Design, synthesis and insecticidal-activity evaluation of N-pyridylpyrazolo-5-methyl amines and its derivatives

Article abstract of DOI:10.1002/jhet.4136

In searching for novel insecticidal leads, a series of N-pyridylpyrazolo-5-methyl amines and their derivatives were designed and synthesized. Among the 22 target compounds obtained, bioassays indicated that some of the target compounds exhibited good insecticidal activities against Plutella xylostella (P. xylostella) and Spodoptera frugiperda (S. frugiperda). In particular, compound 9j revealed the best insecticidal activity against P. xylostella, with a LC₅₀ value of 22.11 mg/L, and compound 9q had the best insecticidal activity against S. frugiperda which with 73.99% of mortality rate at 100 mg/L. Structure-activity relationship (SAR) analysis showed that 4-CF₃ at the position of R¹ linked with N-pyridylpyrazole via amide bond could enhance the insecticidal activity of the target compounds. This study provides valuable clues for the further design and optimization of N-pyridylpyrazole derivatives.

Full text of DOI:10.1002/jhet.4136

Design, synthesis and insecticidal-activity evaluation of
N-pyridylpyrazolo-5-methyl amines and its derivatives
*
*
Shuai Yang, Kaijie Xu, Qiuqin Lai, Chen Zhao and Hanhong Xu
State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources and Key
Laboratory of Natural Pesticide and Chemical Biology, Ministry of Education, South China
Agricultural University, Guangzhou 510642, China.
*Corresponding author: zhaoc@scau.edu.cn (Zhao) Tel: +86-20-85285127; hhxu@scau.edu.cn
(Xu) Tel: +86-20-85285127
ABSTRACT: In searching for novel insecticidal leads, a series of N-pyridylpyrazolo-5-methyl
amines and its derivatives were designed and synthesized. Among the 22 target compounds
obtained, bioassays indicated that some of the target compounds exhibited good insecticidal
activities against Plutella xylostella (P. xylostella) and Spodoptera frugiperda (S. frugiperda). In
particular, compound 9j revealed the best insecticidal activity against P. xylostella, with a LC50
value of 22.11 mg/L, and compound 9q had the best insecticidal activity against S. frugiperda
which with 73.99% of mortality rate at 100 mg/L. Structure-activity relationship (SAR) analysis
1
showed that 4-CF at the position of R substituent group linked with N-pyridylpyrazole via amide
3
bond could enhance the insecticidal activity of the target compounds. This study provides valuable
clues for the further design and optimization of N-pyridylpyrazole derivatives.
Keywords: N-pyridylpyrazolo-5-methyl amines, designed and synthesized, insecticidal activity,
Structure-activity relationship
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not been through the copyediting, typesetting, pagination and proofreading process
which may lead to differences between this version and the Version of Record. Please
cite this article as doi: 10.1002/jhet.4136
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1
INTRODUCTION
Insecticides play a vital role in crop protection and food security and indirectly facilitate human
[1,2]
life.
However, with the widespread use and unreasonable application of pesticides, not only has
the resistance of insects become increasingly stronger, but also severely polluted the environment.
The emergence of pest resistance has greatly reduced the effectiveness of pesticides, therefore
[3,4]
studies of new pesticide molecules are still active areas of agrochemicals research.
Heterocyclic compounds are widely used in the fields of medicine and pesticides. It is reported
that about 70% of the commercial pesticide structures in the last 20 years contain at least one
[
5]
heterocyclic ring, therefore, the modification of heterocyclic structure to control pests is a
research content that scientists are interested in, at the same time, there may be unexpected major
[3]
discoveries.
N-pyridylpyrazole as one kind of heterocyclic structure, is widely used in the field of
agrochemicals, after DuPont developed the anthranilic diamide insecticide chlorantraniliprole in
2000, more N-pyridylpyrazole−based products have been successfully developed in recent years.
