Sulfur-bonded organogermanium (IV) complexes of biopotent bases and their antiandrogen and biocidal properties

Article abstract of DOI:10.1080/10426500701641452

In the search for the better fungicides, bactericides and antiandrogen agents, studies have been carried out to assess the growth-inhibiting potential of the newly synthesized organogermanium(IV) complexes against various pathogenic fungal and bacterial s

Full text of DOI:10.1080/10426500701641452

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Sulfur-Bonded
Organogermanium (IV)
Complexes of Biopotent Bases
and Their Antiandrogen and
Biocidal Properties
Monika Swami a & R. V. Singh a
a Department of Chemistry , University of
Rajasthan , Jaipur, India
Published online: 04 Jun 2008.
To cite this article: Monika Swami & R. V. Singh (2008) Sulfur-Bonded
Organogermanium (IV) Complexes of Biopotent Bases and Their Antiandrogen and
Biocidal Properties, Phosphorus, Sulfur, and Silicon and the Related Elements, 183:6,
1350-1364, DOI: 10.1080/10426500701641452
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Phosphorus, Sulfur, and Silicon, 183:1350–1364, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701641452
Sulfur-Bonded Organogermanium (IV) Complexes
of Biopotent Bases and Their Antiandrogen
and Biocidal Properties
Monika Swami and R. V. Singh
Department of Chemistry, University of Rajasthan,
Jaipur, India
In the search for the better fungicides, bactericides and antiandrogen agents, stud-
ies have been carried out to assess the growth-inhibiting potential of the newly
synthesized organogermanium(IV) complexes against various pathogenic fungal
and bacterial strains as well as on reproductive organs of the male albino rats.
The results of these studies have been compared with the standard fungicide Bav-
istin and bactericide Streptomycin. The studies demonstrate that the ligands and
their trimethylgermanium(IV) complexes have comparable antimicrobial activity.
The results also indicated that the weights of the body and vital organs were not
affected after the treatment suggesting that the complexes have no side effect or
toxicological effect and maintained normal physiology of the animals throughout
the experiment. It has also been revealed that the organogermanium(IV) complexes
showed more antifertility effect than the bases. These complexes were synthesized
by the reactions of trimethylgermanium(IV) chloride with biologically potent N∩SH
donor bases and characterized by elemental analyses, conductance measurements,
1
13
molecular weight determinations and IR, H NMR, C NMR and electronic spec-
tral studies.
Keywords Antiandrogen aspect; benzothiazolines and biopotent bases; biocidal proper-
ties; triorganogermanium(IV) complexes
INTRODUCTION
With the ever-growing world population, contraception is an important
health issue for the 21st century. Fertility is an issue of global and na-
tional public issues concerning the rapid growth of the country. The
rapid increase of population has an adverse effect on the national econ-
omy and as the increase is only limited to the developing countries, the
Received 21 July 2007; accepted 22 July 2007.
The authors are thankful to CSIR, New Delhi for financial assistance in the form of
grant No. 01(1956)/EMR-II/2004.
Address correspondence to R.V. Singh, Department of Chemistry, University of
Rajasthan, Jaipur 302004, India. E-mail: rvsjpr@hotmail.com
1350

