A Review on Penthiopyrad: A Novel Pyrazole Amide Pesticide

doi:10.11924/j.issn.1000-6850.casb2021-0908

Abstract

Abstract:

To elaborate the ecological exposure risk and environmental fate of a novel pyrazole amide fungicide penthiopyrad, the authors summarized the synthesis path, biological activity, ecological toxicology, analytical methodology and environmental fate of penthiopyrad, as well as its application prospects. Penthiopyrad exhibited a significant inhibitory effect on fungal spore germination, and the prevention effect was better than the treatment effect. High ecotoxicity of penthiopyrad was observed to aquatic organisms, whereas obvious enantioselective differences were demonstrated to cell viability and oxidative stress. Further studies were recommended to investigate the fate characteristic and aquatic ecotoxicology of penthiopyrad under various circumstances, especially focus on the molecular mechanism of enantioselectivity. The chiral enantiomer of penthiopyrad with high-activity and low-risk was also explored to develop a scientific and accurate risk assessment system, and to reduce the high potential exposure risks to aquatic biological safety and human reproductive health.

Key words: penthiopyrad, synthesis path, biological activity, ecological toxicology, environmental fate

CLC Number:

S482.26

HAN Wenhao, YAN Zhenmin, WU Yanbing, CAI Guanghui, ZHAO Lilin, LI Wei, CHEN Zenglong. A Review on Penthiopyrad: A Novel Pyrazole Amide Pesticide[J]. Chinese Agricultural Science Bulletin, 2022, 38(24): 124-130.

