Next Article in Journal
Indomethacin: Effect of Diffusionless Crystal Growth on Thermal Stability during Long-Term Storage
Next Article in Special Issue
Synthesis and Structure–Activity Analysis of Novel Potential Antifungal Cyclotryptamine Alkaloid Derivatives
Previous Article in Journal
Carbon Dots-Based Fluorescence Assay for the Facile and Reliable Detection of Ag+ in Natural Water and Serum Samples
Previous Article in Special Issue
Synthesis, Characterization and Biological Evaluation of Benzothiazole–Isoquinoline Derivative
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 28
Issue 4
10.3390/molecules28041567
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

2-Phenylpyridine Derivatives: Synthesis and Insecticidal Activity against Mythimna separata, Aphis craccivora, and Tetranychus cinnabarinus

by
Wenliang Zhang
,
Jingjing Chen
and
Xiaohua Du
*
Catalytic Hydrogenation Research Center, Zhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology, Zhejiang Green Pesticide Collaborative Innovation Center, Zhejiang University of Technology, Hangzhou 310014, China
*
Author to whom correspondence should be addressed.
Molecules 2023, 28(4), 1567; https://doi.org/10.3390/molecules28041567
Submission received: 22 December 2022 / Revised: 27 January 2023 / Accepted: 2 February 2023 / Published: 6 February 2023
(This article belongs to the Special Issue Design, Synthesis and Biological Activity of Nitrogen-Containing Heterocyclic Compounds)
Browse Figures
Review Reports Versions Notes

Abstract

:
The increase in the insecticide resistance of pests, such as Mythimna separata, Aphis craccivora Koch, and Tetranychus cinnabarinus, necessitates the development of new heterocyclic compounds with high insecticidal activity. A series of novel 2-phenylpyridine derivatives containing N-phenylbenzamide moieties were designed and synthesised with Suzuki–Miyaura cross-coupling, nucleophilic substitution, and amidation reactions. The reaction conditions in each step are mild, and the product is easy to separate (yield is about 85%). The structures of the compounds were characterised using 1H and 13C NMR spectroscopy and HRMS. Moreover, the insecticidal activity of the compounds was analysed using the leaf dipping method. The compounds 5a, 5d, 5g, 5h, and 5k at 500 mg/L exhibited 100% inhibition against Mythimna separata. Therefore, the 2-phenylpyridine moieties have the potential to lead to the discovery of novel and effective insecticides.

1. Introduction

Pyridine is a nitrogen-containing heterocyclic compound. Pyridine derivatives exhibit various biological activities and are generally used to protect crops. Herbicides [1,2], fungicides [3,4,5,6], insecticides [7,8,9], and plant growth regulators [10,11] generally contain pyridine-based compounds. Compounds containing 2-phenylpyridine have exhibited high biological activity [12,13]; hence, herbicides [14], fungicides [15], and insecticides [16] containing 2-phenylpyridine are frequently reported (Figure 1).
Amide compounds are of fundamental importance in pesticide chemistry [17]. Many pesticides, such as insecticides [18,19], fungicides [20], and herbicides [21], contain amide-based compounds (Figure 2). Chlorantraniliprole [22,23], a commercial insecticide created by DuPont, is a new, efficient, and low-toxicity systemic insecticide that not only exhibits high activity against pests but is also safe for users and beneficial for insects. Owing to its excellent efficacy, chlorantraniliprole has been widely used to protect crops, such as soybean, rice, cotton, and corn.
The resistance of pests toward insecticides has increased and considerably affected the growth and harvest of crops [24,25]. Wang et al. demonstrated that flubendiamide exhibited certain insecticidal activity against a series of pests such as lepidoptera pests [26]. A class of chlorantraniliprole analogues was prepared by Ying et al. using pyridyl pyrazolidone carboxylic acid compounds and benzoic acid derivatives as the starting materials, which showed good insecticidal activity [27]. Liu et al. reported that a class of novel phenylpyridine derivatives exhibited excellent insecticidal activity against harmful mites such as Tetranychus cinnabarinus, etc., and can obtain very good effects at a very low dose. [16]. Phenylpyridine [13,14] and amide [17,18,19] are important components of pesticides; therefore, we designed a series of new chemicals whose structures were based on these two compounds. To obtain highly active compounds, 11 2-phenylpyridine compounds containing N-phenylbenzamide moieties were synthesised according to the substructure link principle. The synthesised compounds were analysed using high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy, and their insecticidal activity against Mythimna separata (MS.), Aphis craccivora Koch (AC.), and Tetranychus cinnabarinus was determined.

