农药中间体3，5，6-三氯吡啶-2-醇钠的合成

本文介绍了3,5,6-三氯吡啶-2-醇钠的合成方法,以三氯乙酰氯为起始原料,经过加成、环化、芳构化制备,产品含量可达93．8％,总收率为71．2％（以三氯乙酰氯计）。     

毒死蜱及其代谢物3,5,6-三氯-2-吡啶酚在黄瓜腌制过程中的残留水平变化

采用超高效液相色谱-串联质谱(UPLC-MS/MS)检测了毒死蜱及其有毒代谢物3,5,6-三氯-2-吡啶酚(TCP)在黄瓜腌制加工过程中残留水平的变化。结果表明:用水常规清洗能使黄瓜中毒死蜱的残留水平降低34%,清洗后的黄瓜经初腌和复腌2次处理后,其中毒死蜱的残留水平有所升高,3步处理的总加工因子为0.97;清洗对TCP的残留水平影响不大(仅降低2.6%),但经初腌和复腌处理后,其残留水平明显高于清洗前,3步加工的总加工因子为1.63。本研究表明,黄瓜经腌制前后毒死蜱的残留水平无明显变化,而代谢物TCP的残留水平明显升高。     

毒死蜱多克隆抗体的制备

以三氯硫磷为起始原料,经三步反应合成得到毒死蜱半抗原O-乙基O-(3,5,6-三氯-2-吡啶基)N-(3-羧丙基)硫逐磷酸胺 (简称CHBu),此半抗原分别与牛血清蛋白(BSA)和卵清蛋白 (OVA)用碳二亚胺法和混合酸酐法通过偶联反应得到免疫抗原和包被抗原,其结合比分别为 14.6 ∶ 1 和6.2 ∶ 1。用所得的免疫原免疫兔子获得了高效价(抗血清: 2.56×104; 冻干粉: 2.56×106)、高亲和性、特异性好的多克隆抗体。交叉反应试验表明,该抗体与毒死蜱各结构类似物交叉反应率均小于4%;亲和性试验表明,在1~500 ng/mL浓度范围内,抑制率与浓度呈线性关系,线性回归方程为 y=23.503 lg(x)+28.556,r=0.991 9,抑制中浓度I50=8.2 ng/mL,最低检测限为1.0 ng/mL。     

新型吡唑酰胺类化合物的合成及其工艺研究

以2,3,5-三氯吡啶肼,康宽酸为起始原料反应合成新型吡唑酰胺类化合物,该化合物对小菜蛾的生物活性较高。通过正交试验进行优化,确定了其合成的最佳工艺方案:以乙腈作为溶剂,用碳酸钾作为缚酸剂,在吡啶肼和康宽酰氯的摩尔比为1∶3时,产物的产率最高达到97.4%。试验的结果表明:摩尔比和温度是反应的主要影响因素。     

2种吡啶类除草剂对天山假狼毒群落影响和禾本科牧草产草量及安全性评价

2013—2014年在新疆昭苏县乌鲁空盖草原选用270 g/L三氯吡氧乙酸丁氧基乙酯·氯氨吡啶酸钾盐水乳剂和21%氯氨吡啶酸水剂不同浓度对草原毒草——天山假狼毒进行群落影响试验。研究结果表明,270 g/L三氯吡氧乙酸丁氧基乙酯·氯氨吡啶酸钾盐水乳剂和21%氯氨吡啶酸水剂不同浓度均对天山假狼毒群落生长产生影响,与使用浓度呈正相关;其中使用270 g/L三氯吡氧乙酸丁氧基乙酯·氯氨吡啶酸钾盐水乳剂6 000 m L/hm2明显抑制天山假狼毒群落正常生长,并且对禾本科牧草安全性较高,同时禾本科牧草数量和产草量明显增加,可作为防除天山假狼毒群落生长的化学药剂。     

