Synthesis and biological activity of novel phosphonate derivatives containing of pyridyl and 1,2,3-triazole rings

Article abstract of DOI:10.1080/10426500701578522

In order to search for novel agrochemicals with high activity and low toxicity, a series of phosphonate derivatives containing 1,2,3-triazolyl and pyridyl rings were synthesized using 2-chloro-5-(chloromethyl)-pyridine as the starting material. IR, 1 H NM

Full text of DOI:10.1080/10426500701578522

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Synthesis and Biological
Activity of Novel Phosphonate
Derivatives Containing of
Pyridyl and 1,2,3-Triazole
Rings
Xiao-Bao Chen a & De-Qing Shi a
a Key Laboratory of Pesticide and Chemical Biology
of Ministry of Education, College of Chemistry ,
Central China Normal University , Wuhan, Hubei, P.
R. China
Published online: 09 May 2008.
To cite this article: Xiao-Bao Chen & De-Qing Shi (2008) Synthesis and Biological
Activity of Novel Phosphonate Derivatives Containing of Pyridyl and 1,2,3-Triazole
Rings, Phosphorus, Sulfur, and Silicon and the Related Elements, 183:5, 1134-1144,
DOI: 10.1080/10426500701578522
To link to this article: http://dx.doi.org/10.1080/10426500701578522
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Phosphorus, Sulfur, and Silicon, 183:1134–1144, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701578522
Synthesis and Biological Activity of Novel Phosphonate
Derivatives Containing of Pyridyl and 1,2,3-Triazole Rings
Xiao-Bao Chen and De-Qing Shi
Key Laboratory of Pesticide and Chemical Biology of Ministry of
Education, College of Chemistry, Central China Normal University,
Wuhan, Hubei, P. R. China
In order to search for novel agrochemicals with high activity and low toxicity, a
series of phosphonate derivatives containing 1,2,3-triazolyl and pyridyl rings were
synthesized using 2-chloro-5-(chloromethyl)-pyridine as the starting material. IR,
1 H NMR, 31P NMR, MS, and elemental analyses confirmed their structures. The
crystal structure of 5a was determined by single crystal X-ray diffraction. Prelimi-
nary bioassays indicated that some of them possess good herbicidal and moderate
fungicidal activities.
Keywords 1,2,3-triazole; α-hydroxyalkylphosphonate; biological activity; pyridine
INTRODUCTION
It is well known that many triazole-related molecules play an important
role in the development of agrochemicals such as insecticides, nemato-
cides, acaricide, and plant-growth regulators.1−4 In the study of phar-
maceuticals and agrochemicals, the introduction of pyridine into the
parent compounds may improve the properties and biological activities
of the compounds, and many pyridyl containing compounds are known
to possess a wide range of biological and pharmacological activities,5−8
as well as low toxicity toward mammals. Moreover, a variety of the
reports regarding synthetic studies of the α-hydroxyalkylphosphonate
derivatives have been presented due to the chemical and biological in-
terests such as its strong inhibitory effects against various enzymes.9−10
As a continuation of our research work—with an attempt to find novel
agrochemicals having high activity and low toxicity11−12— in this paper,
Received 29 June 2007; accepted 10 July 2007.
The authors are grateful to the Natural Science Foundation of China (grant No.
20302002) for financial support.
Address correspondence to De-Qing Shi, Key Laboratory of Pesticide and Chemical
Biology of Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan 430079, Hubei, P. R. China. E-mail: chshidq@mail.ccnu.edu.cn
1134