2. Results and Discussion

2.1. Chemistry

The compounds were synthesised as illustrated in Scheme 1. Compound 3 was synthesised using Suzuki–Miyaura cross-coupling of 2,3-dichloro-5-trifluoromethylpyridine (1) and 4-hydroxyphenylboronic acid (2), whereas 4 was synthesised using the nucleophilic substitution of 3 with 5-fluoro-2-nitrobenzoic acid. Using 4 and O-(1H-benzotriazol-1-yl)-N,N,N′,N′-tetramethyiuronium hexalfuorophosphate (HBTU) as the reactants and CH2Cl2 as the solvent, a series of designed compounds were obtained in high yields using an amidation reaction. The target compounds (5a–5k) were analysed using HRMS and NMR. All spectral and analytical data were consistent with the assigned structures (Supplementary Materials).

2.2. Greenhouse Insecticidal Activity Assays

As shown in Table 1, all compounds exhibited high insecticidal activities against Mythimna separata but were ineffective against Tetranychus cinnabarinus. Among the tested compounds, 5b, 5d, 5g, 5h, and 5k displayed 100% inhibitory activities against Mythimna separata. However, the rest of the tested compounds showed lower inhibitory activities of ~70% against Mythimna separata.
The relationship between the structure and activity of the compounds was investigated, and we found that when the substituent in the second position of the benzene was methoxy or in the third position was chlorine, trifluoromethyl, and trifluoromethoxy, the insecticidal activities of the synthesised compounds were optimal. Further studies on the insecticidal activity of 2-phenylpyridine compounds containing N-phenylbenzamide moieties are in progress.

3. Materials and Methods

3.1. Instrumentation

All reagents and other materials were purchased from commercial sources and used without additional purification unless otherwise noted. A B-545 melting point instrument was used to determine the melting point, without calibration. A Bruker AV-400 or AV-500 MHz spectrometer was used to generate NMR spectra, with CDCl3 as the solvent. An Agilent 6545 Q-TOF liquid chromatography-mass spectrometer was used for mass spectrometry.

3.2. Synthesis

The synthesis of the compounds is outlined in Scheme 2. Compound 3 was synthesised using Suzuki–Miyaura cross-coupling, 4 using nucleophilic substitution, and 5a–5k were synthesised using an amidation reaction.

3.2.1. General Approach to the Synthesis of 3

To a stirred solution of 2,3-dichloro-5-(trifluoromethyl)pyridine (1.08 g, 5 mmol), 4-hydroxybenzeneboronic acid (0.76 g, 5.5 mmol), potassium carbonate (1.38 g, 10 mmol), and triphenylphosphine (0.13 g, 10 mol%) in acetonitrile (10 mL) and methanol (10 mL), palladium(II) acetate (0.06 g, 5 mol%) was added under a nitrogen atmosphere. The mixture was stirred at 50 °C for 6 h, and water was then slowly added to the reaction solution. The mixture was extracted thrice (30 mL × 3) with ethyl acetate, and the combined organic layers were then washed with brine and dried over MgSO4. The solution was concentrated in vacuo and 3 was obtained using recrystallisation in ethanol and water.

3.2.2. General Approach to the Synthesis of 4

Caesium carbonate (60 mmol) was added to a stirred solution of 4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl) phenol (20 mmol) in N,N-dimethylformamide (100 mL). The mixture was stirred for approximately 0.5 h and then 5-fluoro-2-nitrobenzoic acid (21 mmol) was added. The mixture was then stirred at 100 °C for 9 h. Water was then slowly added to the reaction solution to quench the reaction. The mixture was extracted thrice (30 mL × 3) with ethyl acetate. The combined organic layers were then washed with brine and dried over MgSO4. The solution was concentrated in vacuo, and 4 was used directly for the next reaction.

