高比活度碳-14标记毒氟磷的合成与分析

以[14C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱（RP-HPLC）纯化获得标记物纯品14C-毒氟磷（N-[2-（4-甲基苯并[2-14C]噻唑基）]-2-氨基-2-氟代苯基-O,O-二乙基甲基膦酸酯,38.3 mCi）。7步反应的化学收率/放化收率为10%。其结构经核磁共振氢谱、质谱和放射性高效液相色谱（HPLC-FSA）分析确认。放射性薄层成像分析（TLC-IIA）、高效液相色谱-液体闪烁测量联用分析（HPLC-LSC）、高效液相色谱-流动液体闪烁测量/二极管阵列检测器/质谱联用分析（HPLC-FSA/PDA/MS）和LSC分析表明,14C-毒氟磷的放化纯度和化学纯度均大于98%,比活度为58.0 mCi/mmol,可作为放射性示踪剂,用于毒氟磷的代谢和环境行为等研究。     

新型含吡唑杂环邻氨基苯甲酰胺类化合物的合成与杀螨活性

以氯虫苯甲酰胺和氟虫腈的结构为基础,通过活性亚结构拼接的方法,设计合成了24个新型含吡唑杂环邻氨基苯甲酰胺类化合物,其结构经1H NM R、IR及APCI-M S表征。初步生物活性测试结果表明:化合物5-溴-N-[4-氯-2-甲基-6-(甲氨基甲酰基)苯基]-1-1-[2,6-二氯-4-(三氟甲基)苯基]-4-三氟甲基亚磺酰基-1H-吡唑-3-甲酰胺(5k)和5-溴-N-[4-溴-2-甲基-6-(甲氨基甲酰基)苯基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-三氟甲基亚磺酰基-1H-吡唑-3-甲酰胺(5l)在500 mg/L下对朱砂叶螨Tetranychus cinnabarinus的致死率为100%,但在100 mg/L下其致死率则分别降至30%和50%。所得结果可为邻氨基苯甲酰胺类化合物构效关系研究提供参考。     

氯虫苯甲酰胺

理化性质：氯虫苯甲酰胺属邻甲酰氨基苯甲酰胺类杀虫剂。纯品外观为白色晶体;熔点：208℃-210℃;分解温度：330℃;蒸气压（20℃）：6．3×10Pa：分配系数：正辛醇／水LogPow=2．86（pH7,20℃）;化学名称：3-溴-N-[4-氯-2-甲基-6-[（甲氨基甲酰基）苯]-1-（3-氯吡啶-2-基）-1-氢-吡唑-5-甲酰胺：结构式：     

嘧啶联吡唑甲酰胺类化合物的合成及除草活性

设计合成了一系列结构新颖的嘧啶联吡唑甲酰胺类化合物5a~5o,其结构均经过1H NM R和MS分析确证。初步生物活性测试结果表明:在有效成分150 g/hm2剂量下苗后茎叶喷雾处理时,化合物(R)-N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5c)、N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-N-甲基-3-三氟甲基-1H-吡唑-4-甲酰胺(5i)和N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-3-三氟甲基-1H-吡唑-4-甲酰胺(5k)对繁缕Stellaria media的抑制率高达90%以上;而同样剂量下苗前土壤喷雾处理时,化合物N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5b)和5c对繁缕的抑制率达100%。该类结构化合物有望作为除草先导化合物进行开发。     

N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺的合成

高效低成本合成N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺。以2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯和碳酸氢钠为原材料,5%Pt/C为催化剂,通入氢气还原得N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺,并对不同条件下的试验结果进行了分析。优化条件为氢气进气压力为0.2Mpa,5%Pt/C催化剂与2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯的配比为5∶60,温度为30℃,反应时间为4h。该反应条件下产物反应收率≥97%,含量≥97%,生产成本低、操作简便非常适合工业化生产。     

含苯丙氨酸和1H-茚-1-酮类氯虫苯甲酰胺类似物的合成及杀虫活性

为了开发新的杀虫化合物，以氯虫苯甲酰胺为先导，2-甲基-3-氨基苯甲酸为起始原料，经过卤化生成5-氯-3-甲基-2-氨基苯甲酸；再与3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-甲酸进行缩合反应，生成6-氯-2-(3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-基)-8-甲基-4H-3,1-苯并噁嗪-4-酮；最后引入苯丙氨酸片段并经环化反应，分别合成了两个系列共计23 个新化合物( 4 和 5 )，其中化合物 4 为含苯丙氨酸的氯虫苯甲酰胺类似物，化合物 5 为由化合物4环化生成的含1H-茚-1-酮片段的氯虫苯甲酰胺类似物，所有化合物的结构均通过核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱(HRMS)的表征及确证。初步室内杀虫活性测试结果表明，多数目标化合物对黏虫Mythinma separata具有较高的杀虫活性，其中14个化合物在100 mg/L下对黏虫Mythinma separata的致死率为100%，化合物 5k ( 1H-茚-1-酮片段中取代基为羟基 ) 在4和0.8 mg/L下的致死率分别为90%和70%，其LC₅₀值为0.55 mg/L。分子对接结果表明，化合物 5k 与氯虫苯甲酰胺一样，也是作用于鱼尼汀受体(RyR)，但与靶标结合的氨基酸残基不同，这种差异可能对黏虫的抗药性治理研究有益。     

