Kresoxim-methyl Derivatives: Synthesis and Herbicidal Activities of (Pyridinylphenoxymethylene)phenyl Methoxyiminoacetates

Article abstract of DOI:10.1021/acs.jafc.7b02710

A series of new kresoxim-methyl derivatives, (pyridinylphenoxymethylene)phenyl methoxyiminoacetates, were synthesized and their structures were confirmed by NMR and high-resolution mass spectrometry (HRMS). Although derived from a fungicide, the bioassays indicated that several new compounds had good herbicidal activities. At 37.5 g a.i./ha, compound 5c showed 100% inhibition against Abutilon theophrasti, Amaranthus retroflexus, and Eclipta prostrata, which was better than mesotrione. Compound 5e had a broad herbicidal spectrum against broadleaf weeds. The present work indicates that 5c and 5e may serve as new candidates for potential herbicides.

Full text of DOI:10.1021/acs.jafc.7b02710

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Article
Kresoxim-methyl Derivatives: Synthesis and Herbicidal activities
of (Pyridinylphenoxymethylene)phenyl Methoxyiminoacetates
Yang-Yang Cao, Da-Jie Mao, Wei-Wei Wang, and Xiao-Hua Du
J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b02710 • Publication Date (Web): 07 Jul 2017
Downloaded from http://pubs.acs.org on July 18, 2017
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Kresoximꢀmethyl Derivatives: Synthesis and Herbicidal Activities
of (Pyridinylphenoxymethylene)phenyl Methoxyiminoacetates
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Yangꢀyang Cao,† Daꢀjie Mao,†,‡ Weiꢀwei Wang,† and Xiaoꢀhua Du∗,
†Catalytic Hydrogenation Research Center, Zhejiang University of Technology,
Zhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology,
Zhejiang Green Pesticide Collaborative Innovation Center, Hangzhou 310014, PR China
‡Ninhua Co. Ltd., Ningbo 315000, PR China
∗
Corresponding author (Tel: +86-571-88320430; Fax: +86-571-88320066; E-mail: duxiaohua@zjut.edu.cn).
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Abstract
A series of new kresoximꢀmethyl derivatives, (pyridinylphenoxymethylene)phenyl
methoxyiminoacetates, were synthesized and their structures were confirmed by NMR and
HRMS. Although derived from a fungicide, the bioassays indicated that several new
compounds had good herbicidal activities. At 37.5 g a.i./ha, compound 5c showed 100%
inhibition against Abutilon theophrasti, Amaranthus retroflexus and Eclipta prostrata,
which was better than mesotrione. Compound 5e had a broad herbicidal spectrum against
broadleaf weeds. The present work indicates that 5c and 5e may serve as new candidates
for potential herbicides.
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Keywords: Pyridinylphenyl, Methoxyiminoacetate, Synthesis, Herbicidal activity
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Introduction
Strobilurins, an important family of fungicides, have been widely identified as one of the
most promising lead compounds for the development of a new generation of industrial
fungicides for crop protection.1ꢀ6 Since the successful development of kresoximꢀmethyl and
azoxystrobin, many chemists have studied strobilurins. At present, the modification of these
new compounds is mainly concentrated in the side chain,7ꢀ11 including the structure of
benzothiazole,12,13 chalcone,14 Nꢀacetyl pyrazoline,15 pyrazole,16 and quinoxaline17
structures. Some new strobilurin derivatives which were introduced of pyridine structure in
the side chain showed excellent biological activities,18ꢀ20 however, few of them with good
herbicidal activity have been reported.
Substituted phenylpyridines described by Schaefer et al.21,22 showed good herbicidal
activity. Liu et al.23 also reported that some substituted benzenesulfonamides with
phenylpyridine moieties showed better herbicidal activities than mesotrione.
In our research on the fungicidal activities of kresoximꢀmethyl derivatives,24 some
serious phytotoxities by several methoxyiminoacetate compounds containing
phenylpyridine moieties were found, which raised our interest in the study of herbicidal
activity of this kind of compounds. Herein, a series of new structural kresoximꢀmethyl
derivatives were obtained by splicing the phenylpyridine structure with the active structure
of kresoximꢀmethyl. These newly synthesized compounds were characterized by 1H NMR,
13C NMR, and HRMS. Furthermore, the herbicidal activities were investigated with in vitro,
glasshouse and field tests.
Materials and methods
Synthesis. All starting materials and reagents were commercially available and used
without further purification except as indicated. Solvents, such as dichloromethane,
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dimethylformamide, isopropanol, ethyl acetate, petroleum ether, and acetone were
purchased from Shanghai Lingfeng Chemical Reagent Co. Ltd. (Shanghai, China).
Chemical
reagents,
such
as
4ꢀhydroxyphenylboronic
acid,
were
2,3ꢀDichloroꢀ5ꢀ(trifluoromethyl)pyridine,
and
2ꢀBromoꢀ3,5ꢀdichloropyridine
1
purchased from Shanghai Shaoyuan Co. Ltd. (Shanghai, China). H NMR and 13C NMR
spectra were recorded on an AVANCE III spectrometer (Bruker, Hangzhou, China) at 500
and 125 MHz NMR, respectively. High resolution mass spectrometry (HRMS) were
recorded on a model 6545 QꢀTOF LCMS spectrometer equipped with an ESI source and
controlled by MassHunter software (Agilent, Hangzhou, China). Melting points were taken
on a Bꢀ545 melting point apparatus (Buchi, Hangzhou, China) and were uncorrected.
An overview synthesis of (pyridinylphenoxymethylene)phenyl methoxyiminoacetates
is shown in Figure 1.
