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1.
J. SABADIE 《Weed Research》1991,31(5):309-316
Alcoholysis and acid chemical hydrolysis of chlorsulfuron Alcoholysis of chlorsulfuron by methanol or ethanol only involved the urea function of the molecule. The formation of carbamate indicated that isocyanate was probably involved as an intermediate. The chemical degradation of chlorsulfuron in acidic aqueous solution involved two pathways: hydrolysis of the urea function and hydrolysis of the methoxy radical. Increasing the temperature from 25 to 55°C en-hanced the rate of the reaction and favoured hydrolysis of the urea function. Decreasing the pH from 6-0 to 2-4 strongly accelerated degradation and lowered the activation energy without affecting selectivity. Other factors, such as the presence of clays or cations of various transition metals, generally had only limited effects.  相似文献   

2.
The degradation in the liquid phase of rimsulfuron and its commercial 250 g kg−1 WG formulation (Titus®) was investigated. Photolysis reactions were carried out at 25 °C by a high-pressure mercury arc (Hg-UV) and a solar simulator (Suntest), while the hydrolysis rate was determined by keeping aqueous buffered samples in the dark. The effects of solvent and water pH on reaction kinetics were studied, and the results compared to literature data. Photoreactions of the commercial product in organic solvents were faster than pure rimsulfuron. Under simulated sunlight in water, the half-life for the photolysis reaction ranged from one to nine days at pH 5 and 9, respectively. The hydrolysis rate was as high as the photolysis rate, but decreased on increasing water pH. The main metabolite identified in neutral and alkaline conditions as well as in acetonitrile was N-[(3-ethylsulfonyl)-2-pyridinyl]-4,6-dimethoxy-2-pyridinamine, while N-(4,6-dimethoxy-2-pyrimidinyl)-N-[(3-(ethylsulfonyl)-2-pyridinyl)]urea and minor metabolites prevailed in acidic conditions. © 1999 Society of Chemical Industry  相似文献   

3.
The influence of 1 and 50 mg active ingredient (AI) kg-1 soil of 17 fungicides on transformations of urea nitrogen in soil was studied by determining the amounts of urea hydrolysed and the amounts of nitrate and nitrite produced when samples of two coarse-textured and two fine-textured soils were incubated aerobically for various times after treatment with urea. When applied at the rate of 1 mg AI kg-1 soil, anilazine, benomyl, captan, chloranil, mancozeb and thiram retarded urea hydrolysis in the two coarse-textured soils and maneb retarded urea hydrolysis in all four of the soils used. Most of the fungicides tested retarded nitrification of urea nitrogen in the two coarse-textured soils when applied at the rate of 1 mg AI kg-1 soil, but only etridiazole markedly retarded nitrification of urea nitrogen in all of the soils used when applied at this rate. When the fungicides were applied at the rate of 50 mg AI kg-1 soil, anilazine, captan, chloranil, fenaminosulf, folpet, maneb, mancozeb and thiram retarded urea hydrolysis in the four soils studied, and all fungicides tested except chloroneb, fenarimol and iprodione retarded nitrification of urea nitrogen in these soils. One-way analysis of variance and correlation analyses indicated that the inhibitory effects of the 17 fungicides tested on nitrification of urea nitrogen in soil increased with decrease in the organic-matter content and increase in the sand content of the soil. © of SCI.  相似文献   

4.
The hydrolysis of triasulfuron, metsulfuron‐methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH‐sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2–6.2) than under neutral and moderately alkaline conditions (8.2–9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo‐first‐order kinetics. There were no significant differences (P = 0.05) in the rate constants (k, day−1) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the ‘rate constant’ on pH. The hydrolysis involving attack by neutral water was at least 100‐fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O‐demethylation of metsulfuron‐methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural alkaline soils. © 2000 Society of Chemical Industry  相似文献   