3.2.3. General Approach to the Synthesis of 5a–5k

Substituted aniline (2.2 mmol) was added to a stirred solution containing 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitrobenzoic acid (2 mmol), HBTU (2.2 mmol), and triethylamine (2.2 mmol) in CH2Cl2 (15 mL). The mixture was stirred at 25 °C for 8 h. A saturated potassium bisulphate solution was then added to the reaction solution, and the mixture was extracted thrice (30 mL × 3) with ethyl acetate. The combined organic layers were then washed with brine and dried over MgSO4. The solution was concentrated in vacuo and then subjected to silica gel column chromatography using petroleum ether/ethyl acetate (7:1, v/v) to obtain the target compounds (5a–5k).
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitro-N-phenylbenzamide (5a): White solid, yield 76.5%. m.p. 193.2–195.1 °C; 1H NMR (500 MHz, CDCl3) δ 8.85 (s, 1H), 8.11 (d, J = 9.1 Hz, 1H), 8.08 (d, J = 1.5 Hz, 1H), 7.92 (s, 1H), 7.87 (d, J = 8.6 Hz, 2H), 7.54 (d, J = 7.8 Hz, 2H), 7.34 (t, J = 7.8 Hz, 2H), 7.22 (d, J = 8.6 Hz, 2H), 7.16 (dd, J = 7.0, 3.8 Hz, 2H), 7.12 (dd, J = 9.1, 2.6 Hz, 1H); 13C NMR (101 MHz, CDCl3) 162.05, 155.47, 144.38, 137.14, 135.55, 131.91, 130.19, 129.21, 127.50, 125.30, 120.51, 120.14, 118.54, 117.00. HRMS calcd. for C25H14ClF3N3O4 [M–H]− 512.0630, found 512.0628.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-N-(3-chlorophenyl)-2-nitrobenzamide (5b): White solid, yield 73.8%. m.p. 209.4–211.7 °C; 1H NMR (500 MHz, CDCl3) δ 8.77 (d, J = 1.1 Hz, 1H), 8.09 (d, J = 9.3 Hz, 1H), 8.00 (d, J = 1.6 Hz, 1H), 7.81 (d, J = 8.6 Hz, 2H), 7.60 (d, J = 6.5 Hz, 2H), 7.34 (d, J = 7.6 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 7.16 (s, 1H), 7.14 (s, 1H), 7.10 (s, 1H), 7.09–7.08 (m, 1H), 7.08–7.06 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 163.96, 162.15, 158.52, 155.37, 144.37, 144.33, 144.29, 140.14, 138.28, 135.61, 135.57, 135.11, 134.84, 134.45, 131.92, 130.17, 127.53, 125.32, 120.56, 120.18, 118.66, 118.41, 116.86. HRMS calcd. for C25H13Cl2F3N3O4 [M–H]− 546.0241, found 5446.0239.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-N-(2,4-dimethylphenyl)-2-nitrobenzamide (5c): White solid, yield 77.6%. m.p. 175.1–177.2 °C; 1H NMR (500 MHz, CDCl3) δ 8.77 (s, 1H), 8.04 (t, J = 8.7 Hz, 1H), 7.98 (dd, J = 9.5, 1.4 Hz, 1H), 7.83–7.74 (m, 2H), 7.51 (d, J = 7.9 Hz, 1H), 7.28 (d, J = 17.3 Hz, 1H), 7.15 (d, J = 5.7 Hz, 1H), 7.12 (dd, J = 14.7, 6.8 Hz, 2H), 7.03 (dd, J = 9.0, 2.6 Hz, 1H), 6.95 (d, J = 10.8 Hz, 2H), 2.22 (s, 3H), 2.15 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.31, 161.93, 158.57, 155.56, 144.34, 140.45, 136.20, 135.80, 135.58, 135.55, 134.31, 131.94, 131.87, 131.33, 130.74, 130.19, 127.45, 126.19, 124.43, 124.01, 120.06, 118.27, 117.45, 21.29, 17.65. HRMS calcd. for C27H18ClF3N3O4 [M–H]− 540.0943, found 540.0946.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-N-(2-methoxyphenyl)-2-nitrobenzamide (5d): Yellow solid, yield 80.3%. m.p. 151.3–154.2 ℃; 1H NMR (500 MHz, CDCl3) δ 8.86 (d, J = 0.9 Hz, 1H), 8.45 (dd, J = 7.9, 1.2 Hz, 1H), 8.18 (d, J = 9.1 Hz, 1H), 8.08–8.03 (m, 2H), 7.89 (d, J = 8.6 Hz, 2H), 7.25 (s, 1H), 7.24–7.21 (m, 2H), 7.16 (dd, J = 9.1, 2.7 Hz, 1H), 7.13–7.10 (m, 1H), 7.02 (t, J = 7.4 Hz, 1H), 6.91 (d, J = 7.7 Hz, 1H), 3.86 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 163.40, 161.90, 158.56, 155.56, 148.01, 144.38, 144.34, 140.55, 135.76, 135.58, 134.31, 131.88, 130.17, 127.47, 127.17, 126.51, 124.66, 121.27, 120.22, 120.09, 118.41, 117.18, 110.08, 55.73. HRMS calcd. for C26H16ClF3N3O5 [M–H]− 542.0736, found 542.0741.
Description of N-(3-chloro-2-methylphenyl)-5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitrobenzamide (5e): White solid, yield 81.9%. m.p. 172.3–174.6 °C; 1H NMR (500 MHz, CDCl3) δ 8.86 (s, 1H), 8.15 (t, J = 8.6 Hz, 1H), 8.08 (d, J = 1.6 Hz, 1H), 7.88 (t, J = 7.6 Hz, 2H), 7.65 (d, J = 7.9 Hz, 1H), 7.53 (d, J = 12.6 Hz, 1H), 7.27 (s, 1H), 7.24 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 2.0 Hz, 1H), 7.18 (t, J = 7.2 Hz, 1H), 7.14 (dd, J = 9.2, 2.4 Hz, 1H), 2.31 (s, 3H); 13C NMR 101 MHz, CDCl3) δ 164.36, 162.11, 158.52, 155.42, 144.36, 140.31, 135.71, 135.60, 135.56, 135.31, 135.09, 134.83, 134.45, 131.91, 130.20, 129.49, 127.58, 127.41, 127.16, 123.28, 120.11, 118.43, 117.25, 14.74. HRMS calcd. for C26H15Cl2F3N3O4 [M–H]− 560.0397, found 560.0399.