Synthesis of Intermediates A (3a-3p). 4ꢀ(3ꢀChloroꢀ5ꢀtrifluoromethylpyridinꢀ2ꢀyl)
phenol, 3c, as an example. 2,3ꢀDichloroꢀ5ꢀtrifluoromethylpyridine (5 mmol, 1.08 g),
4ꢀhydroxybenzeneboronic acid (5.5 mmol, 0.76 g), potassium phosphate tribasic (10 mmol,
4.25 g) and bis(triphenylphosphine)palladium(II) chloride (0.5 mol%, 0.056 g) in a mixture
of 10 mL of isopropanol and 10 mL of water were stirred at 60 °C for 3 h in a nitrogen
atmosphere. Thereafter, the reaction solution was poured into water, followed by extraction
with ethyl acetate three times. The organic layers were combined, washed with an aqueous
saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated.
The residue was subjected to recrystallization using ethanol and water at the temperature of
70 °C to obtain 1.15 g white solid of intermediate 3c.
The other intermediates were synthesized by the same method.
Synthesis of Intermediate B (4). Methyl (2ꢀchloromethyl)ꢀαꢀmethyloximinobenzene
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acetate was synthesized according to the previously reported route,25,26 which is shown in
Figure 2.
Synthesis
of
Kresoxim-methyl
Derivatives.
Methyl
(E)ꢀαꢀ(methoxyimino)ꢀ2ꢀ((4ꢀ(3ꢀchloroꢀ5ꢀtrifluoromethylpyridinꢀ2ꢀyl)phenoxy)methyl)benz
ene acetate is described as an example. 3c (3 mmol, 0.87 g), 10 mL of dimethylformamide
(DMF) and sodium hydride (4.5 mmol, 0.18 g) were stirred at room temperature for 30 min.
Then, 4 (3.6 mmol, 0.89 g) was added and the reaction was stirred at 60 °C for 10 h.
Thereafter, the reaction solution was poured into water, followed by extraction with ethyl
acetate three times. The organic layers were combined, washed with an aqueous saturated
sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated. The
residue was subjected to silica gel column chromatography using petroleum
ether/dichloromethane/acetone (10:1:1, v/v/v) to obtain 5c as a white solid, m.p.
97.2ꢀ98.7 °C.
The remaining compounds were synthesized using the synthetic method of 5c.
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5a. Yield: 78.7%. Yellow solid. M.p. 89.8ꢀ91.6 °C. H NMR (500MHz, CDCl3) δ: 8.86
(d, J=1.1Hz, 1H), 8.02 (d, J=1.6Hz, 1H), 7.41ꢀ7.34 (m, 5H), 7.16ꢀ7.14 (m, 1H), 7.10 (td,
J=7.5, 1.0Hz, 1H), 6.93 (d, J=8.5, 1H), 4.98 (s, 2H), 4.04 (s, 3H), 3.85 (s, 3H). 13C NMR
(125MHz, CDCl3) δ: 163.18, 159.48 (d, J=1.25Hz), 155.71, 149.01, 143.92 (q, J=3.75Hz),
135.23, 134.02 (q, J=3.75Hz), 132.44, 130.92, 130.24, 129.63, 127.72 (q, J=78.75Hz),
126.68, 126.43, 126.16, 125.81, 123.92, 121.75, 121.20, 112.84, 68.19, 63.86, 53.04.
HRꢀMS: (M+Na)+, C23H18ClF3N2O4Na, calculated: 501.0799, found: 501.0804.
5b. Yield: 80.2%. White solid. M.p. 88.3ꢀ89.9 °C. 1H NMR (500MHz, CDCl3) δ: 9.04 (d,
J=1.0Hz, 1H), 8.59 (d, J=1.5Hz, 1H), 7.56 (d, J=7.4Hz, 1H), 7.47ꢀ7.39 (m, 3H), 7.29 (d,
J=7.65Hz, 1H), 7.24 (dd, J=7.5, 1.25Hz, 1H), 7.21ꢀ7.20 (m, 1H), 7.07ꢀ7.05 (m, 1H), 4.98 (s,
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2H), 3.89 (s, 3H), 3.70 (s, 3H). 13C NMR (125MHz, CDCl3) δ: 163.26, 159.63, 158.21,
149.43, 144.12 (q, J=3.75Hz), 138.18, 135.30 (q, J=3.75Hz), 135.02, 130.26, 129.60,
129.39, 129.31, 128.61, 127.83 (d, J=1.25Hz), 126.13 (q, J=32.5Hz), 123.80, 122.17,
121.63, 116.31, 115.74, 68.53, 63.81, 52.95. HRꢀMS: (M+Na)+, C23H18ClF3N2O4Na,
calculated: 501.0799, found: 501.0801.
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5c. Yield: 85.5%. White solid. M.p. 97.2ꢀ98.7 °C. 1H NMR (500MHz, CDCl3) δ: 8.82 (d,
J=0.9Hz, 1H), 8.02 (d, J=1.5Hz, 1H), 7.78ꢀ7.75 (m, 2H), 7.57 (d, J=7.5Hz, 1H), 7.49ꢀ7.41
(m, 2H), 7.24 (d, J=7.5, 1.2Hz, 1H), 7.02ꢀ7.00 (m, 2H), 5.04 (s, 2H), 4.05 (s, 3H), 3.87 (s,
3H). 13C NMR (125MHz, CDCl3) δ: 163.18, 159.54, 159.20, 149.35, 144.05 (q, J=3.8Hz),
135.22 (q, J=3.3Hz), 134.80, 130.97, 129.67 (d, J=5Hz), 129.53, 129.37, 128.56, 127.77 (d,
J=13.2Hz), 125.35 (q, J=33.75Hz), 122.74 (q, J=271.25Hz), 114.34, 77.28, 77.03, 76.78,
68.37, 63.74, 52.87, 43.79. HRꢀMS: (M+Na)+, C23H18ClF3N2O4Na, calculated: 501.0799,
found: 501.0799.
