Design, synthesis, and insecticidal activity of 1,5-diphenyl-1-pentanone analogues

Article abstract of DOI:10.1002/cjoc.201180409

Three series of novel 1,5-diphenyl-1-pentanone derivatives were designed and synthesized. Their structures were characterized by IR, ¹H NMR techniques, and elemental analysis. The insecticidal activities of the new compounds were preliminarily evaluated. The bioassay results indicated that the compounds X11-X30 displayed better aphicidal activity against Aphis gossypii than compounds X1-X10 and the lead compound (E)-1,5-diphenyl-1-penten-1-one (A). The inhibitory rates of compounds X6 and X29 were 100% against Plutella xylostella (L.) at 600 mg·L^-1. Compounds X12, X13, X19, X24, X25, X26 and X27 showed higher insecticidal activity against Tetranychus cinnabarinus (Boisduval) at 600 mg·L^-1 than the lead compound (A).

Full text of DOI:10.1002/cjoc.201180409

FULL PAPER
Design, Synthesis, and Insecticidal Activity of
1,5-Diphenyl-1-pentanone Analogues
Yang, Shaoxianga(杨绍祥)
Kang, Tieniua(康铁牛)
Sun, Yufenga(孙玉凤)
Ling, Yun*,a(凌云)
Rui, Changhuib(芮昌辉)
Cui, Zininga(崔紫宁)
Yang, Xinlinga(杨新玲)
a Key Laboratory of Pesticide Chemistry and Application, Ministry of Agriculture, Department of Applied
Chemistry, College of Science, China Agricultural University, Beijing 100193, China
b Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, China
Three series of novel 1,5-diphenyl-1-pentanone derivatives were designed and synthesized. Their structures
1
were characterized by IR, H NMR techniques, and elemental analysis. The insecticidal activities of the new com-
pounds were preliminarily evaluated. The bioassay results indicated that the compounds X11— X30 displayed better
aphicidal activity against Aphis gossypii than compounds X1— X10 and the lead compound (E)-1,5-diphenyl-1-
penten-1-one (A). The inhibitory rates of compounds X6 and X29 were 100% against Plutella xylostella (L.) at 600
mg•L－ 1. Compounds X12, X13, X19, X24, X25, X26 and X27 showed higher insecticidal activity against
Tetranychus cinnabarinus (Boisduval) at 600 mg•L－ 1 than the lead compound (A).
Keywords Stellera chamaejasme L., (E)-1,5-diphenyl-1-penten-1-one, analogue, synthesis, design, insecticidal
activity
Introduction
1,5-diphenyl-1-pentanone analogues with better aphi-
cidal activity when the electron density of carbonyl in
the analogues increased. Eight new analogues in which
the 1-phenyl was replaced by different nitrogen hetero-
cycles, also exhibited good insecticidal activity against
Synthetic insecticides play an essential role in agri-
cultural pest management. Strategies to control pests
with classic insecticides, such as pyrethroids, organo-
phosphorus and carbamate insecticides, however, have
led to some side effects, notably environmental con-
tamination and resistant strains generation.1 Therefore,
the novel active molecule has become the focus in pes-
ticide discovery for decades and continues to be an ac-
tive area nowadays.2 The active component with novel
structure from a plant extract is often used as a lead for
new insecticide discovery to overcome their drawbacks
such as instability, complex structure and limited insec-
ticidal spectrum. Pyrethroids and neonicotinoids are
successful example insecticides discovered basically
from the natural plant products.3
(E)-1,5-Diphenyl-2-penten-1-one (A), extracted
from Stellera chamaejasme L, showed good insecticidal
property and antifeedant activity against Aphis gossypii
Glov, Schizaphis graminum Rondani4 and Myzus persi-
cae Sulzer.5 Compound A is similar in structure to these
active compounds possessing a phenyl-carbonyl-phenyl
skeleton, such as daphneolone, chalcones, dihydrochal-
cones, 2-phenylethyl benzoate, dibenzyl ketone and
flavonoids. Thus, A is regarded as a lead for new insec-
ticide discovery. Hou et al.6,7 reported some
－
1 8
Aphis gossypii at 600 mg•L .
The reported insecticidal spectrum of 1,5-diphenyl-
1-pentanone and its analogues is mainly limited in
aphids. In order to find novel compounds with wide
insecticidal spectra, the title compound X (Figure 1)
was herein designed, in which the 1-phenyl of com-
pound A was replaced with 3-substituent-4-nitroimino-
1,3,5-oxadiazinanes, an active group of neonicotinoid
insecticide, thiamethoxam.13-18 In the meantime, the
linkage length of compound A was reduced from
five-carbon to three-carbon so as to investigate the bio-
logical effects of varying carbon number in linkage. The
title compound X was synthesized with the method in
Scheme 1. Their biological activities against different
kinds of pests were preliminarily evaluated.
Experimental
Materials and methods
Melting points (m.p.) were recorded on a Yanagi-
1
moto MFG. Co., which was uncorrected. H NMR
spectra were obtained at 300 MHz using a Bruker
*
E-mail: lyun@cau.edu.cn
Received April 15, 2011; revised June 23, 2011; accepted July 29, 2011.
Project supported by the National Key Project for Basic Research (No. 2010CB126104), the National Key Technology R&D Program (No.
2011BAE06B05-5) and Innovation Fund for Graduate Student of China Agricultural University.
2394
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Chin. J. Chem. 2011, 29, 2394— 2400

Design, Synthesis, and Insecticidal Activity of 1,5-Diphenyl-1-pentanone Analogues
Figure 1 The structures of the lead compound A, thiamethoxam and title compound X.