[6]
[7,8]
For example, cyantraniliprole (DuPont),
cyclaniliprole (Ishihara Sangyo Kaisha),
[9]
tetraniliprole (Bayer),
tetrachlorantraniliprole (Shenyang Research Institute of Chemical
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[10]
Industry), and all of these products have a broad spectrum of Lepidopera, Diptera, Coleoptera
and other species of pests (Fig.1). Extensive practical interest in this important part of
N-pyridylpyrazole has led to continuous efforts to develop effective compounds, meanwhile, more
[11-13]
and
more
literatures
regarding
N-pyridylpyrazole
with
fungicidal
and
[14,15]
insecticidal
activities have been published in previous articles. Many studies have reported the
lead modification of chlorantraniliprole through amide bonds or different linker between
N-pyridylpyrazole and benzene ring, but in this work, we changed the “-CONH-” position of
N-pyridylpyrazole, and the structure containing N-pyridylpyrazolo-5-methyl amine as
[16-21]
pharmacophore,
linked to some active fragments via amide bonds was designed and
[22]
synthesize (Fig. 2).
These fragments are selected from some pesticide structures including
heterocyclic and benzene rings. We conjectured that the introduction of some active fragments in
combination with N-pyridylpyrazole methanamine may change the insecticidal spectrum and
insecticidal activities of pyridylpyrazole−containing anthranilic diamides insecticides. 22 novel
amide derivatives containing N-pyridylpyrazole moiety were designed and synthesized, and their
insecticidal activities against Plutella xylostella (P. xylostella) and Spodoptera frugiperda (S.
frugiperda) were evaluated. Structure-activity relationship of these new compounds was
discussed.
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Figure 1. Chemical structures of commercial insecticides containing pyridylpyrazole scaffold.
Figure 2. Design strategy of the target compounds.
2
EXPRTIMENTAL
2.1 General information
For all reactions, solvents and chemical reagents were purchased from commercial sources and
used as received. Column chromatography purification was performed using silica gel. Melting
1
13
points were determined using an X-6 apparatus and the thermometer was uncorrected, H and C
spectra were recorded on a Bruker AV-600 MHz spectrometer with CDCl or DMSO-d as solvent
3
6
and TMS as internal standard. Analytical thin-layer-chromatography (TLC) was carried out on
precoated plates (silica gel GF254), and spots were visualized with ultraviolet (UV) light.
2
.2 General Procedure for the Preparation of the Intermediate 5.
As shown in Scheme 1, the intermediates 5 were prepared by the literature.
.3 General Procedure for the Preparation of the Intermediate 6.
[23]
2
A mixture of compound 5 (10.0 mmol), HOBt (12.0 mmol), EDCI (12.0 mmol) in MeCN (30
mL) was stirred at room temperature for 2 h. The mixture was then slowly added to ammonium
hydroxide (NH ·H O, 5 mL, 25%, v/v) at 0−10 ℃ and maintained this temperature until the
3
2
reaction was completed. Solvent concentrated in vacuo and saturated aqueous NaHCO (30 mL)
3
was added. The mixture was extracted with EtOAc (30 mL×3), the combined organic layer was
washed with water (100 mL) and brine (100 mL), dried over anhydrous Na SO , concentrated in
2
4
vacuo and purified through column chromatography to obtain compound 6 with yields of 87%.
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2.4 General Procedure for the Preparation of the Key Intermediate 7.
To a three−necked flask, intermediate 6 (5.0 mol) dissolved in anhydrous tetrahydrofuran (THF,
2
0 mL) at 0 C, lithium aluminum hydride (LiAlH , 2.5 mol/L in THF, 2.4 mL) is slowly added to
4
the solution with stirring. And then, the mixture was stirred at room temperature, when the
reaction was complete according to TLC analysis, bring the temperature of the reaction solution to
0
C, 1N NaOH was added and keep stirring for 2h. Filter the mixture and spin the filtrate in
vacuo. Water (50 mL) was then added, and the mixture was extracted with EtOAc (20 mL×3). The
combined organic layer was washed with water (60 mL) and brine (60 mL), dried over anhydrous
Na SO , concentrated in vacuo and purified through column chromatography to obtain the key
2
4
intermediate 7 with yields of 81%.