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5d. Yield: 80.6%. Yellow solid. M.p. 95.0ꢀ96.7 °C. H NMR (500MHz, CDCl3) δ: 8.55
(d, J=2.1Hz, 1H), 7.81 (d, J=2.1Hz, 1H), 7.56 (d, J=7.4Hz, 1H), 7.45ꢀ7.30 (m, 5H), 7.23
(dd, J=7.5, 1.2Hz, 1H), 7.00ꢀ6.99 (m, 1H), 5.03 (s, 2H), 4.01 (s, 3H), 3.82 (s, 3H). 13H
NMR (125MHz, CDCl3) δ: 163.24, 158.15, 154.39, 149.42, 146.39, 138.37, 137.43, 135.09,
130.52, 130.18, 129.56, 129.36, 129.18, 128.56, 127.81, 127.77, 122.11, 115.76, 115.64,
68.45, 63.79, 52.94. HRꢀMS: (M+Na)+, C22H18Cl2N2O4Na, calculated: 467.0536, found:
467.0536.
5e. Yield: 78.9%. White solid. M.p. 107.5ꢀ110.6 °C. 1H NMR (500MHz, CDCl3) δ: 8.53
(d, J=2.15Hz, 1H), 7.81 (d, J=2.15Hz, 1H), 7.70ꢀ7.67 (m, 2H), 7.57 (d, J=7.6Hz, 1H),
7.48ꢀ7.40 (m, 2H), 7.23 (dd, J=7.53, 1.2Hz, 1H), 6.70ꢀ6.98 (m, 2H), 5.02 (s, 2H), 4.05 (s,
13
3H), 3.86 (s, 3H). C NMR (125MHz, CDCl3) δ: 163.27, 159.17, 154.20, 149.44, 146.38,
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137.45, 135.00, 130.77, 129.95, 129.94, 129.88, 129.85, 129.60, 129.41, 128.60, 127.85,
127.79, 114.37, 114.36, 68.41, 63.83, 52.97. HRꢀMS: (M+Na)+, C22H18Cl2N2O4Na,
calculated: 467.0536, found: 467.0535.
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5f. Yield: 77.8%. Yellow oil. H NMR (500MHz, CDCl3) δ: 8.50 (d, J=0.5Hz, 1H),
7.58ꢀ7.53 (m, 4H), 7.47ꢀ7.37 (m, 3H), 7.24ꢀ7.22 (m, 1H), 6.99 (dd, J=7.9, 2.4Hz, 1H), 5.03
(s, 2H), 4.03 (s, 3H), 3.85 (s, 3H). 13C NMR (125MHz, CDCl3) δ: 163.31, 158.63, 149.50,
144.30, 144.26, 135.73, 135.11, 129.58, 129.53, 128.61, 127.98, 127.87, 124.49, 124.30,
121.54, 121.49, 116.12, 114.93, 114.89, 68.53, 63.84, 52.98. HRꢀMS: (M+Na)+,
C22H18ClFN2O4Na, calculated: 451.0831, found: 451.0831.
5g. Yield: 75.7%. White solid. M.p. 129.0ꢀ131.8 °C. 1H NMR (500MHz, CDCl3) δ: 8.47
(d, J=0.5Hz, 1H), 7.91 (dd, J=8.8, 1.5Hz, 2H), 7.57 (d, J=7.4Hz, 1H), 7.52 (dd, J=10.55,
2.0Hz, 1H), 7.48ꢀ7.40 (m, 2H), 7.23 (dd, J=7.5, 1.2Hz, 1H), 7.02ꢀ6.99 (m, 2H), 5.03 (s, 2H),
13
4.04 (s, 3H), 3.87 (s, 3H). C NMR (125MHz, CDCl3) δ: 163.28, 158.43 (d, J=261.25Hz),
155.28, 149.42, 144.13 (d, J=6.25Hz), 144.03, 134.95, 130.04, 129.99, 129.61, 129.54 (d,
J=3.75Hz), 129.41, 128.61, 127.88, 127.80, 127.35 (d, J=5Hz), 124.20 (d, J=23.75Hz),
114.80, 114.79, 68.39, 63.84, 52.99. HRꢀMS: (M+Na)+, C22H18ClFN2O4Na, calculated:
451.0831, found: 451.0831.
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5h. Yield: 70.8%. Colorless oil. H NMR (500MHz, CDCl3) δ: 8.37 (s, 1H), 7.56 (d,
J=7.55Hz, 1H), 7.46ꢀ7.38 (m, 3H), 7.34 (t, J=7.9, 7.9Hz, 1H), 7.21 (d, J=7.35Hz, 1H), 7.10
(d, J=7.55Hz, 1H), 7.04 (s, 1H), 6.94 (dd, J=8.23, 2.33Hz, 1H), 5.01 (s, 2H), 4.00 (s, 3H),
3.82 (s, 3H), 2.36 (s, 3H), 2.26 (s, 3H). 13C NMR (125MHz, CDCl3) δ: 163.21, 158.13,
155.64, 149.42, 147.22, 141.89, 139.08, 135.32, 131.53, 130.18, 129.51, 129.27, 129.11,
128.46, 127.70, 127.61, 121.82, 115.17, 114.50, 68.23, 63.75, 52.88, 19.69, 17.90. HRꢀMS:
(M+H)+, C24H25N2O4, calculated: 405.1809, found: 405.1809.
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5i. Yield: 74.3%. Cream yellow solid. M.p. 107.4ꢀ108.9 °C. H NMR (500MHz, CDCl3)
δ: 8.35 (d, J=1.25Hz, 1H), 7.58 (d, J=7.5Hz, 1H), 7.47ꢀ7.39 (m, 5H), 7.23 (dd, J=7.55,
1.2Hz, 1H), 6.98ꢀ6.95 (m, 2H), 5.00 (s, 2H), 4.05 (s, 3H), 3.86 (s, 3H), 2.35 (s, 3H), 2.34 (s,
3H). 13C NMR (125MHz, CDCl3) δ: 163.30, 158.12, 155.43, 149.49, 147.22, 139.26,
135.24, 133.41, 131.17, 130.24, 130.18, 130.08, 129.58, 129.39, 128.53, 127.84, 127.76,
115.40, 114.38, 68.37, 63.83, 52.97, 20.04, 17.91. HRꢀMS: (M+H)+, C24H25N2O4,
calculated: 405.1809, found: 405.1809.