Novel Phosphonate Derivatives
1135
we wish to report the synthesis and biological activities of the target
compounds 5, in which a pyridyl and 1,2,3-triazolyl rings are introduced
to α-hydroxyalkylphosphonate moiety.
RESULTS AND DISCUSSION
Synthesis and Structure of the Title Compounds 5
A series of novel phosphonate derivatives containing 1,2,3-triazolyl and
pyridyl rings 5a∼h were synthesized as shown in Scheme 1.
R1 = C6H5, R2 = C2H5 (5a); R1 = 4-ClC6H4, R2 = CH3 (5b); R1 = 2,4-Cl2C6H3,
R2 = C2H5 (5c); R1 = C6H5, R2 = CH3 (5d); R1 = 4-CH3OC6H4, R2 = C2H5 (5e);
R1 = 2-ClC6H4, R2 = CH3 (5f); R1 = 4-ClC6H4, R2 = CH3 (5g); R1 = CH3, R2 =
CH3 (5h)
SCHEME 1
5-(Azidomethyl)-2-chloro-pyridine 2 can be prepared from the corre-
sponding chloride 1 with sodium azide in dry ethanol. 1-[(6-Chloro-
pyridin-3-yl) methyl]-4-ethoxycarbonyl-5-methyl-1H-1,2,3-triazole 3
can be conveniently synthesized via the cyclization of compound 2 with
ethyl acetylacetate and anhydrous potassium carbonate in DMSO. Car-
bonyl chloride 4 can be obtained in a moderate yield by the saponifi-
cation of compound 3 followed by the reaction with thionyl chloride.
Carbonyl chloride 4 reacted with various α-hydroxyalkylphosphonates
in triethylamine-chloroform system at room temperature to give the
target compounds 5 in good yields (78∼93%).
The addition of a base (triethylamine or pyridine) was essential to
the condensation reaction. Without triethylamine or pyridine, the reac-
tion was greatly slowed and the yields were very low even at refluxing
temperature. Moreover, the reactions are significantly affected by the
electronic and stereo-hindered effects of α-hydroxyalkylphosphonates.
When the electron-withdrawing substituents are attached to α-
hydroxyalkylphosphonates, the reactions undergo much faster than
that of electron-donating one.

1136
X.-B. Chen and D.-Q. Shi
FIGURE 1 The molecular structure of 5a, showing 50 % probability displace-
ment ellipsoids and the atom-numbering scheme. Both disorder components
are shown.
Their structures of compounds 5 were confirmed by IR, 1H NMR, 31
P
NMR, EI-MS, and elemental analyses, all spectra data were consistent
with the assigned structures, which were listed in the experimental
part.
Moreover, in order to confirm its structure and investigate its stere-
ochemistry, a single crystal of 5a was obtained from acetone and
petroleum ether (1:1 v/v) solvent system. X-ray diffraction analysis in-
dicated that the single crystal of 5a is triclinic, space group P-1, cell
˚
parameters A = 8.530 (1), B = 9.621 (1), C = 14.639 (1) A, α = 95.865
◦
3
˚
(2), β = 92.955 (2), γ = 90.536 (2) , V = 1193.4 (2) A , Z = 2, Dx =
1.333 g/cm3, F (000) = 500, µ = 0.266 mm,−1 and final R = 0.0656,
wR = 0.1720 for 4282 reflections (I > 2σ(I)). Figures 1 and 2 are the
molecular structure of compound 5a and packing of the molecules in
the unit cell, respectively.
The selected bond distances and angles are listed in Table I. The C9-
N4 and C8-N2 bonds are significantly shorter than a normal single C N
bond13 and are close to the value for a C N bond,14 this indicates sig-
nificant electron delocalization in the triazolyl system. The O5-P1-O4,
◦
˚
TABLE I Selected Geometric Parameters (A, )
C8-N2
1342 (3)
C9-N4
1.364 (3)
O5-P1-O4
O5-P1-O3
O4-P1-O3
116.88 (15)
117.06 (16)
102.06 (17)
O5-P1-C11
O4-P1-C11
O3-P1-C11
113.10 (13)
105.50 (13)
100.20 (13)

Novel Phosphonate Derivatives
1137
FIGURE 2 Packing of the molecules in the unit cell, showing the formation of
C-H. . . O hydrogen bonds (dashed lines).
O5-P1-O3, and O5-P1-C11 bond angles are larger than the O4-P1-O3,
O4-P1-C11, and O3-P1-C11, indicating a distorted tetrahedral config-
uration for the P atom. Intra- and intermolecular C-H. . . O hydrogen
bonds contribute strongly to the stability of the molecular configura-
tion (Figure 2 and Table II). In addition, short intermolecular distances
between the centroids of the N1-C1/C2/C3-C4-C5 rings (centroid Cg1)
and the parallel pyridine rings of adjacent molecules indicate the pres-
ence of π − π stacking interactions in the crystal structure,15 with ◦a
˚
centroid-to-centroid distance of 3.841 (2) A, dihedral angle of 0.00 (1) ,
˚
and a shortest interplanar distance of 3.478 (1) A; symmetry code: (i)
-1-x, 2-y, -z.
Biological Activities
Herbicidal Activity
The herbicidal activity of the title compounds 5 against Brassica
napus (oil rape) and Echinochloa crus-galli (barnyard grass) were mea-
sured according to the method described in the experimental section.

