Synthesis and insecticidal evaluation of novel N- pyridylpyrazolecarboxamides containing different substituents in the ortho-position

Article abstract of DOI:10.1002/cjoc.201180295

In order to look for novel insecticides containing N-pyridylpyrazole, ten novel pyrazolecarboxamides containing different ortho-substituents in the aniline part were synthesized, and their structures were characterized by ¹H NMR, ¹³C

Full text of DOI:10.1002/cjoc.201180295

FULL PAPER
Synthesis and Insecticidal Evaluation of Novel
N-Pyridylpyrazolecarboxamides Containing Different
Substituents in the ortho-Position
Feng, Qi(冯启)
Yu, Guanping(于观平)
Xiong, Lixia(熊丽霞)
Wang, Mingzhong(王明忠)
Li, Zhengming*(李正名)
State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, Nankai University,
Tianjin 300071, China
In order to look for novel insecticides containing N-pyridylpyrazole, ten novel pyrazolecarboxamides containing
different ortho-substituents in the aniline part were synthesized, and their structures were characterized by 1H NMR,
13C NMR and HRMS. The single crystal structure of 10b was determined by X-ray diffraction. Their evaluated in-
secticidal activity against oriental armyworm (Mythimna separata) indicated that all the compounds exhibited mod-
erate insecticidal activities.
Keywords insecticidal activity, N-pyridylpyrazole, pyrazolecarboxamide, ortho-substituents
Introduction
Since the introduction of chlorantraniliprole (Figure
1, A) as an insecticide for crop protection in recent
years,1 several anthranilic diamides insecticides have
been developed due to their high potency, low mam-
malian toxicity, broad insecticidal spectra, and new
mode of action.2,3 From their chemical structures, two
features are evident: one is the N-pyridylpyrazole moi-
ety, the other is the anthranilamide moiety. Previous
research indicated that some modification focused on
the anthranilamide while preserving the N-pyridyl-
pyrazole.4 However, the amides in the ortho-position
have been changed a lot in the reported patents, such as
heterocyclic groups,5,6 N-alkoxy amides,7 cyano-
containing amides,8 etc. Recently a novel pyrazolecar-
boxamide with thiadiazol group in the ortho-position
(Figure 1, B, JS 9117) was reported with high insecti-
cidal activity,9,10 indicating the ortho-position is still
attractive in further modification. In this article, novel
pyrazolecarboxamides containing different ortho-
substituents in the aniline part, including methylene
acohols, methylene amines, aldehydes, oximes and thi-
azolidines, were synthesized as shown in Scheme 1 and
their insecticidal activity against oriental armyworm
was tested accordingly.
Figure 1 Chemical structures of compounds A and B.
Bruker AV-400 spectrometer in CDCl3 or DMSO-d6
solution with tetramethylsilane as the internal standard,
High-resolution mass spectrometry (HRMS) data were
obtained on a Varian QFT-ESI instrument. The melting
points were determined on an X-4 binocular microscope
melting point apparatus (Beijing Tech Instruments Co.,
Beijing, China) and were uncorrected. Manganese di-
oxide (activated, tech.) was purchased from Alfa Aesar.
Reagents were all analytically pure. All solvents and
liquid reagents were dried by standard methods in ad-
vance and distilled before use. Chlorantraniliprole was
synthesized according to the literature11 and used as
control.
General procedure
The intermediate 3-bromo-1-(3-chloro-2-pyridyl)-
1H-pyrazole-5-caboxylic acid (4) was synthesized ac-
cording to procedure reported by Dong et al.11 The title
compounds were prepared as shown in Scheme 1.
Experimental
Materials and instruments
NMR spectra were recorded at 400 MHz using a
*
E-mail: nkzml@vip.163.com; Tel.: 0086-022-23505376; Fax: 0086-022-23505948
Received November 27, 2010; revised March 21, 2011; accepted April 12, 2011.