Description of N-(4-chloro-2-methylphenyl)-5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitrobenzamide (5f): White solid, yield 80.2%. m.p. 199.2–201.7 °C; 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 8.21 (d, J = 9.1 Hz, 1H), 8.10 (s, 1H), 7.91 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 8.3 Hz, 1H), 7.28–7.16 (m, 7H), 2.29 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.20, 162.10, 158.51, 155.44, 144.41, 144.37, 140.33, 135.60, 135.57, 135.40, 134.45, 133.24, 132.08, 131.91, 131.41, 130.48, 130.19, 127.58, 126.98, 125.35, 120.12, 118.47, 117.56, 117.23, 17.92. HRMS calcd. for C26H15Cl2F3N3O4 [M–H]− 560.0397, found 560.0402.
Description of N-(5-chloro-2-methylphenyl)-5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitrobenzamide (5g): white solid, yield 74.9%. m.p. 184.2–186.4 °C; 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 8.21 (d, J = 9.1 Hz, 1H), 8.10 (s, 1H), 7.91 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 8.3 Hz, 1H), 7.28–7.16 (m, 7H), 2.29 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.10, 162.14, 158.53, 155.41, 144.39, 140.25, 135.68, 135.60, 135.27, 134.46, 132.25, 131.92, 131.51, 130.20, 127.98, 127.56, 126.57, 126.24, 126.08, 123.61, 120.15, 118.49, 117.18, 17.32. HRMS calcd. for C26H15Cl2F3N3O4 [M–H]− 560.0397, found 560.0404.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitro-N-(3-(trifluoromethoxy)phenyl)benzamide (5h): brown solid, yield 76.1%. m.p. 140.2–141.4 °C; 1H NMR (500 MHz, CDCl3) δ 8.85 (s, 1H), 8.12 (t, J = 7.6 Hz, 1H), 8.08 (d, J = 1.6 Hz, 1H), 7.87 (d, J = 7.0 Hz, 2H), 7.85 (d, J = 7.1 Hz, 1H), 7.46–7.42 (m, 4H), 7.22 (d, J = 8.6 Hz, 2H), 7.13 (dd, J = 8.4, 5.8 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 185.24, 164.30, 162.18, 158.52, 155.31, 144.34, 144.30, 139.95, 137.74, 135.62, 135.58, 134.93, 134.43, 131.90, 131.65, 130.23, 129.75, 127.45, 123.57, 121.76, 120.19, 118.61, 117.14, 116.82. HRMS calcd. for C26H13ClF6N3O5 [M–H]− 596.0415, found 596.0410.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-N-(2,4-difluorophenyl)-2-nitrobenzamide (5i): White solid, yield 78.1%. m.p. 159.1–161.5 °C; 1H NMR (400 MHz, CDCl3) δ 8.84 (s, 1H), 8.25 (s, 1H), 8.09 (dd, J = 5.1, 3.7 Hz, 2H), 7.86 (d, J = 8.6 Hz, 2H), 7.52 (s, 1H), 7.42 (d, J = 8.1 Hz, 1H), 7.33 (t, J = 8.2 Hz, 1H), 7.22 (d, J = 8.5 Hz, 2H), 7.15 –7.10 (m, 2H), 7.02 (d, J = 8.1 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 163.78, 162.18, 158.52, 155.36, 144.36, 140.24, 135.60, 134.94, 134.50, 131.93, 130.20, 127.62, 126.25, 123.49, 123.38, 120.21, 118.70, 116.89, 111.70, 111.48, 103.80. HRMS calcd. for C25H13ClF5N3O4 [M–H]− 548.0422, found 548.0422.
Description of 5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitro-N-(3-(trifluoromethyl)phenyl)benzamide (5j): white solid, yield 74.3%. m.p. 146.1–148.7 °C; 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.10 (s, 1H), 7.89 (d, J = 8.7 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 7.22 (d, J = 8.7 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 4.59 (d, J = 5.4 Hz, 2H), 3.82 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.24, 162.15, 158.53, 155.33, 149.53, 144.33, 144.29, 139.91, 138.62, 135.61, 135.58, 134.95, 134.39, 131.88, 130.22, 127.40, 126.57, 126.23, 120.16, 118.57, 118.44, 117.16, 116.83, 113.20. HRMS calcd. for C26H13ClF6N3O4 [M–H]− 596.0453, found 596.0447.
Description of N-(4-acetylphenyl)-5-(4-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)phenoxy)-2-nitrobenzamide (5k): white solid, yield 77.6%. m.p. 196.1–198.3 °C; 1H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.19 (d, J = 8.9 Hz, 1H), 8.09 (s, 1H), 8.04 (s, 1H), 7.97 (d, J = 8.5 Hz, 2H), 7.89 (d, J = 8.5 Hz, 2H), 7.69 (s, 1H), 7.25–7.16 (m, 5H), 2.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.01, 162.17, 158.49, 155.34, 144.38, 144.34, 144.31, 141.60, 140.13, 135.58, 135.07, 134.49, 133.59, 131.93, 130.20, 129.82, 127.55, 120.16, 119.55, 118.73, 116.84, 29.71, 26.52. HRMS calcd. for C27H16ClF3N3O5 [M–H]− 554.0736, found 554.0737.

