Novel chlorantraniliprole derivatives as potential insecticides and probe to chlorantraniliprole binding site on ryanodine receptor

Article abstract of DOI:10.1016/j.bmcl.2014.02.053

The lepidopteran pests such as diamondback moth are the regularly harmful pests of crops in the world, which brings enormous losses in crop production. Chlorantraniliprole is an anthranilic diamide insecticide registered for the control of lepidopteran pests with high insecticidal activity, however with uncertain binding site action target of chlorantraniliprole on ryanodine receptor, a series of new chlorantraniliprole derivatives were synthesized and the insecticidal activities of these compounds against diamondback moth were evaluated with chlorantraniliprole and indoxacarb as control. All compounds except 8h, 8p and 8t exhibited varying degree of activities against diamondback moth. Especially, compounds 8c, 8i, 8k and 8l displayed good insecticidal activities against diamondback moth and the activities are even better than that of indoxacarb during 72 h period. The K_i values of all synthesized compounds were calculated through autodocking program respectively. The relationship between calculation value of molecular docking and results of insecticidal activities indicated that the proposed specific receptor, the membrane-spanning domain protein of diamondback moth ryanodine receptor in our study might have chlorantraniliprole binding sites.

Full text of DOI:10.1016/j.bmcl.2014.02.053

Bioorganic & Medicinal Chemistry Letters 24 (2014) 1987–1992
Contents lists available at ScienceDirect
Bioorganic & Medicinal Chemistry Letters
journal homepage: www.elsevier.com/locate/bmcl
Novel chlorantraniliprole derivatives as potential insecticides
and probe to chlorantraniliprole binding site on ryanodine receptor
Min Luo a, Qichao Chen a, Jin Wang a, Changyan Hu a, Jing Lu b, Xiaomin Luo b, Dequn Sun a,
⇑
a Marine College, Shandong University at Weihai, No. 180, Wenhua West Road, Weihai 264209, PR China
b Shanghai Institute of Materia Medica, Chinese Academy of Sciences, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The lepidopteran pests such as diamondback moth are the regularly harmful pests of crops in the world,
which brings enormous losses in crop production. Chlorantraniliprole is an anthranilic diamide insecti-
cide registered for the control of lepidopteran pests with high insecticidal activity, however with uncer-
Received 16 September 2013
Revised 5 February 2014
Accepted 19 February 2014
Available online 3 March 2014
tain binding site action target of chlorantraniliprole on ryanodine receptor,
a series of new
chlorantraniliprole derivatives were synthesized and the insecticidal activities of these compounds
against diamondback moth were evaluated with chlorantraniliprole and indoxacarb as control. All com-
pounds except 8h, 8p and 8t exhibited varying degree of activities against diamondback moth. Especially,
compounds 8c, 8i, 8k and 8l displayed good insecticidal activities against diamondback moth and the
activities are even better than that of indoxacarb during 72 h period. The Ki values of all synthesized com-
pounds were calculated through autodocking program respectively. The relationship between calculation
value of molecular docking and results of insecticidal activities indicated that the proposed specific
receptor, the membrane-spanning domain protein of diamondback moth ryanodine receptor in our study
might have chlorantraniliprole binding sites.
Keywords:
Chlorantraniliprole derivatives
Insecticidal activities
Molecular docking
Ryanodine receptor
Binding site
Ó 2014 Elsevier Ltd. All rights reserved.
The diamondback moth is the harmful pest of crops in the
world. They have become the difficult pests to control because of
their resistance to various types of traditional insecticides, thus
bringing about enormous losses in crop production.1–3 Recently
two classes of synthetic chemicals, the phthalic diamides (fluben-
diamide4–9 Fig. 1) and the anthranilic diamides (chlorantranilipro-
le10,11 and cyantraniliprole,12 Fig. 1) emerge resulting in
commercial insecticides that target insect ryanodine receptors.13,14
They have exceptional insecticidal activities on a range of Lepidop-
teran pests and other orders, such as Coleoptera, Diptera, Isoptera
and Hemiptera. Especially, chlorantraniliprole, the first anthranilic
diamide insecticide registered for the control of lepidopteran pests
has high selectivity, which accounts for its low mammalian toxicity
and favorable environmental profile. It acts by activating the insect
ryanodine receptor (Fig. 2), which is a non-voltage-gated calcium
channel to affect calcium release from intracellular stores by lock-
ing channels in a partially opened state, an assignment based on
electrophysiological and Ca2+-release studies.15,16 Therefore, chlo-
rantraniliprole analogues have attracted considerable research
attention and the ryanodine receptor has been regarded as one of
the targets for novel insecticide discovery.
