Design, synthesis and biological activities of novel benzoyl hydrazines containing pyrazole

Article abstract of DOI:10.1002/cjoc.201100347

In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8 novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characterized by ¹H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that most of title compounds exhibited certain insecticidal activities against Mythimna separata Walker at 200 mg·L ^-1 but excellent fungicidal activities against six fungus at 50 mg·L^-1, which were better than the control. Eight novel benzoyl hydrazines containing pyrazole were designed and synthesized. The preliminary results of biological activity assessment indicated that most of title compounds exhibited certain insecticidal activities against Mythimna separata Walker at 200 mg·L^-1 but excellent fungicidal activities against six fungus at 50 mg·L^-1, which were better than the control. Copyright

Full text of DOI:10.1002/cjoc.201100347

FULL PAPER
DOI: 10.1002/cjoc.201100347
Design, Synthesis and Biological Activities of Novel
Benzoyl Hydrazines Containing Pyrazole
Yan, Tao(闫涛)
Yu, Shujing(于淑晶)
Liu, Pengfei(刘鹏飞)
Liu, Zhuo(刘卓)
Wang, Baolei(王宝雷)
Xiong, Lixia(熊丽霞)
Li, Zhengming*(李正名)
State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, National Pesticide
Engineering Research Center, Nankai University, Tianjin 300071, China
In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8
novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characterized
by 1H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that most of title
compounds exhibited certain insecticidal activities against Mythimna separata Walker at 200 mg•L－ but excellent
1
fungicidal activities against six fungus at 50 mg•L－1, which were better than the control.
Keywords benzoyl hydrazines, pyrazole, synthesis, insecticidal activities, fungicidal activities
Introduction
tive played an important position in the field of agro-
chemicals because they exhibited a wide range of bio-
logical activities,[1-8] especially insecticidal activities
(compounds a, b, c, Scheme 1)[1-5] and fungicidal activi-
ties (compounds d, e, Scheme 1).[5,6]
In order to overcome resistance and ecobiological
problems in association with conventional insecticides
or fungicides, there is an urgent requirement to explore
novel bioactive molecules. Currently, pyrazole deriva-
Scheme 1 Some representative structures of pyrazole and acylhydrazine moiety and the strategy of title compounds’ design
*
E-mail: nkzml@vip.163.com; Tel.: 0086-022-23503732; Fax: 0086-022-23505948
Received September 16, 2011; accepted October 25, 2011; published online March 7, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100347 or from the author.
Chin. J. Chem. 2012, 30, 919—923
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919

Yan et al.
FULL PAPER
More recently, acylhydrazine derivatives have be-
come one of the focuses in the development of agro-
chemicals because of their high biological activities
such as insecticidal activities,[9,10] enzyme inhibitors,[11]
antivirus activities,[12] herbicidal activity,[13] fungicide
activities,[14,15] and antitumor activities.[16,17] Some ex-
amples of diacylhydrazines were presented in Scheme 1
(compounds f, g). Moreover, acylhydrazine group is an
electron-rich group in which nitrogen can easily form
hydrogen bond with various types of biological en-
zymes.
In consideration of the above viewpoints, a series of
title compounds containing acylhydrazine group and
pyrazole moiety were synthesized and characterized by
1H NMR, HRMS and biological activity test. The syn-
thetic procedure was outlined in Scheme 2.
173—174 ℃ (lit.[18] m.p. 175—176 ℃).
3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-
carboxylic acid (3b) Yellow solid, yield 87.9%, m.p.
198—200 ℃ (lit.[18] m.p. 197—200 ℃ ).
Phenylhydrazine (6a) Oily liquid, yield 71.7%,
b.p. 243 ℃ (lit.[21] b.p. 243.5 ℃).
4-Chlorphenylhydrazine
hydrochloride
(5b)
White solid, yield 64.3%, m.p. 215—216 ℃ (dec.)
[lit.[22] m.p. 216 ℃ (dec.)].
2,4-Dichlorophenylhydrazine hydrochloride (5c)
White solid, yield 48.5%, m.p. 191—193 ℃ (lit.[19]
m.p. 193—194 ℃).
2,6-Dimethyl phenylhydrazine hydrochloride (5d)
White soild, yield 72.0%, m.p. 209—211 ℃ (dec.)
[lit.[20] m.p. 211 ℃ (dec.)].
General synthetic procedure for title compounds
Experimental
Synthetic route of title compounds was shown in
Scheme 2. The synthetic procedure was described below.
