N,N'-Bis(2-mercaptophenyl)propane-1,3-diamine as a new organic ligand of the N2S2 type and its coordination compound with nickel(II)

Article abstract of DOI:10.1007/s11172-010-0121-4

A method for the synthesis of new tetradentate organic ligand of the N2S2 type, viz., N,N'-bis (2-mercaptophenyl)propane-1,3-diamine has been developed, starting from 2-(tert-butyl thio)aniline and malonyl dichloride. Coordination compound of this ligand

Full text of DOI:10.1007/s11172-010-0121-4

Russian Chemical Bulletin, International Edition, Vol. 59, No. 3, pp. 544—549, March, 2010
544
N,N´ꢀBis(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamine as a new organic ligand
of the N2S2 type and its coordination compound with nickel(II)
V. V. Frolov,a A. G. Mazhuga,b E. K. Beloglazkina,b N. V. Zyk,b and M. P. Egorova
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 8941
bDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 2292. Eꢀmail: bel@org.chem.msu.ru
A method for the synthesis of new tetradentate organic ligand of the N2S2 type, viz., N,N´ꢀbisꢀ
(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamine has been developed, starting from 2ꢀ(tertꢀbutylꢀ
thio)aniline and malonyl dichloride. Coordination compound of this ligand with NiII according
to the Xꢀray diffraction data has a squareꢀplanar geometry of the metal ion coordination sphere.
Key words: nickel(II), transition metal complexes, N2S2 ligands.
Active centers of many redox enzymes contain transiꢀ
One of promising classes of N,Sꢀcontaining ligands
for the synthesis of metalloenzyme analogs are thioꢀsubꢀ
stituted amines. Earlier, we have synthesized a series of
acyclic and macrocyclic amino and imino sulfides of the
N2S2 type, the orthoꢀaminobenzenethiol derivatives,19,20
some of which proved capable of reversible electrochemiꢀ
cal reduction and, therefore, are promising as catalysts of
oxidationꢀreduction reactions.
tion metal ions (Cu ions in hydrogenases and oxygenasꢀ
es, Co and Ni ions in synthases, transferases, and isoꢀ
merases) coordinated with the nitrogen and sulfur atꢀ
oms of the amino acid fragments.1—3 The synthesis of
lowꢀmolecularꢀweight N,Sꢀcontaining ligands and their
complex compounds, simulating geometric specificiꢀ
ties of natural metalloenzymes and being their functional
analogs, is of significant interest from the point of view
of possible catalytic activity. Nowadays, lowꢀmolecuꢀ
larꢀweight complexes of nickel, cobalt, and copper
are used for catalysis of a wide range of organic reacꢀ
tions including reactions of asymmetric synthesis, epoxiꢀ
dation of alkenes,4—6 cyclopropanation,7 aziridinaꢀ
tion,8 oxidation of sulfides,9,10 the Diels—Alder reacꢀ
tions,11 activation of the CH bonds,12,13 epoxide ring
opening.14—18
In the most naturally occurring metalloenzymes, the
metal atom is in the squareꢀplanar (or distorted tetraꢀ
hedron) ligand environment; the apical positions in the
coordination sphere are spatially available for the coordiꢀ
nation with one or two additional ligands and can be ocꢀ
cupied by molecules of substrate and reagent in the process
of catalytic cycle. Therefore, squareꢀplanar complexes
are of the highest interest as the models of metalꢀconꢀ
taining enzymes. In addition to spatial criteria, electronic
factors should be considered as well. From this point
of view, it is desirable the presence in the ligand molecule
of soft donors capable of effective stabilization of the
lowꢀvalent state of metal ions, the intermediates of cataꢀ
lytic cycles in the oxidation reactions, for example, of
sulfur atoms.