In the previous study,17–21 several modifications around chlo-
rantraniliprole skeleton have demonstrated the discovery of novel
insecticides and showed high insecticidal activities. Most modifica-
tions focused on three parts: the pyrazole moiety (Fig. 3A), amide
moiety (Fig. 3B), anthraniloyl moiety (Fig. 3C). Zheng-ming Li re-
search group17 reported several derivatives with good insecticidal
activities after modification of the pyrazole moiety. Yang S. group18
synthesized several derivatives containing hydrazone structures.
The studies22–25 found that amide group is a highly efficient and
key pharmacophore used widely in insecticides design. Anthranil-
oyl moiety is modified by incorporation of cyan group instead of
chlorine group since cyan group sometimes can affects bioactivi-
ties considerably.26–28 However, all these studies focusing on the
synthesis and activity study of chlorantraniliprole derivatives
hadn’t explored the chlorantraniliprole binding site(s) on molecu-
lar level and the exact chlorantraniliprole binding site(s) on insect
ryanodine receptor have not been confirmed and are still unclear.
Such situation impedes the rational design of potential leading
compounds.
Nauen and co-workers29 reported that a point mutation in
C-terminal membrane-spanning domain of some the ryanodine
receptor led to give a glycine with a glutamic acid substitution
(G4946E) and suggested that this single amino acid substitution
is associated with the diamide insecticides resistance. Lei Guo
⇑
Corresponding author. Tel.: +86 631 5688537; fax: +86 631 5688303.
E-mail address: dequn.sun@sdu.edu.cn (D. Sun).
http://dx.doi.org/10.1016/j.bmcl.2014.02.053
0960-894X/Ó 2014 Elsevier Ltd. All rights reserved.

1988
M. Luo et al. / Bioorg. Med. Chem. Lett. 24 (2014) 1987–1992
CF3
CF3
O
Br
N
Br
N
F
H
N
H
N
O
O
N
H
O
H
N
H
N
N
N
Cl
Cl
I
HN
O
O
N
N
S
O
Cl
NC
O
Flubendiamide
Chlorantraniliprole
Cyantraniliprole
Figure 1. Insecticides acting on the insect ryanodine receptor.
compounds 8a–8t, chlorantraniliprole and indoxacarb were tested
by the leaf dip method.34 All compounds except 8h, 8p and 8t
exhibited varying degree of activity against diamondback moth
at the concentration of 4 mg/L. Especially, compounds 8c, 8i, 8k
and 8l exhibited similar insecticidal activities with chlorantranili-
prole and indoxacarb at the concentration of 4 mg/L after 120 h.
While at the concentration of 2 mg/L and 1 mg/L, they still showed
low to middle activities after 120 h (Table 1).
LC50 values (Table 2) of compounds 8c, 8i, 8k and 8l (6.882,
2.599, 2.835 and 2.393 mg/L respectively) were much lower than
that of indoxacarb (11.187 mg/L) after 72 h, which means that
the four compounds could be the better fast-acting insecticide than
indoxacarb. After 96 h and 120 h, compound 8l still has similar
LC50 value with that of indoxacarb. The LC50 values of compounds
8i, 8k and 8l were about double of that of chlorantraniliprole dur-
ing different action periods. However, LC50 value of compound 8c
decreased dramaticlly from 6.882 to 1.833 mg/L when action per-
iod changed from 72 to 120 h.
The preliminary structure–activity relationship (SAR) was dis-
cussed. All compounds with cyano group (R2 = CN) instead of chlo-
ride group in the anthraniloyl moiety commonly had very low
insecticidal activities. For example, compounds 8o, 8p, 8q, 8r, 8s
and 8t (Table 1) had activities less than 25%.