Scheme 1 General synthetic route for the title compounds X1— X30
NNO2
NR1
O
NNO2
NNO2
HCHO
H2O
HN
R1NH2
II
+
H2N
NH2
HCOOH
H2N
OH
NHR1
I
III
IVa — IVc
O
O
O
NNO2
NR1
O
O
Py
SOCl2
IV
MeCN/Py
R2
R2
N
+
R2
HOOC
COOH
R2
Cl
H
Piperidine
VII
VI
V
VIII
X
X1: R1 = Me, R2 = 4-F-C6H4; X2: R1 = Me, R2 = 4-Cl-C6H4; X3: R1 = Me, R2 = 4-Br-C6H4; X4: R1 = Me, R2 = 2,4-Cl2-C6H3;
X5: R1 = Me, R2 = 4-OMe-C6H4; X6: R1 = Me, R2 = 4-OEt-C6H4; X7: R1 = Me, R2 = 3-Me-C6H4; X8: R1 = Me, R2 = Phenyl;
X9: R1 = Me, R2 = 2-Furyl; X10: R1 = Me, R2 = Thienyl; X11: R1 = Et, R2 = 4-F-C6H4; X12: R1 = Et, R2 = 4-Cl-C6H4;
X13: R1 = Et, R2 = 4-Br-C6H4; X14: R1 = Et, R2 = 2,4-Cl2-C6H3; X15: R1 = Et, R2 = 4-OMe-C6H4; X16: R1 = Et, R2 = 4-OEt-C6H4;
X17: R1 = Et, R2 = 3-Me-C6H4; X18: R1 = Et, R2 = Phenyl; X19: R1 = Et, R2 = 2-Furyl; X20: R1 = Et, R2 = Thienyl;
X21: R1 = i-Pr, R2 = 4-F-C6H4; X22: R1 = i-Pr, R2 = 4-Cl-C6H4; X23: R1 = i-Pr, R2 = 4-Br-C6H4; X24: R1 = i-Pr, R2 = 2,4-di-Cl-C6H3;
X25: R1 = i-Pr, R2 = 4-OMe-C6H4; X26: R1 = i-Pr, R2 = 4-OEt-C6H4; X27: R1 = i-Pr, R2 = 3-Me-C6H4; X28: R1 = i-Pr, R2 = Phenyl;
X29: R1 = i-Pr, R2 = 2-Furyl; X30: R1 = i-Pr, R2 = Thienyl
Avance DPX300 spectrometer in CDCl3 solution with
tetramethylsilane as the internal standard. Elemental
analyses were determined on ST-Carloerba. Co. ele-
mental analyzer.
obtained by the similar method.
Ivb: white crystals (2.8 g, 86.8%), m.p. 120.0—
122.0 ℃ (Lit.19 117.0—118.0 ℃).
Ivc: white crystals (1.5 g, 38.2%), m.p. 108.0—
110.0 ℃ (Lit.19 108.0—109.0 ℃).
Synthetic procedure for 1-methyl-2-nitroguanidine
IIIa
Synthetic procedure for cinnamic acid VII
Take IIIa as the example,19 21.0 g (0.2 mol) of ni-
troguanidine and 40% aqueous methylamine (20 g, 0.25
mol) were added to absolute water (150 mL) in a 500
mL three-necked round-bottomed flask. The solution
was stirred at room temperature for 24 h. The solid was
collected by filtration, and then dried to obtain com-
pound IIIa in white crystal (20.7 g, 88.2%), m.p. 160.0
—162.0 ℃ (Lit.19 160.0—161.0 ℃). IIIb and IIIc
were obtained by the similar method.
0.3 g (2.86 mmol) of malonic acid was added to
stirred solution of the corresponding aldehyde (1.3
mmol) in pyridine (15 mL) and piperidine (1.5 mL).
The mixture was heated to reflux for 1 h. The reaction
mixture was neutralized with 1 mol•L－ hydrochloric
1
acid in an ice bath. White crystals were separated out,
filtered and washed with cooled water. Recrystallization
from aqueous ethanol (Vwater∶Vetanol＝1∶1) afforded
the corresponding acids VII with yields of 90%—
96%.20
IIIb: white crystals (22.7 g, 86.8%), m.p. 146.0—
148.0 ℃ (Lit.19 145.0—146.0 ℃).
IIIc: white crystals (18.5 g, 46.2%), m.p. 128.0—
130.0 ℃ (Lit.19 126.0—127.0 ℃).
Synthetic procedure for the title compounds X
A mixture containing intermediate VII (7 mmol) and
thionyl chloride (100 mmol) was added into a 50 mL
flask equipped with a condenser and refluxed for 8 h.
After cooled to room temperature, the excess thionyl
chloride was distilled off via vacuum. The residue was
reacted with III (7 mmol) in 20 mL acetonitrile for 8 h
at refluxing temperature with pyridine as an acid accep-
tor. The solvent was removed under reduced pressure to
give crude products. The products were purified by
column chromatography on silica gel with ethyl acetate
and petroleum (60—90 ℃) at a volume ratio of 1∶1 as
an eluent. The yields and melting points of the title
Synthetic procedure for N-(3-methyl-1,3,5-oxadia-
zinan-4-ylidene)nitramide IVa
1∶1 mixture of formaldehyde (37%, 20 mL) and
formic acid (80%, 20 mL) was added to
1-methyl-2-nitroguanidine (IIIa, 2.4 g) in a 100 mL
three-necked round-bottomed flask. The resulting mix-
ture was heated to 75 ℃ for 12 h. After cooled to 0 ℃,
and adjusted to pH 8.0 with concentrated hydrochloric
acid, the white solid was filtered and dried to get com-
pound IVa. White crystals (2.6 g, 81.2%), m.p. 140.0—
141.0 ℃ (Lit.19 143.0—144.0 ℃). IVb and IVc were
Chin. J. Chem. 2011, 29, 2394— 2400
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www.cjc.wiley-vch.de
2395

Yang et al.
FULL PAPER
NCH2O), 6.88 (d, J＝15.46 Hz, 1H, ＝CHC＝O),
6.97—7.01 (m, 2H, ArH-2,6), 7.60—7.68 (m, 3H,
ArH-3,5, CH＝C); IR (KBr) ν: 3070, 1675, 1598, 1571,
compounds X1—X30 are listed as follows. Their struc-
1
tures were confirmed by IR, H NMR techniques and
elemental analysis.
－
1
1512, 1338, 1106 cm . Anal. calcd for C14H16N4O5: C
53.89, H 5.43, N 16.76; found C 53.78, H 5.49, N 16.49.
N-[3-Methyl-5-((E)-3-m-tolylacryloyl)-1,3,5-oxadia-
zinan-4-ylidene]nitramide (X7): Yellow powdery
N-{3-[(E)-3-(4-Fluorophenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X1): White
1
powdery crystals, yield 71.4%, m.p. 110—112 ℃; H
NMR (CDCl3, 300 MHz) δ: 3.05 (s, 3H, NCH3), 5.10 (s,
2H, OCH2N), 5.38 (s, 2H, NCH2O), 7.01 (d, J＝15.57
Hz, 1H, ＝CHC＝O), 7.27—7.34 (m, 2H, ArH-2,6),
7.69 (d, J＝15.63 Hz, 1H, CH＝C), 7.73—7.80 (m, 2H,
ArH-3,5); IR (KBr) ν: 3085, 1679, 1616, 1599, 1547,
1
crystals, yield 68.0%, m.p. 100—102 ℃; H NMR
(CDCl3, 300 MHz) δ: 2.34 (s, 3H, Ar-CH3), 3.08 (s, 3H ,
NCH3), 5.10 (s, 2H, OCH2N), 5.38 (s, 2H, NCH2O),
7.25 (d, J＝15.57 Hz, 1H, ＝CHC＝O), 7.26—7.50 (m,
4H, ArH-2,4,5,6), 7.63 (d, J＝15.54 Hz, 1H, CH＝C);
IR (KBr) ν: 3023, 1672, 1613, 1568, 1504, 1334, 1103
－
1
1507, 1336 cm . Anal. calcd for C13H13FN4O4: C 50.65,
H 4.25, N 18.17; found C 50.45, H 4.51, N 18.50.