Project supported by the National Basic Research Program of China (No. 2010CB126106) and the National Natural Science Foundation of China
(No. 20872069)
Chin. J. Chem. 2011, 29, 1651— 1655
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Feng et al.
FULL PAPER
Scheme 1 General synthetic procedure of title compounds 5— 11
(2-Amino-5-chloro-3-methylphenyl) methanol (2)
The solution of compound 1 (60.0 mmol) in 20 mL of
THF was added dropwise to an ice-cold mixture of lith-
ium aluminium hydride (0.120 mol) in 60 mL of THF
with the temperature maintained below 5 ℃ throughout.
After stirring at 5 ℃ for 3 h, 60 mL of 5% sodium hy-
droxide solution was added to quench the reaction. The
resulting mixture was extracted with ethyl acetate (40
mL×3). The combined extracts were washed with brine,
dried with anhydrous sodium sulfate and evaporated to
give the title compound as a dust-color solid. Yield
97.0%, m.p. 83—85 ℃; 1H NMR (CDCl3, 400 MHz) δ:
7.02 (d, J＝2.4 Hz, 1H, Ar-H), 6.93 (d, J＝2.4 Hz, 1H,
Ar-H), 4.63 (s, 2H, Ar-CH2), 2.16 (s, 3H, Ar-CH3); 13C
NMR (CDCl3, 100 MHz) δ: 142.6, 129.9, 126.5, 125.5,
124.4, 121.9, 63.9, 17.2.
portion of manganese dioxide (2.0 mmol) was added
and the stirring was continued overnight. Silica gel (2.0
g) was added and the mixture was evaporated, the re-
sulting black powder was applied to flash chromatogra-
phy on silica gel with petroleum ether/ethyl acetate (4/1,
V/V) to give the title compound as a yellow solid. Yield
77.0%, m.p. 114—116 ℃; 1H NMR (CDCl3, 400 MHz)
δ: 9.81 (s, 1H, CHO), 7.35 (s, 1H, Ar-H), 7.21 (s, 1H,
Ar-H), 6.23 (br s, 2H, Ar-NH2), 2.16 (s, 3H, Ar-CH3);
13C NMR (CDCl3, 100 MHz) δ: 193.1, 147.0, 135.6,
132.2, 124.9, 120.3, 117.8, 16.5.
3-Bromo-N-(4-chloro-2-(hydroxymethyl)-6-meth-
ylphenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-
carboxamide (5) Carboxylic acid 4 (1.0 mmol) was
dissolved in 20 mL of dichloromethane under stirring;
oxalyl chloride (1.5 mmol) and a drop of DMF were
added successively. After stirring for 2 h at room tem-
perature, dichloromethane was removed in vacuum. The
residue was dissolved in 20 mL of dichloromethane, and
then added dropwise to an ice-cold solution of com-
pound 2 (1.0 mmol), pyridine (1.0 mmol) in 20 mL of
2-Amino-5-chloro-3-methylbenzaldehyde
(3)
Manganese dioxide (4.0 mmol) was added to a solution
of compound 2 (2.0 mmol) in 20 mL of dichloro-
methane in one portion. The resulting mixture was
stirred at room temperature for 6 h, then an additional
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Synthesis and Insecticidal Evaluation of Novel N-Pyridylpyrazolecarboxamides
The general synthetic procedure for the compounds
8a— 8d
dichloromethane. The mixture was stirred at room tem-
perature for 2 h before it was washed with 2 mol/L hy-
drochloric acid, saturated sodium bicarbonate solution
and brine successively. The organic layer was dried
with sodium sulfate and evaporated. The residue was
subjected to flash chromatography on silica gel with
petroleum ether/ethyl acetate (2/1, V/V) to give the title
compound as white solid. Yield 50.0%, m.p. 92—94 ℃;
1H NMR (CDCl3, 400 MHz) δ: 8.51 (s, 1H, CONH),
8.42 (dd, J＝1.4, 4.6 Hz, 1H, Ar-H), 7.87 (dd, J＝1.6,
8.0 Hz, 1H, Ar-H), 7.37 (dd, J＝4.4, 8.0 Hz, 1H, Ar-H),
7.15 (d, J＝2.0 Hz, 1H, Ar-H), 7.10 (d, J＝2.0 Hz, 1H,
Ar-H), 6.90 (s, 1H, Ar-H), 4.48 (s, 2H, Ar-CH2), 2.15 (s,
3H, Ar-CH3); 13C NMR (CDCl3, 100 MHz) δ: 156.1,
148.6, 146.8, 139.3, 139.1, 137.6, 137.3, 132.8, 131.8,
130.6, 128.9, 128.2, 126.8, 125.9, 110.4, 63.1, 18.＋5;
HRMS calcd for C17H13BrCl2N4O2Na ([M ＋ Na] )
476.9494, found 496.9491.