1138
X.-B. Chen and D.-Q. Shi
The preliminary results of bioassay showed that some of compounds
5 possess potent and selective herbicidal activities against dicotyle-
donous weeds such as oil rape at the dosage of 100 mg/L. For example,
compounds 5c, 5d, and 5g exhibit 77.6%, 76.5%, and 62.4% inhibitory
activity against root of rape, respectively. It is also found that com-
pounds 5 exhibit a stronger inhibitory effect against root of rape than
that of stem (see Table III).
Fungicidal Activities
The preliminary fungicidal activities of the target compounds 5 were
evaluated by the classic plate method at a concentration of 100 mg/L.
The six fungi used, Fusarium oxysporium, Rhizoctonia solani, Botrytis
cinereapers, Gibberella zeae, Dothiorella gregaria, and Colletotrichum
gossypi, belong to the group of field fungi and were isolated from corre-
sponding crops. The activity data were listed in Table III. The results
indicated that most of compounds 5 exhibit moderate to weak inhibitory
activities against the above six fungi.
EXPERIMENTAL
Melting points were determined with a WRS-1B digital melting point
apparatus, and uncorrected. 1H NMR and 31P NMR spectra were
recorded with a VARIAN MERCURY-PLUS400 spectrometer with TMS
and 85% H3PO4 as the internal and external references, respectively,
and CDCl3 as the solvent; while mass spectra were obtained with a
Finnigan TRACEMS2000 spectrometer using the EI method. IR spec-
tra were measured by a NICOLET NEXUS470 spectrometer. Elemental
analyses were performed with an ELEMENTAR Vario EL III CHNSO
elementary analyzer. X-ray diffraction analysis was carried out with a
BRUKER SMART APEX CCD X-ray diffraction instrument. All of the
solvents and materials were reagent grade and purified as required.
α-hydroxyalkylphosphonate was prepared according to the literature
procedure.15−16
◦
˚
TABLE II Hydrogen-bond Geometry (A, )
D-H. . .A
D-H
H. . . A
D. . . A
D-H. . . A
C7-H7B. . . O1
C2-H2. . . O1i
0.96
0.93
2.59
2.44
3.158 (3)
3.333 (3)
118
162
Symmetry code: (i) x, y+1, z.

1139

1140
X.-B. Chen and D.-Q. Shi
Synthesis of 5-(Azidomethyl)-2-chloro-pyridine 2
Sodium azide (7.8 g, 0.12 mol) was added to a solution of 2-chloro-5-
(chloromethyl)-pyridine (16.1 g, 0.1 mol) in dry ethanol (80 mL) and
refluxed for 6 hours (monitored by thin-layer chromatography). The
workup involved stripping of the solvent followed by addition of water
and extraction of the product mixture into CH2Cl2, after phase separa-
tion, drying over anhydrous sodium sulfate, filtration and evaporation,
compound 2 was obtained as an amber oil (yield: 95%), which can be
used without further purification.1H NMR (CDCl3, 400 MHz) δ: 4.45
(s, 2H, CH2), 7.53 (d, J = 8.0 Hz, 1H, Py-H), 7.66 (d, J = 8.0 Hz, 1H,
Py-H), 8.38 (s, 1H, Py-H).
Synthesis of 1-[(6-chloro-pyridin-3-yl)methyl]-4-
ethoxycarbonyl-5-methyl-1H-1,2,3-triazole 3
5-(azidomethyl)-2-chloro-pyridine 2 (8.4 g, 50 mmol) and ethyl acetylac-
etate (6.5 g, 50 mmol) were added to a suspension of milled potassium
carbonate (3.45 g, 25 mmol) in DMSO (50 mL). The mixture was stirred
at room temperature for 6 h (monitored by thin-layer chromatography)
and poured to water (500 mL). The solid was collected by filtration,
washed with water and diethyl ether, respectively, and dried to give 3
as a light yellow solid (yield: 95%, m.p. 88–90◦C). 1H NMR (CDCl3,
400 MHz) δ: 1.42 (t, 3H, OCH2CH3), 2.52 (s, 3H, CH3), 4.42 (q, 2H,
OCH2CH3), 5.54 (s, 2H, CH2), 7.35 (d, J = 8.4 Hz, 1H, Py-H), 7.45 (d,
J = 8 Hz, 1H, Py-H), 8.34 (s, 1H, Py-H).
Synthesis of 1-[(6-chloro-pyridin-3-yl)methyl]-5-methyl-1H-
1,2,3-triazole-4-carbonyl chloride 4
A mixture of 3 (8.4 g, 30 mmol), NaOH powder (1.8 g, 45 mmol) and wa-
ter (50 mL) was refluxed for 2 h; after cooling, the solution was acidified
with 10% HCl to pH 4, The solid was collected by filtration and dried to
give carboxylic acid as a light yellow solid, yield: 96%, m.p. 159∼161◦C.
1H NMR (DMSO-d6, 400 MHz) δ: 2.51 (s, 3H, CH3), 5.69 (s, 2H, CH2),
7.53 (d, J = 8 Hz, 1H, Py-H), 7.69 (d, J = 8 Hz, 1H, Py-H), 8.41 (s, 1H,
Py-H), 13.06 (s, br, 1H, OH).
A mixture of carboxylic acid (2.52 g, 10 mmol) and thionyl chloride
(3.54 g, 30 mmol) in chloroform (30 mL ) was refluxed for 5–6 h. After
the removal of solvent and excess thionyl chloride under vacuum, chlo-
roform (30 mL) was added, filtered and evaporated to get 4 as a light
yellow solid (yield: 85%, m.p. 105–107◦C), which can be used without
further purification.