3.3. Insecticidal Activity Test

The insecticidal activities of 5a–5k against Mythimna separata, Aphis craccivora Koch, and Tetranychus cinnabarinus were evaluated according to a previously reported method [28,29,30]. First, all test compounds were dissolved in N,N-dimethylformamide containing 0.1% Tween-80 emulsifier and were then diluted to the corresponding dosage with distilled water. Appropriate amounts of corn leaves were fully soaked in liquid medicine for 10 s, dried naturally in the shade, and placed in a culture dish with filter paper. The larvae of Mythimna separata, Aphis craccivora Koch, and Tetranychus cinnabarinus were placed indoors on the processed corn leaves at 24–27 °C. The results were obtained after three days; the insect was touched with a brush, and it was regarded dead if there was no response. The control check (CK) group used only distilled water without any compounds, and the results of insecticidal activities are reported in Table 1.

4. Conclusions

A series of new 2-phenylpyridine derivatives containing N-phenylbenzamide moieties were designed and synthesised as possible insecticidal candidates. Compounds 5b, 5d, 5g, 5h, and 5k exhibited high insecticidal activities (100%) against Mythimna separata at 500 mg/L. Thus, the results of this study will provide a novel direction for the further use of 2-phenylpyridine derivatives as insecticides.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules28041567/s1, Figures S1–S22: 1H NMR and 13C NMR spectra of target compounds 5a–5k.

