Synthesis and biological activities of O-alkyl, O-aryl,O-{Z-[1-phenyl-2- (1H-1,2,4-triazol-1-yl)ethylidene]amino} phosphorothioates

Article abstract of DOI:10.1080/10426500802454102

A series of title compounds 2 were efficiently synthesized via the condensation of 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone oxime with various asymmetric thiophosphoryl chlorides in sodium hydroxide powder and acetonitrile system. The structures of titl

Full text of DOI:10.1080/10426500802454102

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Synthesis and Biological
Activities of O-Alkyl, O-Aryl,
O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino}
Phosphorothioates
Liu Meng a & De-Qing Shi a
a Key Laboratory of Pesticide & Chemical Biology of
Ministry of Education, College of Chemistry , Central
China Normal University , Wuhan, Hubei, P. R. China
Published online: 04 Sep 2009.
To cite this article: Liu Meng & De-Qing Shi (2009) Synthesis and Biological Activities
of O-Alkyl, O-Aryl, O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethylidene]amino}
Phosphorothioates, Phosphorus, Sulfur, and Silicon and the Related Elements, 184:9,
2314-2323
To link to this article: http://dx.doi.org/10.1080/10426500802454102
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Phosphorus, Sulfur, and Silicon, 184:2314–2323, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802454102
Synthesis and Biological Activities of O-Alkyl, O-Aryl,
O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethylidene]amino}
Phosphorothioates
Liu Meng and De-Qing Shi
Key Laboratory of Pesticide & Chemical Biology of Ministry of
Education, College of Chemistry, Central China Normal University,
Wuhan, Hubei, P. R. China
A series of title compounds 2 were efficiently synthesized via the condensation
of 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone oxime with various asymmetric thio-
phosphoryl chlorides in sodium hydroxide powder and acetonitrile system. The
1
31
structures of title compounds 2 were confirmed by IR, H NMR, P NMR, EI-MS,
and elemental analysis. The results of preliminary bioassays indicated that the title
compounds 2 possessed good to moderate insecticidal activity against aphides at
the dosage of 250 mg/L, and some of them exhibited moderate fungicidal activities
at the concentration of 100 mg/L.
Keywords Biological activity; 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone oxime; phos-
phorothioate
INTRODUCTION
Oxime ester derivatives have attracted increasing attention because
of their widespread biological activities. Some of them exhibit good
fungicidal activities1,2 or have been commercialized as insecticides3,4
or herbicides,5,6 which are widely used in worldwide plant protection. It
is well known that many triazole-related molecules play an important
role in the development of agrochemicals such as insecticides, nema-
tocides, acaricide, and plant growth regulators.7−11 As a continuation
of our research work in attempt to find novel agrochemicals with high
activity and low toxicity,12,13 in this article, we report the synthesis
and biological activities of novel oxime phosphorothioates containing
Received 12 June 2008; accepted 5 September 2008.
The project was sponsored by the Natural Science Foundation of China (No. 20302002)
and the Scientific Research Foundation for the Returned Overseas Chinese Scholars,
State Education Ministry (No. [2007] 1108).
Address correspondence to D.-Q. Shi, College of Chemistry, Central China Normal
University, Wuhan 430079, Hubei, P. R. China. E-mail: chshidq@mail.ccnu.edu.cn
2314

Novel Oxime Phosphorothioates
2315
a triazole moiety 2. The synthetic route is shown in Scheme 1. Char-
1
1
acterization was done by IR, H NMR, 31P{ H} NMR, MS, and ele-
mental analyses. The results of preliminary bioassays showed that the
title compounds possess insecticidal and fungicidal activities to some
extent.
SCHEME 1 Synthetic route of title compounds 2.
RESULTS AND DISCUSSION
Synthesis and Structure Determination
Oxime 1 reacted with various thiophosphoryl chlorides to yield the
target compounds 2 in moderate yields. In order to optimize the re-
action conditions, we scanned the different base and solvent systems,
such as Et3N/CH2Cl2, Et3N/CHCl3, pyridine/CHCl3, K2CO3/CH3CN,
NaHCO3/H2O+THF, and NaOH (s)/CH3CN. Finally, we found that the
reaction gave the best result in mild reaction condition in the NaOH
(s)/CH3CN system, and no byproduct was detected by TLC.
The structures of compounds 2a–2m were deduced from their spec-
1
tral data (IR, H NMR, 31P NMR, MS) and elemental analyses. In the
1H NMR spectra of 2, the two protons of the methylene moiety linking
with triazole displayed as a singlet, the signal in the Z isomer is shifted
downfield relative to that of the E isomer owing to the unshielded effect
of a phosphoryl group, and in 31P NMR spectra, the P signal in all of
the title compounds displayed as a singlet, giving chemical shifts in δ
62–64; the C N in all of compounds 2 are in Z configuration, which
can be deduced by NMR analysis and further by compared with one
of its ether analog determined by X-ray diffraction.14 IR spectra of
compounds 2 showed normal stretching absorption bands, indicating
the existence Ar-H (∼3000 cm−1), C N (∼1600 cm−1), P-O-Ar (∼1230
cm−1), P O C (∼1035 cm−1), and P S (∼690 cm−1). The EI mass spec-
tra of compounds 2 revealed the existence of the molecular ion peaks