玉米油甲酯制备及对高效氯氟氰菊酯水乳剂应用效果的影响

为研制并应用绿色溶剂玉米油甲酯以替代5%高效氯氟氰菊酯水乳剂中芳香烃类溶剂,以酸催化法研究了玉米油甲酯最佳合成工艺,采用浸渍法、液滴干燥法、白金吊环法、激光粒度分布仪测定法和点滴法测定了不同用量玉米油甲酯对5%高效氯氟氰菊酯水乳剂最大稳定持留量、液滴干燥时间、表面张力、粒度分布和生物活性的影响。结果表明:醇油摩尔比12∶1、反应温度65℃、反应时间6 h、催化剂浓硫酸用量为油重6%时,玉米油甲酯收率最大为85%;玉米油甲酯溶剂用量由10%提高至30%,5%高效氯氟氰菊酯水乳剂稀释药液在甘蓝、玉米、油菜叶片上的最大稳定持留量呈增大趋势,最大提高率为158.18%;在甘蓝叶片和石蜡载玻片上的干燥时间分别延长16min和17 min;表面张力降低18.4 m N/m;乳粒中位径保持在1μm左右,跨距略有增大。生物活性测定结果显示玉米油甲酯对甜菜夜蛾4龄幼虫的致死率明显提高。表明玉米油甲酯作为5%高效氯氟氰菊酯水乳剂助溶剂,可以保证水乳剂物理稳定性,且可提高药剂施用效果。     

1-（4-氯苯基）-3-吡唑醇的合成工艺

以对氯苯肼为原料经环合、氯化,合成1-（4-氯苯基）-3-吡唑醇。本文研究了其合成工艺和投料比、反应温度、反应时间,催化剂用量和溶剂种类对收率的影响。用IR、1HNMR表征了其结构,在最优条件下,1-（4-氯苯基）-3-吡唑醇合成的总收率为68．35％,含量为98．5％,该路线简单经济,条件温和,收率高,适合工业化生产。     

农药中间体2-氯烟酸的绿色合成工艺

以N,N-二甲基甲酰胺、光气或双(三氯甲基)碳酸酯和丁基乙烯醚为原料合成了3-二甲氨基丙烯醛,再和氰基乙酸乙酯反应,合成2-氰基-5-二甲氨基-2,4-戊二烯酸乙酯,经过环合、水解,合成2-氯烟酸,总收率70. 8%。该工艺反应条件温和,收率高、生产成本低,适合于工业化生产的新工艺。     

毒死蜱对子代雄鼠性激素相关基因mRNA表达的影响

有机磷类农药毒死蜱 (chlorpyrifos,CPF) 可影响雄性动物生殖系统功能。为探究胚胎早期毒死蜱暴露对雄性小鼠生殖功能的影响,于母鼠妊娠后第7天 (gestational day, GD7) 至分娩前1 d每天给予母鼠灌胃染毒10 mg/kg (b.w.) 剂量的毒死蜱,于子代雄鼠出生后第42 天处死,取血液及睾丸,测定睾丸质量,通过酶联免疫法检测血液中睾酮 (testosterone,T) 及促黄体生成素 (luteinizing hormone,LH) 含量,同时采用RT-qPCR方法检测睾丸中与胆固醇及睾酮合成相关的5个基因mRNA表达的变化。结果显示:与对照组相比,毒死蜱染毒组子代鼠睾丸质量增加了16.5%,差异极显著 (P < 0.01);血清中睾酮及促黄体生成素含量分别增加了9.9%和6.2%,但与对照差异不显著 (P > 0.05)。睾丸中胆固醇合成基因HMG-CoA synthase的mRNA表达量升高了72.9%,运输基因StAR的mRNA表达量升高了45.3%;此外,睾丸中睾酮合成基因P450scc、P450-17α和3β-HSD的mRNA表达量分别升高了95.5%、68.9%和112.0%。各基因mRNA的表达量在染毒组与对照组间均差异极显著 (P < 0.01)。研究表明,毒死蜱暴露可影响子代雄鼠睾酮合成相关基因mRNA的表达,推测毒死蜱可能是通过该途径发挥其毒性作用。     

30%毒死蜱微囊悬浮剂中游离毒死蜱的检测方法研究

建立一种有效、普适的方法用于30%毒死蜱微囊悬浮剂中游离毒死蜱的检测方法.试验使用正己烷作为萃取溶剂对样品进行前处理,采用气相色谱法测定游离毒死蜱质量分数,内标法定量.该分析方法的毒死蜱相关系数为0.999 8,变异系数为5.4%,平均回收率为103.70%.该方法操作简单,准确度、精密度及灵敏度均满足要求,可用于30%毒死蜱微囊悬浮剂中游离活性成分的检测.     