To a suspension of intermediate 3 (1 mmol) in di-
chloromethane (10 mL) was added oxalyl chloride (3
mmol) and dimethylformamide (1 drop). The solution
was stirred at room temperature for 3 h, and then the
mixture was concentrated in vacuo to obtain the crude
acid chloride. The crude acid chloride in dichloro-
methane (10 mL) was added dropwise slowly to a
stirred solution of intermediate 2 or 6 (1.2 mmol) in di-
chloromethane (20 mL) in an ice bath. After 20 min,
triethylamine (1 mmol) was added. The solution was
warmed to room temperature and stirred for 12 h, then
Materials and instruments
1H NMR spectra were recorded on a Bruker 400
MHz nuclear magnetic resonance spectrometer with
CDCl3 as the solvent and TMS as 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 melting point appa-
ratus. All the reagents were of analytical grade.
General synthetic procedure for the intermediates
Synthetic route of the intermediates (compounds 2, 3,
5, 6) was shown in Scheme 2. They were prepared re-
ferring to the reported method.[18-20]
diluted with CH2Cl2 (20 mL), and washed with 1 mol•L－
1
aq. HCl solution (10 mL), saturated aq. NaHCO3 (10
mL), and brine (10 mL). The organic extract was sepa-
rated, dried, filtered, concentrated and purified by silica
gel chromatography to afford the desired coupounds 7
or 8.
3-Chloro-2-hydrazinylpyridine (2) White solid,
yield 78.6%, m.p. 163—164 ℃ (lit.[18] m.p. 175—176
℃).
3-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-
carboxylic acid (3a) Yellow solid, yield 78.6%, m.p.
Scheme 2 Synthetic route of title compounds 7 and 8
Cl
X1
N
X1
NH2
N
Cl
N
H
HN
N
Cl
N
N
Cl
N
3
N2H4
reflux
COOH
N
N
N
H
Cl
Cl
O
(COCl)2, CH2Cl2, DMF
N
7
2
1
Cl
X1
N
NH2
X2
NH2
X2
N
X1
N
HN
X3
X4
NH2
HN
N
X4
X2
X4
X4
COOH
(1) NaNO2/HCl
(2) SnCl2
NaOH
H
N
3
HCl
N
H
N
(COCl)2, CH2Cl2, DMF
X2
O
Cl
X3
X3
X3
N
8
4
6
5
3a: X1 = Cl; 3b: X1 = Br; 4a: X2 = H, X3 = H, X4 = H; 4b: X2 = H, X3 = Cl, X4 = H; 4c: X2 = Cl, X3 = Cl, X4 = H; 4d: X2 = CH3, X3 = H, X4 = CH3; 5a: X2 = H,
X3 = H, X4 = H; 5b: X2 = H, X3 = Cl, X4 = H; 5c: X2 = Cl, X3 = Cl, X4 = H; 5d: X2 = CH3, X3 = H, X4 = CH3; 6a: X2 = H, X3 = H, X4 = H; 6b: X2 = H, X3 = Cl, X4
= H; 6c: X2 = Cl, X3 = Cl, X4 = H; 6d: X2 = CH3, X3 = H, X4 = CH3; 7a: X1 = Cl; 7b: X1 = Br; 8a: X1 = Cl, X2 = H, X3 = H, X4 = H; 8b: X1 = Br, X2 = H, X3 = H,
X4 = H; 8c: X1 = Br, X2 = H, X3 = Cl, X4 = H; 8d: X1 = Cl, X2 = Cl, X3 = Cl, X4 = H; 8e: X1 = Br, X2 = Cl, X3 = Cl, X4 = H; 8f: X1 = Br, X2 = CH3, X3 = H, X4 =
CH3
920
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 919—923

Design, Synthesis and Biological Activities of Novel Benzoyl Hydrazines
3-Chloro-N'-1-bis(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbohydrazide (7a) White solid, yield
53.2%, m.p. 181—183 ℃; 1H NMR (CDCl3, 400 MHz) δ:
9.34 (s, 1H, Ar-NHNH), 8.49 (d, J＝4.60 Hz, 1H,
pyridyl-H), 8.05 (d, J＝4.70 Hz, 1H, pyridyl-H), 7.90 (d,
J＝8.00 Hz, 1H, pyridyl-H), 7.55 (d, J＝7.80 Hz, 1H,
pyridyl-H), 7.51 (s, 1H, Ar-NHNH), 7.41 (dd, J＝7.70,
4.90 Hz, 1H, pyridyl-H), 6.89 (s, 1H, pyrazolyl-H), 6.79
(dd, J＝6.60, 1.60 Hz, 1H, pyridyl-H). HRMS calcd for
C14H9Cl3N6O (M＋Na)＋ 404.9796, found 404.9799.
