Synthesis and biological activity of permethrin analogs containing various substituents in position 2 of the cyclopropane ring

Article abstract of DOI:10.1134/S1070428009030026

A number of permethrin derivatives having various substituents (Me, Et, Pr, Ph, PhCH₂, PhCH₂CH₂) in position 2 of the cyclopropane ring were synthesized and assayed for insecticidal activity against typhoid flies, rice wee

Full text of DOI:10.1134/S1070428009030026

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 3, pp. 355–359. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © N.S. Mirzabekova, N.E. Kuz’mina, O.I. Lukashov, N.A. Sokolova, S.N. Golosov, P.V. Kazakov, T.G. Perlova, V.V. Potapova,
V.A. Kheinman, G.B. Ivanova, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 3, pp. 367–371.
Synthesis and Biological Activity of Permethrin Analogs
Containing Various Substituents in Position 2
of the Cyclopropane Ring
N. S. Mirzabekovaa, N. E. Kuz’minaa, O. I. Lukashova, N. A. Sokolovaa, S. N. Golosova,
P. V. Kazakova, T. G. Perlovab, V. V. Potapovab, V. A. Kheinmanb, and G. B. Ivanovab
a State Research Institute of Organic Chemistry and Technology, shosse Entuziastov 23, Moscow, 111024 Russia
e-mail: nsm21@yandex.ru
b All-Russian Research Institute of Chemical Means for Plant Protection, Moscow, Russia
Received June 10, 2008
Abstract—A number of permethrin derivatives having various substituents (Me, Et, Pr, Ph, PhCH2,
PhCH2CH2) in position 2 of the cyclopropane ring were synthesized and assayed for insecticidal activity
against typhoid flies, rice weevils, and black bean aphid and juvenile hormone activity against flour beetle
chrysalises. The examined compounds showed a weak insecticidal activity. Some derivatives were found to
exert knockdown effect analogous to that of commercial pyrethroid tetramethrin; however, unlike permethrin,
they exhibited pronounced juvenile hormone activity.
DOI: 10.1134/S1070428009030026
Pyrethroids constitute a new generation of highly
active synthetic insecticides. Studies performed now-
adays in the field of pyrethroids include synthesis of
new compounds and investigations of mechanisms of
their action, metabolism, and effect on humans [1–6].
We previously synthesized analogs of permethric acid
ethyl ester, which contained alkyl and aryl substituents
in position 2 of the cyclopropane ring, and tested them
for biological activity [7].
clopropanecarboxylic acid ethyl esters were subjected
to transesterification with 3-phenoxybenzyl alcohol in
the presence of potassium tert-butoxide at 100–105°C
(Scheme 1). Analysis of the reaction mixture obtained
from ethyl 2-benzyl-2-methyl-3-(2,2-dichloroethenyl)-
cyclopropane-1-carboxylate showed that, apart from
the target product, 3-phenoxybenzyl 2-benzyl-2-
methyl-3-(2,2-dichloroethenyl)cyclopropane-1-carbox-
ylate (IIa), it contained a minor product, 3-phenoxy-
benzyl 2-benzyl-2-methyl-3-(chloroethynyl)cyclopro-
pane-1-carboxylate (III) (Scheme 2).
In continuation of our studies on structure–activity
relations in the pyrethroid series, in the present work
we synthesized permethrin analogs, 3-phenoxybenzyl
esters of 2,2-disubstituted permethric acid, analyzed
their stereoisomeric composition, and examined side
processes accompanying their formation. For this
purpose, 2,2-disubstituted 3-(2,2-dichloroethenyl)cy-
Compounds II were isolated from the reaction mix-
tures and separated into particular stereoisomers by
column chromatography on silica gel, and their yields
were no less than 60%. Compounds II are light yellow
oily liquids which are insoluble in water and readily
Scheme 1.