Figures/Tables 5

References 51

[1]	胡伟群, 王晓阳, 朱卫刚, 等. 吡唑酰胺类化合物ZJ10520杀菌活性研究[J]. 世界农药, 2021, 43(2):49-52.
[2]	黄铭威. 新型吡唑酰胺类杀菌剂的设计、合成及生物活性研究[D]. 武汉: 华中师范大学, 2020(1):75.
[3]	党铭铭, 刘民华, 柳爱平, 等. 琥珀酸脱氢酶抑制剂类杀菌剂的最新研究进展[J]. 农药, 2020, 59(6):391-396.
[4]	柏亚罗. 吡噻菌胺在SDHI类杀菌剂中增长最快今年或将在中国首登[J]. 农药快讯, 2017(8):40-42.
[5]	魏阁, 高梦琪, 朱晓磊, 等. 靶向琥珀酸脱氢酶的酰胺类杀菌剂的研究进展[J]. 农药学学报, 2019, 21(Z1):673-680.
[6]	华乃震. 杀菌剂吡噻菌胺的作用机理、防治对象及合成.[J]. 农药快讯, 2020(36):7-8
[7]	SDHI类杀菌剂penthiopyrad(吡噻菌胺)可以登记的作物与防控的病害[J]. 农药市场信息, 2018(12):39-39.
[8]	MIYAMOTO T, HAYASHI K, OKADA R, et al. Resistance to succinate dehydrogenase inhibitors in field isolates of Podosphaera xanthii on cucumber: monitoring, cross-resistance patterns and molecular characterization[J]. Pesticide biochemistry and physiology, 2020, 169:104646. doi: 10.1016/j.pestbp.2020.104646 URL
[9]	仇是胜, 柏亚罗. 18个琥珀酸脱氢酶抑制剂类杀菌剂. 农药快讯信息网, 2015.
[10]	秦恩昊. 吡噻菌胺初步市场调研报告[J]. 农化市场十日讯, 2018(24): P.50-53.
[11]	张庆宽. 新颖杀菌剂--吡噻菌胺[J]. 世界农药, 2009, 31(3):53.
[12]	YUUJI Y, HIROYUKI K, KANJI T, et al. Development of a novel fungicide, penthiopyrad[J]. Journal of pesticide science, 2013, 38(3):167-168. doi: 10.1584/jpestics.J13-01 URL
[13]	JMPR. Report of the Joint Meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Core Assessment Group on Pesticide Residues[R]. 2012:271-297.
[14]	仇是胜, 柏亚罗. 琥珀酸脱氢酶抑制剂类杀菌剂的研发进展(Ⅱ)[J]. 现代农药, 2015, 14(1):1-7,20.
[15]	仇是胜, 柏亚罗. 琥珀酸脱氢酶抑制剂类杀菌剂的研发进展(Ⅰ)[J]. 现代农药, 2014, 13(6):1-7,47.
[16]	李为忠, 阎士江, 王凤莲. 新杀菌剂MTF-753[J]. 农药, 2005(3):130-131.
[17]	中国农药信息网. (URL:http://www.chinapesticide.org.cn/hysj/index.jhtml).
[18]	LEWIS K A, TZILIVAKIS J, WARNER D, et al. An international database for pesticide risk assessments and management[J]. Human and ecological risk assessment: an international journal, 2016, 22(4):1050-1064. doi: 10.1080/10807039.2015.1133242 URL
[19]	李红, 敬同坊, 李同宾, 等. 琥珀酸脱氢酶抑制剂类杀菌剂水生生态毒理学研究进展[J]. 农药学学报, 2021, 23(3):446-455.
[20]	陈倩. 吡噻菌胺的合成工艺研究[D]. 上海: 华东理工大学, 2012(7):83.
[21]	杜友兴. 2-(4-甲基戊基-2-基)-3-氨基噻吩的合成研究[J]. 宁夏大学学报:自然科学版, 2019, 40(4):370-374.
[22]	熊力. 杀菌剂啶酰菌胺和吡噻菌胺的合成工艺研究[D]. 武汉: 华中师范大学, 2013(4):57.
[23]	KATSUTA H, ISHII S, TOMIYA K, et al. A process for preparing 2-alkyl-3-aminothiophene derivative and 3-aminothiophene derivative:EP, 20000105331[P]. US, 2001.
[24]	杨汪松, 陈伟, 李华, 等. 吡噻菌胺关键中间体的制备研究进展[J]. 农药, 2020, 59(4):253-255,260.
[25]	金迪, 朱超云, 代金华, 等. 1-甲基-3-三氟甲基-1H-吡唑-4-甲酸的合成研究进展[J]. 现代盐化工, 2020, 47(6):18-20.
[26]	陈倩, 廖道华, 张曙光, 等. 1-甲基-3-三氟甲基-1H-吡唑-4-甲酰氯的合成[J]. 农药, 2012, 51(8):569-572.
[27]	YOJI A, TOMOTAKA M, HIDEKI U, et al. Preparation of 3-dimethylaminoacrylonitrile derivatives or their saltsin high yield:JP,2010024199A[P]. 2010-02-04.
[28]	NENAJDENKO V G, SANIN A V, BALENKOVA E S. Preparation of α,β-unsaturated ketones bearing a trifluoromethyl group and their application in organic synthesis[J]. Molecules, 1997, 2(12):186-232. doi: 10.3390/21200186 URL
[29]	李郁锦, 高建荣, 贾建洪, 等. 一种β-氨基丙烯酮类化合物的合成方法:CN, 101260062[P]. 2008-09-10.
[30]	KOLODZIEJCZYK K, ROIBAN G D, SCHNÜRCH M, et al. Synthesis of potential fungicides based on N -(3-furanyl) pyrrolecarboxamides and N-(3-furanyl)pyrazolecarboxamides[J]. Monatshefte fuer chemie/chemical monthly, 2009, 140(11):1349-1359.
[31]	窦倩倩, 王晓钟, 张玲玲, 等. 1-甲基-3-三氟甲基-4-吡唑甲酸的合成[J]. 高校化学工程学报, 2012, 26(3):470-474.