3-Bromo-N'-1-bis(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbohydrazide(7b) White solid, yield
60.0%, m.p. 185—187 ℃; 1H NMR (CDCl3, 400 MHz) δ:
9.28 (s, 1H, Ar-NHNH), 8.49 (d, J＝4.70 Hz, 1H,
pyridyl-H), 8.05 (d, J＝3.90 Hz, 1H, pyridyl-H), 7.90 (d,
J＝8.00 Hz, 1H, pyridyl-H), 7.54 (d, J＝7.80 Hz, 1H,
pyridyl-H), 7.52 (s, 1H, Ar-NHNH), 7.41 (dd, J＝8.00,
4.70 Hz, 1H, pyridyl-H), 6.97 (s, 1H, pyrazolyl-H), 6.79
(dd, J＝7.70, 4.90 Hz, 1H, pyridyl-H). HRMS calcd for
C14H9BrCl2N6O (M＋H)＋ 426.9471, found 426.9479.
3-Chloro-1-(3-chloropyridin-2-yl)-N'-phenyl-1H-
pyrazole-5-carbohydrazide (8a) White solid, yield
68.5%, m.p. 148—149 ℃; 1H NMR (CDCl3, 400 MHz) δ:
8.39 (d, J ＝3.90 Hz, 1H, pyridyl-H), 8.33 (s, 1H,
Ar-NHNH), 7.87 (d, J＝8.00 Hz, 1H, pyridyl-H), 7.37
(dd, J＝8.00, 4.70 Hz, 1H, pyridyl-H), 7.21 (t, J＝7.80
Hz, 2H, Ar-H), 6.91 (t, J＝7.30 Hz, 1H, Ar-H), 6.77 (d,
J＝7.90 Hz, 2H, Ar-H), 6.71 (s, 1H, pyrazolyl-H), 6.11 (d,
J ＝ 3.10 Hz, 1H, Ar-NHNH). HRMS calcd for
C15H11Cl2N5O (M＋Na)＋ 370.0233, found 370.0235.
3-Bromo-1-(3-chloropyridin-2-yl)-N'-phenyl-1H-
pyrazole-5-carbohydrazide (8b) White solid, yield
54.6%, m.p. 150—152 ℃; 1H NMR (CDCl3, 400 MHz) δ:
8.42 (d, J＝4.70 Hz, 1H, pyridyl-H), 8.19 (d, J＝3.20 Hz,
1H, Ar-NHNH), 7.88 (d, J＝8.10 Hz, 1H, pyridyl-H),
7.38 (dd, J＝8.00, 4.70 Hz, 1H, pyridyl-H), 7.21 (t, J＝
7.90 Hz, 2H, Ar-H), 6.91 (t, J＝6.30 Hz, 1H, Ar-H), 6.84
(s, 1H, pyrazolyl-H), 6.78 (d, J＝7.80 Hz, 2H, Ar-H),
6.11 (d, J＝3.70 Hz, 1H, Ar-NHNH). HRMS calcd for
C15H11BrClN5O (M＋Na)＋ 413.9728, found 413.9722.
3-Bromo-N'-(4-chlorophenyl)-1-(3-chloropyridin-
6.41 (s, 1H, Ar-NHNH). HRMS calcd for C15H9Cl4N5O
(M＋Na)＋ 437.9453, found 437.9452.
3-Bromo-1-(3-chloropyridin-2-yl)-N'-(2,4-dichlo-
rophenyl)-1H-pyrazole-5-carbohydrazide
(8e)
1
White solid, yield 66.3%, m.p. 174—176 ℃; H NMR
(CDCl3, 400 MHz) δ: 8.44 (d, J＝3.40 Hz, 1H, pyridyl-H),
8.08 (d, J＝2.40 Hz, 1H, Ar-NHNH), 7.91 (d, J＝8.00 Hz,
1H, pyridyl-H), 7.41 (dd, J ＝8.10, 4.70 Hz, 1H,
pyridyl-H), 7.28 (d, J＝2.20 Hz, 1H, Ar-H), 7.12 (d, J＝
8.70 Hz, 1H, Ar-H), 6.89 (s, 1H, pyrazolyl-H), 6.80 (d,
J ＝8.70 Hz, 1H, Ar-H), 6.41 (d, J＝2.80 Hz, 1H,
Ar-NHNH). HRMS calcd for C15H9BrCl3N5O (M＋Na)＋
481.8948, found 481.8945.