Alkylamine (0.60 mmol) was added to a solution of
compound 7 (0.60 mmol) in 20 mL ethanol. The result-
ing solution was stirred at room temperature for 2 h, and
then the solvent was evaporated. The residue was dis-
solved in methanol (20 mL), and sodium borohydride
(0.80 mmol) was added. The reaction was stirred for 2 h,
and then most of the solvent was evaporated. Ethyl ace-
tate (50 mL) was added to the residue, which was
washed with potassium carbonate solution (10%, 40 mL)
and brine successively. The resulting organic phase was
concentrated and subjected to flash chromatography on
silica gel with petroleum ether∶ethyl acetate (1∶1,
V/V) to give the title compounds 8a—8d.
3-Bromo-N-(4-chloro-2-methyl-6-((methylamino)-
methyl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-
5-carboxamide (8a) White solid, yield 50.2%, m.p.
1
2-(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-
5-carboxamido)-5-chloro-3-methylbenzyl acetate (6)
Acetyl chloride (0.52 mmol) was added dropwise to an
ice-cold solution of compound 5 (0.50 mmol) in 10 mL
of pyridine. After stirring for 2 h, 40 mL of water was
added to quench the reaction and the solution was ex-
tracted with ethyl acetate (40 mL×3). The extracts
were combined, washed with 2 mol/L hydrochloride
acid and brine, dried, then evaporated. The resulting
residue was applied to flash chromatography on silica
gel with petroleum ether/ethyl acetate (2/1, V/V) to give
the title compound as white solid. Yield 95.8%, m.p. 77
134—136 ℃; H NMR (CDCl3, 400 MHz) δ: 10.80 (br
s, 1H, CONH), 8.50 (d, J＝4.4 Hz, 1H, Ar-H), 7.88 (d,
J＝8.0 Hz, 1H, Ar-H), 7.41 (dd, J＝4.8, 8.0 Hz, 1H,
Ar-H), 7.18 (s, 1H, Ar-H), 7.06 (s, 1H, Ar-H), 6.94 (s,
1H, Ar-H), 3.76 (s, 2H, CH2), 2.48 (s, 3H, CH3NH),
2.20 (s, 3H, Ar-CH3).
3-Bromo-N-(4-chloro-2-((isopropylamino)methyl)-
6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-
5-carboxamide (8b) White solid, yield 85.0%, m.p.
161—163 ℃; 1H NMR (CDCl3, 400 MHz) δ: 10.96 (brs,
1H, CONH), 8.50 (dd, J＝1.4, 4.6 Hz, 1H, Ar-H), 7.87
(dd, J＝1.2, 8.0 Hz, 1H, Ar-H), 7.40 (dd, J＝4.8, 8.0 Hz,
1H, Ar-H), 7.16 (s, 1H, Ar-H), 7.06 (s, 1H, Ar-H), 6.92
(s, 1H, Ar-H), 3.78 (s, 1H, CH2), 2.88—2.82 (m, 1H,
CH), 2.19 (s, 3H, Ar-CH3), 1.15 (d, J＝6.4 Hz, 6H,
CH3).
