Comparative structural and fungicidal studies of Mono-methyl phthalate and its Tin(IV) derivatives

Article abstract of DOI:10.1134/S0036023607010172

The results of an investigation into the fungicidal properties of some organotin(IV) compounds with Mono-methyl phthalate are reported. The compounds were characterized by various spectroscopic techniques including ¹H-¹³C-¹¹⁹Sn-NMR, FT-IR, and ¹¹⁹Sn M?ssbauer studies. On the basis of these techniques, all the complexes show penta coordination with a trigonal bipyramidal environment around the tin. The synthesized compounds were tested against a number of plant pathogenic fungi. The fungicidal data reveal that the tri-phenyltin(IV) compound proves to be a powerful fungicide. Comparison between the fungicidal activity of the trialkyltin(IV) compounds shows that the tri-phenyl tin(IV) complex is most active against all plant pathogens; the rest of the complexes also exhibit significant antifungal activity but less than the former one. Nauka/Interperiodica 2007.

Full text of DOI:10.1134/S0036023607010172

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2007, Vol. 52, No. 1, pp. 102–107. © Pleiades Publishing, Inc., 2007.
PHYSICAL METHODS
OF INVESTIGATION
Comparative Structural and Fungicidal Studies of Mono-Methyl
Phthalate and Its Tin(IV) Derivatives1
Wajid Rehmana, Musa Kaleem Balocha, and Amin Badshahb
a Department of Chemistry, Gomal University, Dera Ismail Khan, Pakistan
b Department of Chemistry, Quaid-e-Azam University, Islamabad, Pakistan
e-mail: sono_waj@yahoo.com
Received December 7, 2005
Abstract—The results of an investigation into the fungicidal properties of some organotin(IV) compounds with
Mono-methyl phthalate are reported. The compounds were characterized by various spectroscopic techniques
1
including H- 13C- 119Sn-NMR, FT-IR, and 119Sn Mössbauer studies. On the basis of these techniques, all the
complexes show penta coordination with a trigonal bipyramidal environment around the tin. The synthesized
compounds were tested against a number of plant pathogenic fungi. The fungicidal data reveal that the tri-phe-
nyltin(IV) compound proves to be a powerful fungicide. Comparison between the fungicidal activity of the tri-
alkyltin(IV) compounds shows that the tri-phenyl tin(IV) complex is most active against all plant pathogens;
the rest of the complexes also exhibit significant antifungal activity but less than the former one.
DOI: 10.1134/S0036023607010172
1
The use of organotin(IV) compounds in agriculture as the best alkyl compounds. This compound was consid-
antifungal agents has been practiced for the last 25 years. ered to be a powerful fungicide and was well-tolerated
As early as 1929, there were reports of the biological by many plants even at concentrations greater than
activity of organotins [1, 2], followed by the classic those required for the control of pathogenic fungi.
studies in 1950s by van der Kerk and Liujten exploring
the in vitro fungicidal and antibacterial behavior of
organotin(IV) compounds [3, 4]. The major advantage
possessed by organotins is that while these derivatives
are toxic to the target species, the inorganic byproduct
is not particularly toxic to humans in comparison with
other potential metals, viz., mercury, copper, and cad-
mium.
With the R3SnX compounds (R = phenyl, in partic-
ular), the phytotoxicity was found to be influenced by
the nature of the X moiety. Phytotoxicity was greatest
for X = chloride and sulphate, and less when X = ace-
tate and hydroxide. Further evidence of the influence of
the X moiety was given by Blunden et al. [7]. Blunden
reported data for various triorganotin compounds
(including those in which R = phenyl) and X was the
Unlike these metals, tin is not, in any of its oxidation anionic form of an organic chelating ligand, namely
states, regarded as a particularly toxic metal. However, 3-hydroxyflavone, quinolin-8-ol, quinolin-8-thiol and
this contrasts with its organo derivatives, in which tin 1.3–diphenyl propane-1.3 dione. Tests were carried out
has been shown to be highly toxic in certain instances. against the potato blight fungus Phytophthora infestans
Van der Kerk and Liujten studied the range of organotin and vine downy mildew fungus Plasmopara viticola. It
compounds: R4Sn, R3SnX, R2SnX2, and RSnX3 (where was shown that the group X can in some instances sig-
nificantly affect the biological properties.