2316
L. Meng and D.-Q. Shi
and anticipant fragmentation peaks, which were in good accordance
with the given structures of products.
Biological Activities
Insecticidal Activity
Compounds 2a–2m were tested for insecticidal activity against
aphides by dipping at the dosage of 250 mg/L. Preliminary bioassay
results show that the title compounds possess good insecticidal activ-
ity. For example, compounds 2a and 2l exhibited 86.7% and 78.9%
inhibitory rates against aphides, respectively. The structure–activity
relationships are not very clear and are under investigation. The re-
sults of the insecticidal activities are listed in Table I.
Fungicidal Activities
The preliminary fungicidal activity of the target compounds 2 was
evaluated by the classic plate method at a concentration of 100 mg/L.
The six fungi used, Fusarium oxysporium, Rhizoctonia solani, Botrytis
cinereapers, Gibberella zeae, Dothiorella gregaria, and Colletotrichum
gossypi, belong to the group of field fungi and were isolated from corre-
sponding crops. The activity data were also listed in Table I. The results
indicated that most of compounds 2 exhibit moderate to weak inhibitory
activities against the above six fungi. For example, compound 2l exhib-
ited 87.5%, 81.0%, 73.9%, 48.3%, 81.8%, and 83.3% inhibitory activity
against the six fungi, respectively.
In conclusion, a series of novel oxime phosphorothioates containing
a triazole moiety 2 were synthesized, and their biological activities
were tested. The results showed that some of the title compounds 2
possessed good insecticidal activity against aphides at the dosage of
250 mg/L, and some of them displayed moderate fungicidal activity.
EXPERIMENTAL
Melting points were determined with a WRS-1B digital melting point
apparatus and are uncorrected. 1H and 31P NMR spectra were recorded
on Varian MERCURY-PLUS400 (400 MHz) spectrometer with CDCl3
as the solvent and TMS and 85% H3PO4 as the internal and external
references, respectively; mass spectra were obtained with a Finnigan
TRACEMS2000 spectrometer using the EI method; IR spectra were
measured by a Nicolet NEXUS470 spectrometer; elemental analyses
were performed with an Elementar Vario EL CHNSO elementary ana-
lyzer. All of the solvents and materials were reagent grade and purified