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5j. Yield: 68.9%. Yellow solid. M.p. 104.7ꢀ105.9 °C. H NMR (500MHz, CDCl3) δ:
8.45ꢀ8.44 (m, 1H), 7.83ꢀ7.82 (m, 1H), 7.59ꢀ7.57 (m, 1H), 7.47ꢀ7.33 (m, 3H), 7.27ꢀ7.20 (m,
3H), 6.97ꢀ6.94 (m, 1H), 5.01 (s, 2H), 4.02 (s, 3H), 3.83 (s, 3H), 2.39 (s, 3H). 13C NMR
(125MHz, CDCl3) δ: 163.24, 158.00, 154.98, 149.43, 148.46, 141.59, 140.71, 135.24,
133.46, 129.54, 129.31, 128.99, 128.49, 127.80, 127.67, 122.17, 119.22, 115.58, 115.29,
68.35, 63.80, 52.93, 17.57. HRꢀMS: (M+Na)+, C23H21BrN2O4Na, calculated: 491.0577,
found: 491.0577.
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5k. Yield: 65.3%. Yellow solid. M.p. 142.1ꢀ143.6 °C. H NMR (500MHz, CDCl3) δ:
8.43ꢀ8.42 (m, 1H), 7.81ꢀ7.80 (m, 1H), 7.63ꢀ7.61 (m, 2H), 7.58ꢀ7.57 (m, 1H), 7.48ꢀ7.39 (m,
2H), 7.23 (dd, J=7.53, 1.23Hz, 1H), 6.98ꢀ6.96 (m, 2H), 5.02 (s, 2H), 4.05 (s, 3H), 3.86 (s,
13
3H), 2.37 (s, 3H). C NMR (125MHz, CDCl3) δ: 163.26, 158.68, 154.71, 149.43, 148.41,
141.73, 135.11, 132.95, 132.20, 130.71, 129.57, 129.36, 128.53, 127.79, 127.77, 125.77,
122.06, 119.13, 114.13, 68.33, 63.83, 52.96, 17.52. HRꢀMS: (M+Na)+, C23H21BrN2O4Na,
calculated: 491.0577, found: 491.0577.
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5l. Yield: 60.6%. Colorless oil. H NMR (500MHz, CDCl3) δ: 8.51 (d, J=1.95Hz, 1H),
7.58 (d, J=1.2Hz, 1H), 7.35ꢀ7.32 (m, 5H), 7.15ꢀ7.13 (m, 1H), 7.08 (t, J=7.35, 7Hz, 1H),
6.92 (d, J=8.2Hz, 1H), 4.92 (s, 2H), 4.03 (s, 3H), 3.85 (s, 3H), 2.19 (s, 3H). 13C NMR
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(125MHz, CDCl3) δ: 163.17, 155.50, 155.12, 149.02, 145.25, 136.88, 135.29, 134.26,
130.56, 130.35, 129.81, 129.60, 129.38, 128.25, 127.99, 127.34, 126.66, 121.47, 113.06,
68.20, 63.84, 53.03, 18.97. HRꢀMS: (M+H)+, C23H22ClN2O4, calculated: 425.1263, found:
425.1263.
1
5m. Yield: 62.8%. Brown oil. H NMR (500MHz, CDCl3) δ: 8.54 (d, J=1.65Hz, 1H),
7.68 (s, 1H), 7.56 (d, J=7.4Hz, 1H), 7.46ꢀ7.36 (m, 3H), 7.21 (dd, J=7.55, 1.2Hz, 1H), 7.11
(d, J=7.5Hz, 1H), 7.03 (s, 1H), 6.98 (dd, J=8.2, 2.15Hz, 1H), 5.02 (s, 2H), 4.00 (s, 3H),
3.83 (s, 3H), 2.30 (s, 3H). 13C NMR (125MHz, CDCl3) δ: 163.17, 158.16, 156.53, 149.36,
145.48, 140.69, 137.84, 135.14, 132.30, 130.21, 129.50, 129.28, 128.50, 127.66, 125.77,
121.64, 115.14, 114.94, 68.28, 63.73, 53.38, 52.87, 19.72. HRꢀMS: (M+H)+, C23H22ClN2O4,
calculated: 425.1263, found: 425.1263.
1
5n. Yield: 61.9%. Brown oil. H NMR (500MHz, CDCl3) δ: 8.47 (s, 1H), 7.58ꢀ7.40 (m,
6H), 7.23 (d, J=7.25Hz, 1H), 6.98 (s, 2H), 5.01 (s, 2H), 4.05 (s, 3H), 3.87 (s, 3H), 2.38 (s,
3H). 13C NMR (125MHz, CDCl3) δ: 163.26, 158.47, 156.39, 149.44, 145.57, 145.56,
137.90, 135.06, 132.32, 132.02, 130.21, 130.20, 129.76, 129.58, 129.39, 128.54, 127.80,
114.49, 114.48, 68.38, 63.82, 52.96, 20.13. HRꢀMS: (M+Na)+, C23H21ClN2O4Na, calculated:
447.1082, found: 447.1082.