R is an alkyl moiety linked to the tin atom and X is a
molecular species not part of the organotin moiety).
The results of these authors gave rise to the following
order of increasing activity:
In the past, a number of organotin(IV) complexes
have been synthesized and characterized together with
their biological properties [8–12]. The present commu-
nication is about the comparative structural and fungi-
cidal study of the system R3SnX, where R = methyl,
ethyl, butyl, phenyl, or benzyl and X = mono-methyl
phthalate.
RSnX3 < R2SnX2 < R4Sn < R3SnX,
where R = Alkyl and X = Cl.
Latter investigations in this field [5, 6] claimed that,
while the tri-alkyltin compounds might be considered
powerful fungicides, at the concentration required they
appeared to be too phytotoxic. On the other hand, the
tri-aryl derivative (triphenyltin acetate) was found to
have a fungicidal effect 10–20 times less than that of
EXPERIMENTAL
All the tri-organotin(IV) compounds except tri-ben-
zyltin chloride were purchased from Fluka and were
used as such. Tri-benzyltin chloride was synthesized
from the literature method [13]. All the reactions were
1
The text was submitted by the authors in English.
102

COMPARATIVE STRUCTURAL AND FUNGICIDAL STUDIES
103
carried out under anhydrous and oxygen-free atmo-
SPECTROSCOPIC DATA
sphere. The solvents used were dried before use accord-
ing to the literature method [14].
Details are given below for each compound, using
the following conventions.
The melting points were measured on a Reichert
thermometer of F.G. Bode Co. Austria. IR spectra were
obtained in KBr using a Perkin Elmer FT IR-1605 spec-
trophotometer. Elemental analyses were carried out on
aYanaco MT-3 high-speed CHN analyzer with an anti-
pyrene as a reference compound. The amount of tin was
determined using inductively coupled plasma atomic
emission spectrometry (ICP-AES) method on ARL
Abbreviations: s, singlet; t, triplet; m, complex pat-
tern; n.o, not observed; sr, strong; med, medium; w, weak;
br, broad; sh, shoulder.
LIGAND ACID (HL)
Yield: 88%. Physical state: solid; mp = 78°C; Mol
formula: C9H8O4; Mol wt: 180; Recrystalliztion sol-
vent: chloroform.
Elemental analysis: The calculated values are given
in parentheses. C: 59.98(60.00); H: 4.42(4.44).
1
3410. The H, 13C, and 119Sn NMR spectra were
recorded on a multinuclear FT NMR 200 MHz of JEOL
using TMS as an internal standard. Some of the 13C
spectra were measured on Bruker AM 270 instruments
13
at 50 MHz with a C probe. The Mossbauer spectra
IR (KBr, cm–1): 3027w (νCH); 1715sr (νC=O);
were recorded at 80 K on a Cryophysics instrument
3050br (νOH).
equipped with a 15 m Ci Ca 119SnO3 source.
1H NMR (CDCl3): H-1: 3.80 s [3H, OMe]; H-4:
7.75–7.80 m [1H, phenyl proton]; H-5: 7.38–7.40 m
[1H, phenyl proton]; H-6: 7.41–7.43 m [1H, phenyl
proton]; H-7: 7.55–7.58 m [1H, phenyl proton]; H-11:
12.5 s [1H, OH].
ANTIFUNGAL ACTIVITY
The different concentrations (50, 100, 250 and 500 ppm)
of ligand and the test compounds (1–4) were used to
study the effect on germination of C. gloeosporiodes, A.
brassicicola, A. brassicae, C. capsici and H. graminium
by the hanging drop method developed by Brian [15].
