Article pubs.acs.org/JAFC
Research on Controllable Degradation of Novel Sulfonylurea Herbicides in Acidic and Alkaline Soils Shaa Zhou,† Xue-Wen Hua,‡ Wei Wei,† Yu-Cheng Gu,§ Xiao-Qing Liu,† Jing-Huo Chen,† Ming-Gui Chen,† Yong-Tao Xie,† Sha Zhou,† Xiang-De Meng,† Yan Zhang,† Yong-Hong Li,† Bao-Lei Wang,† Hai-Bin Song,† and Zheng-Ming Li*,† †
State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071, China ‡ College of Agriculture, Liaocheng University, Liaocheng 252000, China § Jealott’s Hill International Research Centre, Syngenta, Bracknell, Berkshire, RG42 6EY, U.K. S Supporting Information *
ABSTRACT: The degradation issue of sulfonylurea (SU) has become one of the biggest challenges that hamper the development and application of this class of herbicides, especially in the alkaline soils of northern China. On the basis of the previous discovery that some substituents on the fifth position of the benzene ring in Chlorsulfuron could hasten its degradation rate, apparently in acidic soil, this work on Metsulfuron-methyl showed more convincing results. Two novel compounds (I-1 and I-2) were designed and synthesized, and they still retained potent herbicidal activity in tests against both dicotyledons and monocotyledons. The half-lives of degradation (DT50) assay revealed that I-1 showed an accelerated degradation rate in acidic soil (pH 5.59). Moreover, we delighted to find that the degradation rate of I-1 was 9−10-fold faster than that of Metsulfuronmethyl and Chlorsulfuron when in alkaline soil (pH 8.46), which has more practical value. This research suggests that a modified structure that has potent herbicidal activity as well as accelerated degradation rate could be realized and this approach may provide a way to improve the residue problem of SUs in farmlands with alkaline soil. KEYWORDS: sulfonylurea herbicide, Metsulfuron-methyl, herbicidal activity, soil degradation, DT50
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INTRODUCTION Sulfonylurea (SU) herbicides have been widely applied due to their ultralow dosage, broad spectra, and good selectivity.1,2 Their sole target is acetolactate synthase (ALS), which exists only in plants and microbes, not in mammals. The inhibition of ALS results in the disruption of the synthesis of three essential amino acids in meristem and eventually in the death of weeds.3−6 Many sulfonylurea herbicides have been introduced into China and are widely available in the Chinese plant-protection market.7 The common cultivation practice in China is to rear two or three different crops successively within a year on the same plot of land. The short crop cycles demand herbicides with high activity, low toxicity, and fast degradation rate. Due to the relatively long persistence of Chlorsulfuron, Metsulfuronmethyl, and Ethametsulfuron, which can injure the next season’s crops, including wheat, corn, paddy rice, cotton, and bean,8−10 the Ministry of Agriculture of China suspended their field application in 2014.11 From an environmental and ecological standpoint, we took a green approach to study this issue according to Anastas and Warner’s 10th principle of green chemistry: design for degradation.12 pH is one of the most important factors that influences the degradation rate of sulfonylurea herbicides in soil. Walker et al. reported that the DT50 of Metsulfuron-methyl was 23 days in pH 5.8 soil and 73 days in pH 7.3 soil.13 Yadav et al. found that there was 83% dissipation of Metsulfuron-methyl in low pH 5.6 soil and 53% in high pH 8.1 soil after 120 days.14 After research © 2017 American Chemical Society
of the hydrolysis of sulfonylurea herbicides in water at different pH values, we concluded that the fifth position on the benzene ring in SU structures is the key factor influencing their degradation behaviors.15−18 Our previous study reported that the introduction of some substituents onto the fifth position of the benzene ring in Chlorsulfuron could speed up its degradation rate in acidic soil relatively.19,20 On the basis of these previous findings, dimethylamino and diethylamino groups were introduced into the Metsulfuron-methyl structure (Figure 1) to investigate their influence on biological activities as well as soil degradation behaviors. Considering the difference of soil pH in China and that the soil degradation of sulfonylurea herbicides has strong negative correlation with soil pH,13,14,21 two representative standard soil samples (pH 5.59 from the Jiangxi Province and pH 8.46 from the Hebei Province) were selected to carry out our research.
