Nematicidal, insecticidal, antifertility, antifungal and antibacterial activities of salicylanilide sulphathiazole and its manganese, silicon and tin complexes

Article abstract of DOI:10.1080/10426500490464050

A facile synthesis and studies on the stereochemistry and biochemical aspects of some organosilicon(IV), organotin(IV), and manganese(II) complexes derived from imine having N^∩N^∩O donor system is reported. The imine was prepared by t

Full text of DOI:10.1080/10426500490464050

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Phosphorus, Sulfur, and Silicon and the Related
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NEMATICIDAL, INSECTICIDAL, ANTIFERTILITY,
ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES OF
SALICYLANILIDE SULPHATHIAZOLE AND ITS MANGANESE,
SILICON AND TIN COMPLEXES
Mukta Jain a , Shweta Gaur a , S. C. Diwedi b , S. C. Joshi c , R. V. Singh a & Anil Bansal d
a Department of Chemistry , Jaipur, India
b Department of Botany , Jaipur, India
c Department of Zoology , Jaipur, India
d Department of Chemistry , Baroda, Gujarat, India , 390 002
Published online: 16 Aug 2010.
To cite this article: Mukta Jain , Shweta Gaur , S. C. Diwedi , S. C. Joshi , R. V. Singh & Anil Bansal (2004) NEMATICIDAL,
INSECTICIDAL, ANTIFERTILITY, ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES OF SALICYLANILIDE SULPHATHIAZOLE AND ITS
MANGANESE, SILICON AND TIN COMPLEXES, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:8, 1517-1537, DOI:
10.1080/10426500490464050
To link to this article: http://dx.doi.org/10.1080/10426500490464050
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Phosphorus, Sulfur, and Silicon, 179:1517–1537, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490464050
NEMATICIDAL, INSECTICIDAL, ANTIFERTILITY,
ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES
OF SALICYLANILIDE SULPHATHIAZOLE AND ITS
MANGANESE, SILICON AND TIN COMPLEXES
Mukta Jain,a Shweta Gaur,a S. C. Diwedi,b S. C. Joshi,c
R. V. Singh,a and Anil Bansald
Department of Chemistry, University of Rajasthan, Jaipur,
India;a Department of Botany, University of Rajasthan, Jaipur,
India;b Department of Zoology, University of Rajasthan, Jaipur,
India;c and Department of Chemistry, M.S. University,
Baroda - 390 002, Gujarat, Indiad
(Received November 17, 2003; accepted January 1, 2004)
A facile synthesis and studies on the stereochemistry and biochemical
aspects of some organosilicon(IV), organotin(IV), and manganese(II)
complexes derived from imine having N∩N∩O donor system is re-
ported. The imine was prepared by the condensation of salicylanilide
with sulphathiazole. This imine reacts with organosilicon(IV)chloride,
organotin(IV)chloride, and hydrated manganese(II) chloride to yield
compounds having M O and M←N bonds. The structures of the com-
pounds have been elucidated by physicochemical and spectral (IR, 1H
NMR, 13C NMR, 29Si NMR, 119Sn NMR, and ESR) studies, which
clearly point to a trigonal bipyramidal geometry around silicon(IV) and
tin(IV), and tetrahedral geometry around manganese(II), as the active
lone pair of the nitrogen is also included in the coordination sphere. In
the search for better fungicides and bactericides, studies were conducted
to assess the growth-inhibiting potential of the synthesized complexes
against various pathogenic fungal and bacterial strains. These com-
plexes are highly active against nematode ( Meloidogyne incognita) and
insect ( Trogoderma granarium). The activity will be increased with in-
creasing concentration. These studies demonstrate that the concentra-
tions reached levels that are sufficient to inhibit and kill the pathogens.
All compounds have also been found to act as sterilizing agents by re-
ducing the production of sperm in male mice.
Keywords: Insecticides; manganese complexes; nematodes; pesticides;
silicon complexes; tin complexes
The authors are grateful to the University Grants Commission, New Delhi, India for
financial assistance.
Address correspondence to Professor R. V. Singh, Department of Chemistry, Univer-
sity of Rajasthan, Jaipur–302 004, India. E-mail: kudiwal@datainfosys.net
1517