13C NMR (CDCl3): C-1: 50.80; C-2: 165.7; C-3:
130.5; C-4: 126.9; C-5: 130.3; C-6: 128.5; C-7: 128.1;
C-8: 129.5; C-9: 168.7.
The germination of the spores was observed under
microscope after eight hours of incubation. The per-
centage inhibition of spore germination was calculated
as follows:
Compound 1: (tri-methyltin complex)
Yield: 77%. Physical state: solid; mp = 105°C; Mol
formula: C12H16O4Sn; Mol wt: 344; Recrystallization
solvent: chloroform/petroleum ether.
Elemental analysis: The calculated values are given
in parentheses. C: 41.82(41.86); H: 4.61(4.65); Sn:
34.85 (34.88).
IR (KBr, cm–1): 3035w (νCH aromatic); 1630sr
(νOCO)as; 1265sr (νOCO)s; ∆ν = 365; 1710 (νC=O);
542sr (ν Sn–C); 468sh(νSn–O).
% Inhibition of spore germination
Total number of ungerminated spores
-----------------------------------------------------------------------------------------
Total number of spores
=
× 100
SYNTHESES
Preparation of Mono-methyl Phthalate. (HL)
(Scheme 1)
1H NMR (CDCl3): H-1: 3.81s [3H, OMe]; H-4:
7.77–7.78 m [1H, phenyl proton]; H-5: 7.40–7.42 m
[1H, phenyl proton]; H-6: 7.42–7.43 m [1H, phenyl
proton]; H-7: 7.58–7.60 m [1H, phenyl proton]; H-α:
−2.1 s.
The Phthalic Anhydride (50 mmol) was refluxed in
excess of dry methanol for eight hours under anhydrous
conditions; excess of solvent was removed under
reduced pressure. The solid product thus obtained was
then recrystallized from chloroform. Yield: 80%, mp:
77–78°C.
13C NMR (CDCl3): C-1: 50.82; C-2: 165.8; C-3:
130.7; C-4: 127.1; C-5: 130.5; C-6: 128.6; C-7: 128.2;
C-8: 129.8; C-9: 170.2; C-α: 12.5 1J [595.5].
119Sn NMR (CDCl3): –185.8 ppm.
Preparation of the Complexes (Scheme 2)
119Sn Mössbauer (CDCl3, mm/s): Q.S: 2.35; I.S:
1.28; Q.S/I.S = 1.07; Γ1: 0.84; Γ2: 0.82.
To a hot methanolic solution of ligand (5 mmol),
5 mmol of tri-methyl, tri-ethyl, tri-butyl, tri-phenyl, or
tri-benzyltin chloride was added; after refluxing for half
an hour, 5 mmol of tri-ethylamine was added to the
above mixture. This reaction mixture was refluxed for
8–10 hours under nitrogen. The solid (tri-ethylamine
chloride) formed during the mixing was centrifuged
and the solvent was removed under vaccum. A solid
Compound 2: (tri-ethyltin complex)
Yield: 70%. Physical state: solid; mp = 120°C;
color: white; Mol formula: C15H22O4Sn; Mol wt: 386;
Recrystallization solvent: chloroform/petroleum ether.
Elemental analysis: The calculated values are
product formed, which was then recrystallized from given in parentheses. C, 46.60(46.63); H, 5.66(5.69);
chloroform and petroleum ether (40–60°C).
Sn, 30.95(31.08).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 52 No. 1 2007

104
WAJID REHMAN et al.
IR (KBr, cm–1): 3032w (νCH aromatic); 1638sr
13C NMR (CDCl3): C-1: 50.83; C-2: 165.8; C-3:
130.9; C-4: 127.3; C-5: 130.6; C-6: 128.7; C-7: 128.3;
C-8: 129.9; C-9: 170.7; C-α: 16.4 1J [785.5]; C-β: 27.2
2J [20.2]; C-γ: 26.4 3J[63.7]; C-δ: 12.9 4J [n.o].
(νOCO)as; 1265sr (νOCO)s; ∆ν = 273; 1718sr(νC=O);
535sh (νSn–C): 478sr (νSn–O).