3-Bromo-1-(3-chloropyridin-2-yl)-N'-(2,6-dimeth-
ylphenyl)-1H-pyrazole-5-carbohydrazide (8f) White
solid, yield 57.7%, m.p. 152—154 ℃; 1H NMR (CDCl3,
400 MHz) δ: 8.29 (d, J＝4.70 Hz, 1H, pyridyl-H), 8.17 (d,
J＝3.70 Hz, 1H, Ar-NHNH), 7.90 (d, J＝8.00 Hz, 1H,
pyridyl-H), 7.38 (dd, J＝8.00, 4.70 Hz, 1H, pyridyl-H),
6.97 (d, J＝7.40 Hz, 2H, Ar-H), 6.90 (t, J＝6.40 Hz, 1H,
Ar-H), 6.73 (s, 1H, pyrazolyl-H), 6.09 (d, J＝4.00 Hz, 1H,
Ar-NHNH), 2.32 (s, 6H, CH3). HRMS calcd for
C17H15BrClN5O (M＋Na)＋ 442.0041, found 442.0044.
Biological assay
The insecticidal activities of title compounds against
Mythimna separate were tested according to the re-
ported method.[18] Chlorothalonil was used as a control.
The insecticidal activities of those compounds at the
dose of 200 mg•L－ were summarized in Table 1; The
1
fungicidal activities of title compounds were tested in
vitro against Fusarium omysporum, Physalospora piri-
cola, Alternaria solani, Cercospora arachidicola, Gib-
berella sanbinetti, Phytophthora capsici and their rela-
tive inhibitory ratio (%) had been determined by the
application of the mycelium growth rate method.[23]
Phenazine-1-carboxylic acid was used as a control. Af-
ter the mycelia grew completely, the diameters of the
mycelia were measured and the inhibition rate was cal-
culated according to the formula I＝(D1－D2)/D1×
100%. In the formula, I is the inhibition rate, D1 is the
average diameter of mycelia in the blank test, and D2 is
the average diameter of mycelia in the presence of those
compounds. The inhibition ratio of those compounds at
the dose of 50 mg•L－1 was summarized in Table 1. The
EC50 of compounds 8b, 8c, 8e and phenazine-1-car-
boxylic acid had been experimented and calculated by
the Scatchard method. The results were summarized in
Table 2.
2-yl)-1H-pyrazole-5-carbohydrazide (8c)
White
solid, yield 69.5%, m.p. 167—169 ℃; 1H NMR (CDCl3,
400 MHz) δ: 8.42 (d, J＝4.50 Hz, 1H, pyridyl-H), 8.18 (s,
1H, Ar-NHNH), 7.89 (d, J＝8.00 Hz, 1H, pyridyl-H),
7.40 (dd, J＝7.90, 4.70 Hz, 1H, pyridyl-H), 7.17 (d, J＝
8.40 Hz, 2H, Ar-H), 6.85 (s, 1H, pyrazolyl-H), 672 (d,
J＝8.50 Hz, 2H, Ar-H), 6.10 (d, J＝2.40 Hz, 1H,
Ar-NHNH). HRMS calcd for C15H11BrCl2N5O (M－
H)－ 423.9373, found 423.9378.
3-Chloro-1-(3-chloropyridin-2-yl)-N'-(2,4-dichlo-
Results and Discussion
rophenyl)-1H-pyrazole-5-carbohydrazide
(8d)
1
Synthesis
White solid, yield 51.6%, m.p. 173—175 ℃; H NMR
(CDCl3, 400 MHz) δ: 8.43 (d, J＝4.50 Hz, 1H, pyridyl-H),
8.14 (s, 1H, Ar-NHNH), 7.90 (d, J＝8.10 Hz, 1H,
pyridyl-H), 7.41 (dd, J＝8.00, 4.70 Hz, 1H, pyridyl-H),
7.27 (s, 1H, Ar-H), 7.12 (d, J＝8.70 Hz, 1H, Ar-H), 6.80
(s, 1H, pyrazolyl-H), 6.79 (d, J＝5.60 Hz, 1H, Ar-H),
The synthetic procedures were shown in Scheme 2.
Firstly, the intermediates (compounds 2, 3, 5 and 6)
were synthesized referring to a reported methods.[18-20]
Then further reaction with the compound 3 afforded title
compounds 7 and 8. Compounds 5b—5d were reacted
Chin. J. Chem. 2012, 30, 919—923
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www.cjc.wiley-vch.de
921

Yan et al.
FULL PAPER
with sodium hydroxide, then the reactant was extracted
with dichloromethane and dried with sodium sulfate in
N2 to gain the solution of compounds 6b—6d. These
solution further reacted immediately in N2 due to their
unstability. All title compounds were purified by column
chromatography on silica gel using petroleum ether (60
—90 ℃)/ethyl acetate as the gradient eluent. All title
compounds were confirmed by H NMR and HRMS.