1518
M. Jain et al.
INTRODUCTION
Imines bonding through nitrogen1 and oxygen atoms of biologically ac-
tive ligands provide models for metal ligand-binding sites in several
enzymes. Considerable importance has been given to the metal com-
plexes of these ligands on account of their biological properties. They
are known to function as antimicrobial, antifertility, antimalarial, and
antileukemic agents.1 The sulphonamides have long been known to pos-
sess conspicuous biocidal activity, and the ligands derived from them
also inherit these characteristics. The heterocyclic compounds with both
sulphur and nitrogen atoms in the ring system have also been used in
the synthesis of biologically active complexes.
The rapid rise in the industrial, agricultural, biological, and medical
applications of organosilicon(IV),2 organotin(IV),3 and manganese(II)4
compounds during the last few decades have led to their accu-
mulation in the environment and in biological systems. Hydrated
manganese(II), organotin(IV), and organosilicon(IV) complexes with
sulphonamide imines having N∩N donor system have been described in
the literature5−12 for their high activity/toxicity against the root-knot
nematode Meloidogyne incognita, pathogenic fungi, viz. Aspergillus
niger, Fusarium oxysporum, Macrophomina phaseolina, Alternaria Al-
ternata, and bacteria, viz. Escherichia coli, Klebsiella aerogenous, Pseu-
domonas cepacicola, and Staphylococcus aureus. The biochemistry of
synthetic organometallics has been a subject of active research, and
its importance may be judged by the large number of articles in the
literature13 relating to their biochemical significance. However, it is
noteworthy that the biological activity gets enhanced on undergoing
complexation with metal ions.14 Stereochemical and biochemical as-
pects of some of the organosilicon(IV) and organotin(IV) complexes of
salicylanilide and its thiosemicarbazone have been described.15
EXPERIMENTAL
Adequate care was taken to keep the organosilicon(IV), organotin(IV),
and manganese(II) complexes, chemicals, and glass apparatus free from
moisture. Clean and well-dried glass apparatus fitted with quickfit in-
terchangeable standard ground joints was used throughout the exper-
imental work. All the chemicals and solvents used were dried and pu-
rified by standard methods.
Preparation of the Ligand
The synthesis of this ligand was carried out by dissolving salicylanilide
in water and sulphathiazole in alcohol. The solutions were then mixed

Salicylanilide Sulphathiazole and Metal Complexes
1519
together and refluxed for five/six hours. After cooling, the precipitate
of sulphonamide imine was purified by recrystallization from the same
solvent. The analysis and physical properties of this ligand are given
in Table I.
Synthesis of the Organometal(IV) Complexes
For the preparation of these complexes, a calculated amount of
Me2SiCl2, Ph2SiCl2, Ph3SiCl, Me2SnCl2, Ph2SnCl2, and Ph3SnCl in
about 30 ml of methanol in a round bottom flask were taken, and a
requisite amount of sodium salt of the ligand in the same solvent was
added to this solution. The contents were refluxed over a fractionating
column for 12–14 h. After the completion of the reaction, the excess of
the solvent was removed and NaCl was precipitated out and removed
by filtration. The complexes were subsequently dried for 3–4 h and then
repeatedly washed with methanol and n-hexane so as to ensure their
purity and then dried a second time under reduced pressure. The syn-
thetic details and elemental analyses of the resulting silicon complexes
are listed in Table I.
Synthesis of the Manganese(II) Complexes
Hydrated manganese dichloride MnCl2 · 4H2O was dissolved in
methanol, and the methanolic solution of the ligand was added to it
in 1:1 molar ratio. The mixture was heated under reflux for 10–12 h.
The solvent was removed and the products obtained were washed with
n-hexane and dried in vacuo. The details of these reactions and the
analyses of the resulting products are recorded in Table I.
Based on the coordination sites available in the ligand system, this
behaves as bibasic tridentate, as shown in Scheme 1.
Analytical Methods and Physical Measurements
Nitrogen and sulfur were estimated by the Kjeldahl’s and Messenger’s
methods, respectively. Silicon and tin were determined gravimetrically
as SiO2 and SnO2. The conductance was measured with a conductivity
bridge type 304 Systronics model, and the molecular weights were de-
termined by the Rast Camphor method. Magnetic measurements were
carried out at room temperature by the Gouy’s method using NiCl2
solution as the calibrant.
Infrared (IR) spectra were recorded on a Perkin-Elmer 577 Grating
Spectrophotometer in the range 4000-200 cm−1, as Nujol mulls using
CsI Cell. 1H NMR spectra were recorded in DMSO-d6, 13C and 29Si/119Sn

1520

Salicylanilide Sulphathiazole and Metal Complexes
1521
SCHEME 1 Ligand synthesis.
NMR spectra were recorded in methanol, using TMS as the inter-
nal/external standard for 1H, 13C, 29Si NMR, and 119Sn NMR spectra.
RESULTS AND DISCUSSION
The reactions of triphenylchlorosilane, diphenyldichlorosilane,
dimethyldichlorosilane, triphenyltinchloride, diphenyltindichloride,
and dimethyltindichloride with the sodium salt of salicylanilidesul-
phathiazole in 1:1 molar ratio in perfectly dry methanol give products
of the types R2M(N∩N∩O) or R3M(HN∩N∩O). The reactions proceed
smoothly with the precipitation of NaCl. These reactions can be
represented by the following equations:
Na
R2MCl2 + HN∩N∩OH −−→ R2M(N∩N∩O) + 2NaCl
MeOH
Na
Ph3MCl + HN∩N∩OH −−→ Ph3M(NH∩N∩O) + NaCl
MeOH