By now, several NiII coordination compounds with
tetradentate N,Sꢀcontaining ligands of the series of
N,N´ꢀbisꢀorthoꢀmercaptophenylꢀsubstituted alkanediꢀ
amines have been described in the literature.21—25 1,2ꢀDiꢀ
aminoethane derivatives serve as the ligands in all these
complexes. Probably, this is due to the simple synthesis of
such organic compounds, which are easy to obtain by reꢀ
duction of the corresponding diimines or thiazolidines,
the condensation products of glyoxal and orthoꢀmercapꢀ
toꢀsubstituted anilines.26 However, all the known by now
nickel(II) coordination compounds with neutral N,N´ꢀbisꢀ
(2ꢀmercaptophenyl)ethaneꢀ1,2ꢀdiamines (see Refs above)
have octahedron geometry of the coordination environꢀ
ment. N,N´ꢀBis(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamines
contain longer polymethylene bridge between the nitroꢀ
gen atoms, which increases its conformational lability and
can lead to the formation of complexes with other geomeꢀ
try. Nevertheless, there is no literature data on ligands of
the N2S2 type, i.e., 1,3ꢀdiaminopropane derivatives. In
the present work, we suggest a convenient method for the
preparation of N,N´ꢀbis(2ꢀmercaptophenyl)propaneꢀ1,3ꢀ
diamine (in the dihydrochloride form) and its coordinaꢀ
tion compound with NiII starting from orthoꢀaminobenꢀ
zenethiol and malonyl dichloride.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 532—532, March, 2010.
1066ꢀ5285/10/5903ꢀ0544 © 2010 Springer Science+Business Media, Inc.

N,N´ꢀbis(2ꢀthiophenyl)propaneꢀ1,3ꢀdiamine
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
545
Results and Discussion
results. The first method requires relatively timeꢀconsumꢀ
ing and complicated isolation of the thiol including purifiꢀ
cation by column chromatography, which is accompaꢀ
nied by significant oxidation of the thiol to disulfide. Obꢀ
viously, this method can be applied only to the final prodꢀ
ucts stable in air. Aluminum tribromide is a strong Lewis
acid and in the case of compounds studied causes cleavage
of the molecule at both the C—S and the C—N bonds. In
contrast to this, trityl and tertꢀbutyl protecting groups are
stable in basic and weakly acidic media, as well as in the
most reducing processes. Removal of such a protection is
performed by reflux in concentrated hydrochloric31 or triꢀ
fluoroacetic acids;32 the yields are quantitative, whereas
the excess of acid can be then removed by heating the
solution under argon at reduced pressure to prevent oxidaꢀ
tion of the thiol. We have chosen more available tertꢀbutyl
protecting group, this allowed us to obtain the target prodꢀ
uct in preparative yield.
Aminosulfide 1 obtained in the first step of the syntheꢀ
sis was further involved into the reaction with malonyl
dichloride to yield diamide 2. Initially, we planned to
conduct direct alkylation of the amino group in protectꢀ
ed orthoꢀaminobenzenethiol with dibromoethane, howevꢀ
er, this reaction gave no satisfactory results. As an alterꢀ
native, alkylation of the amino group was carried
out in two synthetic steps: with initial acylation of the
amino group and subsequent reduction of the amide
obtained.
It is known from the literature27 that the reaction of
1,3ꢀdicarbonyl compounds and orthoꢀaminobenzenethiol
usually stops at the stage of monoimine and, therefore, the
method successfully used in the synthesis of N,N´ꢀbisꢀ
(2ꢀmercaptophenyl)ethaneꢀ1,2ꢀdiamines, reduction of diꢀ
imines, is not suitable for the preparation of 1,3ꢀdiaminoꢀ
propane derivatives. An alternative is alkylation or acylaꢀ
tion of orthoꢀaminobenzenethiol at the nitrogen atom
with 1,3ꢀdihaloalkane or 1,3ꢀdicarboxylic acyl dichloꢀ
ride. However, undesirable competing alkylation at the
sulfur atom is possible in this case, hence it is necessary
to preliminary protect the SH group in the starting
compound.
We synthesized N,N´ꢀbis(2ꢀmercaptophenyl)propaneꢀ
1,3ꢀdiamine hydrochloride (4) in four steps (Scheme 1).
