Synthesis, crystal structure and biological activity of N′-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2, 3-thiadiazole-5- formylhydrazine

Article abstract of DOI:10.1007/s10870-011-0189-1

The title compound, N'-tert-butyl-N-(3-methoxylbenzoyl)- N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine (C₁₆H ₂₀N₄O₃S) was prepared from the reaction of 4-methyl-1, 2,3-thiadiazole-5-carbonyl chloride with N'-tert-Butyl-3- methoxylbenzohydrazine, and its structure was characterized by ¹Hydrogen Nuclear Magnetic Resonance, High-Resolution Mass Spectrometry, IR spectra, and single crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group P 21/c with cell parameters a = 17.986(2) A, b = 8.0180(10) A, c = 12.0190(14) A, α = 90°, β = 91.160(5)°, γ = 90°, V = 1732.9(4) A ³, Z = 4, D_c = 1.335 g/cm³, l (Mo Ka) = 0.209 mm^-1, F (000) = 736, R = 0.0367 and wR = 0.0932. X-ray diffraction analysis indicates that all rings in the title compound are non-planar. The bioassay results indicated that, the title compound had good fungicide activity against Sclerotinia sclerotiorum, certain extent of insecticidal activity against Plutella xylostella L. Springer Science+Business Media, LLC 2011.

Full text of DOI:10.1007/s10870-011-0189-1

J Chem Crystallogr (2011) 41:1860–1865
DOI 10.1007/s10870-011-0189-1
ORIGINAL PAPER
Synthesis, Crystal Structure and Biological Activity
of N0-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,
3-thiadiazole-5-formylhydrazine
•
Jie Huang Huan Wang Zhi-Jin Fan Hai-Bin Song
•
•
•
•
•
Hui Zhao Yun Huang Polina E. Prokhorova
•
•
Nataliya P. Belskaya Yury Yu. Morzherin Vasiliy A. Bakulev
•
Received: 29 March 2011 / Accepted: 26 September 2011 / Published online: 5 October 2011
Ó Springer Science+Business Media, LLC 2011
Abstract The title compound, N0-tert-butyl-N-(3-meth-
oxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine
(C16H20N4O3S) was prepared from the reaction of 4-methyl-1,
2,3-thiadiazole-5-carbonyl chloride with N0-tert-Butyl-3-
methoxylbenzohydrazine, and its structure was char-
acterized by 1Hydrogen Nuclear Magnetic Resonance,
High-Resolution Mass Spectrometry, IR spectra, and single
crystal X-ray diffraction. The crystal of the title compound
belongs to monoclinic system, space group P 21/c with
Sclerotinia sclerotiorum, certain extent of insecticidal activity
against Plutella xylostella L.
Keywords X-ray diffraction ꢀ Single crystal structure ꢀ
Synthesis ꢀ Diacylhydrazine ꢀ Biological activity
Introduction
˚
cell parameters a = 17.986(2) A, b = 8.0180(10) A, c =
˚
Diacylhydrazines are non-steroidal molting hormone ago-
nists [1], which have been identified as one of the most
important new class of insect growth regulators with
unique action, simple structure, low toxicity to vertebrates,
and high insecticidal selectivity [2–5]. N0-tert-butyl-N,N0-
dibenzoylhydrazine (RH-5849) was the first nonsteroidal
ecdysone agonist reported in 1988. Tebufenozide (RH-
5992) was firstly commercialized by Rohm & Haas Com-
pany [6]. A variety of diacylhydrazine derivatives have
been designed and synthesized for the purpose of obtaining
new compounds with higher insecticidal activity after-
wards. For example, methoxyfenozide (RH-2485), halofe-
nozide (RH-0345), and chromafenozide (ANS-118) were
commercialized as high ecdysone agonists [4]. Diacy-
lhydrazines possess two phenyl groups in one molecule;
Replacement of the phenyl group(s) by a heterocycle
group is effective measures in novel pesticide develop-
ment because heterocyclic groups are usually bioactive
substructure. 1,2,3-Thiadiazoles as an important active
substructure of heterocyclic compounds have various bio-
logical activities, some 1,2,3-thiadazoles are commercial-
ized as plant activators [7, 8], many 1,2,3-thiadizole
derivatives have been reported with antiviral [9, 10], anti-
tumor [11], antibacterial [12], fungicidal [13–15], and
insecticidal activities [16]. Moreover, 1,2,3-thiadiazole
ring possesses the property of easy breakdown into low
˚
12.0190(14) A, a = 90°, b = 91.160(5)°, c = 90°, V =
3
3
˚
1732.9(4) A , Z = 4, Dc = 1.335 g/cm , l (Mo Ka) = 0.209
mm-1, F (000) = 736, R = 0.0367 and wR = 0.0932. X-ray
diffraction analysis indicates that all rings in the title
compound are non-planar. The bioassay results indicated that,
the title compound had good fungicide activity against
Jie Huang and Huan Wang contributed equally to this work.
