Stereoselective synthesis and biological activities of O-(E)-1-{1-[6- chloropyridin-3-yhmethyl]-5-methyl-1 H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl- O-arylphosphorothioates

Article abstract of DOI:10.1002/hc.20367

To find novel lead compounds having high insecticidal activity, a series of phosphorothioate derivatives containing 1,2,3-triazole and pyridine rings were synthesized by the reaction of 1-{1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H- 1,2,3-triazol-4-yl}e

Full text of DOI:10.1002/hc.20367

Heteroatom Chemistry
Volume 19, Number 1, 2008
Stereoselective Synthesis and Biological
Activities of O-(E)-1-{1-[(6-Chloropyridin-
3-yl)methyl]-5-methyl-1H-1,2,3-triazol-
4-yl}ethyleneamino-O-ethyl-
O-arylphosphorothioates
Xiao-Fei Zhu, Xiao-Bao Chen, Man Yan, De-Qing Shi,
and Ke-Rong Ding
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry,
Central China Normal University, Wuhan 430079, Hubei, PR China
Received 31 October 2006; revised 29 November 2006
INTRODUCTION
ABSTRACT: To find novel lead compounds hav-
ing high insecticidal activity, a series of phos-
phorothioate derivatives containing 1,2,3-triazole
and pyridine rings were synthesized by the reac-
tion of 1-{1-[(6-chloropyridin-3-yl)methyl]-5-methyl-
1H-1,2,3-triazol-4-yl}ethanone oxime with phospho-
rochloridothioates. Their structures were confirmed
Neonicotinoid insecticides as nicotinic acetylcholine
receptor inhibitors have attracted increasing at-
tention because of their safety, low toxicity and
high activities [1,2]. Seven neonicotinoids, which
have a pyridine-like moiety, have been commer-
cialized. Many structure–activity relationships for
these neonicotinoids have been reported [3,4]. It was
found that most biologically active nicotinic com-
pounds contain an 3-(aminomethyl)pyridine moiety
[5]. The 1,2,3-triazole ring has been known for more
than one hundred years. However, it was till recent
decades that the 1,2,3-triazole chemistry developed
very fast due to the discovery of the diverse biologi-
cally active triazole derivatives. Many of them have
been used as insecticides, nematocides, acaricides,
and plant growth regulators [6–12]. Thiophosphor-
ate oxime ethers and their derivatives play an im-
portant role in pesticide science [13,14]. As a con-
tinuation of our research work in an attempt to find
novel lead compounds having low toxicity and high
insecticidal activity [15], we designed and synthe-
sized a type of novel phosphorothioates containing
pyridine and triazole rings. Structures of the prod-
1
by IR, H NMR, 31P NMR, mass spectrometry, and
elemental analyses. The structure of 6c was deter-
mined by single crystal X-ray diffraction, which is
thermodynamically stable E isomer. The results of
preliminary bioassay indicate that some title com-
pounds possess insecticidal activity to some ex-
ꢀ
C
tent.
2008 Wiley Periodicals, Inc. Heteroatom Chem
19:15–20, 2008; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20367
Correspondence to: De-Qing Shi; chshidq@yahoo.com.cn.
Contract grant sponsor: Natural Science Foundation of China.
1
ucts were characterized by IR, H NMR, 31P NMR,
Contract grant number: 20302002.
2008 Wiley Periodicals, Inc.
c
ꢀ
mass spectrometry, and elemental analyses. Results
15

16 Zhu et al.
SCHEME 1 Synthetic routes of the title compounds 6
of the preliminary bioassay indicate that the title
compounds possess potential insecticidal activities
to some extent.
To optimize the reaction conditions, we at-
tempted to react 1-{1-[(6-chloropyridin-3-yl)meth-
yl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone oxime 4
with phosphorochloridothioates 5a–5i in var-
ious base-solvent systems (e.g., Et3N/CH2Cl2,
Et3N/CH3CN, Et3N/toluene, NaOH/CH3CN, NaOH/
DMF, and NaOH/toluene). Finally, we found that the
reaction can take place smoothly in the presence of
sodium hydroxide in acetonitrile at room tempera-
ture to give the target products 6 in good yield (77%–
89%). Compounds 6a–6i were characterized by IR,
1H NMR, 31P NMR, EI-MS, and elemental analyses,
which are listed in the experimental part.