2.5 General Procedure for the Preparation of the Target Compounds 8a−8b.
A mixture of intermediate 7 (1.0 mmol), barium carbonate (K CO , 977.46 mg, 3.0
2
3
mmol), 2-pentenenitrile (1.5 mmol) or dimethyl Fumarate (1.25 mmol) in dry MeCN (10 mL) was
stirred at 60 C for 2−3 h. The progress of the reaction was monitored by TLC. After cooling to
room temperature, the solvent was removed under reduced pressure and then water (20 mL) was
added. The mixture was extracted with EtOAc (10 mL×3). The combined organic layer was
washed with water (50 mL) and brine (50 mL), dried over anhydrous Na SO , concentrated in
2
4
vacuo and purified through column chromatography to obtain the corresponding compound with
yields of 93−95%.
2.6 General Procedure for the Preparation of the Target Compounds 9a.
Intermediate 7 (1.0 mmol) and triethylamine (Et N) were dissolved in dry DCM (5 mL), then
3
acetyl chloride added dropwise to the mixture at 0 C. The reaction mixture was stirred at r. t. for
4 h and diluted with DCM (10 mL), washed with aqueous HCl (1.0 mol/L, 20 mL), saturated
aqueous NaHCO (30 mL), brine (30 mL), dried over anhydrous Na SO , concentrated in vacuo
2
3
2
4
and purified through column chromatography to obtain the compounds 9a with yields of 91%.
2.7 General Procedure for the Preparation of the Target Compounds 9b−9t.
A mixture of intermediate 7 (1.0 mmol), DCC (1.8 mmol), DMAP (0.12 mmol) and the
corresponding carboxylic acids (1.5 mmol) in DCM (10 mL) was stirred at room temperature.
When the reaction was complete according to TLC analysis, the mixture was diluted by DCM (20
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mL), washed by water (40 mL), aqueous HCl (0.1 mol/L, 40 mL), saturated aqueous NaHCO (40
3
mL), brine (40 mL), dried over anhydrous Na SO , concentrated in vacuo and purified through
2
4
column chromatography to obtain the compounds 9b−9t with yields of 70−95%.
2.8 General Procedure for the bioassays with P. xylostella
Insecticidal activities of synthesized compounds and control (chlorantraniliprole) against
third-instar larvae of P. xylostella were tested indoors. Each of the test compounds was dissolved
in DMSO and diluted with distilled water containing Tween 80 (0.1%, v/v) to obtain desired
concentrations. The leaf disks (1.8 cm in diameter) were cut from fresh cabbage grown in
greenhouse, dipped in test solution for 30 s, and allowed to dry naturally. The treated leaf disks
were placed in petri dishes (9 cm in diameter) lined with filter paper, and 10 third-instar larvae of
P. xylostella raised in laboratory were transferred to each petri dish. Petri dishes were then
incubated at 26 C, 85% relative humidity, and a photoperiod of 16:8 h (light/dark). Three
replicates were carried out for each experiment. Mortalities were determined 48 h after treatment.
The LC50 values were calculated by SPSS software, and the corrected mortality rates were
obtained as follows:
mortality of treatment – mortality of control
corrected mortality (%) =
× 100%
1
– mortality of control
.9 General Procedure for the bioassays with S. frugiperda
Insecticidal activities of target compounds and control (chlorantraniliprole) against S.
2
frugiperda were tested indoors. Each of the test compounds was dissolved in DMSO and diluted
to 100 mg/L with distilled water containing Tween 80 (0.1%, v/v). Leaves of young corn at
bell−opening stage were cut into 5 cm in length, soaked in solution of test compound for 10 s,
dried naturally, wrapped in wet absorbent cotton to moisturize the lower edge of the leaves, and
placed in petri dishes (9 cm in diameter). Leaves treated with DMSO in distilled water containing
Tween 80 (0.1%, v/v) were used as blank control. Ten second−instar larvae of well−developed S.
frugiperda raised in laboratory were placed in each petri dish containing corn leaves, and 3
replicates were carried out for each experiment. Petri dishes were then incubated at 26 C, 85%
relative humidity, and a photoperiod of 16:8 h (light/dark). Mortalities were determined 48 h after
treatment.