R2
R1
R2
R1
O
t-BuOK
OH
+
Cl2C
Cl2C
OEt
O
O
O
O
Ia–Ih
IIa–IIh
R1 = Me, R2 = PhCH2 (a); R1 = Et, R2 = PhCH2 (b); R1 = Me, R2 = PhCH2CH2 (c); R1 = Me, R2 = Ph (d); R1 = R2 = Et (e); R1 = Et,
R2 = Pr (f); R1 = Me, R2 = Et (g); R1 = R2 = Pr (h).
355

MIRZABEKOVA et al.
356
Scheme 2.
Me
Me
Ph
Cl2C
O
O
O
Me
Ph
OEt
O
O
t-BuOK
OH
IIa
+
Cl2C
Ph
O
Ia
O
ClC
O
III
soluble in common organic solvents. Their purity was
checked by TLC, HPLC, and spectral measurements,
and the structure was confirmed by IR and NMR spec-
troscopy, mass spectrometry (GC–MS), and elemental
analysis. The mass spectra of the new pyrethroids
contained the molecular ion peaks, and their IR spectra
displayed absorption bands at about 1735 and
1650 cm–1, which are typical of ester carbonyl group
and double C=C bond, respectively.
Biological assay of the synthesized compounds by
the complete screening procedure [11, 12] revealed
their weak insecticidal activity against test insects. The
mode of action (knockdown effect) of some deriva-
tives, namely of compounds IIa–IIc and IIg, was anal-
ogous to that of commercial pyrethroid tetramethrin.
On the other hand, biological tests showed that the new
compounds acquired some specific properties which
distinguish them from permethrin. Although neither
high insecticidal nor acaricidal activity was found,
compounds II exhibited pronounced juvenile hormone
activity (score 7–8 according to Schmialek). They also
showed weak phytotoxicity against plant leaves.
The stereoisomeric structure of the products was
1
determined by H and 13C NMR spectroscopy. Signals
were assigned to particular diastereoisomers on the
basis of their position, multiplicity, and intensity, as
1
well as of the data of two-dimensional H–1H COSY
Using PASS software [13] we analyzed the pos-
sibility of using the newly synthesized permethrin
analogs in pharmacology. It was found with a prob-
ability of 50% that some of the obtained compounds
possessing no appreciable insecticidal activity (toxic-
ity) should act as fibrinogen receptor antagonists and
agents for the treatment of Alzheimer disease, inhibit
synthesis of cholesterol, stimulate synthesis of acetyl-
choline, and exhibit estrogenic and antiestrogenic
activity.
1
[8] and H–13C HSQC experiments [9]. Steric con-
figuration of phenoxybenzyl esters II was established
using two-dimensional ROESY spectra [10]. The pres-
ence in the ROESY spectra of cross peaks between
protons in particular substituents unambiguously
indicated their cis or trans (no cross peak) orientation
with respect to the cyclopropane ring plane. The data
in table show the presence or absence of cross peaks
between protons in the 2-benzyl fragment, 2-methyl
group, and 3-dichlorovinyl substituent and 1-H and
3-H protons in the ROESY spectra of different dia-
stereoisomers of 3-phenoxybenzyl 2-benzyl-3-(2,2-di-
chlorovinyl)-2-methylcyclopropane-1-carboxylate (the
complete spectra are available from the authors upon
request by e-mail: nsm21@yandex.ru).