N-{3-[(E)-3-(4-Chlorophenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X2): White
－
1
cm . Anal. calcd for C14H16N4O4: C 55.26, H 5.30, N
18.41; found C 55.33, H 5.44, N 18.43.
1
N-(3-Cinnamoyl-5-methyl-1,3,5-oxadiazinan-4-ylid-
ene)nitramide (X8): White powdery crystals, yield
71.0%, m.p. 120—121 ℃; 1H NMR (CDCl3, 300 MHz)
δ: 3.08 (s, 3H, NCH3), 5.10 (s, 2H, OCH2N), 5.38 (s, 2H,
NCH2O), 7.05 (d, J＝15.64 Hz, 1H, ＝CHC＝O),
7.43—7.71 (m, 6H, Ph, CH＝C); IR (KBr) ν: 3077,
powdery crystals, yield 72.1%, m.p. 160—161 ℃; H
NMR (CDCl3, 300 MHz) δ: 3.08 (s, 3H, NCH3), 5.11 (s,
2H, OCH2N), 5.39 (s, 2H, NCH2O), 7.07 (d, J＝15.62
Hz, 1H, ＝CHC＝O), 7.51—7.55 (m, 2H, ArH-2,6),
7.65—7.73 (m, 3H, ArH-3,5, CH＝C); IR (KBr) ν:
－
1
3032, 1684, 1621, 1580, 1491, 1333, 1096 cm . Anal.
calcd for C13H13ClN4O4: C 48.08, H 4.04, N 17.25;
found C 48.35, H 4.16, N 17.44.
－
1
1677, 1616, 1573, 1505, 1338, 1028 cm . Anal. calcd
for C13H14N4O4: C 53.79, H 4.86, N 19.30; found C
53.75, H 4.98, N 19.32.
N-{3-[(E)-3-(4-Bromophenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X3): White
N-{3-[(E)-3-(Furan-2-yl)acryloyl]-5-methyl-1,3,5-
oxadiazinan-4-ylidene}nitramide (X9): Brown powdery
1
powdery crystals, yield 69.0%, m.p. 148—150 ℃; H
1
crystals, yield 56.0%, m.p. 113—115 ℃; H NMR
NMR (CDCl3, 300 MHz) δ: 3.08 (s, 3H, NCH3), 5.10 (s,
2H, OCH2N), 5.38 (s, 2H, NCH2O), 7.08 (d, J＝15.56
Hz, 1H, ＝CHC＝O), 7.62—7.68 (m, 5H, ArH-2,3,5,6,
CH＝C); IR (KBr) ν: 3031, 1684, 1621, 1582, 1484,
1399, 1069 cm－ 1. Anal. calcd for C13H13BrN4O4: C
42.29, H 3.55, N 15.18; found C 42.57, H 3.60, N 15.30.
N-{3-[(E)-3-(2,4-Dichlorophenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X4): Light
yellow powdery crystals, yield 73.0%, m.p. 180—181
℃; 1H NMR (CDCl3, 300 MHz) δ: 3.08 (s, 3H, NCH3),
5.11 (s, 2H, OCH2N), 5.39 (s, 2H, NCH2O), 7.15 (d, J＝
15.49 Hz, 1H, ＝ CHC ＝ O), 7.58 — 7.59 (m, 1H,
ArH-6), 7.77—7.86 (m, 3H, ArH-3,5, CH＝C); IR (KBr)
(CDCl3, 300 MHz) δ: 3.07 (d, J＝2.69 Hz,, 3H, NCH3),
5.09 (d, J＝1.70 Hz, 2H, OCH2N), 5.33 (d, J＝1.11 Hz,
NCH2O), 6.65—6.75 (m, 2H, Fu-4 H, ＝CHC＝O),
7.00—7.09 (m, 1H, Fu-3 H), 7.44 (d, J＝15.32 Hz, 1H,
CH＝C), 7.89 (t, J＝1.17 Hz, 1H, Fu-5 H); IR (KBr) ν:
－
1
3031, 1679, 1616, 1575, 1329, 1100 cm . Anal. calcd
for C11H12N4O5: C 47.15, H 4.32, N 19.99; found C
47.42, H 4.39, N 19.90.
N-{3-Methyl-5-[(E)-3-(thiophen-2-yl)acryloyl]-1,3,5-
oxadiazinan-4-ylidene}nitramide
(X10):
Brown
1
powdery crystals, yield 76.0%, m.p. 106—108 ℃; H
NMR (CDCl3, 300 MHz) δ: 3.07 (s, 3H, NCH3), 5.09 (d,
J＝2.51 Hz, 2H, OCH2N), 5.34 (s, 2H, NCH2O), 6.72 (d,
J＝15.27 Hz, 1H, ＝CHC＝O), 7.15—7.18 (m, 1H,
Thiophene-4 H), 7.56—7.58 (m, 1H, Thiophene-3 H),
7.76 (d, J＝5.07 Hz, 1H, Thiophene-5 H), 7.87 (d, J＝
15.26 Hz, 1H, CH＝C); IR (KBr) ν: 3080, 1670, 1597,
－
1
ν: 3076, 1682, 1623, 1585, 1498, 1378, 1097 cm .
Anal. calcd for C13H12Cl2N4O4: C 43.47, H 3.37, N
15.60; found C 43.71, H 3.60, N 15.64.
N-{3-[(E)-3-(4-Methoxyphenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X5): Yellow
－
1
1
1570, 1323, 1103 cm . Anal. calcd for C11H12N4O4S: C
44.59, H 408, N 18.91; found C 44.53, H 4.10, N 18.65.