Author Contributions

W.Z. and J.C. performed the experiments; W.Z. prepared the manuscript; X.D. designed the materials and supervised the project; and X.D. revised the paper. All authors have read and agreed to the published version of the manuscript.

Funding

This study received no external funding.

Data Availability Statement

Not applicable.

Acknowledgments

We are grateful to Dong-Song Han (Zhejiang Research Institute of Chemical Industry) for helping with the bioactivity assays.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Zhu, Q.-H.; Chen, L.-Y.; Li, L.-J.; Li, H.-Y.; Zhang, L.-Z.; Zhao, N.-X.; Xu, Y.-G. Preparation Method of Fluorochloropyridine Ester. CN Patent CN 113603637, 5 November 2021. [Google Scholar]
  2. Jason, S.K.; David, J.C.; Abraham, D.S.; Megan, E.D.; Brian, M.; Ronald, B.L. Method of Preparing Benzyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate. U.S. Patent US 20180162814, 14 June 2018. [Google Scholar]
  3. Yoshinobu, J.; Akihiro, T. Herbicidal Agent Composition and Weed Control Method. U.S. Patent US 20220322666, 4 March 2021. [Google Scholar]
  4. Mansfield, A.J.; Cooke, T.; Thomas, P.S.; Coqueron, P.Y.; Vors, J.P.; Briggs, G.G.; Lachaise, H.; Rieck, H.; Desbordes, P.; Grosjean, M.C. Novel 2-pyridylethylbebzamide Derivative. WO Patent WO 2004026088, 26 February 2004. [Google Scholar]
  5. Bristow, J.T. Process for Preparing Boscalid. WO Patent WO 2018024145, 7 February 2018. [Google Scholar]
  6. Yang, C.-H.; Geng, L.-W.; Zhou, D.-F.; Peng, L.; Zhang, H.; Cui, D.-L.; Li, Z.-N.; Wang, L.-Q.; Zang, S.-G.; Zhang, Z.-Y. N-(2-substituted phenyl)-N-methoxy carbamates and their preparation and use thereof. EP Patent EP 1845086, 10 August 2006. [Google Scholar]
  7. Yang, G.-F.; Li, J. Preparation of Dichloroallyl ether Compound and Their Application as the Insecticide Agents. CN Patent CN 104974083, 14 October 2015. [Google Scholar]
  8. Ke, S.-Y.; Yang, Z.-W.; Zhang, Z.-G.; Wang, K.-M.; Liang, Y. Preparation of Bisamide Structure-Containing Heterocyclic Imine Derivatives Useful as Pesticides. CN Patent CN 105622534, 1 June 2016. [Google Scholar]
  9. Jeschke, P.; Velten, R.; Schenke, T.; Schallner, O.; Beck, M.; Pontzen, R.; Malsam, O.; Reckmann, U.; Nauen, R.; Gorgens, U. Preparation of 4-[(pyridin-3-ylmethyl)amino]-5H-furan-2-ones as Insecticides. DE Patent DE 102006015467, 4 October 2007. [Google Scholar]
  10. Robert, H.; Christine, G.; Robert, S. N-phenyl-N’-(pyridinyl-N-oxide)urea Plant Regulators. U.S. Patent US 4787931, 29 November 1988. [Google Scholar]
  11. Yang, S.-X.; Chen, R.-Y.; Chen, J.-L. Preparation of 3-(2-pyridyl) Propanol. CN Patent CN 85102587, 10 February 1986. [Google Scholar]
  12. Cai, Z.-F.; Cao, Y.-Y.; Du, X.-H. Synthesis of Novel a-Trifluoroanisole Derivatives Containing Phenylpyridine Moieties with Herbicidal Activity. Int. J. Mol. Sci. 2022, 23, 11083. [Google Scholar] [CrossRef]
  13. Cao, Y.-Y.; Mao, D.-J.; Wang, W.-W.; Du, X.-H. Kresoxim-methyl derivatives: Synthesis and herbicidal activities of (pyridinylphenoxymethylene)phenyl methoxyiminoacetates. J. Agric. Food Chem. 2017, 65, 6114–6121. [Google Scholar] [CrossRef] [PubMed]