吡蚜酮·氯虫苯甲酰胺25%悬浮剂高效液相色谱分析

采用高效液相色谱法分析吡蚜酮.氯虫苯甲酰胺复配制剂,使用C18反相柱和紫外可变波长检测器,以甲醇-水为流动相,用外标法对有效成分进行分析和定量。吡蚜酮和氯虫苯甲酰胺的标准偏差分别为0.031、0.035,变异系数分别为0.15%和0.34%,平均回收率分别为99.3%和98.5%。     

氯虫苯甲酰胺和吡唑醚菌酯在铁皮石斛中的残留及消解动态

建立了QuEChERS-液相色谱-质谱联用 (LC-MS/MS) 同时测定铁皮石斛茎和叶中氯虫苯甲酰胺和吡唑醚菌酯残留量的分析方法,并采用该方法研究了这2种农药在铁皮石斛中的消解动态及最终残留量。样品经乙腈提取,用N-丙基乙二胺 (PSA)、C₁₈和石墨化碳 (PC) 净化。正离子电离,多反应监测模式,LC-MS/MS测定,外标法定量。结果表明:在0.10~60 mg/kg添加水平下,氯虫苯甲酰胺在铁皮石斛茎和叶中的平均回收率为74%~90%,相对标准偏差 (RSD) 为3.2%~4.1%;吡唑醚菌酯在铁皮石斛茎和叶中的平均回收率为75%~104%, RSD为1.7%~4.4%。样品中氯虫苯甲酰胺和吡唑醚菌酯的定量限 (LOQ) 均为 0.1 mg/kg。氯虫苯甲酰胺和吡唑醚菌酯在铁皮石斛中消解较慢,120 d时,氯虫苯甲酰胺在铁皮石斛茎和叶中的降解率分别为40%和72%,吡唑醚菌酯在铁皮石斛茎和叶中的降解率分别为80%和94%。吡唑醚菌酯在铁皮石斛叶中的消解半衰期为38.1 d。5%氯虫苯甲酰胺悬浮剂按有效成分37.5 g/hm2施药1~2次,施药间隔为7 d,当采收间隔期为30 d时,氯虫苯甲酰胺在茎和叶中的残留量均小于3 mg/kg。25%吡唑醚菌酯水分散粒剂按有效成分187.5 g/hm2施药2~3次,施药间隔为7 d,当采收间隔期为90 d时,吡唑醚菌酯在茎和叶中的残留量均小于8 mg/kg。     

35%丙硫菌唑·吡唑醚菌酯·氯虫苯甲酰胺种子处理悬浮剂液相色谱分析方法

本文采用高效液相色谱法,以乙腈和酸水为流动相,使用ZORBAX80? ExtendC_(18)不锈钢柱和二极管阵列检测器,在254nm波长下对混剂中丙硫菌唑、吡唑醚菌酯和氯虫苯甲酰胺进行分离和定量分析。结果表明,该方法测得丙硫菌唑、吡唑醚菌酯和氯虫苯甲酰胺的线性相关系数分别为0. 999 9、0. 999 8、1. 000 0;标准偏差分别为0. 04、0. 04、0. 08;变异系数分别为0. 67%、 0. 58%、 0. 35%;平均回收率分别为99. 95%、100. 17%、99. 88%。     

氯虫苯甲酰胺·噻虫胺颗粒剂高效液相色谱分析

本文采用高效液相色谱法,以甲醇加0.1%的磷酸水溶液为流动相,使用C_(18)色谱柱和二极管阵列检测器,在240nm波长下对氯虫苯甲酰胺·噻虫胺颗粒剂进行分离和测定。结果表明,该分析方法条件下氯虫苯甲酰胺和噻虫胺的线性相关系数(r~2)分别为0.999 6和0.993 2,标准偏差分别为0.002和0.006,变异系数分别为0.53%和0.49%,平均回收率分别为99.69%和100.08%。     