N-{3-Ethyl-5-[(E)-3-(4-fluorophenyl)acryloyl]-1,3,5-
oxadiazinan-4-ylidene}nitramide (X11): White powdery
powdery crystals, yield 72.0%, m.p. 131—133 ℃; H
NMR (CDCl3, 300 MHz) δ: 3.07 (s, 3H, NCH3), 3.81 (s,
OCH3), 5.09 (s, 2H, OCH2N), 5.36 (s, 2H, NCH2O),
6.89 (d, J＝15.54 Hz, 1H, ＝CHC＝O), 6.99—7.02 (d,
J＝8.79 Hz, 2H, ArH-2,6), 7.63—7.68 (m, 3H, ArH-3,5,
CH＝C); IR (KBr) ν: 2941, 1697, 1622, 1596, 1513,
1
crystals, yield 31.5%, m.p. 168—170 ℃; H NMR
(DCCl3, 300 MHz) δ: 1.35 (t, J＝7.23 Hz, 3H, CCH3),
3.67—3.71 (m, 2H, CH2C), 4.93 (s, 2H, OCH2N), 5.36
(s, 2H, NCH2O), 6.90 (d, J＝15.00 Hz, 1H, ＝CHC＝
O), 7.03—7.11 (m, 2H, ArH-2,6), 7.53—7.59 (m, 2H,
ArH-3,5), 7.81 (d, J＝15.42 Hz, 1H, CH＝C); IR (KBr)
－
1
1343, 1099 cm . Anal. calcd for C14H16N4O5: C 52.50,
H 5.03, N 17.49; found C 52.69, H 5.25, N 17.41.
N-{3-[(E)-3-(4-Ethoxyphenyl)acryloyl]-5-methyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X6): Yellow
－
1
1
ν: 3006, 1679, 1616, 1570, 1511, 1270, 1041 cm .
Anal. calcd for C14H15FN4O4: C 52.17, H 4.69, N 17.18;
found C 52.13, H 4.61, N 17.36.
powdery crystals, yield 68.0%, m.p. 120—122 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.31—1.36 (t, J＝8.62 Hz,
CH2CH3,), 3.07 (s, 3H, NCH3), 4.05—4.12 (t, J＝6.96
Hz, CH2CH3), 5.10 (s, 2H, OCH2N), 5.36 (s, 2H,
N-{3-[(E)-3-(4-Chlorophenyl)acryloyl]-5-ethyl-1,3,5-
2396
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Chin. J. Chem. 2011, 29, 2394— 2400

Design, Synthesis, and Insecticidal Activity of 1,5-Diphenyl-1-pentanone Analogues
1
oxadiazinan-4-ylidene}nitramide (X12): White powdery
crystals, yield 28.2%, m.p. 147—148 ℃; H NMR
(CDCl3, 300 MHz) δ: 1.33—1.37 (m, 3H, CCH3), 2.37
(s, 3H, ArCH3), 3.64—3.76 (m, 2H, CH2C), 4.92 (s, 2H,
OCH2N), 5.36 (s, 2H, NCH2O), 6.93 (d, J＝15.39 Hz,
1H, ＝CHC＝O), 7.20—7.23 (m, 1H, ArH-2), 7.24—
7.30 (m, 1H, ArH-4), 7.36—7.38 (m, 2H, ArH-5,6),
7.83 (d, J＝15.48 Hz, 1H, CH＝C); IR (KBr) ν: 2945,
1
crystals, yield 22.4%, m.p. 172—174 ℃; H NMR
(CDCl3, 300 MHz) δ: 1.26 (t, J＝7.20 Hz, 3H, CCH3),
3.69—3.73 (m, 3H, CH2C), 4.93 (s, 2H, OCH2N), 5.37
(s, 2H, NCH2O), 6.96 (d, J＝15.39 Hz, 1H, ＝CHC＝
O), 7.44 (d, J＝8.49 Hz, 2H, ArH-2,6), 7.52 (d, J＝8.55
Hz, 2H, ArH-3,5), 7.78 (d, J＝15.48 Hz, 1H, CH＝C);
IR (KBr) ν: 3076, 1702, 1628, 1589, 1570, 1226, 1092
－
1
1676, 1611, 1562, 1506, 1272, 1039 cm . Anal. calcd
for C15H18N4O4: C 56.60, H 5.70, N 17.60; found C
56.60, H 5.58, N 17.68.
－
1
cm . Anal. calcd for C14H15ClN4O4: C 49.64, H 4.46,
N 16.54; found C 49.69, H 4.35, N 16.63.
N-{3-[(E)-3-(4-Bromophenyl)acryloyl]-5-ethyl-1,3,5-
oxadiazinan-4-ylidene}nitramide (X13): White powdery
N-(3-Cinnamoyl-5-ethyl-1,3,5-oxadiazinan-4-yli-
dene)nitramide (X18): Yellow powdery crystals, yield
18.3%, m.p. 168—170 ℃.; 1H NMR (CDCl3, 300 MHz)
δ: 1.35 (t, J＝7.26 Hz, 3H, CCH3), 3.65—3.69 (m, 2H,
CH2C), 4.92 (s, 2H, OCH2N), 5.36 (s, 2H, NCH2O),
6.96 (d, J＝15.39 Hz, 1H, ＝CHC＝O), 7.37—7.41 (m,
3H, ArH-2,3,4), 7.55—7.58 (m, 2H, ArH-5,6), 7.86 (d,
J＝15.39 Hz, 1H, CH＝C); IR (KBr) ν: 3081, 1678,
1
crystals, yield 25.0%, m.p. 174—176 ℃; H NMR
(CDCl3, 300 MHz) δ: 1.36 (t, J＝7.20 Hz, 3H, CCH3),
3.65—3.76 (m, 2H, CH2C), 4.93 (s, 2H, OCH2N), 5.37
(s, 2H, NCH2O), 6.94 (d, J＝15.39 Hz, 1H, ＝CHC＝
O), 7.26—7.38 (m, 2H, ArH-2,6), 7.48—7.52 (m, 2H,
ArH-3,5), 7.80 (d, J＝15.48 Hz, 1H, CH＝C); IR (KBr)
－
－
1
1
ν: 3077, 1700, 1628, 1586, 1486, 1295, 1071 cm .
Anal. calcd for C14H15BrN4O4: C 43.88, H 3.95, N
14.62; found C 43.80, H 3.94, N 14.63.
1614, 1568, 1271, 1503, 1040 cm . Anal. calcd for
C14H16N4O4: C 55.26, H 5.30, N 18.41; found C 55.25,
H 5.22, N 18.69.