Most of researches preserve the anthranilic amide moiety, which
indicated that this structure is a key pharmacophore in this kind of
compounds.35 The number of methylenes group in amide moiety
was an important factor for insecticidal activities and two methyl-
enes group is the most favour for high activity (Table 3). For exam-
ple, compounds 8c, 8i, 8k, 8l and 8n (n = 2) had activities
approximately 90–97%, while compounds 8e, 8g and 8h (n = 3 or
4) showed much lower insecticidal activities. Obviously, when R4
and R5 have the same substitution groups, for example, 8c/8e
(R4 = R5 = methyl group), 8d/8g/8h (R4 = R5 = ethyl group), the
insecticidal activities reduced dramatically when number of meth-
ylenes group changed from 2 to 3 and 4. Besides the number of
methylenes group, the substitution of R4 or R5 at the tail of amide
moiety is also the important element for insecticidal activities.
When one of the R4 or R5 was substituted by hydrogen, all com-
pounds, such as 8j, 8k, 8l and 8n displayed relatively high activities,
which indicated that secondary amine at the tail of the amide moi-
ety was a necessary pharmacophore of insecticidal activity. While,
both R4 and R5 were substituted by alkyl groups to generate tertiary
amine at end of amide moiety, most of compounds (8d, 8e, 8g and
8h) except 8i with high activity displayed relatively lower activities.
It indicated that the number of methylenes may be the main reason
for influencing insecticidal activities. And more compounds with
high activities could be designed based on the number of methyl-
enes and the substitution condition in the terminal of amide moiety.
We hypothesized that the membrane-spanning domain protein
of the ryanodine receptor has the binding site(s), and it might be
the scpecific receptor for chlorantraniliprole. In our study, two
second amino acid sequences of the membrane-spanning domain
Figure 2. Schematic representation of the ryanodine receptor and the important
associated proteins.
R1
B
H
N
A
O
R3
R2
H
N
N
N
Cl
O
N
C
Figure 3. Chemical structures of anthranilic diamides.
et al.30 revealed that the G4946E mutation was strongly associated
with the chlorantraniliprole resistance in Plutella xylostella, and
reduced binding affinity of PxRyR to the chlorantraniliprole
through the analysis of Kd values. Therefore, we hypothesized
and proposed that the membrane-spanning domain protein of
the ryanodine receptor, a tetramer of four identical subunits, which
regulates flow of calcium ions, might have the scpecific binding
site for chlorantraniliprole. In this work, we choosed the mem-
brane-spanning domain protein as the possible acceptor for study.
Through studying the relationship between the Ki values of molec-
ular docking and results of insecticidal activities, we wanted to
provid some experimental envidence for the scpecific binding site
for chlorantraniliprole.
Starting from 2,3-dichloropyridine (Scheme 1), the important
intermediate 7 was obtained in six steps by the similar methods
in literature.11,31–33 Compounds 8a–8t were conveniently obtained
by treatment of 7 with different amines without any other catalyst
(or strong base) in room temperature. It was found that both tetra-
hydrofuran and dichloromethane were suitable solvents for most
of reactions, except that acetone was needed for preparation of
compound 8m due to its good solubility in acetone.