5o. Yield: 55.5%. White solid. M.p. 123.0ꢀ125.2 °C. 1H NMR (500MHz, CDCl3) δ: 8.59
(d, J=1.95Hz, 1H), 7.76 (d, J=1.65Hz, 1H), 7.56 (d, J=7.45Hz, 1H), 7.46ꢀ7.34 (m, 3H),
7.21 (dd, J=7.4, 1.1Hz, 1H), 7.08 (d, J=7.6Hz, 1H), 7.02ꢀ7.01 (m, 1H), 6.96 (dd, J=8.2,
2.1Hz, 1H), 5.01 (s, 2H), 4.00 (s, 3H), 3.83 (s, 3H), 2.27 (s, 3H). 13C NMR (125MHz,
CDCl3) δ: 163.24, 158.23, 156.80, 149.41, 147.57, 140.89, 140.48, 135.18, 132.97, 129.57,
129.38, 129.31, 128.55, 127.73, 127.71, 121.64, 119.01, 115.13, 115.12, 68.35, 63.80,
52.94, 19.75. HRꢀMS: (M+H)+, C23H22BrN2O4, calculated: 469.0757, found: 469.0756.
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5p. Yield: 58.7%. White solid. M.p. 107.4ꢀ110.2 °C. 1H NMR (500MHz, CDCl3) δ: 8.58
(d, J=1.9Hz, 1H), 7.76 (d, J=1.55, 1H), 7.57 (d, J=7.55Hz, 1H), 7.47ꢀ7.42 (m, 4H), 7.23
(dd, J=7.55, 1.15Hz, 1H), 7.00ꢀ6.97 (m, 2H), 5.01 (s, 2H), 4.05 (s, 3H), 3.86 (s，3H), 2.38
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
(s, 3H). 13C NMR (125MHz, CDCl3) δ: 163.27, 158.53, 156.67, 149.43, 147.68, 140.80,
135.05, 132.60, 132.18, 130.20, 130.19, 129.58, 129.39, 128.55, 127.81, 127.80, 118.47,
114.53, 114.52, 68.39, 63.83, 52.97, 20.12. HRꢀMS: (M+Na)+, C23H21BrN2O4Na, calculated:
491.0577, found: 491.0577.
Herbicidal Activities Assay in Petri Dish Tests. Wheat, sorghum, barnyard grass,
cucumber, rape and radish seeds were selected as the test targets. The germinated seeds
were placed in the 9 cm inner diameter petri dish respectively with two layers of filter
papers and 9 mL of each new compound solutions at 100 mg/L were added into the petri
dish. Afterwards, the petri dish were placed in an artificial climate chamber at a temperature
of 28 °C, light intensity of 300 Lux, and relative humidity of 75%. The root and stem
inhibition rate of all the test targets were investigated after 7 d. The results are showed in
Table 1.
Herbicidal Activities Assay in Glasshouse Tests. All plant materials were obtained
from the Bioassay Testing and Safety Assessment Center in Zhejiang Research Institute of
Chemical Industry. The herbicidal activities of all target compounds against monocotyledon
weeds such as Digitaria sanguinalis, Echinochloa crusgalli, Setaria viridis, Alopecurus
aequalis, Polypogon fugax, and Poa annua and dicotyledon weeds such as Abutilon
theophrasti, Amaranthus retroflexus, Eclipta prostrata, Brassica juncea, Chenopodium
serotinum, and Stellaria media were evaluated according to a previously reported
procedure.27ꢀ29 Mesotrione and pyribambenzꢀisopropyl were selected as controls. All test
compounds were formulated as a 100 g/L emulsified concentrates by using DMF as solvent
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and Tweenꢀ80 as emulsification reagent. The concentrates were diluted with water to obtain
the required concentration and applied to potꢀgrown plants in a greenhouse. Plastic pots
with a diameter of 7.5 cm were filled with soil to a depth of 5.6 cm containing 33.3%
garden soil and 66.7% nursery substrates. The seeds of the test plants were sown separately
according to species. Approximately 12 seeds of the tested weeds were sown in the soil at
the depth of 0.2 cm and grown at 15ꢀ30 °C in a greenhouse. The diluted formulation
solutions were applied for preꢀemergence treatment 24 h after the weeds were sown. For
postꢀemergence treatment, all weeds were treated at the 3ꢀleaf stage. The preꢀ and
postꢀemergence application rates were estimated as 150 g a.i./ha. Untreated seedlings were
used as the control group, and the solvent (DMF+Tweenꢀ80) treated seedlings were used as
the solvent control group. Herbicidal activity was evaluated visually 15ꢀ20 d postꢀtreatment.
The DMF+Tweenꢀ80 control displayed no herbicidal activity, and the results are reported in
Tables 2 and 3.
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214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
Evaluation was on a scale from 0 to 100, where 0 means no damage or normal growth
and 100 means no emergence of the plants or complete destruction of at least the
aboveꢀground parts.
Herbicidal Activities Assay in Field Tests. The field tests were performed on the basis
of field efficacy trials of Chinese pesticide standards (GB/T17980.40ꢀ2000) in Hangzhou,
China. The test weeds in the maize field were at 3ꢀ4 leaf stage and the maize were at 4ꢀ5
leaf stage. The controlling weeds comprised the following species: Eclipta prostrate,
Amaranthus retroflexus, Portulaca oleracea, Digitaria sanguinalis, Eleusine indica, and
Cyperus iria in Hangzhou, China. The application rate for treatment was 18.75, 37.5, 75,
150 and 300 g a.i./ha (5c or 5e 5% EC (emulsifiable concentrate)). The application rate for
treatment of mesotrione which was used as the control was 75 and 150 g a.i./ha (mesotrione
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257
9% SC (suspension concentrate)). Formulas used in these tests are as follows: Control
effect (%) = (the number of live weeds in the control area − the number of live weeds in the
treated area) / the number of live weeds in the control area × 100%. The results are reported
in Tables 4 and 5.
Herbicidal Spectrum Test. The herbicidal activities of the compounds 5c and 5e against
about 22 broadleaf weeds were evaluated according to the same procedure in a glasshouse.