新型1H-吡唑-5-甲酰基氨基脲类化合物的合成及生物活性

采用活性亚结构拼接和生物合理设计的方法,将4-氯-1-甲基-3-乙基-5-吡唑甲酰肼与取代苯基异氰酸酯反应得到14个新的含氨基脲的吡唑类化合物。其结构经IR、1H NMR、质谱和元素分析确证。初步生物活性实验结果表明, 化合物1-( 4-氯-3-乙基-1-甲基-1H-吡唑-5-甲酰基) -4-(2-甲基苯基)氨基脲( 4g) , 1-( 4-氯-3-乙基-1-甲基-1H-吡唑-5-甲酰基) -4-( 4-氯苯基)氨基脲( 4b)在500μg /mL 剂量下对小麦白粉病菌Bumeria graminis和粘虫Mythimna separata 的抑制率和致死率分别达到90%和100%。     

含大体积取代基的吡唑并三嗪酮类化合物的合成及除草活性

以1-(取代)苯基-5-氨基-1H-吡唑-4-甲酸乙酯或1-叔丁基-5-氨基-1H-吡唑-4-甲酰氯和2-甲基-4-炔丙基-6-氨基-7-氟-2H-苯并[b][1,4]-噁嗪-3(4H)-酮为初始原料，分别通过不同的合成路线，得到22个未见文献报道的含大体积取代基的吡唑并三嗪酮类化合物，所有化合物的结构均通过核磁共振氢谱(1H NMR)和高分辨质谱(HRMS)确证。初步生物活性测定结果表明:在375 g/hm2处理剂量下，大部分目标化合物表现出一定的除草活性，其中化合物 4h 、 4i 和 4j 对反枝苋Amaranthus retroflexus生长的抑制率接近100%。     

氨基甲酸-2-氯吡啶-5-甲酯化合物的合成与抑菌活性

以芳香硝基化合物、2-氯-5-吡啶甲醇和一氧化碳为原料,在Pd-Fe/Ti O2催化下进行羰基化反应,合成了11个新型氨基甲酸-2-氯吡啶-5-甲酯化合物,其结构经1H NM R和M S表征。初步抑菌活性测定结果表明:在50 mg/L下,大多数目标化合物对4种供试病原菌具有一定的抑制活性,其中化合物3f(4-甲氧基苯基氨基甲酸-2-氯吡啶-5-甲酯、3h(2,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)和3j(3,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)对小麦赤霉病菌Gibberella zeae的抑制率达77.3%以上,3f对苹果轮纹病菌Physalospora piricola的抑制率达82.5%,与对照药多菌灵接近;所有化合物在50 mg/L下对番茄灰霉病菌Botrytis cinerea的抑制活性均优于对照药多菌灵。     

Degradation of the sulfonylurea herbicide LGC-42153 in flooded soil

LGC-42153, 2-fluoro-1-[3-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)pyridin-2-yl] propyl methoxyacetate, is a new sulfonylurea herbicide for use in rice. Its breakdown and metabolism was studied in soil under flooded conditions using two radioactive tracer compounds labelled at either the propyl group or the pyrimidine ring. The half-life of LGC-42153 was approximately 3.0 days. The mass balance over 120 days ranged from 94.0 to 104.2% of applied radiocarbon, and no significant amount of volatiles or [14C]carbon dioxide were observed. Solvent non-extractable radiocarbon reached about 11-14% of applied radiocarbon at 120 days after treatment. The major metabolic reaction was the cleavage of the carboxyl ester bond to give 1-(4,6-dimethoxypyrimidin-2-yl)-3-[2-(1-hydroxy-2-fluoropropyl)pyridine-3-sulfonyl]urea, which underwent hydrolysis of the sulfonylurea bridge giving 2-(1-hydroxy-2-fluoro)propyl-3-pyridinesulfonamide and 4,6-dimethoxy-2-aminopyrimidine.     