1
—79 ℃; H NMR (CDCl3, 400 MHz) δ: 9.29 (s, 1H,
CONH), 8.46 (dd, J＝1.4, 4.6 Hz, 1H, Ar-H), 7.86 (dd,
J＝1.2, 8.2 Hz, 1H, Ar-H), 7.38 (dd, J＝4.8, 8.0 Hz, 1H,
Ar-H), 7.25 (d, J＝2.0 Hz, 1H, Ar-H), 7.22 (d, J＝2.4
Hz, 1H, Ar-H), 7.10 (s, 1H, Ar-H), 4.99 (s, 2H, CH2),
2.19 (s, 3H, CH3CO), 2.11 (s, 3H, Ar-CH3); 13C NMR
(CDCl3, 100 MHz) δ: 172.4, 155.8, 149.0, 146.9, 139.0,
138.8, 138.5, 133.0, 132.7, 131.9, 131.6, 129.0, 128.6,
128.2, 125.8, 110.3, 63.1, 21.0, 1＋8.7; HRMS calcd for
C19H15BrCl2N4O3Na ([M ＋ Na] ) 474.9335, found
474.9335.
N-(2-((tert-butylamino)methyl)-4-chloro-6-methyl-
phenyl)-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyra-
zole-5-carboxamide (8c) White solid, yield 97.5%,
1
m.p. 60—62 ℃; H NMR (CDCl3, 400 MHz) δ: 10.96
(br s, 1H, CONH), 8.48 (dd, J＝1.2, 4.8 Hz, 1H, Ar-H),
7.82 (dd, J＝1.2, 4.8 Hz, 1H, Ar-H), 7.36 (dd, J＝4.8,
8.0 Hz, 1H, Ar-H), 7.12 (s, 1H, Ar-H), 7.05 (s, 1H,
Ar-H), 6.91 (s, 1H, Ar-H), 3.71 (s, 2H, CH2), 2.15 (s,
3H, Ar-CH3), 1.15 (s, 9H, C(CH3)3).
3-Bromo-N-(4-chloro-2-formyl-6-methylphenyl)-
1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide
(7) This compound was prepared following the same
procedure described for compound 5 using 2-amino-5-
chloro-3-methylbenzaldehyde (3) instead of compound
2. Yellow solid, yield 60.0%, m.p. 86—88 ℃; 1H NMR
(CDCl3, 400 MHz) δ: 9.95 (s, 1H, CHO), 9.91 (s, 1H,
CONH), 8.46 (d, J＝4.4 Hz, 1H, Ar-H), 7.86 (d, J＝8.0
Hz, 1H, Ar-H), 7.58 (s, 1H, Ar-H), 7.46 (s, 1H, Ar-H),
7.39 (dd, J＝4.4, 8.0 Hz, 1H, Ar-H), 7.09 (s, 1H, Ar-H),
2.21 (s, 3H, Ar-CH3); 13C NMR (CDCl3, 100 MHz) δ:
193.0, 155.7, 148.7, 146.9, 139.1, 138.9, 137.8, 137.0,
134.2, 132.1, 132.0, 129.1, 128.9, 128.3, 125.8, 110.＋9,
19.1; HRMS calcd for C17H11BrCl2N4O2Na ([M＋Na] )
518.9591, found 518.9597.