Because of the C N bond, it probably existed
in E- and Z isomers in compound 4 and target
molecules 6a–6i. In 1H NMR spectra, the CH3(1)
group protons (Fig. 1) of the E isomer is shifted
downfield relative to that of the Z isomer, owing
to its shorter distance between the oxygen atom
in C N O moiety and stronger deshielding effect
[13]. In this article, both compounds 4 and 6 exist as
RESULTS AND DISCUSSION
Synthesis and Structure of the Products
We synthesized a series of novel phosphoroth-
ioate derivatives (6a–6i) containing 1,2,3-triazole
and pyridine rings as shown in Scheme 1.
2-Chloro-5-(chloromethyl)pyridine
1
was
treated with sodium azide in dry ethanol under
reflux to obtain 5-azidomethyl-2-chloropyridine
2, which was cyclized to compound 3 with acety-
lacetone in DMSO in the presence of anhydrous
potassium carbonate. Treatment of compound 3
with hydroxylamine hydrochloride and sodium
hydroxide afforded oxime compound 4, which re-
acted with various phosphorochloridothioates 5 in
anhydrous acetonitrile to give the title compounds 6.
FIGURE 1 Stereo-configurations of compound 4 and 6.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Insecticidal Activity of Phosphorothioate Derivatives Containing 1,2,3-Triazole and Pyridine Rings 17
FIGURE 2 Molecular structure of 6c (50% probability ellipsoids, arbitrary atom numbering).
1
3
β = 76.631(2)◦, γ = 68.565(2)◦, V = 1144.7(3) A ,
˚
E isomers, which were confirmed by H NMR and
single crystal X-ray diffraction studies.
Z = 2, Dc = 1.352 g/cm3, F(0 0 0) = 484, µ = 0.36
mm−1, and final R= 0.060, wR = 0.174 for 3111 re-
flections (I > 2σ(I)). Figures 2 and 3 show the
molecular structure of compound 6c and packing
of the molecules in the unit cell, respectively. The
selected bond distances and angles are listed in
Table 1. The S1 P1 O1, S1 P1 O2, and S1 P1 C3
angles are larger than the O1 P1 O2, O1 P1 C3,
To confirm its molecular configuration and in-
vestigate its stereochemistry, a single crystal of 6c
was obtained from ethyl acetate and petroleum ether
(1:3 v/v) solvent system. X-ray diffraction analy-
sis indicated that the single crystal of 6c is tri-
clinic, space group P-1, cell parameters a = 8.549(1)
◦
˚
˚
˚
A, b= 10.746(1) A, c= 13.805(2) A, α = 89.373(2) ,
FIGURE 3 Packing of the molecules in the unit cell, showing the formation of C H· · ·O and C H· · ·S hydrogen bonds (dashed
lines).
Heteroatom Chemistry DOI 10.1002/hc

18 Zhu et al.
was uncorrected. 1H NMR and 31P NMR spectra were
recorded on a VARIAN MERCURY-PLUS400 spec-
trometer, with TMS and 85% H3PO4 as the internal
and external references, respectively, and CDCl3 as
the solvent, while mass spectra were obtained on a
Finnigan TRACEMS2000 spectrometer using the EI
method. IR spectra were measured by a NICOLET
NEXUS470 spectrometer. Elemental analyses were
performed on an ELEMENTAR Vario ELꢁꢁCHNSO
elementary analyzer. X-ray diffraction analysis was
carried out with a BRUKER SMART APEX CCD
X-ray diffraction instrument. All of the solvents and
materials were reagent grade and purified as re-
quired. 5-Azidomethyl-2-chloropyridine 2 and phos-
phorochloridothioates 5 were prepared according to
the literature procedure [17,18].
TABLE 1 Selected Geometric Parameters
˚
Bond length (A)
O1 P1
O2 P1
1.588(2)
O3 P1
P1 S1
1.577(2)
1.903(1)
1.555(3)
Bond angle (◦)
O2 P1 O3
O2 P1 O1
O3 P1 O1
103.2(1)
99.7(1)
O2 P1 S1
O3 P1 S1
O1 P1 S1
117.6(1)
115.9(1)
116.8(1)
100.9(1)
and O2 P1 C3 angles, indicating a distorted config-
uration of the P atom.
In the crystal, weak intermolecular C H· · ·N hy-
drogen bonds link molecules into rows along the c
axis, while weak, inversion related C H· · ·S hydro-
gen bonds join parallel rows forming a network (Fig.