In the first step, orthoꢀaminobenzenethiol was alkylatꢀ
ed with tertꢀbutyl alcohol in aqueous sulfuric acid for the
protection of the SH group; protonation of the amino
group under these conditions interferes alkylation of the
nitrogen atom. Several protecting groups for the benꢀ
zenethiol SH groups are described in the literature. We
tried the most simple from them, acetyl protection. It is
stable under conditions of further reactions, however, the
reaction of orthoꢀaminobenzenethiol with acetyl chloride
or acetic anhydride is unselective and proceeds at both the
nitrogen and the sulfur atoms. The benzylation with benꢀ
zyl chloride in the presence of sodium ethoxide28 proceedꢀ
ed selectively due to the higher nucleophilicity of the sulꢀ
fur atom as compared to the amino group, moreover, the
benzyl protection is stable in the presence of most acids
and bases; however, the both methods described for the
removal of this protection, viz., reduction of benzyl sulfide
with sodium in liquid ammonia29 and cleavage with aluꢀ
minum tribromide28 or trichloride,30 gave no satisfactory
The third step of the synthesis included reduction of
diamide 2 to the corresponding diamine using complex of
boron hydride with tetrahydrofuran. Lithium aluminum
hydride33,34 and boron hydrides35,36 are the most known
reducing agents for amides. Attempted reduction of diꢀ
amide 2 upon the action of LiAlH4 in tetrahydrofuran
gave a complex mixture of products, from which we failed
to isolate the target diamine in the pure form even after
Scheme 1

546
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Frolov et al.
C(22)
purification by column chromatography. After the reacꢀ
tion of 2 with NaBH4 in the presence of BF3•OEt2, the
starting amide was isolated from the reaction mixture
in quantitative yield. Reduction with the complex boꢀ
rane—tetrahydrofuran36 proved the optimum method for
the synthesis of the target diamine 3, which was isolated
from the reaction mixture by column chromatography in
52% yield.
The protecting tertꢀbutyl group was removed from the
synthesized diaminoꢀbisꢀsulfide 3 by reflux in aqueous
hydrochloric acid. The ligand 4 obtained is stable in aqueꢀ
ous solution as a hydrochloride; however, it is rapidly oxiꢀ
dized to disulfide on the transformation to the free base by
treatment with equivalent amount of 1 M aqueous КOH.
Therefore, for further preparation of coordination comꢀ
pound 5 it is convenient to use aqueous solution of diꢀ
hydrochloride 4 without isolation and additional purificaꢀ
tion of the ligand.
C(11)
Cl(1)
C(12)
C(20)
C(13)
C(10)
S(1)
C(6)
S(2)
C(23)
H(1N2)
C(21)
C(5)
C(4)
H(1N)
C(15)
N(2)
C(2)
C(16)
C(17)
H(2N2)
C(3) N(1)
C(1)
C(8)
C(7)
C(14)
C(9)
C(19)
C(18)
Fig. 1. Molecular structure of compound 3a.
The most important bond distances and bond angles
for compounds 3a and 5 are given in Tables 1 and 2. Moꢀ
lecular structures of compounds 3a and 5 are shown in
Figs 1 and 2; the molecule packing in the crystal structure
of 5 is shown in Fig. 3.
In the molecule 3a, the donor nitrogen and sulfur atꢀ
oms of each of two aminobenzenethiol groups are arranged
in the same plane with the carbon atoms of the benzene
rings bound to them. However, all four donor atoms of the
N2S2 system are not placed in one plane; the angle beꢀ
tween the planes of two N—C—C—S fragments is ~70°.
The C—S—C angles are 106.25 and 101.50° that is typical
for aryl alkyl sulfides.
Method of slow diffusion of the compound 4 solution
in CH2Cl2 into the solution of nickel chloride hexahydrate
in ethanol was used for obtaining NiII complex compound.
This results in the isolation of coordination compound 5
(Scheme 2), the structure of which was confirmed by the
Xꢀray diffraction data.