Novel Phosphonate Derivatives
1141
General Procedure for the Preparation of O,O-dialkyl
1-[(6-Chloro-pyridin-3-yl)methyl]-5-methyl-1H-1,2,3-triazol-4-yl
carbonyloxy substituted methyl phosphonate 5a–h.
A solution of 4 (0.59 g, 2.2 mmol) in anhydrous chloroform (10 mL)
was added dropwise to a stirred mixture of α-hydroxyalkylphosphonate
(2 mmol) and triethylamine (0.22 g, 2.2 mmol) in chloroform (25 mL) at
0∼5◦C. After the addition complete, the mixture was stirred at room
temperature for 6 h until the reaction was complete (monitored by thin-
layer chromatography). The workup involved washing with dilute hy-
drochloride acid, saturated sodium bicarbonate and brine, respectively.
After phase separation, drying over anhydrous sodium sulfate, filtra-
tion, and evaporation, the residue was purified by flash column chro-
matography on silica gel using acetone and petroleum ether (1:1 v/v)
as eluent, giving the target compound 5a-h in 85∼93% yields.
O,O-Diethyl 1-[(6-chloropyridin-3-yl) methyl]-5-methyl-1H-1,
2,3-triazol-4–ylcarbonyloxy-phenylmethyl phosphonate (5a)
White solid, m.p. 145–147◦C, yield: 85%; 1H NMR (CDCl3, 400 MHz)
δ: 1.22–1.26 (m, 6H, 2OCH2CH3), 2.55 (s, 3H, CH3), 4.06–4.10 (m, 4H,
2OCH2CH3), 5.52 (s, 2H, CH2), 6.38 (d, J = 13.2 Hz, 1H, CH), 7.27–7.58
(m, 7H, Ar-H, Py-H), 8.37 (s, 1H, Py-H); 31P NMR (CDCl3, 162 MHz) δ:
15.24; IR (KBr) υ:1717 (C O), 1469, 1234 (P O), 1188 (C-O-C), 1034
(P-O-C), 976 (P-C); MS (70 eV) m/z (%): 478 (M+, 8.7), 341 (26.3), 236
(27.3), 234 (80.0), 137 (15.6), 126 (100), 110 (5.7), 91 (56.1), 81 (24.8),
77 (16.7); Anal. Calcd. for C21H24ClN4O5P: C 52.67, H 5.05, N 11.70;
found: C 52.49, H 5.31, N 11.99.
O,O-Diethyl 1-[(6-chloropyridin-3-yl) methyl]-5-methyl-1H-
1,2,3-triazol-4-ylcarbonyloxy-4-chlorophenylmethyl
phosphonate (5b)
1
Yellow oil, yield: 88%; H NMR (CDCl3, 400 MHz) δ: 1.27–1.31 (m,
6H, 2OCH2CH3), 2.17 (s, 3H, CH3), 4.14–4.18 (m, 4H, 2OCH2CH3), 5.51
(s, 2H, CH2), 6.77 (d, J = 14.0 Hz, 1H, CH), 7.30–7.51 (m, 5H, Ar-H, Py-
H), 7.69 (d, J = 8.4 Hz, 1H, Py-H), 8.36 (s, 1H, Py-H); IR (KBr, cm−1)υ:
1732 (C O), 1462, 1259 (P O), 1163 (C-O-C), 1024 (P-O-C), 974 (P-C);
MS (70 eV) m/z (%): 512 (M+, 7.0), 276 (58.9), 236 (42.7), 137 (58.3),
126 (100), 110 (14.4), 91 (12.7), 81 (32.4), 77 (10.6); Anal. Calcd. for
C21H23Cl2N4O5P: C 49.14, H 4.52, N 10.91; found: C 49.39, H 4.34,
N 10.63.