Degradation of bifenthrin,chlorpyrifos and imidacloprid in soil and bedding materials at termiticidal application rates

Organophosphorus, pyrethroid and chloronicotinyl insecticides have been used to control termites in building structures in recent years. We investigated the degradation behaviour of three insecticides (bifenthrin, chlorpyrifos and imidacloprid) at termiticidal application rates under standard laboratory conditions (25 °C, 60% field moisture capacity and darkness) for 24 months. The study was carried out on one soil and two bedding materials (sand-dolomite and quarry sand), which are commonly used under housing in Australia. Experiments were also conducted to examine the effect of soil moisture on the degradation of these insecticides. Insecticide residues in the samples collected at different days after application were measured by high performance liquid chromatography (HPLC). The rate of degradation of bifenthrin and imidacloprid insecticides was adequately described by a first-order kinetic model (r² = 0.93–0.97). However, chlorpyrifos degradation was biphasic, showing an initial faster degradation followed by a slower rate. Therefore, the degradation data during the slower phase only (after a two-month period) followed the first-order law (r² = 0.95). Soil moisture had little effect on degradation of imidacloprid and bifenthrin. Among the three insecticides, bifenthrin and imidacloprid were most stable and chlorpyrifos the least. Chlorpyrifos showed a major loss (75–90%) of residue during the 24 months incubation period. In the bedding materials, simultaneous accumulation of the primary metabolite of chlorpyrifos, TCP (3,5,6-trichloro-2-pyridinol) was observed. Hydrolysis appeared to have caused the observed rapid loss of chlorpyrifos, especially in the highly alkaline bedding materials (sand-dolomite and quarry sand). © 1999 Society of Chemical Industry     

Residues of chlorpyrifos in various crops II. Residues after field treatments

Five agricultural crops were treated with OO-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate (chlorpyrifos) granular or emulsifiable concentrate formulations at dosages from 0.5 to 6.0 kg (a.i.)/ha and at different periods before harvest. Chlorpyrifos residues were determined by gas chromatography after extraction and sweep co-distillation clean-up. Low residue levels were found. The average values in lettuce were 0.046 and 0.070 part/million, in sugar beet leaves 0.037 to 0.128 part/million and roots <0.005 to 0.038 part/million; no chlorpyrifos was detected in carrots, potatoes and cured tobacco leaves at the limit of the method (0.005 part/million).     

Deposition,mobility and persistence of sprinkler-irrigation-applied chlorpyrifos on corn foliage and in soil

The insecticide chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) was applied to sweet corn (Zea mays L.) by chemigation, injecting either an emulsifiable formulation or technical chlorpyrifos dissolved in soybean oil into 0·25 cm or 1·27 cm sprinkler-applied irrigation water. Half of the plots treated with chlorpyrifos in 0·25 cm water were immediately irrigated further with 1·27 cm water without chlorpyrifos. Half the plots treated with chlorpyrifos in 1·27 cm water were irrigated with another 1·27 cm water without chlorpyrifos 10 days later. Neither the volume of water used to apply the insecticide nor subsequent irrigation affected chlorpyrifos residues on the corn foliage or in the soil. Chemigation of the soybean oil solution resulted in three times more chlorpyrifos on the foliage than chemigation of the emulsion formulation, apparently because of greater adhesion of the oil droplets to the foliar surface. Chlorpyrifos residues in foliage declined with an initial half-life of one day. Chlorpyrifos on or near the soil surface declined with an initial half-life of approximately four days.     

