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Y.-B. Chen et al. / Chinese Chemical Letters 24 (2013) 673–676
proposed that compound 1 was prepared via self-condensation of
2-amino-6-bromobenzoic acid, and then coupled with methyl-
amine. With the key intermediate 1 in hand, conversion of 1–2 was
then carried out with thiobenzyl alcohol in the DMF using K2CO3 as
acid acceptor. Fortunately, owing to the electronic effect of
aromatic substitutes, the amino group deactivated the bromo
group in the same aromatic ring, so that compound 2 was the
major product with the yield of 65%, which was further convinced
by comparing 1H NMR data of compound 1 and 2 (see Supporting
information). Various carboxylic acids were treated with thionyl
chrolide and then coupled with intermediate 2 in the presence of
DIPEA to provide the title compounds of amide 3a–w in moderate
to good yields. By oxidation of the compound 3b with MCPBA,
compound 4a could be easily prepared in high yields.
compounds exhibited excellent insecticidal activities against T.
cinnabarinus, which showed some differences in activities com-
pared with anthranilic diamides analogs. Further studies on the
structural optimizations and the special activities of the title
compounds are in progress.
Acknowledgments
This work was financial supported by National Basic Research
Program of China (973 Program, No. 2010CB126100), National
High Technology Research and Development Program of China
(863 Program, No. 2011AA10A207). This work was also partly
supported by National Key Technology R&D Program of China (No.
2011BAE06B01).
3.2. Insecticidal activities
Appendix A. Supplementary data
To evaluate the overall insecticidal activities of anthranilic
diamides with benzyl sulfide, two representative insects from two
different orders (Lepidoptera and Acarina) were selected as the
target pest. The testing results against two insects were listed in
Table 1. For comparative purposes, avermectins as control was also
tested under the same conditions.
Supplementary data associated with this article can be found, in
References
Insecticidal test for armyworm (M. sepatara): The larvicidal
activity against armyworm was summarized in Table 1. The title
compounds 3a–3e exhibited 100% mortality against armyworm at
500 mg/L; the other compounds 3f–3i and 3u–3w showed
moderate to high activities, and had 50 %–90 % mortality at
500 mg/L. This suggested that activities varied significantly
depending on the types and patterns of the substituents. When
R was substituted by F, Cl, Br, OCF3, OCH3, CN and NO2 in the
benzene ring and heterocycle, most of compounds showed
activities except for introduction of CF3 and I group. Replacement
of substituents in the benzene ring with acetyl unit, compound 3o
was inactive against armyworm. Unexpectedly, the oxidated
compound 4a originated from 3b lost the activities against
armyworm, which gave us some hints to stop further modifications
on the sulfur into the sulfoxide. The results showed that most of the
title compounds without the N-pyridylpyrazole moiety still
exhibited insecticidal activities against armyworm, which implied
a new molecular design to obtain active compounds against
armyworm.
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3c, 3j, 3k, 3l, 3m and 3t displayed excellent insecticidal activities
against T. cinnabarinus (Table 1) and had >80% mortality at the
concentration of 500 mg/L. Moreover, when the test concentration
was lowered to 100 mg/L, the activity of compound 3a, 3j and 3s
was 60%, 10% and 10%, respectively. It was concluded that the
substituted benzene ring was favorable for activities compared
with heterocycle and acetyl unit. The bioassay results suggested
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4. Conclusion
In conclusion, a series of novel anthranilic diamides derivatives,
which altered N-pyridylpyrazole moiety and endowed with benzyl
sulfide scaffold, were designed and synthesized in this study.
The insecticidal activities of the title compounds against army-
worm (M. sepatara) at 500 mg/L were evaluated; activities were
significantly influenced by the substituents. In particular, the
preliminary bioassays indicated that one-third of the synthesized