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded at
300 ±1 K on a Bruker Avance-300 spectrometer at
300.13 and 75.47 MHz, respectively, using CDCl3 as
Cross peaks in the ROESY spectra of different diastereoisomers of 3-phenoxybenzyl 2-benzyl-2-methyl-3-(2,2-dichloro-
vinyl)cyclopropane-1-carboxylate (IIa)
Diastereoisomer PhCH2/HC=CCl PhCH2/1-H
PhCH2/3-H
2-CH3/HC=CCl
2-CH3/1-H
2-CH3/3-H
–
–
+
+
+
–
+
–
+
+
–
–
+
+
–
–
–
+
–
+
–
–
+
+
(1R*,2R*,3R*)
(1R*,2S*,3S*)
(1R*,2R*,3S*)
(1R*,2S*,3R*)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

SYNTHESIS AND BIOLOGICAL ACTIVITY OF PERMETHRIN ANALOGS
357
solvent and tetramethylsilane as internal reference. The
one- and two-dimensional experiments were per-
formed according to standard procedure [8–10]. The
IR spectra were measured on a Perkin–Elmer 1720
spectrometer from solutions in carbon tetrachloride or
neat substances (film). The mass spectra (electron
impact) were obtained on a Fisons Trio 1000 GC–MS
system with a quadrupole mass analyzer. HPLC anal-
ysis was performed on a Millikhrom AO-2 liquid
chromatograph equipped with a UV detector and a C18
reversed-phase column; eluents: A (aqueous phase):
90% buffer (100 ml of distilled water, 0.2 ml of 10%
trimethylamine, and 100 μg of heptanesulfonic acid) +
10% acetonitrile or distilled water without ionogenic
compounds (constant pH value); B (organic phase):
90% acetonitrile + 10% distilled water. The progress of
reactions was monitored by TLC on Silica gel 60 F254
plates (Merck) using hexane–benzene (1:1) or ben-
zene–diethyl ether (9:1) as eluent; spots were visual-
ized under UV light or by treatment with a solution of
phosphomolybdic acid. The products were isolated
from the reaction mixtures by column chromatography
on silica gel 60 (0.040–0.063 mm; Merck) using
Kontes glass columns and the same eluents as
indicated above.
(3H, CH3), 1.85 d (1H, CH), 2.27 d (1H, CH), 2.60 m
(1H, CH2), 2.67 m (1H, CH2), 5.04 m (2H, CH2),
5.69 d (1H, CH), 7.00–7.40 m (14H, Harom);
(1R*,2S*,3S*) isomer: 1.00 s (3H, CH3), 1.66 d (1H,
CH), 2.48 q (1H, CH), 2.84 d.d (1H, CH2), 2.95 m
(1H, CH2), 4.95 m (2H, CH2), 5.53 d (1H, CH), 6.98–
7.46 m (14H, Harom). 13C NMR spectrum (CDCl3), δC,
ppm: (1R*,2S*,3R*) isomer: 25.72, 29.13, 31.81,
32.84, 34.01, 65.65, 118.25, 118.41, 119.03, 121.00,
122.04, 122.77, 123.49, 124.80, 127.03, 128.34,
129.89, 129.93, 137.85, 141.65, 156.90, 157.52, 171.5;
(1R*,2R*,3R*) isomer: 13.02, 30.23, 30.72, 31.05,
47.10, 65.50, 118.30, 118.44, 119.11, 120.84, 122.04,
122.69, 123.40, 124.80, 127.01, 128.83, 129.81,
129.88, 137.94, 141.65, 156.92, 157.50, 170.74;
(1R*,2R*,3S*) isomer: 17.42, 32.20, 32.80, 34.54,
42.02, 65.65, 118,35, 118.44, 119.13, 122.04, 122.21,
122.77, 123.49, 126.60, 127.03, 128.34, 129.89,
129.93, 137.85, 141.65, 156.90, 157.62, 171.50;
(1R*,2S*,3S*) isomer: 19.92, 32.40, 33.41, 34.72,
38.90, 65.68, 118.29, 118.42, 119.09, 122.02, 122.20,
122.79, 123.47, 126.00, 127.13, 128.34, 129.89,
129.93, 137.92, 141.95, 156.88, 157.60, 171.30. Mass
spectrum: m/z 466 [M]+. Found, %: C 69.05; H 4.39;
Cl 14.79. C27H23Cl2O3. Calculated, %: C 69.53;
H 4.98; Cl 15.20. M 466.40.
3-Phenoxybenzyl alcohol and potassium tert-butox-
ide were commercial products, and initial 2,2-disub-
stituted permethric acid ethyl esters were synthesized
according to the procedure described in. [7].