Fate of few pesticide-metabolizing enzymes in the marine cyanobacterium Phormidium valderianum BDU 20041 in perspective with chlorpyrifos exposure

The marine cyanobacterium Phormidium valderianum BDU 20041 is able to dwell and grow in the presence of chlorpyrifos (O,O-diethyl-O-[3,5,6-trichloro-2-pyridyl] phosphorothioate), a phosphorothioate insecticide, at a concentration of 45 ppm. Chlorpyrifos exposure resulted in stunted growth of P. valderianum, and a 48-h exposure revealed increase in activity of pesticide-metabolizing enzymes, such as polyphenol oxidase, catalase, superoxide dismutase, esterase, and glutathione S-transferase. Among the three classes of esterases P. valderianum BDU 20041 was found to use esterases A in the metabolization of chlorpyrifos. Increased activity of catalase and superoxide dismutase clearly depicted the provoked state of oxidative stress, concurrently this circuitously proving the triggered mode of reactive oxygen species mediated degradation of chlorpyrifos.     

Chlorpyrifos degradation in soil at termiticidal application rates

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is an organophosphorus insecticide applied to soil to control pests both in agricultural and in urban developments. Typical agricultural soil applications (0.56 to 5.6 kg ha^?1) result in initial soil surface residues of 0.3 to 32 μg g^?1. In contrast, termiticidal soil barrier treatments, a common urban use pattern, often result in initial soil residues of 1000 μg g^?1 or greater. The purpose of the present investigation was to understand better the degradation of chlorpyrifos in soil at termiticidal application rates and factors affecting its behaviour. Therefore, studies with [¹⁴C]chlorpyrifos were conducted under a variety of conditions in the laboratory. Initially, the degradation of chlorpyrifos at 1000 μg g^?1 initial concentration was examined in five different soils from termite-infested regions (Arizona, Florida, Hawaii, Texas) under standard conditions (25°C, field moisture capacity, darkness). Degradation half-lives in these soils ranged from 175 to 1576 days. The major metabolite formed in chlorpyrifos-treated soils was 3,5,6-trichloro-2-pyrid-inol, which represented up to 61% of applied radiocarbon after 13 months of incubation. Minor quantities of [¹⁴C]carbon dioxide (< 5%) and soil-bound residues (? 12%) were also present at that time. Subsequently, a factorial experiment examining chlorpyrifos degradation as affected by initial concentration (10, 100, 1000 μg g^?1), soil moisture (field moisture capacity, 1.5 MPa, air dry), and temperature 15, 25, 35°C) was conducted in the two soils which had displayed the most (Texas) and least (Florida) rapid rates of degradation. Chlorpyrifos degradation was significantly retarded at the 1000 μg g^?1 rate as compared to the 10 μg g^?1 rate. Temperature also had a dramatic effect on degradation rate, which approximately doubled with each 10°C increase in temperature. Results suggest that the extended (3–24 + years) termiticidal efficacy of chlorpyrifos observed in the field may be due both to the high initial concentrations employed (termite LC ₅₀ = 0.2– 2 μg g^?1) and the extended persistence which results from employment of these rates. The study also highlights the importance of investigating the behaviour of a pesticide under the diversity of agricultural and urban use scenarios in which it is employed.     

Single and simultaneous exposure of acetylcholinesterase to diazinon, chlorpyrifos and their photodegradation products