2317

2318
L. Meng and D.-Q. Shi
as required. Asymmetric thiophosphoric chlorides were prepared ac-
cording to the procedures in the literature.15−16
Preparation of 1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone
Oxime (1)
1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone (3.7 g, 20 mmol), hydroxyl
ammonium chloride (2.3 g, 32 mmol), and ethanol (25 mL) were added
to a 50 mL flask. The mixture was stirred at room temperature until
the reaction was complete (monitored by thin layer chromatography),
and the solid was filtered and recrystallized from methanol to give a
light yellow solid (2.55 g, yield 56%), mp: 160–162◦C. Anal. Calcd. for
C10H10N4O (%): C, 59.40; H, 4.98; N, 27.71. Found: C, 59.56; H, 5.04; N,
27.53.
General Procedure of the Preparation of O-Alkyl, O-Aryl,
O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethylidene]amino}
Phosphorothioates (2)
1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone oxime (0.41 g, 2 mmol),
NaOH powder (0.08 g, 2 mmol), and anhydrous acetonitrile (10 mL)
were added into a three-necked flask at 298 K. After vigorously stirring
for 5 ∼ 10 min, then thiophosphoryl chloride (2 mmol) in acetonitrile
(5 mL) was added dropwise. The mixture was allowed to stir at room
temperature for 5–8 h until the reaction was complete (monitored by
thin-layer chromatography). The solid was filtered off, and the filtrate
was concentrated under vacuum. The residue was purified by column
chromatography on silica gel using petroleum ether:acetone (2:1 v/v)
as the eluent, giving a light yellow oil .
O-Ethyl, O-Phenyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-
yl)ethylidene]amino} Phosphorothioate (2a)
Yellow oil, Yield: 63%; IR (KBr, cm−1) υ: 3063, 2984 (Ar-H), 1592
1
(C N), 1489, 1446 (Ar), 1203 (P-O-Ar), 1025 (P O C), 691 (P S); H
NMR: δ 1.38 (t, J = 7.2 Hz, 3H, CH3), 4.30–4.34 (m, 2H, CH2CH3), 5.50
(s, 2H, CH2), 7.18–7.88 (m, 10H, Ar-H), 7.92 (s, 1H, Tr-H), 8.23 (s, 1H,
1
Tr-H); 31P{ H} NMR (162 MHz) δ: 62.16; MS m/z (%): 402 (M+, 18.3),
309 (5.9), 218 (6.8), 186 (28.7), 171(36.4), 104 (71.8), 103 (100), 82 (58.3),
77 (93.6), 76 (79.2), 65 (52.8), 51 (72.7). Anal. Calcd. for C18H19N4O3PS:
C 53.72, H 4.76, N 13.92. Found C 53.53, H 5.07, N 13.75.

Novel Oxime Phosphorothioates
2319
O-Methyl, O-Phenyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-
yl)ethylidene]amino} Phosphorothioate (2b)
Yellow oil, Yield: 70%; IR (KBr, cm−1) υ: 3061, 2934 (Ar-H), 1585
1
(C N), 1492, 1451 (Ar), 1228 (P-O-Ar), 1175 (P O C), 698 (P S); H
NMR: δ 3.93 (d, J = 14.4 Hz, 3H, OCH3), 5.50 (s, 2H, CH2), 7.18–7.87
1
(m, 10H, Ar-H), 7.92 (s, 1H, Tr-H), 8.23 (s, 1H, Tr-H); 31P{ H} NMR
(162 MHz) δ: 62.35; MS m/z (%): 389 (M+1, 13.3), 343 (41.7), 341 (66.9),
297 (34.4), 295 (58.6), 251 (23.7), 232 (33.1), 218 (68.5), 185 (80.2), 109
(14.8), 103 (35.2), 82 (42.7), 77 (100), 65 (47.3), 55 (80.3). Anal. Calcd.
for C17H17N4O3PS: C 52.57, H 4.41, N 14.43. Found C 52.67, H 4.29, N
14.17.
O-Ethyl, O-(4-Totyl), O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-
yl)ethylidene]amino} Phosphorothioate (2c)
Yellow oil, Yield: 66%; IR (KBr, cm−1) υ: 3061, 2983 (Ar-H), 1584
(C N), 1492, 1446 (Ar), 1227 (P-O-Ar), 1177, 1035 (P O C), 694 (P S);
1H NMR: δ 1.37 (t, J = 7.2 Hz, 3H, CH2CH3), 2.33 (s, 3H, CH3Ar),
4.28–4.37 (m, 2H, CH2CH3), 5.49 (s, 2H, CH2), 7.05–7.14 (m, 4H, Ar-
H), 7.43–7.51 (m, 3H, Ar-H), 7.86 (d, J = 7.2 Hz, 2H, Ar-H), 7.93 (s,
1
1H, Tr-H), 8.25 (s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 62.28; MS
m/z (%): 417 (M+1, 29.6), 185 (14.4), 103 (19.8), 97 (17.0), 77 (100), 65
(18.0), 55 (26.4), 51 (30.7). Anal. Calcd. for C19H21N4O3PS: C 54.80, H
5.08, N 13.45. Found C 54.64, H 5.17, N 13.61.
O-Ethyl, O-(2-Methoxyphenyl), O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino} Phosphorothioate (2d)
Yellow oil, Yield: 65%; IR (KBr, cm−1) υ: 2983 (Ar-H), 1583 (C N),
1
1486, 1446 (Ar), 1209 (P-O-Ar), 1035 (P O C), 677 (P S); H NMR:
δ 1.40 (t, J = 7.2 Hz, 3H, CH2CH3), 3.83 (s, 3H, ArOCH3), 4.30–4.41
(m, 2H, CH2CH3), 5.56 (s, 2H, CH2), 6.92–7.94 (m, 9H, Ar-H), 8.01 (s,
1
1H, Tr-H), 8.51 (s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 62.55; MS
m/z (%): 432 (M+, 5.5), 309 (57.9), 294 (14.9), 286 (23.1), 276 (21.6),
248 (43.5), 218 (36.8), 186 (39.2), 138 (37.7), 125 (25.8), 103 (53.3), 95
(37.1), 82 (68.9), 77 (100), 65 (46.1), 55 (61.2), 51 (70.8). Anal. Calcd.
for C19H21N4O4PS: C 52.77, H 4.89, N 12.96. Found C 52.90, H 4.63, N
13.17.
O-Ethyl, O-(4-Fluorophenyl), O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-
1-yl)ethylidene]amino} Phosphorothioate (2e)
Yellow oil, Yield: 68%; IR (KBr, cm−1) υ: 2983 (Ar-H), 1585 (C N),
1
1486, 1446 (Ar), 1210 (P-O-Ar), 1036 (P O C), 678 (P S); H NMR: δ
1.37 (t, J = 7.2 Hz, 3H, CH2CH3), 4.28–4.37 (m, 2H, CH2CH3), 5.50 (s,