1522
M. Jain et al.
where HN∩N∩OH is the donor system of the ligand molecule, M =
Si or Sn, and R = Me or Ph. The resulting complexes have been ob-
tained as colored solids soluble in most of the common organic solvents.
Complexes were found to be monomeric, as evidenced by their molecu-
lar weight determinations. The low value of molar conductivity (17–27
ohm−1 cm2 mol−1) of the resulting metal complexes in anhydrous DMF
shows them to be nonelectrolytes in nature. The mode of bonding in
these metal chelates has been proposed on the basis of infrared and
NMR spectral evidences.
IR Spectra
The IR spectrum of the ligand exhibits a strong band due to ν(C N)
at 1615 cm−1, which shifts to lower frequency side, showing the coor-
dination through the azomethine nitrogen. Two broad bands at 3100–
3410 cm−1 due to ν(OH/NH) arise in the spectrum of the ligand. The
band due to ν(OH) is absent in the metal complexes, while that due
to ν(NH) remains at the same position in case of triphenyl complexes,
showing the bonding through the oxygen atom8 and noninvolvement
of NH group in bonding, respectively. In the IR spectra of dimethyl
and diphenyl metal complexes the bands due to ν(NH/OH) remain ab-
sent, showing the bonding of phenolic oxygen and (NH) nitrogen to the
metal atom after the deprotonation of the functional groups. New bands
in the regions 418–423 cm−1, 527–532 cm−1, 580–585 cm−1, and 620–
623 cm−1 are due to ν(Sn←N), ν(Sn O), ν(Si←N), and ν(Si O) modes,
respectively, which further support the coordination through azome-
thine nitrogen to the metal atom and bonding of oxygen with the metal
atom.8−10
Reaction of hydrated Manganese(II) chloride with bibasic tridentate
sulphonamide imine in unimolar ratio in methanol proceeds as depicted
below.
1:1
MnCl2 · 4H2O + HN∩N∩OH −→ [Mn(H2O)(N∩N∩O)] + 3H2O + 2HCl
MeOH
This reaction is quite facile and the yield is almost quantitative. The re-
sulting complex is colored solid, and its composition is supported by the
elemental analyses. The nonelectrolytic nature of the complex has been
proposed on the basis of molar conductance value, which is 15 ohm−1
cm2 mol−1. The molecular weight determinations show the monomeric
nature of the complex. This is soluble in methanol, DMF, and DMSO.
On complexation the bands due to ν(OH) and ν(NH) disappear, in-
dicating chelation through phenolic oxygen and nitrogen of ( NH ).
New bands at 465 cm−1 and 372 cm−1 due to ν(Mn O) and ν(Mn←N)

Salicylanilide Sulphathiazole and Metal Complexes
1523
appear in the spectrum of the complex, also indicating the pattern of
complexation.6 A new band also appears at ca 700 cm−1, which is due
to the coordinated water molecule.
1H NMR Spectra
The proton magnetic resonance spectral data of the ligand and its cor-
1
responding metal complexes have been recorded in DMSO-d6. The H
NMR spectrum of the ligand shows a signal at δ 10.28 ppm due to
NH proton, which remains in the case of triphenyl metal complexes
at almost the same position, showing noninvolvement of NH group in
bonding. A signal at δ 12.10 ppm due to OH proton disappears in the
spectra of the complexes, indicating the bonding through oxygen to the
metal atom. However, in case of diorganometal complexes, disappear-
ance of NH and OH signals in the organometallic derivatives indicates
the coordination of the azomethine nitrogen as well as covalent bond
formation between metal and oxygen and nitrogen due to the deproto-
nation. Further, in the spectra of the metal complexes a downfield shift
(δ 8.30–7.10 ppm) in the position of the aromatic protons also indicates
the coordination of azomethine nitrogen to the metal atom.
13C NMR Spectra
The 13C NMR spectral data for the ligand and its metal complexes in
MeOH support the coordination of salicylanilidesulphathiazole through
the azomethine nitrogen.11,12 The shifts in the positions of carbon atoms
adjacent to atoms involved in complex formation indicate the bonding
pattern of the complexes. The downfield shift of signals attached to
azomethine nitrogen from δ 168.24–162.50 ppm in the spectra of the
complexes further supports the involvement of the azomethine group
in complexation.
29Si and 119Sn NMR Spectra
In order to confirm the geometry of the complexes, 29Si NMR
and 119Sn NMR spectra were recorded in MeOH. Sharp signals
at δ −92, −98, and −95 ppm are assigned to Ph3Si(HN∩N∩O),
Me2Si(N∩N∩O), and Ph2Si(N∩N∩O) complexes, respectively, which have
penta-coordinated states around the silicon atom. Similarly, in case of
tin complexes5−9 sharp signals at δ −145, −120, and −135 ppm are in-
dicating the penta-coordinated state around the tin atom for Ph3Sn
(HN∩N∩O), Me2Sn(N∩N∩O), and Ph2Sn(N∩N∩O) type of complexes,
respectively.