3
RESULTS AND DISCUSSION
3.1 Synthesis
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As is shown in scheme 1, intermediates 5, 6 and key intermediate 7 (N-pyridylpyrazole
[23-25]
containing amino) were synthesized by the methods reported in the literature.
As shown in
Scheme 2, the target compounds 8a−8b were obtained by intermediate 7, different olefins and
[26]
potassium carbonate with yield of 93−95%.
The target compound 9a was synthesized by
intermediate 7 with acetyl chloride with yield of 91%. Compound 7 was condensed with the
corresponding carboxylic acid to obtain the target compounds 9b−9t with yield of 70−95%. The
1
13
target compounds 8a, 8b and 9a−9t were identified by H NMR and C NMR and provided in
Supplementary data. The data for key intermediate 7 and target compound 9j were shown below.
(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)methanamine (7). White solid, yield: 81%;
1
H NMR (600 MHz, Chloroform-d) δ 11.19 (s, 1H, -NH ), 8.08 (dd, J = 5.0, 1.5 Hz, 1H,
2
pyridine-H), 7.50 (dd, J = 7.7, 1.6 Hz, 1H, pyridine-H), 6.65 (dd, J = 7.7, 5.0 Hz, 1H, pyridine-H),
1
3
6
.20 (s, 1H, pyrazol-H), 5.50 (t, J = 5.6 Hz, 1H, -NH ), 4.59 (d, J = 6.1 Hz, 2H, -CH -); C NMR
2
2
(151 MHz, Chloroform-d) δ 153.76, 145.72, 144.21, 136.75 , 126.11, 115.99, 114.24, 106.54,
+
3
6.31. ESI-MS m/z: calcd for C H BrClN ([M+H] ), 286.96; found, 286.91.
9
8
4
N-((3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)methyl)-4-(trifluoromethyl)benzamide
1
(
9j). White solid, yield: 74%; H NMR (600 MHz, Chloroform-d) δ 8.13 (d, J = 8.2 Hz, 1H,
pyridine-H), 8.03 (dd, J = 4.9, 1.5 Hz, 2H, Ph-H), 7.76 (d, J = 8.3 Hz, 2H, Ph-H), 7.48 (dd, J = 7.7,
.6 Hz, 1H, pyridine-H), 6.59 (dd, J = 7.7, 4.9 Hz, 1H, pyridine-H), 6.53 (s, 1H, pyrazol-H), 5.87
1
1
3
(
t, J = 6.5 Hz, 1H, -NH-), 5.09 (d, J = 6.3 Hz, 2H, -CH -); C NMR (151 MHz, Chloroform-d) δ
2
1
1
3
66.55, 153.10, 148.74, 145.97, 136.39 (2C, Ph-C), 135.13, 134.38 (q, J = 33.0 Hz), 132.45,
31.82 (2C, Ph-C), 125.08 (q, J = 3.7 Hz), 123.52 (q, J = 272.9 Hz, -CF ), 115.66, 114.16, 113.91,
3
+
7.87. ESI-MS m/z: calcd for C H BrClF N O ([M+H] ), 458.98; found, 458.97.
17
11
3
4
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Scheme 1. Synthetic route of intermediate 7.
Scheme 2. Synthetic route of the target compounds 8a, 8b and 9a−9t.
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3.2 Insecticidal activities and structure-activity relationship analysis
In this study, the insecticidal activities of the target compounds 8a−8b and 9a−9t against P.
xylostella (third-instar Larvae) and S. frugiperda (second-instar larvae) were evaluated using the
[27,28]
previously reported methods.