Scheme 2
The nickel atom in compound 5 is coordinated by two
sulfur and two nitrogen atoms of the organic ligand and
has squareꢀplanar ligand environment. The Ni atom is
placed almost strictly in the plane of N2S2 atoms of the
macrocyclic ligand. The S—Ni—N angles are close to 90°,
the angle S(1)—Ni—S(2) is somewhat less than 90°,
whereas the angle N(1)—Ni—N(2), vice versa, is someꢀ
what larger than 90°, that, most likely, is due to the differꢀ
ent number of carbon atoms in the chelating cycles. The
benzene ring planes are virtually coplanar to the basic
plane of the ligand (determined by the N, S, and Ni atꢀ
oms) and to each other. All three carbon atoms of the
In the literature, there are known examples of removal
of tertꢀbutyl protection from mercapto groups in the comꢀ
plexation reactions; however, our effort to synthesize comꢀ
plex 5 by reflux of bisꢀsulfide 3 with ethanolic solution of
nickel chloride resulted in only diamine 3 monohydroꢀ
chloride (compound 3a), which was also characterized by
the Xꢀray diffraction data (Scheme 3).
Table 1. Selected bond distances (d), bond (ω) and
dihedral (θ) angles in compound 3a
Scheme 3
Value
Bond
Value
d/Å
C(1)—N(2)
1.509(2)
C(15)—S(2)
1.7716(17)
Bond angle
ω/deg
C(15)—S(2)—C(20)
S(2)—C(15)—C(14)
C(14)—N(2)—C(1)
101.50(8)
120.67(14)
112.27(13)
Dihedral angle
θ/deg
S(1)—C(5)—C(4)—N(1)
1.7(2)

N,N´ꢀbis(2ꢀthiophenyl)propaneꢀ1,3ꢀdiamine
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
547
Table 2. Selected bond distances (d), bond (ω) and diꢀ
hedral (θ) angles in compound 5
C(8)
C(7)
C(9)
C(5)
Parameter
Bond
Value
H(1N)
H(2N)
C(11)
C(4)
d/Å
N(1)
Ni(1)
C(6)
N(2)
C(10)
Ni(1)—N(1)
Ni(1)—N(2)
Ni(1)—S(1)
Ni(1)—S(2)
1.952(3)
1.958(3)
2.1517(11)
2.1622(11)
C(12)
C(13)
C(3)
C(2)
C(15)
C(1)
C(14)
S(1)
S(2)
Bond angle
ω/deg
S(1)—Ni(1)—N(1)
N(1)—Ni(1)—N(2)
S(2)—Ni(1)—N(2)
C(1)—S(1)—Ni(1)
C(15)—S(2)—Ni(1)
C(6)—N(1)—C(7)
C(6)—N(1)—Ni(1)
90.13(10)
92.22(13)
90.46(10)
98.78(13)
98.34(13)
111.3(3)
Fig. 2. Molecular structure of compound 5. The Figure shows
one of two crystallographically independent molecules.
methylene groups between nitrogen atoms are on the same
side of the basic plane. Such a configuration, probably, is
due to the chair conformation of the sixꢀmembered
NiN2C3 ring.
115.0(2)
Dihedral angle
θ/deg
In conclusion, a method for the preparation of new
tetradentate organic ligand of the N2S2 type, viz., N,N´ꢀbisꢀ
(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamine, has been deꢀ
veloped starting from available 2ꢀ(tertꢀbutylthio)ꢀ
aniline and malonyl dichloride. A coordination compound
of this ligand with NiII has been synthesized, which acꢀ
cording to the Xꢀray diffraction data has the squareꢀplaꢀ
nar geometry of the metal ion coordination environment,
which makes it promising for further study on cataꢀ
lytic activity in oxidation and electroinduced reduction
reactions.
S(1)—C(1)—C(6)—N(1)
Ni(1)—N(1)—C(6)—C(1)
0.2(4)
2.1(4)
Experimental
The reaction courses were monitored by TLC on a fixed
layer of silica gel (Silufol plates). Preparative chromatographic
separation of reaction mixtures was carried out on columns with
silica gel (70/230) and hexane—dichloromethane (1 : 1) solvent
mixture as the eluent.
a
0
c
b
Fig. 3. Molecular packing in the crystal structure of complex 5.

548
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Frolov et al.