J. Huang ꢀ Y. Huang (&)
Department of Plant Pathology, Sichuan Agricultural University,
No. 555 Northeast Road, Wenjiang District, Chengdu 611130,
Sichuan, China
e-mail: 5787huangyun@sina.com
J. Huang ꢀ H. Wang ꢀ Z.-J. Fan (&) ꢀ H.-B. Song ꢀ H. Zhao
State Key Laboratory of Elemento Organic Chemistry,
Nankai University, 94 Weijin Road, Nankai District,
Tianjin 300071, China
e-mail: fanzj@nankai.edu.cn
P. E. Prokhorova ꢀ N. P. Belskaya ꢀ Y. Yu. Morzherin ꢀ
V. A. Bakulev
The Ural Federal University Named after the First
President of Russia B. N. Yeltsin, Yeltsin UrFU,
Ekaterinburg, Russia 620002
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J Chem Crystallogr (2011) 41:1860–1865
1861
Scheme 1 Molecule structure
and synthesis of the target
compound
CH3
O
C
O
C
N
O
O
CH3
N
NaOH/H2O, CH2Cl2
H3CO
H3CO
H3CO
S
COCl
N
Cl
N
NH
N
N
•
t-Bu NHNH2
HCl
H
NH
S
Triethylamine
t-Bu
t-Bu
molecular weight compounds through release of N2, it
favors the characteristics of environmentally friendly pes-
ticide candidates with low toxicity [17]. Our previous
studies discovered some new 1,2,3-thiadizoles with fungi-
cidal activity, antiviral activity and systemic acquired
resistance [13, 18, 19], and two types of diacylhydrazines
containing 1,2,3-thiadiazoles with carbonyl in N or N0
independently had good insecticidal activity [20, 21].
In this paper, another type of diacylhydrazines con-
taining 1,2,3-thiadiazoles with two carbonyl in one N atom
was designed and synthesized, the target compound N0-tert-
butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-
5-formyl)hydrazine was synthesized according to the
routine described in Scheme 1, its crystal structure and
biological activity were also detected.
mixture was then stirred for 15 min. After the addition of
3-methoxylbenzoyl chloride (1.98 g, 0.116 mol) in batches,
the mixture was further stirred in an ice-water bath for
0.5 h. Then the mixture was permitted to stir for another 5 h
at room temperature. The reaction mixture was washed with
water (3 9 10 mL) followed by brine (10 mL), the organic
layer was dried over anhydrous sodium sulfate, after fil-
tration, the solvent was removed under vacuum to give the
compound N0-tert-Butyl-3-methoxylbenzohydrazine, yield
was not optimized. According to the previous work,
4-methyl-1,2,3-thiadiazole-5-carbonyl chloride was syn-
thesized from 4-methyl-1,2,3-thiadiazole-5-carboxylic acid
according to Ref. [18]. A solution of 4-methyl-1,2,3-thia-
diazole-5-carbonyl chloride (3.3 mmol) in dichloromethane
(20 mL) was added dropwise to a stirred mixture of N-tert-
butyl-N0-3-methoxylbenzoyl hydrazine(3.0 mmol), trieth-
ylamine (3.3 mmol), and dichloromethane (20 mL) in an
ice bath for 1 h. Then remove the ice bath, the resultant
mixture was stirred at room temperature for 5 h. The mix-
ture was washed successively with water (3 9 20 mL) and
brine (20 mL), the organic layer was dried over anhydrous
sodium sulfate. After filtration the anhydrous sodium sul-
fate, the solvent was evaporated, the residue was then
purified by column chromatography on silica gel using ethyl
acetate and petroleum ether (60–90 °C) with 1:2 (v/v) as an
eluent to obtain the target compound (0.09 g, 8.61%,
mp = 194–196 °C) as a minor product, another product of
N-tert-butyl-N-4-methyl-1,2,3-thiadiazole-5-yl-N0-3-meth-
oxylphenyl diacylhydrazine as the main product(0.75 g,
71.75%) was obtained, 4-methyl-1,2,3-thiadiazole-5-car-
boxylic acid (0.07 g, 10.49%) was recovered. The solid was
recrystallized in dichloromethane and petroleum ether
which was then analyzed by single crystal techniques.