3, Table 2). In addition, short intermolecular dis-
tances between the centroids of the C8 C9/N2 N4
(Cg1) and the C1 C5/N1 (Cg2) rings of adjacent
molecules indicate the presence of π–π stacking in-
teractions in the crystal [16]. [Cg1–Cg2 = 3.894(2) A;
symmetry code: (i) 1 − x, 3 − y, 2 − z] (Fig. 3). The
X-ray structure of 6c shows that the compound ex-
ist as E isomer (Fig. 2), which is in accord with the
result of 1H NMR analysis.
Synthesis of 1-{1-[(6-Chloropyridin-3-yl)methyl]-
5-methyl-1H-1,2,3-triazol-4-yl}ethanone 3
5-Azidomethyl-2-chloropyridine 2 (8.4 g, 50 mmol)
and acetylacetone (5.0 g, 50 mmol) were added to a
suspension of milled potassium carbonate (20.7 g,
150 mmol) in DMSO (50 mL). The mixture was
stirred at room temperature for 7 h (monitored by
TLC), and then it was poured into water (500 mL).
The solid was collected by filtration, washed with wa-
ter and diethyl ether, and finally dried to give 6.8 g
of 3 (yield: 81%, m.p. 394–395 K).
i
˚
Insecticidal Activity
Compounds 6a–6i were tested for insecticidal activ-
ity against aphides at a concentration of 0.25 g/L.
The results of the preliminary bioassay indicate that
some title compounds possess insecticidal activity to
some extent (Table 3).
1H NMR (CDCl3): δ 2.55 (s, 3H, CH3), 2.69 (s, 3H,
CH3), 5.52 (s, 2H, CH2), 7.36 (d, 1H, Py-H, J = 8.4
Hz), 7.52 (d, 1H, Py-H, J = 11.2 Hz), 8.36 (s, 1H, Py-
H)
Synthesis of 1-{1-[(6-Chloropyridin-3-yl)methyl]-
EXPERIMENTAL
5-methyl-1H-1,2,3-triazol-4-yl}ethanone Oxime
4
Melting points were determined with a WRS-1B dig-
ital melting point apparatus, and the thermometer
Aqueous sodium hydroxide (30% mass concentra-
tion, 4 g, 100 mmol) was added dropwise to a stirred
solution of hydroxylamine hydrochloride (2.2 g,
32 mmol) and 1-{1-[(6-chloropyridin-3-yl)methyl]-
5-methyl-1H-1,2,3-triazol-4-yl}ethanone 3 (5.01 g,
20.0 mmol) in 30 mL ethanol. After the addition was
complete, the solution was stirred under reflux for
4 to 5 h, the solid was filtered off, and the filtrate
was concentrated under vacuum. The residue was
purified by column chromatography on a silica gel
using petroleum ether and ethyl acetate (1:2 v/v) as
the eluent, giving a white solid 2.53 g (yield: 50.6%,
m.p. 445–448 K).
TABLE 2 Hydrogen Bond Geometry
◦
˚
˚
˚
D H· · ·A
D H (A) H· · ·A (A) D· · ·A (A) D H· · ·A ( )
C16 H16· · ·N3i 0.93
C6 H6A· · ·S1ii
2.65
2.98
2.97
3.413(5)
3.877(4)
3.914(3)
140
162
166
C5 H5· · ·S1ii
0.93
0.97
Symmetry codes: (i) x, y, z − 1; (ii) −x + 2, −y + 2, −z + 1.
TABLE 3 Insecticidal Activity of Compounds 6a–6i Against
Aphides (0.25 g/L, Inhibitory Rate %)
IR (KBr, cm−1): ν 3421 (OH), 1419, 1385 (CH3);
1H NMR (CDCl3): δ 1.54 (s, 1H, OH), 2.42 (s, 3H,
CH3), 2.43 (s, 3H, CH3), 5.49 (s, 2H, CH2), 7.34 (d, 1H,
Py-H, J = 8.0 Hz), 7.50 (d, 1H, Py-H, J = 10.8 Hz),
6a
6b
6c
6d
6e
6f
6g
6h
6i
14.0 2.0 13.0 14.0 18.0 25.0 12.0 8.0 1.0
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Insecticidal Activity of Phosphorothioate Derivatives Containing 1,2,3-Triazole and Pyridine Rings 19
8.35 (s, 1H, Py-H); MS m/z (%): 265 (M+, 10.51), 236
(37.07), 126 (100), 90 (22.27), 77 (8.34), 73 (32.86), 63
(15.77).