[32]	HO J O, MASAR U, OKAD A, et al. Facile synthetic methods for 3- and 5-trifluoromethyl-4-trifluoroacetylpyrazoles and their conversion into pyrazole-4-carboxylic acids[J]. Heterocycles, 1992, 34(4):791-798. doi: 10.3987/COM-91-5969 URL
[33]	林瑞华. 吡噻菌胺防治巨峰葡萄灰霉病的效果试验[J]. 落叶果树, 2021, 53(2):51-52.
[34]	MAO X W, WANG Y F, HOU Y P, et al. Activity of the succinate dehydrogenase inhibitor fungicide penthiopyrad against Sclerotinia sclerotiorum[J]. Plant disease, 2020, 104(10):2696-2703. doi: 10.1094/PDIS-10-19-2253-RE URL
[35]	彭昀. 新型SDHI类杀菌剂吡噻菌胺对橡胶树胶孢炭疽菌的生物学活性研究[D]. 海口: 海南大学, 2020(2):54.
[36]	LIANG X Y, PENG Y, ZOU L J, et al. Baseline sensitivity of penthiopyrad against Colletotrichum gloeosporioides species complex and its efficacy for the control of Colletotrichum leaf disease in rubber tree[J]. European journal of plant pathology, 2020(prepublish), 158 (4):965-974 doi: 10.1007/s10658-020-02130-6 URL
[37]	QIAN L, QI S Z, CAO F J, et al. Effects of penthiopyrad on the development and behaviour of zebrafish in early-life stages[J]. Chemosphere, 2019,214.
[38]	United States Environmental Protection Agency Washington (USEPA). D. C. 20460: Penthiopyrad (MTF-753): section 3 new chemical environmental fate and ecological risk assessment, 2011 [EB/OL]. (2012-10-09) [2020-08-09]. (URL:https://cfpub.epa.gov/ecotox/explore.cfm?cas=183675-82-3.)
[39]	PIECHOWICZ B, J SIEŃKO, MYTYCH J, et al. Assessment of risk to honey bees and honey consumers resulting from the insect exposure to captan, thiacloprid, penthiopyrad, and λ-cyhalothrin used in a commercial apple orchard[J]. Environmental monitoring and assessment, 2021, 193(3):1. doi: 10.1007/s10661-020-08746-9 URL
[40]	EFSA. Conclusion on the peer review of the pesticide risk assessment of the active substance penthiopyrad[R]. 2013, 11(2):3111
[41]	ERIC C A, CONSUELO A, ANTONIO A F, et al. High-affinity antibodies from a full penthiopyrad-mimicking hapten and heterologous immunoassay development for fruit juice analysis[J]. Food analytical methods, 2017, 10(12):4013-4023. doi: 10.1007/s12161-017-0974-3 URL
[42]	闫冬艳. 两种新型手性农药对HepG2细胞的对映体选择性毒性研究[D]. 呼和浩特: 内蒙古大学, 2018(12):55.
[43]	刘子琪, 呼啸, 李莉, 等. 呋虫胺立体选择性生物活性、生态毒理及环境行为研究进展[J/OL]. 中国环境科学:1-10[2021-08-02].
[44]	杨欢, 孙伟华, 曹赵云, 等. 改良QuEChERS方法快速测定果蔬中8种新型琥珀酸脱氢酶抑制剂类杀菌剂[J]. 色谱, 2016, 34(11):1070-1076. doi: 10.3724/SP.J.1123.2016.07005
[45]	WU J, ZHI S, JIA C, et al. Dispersive solid-phase extraction combined with dispersive liquid-liquid microextraction for simultaneous determination of seven succinate dehydrogenase inhibitor fungicides in watermelon by ultra high performance liquid chromatography with tandem mass spectrometry[J]. J sep sci., 2019, 42(24):3688-3696. doi: 10.1002/jssc.201900862 URL
[46]	谢海燕. 手性杀菌剂吡噻菌胺在土壤中选择性降解研究[D]. 呼和浩特: 内蒙古大学, 2017(1):61.
[47]	LIU Z Y, CHEN D, HAN J H, et al. Stereoselective degradation behavior of the novel chiral antifungal agrochemical penthiopyrad in soil[J]. Environmental research, 2021, 194:110680. doi: 10.1016/j.envres.2020.110680 URL
[48]	龚蕾, 黄徽, 韩智, 等. QuEChERS-UPLC-MS/MS测定果蔬中18种琥珀酸脱氢酶抑制剂类杀菌剂[J]. 食品科学:1-15[2021-08-02].
[49]	祝子铜, 雷美康, 许源, 等. 液相色谱-串联质谱法测定植物源性产品中5个酰胺类杀菌剂残留[J]. 药物分析杂志, 2018, 38(9):117-124.
[50]	郭庆龙. 一种吡噻菌胺残留量的GC-MS/MS测定方法:CN,105548439A[P]. 2016.
[51]	陈增龙. 呋虫胺对映体选择性环境行为与毒性差异分子机制[D]. 北京: 中国农业科学院, 2017(2):152.