2320
L. Meng and D.-Q. Shi
2H, CH2), 6.95–7.13 (m, 5H, Ar-H), 7.44–.52 (m, 2H, Ar-H), 7.86 (d, J =
1
7.6 Hz, 2H, Ar-H), 7.95 (s, 1H, Tr-H), 8.32 (s, 1H, Tr-H); 31P{ H} NMR
(162 MHz) δ: 62.72; MS m/z (%): 421 (M+1, 30.4), 420 (M+, 50.4), 191
(20.2), 143 (41.6), 114 (20.6), 104 (42.5), 95 (74.8), 91 (65.4), 76 (53.8),
67 (100). Anal. Calcd. for C18H18FN4O3PS: C 51.43, H 4.32, N 13.33.
Found C 51.58, H 4.13, N 13.09.
O-(4-Fluorophenyl), O-Methyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino} Phosphorothioate (2f)
Yellow oil, Yield: 89%; IR (KBr, cm−1) υ: 3061, 2963 (Ar-H), 1600,
1582 (C N), 1486, 1446 (Ar), 1210 (P-O-Ar), 1046 (P O C), 674 (P S);
1H NMR: δ 3.92 (d, J = 13.6 Hz, 3H, OCH3), 5.51 (s, 2H, CH2), 7.01–
1
7.87 (m, 9H, Ar-H), 7.93 (s, 1H, Tr-H), 8.23 (s, 1H, Tr-H); 31P{ H} NMR
(162 MHz) δ: 62.65; MS (70eV) m/z (%): 407 (M+, 2.2), 205 (6.6), 158
(9.2), 135 (13.3), 125 (9.1), 111 (37.6), 103 (27.6), 95 (20.0), 83 (64.2), 77
(100), 63 (36.1), 55 (84.5). Anal. Calcd. for C17H16FN4O3PS: C 50.25, H
3.97, N 13.79. Found C 50.41, H 4.13, N 13.54.
O-(4-Chlorophenyl), O-Ethyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino} Phosphorothioate (2g)
Yellow oil, Yield: 73%; IR (KBr, cm−1) υ: 2983 (Ar-H), 1590 (C N),
1
1486, 1446 (Ar), 1209 (P-O-Ar), 1036 (P O C), 677 (P S); H NMR:
δ 1.37 (t, J = 7.2 Hz, 3H, CH2CH3), 4.25–4.38 (m, 2H, CH2CH3), 5.50
(s, 2H, CH2), 7.11 (d, J = 7.2 Hz, 2H, Ar-H), 7.29 (d, J = 8.4 Hz, 2H,
Ar-H), 7.45–7.52 (m, 3H, Ar-H), 7.85 (d, J = 7.2 Hz, 2H, Ar-H), 7.94 (s,
1
1H, Tr-H), 8.29 (s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 62.72; MS
m/z (%): 437 (M+1, 4.9), 223 (8.4), 205 (23.2), 185 (11.8), 159 (14.0), 127
(12.6), 105 (29.3), 104 (46.1), 99 (55.9), 97 (39.4), 77 (100), 63 (41.8),
55 (83.8). Anal. Calcd. for C18H18ClN4O3PS: C 49.49, H 4.15, N 12.83.
Found C 49.25, H 4.04, N 12.79.
O-Ethyl, O-(4-Nitrophenyl), O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-
1-yl)ethylidene]amino} Phosphorothioate (2h)
Yellow oil, Yield: 60%; IR (KBr, cm−1) υ: 3105, 2984 (Ar-H), 1532
1
(C N), 1475, 1446 (Ar), 1216 (P-O-Ar), 1035 (P O C), 676 (P S); H
NMR: δ 1.40 (t, J = 7.2 Hz, 3H, CH2CH3), 4.28–4.36 (m, 2H, CH2CH3),
5.54 (s, 2H, CH2), 7.33 (d, J = 8.0 Hz, 2H, Ar-H), 7.48–7.54 (m, 3H, Ar-
H), 7.84 (d, J = 7.2 Hz, 2H, Ar-H), 8.00 (s, 1H, Tr-H), 8.23 (d, J = 8.4 Hz,
1
2H, Ar-H), 8.47 (s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 62.86; MS m/z
(%): 448 (M+1, 1.8), 218 (3.6), 188 (5.4), 153 (7.1), 148 (8.1), 125 (30.3),
109 (46.4), 97 (42.6), 63 (100); 51(68.9). Anal. Calcd. for C18H18N5O5PS:
C 48.32, H 4.06, N 15.65. Found C 48.41, H 3.93, N 15.47.