1524
M. Jain et al.
FIGURE 1 Structures of the complexes.
On the basis of the results so far discussed, including the analytical as
well as spectral data, suitable penta-coordinated trigonal bipyramidal
geometrics have been suggested for the metal complexes (Figure 1).7−13
ESR Spectra
The electron spin resonance studies of the Mn(II) complex of salicy-
lanilide sulphathiazole at the room temperature show only one isotropic
signal centered at 2.130 g, indicating a tetra-coordinated structure to
this complex.6
Magnetic Susceptibility Measurements
The magnetic moment value of this complex at the room temperature
is 5.8, which suggests a high spin state for this derivatives with central
manganese atom being surrounded by tetra-coordinated environment
(Figure 2).
FIGURE 2 Structure of the manganese complex.

Salicylanilide Sulphathiazole and Metal Complexes
1525
TABLE II Antifungal Screening Data of the Ligand and Its Metal Complexes
Inhibition (%) After 96 h (Conc. 25, 50, and 100 ppm)
Aspergillus
niger
Macrophomina
phaseolina
Fusarium
oxysporum
Alternaria
alternata
Compound
25 50 100 25 50
100
25 50 100 25 50 100
(SaH-A-StH)
40 51
45 55
49 58
52 62
46 57
50 59
70
75
78
81
77
79
82
73
98
39 50
44 55
50 59
51 61
45 57
52 61
54 64
67
73
76
79
74
77
81
—
96
45 58
49 60
51 63
53 65
50 62
53 64
55 66
65 46 59
69 49 61
75 52 64
77 54 66
71 51 61
75 53 65
78 55 68
67
70
74
77
72
75
79
—
Me2Si(Sa-A-St)
Ph2Si(Sa-A-St)
Ph3Si(Sa-A-StH)
Me2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph3Sn(Sa-A-StH) 53 63
Mn(Sa-A-St)H2O
Bavistin
42 54
69 86
—
—
—
—
—
—
—
72 82
70 91 100 71 86 100
Biocidal Activity
Fungicidal and bactericidal activities of the imine and its metal com-
plexes against pathogenic fungi and bacteria are recorded in Tables II
and III.
EXPERIMENTAL
Radial Growth Method for Antifungal Activity16
Potato dextrose agar medium (glucose, 20 g; starch, 20 g; agar-agar,
20 g; and 1000 ml of H2O) (1:1:1:5) was prepared in flask and ster-
ilized. To this medium was added requisite amount of the compound
TABLE III Antibacterial Screening Data of the Ligand and Its Metal
Complexes Inhibition (mm) After 24 h (Conc. 500 and 1000 ppm)
Klebsiella
Pseudomonas
Staphylococcus
E. coli (−)
aerogenous (−)
cepacicola (−)
aureus (+)
Compound
500 1000 500
1000 500
1000 500
1000
(SaH-A-StH)
8
10
14
15
12
16
17
9
11
15
17
18
16
18
19
10
2
8
9
12
15
17
18
17
18
19
11
5
12
14
16
18
15
17
18
13
2
14
15
17
18
16
17
19
15
5
12
15
16
17
15
16
18
14
15
15
17
18
19
17
19
19
16
17
Me2Si (Sa-A-St)
Ph2Si(Sa-A-St)
Ph3Si(Sa-A-StH)
Me2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph3Sn(Sa-A-StH)
Mn(Sa-A-St)H2O
Streptomycin
12
14
10
13
16
10
3
1

1526
M. Jain et al.
after being dissolved in methanol so as to get a certain final concentra-
tion. A series of concentrations were prepared. The medium was than
poured into the Petri plates and a small disc (0.7 cm) of the fungus
culture was cut with a sterile cork borer and transferred aseptically to
the center of a Petri dish containing the medium with a certain amount
of the compound. Suitable checks were kept so that the culture discs
were grown under the same conditions on potato dextrose media (PDA)
without the compound. These Petri dishes were wrapped in polythene
bags containing a few drops of alcohol and were placed in an incuba-
tor at 25
2◦C. Three replicates were used in each case. After 96 h
the colony diameter compared with check was taken as a measure of
fungitoxicity. The amount of growth inhibition was calculated by the
equation
% inhibition = (dc − dt) × 100 × dc−1
where dc is the diameter of the fungal colony in control or check plate
and dt is the diameter of the fungal colony in test plate.
Paper Disc Plate Method for Antibacterial Activity17
Flat-bottomed 90 mm pyrex petridishes were used. Fifteen milliliters of
agar medium (peptone, 5 g; beef extract, 5 g; NaCl, 5 g; agar–agar, 20 g;
and 1000 ml of distilled water) was pipetted into the petridish. After
the agar solidified, 5 ml of warm seeded agar was applied. The seeded
agar was prepared by cooling the molten agar to 40◦C and then adding
the amount of bacterial suspension. The plate was tilted to ensure even
coverage before the agar solidifies. These dishes with tops in place are
stacked in refrigerator upside down to prevent condensation of mois-
ture. The compounds were dissolved in methanol in 500 and 1000 ppm
concentrations.
Paper discs of Whatman No. 1 with a diameter of 5 mm were soaked
in these solutions of varied concentrations. The discs were dried and
placed on the medium previously seeded with organisms in petri dishes
at suitable distances. The petri plates were stored in an incubator at
28 2◦C for 24 h. The zone of inhibition that formed around each disc
containing the test compound was measured accurately in mm.
Mode of Action18
PDA rich in carbohydrates is utilized as the major nutrient source by
the microbes with the help of various enzymes (viz., amylase, cellu-
lase, and pectinase). Metal-based fungicides inhibit a wide range of
enzymes involved in various metabolic pathways and ultimately cause

