自主设计、合成了系列新型邻胺基苯甲酰胺类化合物,并对其进行了杀虫活性、安全性、毒性、工艺、制剂、温室和/或田间防治效果等研究,获得了Ia、Ib和Ic等系列自主知识产权的高杀虫活性化合物.结果 表明化合物Ic等对咀嚼口器害虫如粘虫和小菜蛾等的活性较邻胺基苯甲酰胺类杀虫剂氯虫苯甲酰胺水平相当或更胜一筹,对刺吸口器害虫如蚜虫等的活性远优于氯虫苯甲酰胺及溴氰虫酰胺.田间药效试验进一步证实,Ic等对咀嚼口器害虫如水稻二化螟、稻纵卷叶螟、甜菜夜蛾等的防治效果相当于或优于氯虫苯甲酰胺,对刺吸口器害虫如蚜虫等的防治效果优于溴氰虫酰胺.新型邻胺基苯甲酰胺类化合物Ic等可作为候选杀虫剂进一步研究开发.

综述了2020年ISO公开的含氟杀虫剂cyclobutrifluram、flupentiofenox、nicofluprole和cyproflanilide及其关键中间体的合成方法,且对其进行了简要介绍.

琥珀酸脱氢酶抑制剂(SDHIs)是继甲氧基丙烯酸酯类和三唑类之后的第三大类杀菌剂,也是近几年来销售额年复合增长率增长最快的杀菌剂.根据现有23个此类商品化杀菌剂可知,该抑制剂结构包括3部分:酸片段(A)、胺片段(B)和酰胺键链接部分(C).概述了近3年报道的琥珀酸脱氢酶抑制剂类新活性化合物的最新研究进展且对其创制经纬进行了简要介绍.

以2,3-二氯丁烯醛酸和4-叔丁基苄氯为原料,采用一锅法合成新型哒嗪酮类杀螨剂哒螨灵(Pyridaben),其结构经质谱和核磁等确证.生测结果表明,哒螨灵不仅具有较好的杀螨活性,而且也具有较好的杀蚜虫和粘虫活性.

[目的]对丙硫菌唑原药进行全分析,明确质量分数大于0.1％的有机杂质的结构及含量.[方法]采用液质联用仪和气质联用仪分别对丙硫菌唑进行定性分析,以高效液相色谱和气相色谱等分析手段对原药及杂质进行定量分析或最低被检测质量分数.[结果]丙硫菌唑原药杂质为甲苯、杂质307和杂质309,而相关杂质硫酮菌唑的最低被检测质量分数为0.002％.[结论]试验不仅提供了一种丙硫菌唑全组分分析,而且对该产品的合成优化具有重要参考价值.

采用高效液相色谱-质谱联用对不同啶氧茵酯原药中的有机杂质进行定性分析.制备了啶氧茵酯原药中的主要杂质标准品.本方法建立了啶氧菌酯原药中有机杂质定性的分析方法,为啶氧茵酯原药质量分析和控制提供了依据.

采用高效液相色谱-质谱联用和液相色谱法对草铵膦原药中的有机杂质进行定性和定量分析.建立了草铵膦有机杂质的定量分析方法:采用高效液相色谱法,使用ZORBAX-SAX色谱柱和紫外检测器,以13.6 9磷酸二氢钾溶于970 mL水中,加30 mL甲醇为流动相,在195 nm波长下测定杂质3-氨基-4-甲氧基4-羰基丁基(甲基)膦酸铵的含量.该分析方法的线性相关系数为0.999 98,标准偏差为0.009,变异系数为0.71％,平均回收率为99.42％,最低检出浓度为0.01％.建立了草铵膦原药中有机杂质的定性和定量的分析方法,可以为草铵膦原药质量分析和控制提供依据.

In order to study fungicidal activity of the new compound HNPC-A113 Rhizoctonia solani,Erysiphe graminis and Puccinia polysora were selected as control objects,efficacy of HNPC-A113 against them were studied in greenhouse.Results showed that HNPC-A113 had good control effect against Rhizoctonia solani,Erysiphe graminis and Puccinia polysora.HNPC-A113 had high fungicidal activity against Rhizoctonia solani,Erysiphe graminis and Puccinia polysora with EC50 value of 1.06 mg·L-1,1.21 mg ·L-1 and 2.42 mg ·L-1,which were all comparable to that of Thifluzamide,Tluorosilicazole and Tebuconazole with EC50 value of 0.81 mg· L-1,1.27 mg· L-1,2.76 mg·L-1,respectively.HNPC-A113 had a broad spectrum of fungicidal activity,and it was valuable for further research and development.

In order to study the acaricidal activity of HNPC-A14343 and its isomer HNPC-A14344,the acaricidal activity against tetrany chuscinnabarinus of HNPC-A14343/14344 and their 1∶1 mixture by immersion method were studied,and their acaricidal activities against Tetranychus viennensis and Panonychuscitri McGregorwere confirmed in the greenhouse and field trials.The results indicated that HNPC-A14343/14344 exhibited high levels of acaricidal activity against tetranychus cinnabarinus at the value of LC50 0.35～0.41 mg/L.The greenhouse and field trials also showed that the efficacy of HNPC-A14343/14344 against Tetranychus viennensis and Panonychuscitri McGregorwere were comparable to that of spirodiclofen,and HNPC-A14343/14344 were valuable for further research and development.