Nicosulfuron was selected as a control. The postꢀemergence application rates was estimated
as 18.75 g a.i./ha. The results are reported in Table 6.
Crop Selectivity. The conventional three varieties of wheat and three varieties of maize
were planted separately in pots (6.5 cm diameter) containing test soil with Amaranthus
retroflexus distributed evenly in it and grown in a greenhouse. After the plants reached the
3ꢀ or 4ꢀleaf stage, the spraying treatment was conducted at different dosages. The visual
injury and growth state of the individual plants were observed at regular intervals. After 30
d, the herbicidal activity was visually investigated and the fresh weight inhibition rate was
determined. The ED10 values of the crops and the ED90 values of the weeds were calculated
using DPS statistical software to obtain the selectivity coefficient between the crops and the
weeds. Formulas used in these tests are as follows: selectivity coefficient = the ED10 values
of the crops / the ED90 values of the weeds. The results are reported in Table 7.
Results and discussion
Synthetic Chemistry of the Title Compounds. As shown in Figures 2 and 3, all target
compounds were prepared by a multistep synthetic route using substituted pyridines and
phthalide as the starting materials. The reactions of the intermediates A and B, respectively,
via nucleophilic substitution using DMF as the solvent afforded a range of novel
compounds in considerable yields. The target compounds were characterized by NMR and
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HRMS. All spectral and analytical data were consistent with the assigned structures.
Herbicidal Activity. As shown in Table 1, herbicidal activities assay in petri dish tests
indicate that some new compounds integrating a phenylpyridine moiety with
methoxyiminoacetate had a very good inhibitory activity on the growth of targets.
Furthermore, the kresoximꢀmethyl unit was necessary to maintain herbicidal activity. Thus,
a series of target compounds were synthesized and evaluated for their herbicidal ability to
control the harmful weeds using preꢀ and postꢀemergence treatment in the glasshouse and
the field tests. For preꢀemergence treatment in the glasshouse, some designed
kresoximꢀmethyl derivatives were compared to the commercial herbicide pyribambenz
isopropyl. The postꢀemergence herbicidal activities of the rest compounds were tested in a
greenhouse against harmful weeds. The commercial herbicide mesotrione were selected as
the control. As shown in Table 2, at 150 g a.i./ha, compounds 5b, 5c and 5e showed 100%
inhibition against Abutilon theophrasti, Amaranthus retroflexus and Eclipta prostrata for
postꢀemergence treatment, and compounds 5n and 5p also showed greater than 80%
inhibition against these three broadleaf weeds. Furthermore, 5c exhibited excellent
herbicidal activity against all target weeds. The other compounds exhibited general
herbicidal activity. Compounds 5b and 5e showed favourable herbicidal activity against the
other five target weeds except Echinochloa crusgalli for preꢀemergence treatment.
According to further test results as shown in Table 3, at 37.5 g a.i./ha, the activity of 5c
showed nearly 100% inhibition against Abutilon theophrasti, Amaranthus retroflexus and
Eclipta prostrata, which was slightly better than the activity of mesotrione at 150 g a.i./ha
for postꢀemergence treatment. Similarly, 5e also showed good herbicidal activity at 37.5 g
a.i./ha for postꢀemergence treatment.
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Based on the structural analysis of all new compounds, it was found that the herbicidal
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activity of the compound was significantly improved when the benzene ring was attached
to the 2ꢀposition of the pyridine ring. Furthermore, the compounds showed excellent
herbicidal activity when substituted pyridine and active structure of trifloxystrobin were in
the paraꢀposition of the benzene ring. Additionally, containing chloride or trifluoromethyl
groups at the 3ꢀposition and 5ꢀposition on pyridine ring was essential for high herbicidal
activity.
Herbicidal activity results in field test (Tables 4 and 5) showed that the herbicidal activity
of 5c and 5e at 18.75ꢀ300 g a.i./ha against broadleaf weeds (Amaranthus retroflexus,
Eclipta prostrata，and Portulaca oleracea) proved roughly equivalent to the control of 9%
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295
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298
299
300
301
302
303
304
mesotrione SC at 75ꢀ150 g a.i./ha. However, the two test compounds had poor or no
obvious control effect against Gramineae and Cyperaceae weeds, which were significantly
lower than that of mesotrione at the same concentration.
Herbicidal Spectrum. 22 broadleaf weeds were selected for herbicidal test of 5c and 5e.
Table 6 generally showed that the control effect of 5e was better than that of 5c at the
dosage of 18.75 g a.i./ha, and they were all better than that of nicosulfuron. 5e had an
excellent broad herbicidal spectrum against broadleaf weeds.
Crop Selectivity. Compounds 5c and 5e with promising herbicidal activity were chosen
as representatives for further crop selectivity studies. As shown in Table 7, 5c and 5e had a
certain selectivity between wheat/maize and Amaranthus retroflexus, which were better
than nicosulfuron in the wheat field, but slightly lower than nicosulfuron in the maize field.
There were also some differences among different wheat/maize varieties. Crop selectivity
studies indicated that 5c and 5e might be developed as a potential herbicide for wheat and
maize fields.
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In summary, a series of new (pyridinylphenoxymethylene)phenyl methoxyiminoacetates
were designed and synthesized as potential herbicides. The result of in greenhouse and field
tests indicated that some newly synthesized compounds had good herbicidal activities at the
dosage of 37.5 g a.i./ha. Most interestingly, the activity of 5c and 5e against broadleaf
weeds proved slightly better than mesotrione at 37.5 g a.i./ha. The herbicidal assay in field
tests in Hangzhou indicated that 5c and 5e had excellent herbicidal activities. Our results
suggest that 5c and 5e may be new candidates as potential herbicides.
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316
Acknowledgments
This work was financially supported by the National Key Research and Development
Plan (2016YFD0300708).
The herbicidal activities assay of this work was completed by the Bioassay Testing and
Safety Assessment Center in Zhejiang Research Institute of Chemical Industry.