  14. Cao, Y.-Y.; Cai, Z.-F.; Zhang, W.-L.; Du, X.-H. Synthesis and herbicidal activity of novel β-methoxyacrylate derivatives containing a substituted phenylpyridine moiety. Chem. Res. Chin. Univ. 2019, 35, 1008–1011. [Google Scholar] [CrossRef]
  15. Xu, Y.; Wang, H.-T.; Du, X.-H. Design, synthesis, and fungicidal activity of novel N-substituted piperazine-containing phenylpyridines against cucumber downy mildew. Pest Manag. Sci. 2022, 78, 1806–1814. [Google Scholar] [CrossRef] [PubMed]
  16. Liu, C.-L.; Xie, Y.; Song, Y.-Q.; Xu, Y.; Li, K.-K.; Guan, A.-Y.; Yang, J.-C.; Yang, F. Ayrl Pyridine(pyrimidine) Compound and Use Thereof. WO Patent WO 2015032280, 18 March 2015. [Google Scholar]
  17. Jeanguenat, A.; Emery, D.; Hall, R.G.; Iosub, V.A.; Lechapelain, C.; Gagnepain, J.D.H.; Kilaru, J.P.; Phadte, M.; Pitterna, T. Pesticidally Active Azole-Amide Compounds. WO Patent WO 2021122645, 24 June 2021. [Google Scholar]
  18. Lahm, G.P.; Mccann, S.F.; Patel, K.M.; Selby, T.P.; Stevenson, T.M. Method for Controlling Particular Inset Pests by Applying Anthranilamide Compounds. WO Patent WO 03015518, 27 February 2003. [Google Scholar]
  19. Li, B.; Yang, H.-B.; Wang, J.-F.; Yu, H.-B.; Zhang, H.; Li, Z.-N.; Song, Q. 1-Substituted Pyridyl-Pyrazolyl Amide Compousnds and Uses Thereof. US Patent US 8492409, 31 December 2008. [Google Scholar]
  20. Elbe, H.L.; Rieck, H.; Dunkel, R.; Qin, Z.-O.; Mauler-Machnik, A.; Wachendorff-Neumann, U.; Kuck, K.H. Pyrazolylcarboxanilides as Fungicides. WO Patent WO 0300149, 6 February 2003. [Google Scholar]
  21. Munro, D.; Patel, B. Preparation of Benzoic Acid-2′,4′-difluoroanilide Herbicidal Compounds. EP Patent EP 0467473, 22 January 1992. [Google Scholar]
  22. Hao, S.-L.; Cai, Z.-F.; Cao, Y.-Y.; Du, X.-H. Design, synthesis, and acaricidal activity of phenyl methoxyacrylates containing 2-alkenylthiopyrimidine. Molecules 2020, 25, 3379–3390. [Google Scholar] [PubMed]
  23. Panchal, D.M.; Desai, J.K. Process for preparation of insecticidal anthranilamides. WO Patent WO 2022149098, 15 July 2022. [Google Scholar]
  24. Zhao, Y.; Xiong, L.-X.; Xu, L.-P.; Wang, H.-X.; Xu, H.; Li, H.-B.; Tong, J.; Li, Z.-M. Synthesis, crystal structure and biological activity of a novel anthranilic diamide insecticide containing allyl ether. Res. Chem. Intermed. 2013, 39, 3071–3088. [Google Scholar] [CrossRef]
  25. Jeffrey, T.M.; Yong-Jae, K.; Mike, L.; Chen, X.-Q.; Jeff, D.; Malgorzata, W.; Yu, M.; Fu, J.-S.; Chen, X.; Zhang, A.; et al. Discovery of a new class of ghrelin receptor antagonists. Bioorg. Med. Chem. Lett. 2012, 22, 2046–2051. [Google Scholar]
  26. Wang, J.-K.; Liu, S.-J.; Lu, Y.-Q. Method for Synthesizing Flubendiamide. CN Patent CN 1094855, 19 March 2019. [Google Scholar]
  27. Ying, J.-W.; Luo, H.; Song, Y.-Q.; Li, B.; Yang, H.-B. Synthesis and insecticidal activity of cyclaniliprole. Mod. Agrochem. 2016, 15, 28–31. [Google Scholar]
  28. Li, R.; Cheng, S.-H.; Liang, P.-Z.; Chen, Z.-B.; Zhang, Y.-J.; Liang, P.; Zhang, L.; Guo, X.-W. Status of the Resistance of Aphis gossypii Glover, 1877 (Hemiptera: Aphididae) to Afidopyropen Originating from Microbial Secondary Metabolites in China. Toxins 2022, 14, 750. [Google Scholar] [CrossRef] [PubMed]