1H NMR (CDCl3): H-1: 3.81 s [3H, OMe]; H-4:
7.76–7.77 m [1H, phenyl proton]; H-5: 7.41–7.42 m
[1H, phenyl proton]; H-6: 7.42–7.44 m [1H, phenyl
proton]; H-7: 7.57–7.59 m [1H, phenyl proton]; H-α:
1.21q [6H, 3CH2]; H-β: 1.34t [9H, 3CH3].
13C NMR (CDCl3): C-1: 50.82; C-2: 165.9; C-3:
130.8; C-4: 127.3; C-5: 130.5; C-6: 128.9; C-7: 128.4;
C-8: 129.9; C-9: 170.3; C-α: 8.5 [610.5]; C-β: 10.5
[25.7].
119Sn- NMR (CDCl3): –178.5 ppm.
119Sn Mössbauer (CDCl3, mm/s): Q.S: 2.40; I.S:
1.31; Q.S/I.S = 1.07 Γ1: 0.90; Γ2: 0.95.
119Sn NMR (CDCl3): –110 ppm.
119Sn Mössbauer (CDCl3, mm/s): Q.S: 3.48; I.S:
1.31; Q.S/I.S = 2.33; Γ1: 0.95; Γ2: 0.94.
Compound 5: (tri-benzyltin complex)
Yield: 75%. Physical state: solid; mp = 145°C; Mol
formula: C30H28O4Sn; Mol wt: 572; Recrystallization
solvent: chloroform/petroleum ether.
Elemental analysis: The calculated values are given
in parentheses. C, 62.89 (62.93); H, 4.85 (4.89); Sn,
20.93 (20.97).
IR (KBr, cm–1): 3030w (νCH aromatic); 1640med
(νOCO)asym; 1265med (νOCO)sym; ∆ν = 375; 1720sr
(νC=O); 538sr (νSn–C); 472sh (νSn–O).
Compound 3: (tri-butyl tin complex)
Yield: 85%. Physical state: solid; mp = 125°C; Mol
formula: C21H34O4Sn; Mol wt: 470; Recrystalliztion
solvent: chloroform/petroleum ether.
Elemental analysis: The calculated values are given
in parentheses. C, 53.57(53.61); H, 7.19(7.23); Sn,
25.50 (25.53).
IR (KBr, cm–1): 1738 (νC=O); (νOCO)as; (νOCO)s;
∆ν = ; (νSn–C); (νSn–O).
1H NMR (CDCl3): H-1: 3.80 s [3H, OMe]; H-4:
7.76–7.78 m [1H, phenyl protons]; H-5: 7.39–7.40 m
[1H, phenyl protons]; H-6: 7.42–7.44 m [1H, phenyl
proton]; H-7: 7.55–7.57 m [1H, phenyl protons]; H-α:
2.60 s; H-β: 7.59–7.61 m; H-γ: 7.23–7.25 m; H-δ:
7.50–7.54 m; H-ω: 7.56–7.60 m.
13C NMR (CDCl3): C-1: 50.82; C-2: 165.8; C-3:
1H NMR (CDCl3): H-1: 3.82 s [3H,OMe]; H-4:
7.78–7.80 m [1H, phenyl proton]; H-5: 7.41–7.43 m
[1H, phenyl proton]; H-6: 7.45–7.47 m [1H, phenyl
proton]; H-7: 7.59–7.61 m [1H, phenyl proton]; H-α:
1.8–1.9 m; H-β: 1.5–1.6 m; H-γ: 1.45–1.50 m; H-δ:
1.25 t.
130.9; C-4: 127.3; C-5: 130.7; C-6: 128.8; C-7: 128.4;
1
C-8: 130.0; C-9: 170.4; C-α: 30.2 J [610.5]; C-β:
135.5 2J [44]; C-γ: 129.2 3J [60.2]; C-δ: 127.4 4J [11.5];
C-ω: 124.5.
119Sn NMR (CDCl3): –165 ppm.