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Figure Captions
Figure 1. Overview Synthetic Methods of Kresoximꢀmethyl Derivatives.
Figure 2. Synthetic Methods of Intermediate B.
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Table 1. Chemical Structures and Herbicidal Activity Assay in Petri Dish Tests at the
Concentration of 100 mg/L.
barnyard
grass
wheat
sorghum
cucumber
rape
radish
No.
Py
root stem root stem root stem root stem root stem root stem
Iꢀ1
IIꢀ1
Iꢀ2
IIꢀ2
Iꢀ3
3ꢀ(3ꢀFꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀFꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀCF3ꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀCF3ꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀCF3ꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀCF3ꢀpyridinꢀ2ꢀyl)
0
0
0
50
0
0
0
50
0
0
0
0
50
0
0
0
20
0
0
80
50
80
0
0
0
100
0
100
0
80
0
50
0
0
80
0
80
0
0
80
0
80
0
0
50
0
30
0
0
50
0
0
0
0
0
95
0
30
0
0
80
0
80
0
30
0
0
40
0
80
0
0
50
0
80
0
0
0
0
50
0
50
0
IIꢀ3
0
0
0
30
0
0
80
0
Iꢀ4 3ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
IIꢀ4 3ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
Iꢀ5
30
95
30
30
95
30
100 100
30
100 100 100 100
30
4ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
4ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
0
0
0
0
IIꢀ5
50
0
100 100 100 100 100 100 100
100 100
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Table 2. Chemical Structures and Herbicidal Activity of Kresoximꢀmethyl Derivatives by
Preꢀ and Postꢀemergence Treatment in Glasshouse Tests at the Dosage of 150 g a.i./ha.
Abutilon
theophrasti
Amaranthus
retroflexus
Eclipta
prostrata sanguinalis
Digitaria
Echinochloa Setaria
No.
Py
crusgalli
viridis
Postꢀemergence Treatment
2ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
3ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
4ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀClꢀ3ꢀFꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀClꢀ3ꢀFꢀpyridinꢀ2ꢀyl)
3ꢀ(3,5ꢀMe2ꢀpyridinꢀ2ꢀyl)
4ꢀ(3,5ꢀMe2ꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀBrꢀ5ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀBrꢀ5ꢀMeꢀpyridinꢀ2ꢀyl)
2ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀBrꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀBrꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
Mesotrione
0
100
100
0
100
0
0
0
0
0
0
0
0
80
0
0
30
100
100
90
100
80
90
30
30
30
0
0
0
95
30
0
30
0
0
0
0
0
0
0
30
0
30
80
0
0
100
30
0
30
30
0
0
30
0
0
0
0
0
90
30
0
30
30
0
0
30
0
0
0
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
100
100
90
100
90
100
0
50
30
50
0
30
0
30
90
30
90
100
100
30
100
100
30
0
30
85
30
0
30
80
100
95
Preꢀemergence Treatment
2ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
0
100
0
0
100
0
0
0
0
0
0
0
0
0
0
0
100
0
100
50
0
100
100
0
90
0
0
0
85
0
0
100
0
0
0
0
0
0
0
0
0
0
90
75
0
80
0
0
50
0
0
0
0
0
0
0
0
0
0
50
97.5
0
0
30
0
0
0
0
0
0
0
0
0
0
0
0
50
97.5
0
50
0
0
50
0
0
0
0
0
0
0
0
0
0
50
97.5
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
3ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀClꢀ5ꢀCF3ꢀpyridinꢀ2ꢀyl)
3ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
4ꢀ(3,5ꢀCl2ꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀClꢀ3ꢀFꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀClꢀ3ꢀFꢀpyridinꢀ2ꢀyl)
3ꢀ(3,5ꢀMe2ꢀpyridinꢀ2ꢀyl)
4ꢀ(3,5ꢀMe2ꢀpyridinꢀ2ꢀyl)
3ꢀ(3ꢀBrꢀ5ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(3ꢀBrꢀ5ꢀMeꢀpyridinꢀ2ꢀyl)
2ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀClꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
3ꢀ(5ꢀBrꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
4ꢀ(5ꢀBrꢀ3ꢀMeꢀpyridinꢀ2ꢀyl)
Pyribambenz isopropyl
0
0
90
0
80
100
95
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Journal of Agricultural and Food Chemistry
Table 3. Herbicidal Activity of the Selected Compounds by Preꢀ and Postꢀemergence
Treatment in Glasshouse Tests.
Dosage
Abutilon Amaranthus Eclipta
Digitaria Echinochloa Setaria
No.
g a.i./ha theophrasti retroflexus prostrata sanguinalis
crusgalli
viridis
Postꢀemergence Treatment
37.5
30
60
100
100
100
100
100
100
100
100
100
70
90
100
60
70
100
100
97.5
100
100
100
100
100
97.5
100
100
40
50
90
40
50
90
100
0
0
0
50
60
95
0
0
0
0
50
60
100
0
0
0
0
50
50
90
0
75
150
37.5
75
150
37.5
75
150
37.5
75
5b
5c
5e
5n
100
100
100
100
100
100
100
30
50
80
50
60
0
0
0
0
0
0
30
40
50
20
30
30
80
20
30
40
20
30
30
85
20
30
40
20
30
30
80
150
37.5
75
5p
150
150
100
95
Mesotrione
Preꢀemergence Treatment
37.5
0
0
100
0
0
100
0
15
100
20
30
0
0
85
0
0
100
0
0
80
0
0
50
0
0
0
0
0
0
0
0
50
0
0
50
75
150
37.5
75
5b
5e
150
100
Pyribambenz
isopropyl
150
100
95
75
97.5
97.5
97.5
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Journal of Agricultural and Food Chemistry
Page 24 of 30
Table 4. Herbicidal Activity of 5c and 5e in Maize Field Tests (after 20 d).