Salicylanilide Sulphathiazole and Metal Complexes
1527
cell death. Early work on the mode of action of fungicides showed that
these compounds inhibit cell division. It was later shown that specific
site of action is β-tubuline, a polymeric protein found in microtubules—
essential component of the cytoskeleton. Phenyl and amine groups in
complexes affected nucleic acid synthesis and mitochondrial electron
transport.
1. Carbon catabolic regulation. During the periods of rapid utilization
of the carbon source, particularly of glucose or sucrose, either the
formations of enzymes in the secondary metabolic pathways leading
to toxins would be repressed or the activity of these pathways would
be inhibited.
2. Nitrogen catabolic repression. Excessive levels of rapidly assimilated
forms of nitrogen (e.g., ammonium ion) could repress the forma-
tion of enzymes concerned with nitrogen transformation of toxins
intermediates.
3. Feedback regulation. As toxins accumulate, they would in some in-
stances limit their own biosynthesis by inhibiting the activity of one
or more enzymes earlier in their synthetic pathways.
4. Feed back regulation by primary precursors. Primary metabolites
that are precursors of toxins could act similarly by inhibiting en-
zymes in primary pathways.
5. Energy charge regulation. High phosphate levels could reduce the
availability of high-energy phosphate (i.e., ATP and ADP). This
would effectively inhibit a number of key reactions in primary
metabolism, which in turn would cause a reduction in the activity of
secondary pathways linked to the toxin production.
6. Induction. The addition of certain primary metabolites (termed effec-
tors) could induce the formation of enzymes in secondary pathways
leading to the toxin production.
DISCUSSION
All the metal compounds are more active than the parent ligand against
the same microorganism. The increased biocidal activity of the com-
plexes can also be explained by considering the chelation theory.19 The
chelation reduces the polarity of the central ion mainly because of par-
tial sharing of its positive charge with the donor groups and possible
π-electron delocalization over the whole chelate ring. Such chelation in-
creases the lipophilic character of the central atom, which subsequently
favors its permeation through the lipoid layer of the membrane. It is
seen that lower concentration of compounds can check the sporulation

1528
M. Jain et al.
in fungi, and a higher concentration inhibits the growth of organisms
almost completely.
The effect of resonating rings on toxicity may be appraised in the light
of modern electronic theory. According to Gilman, resonance energy is
the energy in excess of the sum of the energy of the separate bonds
making up the molecule. The Arrhenius activation theory states that
the excess of the molecular energy seems to activate molecules and
produce a more rapid rate of chemical reaction. Resonating structures
such as benzene rings (in present case) may serve as powerhouse to
activate potentially reactive groupings. If toxicity is dependent on one
or more chemical reactions, then any molecule that would increase the
rate of chemical reactions must enhance toxicity.20
Hydrolysis plays a very vital role in this subject. Fungal and bacterial
cells accumulate the water-soluble metal/metalloid complexes, which
later dissociate to give free central atom or its complex ion. These ions
denature the proteins. Enzymes are proteins, and it is expected that the
central atoms inactivate these catalysts. However, not all enzymes are
equally inactivated by low concentrations of these complexes; therefore,
low concentration seems to be less effective against growth. Complexes
that have amido groups or reactive halogen atom tend to hydrolyse
to form compounds that have modified activity spectrum. The active
halogen atoms of the complexes get hydrolysed in aqueous suspensions.
The halogen is replaced by hydroxyl ion, and as a result of slight alkaline
pH an increase in activity was observed.
The introduction of a lipophilic substituent,21 either aryl or alkyl,
often conferred toxicity, as did the substitution of polar groups such as,
NH2, NO, OH, and SH. A combination of lipophilic and lipophobic
groups was occasionally more active than either alone.
It is interesting to see that among all metal complexes the triph-
enyltin(IV) derivatives with the present ligand are the most active
ones in inhibiting the growth of microorganisms, and manganese(II)
derivative is the list active. The results of biological activity have been
compared with the conventional fungicidal Bavistin and conventional
bactericide Streptomycin, taken as standards in either cases.
Nematicidal Activity
In India plant parasitic nematodes Meloidogyne incognita and M.
javanica are the most abundant in the plants. M. incognita produces
galls on the roots of many host plants and is responsible for 44.87%
yield loss in brinjal. The root-knot nematode (M. Spp.) produces galls
on the root of many vegetables crops, pulses, some of the fruit crops, to-
bacco, ornamental crops, and causes severe losses. The avoidable yield