为研究NC-510的生物活性,以硫代苯甲酰胺为起始原料,经环化、取代、酰化等一系列反应合成了(E)-2-氰基-1-(2-甲基-4-三氟甲基噻唑-5-基)-2-(2-苯基噻唑-4-基)新戊酸乙烯酯(NC-510),其结构经过1H NMR和MS确证.室内生物活性测试结果初步表明,NC-510对蚕虫蚜的LC50值为0.661 mg/L;在10 mg/L剂量下药后2d对蚕虫蚜表现出94.95％的防治效果,优于相同条件下吡蚜酮对蚕虫蚜的活性80.50％.

Objective To explore blood biomarker of occupational exposure to DMF.Methods 99 workers occupationally exposed to DMF were collected.22 cases without exposure to DMF or other organic solvents were chosen as controls.Concentrations of blood N - methylcarbamoyl adduct, urine N -methylformamide(NMF),urine N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC)were determined. Correlations among the 3 biomarkers above were explored.Results Concentrations of blood N -methylcarbamoyl adduct,urine NMF,urine AMCC were positively correlated with DMF exposure levels. Correlations among the 3 biomarkers above were found through Spearman rank correlation analysis(P <0.01). Conclusions Blood N-methylcarbamoyl adduct could be considered as a new occupational exposure biomarker of DMF.

建立了茶叶和土壤中啶虫脒的气相色谱残留检测方法,啶虫脒最低检出量为0.02 ng,最低检出浓度为0.01 mg/kg.在0.01～1.0 mg/kg添加水平范围内,啶虫脒在茶叶中的平均添加回收率为78.9％～103.8％,相对标准偏差1.37％～3.92％;在土壤中的平均添加回收率为81.8％～91.4％,相对标准偏差2.58％～6.83％.采用田间实验方法研究了啶虫脒的降解动态规律,啶虫脒在湖南、浙江、四川3地的茶叶和土壤中的消解半衰期分别为3.36～8.77 d和1.23～16.5 d,属于极低残留农药.

Ten novel benzotriazinone-3-anime derivatives were designed and synthesized,and their structures were confirmed by 1H NMR and MS spectra.The preliminary bioassay results showed that the title compounds possessed insecticidal activity.At the concentration of 500 mg / L,compands 4c,4d and 7c showed more than 80% insecticidal activities against Mythimna separata;at 500 mg / L,compand 7d showed more than 80 % insecticidal activity against Aphis fabae and more than 70% insecticidal activity against Tetranchus urticae.

To search for compounds with unique biological activities,a series of novel anthranilic diamide derivatives were designed and synthesized,and their structures were characterized by 1H NMR spectroscopy.The results of bioassays indicated that all of the title compounds exhibited 100% insecticidal activities against lepidopte ranpests Mythimna separata at a concentration of 1 000 mg/L.Most of the compounds exhibited good insecticidal activities against Homopteran pests at a concentration of 500 mg/L.For example,14c showed 89.29% insecticidal activities against Aphis fabae,and 14b showed 81.82% insecticidal activities against Nephotettix cincticeps.All of the title compounds exhibited no acaricidal activities against mite at a concentration of 500 mg/L.

The major impurities contained in thiodicarb technical were separated and identified by LC-PDA-MS as the following:methomyl(impurity 1),pyridine hydrochloride(impurity 2),thiodicarb isomer(E,Z)(impurity 3),thiodicarb isomer(E,E)(impurity 4)and sulfur(impurity 5).The content of methomyl was determined by external standard method with LC.

A GC-MS method,using HP-5MS column(30 m×0.25 mm,0.25 μm),was developed to separate and analyze pirimicarb and 4 impuritiesin technical material.Using electron impact(EI)method,pirimicarb and 4 impurities were identified according to standard library and explored the source of impurities according to the synthetic route.The way of dissociation of pirimicarb was discussed.

Objective To explore the feasibility of taking blood N-methylcarbamoyl adduct as an occupational exposure biomarker of DMF.Methods 87 workers occupationally exposed to DMF were taken as the experiment subjects.22 staff unexposed to DMF or any other organic solvents were taken as the controls.Concentration of MVH,the degeneration product of N-methylcarbamoyl adduct,was determined by GC-MS.Results In hemoglobin of DMF exposed workers,MVH in different concentrations was detected,but not in any one of the controls.Concentration of blood N-methylcarbamoyl adduct was positively correlated with DMF exposure levels.Conclusions Blood N-methylcarbamoyl adduct might be considered as a new occupational exposure biomarker of DMF.

HNPC-A8169 is a novel phenoxycarboxylic acid herbicide with intellectual properties,which was designed and created according to the prodrug theory using a new novel intermediate propynyloxy hydroxylamine hydrochloride.Through three years' greenhouse and field trials,HNPC-A8169 shows good efficacy for preventing and killing of some monocotyledons,such as digitaria sanguinalis,setaria viridis and echinochloa crus-galli,at the dose of 15～75 g a.i./hm2.HNPC-A8169 has also been proved to be safe to some dicotyledons,such as rapeseed,cotton and peanuts,or some mondcotyledons such as wheat.