All spectral and analytical data were consistent with the
assigned structures.
100% against Alternaria solani and Gibberella sanbi-
netti. The EC50 of the highly fungicidal activity com-
pounds 8b, 8c, 8e and phenazine-1-carboxylic acid
against Alternaria solani and Gibberella sanbinetti were
shown in Table 2. The EC50 values of them are below
7.5539 against Alternaria solani and below 4.3071
against Gibberella sanbinetti (the control EC50: 18.5021
against Alternaria solani and ＞50.0000 against Gib-
berella sanbinetti). All the data indicated that title com-
pounds could be further studied as lead compounds for
fungicidal activity.
1
Biological activities
The biological activities of title compounds were
listed in Table 1, which exhibited certain insecticidal
Conclusions
activities against Mythimna separata at 200 mg•L－
1
Eight novel benzoyl hydrazines were designed and
synthesized with structures characterized by H NMR
1
(compared with rynaxypyrTM) and excellent antifungal
activities against six fungus at 50 mg•L－ (compared
1
spectra and HRMS. The biological activities of new
compounds were evaluated. The results showed that title
compounds exhibited certain insecticidal and excellent
antifungal activities. The antifungal activities (at 50
with phenazine-1-carboxylic acid). The antifungal ac-
－
1
tivities (at 50 mg•L ) of compounds (8a—8f) were
18.8% to 100.0% against six fungus. Most of them were
better than the control (phenazine-1-carboxylic acid).
For example, the antifungal activities of compounds (8a
—8f) were 61.1% to 100.0% against Gibberella sanbi-
netti (the control 43.1%). Table 1 also showed that the
antifungal activities of compounds 8a and 8b were
－
1
mg•L ) of most compounds (8a—8f) were better than
the control and the EC50 values (8b, 8c and 8e) were
lower than the control, which indicated that title com-
pounds could be further studied as potential lead com-
pounds.
Table 1 Biological activities of title compounds
Insecticidal activ-
ity/%
Antifungal activity/%
Compd.
Mythimna
Fusarium
Physalospora
Alternaria
Cercospora
Gibberella
sanbinetti
Phytophthora
separata
omysporum
piricola
solani
arachidicola
capsici
(200 mg•L－
)
(50 mg•L－
0.0
)
(50 mg•L－
23.1
)
(50 mg•L－
)
(50 mg•L－
9.4
)
(50 mg•L－
)
(50 mg•L－
10.7
7.1
)
1
1
1
1
1
1
1
7a
7b
8a
8b
8c
8d
8e
30
10
20
10
10
20
0
20
100
nt
10.0
15.0
100.0
100.0
80.0
76.2
90.0
90.9
nt
26.7
22.2
100.0
100.0
100.0
61.1
68.9
92.7
nt
2.5
25.0
68.5
63.5
76.9
79.6
69.2
44.1
nt
3.1
80.8
55.0
67.5
61.5
55.5
47.7
ntb
75.0
37.5
75.0
81.3
71.9
18.8
nt
75.0
82.1
50.0
78.1
42.9
54.4
nt
8f
Control-1a
Control-2c
65.4
100.0
100.0
92.3
43.1
82.6
a Control-1 (chlorantraniliprole), c: 1 mg•L－1; b nt, not tested; c Control-2 (Phenazine-1-carboxylic acid), c: 50 mg•L－
.
1
Table 2 EC50 of the compounds 8b, 8c, 8e and control-2 against Alternaria solani and Gibberella sanbinetti
Compd.
Fungus
Y＝a＋bx
EC50
R
Alternaria solani
Gibberella sanbinetti
Alternaria solani
Gibberella sanbinetti
Alternaria solani
Gibberella sanbinetti
Alternaria solani
Gibberella sanbinetti
Y＝3.5076＋1.6995x
Y＝4.1773＋1.4358x
Y＝4.8262＋0.6526x
Y＝4.7974＋0.9921x
Y＝4.3364＋1.0464x
Y＝4.6000＋0.6565x
Y＝4.400＋0.4720x
7.5539
3.7412
1.8465
1.6003
4.3071
4.0670
18.5021
＞50.0000
0.9827
0.9869
0.9619
0.9587
0.9664
0.9881
0.9900
8b
8c
8e
Control-2
Acknowledgement
search Funds for the Central Universities, the National
Natural Science Foundation of China (No. 20872069)
This work was supported by the Fundamental Re-
922
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 919—923

Design, Synthesis and Biological Activities of Novel Benzoyl Hydrazines
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