Sulfur-Bonded Organogermanium (IV) Complexes of Biopotent Bases
1351
problem becomes an acute on the fruits of improvement in the different
sectors, which are being eroded by the growing population. Moreover,
the increasing number of births has a deleterious effect on the health of
mother and child, and it hinders social and economic progress. The regu-
lation of human fertility has global consequences in terms of resources
depletion, population, and poverty. Now, it is one of the priorities of
the national Family Programs, and therefore, there is an urgent need
to improve the access and the quality of contraceptive service in the
country. The primary requisite of an antifertility agent for human is
that it should be non-toxic, non-teratogenic, and it should not interfere
with the normal metabolic and behavioral process. Further, the method
should be reversible. Therefore, exhaustive and prolonged studies on
the safety and efficacy of contraceptive agents including their effect on
progeny in laboratory animals should precede studies on human volun-
teers. Each contraceptive method has its unique advantages and disad-
vantages. The success of any contraceptive method depends not only on
its effectiveness in preventing pregnancy, but on the rate of continua-
tion of proper use, as well. Currently, there are many methods available
for the women including oral contraceptive pills, implants, intrauterine
devices, cervical caps, female condom, and tubule legation but for men,
contraceptive choices are limited, in contrast to the great variety of fe-
male methods men who want to take responsibility for contraception
today have only two option condoms and vasectomy (male sterilization).
Out of the two male methods, although condoms protect against sex-
ually transmitted disease, many couples find them too inconvenient,
expensive, unreliable for long use physiological resistance and a 3–15%
failure rate and vasectomy is not reliably reversible and thus are not
acceptable for those who may want children in the future. Chemicals
can interfere with hormonal control, the male reproductive tract and
directly alter the male reproductive tract function. The chemical con-
trol of fertility in the male has received attention since quite some time
and a large number of synthetic compounds have been tested for their
antispermatogenic and antiadrogenic effects.1 Many simple chemicals
have been shown to be capable of affecting epididymal spermatozoa, so
that they are useless when ejaculated. Chemically their action proba-
bly depends upon donating methyl group to important cell components.
Spermatozoa obtained from the epididymis during the sterile phase
were non-motile.
The organic germanium has been used clinically in many parts of
the world to treat a wide spectrum of illnesses, and has been the sub-
ject of extensive research in many disciplines: pathology, biochemistry,
pharmacology, immunology, oncology, and neurochemistry. Organic ger-
manium has been used in a broad spectrum of regimes—on its own,

1352
M. Swami and R. V. Singh
with diet and stress counseling, and as a drug in clinical trials of can-
cer therapy, in conjunction with chemotherapy, radiation therapy, and
surgery. Drawing these sources of information together gives quite a
solid overview of the fundamental aspects of organic germanium. Mea-
surement of urinary Ge can detect occupational exposure to inorganic
Ge and its compounds. It is prudent to recommend the monitoring of
renal variables in workers exposed to germanium.2 A histological com-
parison of the liver, spleen, bone marrow, circulating young erythro-
cytes, and differential count in mature male and female albino rats
receiving germanium dioxide with their litter controls not receiving
this compound was made.3 The aim of the present investigations is
to find the effect on the testes and accessory sex glands together with
metabolic disturbance and disease when exposed to bases and their ger-
manium(IV) complexes; for these findings, the experiments have been
done on male albino rats.
EXPERIMENTAL
All the experimental work and handling of the compounds was carried
out in the absence of moisture. Chemicals and solvents were dried and
purified by the standard methods.
Preparation of the Bases
The bases, i.e. benzothiazolines, L1H, L2H, and L3H used during
these investigations were prepared4 by the condensation of unimo-
lar ratio of [1-(thien-2-yl)ethanone] (5.20 g, 41.20 mmol), [1-(pyridin-2-
yl)ethanone] (6.20 g, 51.20 mmol) and [1-(furan-2-yl)ethanone] (5.50 g,
49.20 mmol), respectively with 2-mercaptoaniline (2.78 g, 22.20 mmol,
3.39 g, 27.00 mmol, 3.16 g, 25.20 mmol) in dry ethanol (50 mL)) on a
magnetic stirrer for 3–4 h. The crystalline products so obtained were fil-
tered, washed with ethanol, and dried in vacuo for 2 h. Analyses of these
bases for carbon, hydrogen, nitrogen, and sulfur agreed with the theo-
retical values within the limits of experimental errors and the physical
properties are given in Table I.
Synthesis of Trimethylgermanium(IV) Complexes
To a weighed amount of trimethyl germanium chloride (1.0 g, 6.52
mmol) was added the requisite amount of the sodium salt (prepared by
reacting the base with freshly cut sodium metal in 20 mL dry methanol)
(1.66 g, 22.2 mmol, 1.63 g, 26.91 mmol, 1.56 g, 25.2 mmol) of the base
in a dry solvent mixture of benzene (20 mL) and methanol (30 mL).