Dosage Amaranthus Eclipta Portulaca Digitaria Eleusine Cyperus
Management
Total
g a.i./ha retroflexus prostrata oleracea sanguinalis indica
iria
18.75
37.5
75
150
300
18.75
37.5
75
74.3
84.2
89.1
94.1
98.0
73.3
80.2
83.2
90.1
93.1
97.0
100.0
73.4
81.3
87.5
93.8
96.9
71.9
78.1
81.3
87.5
90.6
95.3
100.0
75.0
82.7
88.5
94.2
98.1
73.1
80.8
88.5
92.3
96.2
96.2
100.0
13.2
17.6
22.1
35.3
48.5
1.5
2.9
7.4
10.3
13.2
67.6
82.4
8.0
14.0
20.0
32.0
42.0
0.0
2.0
4.0
6.0
8.0
6.6
39.9
47.1
52.2
60.7
68.4
34.2
38.2
41.7
45.4
47.8
73.2
82.9
13.2
17.4
27.3
38.0
ꢀ2.5
ꢀ1.7
0.8
1.7
2.5
39.7
54.5
5c (5% EC)
5e (5% EC)
150
300
75
Mesotrione
(9% SC)
62.0
78.0
150
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Page 25 of 30
Journal of Agricultural and Food Chemistry
Table 5. Herbicidal Activity of 5c and 5e in Maize Field Tests (after 30 d).
Dosage Amaranthus Eclipta Portulaca Digitaria Eleusine Cyperus
Management
Total
g a.i./ha
18.75
37.5
75
retroflexus prostrata oleracea sanguinalis indica
iria
6.7
75.1
83.5
89.6
93.9
99.2
72.1
78.9
82.7
89.9
93.1
98.3
100.0
74.1
81.7
86.9
93.4
97.0
70.9
77.1
82.0
86.3
91.7
98.1
100.0
78.3
85.0
90.3
94.9
98.2
72.9
79.8
88.5
91.9
95.9
96.9
100.0
11.6
16.4
19.1
30.0
43.7
ꢀ0.4
ꢀ0.7
0.9
7.7
12.4
18.1
32.6
42.8
ꢀ1.5
ꢀ2.3
ꢀ1.9
0.0
39.1
45.6
50.7
58.7
66.9
31.5
34.8
37.9
41.0
43.5
72.9
81.9
13.0
17.3
27.1
37.3
ꢀ4.3
ꢀ2.9
ꢀ1.6
ꢀ1.0
ꢀ0.1
39.4
54.6
5c (5% EC)
5e (5% EC)
150
300
18.75
37.5
75
150
1.6
300
3.9
1.5
Mesotrione
(9% SC)
75
150
68.2
81.6
62.5
77.9
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Journal of Agricultural and Food Chemistry
Page 26 of 30
Table 6. Herbicidal Spectrum Test of 5c and 5e at the Concentration of 18.75 g a.i./ha.
Weeds
Pharbitis nil
Nicosulfuron
5c
80
5e
50
50
50
50
70
40
80
80
80
80
80
100
30
80
30
60
70
50
60
30
30
30
30
Cassia tora
Commelina bengalensis
Bidens pilosa
Abutilon theophrasti
Eclipta prostrata
Xanthium sibiricum
Phytolacca americana
Bidens tripartita
90
80
80
75
100
100
100
95
82.5
100
90
100
90
90
70
90
40
40
80
100
70
40
90
70
30
50
90
Nicandra physaloides
Solanum nigrum
100
100
85
85
100
70
50
100
80
70
80
Amaranthus spinosus
Amaranthus retroflexus
Portulaca oleracea
Clinopodium chinense
Boehmeria nivea
Sonchus asper
Carpesium abrotanoides
Monochoria vaginalis
Ammannia baccifera
Ammannia arenaria
Aster tataricus
50
40
80
85
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Page 27 of 30
Journal of Agricultural and Food Chemistry
Table 7. Crop Selectivity between Wheat/Maize and Amaranthus retroflexus.
correlation
ED90
ED10
selectivity
No.
target
coefficient/R g a.i./ha g a.i./ha coefficient
Amaranthus retroflexus
Wheat 1 (Jimai 22)
0.9806
0.9872
0.9447
0.9939
0.9915
0.9880
0.9613
0.9797
0.9813
0.9175
0.9904
0.9971
0.9843
0.9729
0.9896
0.9908
0.9906
0.9979
0.9747
0.6699
0.8504
14.3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
12.9
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
79.4
151.5
86.9
104.7
148.8
120.8
ꢀ
106.0
207.4
92.4
102.5
148.3
139.7
ꢀ
16.3
97.5
45.7
347.1
975.4
467.5
5.6
10.6
6.1
7.3
10.4
8.5
ꢀ
8.2
16.0
7.1
7.9
11.5
10.8
ꢀ
0.7
4.1
1.9
14.6
41.1
19.7
Wheat 2 (Yangmai 158)
Wheat 3 (Tainong 18)
Maize 1 (Huyunuo 3)
Maize 2 (Nongda 108)
Maize 3 (Chaotian 3)
Amaranthus retroflexus
Wheat 1 (Jimai 22)
Wheat 2 (Yangmai 158)
Wheat 3 (Tainong 18)
Maize 1 (Huyunuo 3)
Maize 2 (Nongda 108)
Maize 3 (Chaotian 3)
Amaranthus retroflexus
Wheat 1 (Jimai 22)
5c
5e
23.7
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Wheat 2 (Yangmai 158)
Nicosulfuron Wheat 3 (Tainong 18)
Maize 1 (Huyunuo 3)
Maize 2 (Nongda 108)
Maize 3 (Chaotian 3)
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Journal of Agricultural and Food Chemistry
Page 28 of 30
Figure 1.
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Page 29 of 30
Journal of Agricultural and Food Chemistry
Figure 2.
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