Meanwhile, chlorantraniliprole was used as a control under the
same conditions. The results of the preliminary bioassays, as listed in Table 1, indicated that the
target compounds 8a−8b and 9a−9t showed insecticidal activities against P. xylostella at 200 mg/L
and 50 mg/L with the values of 0−93.64% and 0−72.59%, respectively, which were all lower than
chlorantraniliprole (mortality rate, 100% and 96.67%, respectively). Compounds 8a, 9a, 9e, 9j, 9l
and 9r exhibited more than 50% values at 50 mg/L. Especially compound 9j displayed 72.59%
values against P. xylostella. In addition, the compounds 8a−8b and 9a−9t with 0−73.99% mortality
rate against S. frugiperda at 100 mg/L and compound 9q had the best activity (mortality rate,
73.99%) lower than chlorantraniliprole (mortality rate, 90.56%).
The 50% lethal concentration (LC ) values of compounds 8a, 9a, 9e, 9j, 9l and 9r against
50
third−instar larvae of P. xylostella were tested as well as for the chlorantraniliprole as a positive
control, and presented in Table 2. As is shown in Table 2, compounds 8a, 9a, 9e, 9j, 9l and 9r
exhibited insecticidal activity against P. xylostella with the LC50 values of 22.11−46.56 mg/L.
Especially, compound 9j had the best insecticidal activity against P. xylostella, with the LC50
values of 22.11 mg/L, but was lower than chlorantraniliprole (2.27 mg/L).
Expansion in this approach, the structure-activity relationships (SAR) were also discussed on
the basis of the insecticidal activity values in Table 1 and 2. As is shown in Table 1, for secondary
amines compounds 8a and 8b, when N-pyridylpyrazole linked to pentanenitrile (8a) possessed
better insecticidal activities at 50 mg/L against P. xylostella with the values of 90.03% than that
compound which linked to methyl dicarboxylate (8b, 10.94%), but the insecticidal activity against
1
S. frugiperda showed the opposite effect. For amides compounds 9a−9g, when R was methyl, the
insecticidal activity against P. xylostella is better than other alkyl groups, heterocyclic or aromatic
ring groups (9a > 9b or 9c, 9a > 9d, 9a > 9e, 9a > 9f, 9a > 9g), and most of them had weak
insecticidal activity against S. frugiperda excepted 9e (which was heterocyclic, mortality rate,
60.66%). Based on the structure 9g, different substituents were introduced into phenyl ring
(
9h−9r), when electron-donating groups -CH , -NH , electron-withdrawing groups -CF , were
3
2
3
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introduced into the phenyl ring, compounds 9j, 9l and 9r showed higher insecticidal activity
against P. xylostella than others. When the electron-withdrawing groups was on the phenyl ring,
the insecticidal activity against S. frugiperda is better than that of electron-donating groups and
-
CF , -F on the phenyl ring, compounds 9j, 9m, 9p and 9q showed higher insecticidal activity than
3
others. At last, in order to enrich the diversity of the structure, some heterocyclic fragment selected
from insecticides, acaricide, fungicides and natural products were introduced. Compare the
synthesized compounds (9b−9c, 9e, 9h−9i, 9k, 9m, 9r−9t), 9e and 9r bearing fragment from
tolfenpyrad and chlorantraniliprole showed higher activity against P. xylostella than 50% at the
concentration of 50 mg/L. In addition, compound 9e had more than 70% insecticidal activity
1
against S. frugiperda at 100 mg/L. Generally speaking, 4-CF at the position of R substituent
3
group linked with N-pyridylpyrazole via amide bond could enhance the insecticidal activity of the
target compounds.