13C NMR (CDCl3): C-1: 50.83; C-2: 165.8; C-3:
119Sn Mössbauer (CDCl3, mm/s): Q.S: 3.50; I.S:
130.9; C-4: 127.3; C-5: 130.6; C-6: 128.7; C-7: 128.3; 1.51; Q.S/I.S = 2.31; Γ1: 0.80; Γ2: 0.81.
C-8: 129.9; C-9: 169.1; C-α: 16.4 1J [652.5]; C-β: 27.2
2J[30.2]; C-γ: 26.4 3J[63.7]; C-δ: 12.9 4J[n.o].
RESULTS AND DISCUSSION
119Sn NMR (CDCl3): –165.5 ppm.
119Sn Mössbauer (CDCl3, mm/s): Q.S: 2.38; I.S:
1.33; Q.S/I.S = 1.05; Γ1: 0.95; Γ2: 0.94.
Reactions of R3SnCl with Mono-methyl phthalate
and tri-ethyl amine in 1 : 1 ratio led to the formation of
complexes according to Scheme 2 Eq. (1).
Compound 4: (tri-phenyl tin complex)
The above reactions were found to be facile and
Yield: 85%. Physical state: solid; mp = 125°C; Mol
formula: C21H34O4Sn; Mol wt: 470; Recrystalliztion
solvent: chloroform/petroleum ether.
Elemental analysis: The calculated values are given in
parentheses. C, 53.58(53.61); H, 7.20(7.23); Sn, 25.48
(25.53).
IR (KBr, cm–1): 3035w (νCH aromatic); 1638med
(νOCO)as; 1280med (νOCO)s; ∆ν = 358; 1728sr
(νC=O); 545sr (νSn–C); 475sh (νSn–O).
were complete within 8–10 h of refluxing. The resulting
complexes were obtained in good yield (70–90%). The
complexes were soluble in methanol, chloroform,
DMSO, and DMF. The elemental analyses obtained for
all the complexes are in good agreement with the pro-
posed 1 : 1 stoichometery between the organotin moi-
ety and the monomethyl phthalate. In the absence of
unequivocal structural data from the X-ray crystal stud-
ies, it is usual to infer structures from the available spectro-
1
13
scopic data. Thus, H NMR, C NMR, IR, 119Sn NMR
and Mössbauer spectroscopy may be employed with vary-
ing degrees of success to ascertain the geometries to orga-
notin(IV) complexes [16].
1H NMR (CDCl3): H-1: 3.81 s [3H, OMe]; H-4:
7.78–7.80 m [1H, phenyl protons]; H-5: 7.40–7.42 m
[1H, phenyl protons]; H-6: 7.42–7.44 m [1H, phenyl
protons]; H-7: 7.57–7.59 m [1H, phenyl protons]; H-α:
1.8–1.9m [3H, CH3]; H-β: 1.5–1.6m [2H, CH2]; H-γ:
1.45–1.50m [2H, CH2]; H-δ: 1.25t [2H, CH2].
R3SnCl + HL + Et3N
R3SnL + Et3N · HCl. (1)
Where R = methyl, ethyl, butyl, phenyl, or benzyl.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 52 No. 1 2007

COMPARATIVE STRUCTURAL AND FUNGICIDAL STUDIES
105
468–482 cm–1 for Sn-C and Sn-O, respectively, further
6
4
7
O H
O
confirm the complexation [18–20].
8
5
1
The H NMR spectra were recorded in CDCl3. A
3
signal at 12.5 ppm (s, 1H) due to a proton of the OH
group of HL disappears after complex formation. As
reported previously [21], magnetically nonequivalent
alkyl protons under diamagnetic shielding upon com-
plexation. This is probably due to conformation, which
the ligand molecule may adopt after complexation. The
signal in the range of 3.80–3.82 ppm is recorded for
methyl protons (s, 3H). Integrations tally with the
expected ratio. Signals for alkyl protons attached to the
tin are observed at their proper positions as reported
earlier [22–24].