3-Bromo-N-(4-chloro-2-((dimethylamino)methyl)-
6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-pyra-
zole-5-carboxamide (8d) White solid, yield 45.0%,
1
m.p. 218—220 ℃; H NMR (CDCl3, 400 MHz) δ:
10.82 (br s, 1H, CONH), 8.49 (d, J＝6.0 Hz, 1H, Ar-H),
7.86 (dd, J＝1.6, 10.8 Hz, 1H, Ar-H), 7.39 (dd, J＝6.2,
10.8 Hz, 1H, Ar-H), 7.16 (s, 1H, Ar-H), 7.00 (s, 1H,
Ar-H), 6.86 (s, 1H, Ar-H), 3.41 (s, 2H, CH2), 2.29 (s,
6H, CH3), 2.19 (s, 3H, Ar-CH3); 13C NMR (CDCl3, 100
MHz) δ: 154.9, 149.1, 146.9, 139.7, 138.9, 134.0, 131.3,
131.1, 130.4, 129.0, 128.9, 128.1, 127.1, 125.8, 109.7,
62.8, 45.0, 19.0; HRMS calcd for C19H19BrCl2N5O ([M
＋H])＋ 482.0150, found 482.0145.
Chin. J. Chem. 2011, 29, 1651— 1655
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FULL PAPER
Compounds 8a—8c were further treated with hy-
drochloric acid gas in ethyl ether to give compounds 9a
—9c.
Hz, 1H, Ar-H), 7.38 (dd, J＝4.4, 8.0 Hz, 1H, Ar-H),
7.21 (s, 1H, Ar-H), 7.19 (s, 1H, Ar-H), 6.92 (s, 1H,
Ar-H), 2.18 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz)
δ: 156.3, 148.0, 147.1, 144.2, 139.5, 139.1 (2C), 132.0,
131.9, 131.8, 130.6, 127.4, 127.1, 126.6, 122.4, 110.＋7,
17.4; HRMS calcd for C17H12BrCl2N5O2Na ([M＋Na] )
489.9445, found 489.9444.
3-Bromo-N-(4-chloro-2-methyl-6-((methylamino)-
methyl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-
5-carboxamide hydrochloride (9a)
White solid,
quantitative yield, m.p. 168—170 ℃; 1H NMR (CDCl3,
400＋MHz) δ: 10.80 (s, 1H, CONH), 9.19 (brs, 2H,
NH2 Cl－ ), 8.52 (d, J＝4.8 Hz, 1H, Ar-H), 8.21 (d, J＝
8.4 Hz, 1H, Ar-H), 7.73 (s, 1H, Ar-H), 7.63 (dd, 1H,
J＝4.8, 8.0 Hz, Ar-H), 7.57 (s, 1H, Ar-H), 7.48 (s, 1H,
Ar-H), 4.01 (t, J＝5.8 Hz, 2H, CH2), 2.55 (t, J＝5.0 Hz,
3H, CH3), 2.17 (s, 3H, Ar-CH3); 13C NMR (CDCl3, 100
MHz) δ: 155.9, 148.3, 147.2, 139.4, 138.9, 133.1, 131.7,
131.6, 130.8, 128.2, 128.1, 127.7, 126.6, 111.4, 47.1,
32.4, 17.8; HRMS calcd for C18H17BrCl2N5O ([M－Cl])＋
467.9984, found 467.9988.
3-Bromo-N-(4-chloro-2-((Z)-methoxyiminometh-
yl)-6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carboxamide (10b) This compound was
prepared following the same procedure described for
compound 10a using methoxamine hydrochloride
instead of hydroxylamine hydrochloride. White solid,
1
yield 90%, m.p. 219—220 ℃; H NMR (CDCl3, 400
MHz) δ: 9.37 (s, 1H, CONH), 8.48 (d, J＝4.0 Hz, 1H,
Ar-H), 8.05 (s, 1H, CH), 7.85 (d, J＝8.0 Hz, 1H, Ar-H),
7.39 (dd, J＝4.8, 8.0 Hz, 1H, Ar-H), 7.22 (s, 2H, Ar-H),
6.96 (s, 1H, Ar-H), 3.97 (s, 3H, OCH3), 2.20 (s, 3H,
Ar-CH3); 13C NMR (CDCl3, 100 MHz) δ: 155.7, 148.7,
148.1, 147.0, 139.3, 139.1, 137.6, 132.3, 132.0, 131.4,
128.8, 128.0, 127.8, 127.2, 125.8, 110.3, 62.6, 19＋.0;
HRMS calcd for C18H14BrCl2N5O2Na ([M ＋ Na] )
503.9595, found 503.9600.