1HNMR (CDCl3, 400 MHz): d 1.22 (s, 9H, C(CH3)3), 2.94
(s, 3H, thiadiazolyl-CH3), 3.90 (s, 3H, –CH3), 5.74 (s, 1H,
NH), 7.20–7.49(m, 4H, Ph–H); HRMS (m/z): (M ? H)?:
349.1329, found: 349.1324; IR (KBr pellet press, m, cm-1):
3347 (NH, st), 2967, 1701 (C = O, st), 1677, 1598, 1488,
1468, 1457, 1372, 1264.
Experimental Procedures
Reagents and Measurements
All reagents and solvents for synthesis and analyses were
of analytical grade, and commercially purchased from J&K
Scientific Ltd. (China) which were used without further
purification. Column chromatography purification was
carried out by using silica gel with ethyl acetate and
petroleum ether 1:2 (v/v) as mobile phase. The melting
point was measured on an XT-4A apparatus without cor-
rection of the thermometer. Infrared (IR) spectra were
recorded on a Bruker Tensor 27 Spectrophotometer in KBr
pellet. Hydrogen Nuclear Magnetic Resonance (1H NMR)
spectra was measured on a Bruker AC-P500 Instrument
(400 MHz) with deutero-chloroform (CDCl3) as the sol-
vent and tetramethylsilane (TMS) as the internal standard.
High-resolution mass spectrometry (HRMS) data was
obtained on an FTICR-MS Varian 7.0T FTICR-MS
instrument. The single crystal structure was determined on
a Rigaku Saturn 724 CCD diffractometer. The equipment
˚
was operated using Mo-Ka radiation (k = 0.71075 A).
Synthesis of the Title Compound
Crystal Data and Structure Determination
To a stirred mixture of tert-butylhydrazine hydrochloride
(2.9 g, 0.0234 mol) in 30 mL dichloromethane, sodium
hydroxide (1.0 g, 96%, 0.024 mol) in water (2 mL) was
added dropwise within 25 min at -10 °C, the reaction
The crystal of the target compound was cultured from
dichloromethane and petroleum ether. The colorless crystal
of the title compound with dimensions of 0.24 9 0.22 9
0.20 mm3 was selected and mounted on a glass fiber for
123

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J Chem Crystallogr (2011) 41:1860–1865
X-ray diffraction analysis. All measurements were made on
Fungi used in this study included Alternaria solani (AS),
Botrytis cinerea (BC), Cercospora arachidicola (CA),
Gibberella zeae (GZ), Phytophthora infestans (Mont) de
Bary (PI), Physalospora piricola (PP), Pellicularia sasakii
(PS), Sclerotinia sclerotiorum (SS), and Rhizoctonia
cerealis (RC).
a Rigaku Saturn 724 CCD diffractometer MoKa radiation
˚
(k = 0.71075 A). The data were collected at a temperature
of -160 1 °C to a maximum 2h value of 56o. A total of
540 oscillation images were collected. Three sweeps of
data were done using w scans from –110.0 to 70.0o in 1.0o
step, at v = 45.0o and / = 0 , 90 and 180o. The exposure
rate was 5.0 [sec/o]. The detector swing angle was -19.92o.