O
O
CH3
Ligand acid HL
Scheme 1
6
7
O
R
8
Sn
R
5
R
O
4
3
The characteristic resonance peaks in the 13C NMR
spectra of the complexes were recorded in CDCl3.
O
O
13C-NMR data is most informative for organotin(IV)
carboxylates. In particular, the one bond 119Sn-13C cou-
pling constants fall in a narrow range, and they can be
fairly diagnostic of the coordination status at tin. The
1J values obtained for organotin derivatives are indica-
CH3
Tri-organotin(IV) complexes
γ
α
α
β
α
β
δ
where R = CH3, CH2 CH3, CH2 CH2CH2 CH3
1
tive of four-coordinated tin. Beside the J values, the
β
γ
γ
δ
13C-NMR spectra of organotin derivatives of Mono-
methyl phthalate are consistent with the following
observations:
α
β
ω
α
δ
and H2C
Scheme 2
• The carboxylic carbon (i.e., C-9) in the organotin
derivatives synthesized resonates at δ (170.2–171.2 ppm)
while in ligand this carbon resonates at δ (168.7 ppm).
This higher shift of δ suggests coordination through
carboxylic oxygen to an organotin(IV) moiety [25].
• The carbons of alkyl groups attached to the tin are
observed at their proper positions [22–24]. 119Sn chem-
ical shift of organotin(IV) compounds covers a range of
600 ppm. The resonance peaks obtained for organotin(IV)
derivatives are in the range of (–110)–(–185.8) ppm
[26, 27].
The Mössbauer quadrupole splitting (Q.S.) and iso-
mer shift (I.S.) values are recorded at 80 K. A guide to
the coordination status of tin in di- and tri-organo-
tin(IV) compounds is provided by the Q.S. : I.S. ratio,
which has a value of >2.1 for five coordination at tin
[28, 29]. Such ratios are obtained for all of the synthe-
sized compounds, on this basis trigonal bipyramidal
geometry is attributed to all the complexes.
SPECTROSCOPIC STUDIES
IR, 1H NMR, 13C NMR, 119Sn NMR, and 119Sn Möss-
bauer studies were explained in the spectroscopic data sec-
tion.
IR spectra were recorded in the range 4000–400 cm−1.
Due to the low symmetry of carboxylate ion, their inter-
actions cannot be identified easily. However, attempts
have been made to correlate the values of characteristic
vibrations like (νCOO), (νCO), (νSn–C), and (νSn–O)
with the literature reports to elucidate the structure of
complexes. The broad band in the range 3050 cm–1 due
to (νOH) present in the spectrum of ligand (HL) is
absent in the case of tin complexes, which shows the
complex formation. The coordination of the complexes
can be determined on the basis of ∆ν[(νCOO)as
–
(νCOO)s. According to the earlier reported work [17],
the value of ∆ν can be divided into three groups:
• When ∆ν > 350 cm–1, there is a higher probability
that the carboxylate group is monodentate, however
other very weak interactions cannot be excluded.
ANTIFUNGAL ACTIVITY
The assessments of the fungal toxicity of the synthe-
sized compounds were based on % inhibition. The
results are summarized in Tables 1–6; Table 1 demon-
strates that the monomethyl phthalates have significant
activity against all plant pathogenic fungi. This activity
is due to the presence of a phenyl group. The activity of
the ligand in question may also be due to the presence
of a hydroxyl group. According to the literature, the
hydroxyl group is so reactive that it enables the toxi-
• When ∆ν < 200 cm–1, the carboxylate group in
such complexes can be considered as bidentate.
• When ∆ν < 350 and > 200 cm–1, such complexes
are considered as being in the intermediate state known
as anisobidentate.
On the basis of the above points, the carboxylate
group is monodentate, as the ∆ν value obtained is greater
than 350. The bands in the range of 542–555 cm–1 and cants to combine with constituents of the living tissues
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 52 No. 1 2007

106
WAJID REHMAN et al.