3-Bromo-N-(4-chloro-2-((isopropylamino)meth-
yl)6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-py-
razole-5-carboxamide hydrochloride (9b)
White
1
solid, quantitative yield, m.p. 163—165 ℃; H NMR
(CDCl3, 400 MHz) δ: 9.97 (s, 1H, CONH), 9.15 (br s,
2H, NH＋2 Cl－ ), 8.45 (d, J＝3.6 Hz, 1H, Ar-H), 7.84 (d,
J＝7.6 Hz, 1H, Ar-H), 7.55 (s, 1H, Ar-H), 7.38—7.34
(m, 2H, Ar-H), 7.27 (s, 1H, Ar-H), 3.82 (s, 2H, CH2),
3.10 (s, 1H, CH), 2.23 (s, 3H, Ar-CH3), 1.18 (d, J＝6.4
Hz, 6H, CH(CH3)2); 13C NMR (CDCl3, 100 MHz) δ:
155.8, 148.4, 147.2, 139.4, 139.3, 138.8, 133.2, 131.8,
131.6, 130.8, 128.8, 127.8, 126.9, 126.7, 111.3, 50.4,
43.4, 18.5, 17.8; HRMS calcd for C20H21BrCl2N5O ([M
－Cl])＋496.0305, found 496.0301.
3-Bromo-N-(4-chloro-2-methyl-6-(thiazolidin-2-
yl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-
carboxamide (11) To a solution of compound 7
(0.17g, 0.37 mmol) and 2-mercaptoethylamine hydro-
chloride (0.084 g, 0.74 mmol) in 20 mL of ethanol, po-
tassium acetate (0.073 g, 0.74 mmol) was added in one
portion. The resulting suspension was stirred at room
temperature for 12 h, and then most of the solvent was
removed in vacuum. The residue was dissolved in 50
mL of ethyl acetate, washed with water and brine. The
ethyl acetate solution was evaporated and then subjected
to flash chromatography using petroleum ether/ethyl
acetate (2/1, V/V) as the eluant to give the title com-
pound as white solid, yield 67.7%, m.p. 177—179 ℃;
1H NMR (CDCl3, 400 MHz) δ: 9.33 (s, 1H, CONH),
8.44 (d, J＝4.4 Hz, 1H, Ar-H), 7.87 (d, J＝8.4 Hz,
Ar-H), 7.51 (s, 1H, Ar-H), 7.37 (dd, J＝4.8, 8.0 Hz, 1H,
Ar-H), 7.19 (s, 1H, Ar-H), 6.92 (s, 1H, Ar-H), 5.56 (s,
1H, CH), 3.39—3.33 (m, 1H, CH), 3.24—3.18 (m, 1H,
CH), 3.11—3.06 (m, 1H, CH), 3.01—2.96 (m, 1H, CH),
2.19 (s, 3H, Ar-CH3); 13C NMR (CDCl3, 100 MHz) δ:
155.4, 148.7, 146.8, 139.5, 139.2, 137.9, 135.7, 132.5,
131.9, 130.8, 128.8, 128.1, 126.5, 125.8, 110.2, 70.2,
51.6, 35.5, 18.6; HRMS calcd for C19H17BrCl2N5OS
([M＋H]＋) 511.9718, found 511.9709.