3-Phenoxybenzyl 2-benzyl-3-(2,2-dichlorovinyl)-
2-ethylcyclopropane-1-carboxylate (IIb). Yield 85%
(65% after chromatographic separation); the product
contained 95% of the main substance. IR spectrum, ν,
3-Phenoxybenzyl 2,2-disubstituted-3-(2,2-di-
chlorovinyl)cyclopropane-1-carboxylates IIa–IIh
(general procedure). A mixture of 10 mmol of ethyl
ester Ia–Ih, 12 mmol of 3-phenoxybenzyl alcohol, and
1 mmol of potassium tert-butoxide was stirred for 4–
6 h at 100–105°C under reduced pressure (1–2 mm).
The light yellow oily product was subjected to column
chromatography on silica gel. The purity of the prod-
ucts was checked by HPLC.
1
cm–1: 1735 (C=O), 1620 (C=C). H NMR spectrum
(CDCl3), δ, ppm: (1R*,2S*,3R*) isomer: 0.83 t (3H,
CH3), 1.07 m (1H, CH2), 1.38 m (1H, CH2), 1.85 d
(1H, CH), 2.06 d.d (1H, CH), 2.92 d (1H, CH2), 3.02 d
(1H, CH2), 5.05 q (2H, CH2 ), 6.45 d (1H, CH), 7.02–
7.42 m (14H, Harom); (1R*,2R*,3R*) isomer: 0.85 t
(3H, CH3), 1.44 m (1H, CH2), 1.50 m (1H, CH2),
1.83 d (1H, CH), 2.12 m (1H, CH), 2.60 d (1H, CH2),
2.77 d (1H, CH2), 5.02 q (2H, CH2), 6.33 d (1H, CH),
7.09–7.25 m (14H, Harom); (1R*,2R*,3S*) isomer:
0.82 t (3H, CH3), 1.35 m (1H, CH2), 1.42 m (1H, CH2),
1.80 d (1H, CH), 2.25 d.d (1H, CH), 2.66 d (1H, CH2),
2.68 d (1H, CH2), 5.08 q (2H, CH2), 5.65 d (1H, CH),
7.09–7.23 m (14H, Harom); 1R*,2S*,3S*) isomer: 0.90 t
(3H, CH3), 1.20 m (1H, CH2), 1.25 m (1H, CH2),
1.68 d (1H, CH), 2.49 m (1H, CH), 2.90 d (1H, CH2),
2.98 d (1H, CH2), 4.98 m (2H, CH2), 5.57 d (1H, CH),
7.10–7.23 m (14H, Harom). 13C NMR spectrum (CDCl3),
δC, ppm: (1R*,2S*,3R*) isomer: 10.37, 30.28, 31.04,
31.25, 31.59, 36.74, 65.65, 118,25, 118.41, 119.03,
120.61, 122.04, 122.67, 123.45, 124.91, 127.02,
128,42, 129.79, 129.90, 137.95, 138.73, 156.90,
3-Phenoxybenzyl 2-benzyl-3-(2,2-dichlorovinyl)-
2-methylcyclopropane-1-carboxylate (IIa). Yield
83% (61% after chromatographic separation); the
product contained 96% of the main substance. IR spec-
1
trum, ν, cm–1: 1735 (C=O), 1620 (C=C). H NMR
spectrum (CDCl3), δ, ppm: (1R*,2S*,3R*) isomer:
1.04 s (3H, CH3), 1.89 d (1H, CH), 2.08 q (1H, CH),
2.90 d.d (1H, CH2), 3.08 m (1H, CH2), 4.95 m (2H,
CH2), 6.49 d (1H, CH), 6.98–7.46 m (14H, Harom);
(1R*,2R*,3R*) isomer: 1.13 s (3H, CH3), 1.93 d (1H,
CH), 2.15 q (1H, CH), 2.61 d.d (1H, CH2), 2.71 m
(1H, CH2), 5.05 m (2H, CH2), 6.29 d (1H, CH), 7.00–
7.43 m (14H, Harom); (1R*,2R*,3S*) isomer: 1.08 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

MIRZABEKOVA et al.