1353

1354

Sulfur-Bonded Organogermanium (IV) Complexes of Biopotent Bases
1355
The reaction mixture was refluxed for 8–9 hours during which a white
solid (NaCl) separated out; the contents were then cooled and filtered.
Benzene (15 mL) was added to the filtrate and it was again refluxed.
The process of refluxing and filtration was repeated two or three times
until all the sodium chloride had precipitated. The solvent was then
removed by distillation under reduced pressure and the resulting prod-
uct repeatedly washed with dry n-hexane and petroleum ether. It was
finally dried in vacuo under reduced pressure. The purity was further
checked by TLC using silica gel-G. The details of the physical properties
and analytical data of the newly synthesized complexes are recorded in
Table I.
Analytical Methods and Physical Measurements
Carbon and hydrogen analyses were carried out at CDRI, Lucknow.
Germanium was determined gravimetrically as GeO2. Nitrogen and
sulfur were determined by the Kjeldahl’s and Messenger’s method,
respectively. Molar conductance measurements were made by using
Systronic conductivity bridge, Model 305. Molecular weights were de-
termined by the Rast Camphor method. The 1H NMR spectra were
recorder on a JEOL FX 90 Q spectrometer in DMSO-d6 using TMS as
the internal standard at 89.55 MHz. 13C NMR spectra were recorded
from saturated solutions using DMSO as a solvent at 22.49 MHz on the
same instrument. The IR spectra were recorded on a Perkin-Elmer 577
grating spectrophotometer in KBr pellets. The electronic spectra were
recorded on a Pye-Unicam SP-8-100 ultraviolet spectrophotometer in
the range, 200–500 nm.
Biocidal Activity
The synthesized organogermanium compounds and bases were tested
for the in vitro growth inhibitory activity against pathogenic fungi, viz.,
Macrophomina phaseolina, Fusarium oxysporum and Aspergillus niger
and bacteria, viz., Staphylococcus aureus, Klebsiella aerogenous, Es-
cherichia coli and Pseudomonas cepacicola. Proper temperature, neces-
sary nutrients, and growth media free from other microorganisms were
employed for the preparation of cultures of fungi and bacteria using
aseptic techniques.5 The Radial Growth Method and Paper-disc Plate
Method were employed to evaluate the antifungal and antibacterial
activities,6 respectively.
Antifungal Activity
A culture of the test fungus was grown on PDA medium (glucose),
starch, agar-agar and 1000 mL of H2O) at 25 2◦C and the compounds

1356
M. Swami and R. V. Singh
after being dissolved in 50, 100, and 200 ppm concentrations in
methanol were mixed in the medium. The linear growth of the fungus
was obtained by measuring the diameter of the colony in petri plates
after four days, and the percentage inhibition was calculated by the fol-
lowing relationship : % inhibition = 100(C-T) × C−1, where C and T are
the diameters of the fungus colony in check and test plate, respectively.
Antibacterial Activity
The nutrient agar medium (peptone, beef extract, agar-agar, and NaCl)
and 5 mm diameter paper discs of Whatman No.1 were used to evaluate
bactericidal activity. The compounds were dissolved in dry methanol in
500- and 1000-ppm concentrations. The filter paper discs were soaked
in different solutions of the compounds, dried, and then placed in the
petri plates previously seeded with the test organism. The plates were
incubated for 24–30 hours at 30 1◦C, and the inhibition around each
disc was measured.
RESULTS AND DISCUSSION
The reactions of trimethyl germanium chloride with the sodium salt
of the bases in the solvent mixture of benzene and methanol proceed
smoothly with the precipitation of sodium chloride, which was removed
by filtration. The complete reaction has been shown with X = pyridine.
All the newly synthesized complexes are colored solids, soluble in
most of the common organic solvents and are non-electrolytes (molar
conductivity below 13 ohm−1cm2mol−1). These are monomeric in nature
(Table I).
Infrared Spectra
The free bases show neither ν(SH) at 2600–2500 cm−1 nor ν(C N) at
1625–1600 cm−1 but show NH stretching band at 3350–3150 cm−1
.
This is an indicative of the benzothiazolines rather than the Schiff base
structure.7 In the spectra of the germanium complexes, bands due to
νNH vibrations disappear indicating the chelation of nitrogen with the
germanium atom, and a new band at about 1600 cm−1 is observed,
which may be assigned to the >C N vibrations. The appearance of this
band suggests that the complexes are germanium—Schiff base deriva-
tives, as the benzothiazoline ring opens to give the Schiff base structure
in the presence of the germanium atom. Several new bands in the ger-
manium complexes in the regions, 680-660 cm−1 and 410–415 cm−1 are