病原体名称	菌丝生长抑制评价		孢子萌发抑制评价
病原体名称	EC₅₀/(mg/kg)	MIC/(mg/kg)	EC₅₀/(mg/kg)	MIC/(mg/kg)
叶斑病菌（Alternaria mali)^[33]	<0.4	6.6	/	/
褐斑病菌(Monilinia mali)^[33]	<0.4	11.6	/	/
菌核病菌(Sclerotinia sclerotiorum)^[33-34]	<0.4	7.3	<0.4	10.4
纹枯病菌(Rhizoctonia solani)^[33]	<0.4	30.2	/	/
灰霉病菌(Botrytis Cinerea)^[33]	0.34	47.9	<0.4	1.4
叶霉病菌(Fulvia fulva)^[33]	/	/	<0.4	6.4
叶锈病菌(Puccinia recondite)^[33]	/	/	<0.4	10.0
白粉病菌(Sphaerotheca cucurbitae)^[33]	/	/	0.9	9.8
黑星病菌(Ⅴenturia nashicola)^[33]	/	/	1.4	8.1
炭疽病菌(Colletotrichum gloeosporioides)^[35-36]	0.243~3.377	/	/	/

病原体名称	菌丝生长抑制评价		孢子萌发抑制评价
病原体名称	EC₅₀/(mg/kg)	MIC/(mg/kg)	EC₅₀/(mg/kg)	MIC/(mg/kg)
叶斑病菌（Alternaria mali)^[33]	<0.4	6.6	/	/
褐斑病菌(Monilinia mali)^[33]	<0.4	11.6	/	/
菌核病菌(Sclerotinia sclerotiorum)^[33-34]	<0.4	7.3	<0.4	10.4
纹枯病菌(Rhizoctonia solani)^[33]	<0.4	30.2	/	/
灰霉病菌(Botrytis Cinerea)^[33]	0.34	47.9	<0.4	1.4
叶霉病菌(Fulvia fulva)^[33]	/	/	<0.4	6.4
叶锈病菌(Puccinia recondite)^[33]	/	/	<0.4	10.0
白粉病菌(Sphaerotheca cucurbitae)^[33]	/	/	0.9	9.8
黑星病菌(Ⅴenturia nashicola)^[33]	/	/	1.4	8.1
炭疽病菌(Colletotrichum gloeosporioides)^[35-36]	0.243~3.377	/	/	/