358
157.52, 171.5; (1R*,2R*,3R*) isomer: 10.31, 18.46,
29.72, 31.04, 36.60, 42.63, 65.50, 118.30, 118.44,
119.11, 120.50, 122.07, 122.69, 123.40, 124.59,
127.07, 128.39, 129.81, 129.88, 137.59, 137.94,
156.92, 157.50, 170.74; (1R*,2R*,3S*) isomer: 10.80,
22.36, 31.66, 34.70, 37.89, 38.36, 65.84, 118.28,
118.40, 119.09, 122.05, 122.40, 122.65, 123.43,
126.25, 127.11, 128.43, 129.78, 129.92, 137.96,
138.08, 156.89, 157.54, 170.74; (1R*,2S*,3S*) isomer:
10.64, 25.47, 32.71, 34.26, 34.48, 38.51, 65.90,
118.27, 118.42, 119.06, 122.06, 122.30, 122.68,
123.44, 126.92, 127.08, 128.39, 129.77, 129.93,
137.94, 138.13, 156.92, 157.50, 170.82. Mass spec-
trum: m/z 480 [M]+. Found, %: C 69.64; H 4.87;
Cl 14.12. C28H25Cl2O3. Calculated, %: C 69.98;
H 5.26; Cl 14.76. M 480.43.
3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2-methyl-
2-(2-phenylethyl)cyclopropane-1-carboxylate (IIc).
Yield 83% (67% after chromatographic separation);
the product contained 95% of the main substance. IR
spectrum, ν, cm–1: 1735 (C=O), 1621 (C=C). 1H NMR
spectrum (CDCl3), δ, ppm: (1R*,2S*,3S*) isomer:
1.07 s (3H, CH3), 1.62 d (1H, CH), 1.65 m (1H, CH2),
1.80 m (1H, CH2), 2.27 t (1H, CH), 2.68 d.d (2H,
CH2), 5.07 s (2H, CH2), 5.58 d (1H, CH), 6.90–7.37 m
(14H, Harom). 13C NMR spectrum (CDCl3), δC, ppm:
(1R*,2S*,3S*) isomer: 17.39, 33.18, 33.19, 33.29,
34.50, 39.34, 65.58, 118.27, 118.40, 119.12, 122.09,
122.38, 122.80, 123.37, 126.90, 127.03, 128.40,
129.89, 129.83, 137.95, 138.95, 156.98, 157.59,
170.81. Mass spectrum: m/z 480 [M]+. Found, %:
C 69.72; H 4.91; Cl 14.27. C28H25Cl2O3. Calculated,
%: C 69.98; H 5.26; Cl 14.76. M 480.43.
171.25. Mass spectrum: m/z 452 [M]+. Found, %:
C 68.77; H 4.12; Cl 15.26. C26H21Cl2O3. Calculated,
%: C 69.03; H 4.69; Cl 15.67. M 452.37.
3-Phenoxybenzyl (2,2-dichlorovinyl)-2,2-diethyl-
cyclopropane-1-carboxylate (IIe). Yield 83% (67%
after chromatographic separation); the product con-
tained 96% of the main substance. IR spectrum, ν,
1
cm–1: 1735 (C=O), 1619 (C=C). H NMR spectrum
(CDCl3), δ, ppm: (1R*,3R*) isomer: 0.71 t (3H, CH3),
0.75 t (3H, CH3), 1.19 m (1H, CH2), 1.44 m (1H, CH2),
1.58 q (2H, CH2), 1.76 d (1H, CH), 1.95 t (1H, CH),
4.99 q (2H, CH2), 6.31 d (1H, CH), 6.30–7.20 m (9H,
Harom); (1R*,3S*) isomer: 0.76 t (3H, CH3), 0.86 t (3H,
CH3), 1.20 m (1H, CH2), 1.39 m (1H, CH2), 1.42 m
(1H, CH2), 1.51 m (1H, CH2), 1.59 d (1H, CH),
2.19 d.d (1H, CH), 5.01 d (2H, CH2), 5.54 d (1H, CH),
13
6.87–7.26 m (9H, Harom). C NMR spectrum (CDCl3),
δC, ppm: (1R*,3R*) isomer: 10.16, 10.24, 17.13, 30.48,
31.03, 31.95, 37.36, 65.78, 118.33, 118.41, 119.04,
120.57, 122.68, 123.46, 124.73, 129.78, 129.94,
137.95, 156.90, 157.58, 170.37; (1R*,3S*) isomer:
10.45, 10.62, 21.80, 25.20, 32.96, 34.40, 39.57, 66.04,
118.34, 118.40, 119.05, 121.84, 122.68, 123.47,
126.97, 129.78, 129.94, 137.95, 156.89, 157.58,
170.87. Mass spectrum: m/z 418 [M]+. Found, %:
C 65.54; H 5.17; Cl 16.34. C23H23Cl2O3. Calculated,
%: C 66.03; H 5.55; Cl 16.95. M 418.36.