5.
The inhibition of eel acetylcholinesterase by the 4-nitrophenyl esters of 2-furyl(methyl)-, methyl(2-thienyl)-, di-2-furyl-, and di-2-thienylphosphinic acid (I, II, III, and IV, respectively) was investigated at pH 6.90 in 0.067 M phosphate buffer (25.0°C) using stopped-flow instrumentation and automated data processing. Our evaluation of the dissociation constant, Kd, the unimolecular bonding rate constant, k2, and the bimolecular reaction constant, ki, are the first reported values for these constants for alkyl/heteroaryl and diheteroaryl esters of phosphinic acids. The largest ki value (19,330 M?1 sec?1) was observed for the reaction of I with the enzyme. The order for the remaining three is II > IV > III. There is no direct relationship between the hydrolysis rates of the esters and their anticholinesterase activities on eel acetylcholinesterase. Likewise, there is no direct relationship between their anticholinesterase activities and the LD50 values in rats.  相似文献   

6.
The kinetics of the hydrolysis reactions of chlorpyrifos-methyl and chlorpyrifos, in the presence of copper(II), have been measured in buffered aqueous solutions. For each reaction, a rate law of the type -d[pesticides]/dt= k2[pesticides][Cu2+] was observed. As the concentration of copper(II) increased, a corresponding increase in the rate of hydrolysis was observed until the concentration of copper(II) reached about 1.0 × 10?2M. At this point, the rate of hydrolysis became independent of the concentration of copper(II) in both reactions. Using the experimental data, a mechanism for each reaction is proposed, in which the copper(II) ion forms a six-membered ring complex with the nitrogen in the ring structure and the sulphur of the phosphorothioate moiety. The rate of hydrolysis increased with increasing pH. At higher pH values, precipitation of Cu2+ was observed and general base-hydrolysis reactions became more and more important. The differences in the rate constant observed is explained using the inductive effect theory of the alkyl group.  相似文献   

7.
Ammonium sulphate and urea, but not potassium sulphate, increased the persistence of carbaryl in a flooded laterite soil with a low native nitrogen content (0.04%), but not in an alluvial soil with a higher nitrogen content (0.11%). Thus, NH4+ but not SO42-, contributed to the increased persistence of carbaryl. Likewise, ammonium sulphate increased the persistence of carbofuran in the laterite soil, but not in the alluvial soil. Significant accumulations of 1-naphthol and 2,3-dihydro-2, 2-dimethylbenzofuran-7-ol (‘carbofuran phenol’), in soils treated with carbaryl or carbofuran, suggested hydrolysis as the major pathway of degradation. Treatment of the two soils with ammonium sulphate, urea or potassium sulphate led to a decrease in soil-bound residues and an increase in the respective hydrolysis products, compared with untreated soils. Sorption studies indicated that NH4+ and SO42- compete with carbaryl, 1-naphthol and carbofuran for sorption and exchange sites in the complex soil system. Evolution of [14C]carbon dioxide from ring-14C in carbaryl and carbofuran was negligible. Consequently, after 40 days, more than 50% of the 14C in [14C]carbaryl and [14C]carbofuran remained in the soils as hydrolysis products (1-naphthol or 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) plus soil-bound residues.  相似文献   

8.
The hydrolysis kinetics of iprodione in alkaline solutions of pH 8.3 to 12 at 25°C have been determined by ultraviolet spectrophotometry. Under these conditions, iprodione leads quantitatively and irreversibly to N-(3,5-dichloroanilinocarbonyl)-N-(isopropylaminocarbonyl)glycine. The reaction is not subject to a general basic catalysis and the rate law takes the form Kobs = KOH- [OH?1]. The activation entropy of -77 J mol?1deg?1, the value of the kinetic solvent isotope effect kOH?/kOD? of 0.79 and the value of 0.60 for the Hammett parameter σ, obtained for the hydrolysis of a series of 3-aryl-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamides are all in agreement with the rate-determining attack by the hydroxyl ion on the carbonyl in the 4-position of the hydantoin ring of the fungicide.  相似文献   