The crystal-to-detector distance was 45.08 mm. The crystal
is monoclinic system, space group P 1 21/c 1, with unit
Insecticide Activity of the Target Compound Against
Plutella xylostella L (PXL)
cell parameters: a = 17.986 (2), b = 8.0180 (10), c =
3
The larvicidal activity of the target compound and the
positive control tebufenozide (RH-5992) against PXL
were tested by leaf film feeding method according to the
reported procedure [20]. Fresh cabbage leaves were
dipped into the 200 lg/mL test water solution for 10 s
which was prepared with a 5% of acetone to help the
compound to dissolve. After air-drying for evaporating
off the acetone and water, the treated leaves were cut
into small pieces and placed in the Petri dishes with
9 cm diameter. Ten indviduals of 2nd instar larvae of
PXL were transferred into the 10 cm diameter of Petri
dish. The Petri dishes were finally fastened with rubbers
and placed in the standard culturation room for 96 h or
120 h at 25 °C with 80% of humidity. The percentage of
mortalities was evaluated according to the corresponding
CK which uses water to dispose only. The insects which
had no reaction when touched by brush pen were
regarded as death insect. Each treatment was repeated for
three times.
˚
˚
12.0190(14) A, V = 1732.9(4) A , Z = 4, density (calcu-
lated) = 1.335 g/cm3, and linear absorption coefficient
0.209 mm-1. In total 19,940 integrated reflections were
collected, reducing to a data set of 4,135 unique with
Rint = 0.0404, and completeness of data (to h = 27.89°) of
99.8%. Data were collected and processed using Crystal
Clear (Rigaku). An empirical absorption correction was
applied using Crystal Clear (Rigaku). The Structure was
solved by direct methods with the SHELXS-97 program
[22]. Refinements were done by the full-matrix least-
squares on F2 with SHELXL-97 [23]. All of the non-H
atoms were refined anisotropically by full-matrix least-
squares to give the final R = 0.0367 and wR = 0.0932
(w = 1/[r2 ((F2o) ? (0.0614P)2 ? 0.0000P], where P =
(F2o ? 2F2c)/3 with (D/r)max = 0.998 and S = 1.035 by
using the SHELXL program. The hydrogen atoms were
located from a difference Fourier map and refined iso-
tropically. The corrections for absorption is multi-scan,
Tmin = 0.9516, Tmax = 0.9594, various relevant details
of the crystallographic experiment are given in Table 1.
Insecticide Activity of the Target Compound Against
Larval Culex Pipiens Pallens (CPP)
Biological Screening
Fungicide Screening
The larvicidal activity of the target compound against CPP
was evaluated according to the reported procedure [20].
The target compound of 2 mg was weighed into a 10 mL
vial; 10 mL of acetone was added to dissolve the com-
pound to prepare 200 lg/mL of mother solution. The
working solution of 2 lg/mL was prepared by diluting
1 mL of mother solution with 89 mL of water and 10 mL
of feeding solution into a 100 mL beaker. Ten CPP of 4th
instar larvae were transfer into the beaker. Thereafter, the
beakers with mosquito larvae were put into the standard
conditioned rooms for further cultivation with temperature
of 25 °C and humidity of 80%. After 24 h or 96 h of
cultivation, the mortalities of the larval were calculated by
the corresponding CK, which was prepared by 1 mL of
acetone for substituting 1 mL of mother solution, the
observation was conducted until all the larvae metamor-
phosized into pupation or died. Tebufenozide was chosen
as a positive control.
Preliminary screening was conducted by fungi growth
inhibition method according to the reference using potato
dextrose agar (PDA) as cultivation medium [13]. A stock
solution of each compound was prepared at 500 lg/mL
using sterilized water containing 2 drops of N,N-dimeth-
ylformamide (DMF) as a solvent, then 1 mL of the stock
solution was transferred into a 10 cm diameter of Petri
dish, 9 mL of PDA was then added to prepare the plate
containing 50 lg/mL of the test compound. Before the
plate solidification, the PDA was thoroughly mixed by
turning around the petri dish in the sterilized operation desk
5 times to scatter the compound in PDA evenly. Then,
4 mm of diameter of fungi cake was inoculated on the plate
and cultured in the culture tank at 24–26 °C. The diameter
of fungi spread was measured 2 days later. Growth inhi-
bition was then calculated using the corresponding control.