3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2-ethyl-2-
propylcyclopropane-1-carboxylate (IIf). Yield 80%
(64% after chromatographic separation); the product
contained 94% of the main substance. IR spectrum, ν,
1
cm–1: 1735 (C=O), 1619 (C=C). H NMR spectrum
(CDCl3), δ, ppm: (1R*,2R*,3R*) isomer: 0.73 t (3H,
CH3), 0.76 t (3H, CH3), 1.15 m (2H, CH2), 1.40 m (1H,
CH2), 1.54 q (1H, CH2), 1.52 m (2H, CH2), 1.64 d (1H,
CH), 1.86 t (1H, CH), 5.07 q (2H, CH2), 6.24 d (1H,
CH), 6.90–7.28 m (9H, Harom); (1R*,2S*,3S*) isomer:
0.70 t (3H, CH3), 0.76 t (3H, CH3), 1.19 m (2H, CH2),
1.35 m (1H, CH2), 1.42 m (1H, CH2), 1.43 m (1H,
CH), 1.48 m (2H, CH2), 2,03 d.d (1H, CH), 5.06 q
(2H, CH2), 5.45 d (1H, CH), 6.90–7.28 m (9H, Harom).
13C NMR spectrum (CDCl3), δC, ppm: (1R*,2R*,3R*)
isomer: 10.14, 10.26, 17.50, 19.43, 30.48, 31.03,
31.95, 37.36, 65.43, 118.46, 118.98, 119.15, 120.17,
122.68, 123.55, 124.85, 129.90, 130.01, 132.57,
156.88, 157.53, 170.54; (1R*,2S*,3S*) isomer: 10.28,
10.96, 19.49, 25.10, 32.23, 32.55, 34.50, 39.05, 67.12,
118.25, 118.42, 121.38, 121.57, 122.67, 123.46,
127.09, 129.67, 129.90, 138.21, 156.89, 157.52,
170.87. Mass spectrum: m/z 432 [M]+. Found, %:
C 66.21; H 5.38; Cl 16.07. C24H25Cl2O3. Calculated,
%: C 66.67; H 5.84, Cl 16.40. M 432.39.