Table 1. Insecticidal Activity of the Target Compounds against P. xylostella and S. frugiperda after
a
treatment 48 h
P. xylostella
S. frugiperda
100 mg/L mortality
rate (%)
compounds
200 mg/L mortality
50 mg/L mortality rate
(%)
rate (%)
8
8
9
9
a
b
a
b
90.03 ± 1.97
51.26 ± 5.53
94.19 ± 5.04
12.22 ± 3.85
55.91 ± 2.26
59.85 ± 6.20
82.32 ± 0.87
42.37 ± 2.80
93.94 ± 10.50
76.86 ± 7.08
0.00 ± 0.00
58.59 ± 6.96
10.94 ± 3.87
60.66 ± 2.71
0.00 ± 0.00
0.00 ± 0.00
11.61 ± 5.69
56.06 ± 6.94
9.14 ± 0.83
50.00 ± 4.55
20.42 ± 2.47
0.00 ± 0.00
72.59 ± 4.49
0.00 ± 0.00
57.88 ± 7.06
29.35 ± 1.84
0.00 ± 0.00
50.23 ± 4.20
3.33 ± 5.77
0.00 ± 0.00
6.11 ± 5.36
9
c
9d
18.46 ± 2.66
60.66 ± 2.71
27.88 ± 8.20
0.00 ± 0.00
0.00 ± 0.00
3.03 ± 5.25
66.07 ± 4.26
22.42 ± 4.20
11.79 ± 3.11
57.63 ± 2.80
9
e
9
f
9
9
g
h
9
i
9
j
86.30 ± 5.48
9.70 ± 10.01
91.38 ± 9.13
78.18 ± 4.81
9k
9
l
9m
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P. xylostella
S. frugiperda
100 mg/L mortality
rate (%)
compounds
200 mg/L mortality
50 mg/L mortality rate
(%)
rate (%)
9
9
9
9
n
o
p
q
85.56 ± 3.85
47.22 ± 4.81
69.70 ± 5.25
75.15 ± 4.20
93.64 ± 5.53
34.24 ± 3.67
40.61 ± 4.58
100 ± 0.00
29.44 ± 4.19
0.00 ± 0.00
12.12 ± 5.25
34.24 ± 3.67
65.56 ± 5.09
3.33 ± 5.77
0.00 ± 0.00
96.67 ± 5.77
48.72 ± 2.22
45.15 ± 5.01
66.51 ± 2.80
73.99 ± 5.49
33.59 ± 5.56
25.76 ± 5.17
18.89 ± 1.92
90.56 ± 0.96
9
r
9
s
9
t
Chlorantraniliprole
a
Corrected mortality rate (mean ± SD, %), SD (Standard Deviation)
Table 2. LC values of the Target Compounds against Third−Instar Larvae of P. xylostella
50
after treatment 48 h
a
Compounds
LC (mg/L)
Regression equation
Y=2.1331 + 1.7412X
Y=2.4325 + 1.6901X
Y=2.4937 + 1.5026X
Y=3.4085 + 1.1837X
Y=2.4309 + 1.6096X
Y=2.7836 + 1.4878X
Y=4.3807 + 1.7427X
r
95% CI (mg/L)
33.11 ~ 59.30
23.83 ~ 45.83
33.53 ~ 64.26
12.83 ~ 38.09
28.67 ~ 54.30
21.21 ~ 44.96
1.66 ~ 3.09
50
8
9
a
a
44.31
33.05
46.56
22.11
39.46
30.88
2.27
0.9898
0.9840
0.9968
0.9933
0.9846
0.9930
0.9721
9e
9j
9l
9r
Chlorantraniliprole
a
CI: 95% confidence interval.
4
CONCLUSION
In conclusion, a series of N-pyridylpyrazolo-5-methyl amines and its derivatives were designed
and synthesized. Bioassays indicated thae some of the target compounds exhibited moderate
insecticidal activities against P. xylostella and S. frugiperda. Especially, compound 9j revealed the
best insecticidal activity against P. xylostella, with a LC50 value of 22.11 mg/L. Our results
provided a practical tool for guiding the design and synthesis of N-pyridylpyrazolo-5-methyl
amines and its derivatives.
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ACKNOWLEDGEMENTS
This work was supported by the National Key Research and Development Program of China
(Grant No. 2018YFD0200300) and National Natural Science Foundation of China (Grant No.
31701826).
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SUPPORTING INFORMATION
Supporting information (which contain information on the synthesis, physical data and
insecticidal activity test methods of the target compounds) associated with the article can be found
in the online version at the end of the article.
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