Sulfur-Bonded Organogermanium (IV) Complexes of Biopotent Bases
1357
SCHEME 1 Synthetic route of the complexes.
due to the Ge←N8 and Ge-S9 stretching vibrations, respectively and
this further lends support to the proposed coordination.
Ultra-Violet Spectra
The ultra-violet spectra of the bases, benzothiazolines consist of two
broad and strong bands around 270 and 315 nm, characteristic of the
cyclic form of the bases. The bands were attributed to the φ − φ* and
π − π* (benzenoid) transitions, respectively.10,11 These bands do not
undergo any change during the complexation. However, an additional
band in the organogermanium (IV) complexes is also observed around
400 nm due to the n-π* electronic transitions of the azomethine group.
The appearance of this new band in the complexes clearly indicated the
formation of the azomethine grouping on complexation and subsequent
isomerization of the bases into the azomethine form.12
13C NMR Spectra
The 13C NMR spectra of the bases and their corresponding germanium
complexes recorded in dry DMSO are given in Table II. A considerable

1358
M. Swami and R. V. Singh
TABLE II 13C NMR Spectral Data (δ, ppm) of the Bases and Their
Corresponding Trimethylgermanium(IV) Complexes
Compound
L2H
C
N/C
N
C
S
CH3
Aromatic
151.24
139.68 13.15 123.19, 121.75, 120.40, 121.80, 125.81,
126.51, 125.73, 125.63, 125.70, 126.90
Me3Ge(L2)
L3H
170.22
148.71
166.70
154.13 14.41 124.26, 121.54, 121.13, 121.98, 126.61,
126.64, 126.24, 125.97, 125.63, 126.65
134.46 11.26 123.44, 120.84, 115.56, 115.18, 113.88,
124.54, 126.38, 128.82, 130.18
152.28 18.64 124.01, 120.70, 121.08, 116.31,
115.86,122.24, 123.67, 12.00, 125.25
Me3Ge(L3)
change in the chemical shift of carbons attached to nitrogen and sulfur
is an indication of the role of these elements in coordination and also an
evidence for the pentacoordinated state for germanium, i.e., the signals
of C N group in the bases L2H and L3H appeared at δ 151.24 and 148.71
ppm, respectively and which shifted at δ 170.22 and 166.70 ppm in the
germanium complexes in the form of C N which clearly indicated that
the benzothiazolines after converting into the Schiff base forms coor-
dinated through the nitrogen atom of the azomethine group. Similarly
the shifting of carbon signals of C S group from δ 139.68 (L2H) and
134.46 ppm (L3H) to δ 154.13 (Me3GeL2) and 152.28 ppm (Me3GeL3),
which also indicates the involvement of sulfur atom in bond formation.
Based on these observations, it is clear that five bonds have been formed
with the germanium atom including one by nitrogen, one by sulfur, and
three by methyl groups and thus the complexes are pentacoordinated.
Several penta-coordinated complexes have also been reported by other
authors in the literature.13,14
1H NMR Spectra
The different signals observed in the proton magnetic resonance spec-
tra of the bases and their corresponding organogermanium(IV) com-
plexes have been recorded in Table III. The broad signals due to the
NH protons in the bases disappear in the case of the organogerma-
nium(IV) complexes and thus confirms the coordination of the germa-
nium with the nitrogen and sulfur atoms. The methyl proton signals in
the bases undergo deshielding and appear at a downfield shifted posi-
tion in the spectra of the complexes again indicating the coordination
of the nitrogen to the germanium atom. The complex multiplet for the
aromatic protons also shows a slight downfield shift in the spectra of
the organogermanium (IV) complexes.