Compounds were tested against Diamondback Moth under
standard laboratory procedures. The insecticidal activities of

M. Luo et al. / Bioorg. Med. Chem. Lett. 24 (2014) 1987–1992
1989
OH
O
N
NH2
N
HN
N
80%NH2NH2.H2O
EtOH, reflux
NaOEt, EtOH
reflux
POCl3 or POBr3
MeCN
Cl
Cl
Cl
Cl
EtO
N
N
NH2
2
1
R1
R1
R1
R2
COOH
6
O
O
O
N
N
N
6a: R2=Cl
N
N
N
5
6b: R2=CN
NaOH, MeOH
H2SO4, K2S2O8
Cl
Cl
Cl
EtO
EtO
HO
N
N
N
MeSO2Cl, Et3N,
MeCN, 0-5 °C
3
4
3a: R1=Cl
3b: R1=Br
5a: R1=Cl
5b: R1=Br
4a: R1=Cl
4b: R1=Br
R1
N
H
R1
O
N
R3
R2
H
N
N
N
R3NH2
N
N
Cl
O
Cl
R2
O
N
N
O
8
7
8a: R1=Cl, R2=Cl or CN
8b: R1=Br, R2=Cl or CN
7a: R1=Cl, R2=Cl or CN
7b: R1=Br, R2=Cl or CN
8k: R1=Br, R2=Cl, R3=
8l: R1=Br, R2=Cl, R3=
N
H
N
8a: R1=Cl, R2=Cl, R3=
N
8b: R1=Br, R2=Cl, R3=
N
H
HO
8c: R1=Br, R2=Cl, R3=
8d: R1=Br, R2=Cl, R3=
8m: R1=Br, R2=Cl, R3=
8n: R1=Br, R2=Cl, R3=
8o: R1=Br, R2=CN, R3=
8p: R1=Br, R2=CN, R3=
8q: R1=Br, R2=CN, R3=
8r: R1=Br, R2=CN, R3=
8s: R1=Br, R2=CN, R3=
N
H
N
N
N
H
N
8e: R1=Br, R2=Cl, R3=
8f: R1=Br, R2=Cl, R3=
8g: R1=Br, R2=Cl, R3=
8h: R1=Br, R2=Cl, R3=
N
N
N
N
N
N
N
8i: R1=Br, R2=Cl, R3=
8j: R1=Br, R2=Cl, R3=
N
H
N
8t: R1=Br, R2=CN, R3=
N
H
N
Scheme 1. General synthetic route for the title compound 8.
protein of diamondback moth ryanodine receptor were selected
from GenBank accession no.JN80102836 and GenBank accession
no.JF92778837 as two possible specific recepotors, which were pro-
posed to bind with a series of small active moleculars to calculate
Ki value through autodock software. The Ki values were used to
evaluate the binding energy between small molecule and the pos-
sible receptor. The analysis of the relationship between Ki and
insecticidal activities of compounds could afford the information
of specific recepotor.
In Table 4, entry 1, seven compounds (8d, 8m, 8a, 8t, 8n, 8c and
8b) except 8t with Ki values exhibited moderate to high insecti-
cidal activities against diamondback moth. The other thirteen com-
pounds could not afford Ki values. Eight of them showed no to low
activities, however, five of them (8g, 8i, 8j, 8k and 8l) exhibited
moderate to high insecticidal activities. The changes of Ki values
and insecticidal activities show no reasonable rhythmicity. While
in Table4, entry 2, eleven compounds (8h, 8j, 8f, 8b, 8g, 8d, 8p,
8i, 8n, 8k and 8c) with Ki values except three of them (8h, 8f
and 8p) exhibited from moderate to high activities against dia-
mondback moth. The other nine compounds (8a, 8e, 8l, 8m, 8o,
8q, 8r, 8s and 8t) with unavailable Ki values except three of them
(8a, 8l and 8m) displayed very low biological activities. This result
could imply that the selected membrane-spanning domain protein
of the diamondback moth ryanodine receptor might have specific
binding site(s) for the chlorantraniliprole (Fig. 4) and its deriva-
tives. This point is worth further studying. However, the docking

1990
M. Luo et al. / Bioorg. Med. Chem. Lett. 24 (2014) 1987–1992
Table 1
Insecticidal activities of compounds 8a–8t, chlorantraniliprole and indoxacarb against diamondback moth
Insecticidal activities (%) at different concentrations
2 mg/L
96
Concentrations
4 mg/L
96
1 mg/L
96
Time (h)
72
120
72
120
72
120
Compounds
8a
8b
8c
8d
8e
8f
51.58
74.44
29.91
57.91
18.76
2.78
60.92
88.89
54.62
60.84
23.92
2.78
68.61
88.89
94.87
65.97
32.11
8.89
6.67
43.33
50
3.03
9.7
16.06
8g
8h
28.79
0
46.67
0
56.67
0
8i
8j
8k
8l
8m
8n
8o
8p
74.55
63.32
77.58
81.72
50.25
47.22
8.33
86.67
75.91
90.61
87.53
64.91
83.33
11.67
0
96.97
78.94
90.61
94.44
82.58
88.89
13.33
0
35.03
49.13
60.1
6.36
12.73
22.73
23.33
41.11
40
65.93
43.33
70
0
3.03
10
20
19.09
36.67
0
8q
8r
8s
8t
6.67
8.33
12.42
0
16.67
8.33
15.21
0
24.17
14.14
21.26
5.59
Chlorantraniliprole
Indoxacarb
94.84
16.85
97.22
87.31
100
97.22
53.89
14.52
80.34
58.39
82.91
79.88
32.12
0
52.12
24.24
68.18
45.45
insecticidal activities and compounds 8a, 8l and 8m with unavail-
able Ki values showed relatively good activities.
