–1: 2940 (NH);
1620 (C=O). Found (%): С, 60.32; Н, 5.77; N, 7.71; S, 17.71.
С18Н20N2O2S2. Calculated (%): С, 60.00; Н, 5.56; N, 7.78; S, 17.78.
6,7,12,13ꢀDibenzoꢀ1,5ꢀdiazaꢀ8,11ꢀdithiacyclotridecanꢀ2,4ꢀ
dione (4). Compound 1 (0.30 g, 1.09 mmol), dimethyl malonate
(0.143 g, 1.09 mmol), and diphenyl ether (5 mL) were placed
into a 50 mL roundꢀbottomed flask equipped with air condenser.
The reaction mixture was refluxed for 5 h and then cooled. The
precipitate that formed was filtered off and recrystallized from
DMSO. The crystalline residue formed 4 h after cooling the
solution to –15 °С. The yield was 0.238 g (64%). 1H NMR
(DMSOꢀd6, δ): 10.18 (s, 2 Н, 2 NH); 7.87 (d, 2 Н arom., J =
= 7.6 Hz); 7.62 (d, 2 Н arom., J = 7.6 Hz); 7.38 (t, 2 Н arom.,
J1 = J2 = 7.6 Hz); 7.19 (t, 2 Н arom., J1 = J2 = 7.6 Hz); 3.60
(s, 2 Н, СОСН2CO); 2.98 (s, 4 Н, 2 СН2S). Found (%): С, 60.01;
Н, 4.25; N, 7.99. С17Н14N2O2S2. Calculated (%): С, 59.65;
Н, 4.09; N, 8.19.
In the experiments for electrochemical study of complexaꢀ
tion, a solution of ligands 3—6 in DMF (5•10–4—10–3 mol L–1
)
was mixed in an electrochemical cell with solutions of
NiCl2•6H2O, СоCl2•6H2O or CuCl2•6H2O in DMF at the
same concentrations at the ratio of 1 : 1. The gold electrode
with surfaceꢀadsorbed ligand was prepared by incubation of the
electrode in a solution of ligand 5 or 6 (10–3 mol L–1) for 1 h. It
was then washed with DMF, air dried, and placed into pure
supporting electrolyte. In the experiments for studying comꢀ
plexation with the ligands adsorbed on the electrode surface,
the gold electrode with the monolayer of ligand 5 or 6 preꢀ
Ligands 5—6 (general procedure). A. 3,3´ꢀdithiodi(propioꢀ
nyl chloride). Powdered 3,3´ꢀdithiodi(propionic acid) (5.00 g,
23.80 mmol) and SOCl2 (11.33 g, 95.20 mmol) were placed into
Ehrlemeyer's flask equipped with reflux condenser connected to
a calcium chloride tube. The flask contents was stirred with
heating on a water bath at 45—50 °C for 3 days. The reaction

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Beloglazkina et al.
mixture slowly darkened and became deep redꢀbrown. It was
heated at 60 °C for 2 h and cooled. Excess of SOCl2 was removed
in vacuo. The yield was 4.32 g (73%). 1H NMR (CDCl3, δ): 3.33
(t, 4 Н, CH2COCl, J = 6.9 Hz); 2.96 (t, 3 Н, SCH2, J = 6.9 Hz).
B. Preparation of macrocyclic ligands. A solution of pyridine
in dry benzene (100 mL) was heated to 75 °С. At this temperaꢀ
ture, a solutions of a diamine and 3,3´ꢀdithiodipropionic acid
(each in dry benzene (60 mL)) were added simultaneously dropꢀ
wise for 6 h and stirred at this temperature for 3 h. Then the
solvent was evaporated in vacuo and the residue was washed with
1 M HCl (100 mL), dried in air, and recrystallized from DMSO.
11,12,17,18ꢀDibenzoꢀ1,10ꢀdiazaꢀ5,6,13,16ꢀtetracyclooctaꢀ
decaneꢀ2,9ꢀdione (5). Compound 5 was prepared from compound 1
(0.50 g, 1.81 mmol) and 3,3´ꢀdithiodi(propionyl chloride) (0.45 g,
1.81 mmol) in the presence of pyridine (1.44 mL, 17.8 mmol) in
a yield of 0.42 g (51%). M.p. 244—246 °C. 1H NMR (DMSOꢀd6, δ):
9.46 (s, 2 H, NH); 7.67 (d, 2 Н arom., J = 7.4 Hz); 7.52
(d, 2 Н arom., J = 7.5 Hz); 7.29 (t, 2 Н arom., J = 7.6 Hz); 7.18
(t, 2 Н arom., J = 6.9 Hz); 3.08 (m, 4 Н, CH2CO); 2.95 (m, 4 H,
CH2S—S); 2.85 (s, 4 H, CH2S). Found (%): С, 50.25; Н, 5.00;
N, 5.60. С20Н22N2O2S4. Calculated (%): С, 53.33; Н, 4.88; N, 6.22.
11,12,19,20ꢀDibenzoꢀ1,10ꢀdiazaꢀ5,6,13,18ꢀtetracycloeicoꢀ
sanꢀ2,9ꢀdione (6) was prepared from compound 2 (0.50 g,
1.64 mmol) and 3,3´ꢀdithiodi(propionyl chloride) (0.41 g,
1.64 mmol) in the presence of pyridine (1.44 mL, 17.8 mmol) in
a yield of 0.57 g (73%). M.p. 264—266 °C. 1H NMR (DMSOꢀd6,
δ): 9.45 (s, 2 H, NH); 7.59 (d, 2 Н arom., J = 7.8 Hz); 7.47
(d, 2 Н arom., J = 7.2 Hz); 7.25 (m., 2 Н arom.); 7.16 (m, 2 Н
arom.); 3.03 (m, 4 Н, CH2CO); 2.81 (m, 8 H, CH2SS + CH2S),
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This work was financially supported by the Russian
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Received October 6, 2008;
in revised form April 21, 2009