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1863
Table 1 Crystal data and
structure refinement for the title
compound
Molecular formula
C16H20N4O3S
348.42
Formula weight
Temperature (K)
Crystal system, space group
l (MoKa)
113 (2)
Monoclinic, P 21/c
0.71075 mm-1
˚
˚
˚
Unit cell dimensions
a = 17.986(2) A; b = 8.0180(10) A; c = 12.0190(14) A;
a = 908; b = 91.160(5)8; c = 908
3
˚
Volume (A )
1732.9 (4)
Z, calculated density (g cm-3
)
4, 1.335
Absorption coefficient (mm-1
)
0.209
F (000)
736
Crystal size (mm)
Theta range/°
Index ranges
0.24 9 0.22 9 0.20
1.13–27.89
-23 B h B 23; -10 B k B 10; -15 B l B 15
19940
Reflections collected
Independent reflections
Completeness to h max
Max and min transmission
4135 [R (int) = 0.0404]
99.8%
0.9594 and 0.9516
4135/0/226
Observed data/restraints/parameters
Goodness of fit on F2
1.035
Final R indices [I [ 2sigma (I)]
R indices (all data)
3
Largest difference peak and hole (e/A )
R1 = 0.0367, wR2 = 0.0932
R1 = 0.0445, wR2 = 0.1008
0.314 and -0.306
˚
Analysis of the Crystallographic Structure
Results and Discussion
The molecular structure and perspective view of the crystal
packing in a unit cell of the title compound are shown in
Figs. 1 and 2, respectively. The selected bond lengths,
angles and torsion angles are listed in Table 2.
Synthesis of the Title Compound
The title compound was synthesized according to
Scheme 1. Intermediate 4-methyl-1,2,3-thiadiazole-5-car-
bonyl chloride was synthesized according to Ref. [18],
N(Et)3 as acid acceptor, 4-methyl-1,2,3-thiadiazole-5-car-
boxylic acid was found to be the main by-product when the
reaction mixture contained excessive of 4-methyl-1,2,3-
thiadiazole-5-carbonyl chloride, 10.49% of 4-methyl-1,2,
3-thiadiazole-5-carboxylic acid was recovered. Another
by-product N(Et)3ꢀHCl was easily to be removed by
washing with water. The results of the column chroma-
tography showed that, the title compound was produced as
minor compound, another main product was obtained as
shown in Scheme 2, the total yields of these two com-
pounds added up to 80.36%, the structures of the title
compound was confirmed by 1H NMR, IR and HRMS
determination [20].
As shown in Table 2. Bond lengths and bond angles
within the thiadiazole ring agree well with the values
reported [24]. The sum of O(1–C(4)–N(3), O(1)–C(4)–C(1)
and N(3)–C(4)–C(1) angles are 360°, indicating the sp2
hybridizationstate of C(4) atom; The sum of O(2)–C(9)–
N(3), O(2)–C(9)–C(10) and N(3)–C(9)–C(10) angles are
360°, indicating the sp2 hybridization state of C(9) atom.
Due to the conjugation of thiadiazole ring and C(4) = O(1)
˚
bond, the bond lengths of C(1) = C(2) (1.3821(18) A) and
˚
N(1) = N(2) (1.3079(16) A) are slightly longer than that of
˚
typical C = C bond (1.34 A) [25] and N = N bond
˚
(1.24 A) [26], respectively, and the bond lengths of C(1)–
˚
C(4) (1.4958(17) A) and C(2)–N(2) (1.3720(18) A) are
˚
˚
slightly shorter than typical C–C bond(1.54 A) [27] and
Scheme 2 Another product of
the reaction
CH3
O
C
N
O
O
O
CH3
CH3
O
N
H3CO
H3CO
S
H3CO
COCl
N
N
N
N
N
N
NH
N
N
+
S
H
H
NH
S
Triethylamine
t-Bu
t-Bu
t-Bu
71.75%
8.61%
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J Chem Crystallogr (2011) 41:1860–1865
and S(1)–C(1)–C(4)–N(3) are 16.4 (2)° and 22.38 (17)°,
respectively, indicating that the acyl amide group and the
thiadiazole ring are non-planar. The torsion angles of
C(16)–O(3)–C(12)–C(11) is -0.2(2)°, indicating that the
methoxyl group and the benzene ring are coplanar. The
dihedral angle formed by the thiadiazole ring and benzene
ring is 52.85°. There are two intermolecular hydrogen
bonds in the structure, C (15)–H (15)ꢀꢀꢀO (2) and N (4)-H
(1)ꢀꢀꢀN (2) as detailed in Table 3.