9.
腐霉利的光解及水解特性研究   总被引:1,自引:0,他引:1  
为研究腐霉利的消解特性,采用乙腈提取,弗罗里硅土柱净化,建立了油菜叶片中腐霉利残留的气相色谱-电子捕获检测器 (GC-ECD) 分析方法;并在室内模拟条件下,研究了腐霉利在油菜叶片表面的光解行为,以及不同初始浓度、不同pH值缓冲液、不同浓度Fe2+、Fe3+ 和NO3–、NO2– 对水溶液中腐霉利光解的影响;通过气相色谱-电子轰击电离源质谱仪 (GC-EIMS) 鉴定了其在甲醇、丙酮和乙腈溶液中的光解产物;同时研究了不同pH值缓冲液和阴、阳离子表面活性剂对腐霉利水解特性的影响。结果表明:腐霉利添加水平为0.05、0.2、2及12 mg/kg时,其在油菜叶片中的平均回收率为80%~100%,相对标准偏差为2.3%~7.8%。腐霉利在油菜叶片表面的消解动态符合一级动力学方程,紫外灯下的消解半衰期为1.03 h。腐霉利在水溶液中的光解速率随其初始浓度的升高而减慢;其在酸性条件下稳定,碱性条件下易光解;NO3–、NO2–、Fe2+ 及Fe3+均可抑制腐霉利在水溶液中的光解,因此可用作为其光猝灭剂。共鉴定出两种腐霉利在甲醇、丙酮和乙腈溶液中的光解产物,分别为其单脱氯化产物C13H12ClNO2和其脱甲基化产物C12H9Cl2NO2。腐霉利在碱性条件下易水解,酸性条件下水解较慢;阴离子表面活性剂十二烷基磺酸钠 (SDS) 对其水解无影响,而阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB) 则可促进其水解。研究结果可为腐霉利的合理使用及其环境安全性评价提供参考。  相似文献   

10.
Alcoholysis and chemical hydrolysis of bensulfuron-methyl   总被引:3,自引:0,他引:3  
J. SABADIE 《Weed Research》1996,36(5):441-448
Alcoholysis (methanol or ethanol) and hydrolysis (pH ≤ 8) of the herbicide bensulfuron-methyl at 30 or 50^C involve only the breakdown of the urea part of the molecule. A high yield of the pyrimidinamine is always obtained, along with the corresponding carbamate (alcoholysis) or benzylsulfonamide (hydrolysis). The latter compound was easily cyclized (pH ≥ 6). In alkaline solution, the carbomethoxy substituent of the aromatic ring was preferentially hydrolysed. In all cases, the alcoholysis and hydrolysis rates could be described well with first-order kinetics. Alcoholysis rate constants of bensulfuron-methyl and bensulfuron ranged from 0.08 to 0.15 d?1 at 30^C. Hydrolysis rate constants of bensulfuron-methyl, bensulfuron and benzylsulfonamide varied strongly with pH. The hydrolysis rate constant of bensulfuron-methyl was minimal around pH 8. The hydrolysis rate constant of bensulfuron decreased with increasing pH, whereas that of benzylsulfonamide increased with increasing pH.  相似文献   

11.
The inhibition of eel acetylcholinesterase and bovine erythrocyte acetylcholinesterase by the 4-nitrophenyl esters of methyl-, ethyl-, and isopropyl(phenyl)phosphinic acid (MPP, EPP, and IPP, respectively) was investigated at pH 6.90 in 0.067 M phosphate buffer (25.0°C) using stopped-flow instrumentation and automated data processing. Our evaluation of the dissociation constant, Kd, the unimolecular bonding rate constant, k2, and the bimolecular reaction constant, ki, are the first reported values for these constants for a homologous series of this class of organophosphorus compounds. The largest k1 value (29,428 M?1 sec?1) was observed for the reaction of eel acetylcholinesterase with 4-nitrophenyl methyl(phenyl)phosphinate. The smallest ki value (9.6 M?1 sec?1) was observed for the reaction of bovine erythrocyte acetylcholinesterase with 4-nitrophenyl isopropyl(phenyl)phosphinate.  相似文献   

12.
吡虫啉和毒死蜱对尿素氮在土壤中转化的影响   总被引:1,自引:1,他引:0  
为了考察杀虫剂施用对尿素态氮在土壤中转化过程的影响,采用室内培养法,通过测定土壤铵态氮和硝态氮质量分数以及反硝化损失的动态变化,研究了在施用尿素的土壤(有效氮含量为200 mg/kg)中分别添加不同剂量的吡虫啉和毒死蜱2种杀虫剂时,杀虫剂对尿素的水解、土壤氮的硝化及反硝化过程的影响。结果表明:吡虫啉和毒死蜱各剂量处理在第3天时对尿素水解具有显著的促进作用(PPPPP<0.01),减少反硝化损失量39.69%。  相似文献   