1H and 13C NMR spectra were recorded on a Varian Mercuꢀ
Table 3. Crystallographic data, experimental and structure reꢀ
finement details for compounds 3a and 5
ryꢀ400 or Bruker Avanceꢀ400 spectrometers (400 MHz (1H) or
100 MHz (13C)) in CDCl3. Electronic spectra were recorded on
a PerkinꢀElmer λꢀ25 spectrometer, IR spectra, on a URꢀ20 specꢀ
trometer in Nujol, mass spectra, on a Finnigan MAT SSQ 7000
GCꢀMS instrument (70 eV, an OVꢀI (25 m) quartz capillary
Parameter
3a
5
Molecular formula
Molecular weight
C23H35ClN2S2
439.10
C15H16N2NiS2
347.13
column with temperature regime: 70 °C (2 min) — 20 deg min–1
280 °C (10 min or 30 min).
—
T/K
120(2)
120(2)
Crystal
size/mm
Crystal system
Space group
Parameters of the unit cell
a/Å
b/Å
c/Å
0.45×0.35×0.20
*
0.55×0.35×0.30
**
Monoclinic
P21/n
The Xꢀray study was performed on a Bruker Smart 1000
CCD frea detector singleꢀcrystal automatic diffractometer
(graphite monochromator, λ(MoKα) = 0.71073 Å, ωꢀscanning).
The structure was solved by the direct method37 and refined by
the fullꢀmatrix anisotropic least square method from F2 for all
the nonhydrogen atoms.38 All the hydrogen atoms were localꢀ
ized objectively and refined in the isotropic approximation. The
crystallographic data, experimental and structure refinement deꢀ
tails for compounds 3a and 5 are given in Table 3.
Triclinic
P–1
7.7895(4)
12.3728(7)
13.2039(7)
99.8880(10)
94.1430(10)
104.6260(10)
1204.08(11)
2
8.1844(7)
19.4128(16)
18.2774(15)
90
91.563(2)
90
2902.9(4)
8
1.589
α/deg
β/deg
γ/deg
2ꢀ(tertꢀButylthio)aniline (1).39 Water (25 mL) and concenꢀ
trated sulfuric acid (34 mL) were placed into a 100ꢀmL roundꢀ
bottom flask equipped with a dropping funnel, thermometer,
and magnetic stirring bar, then tertꢀbutanol (11 mL, 1.2•10–1
mol) was added at 0 °C, followed by a slow addition of 2ꢀamiꢀ
nobenzenethiol (10 g, 8.0•10–2 mol) over 40 min at the same
temperature. The reaction mixture was stirred for 1 h at 0 °C and
poured into a saturated aq. KHSO4 (60 mL), followed by addiꢀ
tion of 30% aq. NaOH at 10—15 °C to pH 9. The mixture was
extracted with diethyl ether (2×20 mL), the ethereal solution
was dried with Na2SO4. The solvent was evaporated at reduced
pressure to yield 2ꢀ(tertꢀbutylthio)aniline (12.50 g, 86%) as
3
V/Å
Z
dcalc/g cm–3
1.211
1.343
Absorption
coefficient/mm–1
F(000)
Range of θ/deg
Ranges of reflection
indices
h
k
1.614
472
1.58—28.00
1440
1.53—30.00
–10 ≤ h ≤ 10
–16 ≤ k ≤ 16
–17 ≤ l ≤ 17
–11 ≤ h ≤ 11
–27 ≤ k ≤ 27
–25 ≤ l ≤ 25
1
a yellowish oil. H NMR, δ: 7.40 (d, 1 H, arom., J = 8.3 Hz);
l
7.18 (t, 1 H, arom., J = 8.4 Hz); 6.77 (d, 1 H, arom., J = 8.3 Hz);
6.71 (t, 1 H, arom., J = 8.4 Hz); 4.46 (br.s, 1 H, NH); 1.35
(s, 9 H, CH3).
Number of reflections
measured/independent
12416/5765
(0.0228)
271
31659/8390
(0.0805)
377
(Rint
)
N,N´ꢀBis[2ꢀ(tertꢀbutylthio)phenyl]malonamide (2). A soluꢀ
tion of compound 1 (5 g, 2.76•10–2 mol) in CH2Cl2 (30 mL) and
Et3N (2.78 g, 2.76•10–2 mol) were placed under Ar into a 100ꢀmL
roundꢀbottom flask equipped with a dropping funnel, thermoꢀ
meter, and magnetic stirring bar, then malonyl dichloride (2.11 g,
1.38•10–2 mol) was added dropwise at 0 °C. The mixture was
stirred for 16 h, followed by addition of 1 M hydrochloric acid to
pH 1. The product was extracted with CH2Cl2 (2×20 mL), washed
with saturated aq. NaHCO3 (2×20 mL) and water (10 mL), dried
with Na2SO4. The solvent was evaporated at reduced pressure to
yield compound 2 (4.96 g, 81%) as a yellow powder, m.p.