N-(2-((tert-Butylamino)methyl)-4-chloro-6-methyl-
phenyl)-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyra-
zole-5-carboxamide hydrochloride (9c) White solid,
quantitative yield, m.p. 268—271 ℃; 1H NMR (CDCl3,
400＋MHz) δ: 10.94 (s, 1H, CONH), 9.01 (br s, 2H,
NH2 Cl－ ), 8.51 (d, J＝4.0 Hz, 1H, Ar-H), 8.20 (d, J＝
8.0 Hz, 1H, Ar-H), 7.77 (s, 1H, Ar-H), 7.63 (dd, J＝4.8,
8.0 Hz, 1H, Ar-H), 7.56 (s, 1H, Ar-H), 7.49 (s, 1H,
Ar-H), 3.97 (s, 2H, CH2), 2.16 (s, 3H, Ar-CH3), 1.37 (s,
9H, C(CH3)3); 13C NMR (CDCl3, 100 MHz) δ: 155.7,
148.4, 147.1, 139.5, 139.3, 138.7, 133.5, 131.7, 131.6,
130.9, 129.5, 127.8, 126.9, 126.7, 111.1, 57.4, 40.5,
25.0, 17.7; HRMS calcd for C21H23BrCl2N5O ([M－Cl])＋
510.0454, found 510.0458.
(Z)-3-Bromo-N-(4-chloro-2-((hydroxyimino)meth-
yl)-6-methylphenyl)-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carboxamide (10a)
Hydroxylamine
hydrochloride (0.30 mmol) was added to a solution of
compound 7 (0.15 mmol) in 10 mL pyridine. After stir-
ring for 12 h at room temperature, ethyl acetate (50 mL)
was added. The mixture was washed with 2 mol/L hy-
drochloric acid, saturated sodium bicarbonate solution
and brine successively. After dried and evaporated, the
title compound was obtained as white solid. Yield 98%,
m.p. 172—174 ℃; 1H NMR (CDCl3, 400 MHz) δ: 9.15
(s, 1H, CONH), 8.44 (dd, J＝1.2, 4.8 Hz, 1H, Ar-H),
8.32 (s, 1H, OH), 8.05 (s, 1H, CH), 7.87 (dd, J＝1.0, 8.2
Biological activity
The insecticidal activities of compounds 5—11 and
chlorantraniliprole were evaluated using the reported
procedure.11 The insecticidal activity against oriental
armyworm was tested by foliar application, individual
corn leaves were placed on moistened pieces of filter
paper in Petri dishes. The leaves were then sprayed with
the test solution and allowed to dry. Then every 10
fourth-instar oriental armyworm larvae were put into
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Chin. J. Chem. 2011, 29, 1651— 1655

Synthesis and Insecticidal Evaluation of Novel N-Pyridylpyrazolecarboxamides
each dish. Percent mortalities were evaluated 2 d after
treatment. Each treatment was replicated for three times.
For comparative purpose, chlorantraniliprole was tested
as control under the same conditions.
Table 1 Insecticidal activities of compounds 5—11 and chlor-
antraniliprole against oriental armyworm
Larvicidal activity/%
Concentration of/(mg•L－
1
)
Comp.
200
100
100
100
50
100
40
50
20
Results and discussion
5
Structure of compound 10b
6
40
7
20
In order to verify the configuration of oxime ether,
compound 10b was recrystallized from ethanol to give a
colorless crystal for X-ray single-crystal diffraction.12
The crystal with dimensions of 0.22 mm×0.20 mm×
0.18 mm was mounted and analyzed on a Rigaku Sat-
urn724 CCD diffractometer with a graphite monochro-
matized MoKα radiation (λ＝0.71073 Å) using the ω
scan mode (1.82°≤θ≤27.89°) at 113 K. The crystal
belongs to a orthorhombic system with space group
Pbca and crystal parameters of a＝21.315(3) Å, b＝
8.3900(10) Å, c＝22.375(3) Å, V＝4001.4(9) A3, Dc＝
1.604 g/cm3, μ＝2.346 mm－ 1, F(000)＝1936, R＝
0.0328, wR＝0.0736 and Z＝8. Crystal structure of 10b
was shown in Figure 2. The average bond lengths and
bond angles of the pyridine ring, the phenyl ring and the
pyrazole ring were normal.13 The pyrazole and the pyri-
dine rings make a dihedral angle of 58.3(3)°. The tor-
sion angle of C(17)-N(5)-O(2)-C(18) indicated that the
C＝N double bond was in the (Z)-configuration.