1142
X.-B. Chen and D.-Q. Shi
O,O-Diethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1,2, 3-triazol-4-ylcarbonyloxy-2,4-dichlorophenylmethyl
phosphonate (5c)
1
Yellow oil, yield: 92%; H NMR (CDCl3, 400 MHz) δ: 1.23–1.26 (m,
6H, 2OCH2CH3), 2.54 (s, 3H, CH3), 4.04–4.07 (m, 4H, 2OCH2CH3), 5.53
(s, 2H, CH2), 6.32 (d, J = 13.6 Hz, 1H, CH), 7.33–7.54 (m, 5H, Ar-H,
Py-H), 8.37 (s, 1H, Py-H); MS (70 eV) m/z (%): 546 (M+, 5.8), 409 (9.4),
310 (14.5), 236 (51.0), 137 (14.4), 126 (100), 110 (16.0), 91 (17.9), 81
(32.8), 77 (4.6); Anal. Calcd. for C21H22Cl3N4O5P: C 46.05, H 4.05, N
10.23; found: C 46.31, H 4.17, N 9.97.
O,O-Dimethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1, 2,3-triazol-4-ylcarbonyloxy-phenylmethyl phosphonate (5d)
Yellow oil, yield: 93%; 1H NMR (CDCl3, 400 MHz) δ: 2.55 (s, 3H, CH3),
3.69–3.72 (m, 6H, 2OCH3), 5.52 (s, 2H, CH2), 6.40 (d, J = 13.6 Hz, 1H,
CH), 7.33–7.59 (m, 6H, Ar-H, Py-H), 8.37 (s, 1H, Py-H); Anal. Calcd. for
C19H20ClN4O5P: C 50.62, H 4.47, N 12.43; found: C 50.49, H 4.63, N
12.58.
O,O-Diethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1,2, 3-triazol-4-ylcarboxyloxy-4-methoxyphenylmethyl
phosphonate (5e)
Yellow oil, yield: 89%; 1H NMR (CDCl3, 400 MHz) δ: 1.21–1.25 (m, 6H,
2OCH2CH3), 2.54 (s, 3H, CH3), 3.80 (s, 3H, OCH3), 4.04–4.08 (m, 4H,
2OCH2CH3), 5.52 (s, 2H, CH2), 6.31 (d, J = 12.8 Hz, 1H, CH), 7.33–7.53
(m, 6H, Ar-H, Py-H), 8.36 (s, 1H, Py-H); MS (70 eV) m/z (%): 508 (M+,
16.9), 371 (10.4), 272 (61.3), 236 (4.58), 137 (10.1), 135 (100), 126 (50.7),
110 (4.1), 91 (8.4), 81 (9.9), 77 (12.4); Anal. Calcd. for C22H26ClN4O6P:
C 51.92, H 5.15, N 11.01; found: C 52.17, H 5.18, N 11.36.
O,O-Dimethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1, 2,3-triazol-4-ylcarboxyloxy-2-chlorophenylmethyl
phosphonate (5f)
Yellow oil, yield: 90%; 1H NMR (CDCl3, 400 MHz) δ: 2.53 (s, 3H, CH3),
3.78-3.82 (m, 6H, 2OCH3), 5.52 (s, 2H, CH2), 6.90 (d, J = 13.2 Hz, 1H,
CH), 7.28-7.40 (m, 4H, Ar-H), 7.50 (d, J = 8.4 Hz, 1H, Py-H), 7.53 (d,
J = 7.6 Hz, 1H, Py-H), 8.36 (s, 1H, Py-H); 31P NMR (CDCl3, 162 MHz)
δ: 16.75; MS (70 eV) m/z (%): 484 (M+, 8.7), 375 (64.6), 248 (13.0), 236
(4.58), 139 (100), 126 (77.1), 110 (18.8), 109 (60.4), 91 (18.8), 81 (7.7),
77 (33.2); Anal. Calcd. for C19H19Cl2N4O5P: C 47.03, H 3.95, N 11.55;
found: C 47.28, H 4.08, N 11.17.