Sulfur-Bonded Organogermanium (IV) Complexes of Biopotent Bases
1359
TABLE III 1H NMR Spectral Data (δ, ppm) of the Bases and Their
Corresponding Trimethylgermanium(IV) Complexes
Compound
NH(S)
Aromatic (m)
Me3Ge (s)
L1H
Me3Ge(L1)
L2H
Me3Ge(L2)
L3H
Me3Ge(L3)
3.42
—
5.40
—
5.44
—
3.10
3.46
3.36
3.60
3.40
3.72
7.36–6.44
7.50–6.65
7.30–6.75
7.50–6.80
7.20–6.42
7.16–6.60
—
1.08
—
0.96
—
0.95
s : singlet; and m : multiplet.
Based on these studies, the structures for the bases and their
organogermanium(IV), complexes have been shown in Figure 1.
Biological Aspects
Fungicidal and bactericidal activities of the bases and their correspond-
ing organogermanium(IV) complexes against pathogenic fungi and bac-
teria are recorded in Tables IV and V.
The results are quite promising. The antimicrobial data reveal that
the complexes are superior to the free bases. The enhanced activity of
the germanium complexes may be ascribed to the increased lipophilic
nature of these complexes arising due to the chelation.15 The activity
increased as the concentration was increased. Further, the results of
bioactivity were compared with the conventional fungicide Bavistin and
the conventional bactericide Streptomycin, taken as standards in either
case.
FIGURE 1 Structure of the complexes.

1360
M. Swami and R. V. Singh
TABLE IV Fungicidal Screening Data of the Bases and Their
Respective Trimethylgermanium(IV) Complexes. Average
Percentage Inhibition after 96 Hours
(Conc. in ppm)
Macrophomina phaseolina
Fusarium oxysporum
Aspergillus niger
Compound
50
100
200
50
100
200
50
100
200
L1H
Me3Ge(L1)
L2H
Me3Ge(L2)
L3H
Me3Ge(L3)
Bavistin
23
36
28
50
15
20
82
31
66
37
69
24
52
75
52
84
40
31
48
24
44
17
33
86
35
72
35
74
27
41
85
58
86
52
38
56
30
56
23
49
91
46
73
41
76
31
58
92
54
95
50
35
100
73
100
42
100
84
100
69
100
90
100
In case of fungicidal activity, it has been observed that all of the
organogermanium (IV) complexes were able to inhibit and kill the
pathogens at 50-ppm concentration, while at the 100-ppm concentra-
tion of only the standard proved invariably fatal. In case of the bac-
tericidal activity, the germanium complexes exhibited remarkable po-
tential in inhibiting the growth of pathogens. It is emphasized that
in some cases the complexes were found to be even more active than
the standard Streptomycin against gram-negative bacteria. Thus, it
can be postulated that further intensive studies of these complexes in
this direction as well as in agriculture could lead to the interesting
results.
TABLE V Bactericidal Screening of the Bases and Their Respective
Trimethylgermanium(IV) Complexes. Inhibition after 24 Hours
(Conc. in ppm)
Diameter of inhibition zone (mm)
Staphylococcus
Klebsiella
Escherichia
Pseudomonas
aureus (+)
aerogenous (−)
coli (−)
cepacicola (−)
Compound
500
1000
500
1000
500
1000
500
1000
L1H
Me3Ge(L1)
L2H
Me3Ge(L2)
L3H
Me3Ge(L3)
Streptomycin
6
12
6
9
4
9
16
8
14
6
4
8
3
8
2
6
3
5
10
5
9
3
4
7
5
10
3
7
8
14
7
13
4
5
11
4
10
2
8
14
6
11
3
7
15
10
17
7
5
8
18
6
2
9
3
17

Sulfur-Bonded Organogermanium (IV) Complexes of Biopotent Bases
1361
Antiandrogen Activity
For checking the efficiency of these compounds as well as the bases,
some experiments have been done on male albino rats (Rattus norvegi-
cus). The rats selected for these studies were with the weights between
200–250 g. These rats were regularly checked for any disease and if
found infected were isolated and treated. The rats were fed on a diet of
rat feed pellets obtained from Hindustan Lever Limited, Mumbai and
water was provided ad libitum. During, these experiments doses of the
bases and their compounds were given orally after mixing in olive oil
with the help of hypodermic syringe having pearl point needle for 60
days and withdrawal for 30 days. After the completion of the treatment,
the fertility test was done. On day 61, the rats were autopsied and blood
was extracted from the heart. The serum was separated and used for
serum biochemistry. Reproductive tissues and vital organs were blotted
free of blood, weighed and used for the tissue biochemistry observations.
The following observations were recorded :
The Body and Organ Weights
The experiments indicated that the body weights of the rats were not
much altered after the treatment of the complexes. However, a general
decrease in the reproductive organ weights was observed in the weights
of the testis (p < 0.001), epididymis (p < 0.001), was deferens (p < 0.01),
seminal vesicle (p < 0.001) and ventral prostate (p < 0.01).
Sperm Dynamics and Fertility
A significant decrease in sperm density in testes and cauda epididymis
were observed in the bases and their germanium complexes. Also, the
sperm motility in Cauda epididymis was decreased significantly in
the bases and their germanium treated rats (p < 0.001) as shown in
Table VI.
Biochemical Changes
When the results of these investigations were compared with the con-
trol, the marked reductions in sialic and protein contents of testes,
epididymis, ventral prostate and seminal vesicle were deserved in
the bases and their organogermanium(IV) complexes treated rats. On
the other hand, a sharp increase in testicular cholesterol and acid
and alkaline phosphatase contents were observed in various treated