N-{3-[(E)-3-(2,4-Dichlorophenyl)acryloyl]-5-ethyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X14): White
N-{3-Ethyl-5-[(E)-3-(furan-2-yl)acryloyl]-1,3,5-
oxadiazinan-4-ylidene}nitramide
(X19):
Brown
1
1
powdery crystals, yield 45.5%, m.p. 139—140 ℃; H
powdery crystals, yield 19.8%, m.p. 131—133 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.34 (t, J＝7.22 Hz, 3H,
CCH3), 3.65 — 3.68 (m, 3H, CH2C), 4.91 (s, 2H,
OCH2N), 5.34 (s, 2H, NCH2O), 6.47—6.49 (m, 1H,
Fu-3 H) , 6.71 (d, J＝3.45 Hz, 1H, Fu-4 H), 6.82 (d, J＝
15.03 Hz, 1H, ＝CHC＝O), 7.48—7.52 (m, 1H, Fu-5
H), 7.59 (d, J＝15.06 Hz, 1H, CH＝C); IR (KBr) ν:
NMR (CDCl3, 300 MHz) δ: 1.36 (t, J＝7.20 Hz, 3H,
CCH3), 3.65 — 3.76 (m, 2H, CH2C), 4.93 (s, 2H,
OCH2N), 5.37 (s, 2H, NCH2O), 6.94 (d, J＝15.39 Hz,
1H, ＝CHC＝O), 7.24 (d, J＝8.52 Hz, 1H, ArH-5),
7.43 (d, J＝2.07 Hz, 1H, ArH-2), 7.63 (d, J＝8.52 Hz,
1H, ArH-4), 7.80 (d, J＝15.48 Hz, 1H, CH＝C); IR
(KBr) ν: 3083, 1708, 1625, 1584, 1504, 1228, 1050
－
1
3093, 1675, 1613, 1567, 1273, 1040 cm . Anal. calcd
for C12H14N4O5: C 48.98, H 4.80, N 19.04; found C
48.91, H 4.63, N 19.09.
－
1
cm . Anal. calcd for C14H14Cl2N4O4: C 45.06, H 3.78,
N 15.01; found C 45.11, H 3.74, N 15.10.
N-{3-Ethyl-5-[(E)-3-(4-methoxyphenyl)acryloyl]-
1,3,5-oxadiazinan-4-ylidene}nitramide (X15): Yellow
N-{3-Ethyl-5-[(E)-3-(thiophen-2-yl)acryloyl]-1,3,5-
oxadiazinan-4-ylidene}nitramide
(X20):
Brown
1
1
powdery crystals, yield 17.2%, m.p. 142—144 ℃; H
powdery crystals, yield 15.2%, m.p. 165—167 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.35 (t, J＝7.22 Hz, 3H,
CCH3), 3.65 — 3.69 (m, 3H, CH2C), 4.92 (s, 2H,
OCH2N), 5.35 (s, 2H, NCH2O), 6.74 (d, J＝15.06 Hz,
1H, ＝CHC＝O), 7.03—7.09 (m, 1H, Thiophene-4 H),
7.34 (d, J＝3.41 Hz, 1H, Thiophene-3 H), 7.44 (d, J＝
5.10 Hz, 1H, Thiophene-5 H), 7.94 (d, J＝15.09 Hz, 1H,
CH＝C); IR (KBr) ν: 3119, 1674, 1599, 1566, 1280,
NMR (CDCl3, 300 MHz) δ: 1.35 (t, J＝7.22 Hz, 3H,
CCH3), 3.66—3.68 (m, 2H, CH2C), 3.84 (s, 3H, OCH3),
4.96 (s, 2H, OCH2N), 5.36 (s, 2H, NCH2O), 6.80—6.91
(m, 3H, ＝CHC＝O, ArH-2,6), 7.51—7.54 (m, 2H,
ArH-3,5), 7.83 (d, J＝15.32 Hz, 1H, CH＝C); IR (KBr)
－
1
ν: 3081, 1674, 1602, 1569, 1515, 1308, 1027 cm .
Anal. calcd for C15H18N4O5: C 53.89, H 5.43, N 16.76;
found C 53.76, H 5.49, N 16.61.
－
1
1043 cm . Anal. calcd for C12H14N4O4S: C 46.44, H
N-{3-[(E)-3-(4-Ethoxyphenyl)acryloyl]-5-ethyl-1,3,5-
4.55, N 18.05; found C 46.40, H 4.41, N 18.12.
oxadiazinan-4-ylidene}nitramide
(X16):
Yellow
N-{3-[(E)-3-(4-Fluorophenyl)acryloyl]-5-isopropyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X21): White
1
powdery crystals, yield 22.3%, m.p. 126—128 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.35 (t, J＝7.22 Hz, 3H,
CCH3), 1.43 (t, J＝7.02 Hz, 3H, OCCH3), 3.64—3.68
(m, 2H, CH2C), 4.04—4.08 (m, 2H, OCH2), 4.91 (s, 2H,
OCH2N), 5.35 (s, 2H, NCH2O), 6.80—6.89 (m, 3H,
＝CHC＝O, ArH-2,6), 7.49—7.52 (m, 2H, ArH-3,5),
7.82 (d, J＝15.36 Hz, 1H, CH＝C); IR (KBr) ν: 3081,
1
powdery crystals, yield 45.5%, m.p. 131—132 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.33 (d, J＝6.84 Hz, 6H,
C(CH3)2), 4.78—4.82 (m, 1H, CHC2), 4.86 (s, 2H,
OCH2N), 5.34 (s, 2H, NCH2O), 6.89 (d, J＝15.39 Hz,
1H, ＝CHC＝O), 7.04—7.10 (m, 2H, ArH-2,6), 7.53—
7.58 (m, 2H, ArH-3,5), 7.82 (d, J＝15.39 Hz, 1H, CH＝
－
1
1696, 1600, 1570, 1512, 1294, 1040 cm . Anal. calcd
for C16H20N4O5: C 55.17, H 5.79, N 16.08; found C
55.07, H 5.63, N 16.00.
C); IR (KBr) ν: 3110, 1674, 1617, 1597, 1544, 1240,
１
1006 cm－ . Anal. calcd for C15H17FN4O4: C 53.57, H
5.09, N 16.66; found C 53.60, H 4.93, N 16.78.
N-[3-Ethyl-5-((E)-3-m-tolylacryloyl)-1,3,5-oxadia-
zinan-4-ylidene]nitramide (X17): Yellow powdery
N-{3-[(E)-3-(4-Chlorophenyl)acryloyl]-5-isopropyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X22): White
Chin. J. Chem. 2011, 29, 2394— 2400
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2397

Yang et al.