Number of variables
of refinement
Qꢀfactor on F2
Number of reflections
with I > 2σ(I)
Rꢀfactors
R1
1.015
2371
1.015
2371
0.0493
0.1237
0.0521
0.0811
wR2
Rꢀfactors (on all the data)
R1
wR2
0.0613
0.1334
0.1200
0.0891
1
100—102 °C. H NMR, δ: 9.83 (br.s, 2 H, NH); 8.56 (d, 2 H,
arom., J = 7.5 Hz); 7.55 (d, 2 H, arom., J = 7.7 Hz); 7.42 (t, 2 H,
arom., J = 7.7 Hz); 7.09 (t, 2 H, arom., J = 7.5 Hz); 5.31 (s, 2 H,
CH2); 1.30 (s, 18 H, CH3). 13C NMR, δ: 164.4, 141.2, 138.8,
130.6, 123.9, 120.9, 120.0, 48.5, 48.7, 30.7. IR, ν/cm–1: 3290
(NH), 1760 (CO). MS, m/z: 431 [MH]+. Found (%): C, 64.37;
H, 7.18; N, 6.43. C23H30N2O2S2. Calculated (%): C, 64.14;
H, 6.98; N, 6.51.
N,N´ꢀBis[2ꢀ(tertꢀbutylthio)phenyl]propaneꢀ1,3ꢀdiamine (3).
Amide 2 (4 g, 9.30•10–3 mol) in THF (40 mL) was placed under
inert gas into a 150ꢀmL roundꢀbottom flask equipped with
a dropping funnel, thermometer, and magnetic stirring bar, folꢀ
lowed by a dropwise addition of a solution of BH3•THF (1 M,
93 mL, 9.30•10–2 mol) in the same solvent at 0 °C. The mixture
was stirred for 3 h at 0 °C, then for 16 h at room temperature and,
after a dropwise addition of CH3OH (75 mL), for another 16 h.
The solvent was evaporated at reduced pressure, CH3OH
* Orange plates.
** Light yellow needles.
(3×30 mL) was added to the residue, followed by evaporation of
the solvent at reduced pressure. The product was purified by
column chromatography on silica gel (hexane—CH2Cl2, 1 : 1)
to yield compound 3 (1.94 g, 52%) as a white powder, Rf = 0.64
(hexane—CH2Cl2, 1 : 1), m.p. 60—62 °C. 1H NMR, δ: 7.42
(d, 2 H, arom., J = 7.9 Hz); 7.27 (m, 4 H, arom.); 6.65 (d, 4 H,
arom., J = 7.9 Hz); 3.32 (t, 4 H, CH2CO, J1 = 6.8 Hz); 2.00
(quint, 2 H, CH2CH2CO, J = 6.8 Hz); 1.31 (s, 18 H, CH3).
13C NMR, δ: 151.0, 139.6, 131.0, 156.7, 116.1, 115.6, 110.3,
47.7, 41.4, 37.1, 29.3. IR, ν/cm–1: 3300 (NH). Found (%):
C, 68.67; H, 8.70; N, 6.84. C23H34N2S2. Calculated (%):
C, 68.66; H, 8.46; N, 6.97.