Salicylanilide Sulphathiazole and Metal Complexes
1529
losses due to M. incognita were estimated to be 28.08, 33.68, 43.48, and
28.60% in Okra, brinjal, french been, and cowpea, respectively.
Nematodes cause heavy economic losses to plants. Estimated overall
average yield loss on the world’s major crop due to damage by plant
parasitic nematodes is 12.3%.22−25
The method followed by obtaining quantities of clean M. incognita
eggs was that of Jain et al.,26 and the step-by-step procedure is as
follows:
1. Brinjal plants infected with M. incognita were harvested from in-
fected pots. The roots were washed thoroughly and cut into small
1–2 cm pieces.
2. The chopped pieces were placed in a beaker in 100 ml of tap water,
500 ml of 1% NaOCl was added, and the suspension was vigorously
shaken for 5 min.
3. After a vigorous shake, the suspension was poured quickly through
nested 150 and 400 mesh sieves. The eggs that were retained on the
400 mesh sieve were washed with a sufficient quantity of distilled
water.
4. Eggs that passed through the 400 mesh sieve (pore size 37 µm) were
recovered by repeated sieving and rinsing.
5. Eggs were eluted from the sieves and transferred to 40 ml of water.
6. A centrifuge tube was two-thirds filled with 20% sucrose solution,
and the egg–water suspension was centrifuged at 500 g for 5 min.
7. A silver layer containing the suspended eggs at the junction of sugar
solution and egg suspension was removed with the help of a pipette
and quickly poured onto a 400 mesh sieve.
8. The eggs retained on the sieve were washed three times with distilled
water thoroughly and collected in a beaker.
9. The eggs obtained by this method were free from debris and therefore
easy to count.
In each nematode hatching dish, 200 eggs were taken and treated with
the treatment. The number of juvenils were counted after 24, 48, and
72 h. After 72 h sieves containing the unhatched eggs were removed
from the test solution, washed thoroughly with distilled water, and left
in distilled water for 24 h to record further hatching, if any.
Water and methanol solutions were used for this experiment. Each
treatment was replicated four times and the mean of four such readings
was taken. The experiment was conducted at room temperature, 30
2◦C. Two hundred eggs of M. incognita were used per replicate sample.
The indirect nematostatic effects of nonfumigant nematicides resulting

1530
M. Jain et al.
from impairment of neuromuscular activity interfere with movement,
feeding, invasion, development, reproduction, fecundity, and hatching
of nematodes is considered more important than their direct killing
action, and hence much smaller amounts of nonfumigant than fumigant
nematicides are needed in plant protection against nematodes.27
Antifertility Activity
Adult colony-bred healthy Wistar rats of proven fertility weighing 200–
250 g were used for this study. The animals were maintained under con-
trolled temperature (22 3◦C) and constant photoperiodic conditions
(12 h light:12 h dark cycle). Commercial rat food pellet (Lipton, India
Ltd.) and water were available ad libitum. The rats were divided ran-
domly into 9 groups containing 6 animals each. Group A served as vehi-
cle (olive oil)-treated controls. In group B the ligand salicylanilidesul-
phathiazole 50 mg/kg b. wt. suspended in olive oil was given orally
for a period of 60 days. Animals of groups C, D, E, F, G, H, and I re-
ceived similar doses of salicyalanilide–sulphathiazole metal complexes
for 60 days.
The animals were screened for fertility test and were weighted and
autopsied for detailed biochemical studies on the last day after fi-
nal dosing. Testes and other reproductive organs were dissected out
and weighted. Sperm motility, sperm density, sialic acid, total protein,
cholesterol, fructose, and acid and alkaline phosphatase were estimated
by standard laboratory techniques.
Male rats exposed to the ligand and its magnesium, tin, and silicon
complexes showed altered reproductive activity.
Body and Organ Weight
There were no significant differences in the body weight of the treated
groups as compared with control at the end of the experimental period.
However, the weights of testes, epididymis, seminal vesicle, and ventral
prostate were decreased significantly in the ligand (P ≤ 0.01) and its
various complexes (P ≤ 0.01 to 0.001).
Sperm Dynamics and Fertility
The sperm motility in cauda epididymis was decreased significantly
in ligand (P ≤ 0.01) and its complexes treated animals (P ≤ 0.001), as
shown in Table IV. Also, a significant decrease in sperm density in testes
and cauda epididymis (P ≤ 0.01 to 0.001) were observed in ligand and
its various complexes treated rats.

