Research on Controllable Degradation of Novel Sulfonylurea

Aug 16, 2017 - The degradation issue of sulfonylurea (SU) has become one of the biggest challenges that hamper the development and application of this...
1 downloads 0 Views 2MB Size
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



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.



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

(7) Phillips McDougall AgriService. Products Section2011 Market; Phillips McDougall, 2012. (8) Liu, L.; Gao, H.; Li, H. Conservation tillage for corn-wheat two crops a year region. Trans. Chin. Soc. Agric. Eng. 2004, 3, 016. (9) Fang, Q.; Yu, Q.; Wang, E.; Chen, Y.; Zhang, G.; Wang, J.; Li, L. Soil nitrate accumulation, leaching and crop nitrogen use as influenced by fertilization and irrigation in an intensive wheat-maize double cropping system in the North China Plain. Plant Soil 2006, 284, 335− 350. (10) Qiu, J.; Tang, H.; Frolking, S.; Boles, S.; Li, C.; Xiao, X.; Liu, J.; Zhuang, Y.; Qin, X. Mapping single-, double-, and triple-crop agriculture in China at 0.5 × 0.5 by combining county-scale census data with a remote sensing-derived land cover map. Geocarto Int. 2003, 18, 3−13. (11) Ministry of Agriculture of the People’s Republic of China. Bulletin of the Ministry of Agriculture of the People’s Republic of China 2014, 53, Announcement No. 2032. (12) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice; Oxford University Press: New York, 1998; p 30. (13) Walker, A.; Cotterill, E. G.; Welch, S. J. Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths. Weed Res. 1989, 29, 281−287. (14) Yadav, D.; Singh, S.; Malik, R.; Yadav, A. Persistence of Metsulfuron-methyl in soil as influenced by soil pH and microbes. Pestology 1998, 12, 31−34. (15) Wang, M. Y.; Mu, X. L.; Guo, W. C.; Li, Y. H.; Li, Z. M. Synthesis and herbicidal activity of novel 5-substituted benzenesulfonylureas. Chem. Res. Chin. Univ. 2007, 23, 674−678. (16) Wang, M.-Y.; Ma, Y.; Li, Z.-M.; Wang, S.-H. 3D-QSAR Study of Novel 5-Substituted Benzenesulfonylurea Compounds. Chem. J. Chin. Univ. 2009, 30, 1361−1364. (17) Cao, G.; Wang, M.-y.; Wang, M.-z.; Wang, S.-h.; Li, Y.-h.; Li, Z.m. Synthesis and herbicidal activity of novel sulfonylurea derivatives. Chem. Res. Chin. Univ. 2011, 27, 60−65. (18) Wang, M.; Ma, Y.; Wang, H.; Cao, G.; Li, Z. Kinetics of the Chemical Hydrolysis and 3D-QSAR Study of 5-Substituted Benzenesulfonylurea Compounds. Chem. J. Chin. Univ. 2016, 37, 1636−1642. (19) Hua, X. W.; Chen, M. G.; Zhou, S.; Zhang, D. K.; Liu, M.; Zhou, S.; Liu, J. B.; Lei, K.; Song, H. B.; Li, Y. H.; Gu, Y. C.; Li, Z. M. Research on controllable degradation of sulfonylurea herbicides. RSC Adv. 2016, 6, 23038−23047. (20) Hua, X.; Zhou, S.; Chen, M.; Wei, W.; Liu, M.; Lei, K.; Li, Y.; Zhou, S.; Wang, B.; Li, Z. Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation. Chin. J. Chem. 2016, 34, 1135−1142. (21) Walker, A.; Welch, S. J. The relative movement and persistence in soil of chlorsulfuron, metsulfuron-methyl and triasulfuron. Weed Res. 1989, 29, 375−383. (22) Wei, W.; Cheng, D. D.; Liu, J. B.; Li, Y. X.; Ma, Y.; Li, Y. H.; Yu, S. J.; Zhang, X.; Li, Z. M. Design, synthesis and SAR study of novel sulfonylureas containing an alkenyl moiety. Org. Biomol. Chem. 2016, 14, 8356. (23) Sheldrick, G. M. SHELXTL, Version 5.0; University of Göttingen: Göttingen, Germany, 2001. (24) Wang, B. L.; Duggleby, R. G.; Li, Z. M.; Wang, J. G.; Li, Y. H.; Wang, S. H.; Song, H. B. Synthesis, crystal structure and herbicidal activity of mimics of intermediates of the KARI reaction. Pest Manage. Sci. 2005, 61, 407−412. (25) Teaney, S. R.; Armstrong, L.; Bentley, K.; Cotterman, D.; Leep, D.; Liang, P. H.; Powley, C.; Summers, J.; Cranwell, S.; Lichtner, F.; Stichbury, R. DPX-KE459A new sulfonylurea for postemergence grass and broadleaf weed control in cereals. Brighton Crop Prot. Conf.Weeds 1995, 1, 49. (26) Jain, A. N. Surflex: fully automatic flexible molecular docking using a molecular similarity-based search engine. J. Med. Chem. 2003, 46, 499−511.

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.



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)



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.



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.