Pyrazole phenyl ether herbicides inhibit protoporphyrinogen oxidase

Two isomeric pairs of pyrazole phenyl ether herbicides [AH 2.429, 4-chloro-1-methyl-5-(4-nitrophenoxy)-3-(trifluoromethyl)-1H-pyrazole; AH 2.430, 4-chloro-1-methyl-3-(4-nitrophenoxy)-5-(trifluoromethyl)-1H-pyrazole; AH 2.431, 5-((4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)oxy)-2-nitrobenzoic acid; and AH 2.432, 5-((4-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-2-nitrobenzoic acid were evaluated for herbicidal activity in both intact plants and in tissue sections. Their capacity to induce accumulation of porphyrins in tissue sections and to inhibit protoporphyrinogen oxidase (Protox) in vitro were determined. In whole plant tests, the order of herbicidal activity was AH 2.430 AH 2.431 > AH 2.429 > AH 2.432. AH 2.430 consistently caused light-dependent membrane leakage in both green and far-red light grown cucumber cotyledon and barley primary leaf tissue sections after incubation for 20 hr in darkness in 0.1 mM solutions. The same treatment caused marked increases in protoporphyrin IX (PPIX) content during the 20-hr dark incubation. AH 2.429 and 2.431 were less effective and not effective in all tissues in causing herbicidal damage and PPIX accumulation. AH 2.432 was ineffective in tissue section assays. Mg-PPIX levels were not significantly affected by any of the compounds. Protochlorophyllide levels were decreased by AH 2.430 and 2.431 in barley and increased by AH 2.429, 2.431, and 2.432 in cucumber. A positive relationship was found between herbicidal activity and the amount of PPIX that was caused to accumulate by each compound. All of the compounds inhibited Protox activity. Positive correlations were found between herbicidal activity in planta over a 300-fold range and in vitro Protox inhibition and the amount of PPIX caused to accumulate in vivo. These data support the view that the pyrazole phenyl ethers exert their herbicidal activity entirely through inhibition of Protox.     

Synthesis and herbicidal activity of new oxazinone herbicides with a long-lasting herbicidal activity against Echinochloa oryzicola

Chemical modification of the herbicide 1-[2-(benzothiazol-2-yl)isopropyl]-4-methyl-3-phenyl-5H-pyrrolin-2-one (MI-2826) has revealed a new oxazinone herbicide, 3-[2-(7-chlorobenzothiazol-2-yl)isopropyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (MI-3069), for use in paddy fields. In comparing the phyototoxicity of the two herbicides to transplanted rice, the latter was superior to the former and kept the same predominant characteristic to control Echinochloa oryzicola Vasin for a long period of time owing to its long-lasting residual effect.     

Degradation of the sulfonylurea herbicide LGC-42153 in flooded soil

LGC-42153, 2-fluoro-1-[3-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)pyridin-2-yl]propyl methoxyacetate, is a new sulfonylurea herbicide for use in rice. Its breakdown and metabolism were studied in soil under flooded condition using radioactive tracers labelled at either the propyl group or the pyrimidine ring. The half-life of LGC-42153 was approximately 3.0 days. The mass balance over 120 days ranged from 94.0 to 104.2% of applied radiocarbon, and no significant amount of volatiles or [14C]carbon dioxide were observed. Solvent non-extractable radiocarbon reached 11 approximately 14% of applied radiocarbon at 120 days after treatment. The major metabolic reaction was the cleavage of the carboxyl ester bond to give 1-(4,6-dimethoxypyrimidin-2-yl)-3-[2-(1-hydroxy-2-fluoropropyl)pyridine-3-sulfonyl]urea, which underwent hydrolysis of the sulfonylurea bridge giving 2-(1-hydroxy-2-fluoro)propyl-3-pyridinesulfonamide and 4,6-dimethoxy-2-aminopyrimidine.     

Herbicide perfluidone (1,1,1-trifluoro-N-[2-methyl-4-(phenylsulfonyl)phenyl]methanesulfonamide): Its metabolism in rats and chickens

Rats and chickens were each given a single oral dose (10 or 100 mg/kg body wt) of 1,1,1-trifluoro-N-[2-methyl-4-(phenylsulfonyl)phenyl-¹⁴C(U)]methanesulfonamide ([¹⁴C]perfluidone). Depending on the size of the dose, from 8.4 to 36.2% of the [¹⁴C] was eliminated in the urine and from 36.4 to 85.4% was eliminated in the feces within 48 hr after dosing. Less than 1% of the [¹⁴C] given to laying hens as [¹⁴C]perfluidone was present in the eggs produced during the first 96 hr after dosing. The percentage of the administered [¹⁴C] that remained in these animals (body with G.I. tract and contents removed) varied from 0.34 (96 hr after dosing) to 1.68% (48 hr after dosing). ¹⁴C-labeled compunds in the urine and feces from the rats and chickens were purified by solvent extraction, column chromatography, and gas-liquid chromatography, and then identified by infrared and mass spectrometry. The parent compound was the major ¹⁴C-labeled component in the urine and feces of both animals. 1,1,1-Trifluoro-N-[2-methyl-4-(3-hydroxyphenylsulfonyl)phenyl]methanesulfonamide was present in the feces of both animals. The proposed structures of other metabolites were 1,1,1-trifluoro-N-hydroxy-N-[2-methyl-4-(phenylsulfonyl)phenyl]methanesulfonamide (rat urine) and 1,1,1-trifluoro-N-{2-methyl-4-[(methylsulfonyl)-phenylsulfonyl]phenyl}methanesulfonamide (chicken urine).