3H, CH3), 2.48 (s, 3H, CH3), 2.57 (s, 3H, CH3), 4.35
(q, 2H, OCH2), 5.50 (s, 2H, CH2), 7.18–7.52 (m, 7H,
Ar-H, Py-H), 8.35 (s, 1H, Py-H); 31P NMR (CDCl3):
62.83; MS m/z (%): 248 (18.61), 218 (47.60), 126
(87.91), 93 (100), 90 (39.75), 73 (23.18), 63 (46.15);
Anal. calcd. for C19H21ClN5O3PS: C, 48.98%; H,
4.54%; N, 15.03%; found: C, 49.17%; H, 4.65%; N,
15.26%.
General Procedure for the Synthesis of O-(E)-1-
{1-[(6-Chloropyridin-3-yl)methyl]-5-methyl-1H-
1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-aryl-
phosphorothioates 6a–6i
A solution of 1-{1-[(6-chloropyridin-3-yl)methyl]-
5-methyl-1H-1,2,3-triazol-4-yl}ethanone oxime (2
mmol) in anhydrous CH3CN (10 mL) and NaOH
powder (2 mmol) was placed in a three-necked flask.
After vigorously stirring for 5 min, a solution of the
phosphorochloridothioates 5 (2 mmol) in anhydrous
CH3CN (5 mL) was added dropwise. After the addi-
tion was complete, the mixture was stirred at room
temperature until the reaction was complete (mon-
itored by TLC). The resulting solid was filtered off
and the filtrate was concentrated under vacuum. The
residue was purified by column chromatography on
a silica gel using petroleum ether and ethyl acetate
(1:1 v/v) as the eluent, giving the corresponding phos-
phorothioates 6a–6i in 77% to 89% yield.
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-2-tol-
ylphosphorothioate (6d). Yellow solid, m.p. 379–
1
381 K, yield: 81.3%; H NMR (CDCl3): δ 1.41 (t, 3H,
CH3), 2.31 (s, 3H, CH3), 2.45 (s, 3H, CH3), 2.56 (s,
3H, CH3), 4.34 (q, 2H, OCH2), 5.50 (s, 2H, CH2),
7.08–7.51 (m, 6H, Ar-H, Py-H), 8.35 (s, 1H, Py-H);
MS m/z (%): 479 (M+, 1.15), 248 (36.78), 232 (59.54),
126 (100), 107 (70.79), 90 (55.18), 73 (20.79), 63
(44.16); Anal. calcd. for C20H23ClN5O3PS: C, 50.05%;
H, 4.83%; N, 14.59%; found: C, 50.18%; H, 4.80%;
N, 14.64%.
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-3-
(trifluoromethyl)phenylphosphorothioate (6e). Yel-
low oil, yield: 85.9%; IR (KBr, cm−1): ν 1586
(CH NO), 1565, 1484, 1460, 1392, 1334 (Ar-H,
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-2,4-dichloro-
phenyl-O-ethylphosphorothioate (6a). Yellow oil,
1
Py-H), 1033 (P O C), 687 (P S); H NMR (CDCl3):
1
yield: 88.7%; H NMR (CDCl3): δ 1.26 (t, 3H, CH3),
δ 1.40 (t, 3H, CH3), 2.45 (s, 3H, CH3), 2.55 (s,
3H, CH3), 4.36 (q, 2H, OCH2), 5.50 (s, 2H, CH2),
7.35–7.53 (m, 6H, Ar-H, Py-H), 8.35 (s, 1H, Py-H);
MS m/z (%): 286 (8.11), 248 (2.41), 161 (100), 126
(79.93), 90 (22.41), 73 (16.15), 63 (13.45); Anal.
calcd. for C20H20ClF3N5O3PS: C, 44.99%; H, 3.78%;
N, 13.12%; found: C, 44.76%; H, 3.95%; N, 13.06%.
2.44 (s, 3H, CH3), 2.57 (s, 3H, CH3), 4.39 (q, 2H,
OCH2), 5.50 (s, 2H, CH2), 7.20–7.52 (m, 5H, Ar-H,
Py-H), 8.35 (s, 1H, Py-H); MS m/z (%): 248 (12.4), 161
(94.6), 126 (100), 90 (28.91), 73 (23.86), 63 (48.24);
Anal. calcd. for C19H19Cl3N5O3PS: C, 42.67%; H,
3.58%; N, 13.10%; found: C, 42.88%; H, 3.46%; N,
13.19%.