1362
M. Swami and R. V. Singh
TABLE VI Altered Sperm Dynamics and Fertility after Treatment
with the Bases and their Germanium Complexes
Sperm density (million/ml)
Sperm motility
Group Compound Cauda epididymis
Testes
Epididymis Fertility test (%)
A
B
C
D
E
F
G
Control
L1H
Me3Ge (L1)
L2H
Me3Ge (L2)
L3H
Me3Ge (L3)
70.0 6.1
45.0 3.2
48.0 5.0
57.0 6.0
44.0 7.0
61.0 4.0
50.0 6.0
1.90 0.20 51.0 1.85
0.72 0.10 25.0 1.80
0.70 0.20 22.0 1.30
0.82 0.11 28.0 1.60
0.73 0.10 26.0 1.70-
1.10 0.10 42.0 1.70
0.80 0.11 30.0 1.80
98 +ve
75 –ve
96 –ve
70 –ve
81 –ve
65 –ve
75 –ve
Values are mean SEM six determinations. Group A compared with Groups B, D,
and F; Group C compared with Group B; Group E compared with Group D; and Group
G compared with Group F.
groups. Seminal vesicular fructose contents were decreased signifi-
cantly (Table VII).
What we have done in the present investigations, the bases and their
germanium complexes were given to the rats at the dose levels of 9–50
mg/kg/day for sixty days. At the completion of the experiments marked
alterations in the weights of testes, epididymis, seminal vesicle, and
ventral prostate were observed. Significant decline in the testes weight
may be due to the decrease in the number of spermatogenic elements
and spermatozoa.16 Reduction in the weights of sex accessory organs
directly support the reduced availability of androgens.17 Suppression of
gonadotropins might have caused decrease in sperm density in testes.18
Low caudal epididymal sperm density may be due to the changes in the
androgen metabolism,19 and 95% negative fertility may be attributed
to lack of forward progression and reduction in the density of sper-
matozoa and altered biochemical milieu of Cauda epididymis. Decline
in the total protein concentration in testes and other accessory repro-
ductive organs indicated suppressed androgen activity.20 Furthermore,
reduced contents of sialic acid in various reproductive organs reported
herein suggest adverse effects on the metamorphosis and maturational
stages of spermatid.21,22 The rise in the testicular cholesterol contents
due to various compounds treatment suggests suppressed androgen
biosynthesis.23 An increase in testicular acid and alkaline phosphatase
activities indicates metabolic disturbance and impairment of the func-
tional integrity of the testes.24 Thus, the present investigations reveal
that the bases and their organogermanium(IV) complexes altered the
reproductive function of male rats and the complexes are more active

1363

1364
M. Swami and R. V. Singh
than the bases themselves in inhibiting the fertility in male rats. Thus,
these compounds may be good antiandrogen agents.
CONCLUSION
The present study explained the formation of penta-coordinated com-
plexes of germanium and which are scanty in the literature. The new
findings of these studies are the biological activity of the present ger-
manium complexes. These complexes show good antiandrogen activity.
Further deep studies in the field can open the door for new contracep-
tives for male in the form of coordination compounds.
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[3] F.S. Hammett and J.E. Nawrey, Jr. J. Exp. Med., 35, 507 (1922).
[4] C. Saxena and R.V. Singh, J. Prakt. Chem., 336, 707 (1994).
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