Table 2
LC50 Values of Compounds 8c, 8i, 8k, 8l, chlorantraniliprole and indoxacarb
In summary, a series of novel chlorantraniliprole derivatives
containing different amide groups and anthraniloyl moiety were
designed and synthesized. The insecticidal activities of the com-
pounds against diamondback moth were evaluated. The results
indicated that compounds except compounds 8h, 8p and 8t exhib-
ited favorable insecticidal activities against diamondback moth.
Especially, compounds 8c, 8i, 8k and 8l dispayed high insecticidal
activities. The preliminary structure–activity relationship of the ti-
tle compounds indicated that compounds with cyano group
(R2 = CN) had low insecticidal activities. The two methylenes
groups and secondary amine in the amide moiety were necessary
factors for increasing insecticidal activities. Furthermore, the
molecular docking result revealed that most of the compounds
with available Ki values exhibited moderate to high activities
against diamondback moth and this relationship between Ki value
a
b
c
Compounds
LC50
LC50
LC50
8c
8i
8k
8l
6.882
2.599
2.835
2.393
1.546
11.187
3.108
2.022
2.124
1.672
0.979
1.698
1.833
1.598
1.937
1.308
0.723
1.092
Chlorantraniliprole
Indoxacarb
a
b
c
72 h.
96 h.
120 h.
software program could affect the accuracy of Ki values, mean-
while, biological diversity of pests played an important role in
experimental activities test. These coefficients could explain why
compounds 8h, 8f and 8p with certain Ki values had low
Table 3
SAR study of several chlorantraniliprole derivatives
R4
H
N
O
R1
N
R5
n
H
N
N
N
Cl
O
R2
N
Compound
The number of methylenes (n)
R4
R5
Insecticidal activities (%) at the concentration of 4 mg/L during 120 h
8c
8e
8d
8g
8h
8i
8j
8k
8l
2
3
2
3
4
2
2
2
2
2
CH3
CH3
CH3
CH3
CH3CH2
CH3CH2
CH3CH2
94.87
32.11
65.97
56.67
0
96.97
78.94
90.61
94.44
88.89
CH3CH2
CH3CH2
CH3CH2
(CH3)2CH
CH3CH2
CH3CH2CH2
(CH3)2CH
CH3
(CH3)2CH
H
H
H
H
8n

M. Luo et al. / Bioorg. Med. Chem. Lett. 24 (2014) 1987–1992
1991
Table 4
Ki values and insecticidal activities against diamondback moth
Entry 1 (compd)
Kia
Insecticidal activitiesc (%)
Entry 2 (compd)
Kib
Insecticidal activitiesc (%)
8d
8m
8a
8t
8n
8c
8b
Controld
8e
5.29 nM
8.87 nM
9.96 nM
68.77 nM
387.88 nM
7.48 mM
8.44 mM
65.97
82.58
68.61
5.59
88.89
94.87
88.89
100
32.11
8.89
56.67
0
96.97
78.94
90.61
94.44
13.33
0
24.17
14.14
21.26
8h
8j
8f
3.64 nM
5.98 nM
8.25 nM
14.4 nM
0
78.94
8.89
88.89
56.67
65.97
0
96.97
88.89
90.61
94.87
100
68.61
32.11
94.44
82.58
13.33
24.17
14.14
21.26
5.59
8b
8g
8d
8p
8i
8n
8k
8c
15.16 nM
17.68 nM
17.85 nM
28.27 nM
64.92 nM
99.57 nM
93.86 nM
50.12 nM
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
50.12 nM
Unavailablee
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
8f
8g
8h
8i
8j
8k
8l
8o
8p
8q
8r
Controld
8a
8e
8l
8m
8o
8q
8r
8s
8t
8s
a
b
c
Ki values (receptor selected from GenBank accession no.JN801028).