N,N´ꢀbis(2ꢀthiophenyl)propaneꢀ1,3ꢀdiamine
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
549
N,N´ꢀBis[2ꢀ(tertꢀbutylthio)phenyl]propaneꢀ1,3ꢀdiamine moꢀ
nohydrochloride (3a). Diamine 3 (0.2 g, 4.98•10–4 mol) in ethaꢀ
nol (25 mL) was placed into a 50ꢀmL roundꢀbottom flask
equipped with a reflux condenser and magnetic stirring bar, then
NiCl2•6H2O (0.12 g, 4.98•10–4 mol) in ethanol (10 mL) was
added. The mixture was refluxed for 12 h with stirring. The
solvent was half evaporated at reduced pressure. The solution
was kept at 0—5 °C until crystals formed. The crystals were filꢀ
tered off, washed with cold ethanol (5 mL), then with diethyl
ether (5 mL) to yield hydrochloride 3a (0.2 g, 92%) as
light brown crystals. Found (%): C, 62.67; H, 8.29; N, 6.57.
C23H35N2S2Cl. Calculated (%): C, 62.94; H, 7.98; N, 6.39.
N,N´ꢀBis(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamine dihydroꢀ
chloride (4). Diamine 3 (0.3 g, 7.45•10–4 mol) was placed under
Ar into a 50ꢀmL roundꢀbottom flask equipped with a reflux conꢀ
denser and magnetic stirring bar, to which conc. hydrochloric
acid (25 mL) was added. The mixture was refluxed for 8 h with
stirring. The solvent was evaporated at reduced pressure to yield
10. T. Fukuda, T. Katsuki, Tetrahedron Lett., 1997, 38, 3435.
11. S. E. Schaus, J. Brenalt, E. N. Jacobsen, J. Org. Chem., 1998,
63, 403.
12. M. D. Kaufman, P. A. Grieco, D. W. Bougie, J. Am. Chem.
Soc., 1993, 115, 11648.
13. J. F. Larrow, E. N. Jacobsen, J. Am. Chem. Soc., 1994,
116, 12129.
14. E. N. Jacobsen, F. Kakiuchi, R. G. Konsler, J. F. Larrow,
M. Tokunaga, Tetrahedron Lett., 1997, 38, 773.
15. M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacobsen,
Science, 1997, 277, 936.
16. J. L. Leighton, E. N. Jacobsen, J. Org. Chem., 1996, 61, 389.
17. L. E. Martinez, J. L. Leighton, D. H. Carsten, E. N. Jacobꢀ
sen, J. Am. Chem. Soc., 1995, 117, 5897.
18. R. L. Paddock, S. B. T. Nguyen, J. Am. Chem. Soc., 2001,
123, 11498.
19. E. K. Beloglazkina, A. G. Mazhuga, A. A. Moiseeva, I. V.
Yudin, F. S. Moiseev, O. I. Shmatova, N. V. Zyk, Izv. Akad.
Nauk, Ser. Khim., 2008, 565 [Russ. Chem. Bull., Int. Ed.,
2008, 57, 577].
20. E. K. Beloglazkina, A. A. Moiseeva, A. A. Chizhevskii, B. N.
Tarasevich, N. V. Zyk, K. P. Butin, Izv. Akad. Nauk,
Ser. Khim., 2003, 1885 [Russ. Chem. Bull., Int. Ed., 2002,
52, 1990].
1
compound 4•2HCl (0.27 g, 100%) as white powder. H NMR,
δ: 7.92 (d, 2 H, arom., J = 7.7 Hz); 7.50 (d, 2 H, arom., J = 8.0 Hz);
7.28 (m, 4 H, arom.); 3.66 (t, CH2CO, 1 H, J = 7.1 Hz); 3.23
(q, CH2CH2CO, 2 H, J = 7.1 Hz). MS, m/z: 289 [MH]+.
[N,N´ꢀBis(2ꢀmercaptophenyl)propaneꢀ1,3ꢀdiamine]nickel(II)
(5). Ethanol (200 μL) was added to a solution of dihydrochloride
4 (0.01 g, 3.45•10–5 mol) in dichloromethane (1 mL) until two
layers were formed. Then a solution of NiCl2•6H2O (8 mg,
3.45•10–5 mol) in ethanol (1 mL) was slowly added. The reꢀ
action mixture was tightly capped and stored until crystals
formed to yield compound 5 (9 mg, 75%) as brown crystals,
21. T. Kawamoto, Y. Kushi, Bull. Soc. Chem. Jpn., 2004, 77, 289.
22. Z. Dori, R. Eisenberg, E. I. Stiefel, H. B. Gray, J. Am. Chem.
Soc., 1970, 92, 1506.