Salicylanilide Sulphathiazole and Metal Complexes
1531
TABLE IV Altered Sperm Dynamics and Fertility After Treatment with the
Ligand and Its Manganese, Silicon, and Tin Complexes
Sperm motility
Sperm density (million/ml)
caudal
Compound
A Control
epididymis
Testes
Epididymis Fertility Test (%)
70.0 6.10
60.0 3.0a
45.0 5.0b
46.0 6.0b
40.0 7.0b
41.0 8.0b
38.0 6.0b
35.0 7.0b
30.0 7.1b
1.90 0.20
51.0 1.85
98 + ve
65 − ve
75 − ve
81 − ve
90 − ve
96 − ve
95 − ve
98 − ve
100 − ve
B (SaH-A-StH)
1.08 0.10a 42.0 1.70a
0.81 0.11a 30.0 1.70b
0.82 0.11a 31.0 1.80b
0.72 0.10b 30.0 1.90b
0.70 0.20b 28.0 1.60b
0.61 0.18b 25.0 1.80b
0.51 0.20b 22.0 1.30b
0.35 0.10b 20.5 1.60b
C Mn(Sa-A-St)H2O
D Me2Si(Sa-A-St)
E Ph2Si(Sa-A-St)
F Ph3Si(Sa-A-StH)
G Me2Sn(Sa-A-St)
H Ph2Sn(Sa-A-St)
I
Ph3Sn(Sa-A-StH)
Values are mean SEM six determinations.
a = P ≤ 0.01; b = P ≤ 0.001.
Group A compared with Group B. Group C compared with Group B. Groups D, E, F,
G, H, and I compared with Group B.
Biochemical Changes
Marked reductions (P ≤ 0.01 to 0.001) in sialic acid and protein con-
tents of testes, epididymis, ventral prostate, and seminal vesicle were
observed in the ligand and its complexes treated animals when com-
pared with control (Table V). However, a sharp increase in testicular
cholesterol, and acid and alkaline phosphatase contents were observed
in various treated groups. Seminal vesicular fructose contents were de-
creased significantly (Table V).
In the present study, ligand and its complexes were administered
to rats at the dose levels 9–50 mg/kg/day for 60 days which brought
about marked alterations in the weights of testes, epididymis, seminal
vesicle, and ventral prostate. Significant decline in the testes weight
may be due to the decrease in number of spermatogenic elements and
spermatozoa.28 Reduction in the weights of sex accessory organs di-
rectly support the reduced availability of androgens.29 Suppression of
gonadotropins might have caused decrease in sperm density in testes.30
Low caudal epididymal sperm density may be due to alterations in an-
drogen metabolism,31 and 65–100% 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 total protein concentration in testes and other accessory reproduc-
tive organs indicated suppressed androgen activity.32 Furthermore, re-
duced contents of sialic acid in various reproductive organs reported
herein suggest adverse effects on the metamorphosis and maturational

1532

Salicylanilide Sulphathiazole and Metal Complexes
1533
stages of spermatid.33 The rise in the testicular cholesterol contents
due to various compounds treatment suggests suppressed androgen
biosynthesis.34 An increase in testicular acid and alkaline phosphatase
activities indicates metabolic disturbance and impairment of the func-
tional integrity of the testes.35
Thus the results of present study reveal that the ligand and its man-
ganese, silicon, and tin complexes altered the reproductive function of
male rats, and the complexes of tin and silicon are more active than the
manganese complex in inhibiting fertility in male rats.
Insecticidal Activity
Many insects cause damage to the stored products and other commodi-
ties such as food, grain, paper, books, furniture, timber, and clothing.
The greatest importance of insects lies in their being pests of crops and
animals. A pest is an animal whose population buildup increases above
certain level of economic injury, and its existence conflicts with human
welfare, convenience, and profit.36
The stock culture was established in the laboratory on the grains of
wheat in large glass jars. Inside the jars, 100 pairs of fresh insects were
released on disinfested wheat grains. Healthy conditions of the stock
culture were maintained by frequent replacement of the state grains
with fresh ones. The jars were kept at 35 2◦C temperature and 60
10% relative humidity. After the stock culture bloomed to its youth, sub-
sequent cultures were also established by releasing few parts of freshly
emerged adult beetles on disinfested wheat grains in smaller glass jars.
After allowing 7–8 days for oviposition, beetles were removed. A con-
tinuous supply for experimentation was thus maintained by repeating
the process every week. Fresh wheat was used for subculture to prevent
the food effects. To rule out the possibilities of infection, all the jars and
grains were sterilized before use. The insects were transferred with the
help of forceps and hairbrushes.
Assessment of the Toxicity of the Chemicals
Ovicidal Action
Eggs were treated by contact method to determine the efficacy of
chemicals as ovicide. A thin film of desired concentration was prepared
by spreading 1 ml of chemical solutions on Petri dishes (5.0 cm diame-
ter). The solvent was allowed to evaporate. Twenty eggs of 0–24 h were
kept in contact with the insecticidal film throughout their incubation
period. A control was also run with each set of experiments in which
the eggs were kept in 1 ml of solvent. Percent egg mortality and percent