Novel Oxime Phosphorothioates
2321
O-Ethyl, O-[3-(Trifluoromethyl)phenyl], O-{Z-[1-Phenyl-2-(1H-
1,2,4-triazol-1-yl)ethylidene]amino} Phosphorothioate (2i)
Yellow oil, Yield: 65%; IR (KBr, cm−1) υ: 3061, 2934 (Ar-H), 1583
(C N), 1491, 1445, 1322 (Ar), 12226 (P-O-Ar), 1172, 1110 (P O C),
1
694 (P S); H NMR: δ 1.38 (t, J = 7.2 Hz, 3H, CH2CH3), 4.31–4.40
(m, 2H, CH2CH3), 5.55 (s, 2H, CH2), 7.41–7.54 (m, 7H, Ar-H), 7.83 (d,
1
J = 7.6 Hz, 2H, Ar-H), 8.00 (s, 1H, Tr-H), 8.55 (s, 1H, Tr-H); 31P{ H}
NMR (162 MHz) δ: 63.07; MS m/z (%): 470 (M+, 3.6), 286 (25.8), 239
(12.2), 237 (6.4), 193 (3.5), 186 (13.2), 178 (8.9), 162 (37.1), 145 (27.3),
143 (22.5), 114 (42.6), 97 (100), 82 (35.1), 75 (32.0), 65 (36.7), 56 (63.0).
Anal. Calcd. for C19H18F3N4O3PS: C 48.51, H 3.86, N 11.91. Found C
48.37, H 3.60, N 11.76.
O-(4-Chloro-2-fluorophenyl), O-Ethyl, O-{Z-[1-Phenyl-2-(1H-
1,2,4-triazol-1-yl)ethylidene]amino} Phosphorothioate (2j)
Yellow oil, Yield: 61%; IR (KBr, cm−1) υ: 2982 (Ar-H), 1580 (C N),
1
1476, 1446, 1387 (Ar), 1232 (P-O-Ar), 1034 (P O C), 694 (P S); H
NMR: δ 1.42 (t, J = 7.6 Hz, 3H, CH2CH3), 4.30–4.32 (m, 2H, CH2CH3),
5.54 (s, 2H, CH2), 7.28–7.97 (m, 8H, Ar-H), 8.04 (s, 1H, Tr-H), 8.35
1
(s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 63.26. Anal. Calcd. for
C18H17ClFN4O3PS: C 47.53, H 3.77, N 13.32. Found C 47.69, H 3.92, N
13.20.
O-(2-Chloro-4-fluorophenyl), O-Ethyl, O-{Z-[1-Phenyl-2-(1H-
1,2,4-triazol-1-yl)ethylidene]amino} Phosphorothioate (2k)
Yellow oil, Yield: 65%; IR (KBr, cm−1) υ: 2985 (Ar-H), 1577 (C N),
1
1486, 1450, 1385 (Ar), 1230 (P-O-Ar), 1036 (P O C), 698 (P S); H
NMR: δ 1.42 (t, J = 7.2 Hz, 3H, CH2CH3), 4.20–4.24 (m, 2H, CH2CH3),
5.64 (s, 2H, CH2), 6.97–7.45 (m, 8H, Ar-H), 7.81 (s, 1H, Tr-H), 7.90
1
(s, 1H, Tr-H); 31P{ H} NMR (162 MHz) δ: 63.25; Anal. Calcd. for
C18H17ClFN4O3PS: C 47.53, H 3.77, N 13.32. Found C 47.37, H 3.87, N
13.55.
O-(2,4-Dichlorophenyl), O-Ethyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino} Phosphorothioate (2l)
Yellow oil, Yield: 82%; IR (KBr, cm−1) υ: 2982 (Ar-H), 1578 (C N),
1
1477, 1446, 1387 (Ar), 1230 (P-O-Ar), 1033 (P O C), 694 (P S); H
NMR: δ 1.41 (t, J = 7.2 Hz, 3H, CH3), 4.37–4.41 (m, 2H, CH2CH3), 5.54
(s, 2H, CH2), 7.20–7.25 (m, 2H, Ar-H), 7.43–7.51 (m, 4H, Ar-H), 7.83 (d,
1
J = 6.0 Hz, 2H, Ar-H), 7.94 (s, 1H, Tr-H), 8.33 (s, 1H, Tr-H); 31P{ H}
NMR (162 MHz) δ: 63.16; MS m/z (%): 473 (2.6), 471 (M+, 6.7), 435 (5.0),
309 (13.8), 279 (15.4), 250 (23.5), 223 (13.5), 222 (22.9), 185 (24.9), 161