FULL PAPER
1
1
powdery crystals, yield 30.2%, m.p. 155—157 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.33 [d, J＝6.81 Hz, 6H,
C(CH3)2], 4.76—4.80 (m, 1H, CHC2), 4.86 (s, 2H,
OCH2N), 5.34 (s, 2H, NCH2O), 6.93 (d, J＝15.39 Hz,
1H, ＝CHC＝O), 7.33—7.37 (m, 2H, ArH-2,6), 7.46—
7.52 (m, 2H, ArH-3,5), 7.79 (d, J＝15.42 Hz, 1H, CH＝
C); IR (KBr) ν: 3067, 1697, 1623, 1592, 1557, 1289,
crystals, yield 35.8%, m.p. 152—153 ℃; H NMR
(CDCl3, 300 MHz) δ: 1.33 [d, J ＝ 6.81 Hz, 6H,
C(CH3)2], 2.37 (s, 3H, ArCH3), 4.79—4.81 (m, 1H,
HC＝C), 4.85 (s, 2H, OCH2N), 5.34 (s, 2H, NCH2O),
6.93 (d, J＝15.39 Hz, 1H, ＝CHC＝O), 7.22—7.29 (m,
2H, ArH-2,4), 7.36 (s, 2H, ArH-5,6), 7.83 (d, J＝15.39
Hz, 1H, CH＝C); IR (KBr) ν: 2978, 1678, 1614, 1586,
－
－
1
1
1091 cm . Anal. calcd for C15H17ClN4O4: C 51.07, H
1539, 1272, 1092 cm . Anal. calcd for C16H20N4O4: C
57.82, H 6.07, N 16.86; found C 57.81, H 5.92, N 16.94.
N-(3-Cinnamoyl-5-isopropyl-1,3,5-oxadiazinan-4-
ylidene)nitramide (X28): Yellow powdery crystals,
4.86, N 15.88; found C 51.19, H 4.68, N 15.98.
N-{3-[(E)-3-(4-Bromophenyl)acryloyl]-5-isopropyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X23): White
1
1
powdery crystals, yield 34.6%, m.p. 166—168 ℃; H
yield 32.8%, m.p. 136—138 ℃; H NMR (CDCl3, 300
NMR (CDCl3, 300 MHz) δ: 1.33 [d, J＝6.81 Hz, 6H,
C(CH3)2], 4.77—4.81 (m, 1H, CHC2), 4.86 (s, 2H,
OCH2N), 5.34 (s, 2H, NCH2O), 6.95 (d, J＝15.30 Hz,
1H, ＝CHC＝O), 7.40—7.44 (m, 2H, ArH-2,6), 7.49—
7.53 (m, 2H, ArH-3,5), 7.78 (d, J＝15.45 Hz, 1H, CH＝
C); IR (KBr) ν: 2982, 1694, 1626, 1560, 1508, 1237,
MHz) δ: 1.33 [d, J＝6.81 Hz, 6H, C(CH3)2], 4.78—4.81
(m, 1H, HC＝C), 4.86 (s, 2H, OCH2N), 5.34 (s, 2H,
NCH2O), 6.96 (d, J＝15.39 Hz, 1H, ＝CHC＝O),
7.37—7.40 (m, 3H, ArH-2,3,4), 7.55—7.58 (m, 2H,
ArH-5,6), 7.86 (d, J＝15.39 Hz, 1H, CH＝C); IR (KBr)
－
1
ν: 2972, 1676, 1614, 1548, 1499, 1240, 1008 cm .
Anal. calcd for C15H18N4O4: C 56.60, H 5.70, N 17.60;
found C 56.72, H 5.57, N 17.80.
－
1
1070 cm . Anal. calcd for C15H17BrN4O4: C 45.35, H
4.31, N 14.10; found C 45.60, H 4.25, N 14.25.
N-{3-[(E)-3-(2,4-Dichlorophenyl)acryloyl]-5-isopro-
N-{3-[(E)-3-(Furan-2-yl)acryloyl]-5-isopropyl-1,3,5-
pyl-1,3,5-oxadiazinan-4-ylidene}nitramide
(X24):
oxadiazinan-4-ylidene}nitramide
(X29):
Brown
1
White powdery crystals, yield 60.7%, m.p. 154—156
℃; 1H NMR (CDCl3, 300 MHz) δ: 1.33 [d, J＝6.81 Hz,
6H, C(CH3)2], 4.76—4.80 (m, 1H, CHC2), 4.86 (s, 2H,
OCH2N), 5.35 (s, 2H, NCH2O), 6.93 (d, J＝15.39 Hz,
1H, ＝CHC＝O), 7.25—7.28 (m, 1H, ArH-5), 7.39—
7.45 (m, 1H, ArH-2), 7.60—7.66 (m, 1H, ArH-4), 8.17
(d, J＝15.41 Hz, 1H, CH＝C); IR (KBr) ν: 3059, 1695,
powdery crystals, yield 26.8%, m.p. 138—140 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.25 [d, J＝6.81 Hz, 6H,
C(CH3)2], 4.54—4.56 (m, 1H, HC＝C), 5.10 (s, 2H,
OCH2N), 5.26 (s, 2H, NCH2O), 6.64—6.68 (m, 1H,
Fu-3 H), 6.75 (d, J＝15.31 Hz, 1H, ＝CHC＝O),
6.98—7.02 (m, 1H, Fu-4 H), 7.49 (d, J＝15.30 Hz, 1H,
CH＝C), 7.87—7.91 (m, 1H, Fu-5 H); IR (KBr) ν: 2976,
－
－
1
1
1635, 1584, 1557, 1236, 1101 cm . Anal. calcd for
C15H16Cl2N4O4: C 46.35, H 4.16, N 14.47; found C
46.60, H 4.08, N 14.59.
1676, 1614, 1549, 1241, 1004 cm . Anal. calcd for
C13H16N4O5: C 50.65, H 5.23, N 18.17; found C 50.77,
H 5.05, N 18.32.