8d
9a
80
9b
100
100
100
100
100
100
100
40
100
100
60
40
9c
10a
10b
60
11
10
Chlorantraniliprole
100
References and note
1
Lahm, G. P.; Stevenson, T. M.; Selby, T. P.; Freudenberger,
J. H.; Cordova, D.; Flexner, L.; Bellin, C. A.; Dubas, C. M.;
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E.; Benner, E. A. Bioorg. Med. Chem. Lett. 2007, 17, 6274.
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//www2.dupont.com/Production_Agriculture/en_US/assets/
downloads/pdfs/Rynaxypyr_Tech_Bulletin. pdf
Lahm, G. P.; Cordova, D.; Barry, J. D. Bioorg. Med. Chem.
2009, 17, 4127.
Feng, Q.; Liu, Z. L.; Xiong, L. X.; Wang, M. Z.; Li, Y. Q.;
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Kruger, B.; Hense, A.; Alig, B.; Fischer, R.; Funke, C.;
Gesing, E. R.; Malsam, O.; Drewes, M. W.; Arnold, C.;
Lummen, P.; Sanwald, E. WO 2007031213, 2007 [Chem.
Abstr. 2007, 146, 358885].
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Clark, D. A.; Finkelstein, B. L.; Lahm, G. P.; Selby, T. P.;
Stevenson, T. M. WO 2003016304, 2003 [Chem. Abstr.
2003, 138, 205057].
Liu, A. P.; Hu, Z. B.; Wang, Y. J.; Wang, X. G.; Huang, M.
Z.; Ou, X. M.; Mao, C. H.; Pang, H. L.; Huang, L. CN
101337959, 2009 [Chem. Abstr. 2009, 150, 168342].
Muehlebach, M.; Craig, G. W. WO 2008064891, 2008
[Chem. Abstr. 2008, 149, 10005].
Zhang, X. N.; Zhu, H. J.; Tan, H. J.; Li, Y. H.; Ni, J. P.; Shi,
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Feng, H. M.; Wang, N. CN 101845043, 2010 [Chem. Abstr.
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8
9
Figure 2 Crystal structure of 10b.
Insecticidal activity
The insecticidal activity of compounds 5 — 11
against oriental armyworm was listed in Table 1. Com-
pound 5 and its acetylated product 6 showed the same
activity, while compounds 10a and 10b containing
oxime groups had the similar trend. The activity of
compounds 9a—9c and 8d with methylene amines sub-
stituted indicated that the change of substituent affected
the activity with the trend CH(CH3)2＞C(CH3)3＞CH3
＞two-methyl substituted, and had a decrease in activity
compared with their amides analogues. In addition, the
thiazolidines 11 did not lead to higher activity compared
to its precursor compound 7.
10 Ni, J. P.; Zhang, Y. N.; Zhang, X. N.; Tan, H. J.; Zeng, X.
Modern Agrochem. 2010, 9, 21 (in Chinese).
11 Dong, W. L.; Xu, J. Y.; Xiong, L. X.; Liu, X. H.; Li, Z. M.
Chin. J. Chem. 2009, 27, 579.
12 Supplementary material CCDC-799316 contains the sup-
plementary crystallographic data for this compound. These
data can be obtained free of charge at www.ccdc.cam.ac.uk/
conts/retrieving or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB 21EZ, UK; fax:
＋44-1223-336033; email: deposit@ccdc. cam. ac. uk.
13 Liu, X. F.; Liu, X. H. Acta Cryst. 2011, E67, O202.
(E1011271 Sun, H.; Lu, Z.)
Chin. J. Chem. 2011, 29, 1651— 1655
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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