ABBREVIATIONS USED AHAS, acetohydroxy acid synthase; DMF-DMA, N,N-dimethylformamide dimethyl acetal; THF, tetrahydrofuran; RT, room temperature; Trp, tryptophan; Arg, aginine



REFERENCES

(1) Levitt, G. Synthesis and Chemistry of Agrochemicals II; ACS Symposium Series 443; American Chemistry Society: Washington, DC, 1991; pp 16−31. (2) Levitt, G. Herbicidal sulfonamides. Patent US 4127405, 1978. (3) Wang, J. G.; Lee, P. K. M.; Dong, Y. H.; Pang, S. S.; Duggleby, R. G.; Li, Z. M.; Guddat, L. W. Crystal structures of two novel sulfonylurea herbicides in complex with Arabidopsis thaliana acetohydroxyacid synthase. FEBS J. 2009, 276, 1282−1290. (4) Duggleby, R. G.; Pang, S. S. Acetohydroxyacid synthase. BMB Rep. 2000, 33, 1−36. (5) Li, Z. M.; Ma, Y.; Guddat, L.; Cheng, P. Q.; Wang, J. G.; Pang, S. S.; Dong, Y. H.; Lai, C. M.; Wang, L. X.; Jia, G. F.; Li, Y. H.; Wang, S. H.; Liu, J.; Zhao, W. G.; Wang, B. L. The structure-activity relationship in herbicidal monosubstituted sulfonylureas. Pest Manage. Sci. 2012, 68, 618−628. (6) Vulliet, E.; Emmelin, C.; Chovelon, J. M.; Guillard, C.; Herrmann, J. M. Photocatalytic degradation of sulfonylurea herbicides in aqueous TiO 2. Appl. Catal., B 2002, 38, 127−137. 7667

DOI: 10.1021/acs.jafc.7b03029 J. Agric. Food Chem. 2017, 65, 7661−7668

Article

Journal of Agricultural and Food Chemistry (27) Pang, S. S.; Guddat, L. W.; Duggleby, R. G. Molecular basis of sulfonylurea herbicide inhibition of acetohydroxyacid synthase. J. Biol. Chem. 2003, 278, 7639−7644. (28) The Institute for the Control of Agrochemicals under the Ministry of Agriculture. Chinese National Standard GB/T 31270.12014. Test guidelines on environmental safety assessment for chemical pesticidesPart 1: Transformation in soils; Oct 10, 2014. (29) National Chemical Standardization Technical Committee. Chinese National Standard GB/T 16631-2008. General rules for high performance liquid chromatography; Jun 18, 2008. (30) Ministry of Agriculture, Pesticide Testing Center. Chinese Agricultural Industry Standard NY/T 788-2004. Guideline on pesticide residue trials; Apr 16, 2004. (31) Levitt, G.; Ploeg, H. L.; Weigel, R. C., Jr.; Fitzgerald, D. J. 2Chloro-N-[(4-methoxy-6-methyl-1, 3, 5-triazin-2-yl) aminocarbonyl] benzenesulfonamide, a new herbicide. J. Agric. Food Chem. 1981, 29, 416−418. (32) Thirunarayanan, K.; Zimdahl, R. L.; Smika, D. E. Chlorsulfuron adsorption and degradation in soil. Weed Sci. 1985, 558−563. (33) Oppong, F. K.; Sagar, G. R. Degradation of triasulfuron in soil under laboratory conditions. Weed Res. 1992, 32, 167−173. (34) Hamaker, J. W.; Goring, C. A. I. Turnover of Pesticide Residues in Soil. ACS Symp. Ser. Am. Chem. Soc. 1976, 9, 219−243. (35) Gençer, N.; Demir, D.; Sonmez, F.; Kucukislamoglu, M. New saccharin derivatives as tyrosinase inhibitors. Bioorg. Med. Chem. 2012, 20, 2811−2821. (36) Dudutienė, V.; Zubrienė, A.; Smirnov, A.; Gylytė, J.; Timm, D.; Manakova, E.; Gražulis, S.; Matulis, D. 4-Substituted-2, 3, 5, 6tetrafluorobenzenesulfonamides as inhibitors of carbonic anhydrases I, II, VII, XII, and XIII. Bioorg. Med. Chem. 2013, 21, 2093−2106. (37) Gazvoda, M.; Kočevar, M.; Polanc, S. In situ formation of vilsmeier reagents mediated by oxalyl chloride: a tool for the selective synthesis of N-sulfonylformamidines. Eur. J. Org. Chem. 2013, 2013, 5381−5386. (38) Chandna, N.; Chandak, N.; Kumar, P.; Kapoor, J. K.; Sharma, P. K. Metal-and solvent-free synthesis of N-sulfonylformamidines. Green Chem. 2013, 15, 2294−2301. (39) Vaidyanathan, G.; Song, H.; Affleck, D.; McDougald, D. L.; Storms, R. W.; Zalutsky, M. R.; Chin, B. B. Targeting aldehyde dehydrogenase: a potential approach for cell labeling. Nucl. Med. Biol. 2009, 36, 919−929. (40) McCourt, J. A.; Pang, S. S.; Guddat, L. W.; Duggleby, R. G. Elucidating the specificity of binding of sulfonylurea herbicides to acetohydroxyacid synthase. Biochemistry 2005, 44, 2330−2338. (41) Chen, P. Q.; Sun, H. W.; Li, Z. M.; Wang, J. G.; Ma, Y.; Lai, C. M. Molecular dynamics simulation of conformational conversion between crystal conformation and active conformation of herbicidal monosulfuron. Chem. J. Chin. Univ. 2007, 28, 278−282. (42) Feng, D. J.; Bai, B.; Wang, H. L.; Suo, Y. R. Novel Fabrication of Biodegradable Superabsorbent Microspheres with Diffusion Barrier through Thermo-Chemical Modification and Their Potential Agriculture Applications for Water Holding and Sustained Release of Fertilizer. J. Agric. Food Chem. 2017, 65, 5896−5907.

7668

DOI: 10.1021/acs.jafc.7b03029 J. Agric. Food Chem. 2017, 65, 7661−7668