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-3-tol-
ylphosphorothioate (6f). Yellow solid, m.p. 344–345
K, yield: 85.4%; IR (KBr, cm−1): ν 1592 (CH NO),
1567, 1491, 1448, 1392, 1327 (Ar-H, Py-H), 1039
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-4-chlorophen-
yl-O-ethylphosphorothioate (6b). Yellow solid, m.p.
1
367–368 K, yield: 87.2%; H NMR (CDCl3): δ 1.40
1
(t, 3H, CH3), 2.46 (s, 3H, CH3), 2.55 (s, 3H, CH3),
4.34 (q, 2H, OCH2), 5.50 (s, 2H, CH2), 7.14–7.53 (m,
6H, Ar-H, Py-H), 8.35 (s, 1H, Py-H); MS m/z (%):
248 (9.63), 128 (100), 126 (95.10), 90 (26.18), 73
(5.41), 63 (6.11); Anal. calcd. for C19H20Cl2N5O3PS:
C, 45.61%; H, 4.03%; N, 14.00%; found: C, 45.72%;
H, 3.97%; N, 13.93%.
(P O C), 697 ( P S); H NMR (CDCl3): δ 1.40 (t,
3H, CH3), 2.32 (s, 3H, CH3), 2.47 (s, 3H, CH3), 2.55
(s, 3H, CH3), 4.40 (q, 2H, OCH2), 5.50 (s, 2H, CH2),
7.34–7.52 (m, 6H, Ar-H, Py-H), 8.35 (s, 1H, Py-H);
31P NMR (CDCl3): 62.68; MS m/z (%): 248 (7.99),
232 (29.74), 126 (100), 107 (34.87), 90 (29.14), 73
(5.31), 63 (5.65); Anal. calcd. for C20H23ClN5O3PS:
C, 50.05%; H, 4.83%; N, 14.59%; found: C, 50.23%;
H, 4.58%; N, 14.85%.
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-phen-
ylphosphorothioate (6c). Yellow solid, m.p. 365–
367 K, yield: 81.0%; IR (KBr, cm−1) ν 1588 (CH NO),
1563, 1487, 1458, 1390, 1342 (Ar-H, Py-H), 1035
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-(2-chloro-4-
fluorophenyl)-O-ethylphosphorothioate (6g). Yellow
1
1
(P O C), 689 (P S); H NMR (CDCl3): δ 1.40 (t,
oil, yield: 82.9%; H NMR (CDCl3): δ 1.41 (t, 3H,
Heteroatom Chemistry DOI 10.1002/hc

20 Zhu et al.
CH3), 2.45 (s, 3H, CH3), 2.57 (s, 3H, CH3), 4.40 (q,
2H, OCH2), 5.50 (s, 2H, CH2), 6.95–7.52 (m, 5H, Ar-
H, Py-H), 8.35 (s, 1H, Py-H); MS m/z (%): 272 (3.31),
248 (28.53), 146 (64.47), 126 (100), 90 (18.73), 73
(6.43), 63 (6.83); Anal. calcd. for C19H19Cl2FN5O3PS:
C, 44.03%; H, 3.69%; N, 13.51%; found: C, 44.32%;
H, 3.51%; N, 13.66%.
cup. The cup was covered with a lid and stored at
25◦C◦19]. The mortality was assessed 2 and 7 days
after treatment. The test was run in triplicate, and
the results were averaged and given as activity rate in
Table 3.
REFERENCES
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-2-
methoxyphenylphosphorothioate (6h). Yellow oil,
yield: 82.9%; 1H NMR (CDCl3): δ 1.41 (t, 3H,
CH3), 2.45 (s, 3H, CH3), 2.56 (s, 3H, CH3), 4.39 (q,
2H, OCH2), 3.81 (s, 3H, CH3), 5.50 (s, 2H, CH2),
6.88–7.51 (m, 6H, Ar-H, Py-H), 8.35 (s, 1H, Py-H);
31P NMR (CDCl3): 63.98; MS m/z (%): 248 (18.53),
126 (100), 123 (95.59), 90 (37.27), 73 (20.62), 63
(37.26); Anal. calcd. for C20H23ClN5O4PS: C, 48.44%;
H, 4.67%; N, 14.12%; found: C, 48.69%; H, 4.47%;
N, 14.03%.