Biological Activity of the Title Compound
The results of insecticidal activity of the title compound
against the PXL is 25% at 400 lg/mL and 10% against
CPP at 2 lg/mL, the corresponding positive control RH-
5992 has 40% of insecticidal activity against the PXL at
200 lg/mL and 100% activity against CPP at 2 lg/mL
respectively. This demonstrates that the compound has a
certain extent insecticidal activity, its insecticidal activity
is lower than that of N or N0 carbonyl substituted 1,2,3-
thiadiazole containing diacylhydrazines. Fungicide activity
against the typical fungi commonly occurring in the Chi-
nese agro-ecosystem was detected at 50 lg/mL in vitro.
The results of the target compound has inhibition of 37%,
44%, 90% against BC, RC, SS respectively, this indicated
that the target compound has a good growth inhibition to
BC, and comparatively good growth inhibition to SS
(Table 4), while the control compound RH5992 only
had 30%, 46%, 54% of inhibition against PI, RC, SS
respectively.
Fig. 1 Molecular structure of the title compound
Fig. 2 Crystal packing of the title compound
˚
All the results indicated that, 1,2,3-thiadiazole was a
very good active substructure for novel pesticide devel-
opment. Changing phenyl group into 1,2,3-thiadiazole kept
the insecticidal activity of diacylhydrazine insecticides.
C–N bond (1.47 A) [28]. Because of the P-p conjugate
˚
effect, the N(3)–C(9) bond (1.4529(15) A) and N(3)–C(4)
˚
bond (1.3903(16) A) is shorter than the typical C–N single
˚
bond (1.47 A). The torsion angles of C(2)–C(1)–C(4)–O(1)
Table 2 Selected bond lengths, angles and torsion angles of the title compound
˚
Bond lengths (A)
S(1)–N(1)
1.6611 (12)
1.7075 (13)
1.3903 (16)
1.3719 (15)
1.3079 (16)
N(3)–N(4)
N(2)–C(2)
O(2)–C(9)
N(4)–C(5)
C(1)–C(2)
1.4202 (15)
1.3720 (18)
1.2079 (15)
1.4929 (17)
1.3821 (18)
C(1)–C(4)
O(1)–C(4)
N(3)–C(9)
O(3)–C(16)
C(12)–C(13)
1.4958 (17)
1.2142 (15)
1.4529 (15)
1.4321 (17)
1.3946 (19)
S(1)–C(1)
N(3)–C(4)
O(3)–C(12)
N(1)–N(2)
Bond angles (°)
N(1)–S(1)–C(1)
C(4)–N(3)–C(9)
O(1)–C(4)–N(3)
O(2)–C(9)–N(3)
Torsion angles (°)
C(4)–N(3)–N(4)–C(5)
C(9)–N(3)–C(4)–O(1)
S(1)–C(1)–C(4)–N(3)
93.19 (6)
N(1)–N(2)–C(2)
N(4)–N(3)–C(9)
O(1)–C(4)–C(1)
O(2)–C(9)–C(10)
113.93 (11)
116.82 (10)
121.33 (11)
123.25 (12)
C(4)–N(3)–N(4)
N(3)–N(4)–C(5)
N(3)–C(4)–C(1)
N(3)–C(9)–C(10)
117.01 (10)
114.24 (10)
116.82 (11)
118.84 (10)
119.99 (11)
121.83 (11)
117.65 (11)
124.41 (11)
17.03 (18)
22.38 (17)
C(9)–N(3)–N(4)–C(5)
N(4)–N(3)–C(4)–C(1)
C(16)–O(3)–C(12)–C(11)
-83.15 (13)
-9.96 (16)
-0.2 (2)
N(4)–N(3)–C(4)–O(1)
C(2)–C(1)–C(4)–O(1)
N(4)–N(3)–C(9)–O(2)
168.56 (11)
16.4 (2)
-29.56 (17)
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J Chem Crystallogr (2011) 41:1860–1865