23. T. Kawamoto, K. Takeda, M. Nishiwaki, T. Aridomi,
T. Konno, Inorg. Chem., 2007, 46, 4239.
m.p. 264—266 °C. IR, ν/cm–1: 3025 (NH). UV: λ = 280 nm,
24. D. Sellmann, W. Prechtel, F. Knock, M. Moll, Z. Naturꢀ
forsch., B., Chem. Sci., 1992, 47, 1411.
1
ε = 12847 L (mol cm)–1, λ = 310 nm, ε = 20139 L (mol cm)–1
.
1
2
1
Found (%): C, 51.94; H, 4.71; N, 8.14. C15H16N2S2Ni. Calcuꢀ
lated (%): C, 51.87; H, 4.61; N, 8.07.
25. D. Sellmann, R. Ruf, F. Knoch, M. Moll, Z. Naturforsch.,
B., Chem. Sci., 1995, 50, 791.
26. M. C. Thompson, D. H. Busch, J. Am. Chem. Soc., 1964,
86, 213.
27. G. Mukherjee, S. Pal, S. N. Poddar, K. Dey, Ind. J. Chem.,
Sect. A, 1991, 30, 952.
28. A. Burawoy, C. Turner, W. Hyslop, J. Chem. Soc., 1954, 82.
29. L. Heinrich, J.ꢀC. Chottard, Synth. Commun., 2001, 31, 1323.
30. A. Arnoldi, A. Bonsignori, P. Melloni, L. Merlini, J. Med.
Chem., 1990, 33, 2865.
31. S. Clavier, O. Rist, S. Hansen, L.ꢀO. Gerlach, Org. Biomol.
Chem., 2003, 1, 4248.
The authors are grateful to the Center of Xꢀray Difꢀ
fraction Studies of the A. N. Nesmeyanov Institute
of Organoelement Compounds, Russian Academy of
Sciences
This work was financially supported by the Russian Founꢀ
dation for Basic Research (Project No. 07ꢀ03ꢀ00584ꢀa)
and the Russian Science Support Foundation.
32. K. Boy, J. Guernon, S.ꢀY. Sit, Bioorg. Med. Chem. Lett.,
2004, 14, 5089.
References
33. H. Finlay, J. Lloyd, M. Nyman, Bioorg. Med. Chem. Lett.,
2008, 18, 2714.
34. C. Aquino, D. Armour, J. Berman, L. Birkemo, J. Med.
Chem., 1996, 39, 562.
35. D. Clive, J. Peng, S. Fletcher, J. Org. Chem., 2008, 73, 2330.
36. G. Sun, N. Uretsky, L. Wallace, G. Shams, J. Med. Chem.,
1996, 39, 4430.
37. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
38. G. M. Sheldrick, Program for the Refinement of Crystal Strucꢀ
tures, University of Göttingen, Germany, 1997.
39. A. Courtin, H.ꢀR. Tobel, G. Auerbach, Helv. Chim. Acta,
1980, 63, 1412.
1. T. C. Harrop, P. K. Mascharak, Acc. Chem. Res., 2004,
37, 253.
2. N. E. Dixon, C. Gazzola, R. L. Blakeley, B. Zerner, J. Am.
Chem. Soc., 1975, 97, 4131.
3. I. M. Wasser, S. de Vries, P. MoлnneꢀLoccoz, I. Schröder,
K. D. Karlin, Chem. Rev., 2002, 102, 1201.
4. A. K. Jorgensen, Chem. Rev., 1989, 89, 431.
5. P. J. Pospisil, D. H. Carsten, E. N. Jacobsen, Chem. Eur. J.,
1996, 2, 974.
6. K. P. Bryliakov, E. P. Talsi, Inorg. Chem., 2003, 42, 7258.
7. T. Fukuda, T. Katsuki, Tetrahedron, 1997, 53, 7201.
8. J. Du Bois, C. S. Tomooka, J. Hong, E. M. Carreira, Acc.
Chem. Res., 1997, 30, 364.
9. C. Bolm, F. Bienewald, Angew. Chem., Int. Ed. Engl., 1995,
34, 2640.
Received July 16, 2009