In vitro inhibition of electric eel acetylcholinesterase (AChE) by single and simultaneous exposure to organophosphorus insecticides diazinon and chlorpyrifos, and their transformation products, formed due to photoinduced degradation, was investigated. Increasing concentrations of diazinon, chlorpyrifos and their oxidation products, diazoxon and chlorpyrifos-oxon, inhibited AChE in a concentration-dependent manner. IC₅₀ (20 min) values, obtained from the inhibition curves, were (in mol/l): (5.1 ± 0.3) × 10⁻⁸, (4.3 ± 0.2) × 10⁻⁶ and (3.0 ± 0.1) × 10⁻⁸ for diazoxon, chlorpyrifos and chlorpyrifos-oxon, respectively, while maximal diazinon concentration was lower than its IC₅₀ (20 min). Calculated K_I values, in mol/l, of 7.9 × 10⁻⁷, 9.6 × 10⁻⁶ and 4.3 × 10⁻⁷ were obtained for diazoxon, chlorpyrifos and chlorpyrifos-oxon, respectively. However, 2-isopropyl-4-methyl-6-pyrimidinol (IMP) and 3,5,6-trichloro-2-pyridinol, diazinon and chlorpyrifos hydrolysis products, did not noticeably affect the enzyme activity at all investigated concentrations. Additive inhibition effect was achieved for lower concentrations of the inhibitors (diazinon/diazoxon ?1 × 10⁻⁴/1 × 10⁻⁸ mol/l i.e., chlorpyrifos/chlorpyrifos-oxon ?2 × 10⁻⁶/3 × 10⁻⁸ mol/l), while an antagonistic effect was obtained for all higher concentrations of the organophosphates. Inhibitory power of 1 × 10⁻⁴ mol/l diazinon irradiated samples can be attributed mostly to the formation of diazoxon, while the presence of non-inhibiting photodegradation product IMP did not affect diazinon and diazoxon inhibitory efficiencies.     

The degradation of residual pesticides and the quality of white clover silage are related to the types and initial concentrations of pesticides

In order to understand the degradation of different residual pesticides of white clover silage and their influence on silage quality, three commonly used orchard pesticides with different concentrations were added to the white clover and fermented for 90 days. The results showed that the degradation rate of cypermethrin and its toxic degradation product 3-phenoxybenzoic acid (3-PBA) was the highest after silage, at different concentrations, both were 100%. The degradation rate of Tebuconazole and chloropyridine was 72.47–80.27% and 47.76–64.82%, of which 3,5,6-trichloro-2-pyridinol (TCP) content, poisonous toxic degradation product, increased 0.0525–0.253 mg·kg⁻¹. The residues of beta-cypermethrin and tebuconazole had reached safety standards after silage. As compared with the control, the contents of lactic acid, acetic acid, and propionic acid increased in the treated samples. The higher concentrations of three pesticides all significantly reduced the lactic acid content of silage (p<0.05). Pesticides had different effects on the nutritional components of white clover silage. Conclusively, silage is a potential way to expand the utilization of covering plants in orchards.     

The aquatic fate of triclopyr in whole-pond treatments

The aquatic fate of the triethylamine salt formulation of triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) was determined in whole-pond applications in closed (no water exchange) systems in California, Missouri and Texas in two studies conducted in 1995 and 1996. These studies determined dissipation rates of triclopyr and its principal metabolites, 3,5,6-trichloropyridinol (TCP) and 3,5,6-trichloro-2-methoxypridine (TMP) in water, sediment and finfish. Ponds at each site containing a healthy biological community were treated at 2.5 mg AE litre-1 triclopyr. Water and sediment samples were collected through 12 weeks post-treatment, and non-target animals were collected through 4 weeks post-treatment. Dissipation rates for triclopyr, TCP and TMP were similar at each of the study sites, despite differences in weather, water quality, biotic community, light transmission and geographic location. Half-lives of triclopyr in water ranged from 5.9 to 7.5 days, while those of TCP and TMP ranged from 4 to 8.8 and 4 to 10 days, respectively. Levels of triclopyr and TCP declined in sediments at half-lives ranging from 2.8 to 4.6 days and 3.8 to 13.3 days, respectively. No TMP was detected in sediment. Triclopyr and TCP cleared from fish in relation to concentrations found in the water column. TMP levels in fish were generally an order of magnitude higher than levels of triclopyr and TCP, particularly in the visceral portion of the animals. No adverse effects on water quality or on the non-target biotic community were found following triclopyr applications. Results of these studies were comparable to those of triclopyr dissipation studies conducted in reservoirs, lakes and riverine systems in Georgia, Florida, Minnesota and Washington, indicating that the degradation and dissipation of triclopyr and its metabolites are similar in representative systems throughout the USA.