1534
M. Jain et al.
corrected egg mortality was calculated by Abbott’s formula.37
Abbott’s Corrected Mortality
% Kill in treated − % Kill in control
=
× 100
100 − % Kill in control
Larvicidal Action
Larvicidal efficacy of chemicals was assessed by feeding method.
First instar larvae separated from subculture were kept in vials con-
taining 5 g of topically treated wheat grains with 1 ml of chemicals.
Larvae were allowed to continue their development on this diet until
the pupae formation. Each dose was replicated thrice. In the control
the food was treated with solvent only. Percent larvae mortality and
percent corrected mortality was calculated by Abbott’s formula.
Pupicidal Action
Last larval instars were stored out from the subculture and were kept
in separate containers on the same rearing media. Pupae of known age
(0–12 h) were taken out and were dipped in the desired concentration
of chemicals. Three replicates were set for each dose along with a con-
trol, and after 96 h, total emergence and pupal mortality was recorded.
Percent pupal mortality and pupal corrected mortality was calculated
by Abbott’s formula.
Adulticidal Action
The adulticidal action was assessed by contact method. Five grams
of wheat grains were treated with 1 ml of respective doses. The solvent
was allowed to evaporate completely. Experiment was replicated thrice
along with a control. Newly emerged adults were taken from the sub-
culture and were released in the plastic vials containing treated food.
Observations were taken after 48 h, and percent corrected mortality
was calculated by Abbott’s formula.
Mode of Action38,39
Insecticides act on target organisms in different ways depending on
their physical and chemical makeup. Some insecticides are physical
poisons causing asphyxiation, some are protoplasmic poisons, and a
few are respiratory poisons, but the majority of them are nerve poisons.
The action of insecticides upsets the normal behaviour and actions of
the target organisms, and the surest and quickest way to achieve this
is to poison the nervous system.

Salicylanilide Sulphathiazole and Metal Complexes
1535
Ovicidal Action
It was observed that few egg shells split and undeveloped larvae
failed to come out of the eggs. It was also observed that some other
treated eggs disfigured and stuck to the surface as dried yellow mass
without showing shell splitting. It can be suggested that probably the
toxic substances of the chemicals interfere with normal embryonic de-
velopment, which in turn may result in certain disturbances during
process of cell division and blastokinesis, thus exhibiting impressive
ovicidal properties against Trogoderma granarium (Table VI).
Larvicidal Action
High larvicidal activities were performed by chemicals. It was ob-
served that earlier larval instars were more sensitive than the later
instars. This suggests that chemicals penetrate into the insect cuticle.
The chemical-treated grains were slowly or much less fed to the larvae
of Trogoderma granarium, which leads to starvation in the developing
larvae.
Pupicidal Action
The pupicidal action of chemicals may be due to the chemical that
enters into the puparium and disrupts the normal metabolic activities
of the developing insect.
TABLE VI Ovicidal Data of the Ligand and Its Metal Complexes
Average
no. of eggs no. of eggs % eggs
level ppm hatched unhatched hatched unhatched mortality
Average
Dose
% eggs
% corrected
Compound
(SaH-A-StH)
(SaH-A-StH)
100
200
100
200
100
200
100
200
100
200
100
200
100
200
100
200
14
12
14
11
12
8
10
6
9
6
11
7
10
5
8
6
8
6
9
8
12
10
14
11
14
9
13
10
15
12
16
70
60
70
55
60
40
50
30
45
30
55
35
50
25
40
20
30
40
30
45
40
60
50
70
55
70
45
65
50
75
60
80
26.31
36.84
26.31
42.10
36.84
57.89
47.36
68.42
52.63
68.42
42.10
63.15
47.36
73.68
57.89
78.94
[Mn(Sa-A-St)H2O]
[Mn(Sa-A-St)H2O]
Me2Si(Sa-A-St)
Me2Si(Sa-A-St)
Ph2Si(Sa-A-St)
Ph2Si(Sa-A-St)
Ph3Si(Sa-A-StH)
Ph3Si(Sa-A-StH)
Me2Sn(Sa-A-St)
Me2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph3Sn(Sa-A-StH)
Ph3Sn(Sa-A-StH)
4

1536
M. Jain et al.
TABLE VII Adulticidal Data of the Ligand and Its Metal Complexes
Average
Dose
level ppm
No. of adults
in each vial
mortality
after 48 h motrality
% adult
% corrected
mortality
Compound
(SaH-A-StH)
(SaH-A-StH)
100
200
100
200
100
200
100
200
100
200
100
200
100
200
100
200
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
5
7
6
9
8
12
10
13
11
15
9
13
11
14
12
14
25
35
30
45
40
60
50
65
55
75
45
65
55
70
60
70
21.05
31.57
26.31
42.10
36.84
57.89
47.36
63.15
52.63
73.68
42.10
63.15
52.63
68.42
57.89
68.42
[Mn(Sa-A-St)H2O]
[Mn(Sa-A-St)H2O]
Me2Si(Sa-A-St)
Me2Si(Sa-A-St)
Ph2Si(Sa-A-St)
Ph2Si(Sa-A-St)
Ph3Si(Sa-A-StH)
Ph3Si(Sa-A-StH)
Me2Sn(Sa-A-St)
Me2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph2Sn(Sa-A-St)
Ph3Sn(Sa-A-StH)
Ph3Sn(Sa-A-StH)
Adulticidal Action
The chemicals that are applied as contact as well as stomach poi-
sons seemed to be the most hazardous to the beetles. When mixed with
their food, these chemicals penetrate rapidly through the body wall of
insects and thereby obstruct the normal respiratory activities of adults
by adversely affecting the spiracles (Table VII). Toxicity in metal com-
plexes increase in this order; manganese < silicon < tin. Dimethyltin
and dimethylsilicon complexes are less active than their triphenyltin
and triphenyl silicon complexes.
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