3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2-methyl-
2-phenylcyclopropane-1-carboxylate (IId). Yield
87% (65% after chromatographic separation); the
product contained 94% of the main substance. IR
spectrum, ν, cm–1: 1735 (C=O), 1621 (C=C). 1H NMR
spectrum (CDCl3), δ, ppm: (1R*,2R*,3R*) isomer:
1.29 s (3H, CH3), 1.76 d (1H, CH), 2.24 t (1H, CH),
4.99 q (2H, CH2), 6.29 d (1H, CH), 6.98–7.38 m (14H,
Harom); (1R*,2S*,3S*) isomer: 1.11 s (3H, CH3), 1.65 d
(1H, CH), 1.97 t (1H, CH), 4.98 q (2H, CH2), 5.60 d
(1H, CH), 6.88–7.41 m (14H, Harom). 13C NMR spec-
trum (CDCl3), δC, ppm: (1R*,2R*,3R*) isomer: 17.85,
30.52, 31.61, 33.94, 65.78, 118.26, 118.42, 119.05,
120.57, 122.69, 123.43, 124.73, 125.01, 126.25,
127.31, 129.78, 129.92, 137.96, 138.08, 156.89,
157.54, 170.37; (1R*,2S*,3S*) isomer: 20.40, 32.41,
33.56, 35.54, 67.80, 118.42, 118.58, 119.06, 122.62,
122.83, 123.44, 126.25, 126.33, 128.34, 128.40,
129.14, 129.82, 137.50, 138.41, 156.99, 157.41,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

SYNTHESIS AND BIOLOGICAL ACTIVITY OF PERMETHRIN ANALOGS
359
3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2-ethyl-2-
methylcyclopropane-1-carboxylate (IIg). Yield 77%
(62% after chromatographic separation); the product
contained 96% of the main substance. IR spectrum, ν,
standard sensitive laboratory strains of typhoid fly
Musca domestica L., rice weevils Calandra oryzae L.,
bean aphides Aphis fabae Scop., and twospotted spider
mite Tetranychus urticae Koch. Tests for juvenile
hormone activity were performed on chrysalises of
flour beetle Tenebrio molitor L. The acute phytotox-
icity was studied on hydrangea or cucumber leaves. All
experiments were carried out in triplicate.
1
cm–1: 1735 (C=O), 1619 (C=C). H NMR spectrum
(CDCl3), δ, ppm: (1R*,2R*,3R*) isomer: 0.83 t (3H,
CH3), 1.19 s (3H, CH3), 1.44 m (1H, CH2), 1.58 q (1H,
CH2), 1.76 d (1H, CH), 2.24 t (1H, CH), 4.99 q (2H,
CH2), 6.29 d (1H, CH), 6.30–7.55 m (9H, Harom);
(1R*,2S*,3S*) isomer: 0.91 t (3H, CH3), 1.05 s (3H,
CH3), 1.29 m (1H, CH2), 1.32 q (1H, CH2), 1.65 d (1H,
CH), 1.97 t (1H, CH), 4.98 q (2H, CH2), 5.60 d (1H,
CH), 6.48–7.44 m (9H, Harom). 13C NMR spectrum
(CDCl3), δC, ppm: (1R*,2R*,3R*) isomer: 10.35, 19.85,
30.52, 31.13, 32.29, 37.83, 65.78, 118.33, 118.41,
119.05, 121.44, 122.67, 123.45, 124.73, 129.78, 129.90,
137.96, 156.79, 156.99, 170.37; (1R*,2S*,3S*) iso-
mer: 10.40, 19.53, 28.35, 28.82, 33.56, 35.54, 67.80,
118.26, 118.48, 119.04, 121.44, 122.71, 123.50,
124.97, 129.81, 130.01, 136.50, 156.94, 157.36,
171.25. Mass spectrum: m/z 404 [M]+. Found, %:
C 65.03; H 4.84; Cl 17.05. C22H21Cl2O3. Calculated,
%: C 65.35; H 5.25; Cl 17.54. M 404.33.
This study was performed under financial support
by the International Scientific and Technical Center
(project no. 2480.2003).
REFERENCES
1. Laskowski, D.A., Reviews of Environmental Contam-
ination and Toxicology, New York: Springer, 2002,
vol. 174, p. 49.
2. Nishii, Y., Maruyama, N., Wakasugi, K., and Tanabe, Y.,
Bioorg. Med. Chem., 2001, vol. 9, p. 33.
3. Galin, F.Z., Rakhimov, R.G., Vyrypaev, E.M., Bogda-
nov, M.P., Amirkhanov, D.V., Furlei, I.I., and Tolsti-
kov, G.A., Russ. J. Org. Chem., 2000, vol. 36, p. 826.
4. Zou, X. and Qiu, Z., J. Fluorine Chem., 2002, vol. 116,
p. 173.