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MATERIALS AND METHODS
Instruments and Materials. All reaction reagents were analytical grade, and all analytical reagents for high-performance liquid chromatograph (HPLC) were HPLC grade, including methanol and acetonitrile. The melting points were determined on an X-4 binocular microscope melting point apparatus (Beijing Tech Instrument Co., Received: Revised: Accepted: Published: 7661
July 2, 2017 August 8, 2017 August 16, 2017 August 16, 2017 DOI: 10.1021/acs.jafc.7b03029 J. Agric. Food Chem. 2017, 65, 7661−7668
Article
Journal of Agricultural and Food Chemistry
Figure 1. Design strategy of target compounds.
Table 1. Analysis Data of Soils mechanical composition (%) siltb
a
−1
soils
soil texture
pH
organic matter (%)
CEC (cmol·kg )
sand
acidic soil alkaline soil
loam clay
5.59 8.46
0.763 0.757
13.55 10.39
36 30
a
clayc
coarse
fine
coarse
fine
10 26
10 8
12 8
32 28
Sand: 1−0.05 mm. bSilt: course, 0.05−0.01 mm; fine, 0.01−0.005 mm. cClay: course, 0.005−0.001 mm; fine, 100
0.9992 0.9978 −
a
The degradation research of these two compounds were conducted in another batch.
The soil degradation behaviors of target compounds in acidic soil (pH 5.59) with Metsulfuron-methyl as a positive control were investigated preliminarily to explore the corresponding relationship between structural modification and soil degradation. From the half-lives of degradation, the degradation rate of dimethylamino-substituted compound I-1 was increased significantly such that its DT50 was 2.85 days, 2-fold faster than that of Metsulfuron-methyl. Furthermore, the degradation rate of I-2, with its DT50 of 5.11 days, was approximately the same as that of Metsulfuron-methyl (5.50 days). 7666
DOI: 10.1021/acs.jafc.7b03029 J. Agric. Food Chem. 2017, 65, 7661−7668
Article
Journal of Agricultural and Food Chemistry
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molecular structures. Considering the particular planting practice in China, which requires an individual cultivation cycle for each crop, convinces us that by modifying SU structures delicately, a control of their degradation rate that is in accordance with the cultivation pattern is possible.42 After further understanding their structure/activity/degradation relationship, it will be possible to optimize the novel herbicidal application in the particular planting system.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jafc.7b03029. 1 H and 13C NMR spectra for the target compounds (PDF) Soil test results in Chinese (PDF) Soil test results in English (PDF) Crystal data of compound I-1 in CIF format (CIF) Crystal data of compound I-1 (PDF)
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AUTHOR INFORMATION
Corresponding Author
*Address: State Key Laboratory of Elemento-Organic Chemistry, Nankai University, No. 94, Weijin Road, Nankai District, Tianjin 300071, China. Phone: +86 022-23503732. Fax: +86 022-23503732. E-mail:
[email protected]. ORCID
Shaa Zhou: 0000-0001-8993-4325 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No. 21272129), State Key Laboratory of Elemento-Organic Chemistry (Nankai University), the Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), and a Syngenta Ph.D. Scholarship. We thank Whittingham William for polishing this article.
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ABBREVIATIONS USED AHAS, acetohydroxy acid synthase; DMF-DMA, N,N-dimethylformamide dimethyl acetal; THF, tetrahydrofuran; RT, room temperature; Trp, tryptophan; Arg, aginine
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REFERENCES
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DOI: 10.1021/acs.jafc.7b03029 J. Agric. Food Chem. 2017, 65, 7661−7668