Table 1. Fungal toxicity effect of ligand acid against all micro- Table 2. Fungi toxicity effect of compound 1 against all micro-
organisms
organisms
% Inhibition (dose ppm)
% Inhibition (dose ppm)
Name of Fungi
Name of Fungi
500
250
100
50
500
250
100
50
C. capsici
58.56
49.54
48.53
52.56
57.50
54.48
40.55
39.52
48.40
48.80
45.50
38.14
32.22
36.16
38.58
39.55
C. capsici
60.35
55.50
66.40
52.50
68.70
59.8
50.53
62.55
55.50
66.98
58.51
52.52
60.44
58.20
63.50
57.14
48.22
59.16
55.58
60.55
C. gloeosporiodes 50.50
C. glocosporiodes
A. brassicicola
A. brassicae
A. brassicicola
A. brassicae
60.40
63.50
60.70
H. graminium
H. graminium
Table 4. Fungi toxicity effect of compound 3 against all micro-
organisms
Table 3. Fungi toxicity effect of compound 2 against all micro-
organisms
% Inhibition (dose ppm)
Name of Fungi
% Inhibition (dose ppm)
Name of Fungi
500
250
100
50
500
250
100
50
C. capsici
82.35
70.8
52.53
82.55
75.50
80.98
65.51
51.52
80.44
70.20
75.50
55.14
44.22
66.16
65.58
68.55
C. capsici
59.50
51.55
51.50
53.50
58.40
57.34
44.25
42.32
50.62
51.37
47.70
40.40
34.54
38.65
40.82
41.53
C. gloeosporiodes 58.50
C. gloeosporiodes 52.45
A. brassicicola
A. brassicae
95.40
94.50
96.70
A. brassicicola
A. brassicae
62.30
65.10
62.22
H. graminium
H. graminium
Table 6. Fungi toxicity effect of compound 5 against all micro-
organisms
Table 5. Fungi toxicity effect of compound against all microor-
ganisms
% Inhibition (dose ppm)
Name of Fungi
% Inhibition (dose ppm)
Name of Fungi
500
250
100
50
500
250
100
50
C. capsici
70.50
68.22
48.45
70.50
68.67
62.45
60.50
45.52
67.40
65.55
59.59
55.10
42.75
63.26
60.76
56.53
C. capsici
75.50
68.22
52.45
82.50
87.91
80.45
60.50
50.52
78.30
72.13
72.56
55.10
45.25
64.16
65.80
62.50
C. glocosporiodes 50.80
C. gloeosporiodes 59.80
A.brassicicola
A. brassicae
H. graminium
74.55
72.45
68.60
A. brassicicola
A. brassicae
90.55
94.45
93.50
H. graminium
ascribed to the polarity of the compound. On coordina-
tion, the charge of the tin ion is greatly reduced due to
the sharing of its positive charge with the donor atoms
and consequent π electron delocalization over the entire
chelate ring manifold. Thus, the lipophilic character of
and as a result of that the tissues lose their ability to
function [30]. The increased activity of organotin(IV)
complexes may be due to the coordination of the
tin(IV) atom with the oxygen of the ligand. The pres-
ence of phenyl groups bonded with tin for compond 2
(triphenyltin complex) is also considered responsible the tri-phenyltin complex increases and promotes its
for the rise of fungicidal activity. The high fungicidal permeation through the lipoid layers of the fungus
activity of the tri-phenyltin(IV) complex may be membrane [31].
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COMPARATIVE STRUCTURAL AND FUNGICIDAL STUDIES
107
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ACKNOWLEDGMENTS
One of the authors, Dr. Amin Badshah, is highly
thankful to Professor Wrackmeyer B, University of
Bayreuth, Germany, for spectral studies. HEJ Research
Institute of Chemistry, University of Karachi, Pakistan
is highly acknowledged for the determination of some
of the bioactivities.Associate ProfessorA. Christofides,
University of Thessalonki, Greece, is thanked for pro-
viding useful research material, and Amanullah
Research Scholar of Chemistry Department Gomal
University, Pakistan is acknowledged for valuable dis-
cussion.
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