N-{3-Isopropyl-5-[(E)-3-(4-methoxyphenyl)acrylo-
N-{3-Isopropyl-5-[(E)-3-(thiophen-2-yl)acryloyl]-
1,3,5-oxadiazinan-4-ylidene}nitramide (X30): Brown
yl]-1,3,5-oxadiazinan-4-ylidene}nitramide
(X25):
1
Yellow powdery crystals, yield 28.2%, m.p. 164—166
℃; 1H NMR (CDCl3, 300 MHz) δ: 1.33 [d, J＝6.81 Hz,
6H, C(CH3)2], 3.83 (s, 3H, OCH3), 4.77—4.81 (m, 1H,
HC＝C), 4.85 (s, 2H, OCH2N), 5.33 (s, 2H, NCH2O),
6.83 (d, J＝15.30 Hz, 1H, ＝CHC＝O), 6.86—6.90 (m,
2H, ArH-2,6), 7.51—7.54 (m, 2H, ArH-3,5), 7.83 (d,
J＝15.30 Hz, 1H, CH＝C); IR (KBr) ν: 3066, 1692,
powdery crystals, yield 42.7%, m.p. 148—150 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.25 [d, J＝6.81 Hz, 6H,
C(CH3)2], 4.54—4.56 (m, 1H, HC＝C), 5.10 (s, 2H,
OCH2N), 5.26 (s, 2H, NCH2O), 6.73 (d, J＝15.25 Hz,
1H, ＝CHC＝O), 7.13—7.19 (m, 1H, Thiophene-4 H),
7.55—7.60 (m, 1H, Thiophene-3 H), 7.57 (m, 1H,
Thiophene-5 H), 7.85 (d, J＝15.27 Hz, 1H, CH＝C); IR
－
－
1
1
1626, 1602, 1553, 1236, 1027 cm . Anal. calcd for
C16H20N4O5: C 55.17, H 5.79, N 16.08; found C 55.32,
H 5.59, N 16.24.
(KBr) ν: 3361, 1692, 1608, 1533, 1237, 1042 cm .
Anal. calcd for C13H16N4O4S: C 48.14, H 4.97, N 17.27;
found C 48.36, H 4.86, N 17.47.
N-{3-[(E)-3-(4-Ethoxyphenyl)acryloyl]-5-isopropyl-
1,3,5-oxadiazinan-4-ylidene}nitramide (X26): Yellow
Biological activity
1
Insecticidal activities of the title compounds X1—
X30 against Aphis gossypii, Plutella xylostella (L.) and
Tetranychus cinnabarinus (Boisduval) were evaluated
(Table 1).
All bioassays were performed on representative test
pests reared in the laboratory. The bioassay was re-
peated at (25±1) ℃ according to statistical require-
ments. All compounds were dissolved in acetone (AP,
Beijing Chemical Reagent, Beijing, China) and diluted
powdery crystals, yield 47.4%, m.p. 162—164 ℃; H
NMR (CDCl3, 300 MHz) δ: 1.32 [d, J＝6.81 Hz, 6H,
C(CH3)2], 1.40—1.43 (m, 3H, CCH3), 4.06—4.08 (m,
2H, CH2C), 4.77—4.80 (m, 1H, HC＝C), 4.84 (s, 2H,
OCH2N), 5.33 (s, 2H, NCH2O), 6.82 (d, J＝15.30 Hz,
1H, ＝CHC＝O), 6.86—6.90 (m, 2H, ArH-2,6), 7.48—
7.54 (m, 2H, ArH-3,5), 7.81 (d, J＝15.33 Hz, 1H, CH＝
C); IR (KBr) ν: 2981, 1679, 1620, 1597, 1544, 1294,
－
1
1047 cm . Anal. calcd for C17H22N4O5: C 56.34, H
－
1
with distilled water containing Triton X-100 (0.1 mg•L )
6.12, N 15.46; found C 56.36, H 5.93, N 15.20.
N-[3-isopropyl-5-((E)-3-m-tolylacryloyl)-1,3,5-oxa-
diazinan-4-ylidene]nitramide (X27): Yellow powdery
to obtain gradient concentrations of 600 mg•L－ and
1
others for bioassays.21 Assessments were made on a
2398
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 2394— 2400

Design, Synthesis, and Insecticidal Activity of 1,5-Diphenyl-1-pentanone Analogues
dead/alive basis, and mortality rates were corrected us-
ing Abbott’s formula.22
lostella (L.) and Tetranychus cinnabarinus (Boisduval).
The results are listed in Table 1.
Insecticidal test for Aphis gossypii The insecti-
cidal activity against Aphis gossypii was tested by
leaf-dip method according to the following procedures.
Cabbage leaves with 40—60 apterous adults were
dipped for 5 s in diluted solutions of the title compounds
All compounds displayed good insecticidal activity
against Aphis gossypii, except X1, X8 and X10. For
instance, the insecticidal activities of compounds X11—
X14, X19, X23, X24, X27 and X30 against Aphis gos-
sypii were 100%, which were much better than 70.1%
of the lead compound A. Some title compounds, such as
X6 and X29 with 100% inhibitory rate, exhibited good
insecticidal activities against Plutella xylostella (L.). All
compounds except X4, X5, X8 and X9 displayed better
activity against Tetranychus cinnabarinus (Boisduval)
than the lead compound A., for instance, the inhibitory
rates of compounds X12, X13, X19, X24, X25, X26 and
X27 were more than 80%, which were much higher than
lead A (24.5%)
The preliminary structure-activity relationship
showed that the compounds containing 3-ethyl-4-nitro-
imino-1,3,5-oxadiazinanes and 3-isopropyl-4-nitro-
imino-1,3,5-oxadiazinanes generally had better aphi-
cidal activity than lead compound A and the compounds
containing 3-methyl-4-nitroimino-1,3,5-oxadiazinanes.
The title compounds X, in which the 1-phenyl of com-
pound A was replaced with 3-substituent-4-nitroimino-
1,3,5-oxadiazinanes, such as X23 and X29, showed
wider insecticidal spectra than lead A. And it also indi-
cated that the title compounds with three-carbon linkage
had broader insecticidal spectra than the compounds
with five-carbon linkage reported in our previous litera-
ture.8 Further studies on structural optimization and
structure-activity relationships of this novel 1,5-diphe-
nyl-1-pentanone derivatives are in progress.
－
1
containing Triton X-100 (0.1 mg•L ), and the excess
dilution was removed with filter paper; the burgeons
were placed in the conditioned room [(25±1) ℃].
－
1
Water containing Triton X-100 (0.1 mg•L ) was used
as control. The mortality rates were evaluated 24 h after
treatment. Each treatment was repeated three times, and
the results were statistically analyzed.
Insecticidal test for Tetranychus cinnabarinus
(Boisduval) The insecticidal activity against Tetrany-
chus cinnabarinus (Boisduval) was tested by leaf-dip
method according to the following procedures. Bean
leaves with 20 adults were dipped for 5 s in diluted so-
lutions of the chemicals containing Triton X-100 (0.1
－
1
mg•L ), and the excess dilution was dried by airing;
the burgeons were placed in the conditioned room [(25
－
1
±1) ℃]. Water containing Triton X-100 (0.1 mg•L )
was used as control. The mortality rates were evaluated
48 h after treatment. Each treatment was repeated three
times, and the results were statistically analyzed.