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Table 3 Intermolecular hydrogen bonds of the title compound
˚
dD–H/A
˚
˚
D–HꢀꢀꢀA
dHꢀꢀꢀA/A
dDꢀꢀꢀA/A
\DHA/(8)
C(15)–H(15)ꢀꢀꢀO(2)i
0.950
N(4)-H(1)ꢀꢀꢀN(2)ii
Symmetry codes: (i) x, 3/2 - y, 1/2 ? z; (ii) x, 1/2 - y, -1/2 ? z
2.440
3.1422 (16)
3.0407 (16)
131.0
0.878 (14)
2.235 (15)
152.5 (14)
Table 4 Insecticidal and fungicidal activity of the title compound (%)
Compd.
AS
BC
CA
GZ
PI
PP
PS
RC
SS
PXL
CPP
Titile compound
RH-5992
14
8
3
2
37
29
2
5
18
15
2
0
16
9
4
1
43
30
4
4
5
3
5
18
10
2
3
44
46
2
1
90
54
4
3
25 6a
10
4
0
24
40
5
100
AS Alternaria solani, PI Phytophthora infestans, BC Botrytis cinerea, CA Cercospora arachidicola, GZ Gibberella zea, PP Physalospora
piricola, PS Pellicularia sasakii, RC Rhizoctonia cerealis, SS Sclerotinia sclerotiorum, PXL Plutella xylostella L., 96 h, 200 lg/mL, CPP Culex
pipiens pallens 2 lg/mL
a
Results of 400 lg/mL
8. Fan ZJ, Liu XF, Liu FL, Bao LL, Zhang YG (2005) Acta Phy-
tophylacica Sin 32:87–92
Supplementary Information
9. Zhan P, Liu XY, Fang ZJ, Li ZY, Pannecouque C, Clercq ED
(2009) Eur J Med Chem 44:4648–4653
Crystallographic data for the structure in this paper have
been deposited with the Cambridge Crystallographic Data
Centre as supplementary publication CCDC 819047.
Copy of the data can be obtained, free of charge, via
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallographic Data Centre, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: ?44 1223 336033;
or e-mail: deposit@ccdc.cam.ac.uk).
10. Zhan P, Liu XY, Li ZY, Fang ZJ, Li Z, Wang DF, Pannecouque
C, Clercq ED (2009) Bioorg Med Chem 17:5920–5927
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Xie YY (2007) Bioorg Med Chem Lett 17:869–873
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Chem 29:179–185
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Zheng QX, Song HB (2010) J Agric Food Chem 58:2630–2636
14. Zuo X, Mi N, Fan ZJ, Zheng QX, Zhang HK, Wang H, Yang ZK
(2010) J Agric Food Chem 58:2755–2762
Acknowledgments This study was funded in part by grants from
the National Natural Science Foundation of China (Nos. 20872071
and 20911120069), the Natural Science Foundation of Tianjin
(10JCZDJC17500), the National Key Project for Basic Research
(2010CB126105), National Key Technology Research and Develop-
ment Program (2011BAE06B02 and 2011BAE06B05) and the
Foundation of Achievements Transformation and Spreading of
Tianjin Agricultural Science and Technology (201002250); The
Common Wealth Specialized Research Fund of China Agriculture
(nyhyzx3-21, 201103016 and 201003029), and the Russian Founda-
tion for Basic Research (Grant Numbers RFBR 08-03-00376a and
RFBR/NNSF 08-03-92208 a).
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Agric Food Chem 58:2715–2719
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