毒性范畴	靶标生物	毒性量级
水生生物毒性	大型溞^[18]	EC₅₀(48 h)：>1.38 mg/L;NOEC (21 d)：0.47 mg/L
	黑头鲦鱼^[19,39]	LC₅₀ (96 h)：290 μg/L;NOEC (33 d)：510 μg/L
	虹鳟鱼^[19,39]	LC₅₀ (96 h)：390 μg/L
	鲤鱼^[19,39]	LC₅₀ (96 h)：570 μg/L
	斑马鱼^[19,38]	胚胎LC₅₀ (96 h)：2770 μg/L;幼鱼LC₅₀ (96 h)：2380 μg/L
	藻类^[18]	EC₅₀ (72 h)：> 1.58 mg/L
禽类生物毒性	禽类^[18]	EC₅₀：>2250 mg/kg;NOEC (21 d)：206.8 mg/kg
哺乳动物毒性	大鼠^[40]	经口LC₅₀> 2000 mg/kg;皮肤LC₅₀> 2000 mg/kg;吸入LC₅₀>5.59 mg/L; 甲状腺滤泡上皮腺瘤（长期NOAEL：27 mg/kg）; 母体体重减少,早期吸收、受孕后存活率、产仔数和妊娠子宫重量降低（发育NOAEL：75 mg/kg）
	小鼠^[40]	肝细胞腺瘤及癌（长期NOAEL：20 mg/kg）
	兔^[40]	流产、体重减轻和胎儿体重轻微减轻（发育NOAEL：250 mg/kg）
	狗^[40]	胆囊水肿（长期NOAEL：54 mg/kg）
其他生物毒性	蜜蜂^[18]	LC₅₀：>500 μg/L
其他生物毒性	蚯蚓^[18]	LC₅₀(14 d)：>500 mg/kg;NOEC：>48 mg/kg

毒性范畴	靶标生物	毒性量级
水生生物毒性	大型溞^[18]	EC₅₀(48 h)：>1.38 mg/L;NOEC (21 d)：0.47 mg/L
	黑头鲦鱼^[19,39]	LC₅₀ (96 h)：290 μg/L;NOEC (33 d)：510 μg/L
	虹鳟鱼^[19,39]	LC₅₀ (96 h)：390 μg/L
	鲤鱼^[19,39]	LC₅₀ (96 h)：570 μg/L
	斑马鱼^[19,38]	胚胎LC₅₀ (96 h)：2770 μg/L;幼鱼LC₅₀ (96 h)：2380 μg/L
	藻类^[18]	EC₅₀ (72 h)：> 1.58 mg/L
禽类生物毒性	禽类^[18]	EC₅₀：>2250 mg/kg;NOEC (21 d)：206.8 mg/kg
哺乳动物毒性	大鼠^[40]	经口LC₅₀> 2000 mg/kg;皮肤LC₅₀> 2000 mg/kg;吸入LC₅₀>5.59 mg/L; 甲状腺滤泡上皮腺瘤（长期NOAEL：27 mg/kg）; 母体体重减少,早期吸收、受孕后存活率、产仔数和妊娠子宫重量降低（发育NOAEL：75 mg/kg）
	小鼠^[40]	肝细胞腺瘤及癌（长期NOAEL：20 mg/kg）
	兔^[40]	流产、体重减轻和胎儿体重轻微减轻（发育NOAEL：250 mg/kg）
	狗^[40]	胆囊水肿（长期NOAEL：54 mg/kg）
其他生物毒性	蜜蜂^[18]	LC₅₀：>500 μg/L
其他生物毒性	蚯蚓^[18]	LC₅₀(14 d)：>500 mg/kg;NOEC：>48 mg/kg

分析方法	基质	定量限LOQ/(μg/kg)	检出限LOD/ (μg/kg)	相关系数(R²)	平均回收率/%	线性范围/(μg/L)	相对标准偏差RSD/%
LC-MS/MS^[45]	西瓜	0.1	0.02~0.04	>0.9970	72.0~111.6	0.1~100	3.4~14.1
LC-MS/MS^[48]	果蔬	1.5~6.0	0.5~2.0	>0.9900	83.6~109.4	0.5-200	1.2~8.4
LC-MS/MS^[13]	动植物源性食品	10.0	/	/	/	/	/
LC-MS/MS^[49]	植物源性产品	10.0	3.0	≥0.9937	83.9~94.5	0.5~500	0.7~14.3
LC-MS/MS^[47]	土壤	10.0	3.0	≥0.9971	74.9~111.3	/	0.5~10.5
HPLC^[46]	土壤	200.0	50.0	>0.9940	76.0~106.0	200~10000	1.5~9.3
GC-MS/MS^[50]	动植物源性食品	/	<0.25	/	86.4~95.3	/	5.0~8.7