Insecticidal test for Plutella xylostella (L.) The
insecticidal activity against Plutella xylostella (L.) was
tested by leaf-dip method according to the following
procedures. Cabbage leaves of 2 cm diameter were
dipped for 5 s in diluted solutions of the chemicals con-
－
1
taining Triton X-100 (0.1 mg•L ), and the excess dilu-
tion was dried by airing, and then 10 2-instar-larvae
were transferred on the leaf. The burgeons were placed
in the conditioned room [(27±1) ℃]. Water containing
Table 1 Insecticidal activity of title compounds X1— X30 at
600 mg•L－
1
－
1
Triton X-100 (0.1 mg•L ) was used as the control. The
mortality rates were evaluated 72 h after treatment.
Each treatment was repeated three times, and the results
statistically analyzed.
Insecticidal activity (relative inhibitory ratio)/%
Tetranychus
Compd.
Aphis gossypii
Plutella xylostella cinnabarinus
(Boisduval)
Results and discussion
A
70.1
42.1
85.0
61.4
67.5
75.0
59.3
57.6
19.7
62.7
25.8
100
80.0
38.9
33.3
5.6
24.5
44.1
38.9
70.3
23.8
17.2
44.7
56.0
15.2
17.4
47.5
69.1
82.2
80.8
Chemical synthesis
X1
The general synthetic route of title compounds X is
shown in Scheme 1. Wherein, the key intermediate
3-substituent-4-nitroimino-1,3,5-oxadiazinanes IV and
substituted cinnamic acid VII were prepared by the
well-described routes, starting from the inexpensive
commercial chemicals. The target compound X was
synthesized by the reaction of different kinds of chloride
VIII and intermediate IV in anhydrous acetonitrile un-
der reflux with pyridine as an acid scavenger. Their
X2
X3
X4
33.3
66.7
100
50.0
61.1
55.6
55.6
30.0
40.0
0
X5
X6
X7
X8
1
X9
structures were characterized by IR, H NMR tech-
niques and elemental analysis.
X10
X11
X12
X13
Bioactivity
100
The title compounds X1—X30 were tested for their
100
insecticidal activity against Aphis gossypii, Plutella xy-
Chin. J. Chem. 2011, 29, 2394— 2400
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2399

Yang et al.
FULL PAPER
Continued
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1
2
3
4
5
6
7
8
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Chin. J. Org. Chem. 2010, 30, 1543 (in Chinese).
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89, 60.
Chen, L.; Wang, X.; Lu, T.; Hou, T.-P. Pest Manag. Sci.
2007, 63, 928.
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Tetranychus
Plutella xylostella cinnabarinus
(Boisduval)
Compd.
Aphis gossypii
X14
X15
X16
X17
X18
X19
X20
X21
X22
X23
X24
X25
X26
X27
X28
X29
X30
100
99.2
98.0
95.5
96.8
100
0
73.3
48.2
57.0
40.0
72.8
81.3
47.2
46.7
37.6
78.4
86.3
81.7
86.9
82.0
47.2
73.3
43.0
10.0
20.0
80.0
40.0
50.0
30.0
40.0
40.0
70.0
50.0
40.0
30.0
0
89.3
93.8
98.4
100
100
9
86.6
83.5
100
10 Lima, L. M. A.; Barreiro, E. J. Curr. Med. Chem. 2005, 12,
23.
11 Liu, Y.-X.; Cai, B.-L.; Li, Y.-H.; Song, H.-B.; Huang, R.-Q.;
Wang, Q.-M. J. Agric. Food Chem. 2007, 55, 3011.
12 Zhao, Q.-Q.; Liu, S.-H.; Li, Y.-H.; Wang, Q.-M. J. Agric.
Food Chem. 2009, 57, 2849.
97.8
98.3
100
70.0
100
20.0
13 Moriie, K.; Ootsu, J.; Hatsutori, Y.; Watanabe, A.; Ito, A.
JP 07224062, 1995 [Chem. Abstr. 1995, 124, 8855].
14 Shiokawa, K.; Tsuboi, S.; Kagabu, S.; Sasaki, S.; Moriya,
K.; Hattori, Y. US 4849432, 1987 [Chem. Abstr. 1988, 108,
21897].
15 Kiriyama, K.; Nishimura, K. Pest. Manag. Sci. 2002, 58,
669.
16 Ishimitsu, K.; Suzuki, J.; Ohishi, H.; Yamada, T.; Hatano,
R.; Takakusa, N.; Mitsui, J. WO 9104965 A1, 1991 [Chem.
Abstr. 1991, 115, 92085].
Conclusions
Thirty novel 1,5-diphenyl-1-pentanone derivatives
were synthesized by the reaction of substituted cin-
namoyl chloride and 3-substituent-4-nitroimino-
1,3,5-oxadiazinanes in acetonitrile under reflux with
pyridine as an acid acceptor. The preliminary bioassay
showed the target compounds exhibited good insecti-
cidal activity against Aphis gossypii. Especially the
compounds X11—X30 displayed good insecticidal ac-
tivity against Aphis gossypii, higher than the lead com-
pound A and compounds X1—X10. Some of them also
showed excellent activities against Plutella xylostella
(L.) and Tetranychus cinnabarinus (Boisduval) at 600
17 Aoki, I.; Tabuchi, T.; Minamida, I. EP 381130, 1990 [Chem.
Abstr. 1991, 114, 61936].
18 Uneme, H.; Iwanaga, K.; Higuchi, N.; Kando, Y.; Okauchi,
T.; Akayama, A.; Minamida, I. Pestic. Sci. 1999, 55, 202.
19 Peter, M. Z. Naturforsch., B: Chem. Sci. 2006, 61, 353.
20 Carolina, M.; Hugo, V.; Joao, X. Eur. J. Pharm. Sci. 2004,
23, 363.
21 Zhao, Y.; Li, Y.-Q.; Wang, S.-H.; Li, Z.-M. Arkivoc 2009,
(xi), 152.
22 Abbott, W. S. J. Econ. Entomol. 1925, 18, 265.
－
1
mg•L . In a summary, the designed title compounds,
with 3-substituent-4-nitroimino-1,3,5-oxadiazinanes and
three-carbon linkage, showed better aphicidal activity
and broader insecticidal spectra than the lead compound
A.
(E1104153 Zhao, C.; Lu, Z.)
2400
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Chin. J. Chem. 2011, 29, 2394— 2400