Ki values (receptor selected from GenBank accession no. JF927788).
The activity was determined at the concentration of 4 mg/L during 120 h.
Chlorantraniliprole.
d
e
Unavailable: compounds couldn’t interact with the selected receptor and Ki values couldn’t be calculated.
(a)
(b)
Figure 4. (a) Interaction of chlorantraniliprole with the transmembrance region protein of the diamondback moth ryanodine receptor (receptor selected from GenBank
accession no. JF927788); (b) Zoomed-in view of the interaction between chlorantraniliprole and amino acids from the active site of the transmembrance region protein.
of molecular docking and insecticidal activities suggested that the
proposed membrane-spanning domain protein of the diamond-
back moth ryanodine receptor might have the special binding
site(s), which is worth of further studying.
References and notes
1. Sayyed, A. H.; Omar, D.; Wright, D. J. Pest Manag. Sci. 2004, 60, 827.
2. Sarfraz, M.; Keddie, B. A. J. Appl. Entomol. 2005, 129, 149.
3. Cao, G.; Han, Z. J. Pest Manag. Sci. 2006, 62, 746.
4. Tohnishi, M.; Nakao, H.; Kohno, E.; Nishida, T.; Furuya, T.; Shimizu, T.; Seo, A.;
Sakata, K.; Fujioka, S.; U. S. Patent 6,559,341, 2003.
5. Tohnishi, M.; Nakao, H.; Furuya, T.; Seo, A.; Kodama, H.; Tsubata, K. Pesticide
Chemistry: Crop Protection, Public Health, Environmental Safety; Wiley-VCH,
2007. Chapter 13.
6. Masaki, T.; Yasokawa, N.; Fujioka, S.; Motoba, K.; Tohnishi, M.; Hirooka, T. J.
Pest. Sci. 2009, 34, 37.
7. Masaki, T. J. Pest. Sci. 2008, 33, 271.
Acknowledgments
We thank Prof. Zhengming LI from Nankai University for the
great help in insecticidal activities study and the generous sugges-
tions for our work. The project was supported by the National
High-Tech Program of China (863 Project No. 2012AA020306).
8. Masali, T.; Yasokawa, N.; Tohnishi, M.; Nishimatsu, T.; Tsubata, K.; Inoue, K.;
Motoba, K.; Hirooka, T. Mol. Pharmacol. 2006, 69, 1733.
9. Sattelle, D. B.; Cordova, D.; Cheek, T. R. Invert. Neurosci. 2008, 8, 107.
10. Lahm, G. P.; Cordova, D.; Barry, J. D. Bioorg. Med. Chem. 2009, 17, 4127.
11. Lahm, G. P.; Selby, T. P.; Freudenberger, J. H.; Stevenson, T. M.; Myers, B. J.;
Seburyamo, G.; Smith, B. K.; Flexner, L.; Clark, C. E.; Cordova, D. Bioorg. Med.
Chem. Lett. 2005, 15, 4898.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.bmcl.2014.02.
053.
12. Hughes, K. A.; Lahm, G. P.; Selby, T. P.; Stevenson, T. M. WO 2004/067528, 2004.
13. Isaacs, A. K.; Qi, S. Z.; Sarpong, R.; Casida, J. E. Chem. Res. Toxicol. 2012, 25, 1571.

1992
M. Luo et al. / Bioorg. Med. Chem. Lett. 24 (2014) 1987–1992
14. Lahm, G. P.; Stevenson, T. M.; Selby, T. P.; Freudenberger, J. H.; Cordova, D.;
Flexner, L.; Bellin, C. A.; Dubas, C. M.; Smith, B. K.; Hughes, K. A.; Hollingshaus,
J. G.; Clark, C. E.; Benner, E. A. Bioorg. Med. Chem. Lett. 2007, 17, 6274.
15. Li, Y. X.; Mao, M. Z.; Li, Y. M.; Xiong, L. X.; Li, Z. M.; Xu, J. Y. Physiol. Entomol.
2011, 36, 230.