[1] (a) Shiokawa, K.; Tsubo, S.; Kagabu, S.; Moriya, K.
EP Patent 192 060, 1986; (b) Rudolf, E.; Ludwig, P.
DE Patent 2 918 775, 1980.
[2] Yamamoto, I.; Yabita, G.; Tomizawa, M.; Hissasomi,
A. J Pestic Sci 1994, 19, 335–339.
[3] Yamamoto, I. Nicotinoid Insecticides and the
Nicotinic Acetylcholine Receptor; Yamamoto, I.;
Casida, J. E. (Eds.); Springer: Tokyo, 1999; pp. 3–27.
[4] Nakaya, N. M.; Ebihara, K.; Matsuno, H.; Kodaka, K.
Pestic Manag Sci 2003, 59, 1016–1022.
[5] Yamamoto, I.; Yabita, G.; Tomizawa, M.; Hissasomi,
A. J Pestic Sci 1994, 19, 335–339.
[6] Ogura, T.; Numata, A.; Ueno, H.; Masuzawa, Y. WO
PCT 039 106, 2000; Chem Abstr 133, 74, 023.
[7] Najim, A. A.; Yaseen, A. A.; Asmehan, A. Heteroat
Chem 2004, 15(4), 380–387.
[8] Willis, R. J. Eur Appl 400 842 (1991); Chem Abstr
114, 164, 247.
O-(E)-1-{1-[(6-Chloropyridin-3-yl)methyl]-5-meth-
yl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-2,3-dimeth-
ylphenyl-O-ethylphosphorothioate (6i). Yellow oil,
[9] Banks, B. J.; Chubb, N. A. Eur Appl 957, 094, 1999;
Chem Abstr 131, 337, 025.
1
yield: 77.3%; H NMR (CDCl3): δ 1.40 (t, 3H, CH3),
2.20 (s, 3H, Ar-CH3), 2.26 (s, 3H, Ar-CH3), 2.45 (s,
3H, CH3), 2.56 (s, 3H, CH3), 4.34 (q, 2H, OCH2), 5.50
(s, 2H, CH2), 6.99–7.52 (m, 5H, Ar-H, Py-H), 8.35
(s, 1H, Py-H); MS m/z (%): 248 (1.50), 126 (74.35),
121 (56.34), 106 (100), 90 (31.42), 73 (10.90), 63
(19.45); Anal. calcd. for C21H25ClN5O3PS: C, 51.06%;
H, 5.10%; N, 14.18%; found: C, 50.92%; H, 5.18%;
N, 13.95%.
[10] Shuto, A.; Kisida, H.; Tsuchiya, T.; Takada, Y.;
Fujimoto, H. WO PCT 9, 529, 175, 1996; Chem Abstr
124, 176, 136.
[11] Richard, B. R.; Ben, C. G. US Patent 4 474 599, 1985;
Chem Abstr 102, 45, 956.
[12] Ingrid, L. K.; Richard, B. R. US Patent 4 775 762,
1989; Chem Abstr 110, 23, 898.
[13] Liu, A. P.; Qu, X. M.; Huang, M. Z.; Wang, X. G.; Liu,
X. P.; Wang, Y. J.; Chen, C.; Yao, J. R. Pestic Manag
Sci 2005, 61, 166–170.
[14] Yang, H. Z.; Wu, Y.; Zhang, Y. F.; Wang, L. X.; Cheng,
M. R. Chem J Chin Univ 1991, 12, 44–48.
[15] Luo, Z.-G.; Shi, D.-Q. J Heterocycl Chem 2006, 43,
1021–1026.
INSECTICIDAL BIOASSAY METHOD:
AGAINST APHIS BY DIPPING
[16] Janiak, C. J Chem Soc Dalton Trans 2000, 3885–3896.
[17] Schneider, P. EP Patent 256 990, 1998; Chem Abstr
109, 6320.
[18] Tolmith, H. Ann N Y Acad Sci 1959, 79, 189.
[19] Kiriyama, K.; Kagabu, S.; Nishimura, K. J Pestic Sci
2004, 29, 43–45.
Two cucumber leaves ca. 8 cm in diameter were
dipped into a water solution of the test compound
for a few seconds until the leaf surface was wet.
After drying, the leaves were place on soil in a pet
cup. Ten second-instar larvae were released into the
Heteroatom Chemistry DOI 10.1002/hc