2322
L. Meng and D.-Q. Shi
(19.3), 135 (29.0), 133 (45.9), 104 (67.7), 97 (45.1), 77 (89.7), 63 (78.7),
51 (100). Anal. Calcd. for C18H17Cl2N4O3PS: C 45.87, H 3.64, N 11.89.
Found C 45.97, H 3.33, N 12.10.
O-(2,4-Dichlorophenyl), O-Methyl, O-{Z-[1-Phenyl-2-(1H-1,2,4-
triazol-1-yl)ethylidene]amino} Phosphorothioate (2m)
Yellow oil, Yield: 88%; IR (KBr, cm−1) υ: 2963 (Ar-H), 1582 (C N),
1508, 1446, 1364 (Ar), 1270 (P-O-Ar), 1208, 1172, 1137 (P O C), 678
1
(P S); H NMR: δ 3.83 (d, J = 13.6 Hz, 3H, OCH3), 5.53 (s, 2H, CH2),
1
7.13–7.82 (m, 8H, Ar-H), 7.84 (s, 1H, Tr-H), 7.95 (s, 1H, Tr-H); 31P{ H}
NMR (162 MHz) δ: 63.04. Anal. Calcd. for C17H15Cl2N4O3PS: C 44.65,
H 3.31, N 12.25. Found C 44.51, H 3.37, N 12.05.
Insecticidal Bioassay Method Against Aphides by Dipping
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
2nd-instar larvae were released into the cup. The cup was covered with
a lid and stored at 25◦C, 50–55% relative humidity (RH), and 14 h
light/10 h dark for 5 days. The mortality was assessed after treatment.
The test was run three times, the results were averaged, 0 means no
effect, and 100% means excellent insecticidal activity, and given as
death rate in Table I.
Fungicidal Activity Testing
The fungicidal activity measurement method was adapted from the one
described by Molina-Torres et al.17 The synthesized target compounds
were dissolved in 0.5–1.0 mL of DMF to the concentration of 1000 mg/L.
The solutions (1 mL) were mixed rapidly with thawed potato glucose
agar culture medium (9 mL) under 50◦C. The mixtures were poured
into Petri dishes. After the dished were cooled, the solidified plates
were incubated with 4 mm mycelium disk, inverted, and incubated at
28◦C for 48 h. Distilled water was used as the blank control. Three
replicates of each test were carried out. The mycelial elongation radius
(mm) of fungi settlements was measured after 48 h of culture. The
growth inhibitory rates were calculated with the following equation:
I = [(C − T)/C] * 100%, where I is the growth inhibitory rate (%) and T
is the treatment group fungi settlement radius (mm). The results are
also given in Table I.

Novel Oxime Phosphorothioates
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