  29. Moores, G.D.; Gao, X.W.; Denholm, I.; Devonshire, A.L. Characterisation of insensitive acetylcholinesterase in insecticide-resistant cotton aphids, Aphis gossypii glover (Homoptera: Aphididae). Pestic. Biochem. Physiol. 1996, 56, 102–110. [Google Scholar] [CrossRef]
  30. Chen, S.-L.; Zhang, Y.; Liu, Y.-X.; Wang, Q.-M. Highly Efficient Synthesis and Acaricidal and Insecticidal Activities of Novel Oxazolines with N-Heterocyclic Substituents. J. Agric. Food Chem. 2021, 69, 3601–3606. [Google Scholar] [CrossRef] [PubMed]
Molecules 28 01567 g001 550
Figure 1. Structures of the reported pyridine-containing compounds.
Figure 1. Structures of the reported pyridine-containing compounds.
Molecules 28 01567 g001
Molecules 28 01567 g002 550
Figure 2. Structures of the reported amide-based compounds.
Figure 2. Structures of the reported amide-based compounds.
Molecules 28 01567 g002
Molecules 28 01567 sch001 550
Scheme 1. Overview of the optimization design of the novel 2-phenylpyridine derivatives.
Scheme 1. Overview of the optimization design of the novel 2-phenylpyridine derivatives.
Molecules 28 01567 sch001
Molecules 28 01567 sch002 550
Scheme 2. Overview of the synthesis of the 2-phenylpyridine derivatives.
Scheme 2. Overview of the synthesis of the 2-phenylpyridine derivatives.
Molecules 28 01567 sch002
Table
Table 1. Insecticide activities (percent inhibition/%) of 5a–5k at 500 mg/L.
Table 1. Insecticide activities (percent inhibition/%) of 5a–5k at 500 mg/L.
CompoundChemical StructureDosage/
(mg/L)		Pest a
RMSACTC
5aH5008000
5b3-Cl500100700
5c2.4-CH3500000
5d2-OCH350010000
5e2-CH3,3-Cl5007000
5f2-CH3,4-Cl5009000
5g2-CH3,5-Cl50010000
5h3-OCF350010000
5i2.4-F5008000
5j3-CF350010000
5k4-CH3CO5009000
chlorantraniliprole/500100100100
CK//000
a MS, Mythimna separata; AC, Aphis craccivora Koch; TC, Tetranychus cinnabarinus. CK, control check.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Zhang, W.; Chen, J.; Du, X. 2-Phenylpyridine Derivatives: Synthesis and Insecticidal Activity against Mythimna separata, Aphis craccivora, and Tetranychus cinnabarinus. Molecules 2023, 28, 1567. https://doi.org/10.3390/molecules28041567

AMA Style

Zhang W, Chen J, Du X. 2-Phenylpyridine Derivatives: Synthesis and Insecticidal Activity against Mythimna separata, Aphis craccivora, and Tetranychus cinnabarinus. Molecules. 2023; 28(4):1567. https://doi.org/10.3390/molecules28041567

Chicago/Turabian Style

Zhang, Wenliang, Jingjing Chen, and Xiaohua Du. 2023. "2-Phenylpyridine Derivatives: Synthesis and Insecticidal Activity against Mythimna separata, Aphis craccivora, and Tetranychus cinnabarinus" Molecules 28, no. 4: 1567. https://doi.org/10.3390/molecules28041567

APA Style

Zhang, W., Chen, J., & Du, X. (2023). 2-Phenylpyridine Derivatives: Synthesis and Insecticidal Activity against Mythimna separata, Aphis craccivora, and Tetranychus cinnabarinus. Molecules, 28(4), 1567. https://doi.org/10.3390/molecules28041567

Article Metrics

Back to TopTop