Novel Phosphonate Derivatives
1143
O,O-Dimethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1,2,3-triazol-4-ylcarboxyloxy-4-chlorophenylmethyl)
phosphonate (5g)
1
Yellow oil, yield: 92 %; H NMR (CDCl3, 400 MHz) δ: 2.54 (s, 3H,
CH3), 3.73-3.78 (m, 6H, 2OCH3), 5.53 (s, 2H, CH2), 6.35 (d, J = 13.2
Hz, 1H, CH), 7.34-7.54 (m, 6H, Ar-H, Py-H), 8.36 (s, 1H, Py-H); 31P
NMR (CDCl3, 162 MHz) δ: 16.81; Anal. Calcd. for C19H19Cl2N4O5P: C
47.03, H 3.95, N 11.55; found: C 46.91, H 3.70, N 11.82.
O,O-Dimethyl 1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-
1, 2,3 -triazol-4-yl carboxyloxy-2-ethyl phosphonate (5h)
Yellow oil, yield: 87%; 1H NMR (CDCl3, 400 MHz) δ: 1.58 (q, J = 6.8
Hz, 3H, CHCH3), 2.53 (s, 3H, CH3), 3.81–3.92 (m, 6H, 2OCH3), 5.53 (q,
J = 7.6 Hz, 1H, CH), 5.59 (s, 2H, CH2), 7.34 (d, J= 8.4 Hz, 1H, Py-H),
7.52 (d, J = 8 Hz, 1H, Py-H), 8.37 (s, 1H, Py-H); 31P NMR (CDCl3, 162
MHz) δ: 21.08; IR (KBr) υ:1736 (C O), 1460, 1244 (P O), 1186 (C-O-C),
1044 (P-O-C), 831 (P-C); Anal. Calcd. for C14H18ClN4O5P: C 43.25, H
4.67, N 14.41; found: C 43.38, H 4.30, N 14.18.
Bioassay Methods
Herbicidal Activities Testing
Herbicidal testing of the newly synthesized compounds 5 was carried
out in a greenhouse, with temperature 23 1◦C, RH 60 5%, light in-
tensity 10 Klux, photoperiod 8 h/day. Twenty seeds of each weed species
including rape and barnyard grass were chosen for testing. Seedlings
were grown in the test plate of 9 cm diameter containing two pieces of
filter paper and 9 mL solution of the tested compound (100 mg/L and
10 mg/L, respectively). Distilled water was used as a comparison com-
pound. The herbicidal activity was assessed as the inhibitory rate in
comparison with the distilled water. The herbicidal rating score based
on visual observation. Range from 0–100 %; 0 means no effect; 100%
means complete killing. The test was run three times, and the results
were averaged and given as activity in Table III.
Fungicidal Activity Testing
The fungicidal activity measurement method was adapted from the
one described by Molina Torres et al.17 The synthesized target com-
pounds were dissolved in 0.5–1.0 mL of DMF to the concentration
of 1000 mg/L. The solutions (1 mL) were mixed rapidly with thawed
potato glucose agar culture medium (9 mL) under 50◦C. The mixtures
were poured into Petri dishes. After the dished were cooled, the solid-
ified plates were incubated with 4 mm mycelium disk, inverted, and

1144
X.-B. Chen and D.-Q. Shi
incubated at 28◦C for 48 h. Water was used as the blank control. Three
replicates of each test were carried out. The mycelial elongation ra-
dius (mm) of fungi settlements was measured after 48 h of culture. The
growth inhibitory rates were calculated with the following equation:
I = [(C − T)/C] * 100%. Here, I is the growth inhibitory rate (%), and
T is the treatment group fungi settlement radius (mm). The results are
also given in Table III.
The bioassays also indicated that most of the 5 compounds did not
display inhibitory effect against aphides and Tetranychus urticae at the
dosage of 250 mg/L, further structure-activity relationships are under
investigation.
CONCLUSIONS
In conclusion, we have synthesized a series of phosphonate deriva-
tives containing 1,2,3-triazolyl and pyridyl rings using 2-chloro-5-
(chloromethyl)-pyridine as the starting material. Preliminary bioas-
says indicated that some of them possess good herbicidal and moderate
fungicidal activities.
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