3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-di-
propylcyclopropane-1-carboxylate (IIh). Yield 63%
(52% after chromatographic separation); the product
contained 95% of the main substance. IR spectrum, ν,
5. Yang Gui-Chun, Cheng Shi-Yuan, Chen Zu-Xing, Shi
Cong-Yun, Wang Shi-Min, and Liu Mu-Guang,
Yingyong Huaxue, 2001, vol. 18, p. 678; Chem. Abstr.,
2002, vol. 136, p. 5761.
6. Ma, J., Huang, R., Feng, L., and Chai, Y., Prog. Nat.
Sci., 2002, vol. 12, p. 271.
7. Mirzabekova, N.S., Kuzmina, N.E., Lukashov, O I.,
Sokolova, N A., Golosov, S.N., Kazakov, P.V., Perlo-
va, T.G., Potapova, V.V., Kheinman, V.A., and Ivano-
va, G.B., Russ. J. Org. Chem., 2008, vol. 44, p. 1139.
1
cm–1: 1735 (C=O), 1619 (C=C). H NMR spectrum
(CDCl3), δ, ppm: (1R*,3R*) isomer: 0.73 t (3H, CH3),
0.75 t (3H, CH3), 1.18 m (4H, CH2), 1.51 m (2H, CH2),
1.55 m (2H, CH2), 1.60 d (1H, CH), 1.86 t (1H, CH),
5.07 s (CH2), 6.24 d (1H, CH), 6.90–7.32 m (9H,
H
arom); (1R*,3S*) isomer: 0.70 t (6H, CH3), 1.19 m
8. Nagayama, K., Kumar, A., Wuthrich, K., and
Ernst, R.R., J. Magn. Reson., 1980, vol. 40, p. 321.
9. Bax, A. and Subramanian, S., J. Magn. Reson., 1986,
(4H, CH2), 1.43 d (1H, CH), 1.48 m (4H, CH2),
2.03 d.d (1H, CH), 5.02 s (CH2), 5.45 d (1H, CH),
6.91–7.36 m (9H, Harom). C NMR spectrum (CDCl3),
13
vol. 67, p. 565
δC, ppm: (1R*,3R*) isomer: 10.29, 13.95, 19.27, 19.50,
30.51, 31.03, 31.94, 33.59, 37.38, 65.43, 118.35,
118.41, 119.15, 120.17, 122.50, 123.70, 124.85,
129.12, 129.79, 137.57, 156.89, 157.34, 170.59;
(1R*,3S*) isomer: 10.28, 13.96, 19.31, 25.10, 31.30,
32.28, 32.55, 34.50, 39.05, 67.12, 118.42, 119.12,
121.38, 121.57, 122.75, 123.58, 127.09, 129.93, 130.02,
138.21, 156.91, 157.62, 170.87. Mass spectrum: m/z
446 [M]+. Found, %: C 66.86; H 5.74; Cl 15.21.
C25H27Cl2O3. Calculated, %: C 67.26; H 6.11;
Cl 15.88. M 446.42.
10. Bax, A. and Davis, D.G., J. Magn. Reson., 1985, vol. 63,
p. 207.
11. Gar, K.A., Metody ispytaniya toksichnosti i effektivnosti
insektitsidov (Methods for Testing Insecticides for
Toxicity and Efficiency), Moscow: Nauka, 1963.
12. Sbornik Vsesoyuznogo Nauchno-Issledovatel’skogo
Instituta Khimicheskikh Sredstv Zashchity Rastenii
(A Collection of Papers of All-Union Research Institute
of Chemical Means for Plant Protection), Roslav-
tsev, S.A., Ed., Moscow, 1978.
13. Poroikov, V., Filimonov, D., et al., PASS 1.901.
Prediction of Activity Spectra for Substances, © 1998–
2004, http://www.ibmh.msk.su//PASS/default.htm.
Estimation of insecticidal and acaricidal activity.
Tests were performed under laboratory conditions on
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009