26. Hughes, K. A.; Lahm, G. P.; Selby, T. P.; Stevenson, T. M. WO2004/067528, 2004.
27. Annan, I. B.; Hughes, K. A.; Lahm, G. P.; Selby, T. P.; Stevenson, T. M. WO2006/
068669, 2006.
28. Schwarz, T.; Snow, T. A.; Santee, C. J.; Mulligan, C. C.; Class, T.; Wadsley, M. P.;
Nanita, S. C. J. Agric. Food Chem. 2011, 59, 814.
16. Cordova, D.; Benner, E. A.; Sacher, M. D.; Rauh, J. J.; Sopa, J. S.; Lahm, G. P.;
Selby, T. P.; Stevenson, T. M.; Flexner, L.; Gutteridge, S.; Rhoades, D. F.; Wu, L.;
Smith, R. M.; Tao, Y. Pestic. Biochem. Physiol. 2006, 84, 196.
17. Feng, Q.; Liu, Z. L.; Xiong, L. X.; Wang, M. Z.; Li, Y. Q.; Li, Z. M. J. Agric. Food.
Chem. 2010, 58, 12327.
29. Troczka, B.; Zimmer, C. T.; Elias, J.; Schorn, C.; Bass, C.; Davies, T. G. E.; Field, L.
M.; Williamson, M. S.; Slater, R.; Nauen, R. Insect Biochem. Mol. Biol. 2012, 42,
837.
30. Guo, L.; Wang, Y.; Zhou, X.; Li, Z.; Liu, S.; Liang Peia, L.; Gaoa, X. Pest Manag. Sci.
2013. doi: 10.1002/ps.3651.
18. Wu, J.; Song, B. A.; Hu, D. Y.; Yue, M.; Yang, S. Pest Manag. Sci. 2012, 68, 801.
19. Jeanguenat. A.; O’sullivan, A. C. WO 2006/061200, 2006.
20. Dong, W. L.; Xu, J. Y.; Xiong, L. X.; Liu, X. H.; Li, Z. M. Chin. J. Chem. 2009, 27, 579.
21. Bruce, L. F.; Stephen, F. M. WO2007/024833, 2007.
31. Lahm, G. P.; Mccann, S. F. WO03/015518, 2003.
32. Berger, R. A.; Flexner, J. L. WO03/024222, 2003.
33. Liu, C. L.; Chai, B. S.; Guang, A. Y.; Zhang, H.; Peng, Y. W.; Wang, J. F.; Li, H. C.; Li,
Z. N. WO2008/134970, 2008.
22. Gnamm, C.; Jeanguenat, A.; Dutton, A. C.; Grimm, C.; Kloer, D. P.; Crossthwaite,
A. J. Bioorg. Med. Chem. Lett. 2012, 22, 3800.
34. Zhao, Q. Q.; Li, Y. Q.; Xiong, L. X.; Wang, Q. M. J. Agric. Food Chem. 2010, 58,
4992.
23. Zhao, Y.; Zhao, L. P.; Tong, J.; Li, Y. Q.; Xiong, L. Y.; Li, F.; Peng, L. N.; Li, Z. M. Mol.
Diversity 2012, 16, 711.
35. Hall, R.G.; Loiseleur, O.; Pabba, J.; Pal, S.; Jeanguenat, A.; Edmunds, A.; Stoller, A.
U.S. Patent 8,399,490, 2013.
24. Ou, J. J.; Zhu, S. K.; Wang, L.; Xu, C.; Liu, F.; Ren, L.; Xu, X.; Wang, Y.; Rui, C. H.;
Liu, S. Z. J. Agric. Food Chem. 2012, 60, 10942.
36. Wang, X. L.; Wu, S. W.; Yang, Y. H.; Wu, Y. D. Pestic. Biochem. Physiol. 2012, 102,
204.
25. Jeanguenat, A. Pest Manag. Sci. 2013, 69, 7.
37. Sun, L.; Rui, C. H.; Yuan, H. Z. Plant Prot. 2012, 38, 118.