13.
J. SABADIE 《Weed Research》1995,35(4):295-302
Degradation of chlorimuron-ethyl The chemical degradation of chlorimuron-ethyl and chlorimuron on various dry minerals (kaolinite, silica, bentonite H+, montmorillonite K10) and on solid humic acid was investigated at 30°C. Hydrolysis of sulfonylurea function was therefore always observed, and followed the same pathway as previously described in acidic aqueous solution. The formed phenyl-sulfonamide was transformed into saccharin on only weakly acidic minerals (kaolinite, silica). A relative affinity between pyrimidamine (hydrolysis product) and strong acidic minerals (bentonite H+, montmorillonite K10) or humic materials was observed.  相似文献   

14.
The determination of rate constants and the calculation of the activation parameters [activation energy (Ea), free energy of activation(ΔG)and entropy of activation (ΔS)] demonstrated the identity of the reaction kinetics of chemical hydrolysis of the chlorinated triazine herbicides simazine, atrazine, propazine and terbuthylazine. Persistence in soil could be estimated, from the hydrolytic half-life time, only in pH regions where these compounds were also sensitive to chemical hydrolysis. In general, the rate of hydrolysis increased in the presence of soil as the result of a catalysing effect of the soil in their breakdown. When half-lives in soil of these triazine herbicides were compared with adsorption constants, a functional relationship was observed in both soil types; as adsorption increased the half-life in soil also increased.  相似文献   

15.
The degradation of the insecticide WL 41706, (±)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, (I), in two soils from Spain and one from the UK has been studied in the laboratory. Samples of (I) labelled separately with 14C in the benzyl ring (uniform labelling) and at C(1) of the cyclopropyl ring were used. The insecticide underwent degradation by hydrolysis at the cyano group to form the amide and carboxylic acid analogues. However, the major degradative route was hydrolysis at the ester linkage leading initially to the formation of 3-phenoxy-benzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid. When a sandy clay soil was treated with [benzyl?14C]-WL 41706 under balance conditions, 14CO2 was evolved at a steady rate and 16 % of the applied radiolabel was detected as 14CO2 over a 26 week period. The rate of degradation of I was most rapid on a moist sandy clay (loss of 50 % initial quantity in 4 weeks) but it was considerably slower on dry sandy clay and moist clay soils (> 16 weeks). Under flooded, anaerobic conditions the rate of hydrolysis of the insecticide was slower than under aerobic conditions and the 3-phenoxybenzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid were found to accumulate over the 24 weeks of the experiment.  相似文献   

16.
混料设计在辣椒不同类型氮肥配比试验研究中的应用   总被引:1,自引:0,他引:1  
采用田间试验,研究了混料设计中的单形重心设计在辣椒控释尿素、普通尿素配肥上的应用,测定了辣椒的产量及其构成,配置了各因子的产量回归方程,解析寻优,对肥料效应及经济效益进行了分析.结果表明,三种氮肥比例为普通尿素U=0.20~0.30,控释尿素D60(控释期60天)=0.40~0.60,控释尿素D30(控释期30天)=0.20~0.40(换算为纯氮实际用量U=150.0~225.0 kg/hm2,D60=300.0~450.0 kg/hm2,D30=150.0~300.0 kg/hm2)的方案,预测最高产量可达85.0 t/hm2.控释尿素D30-D60两者配合施用、普通尿素与控释尿素D30-D60三者配合施用均能显著提高辣椒产量,比普通尿素分别增产24.40、28.26 t/hm2,增产率分别为42.0%和49.0%,产量差异均达极显著水平.施肥效应以D30-D60混合最高,为20.88 t/hm2,达极显著水平.经济效益分析表明,U-D30-D60处理施肥利润为2.440万元/hm2,氮素利用率最高,为60.1%.普通尿素与两种控释尿素按一定比例混合施用有利于提高辣椒产量和增加农民的经济收入.  相似文献   

17.
Hydrolysis of [14C]-radiolabeled 1, 3-dichloropropene (1, 3-D) was studied at pH 5, 7 and 9 at 10, 20 and 30°C in sterile buffered water. The rate of hydrolysis was independent of pH at each temperature, with measured half-lives of 3-1 (±0.l), 11.3 (±0.5) and 51 (±2.3) days at 30, 20 and 10°C, respectively. The activation energy for the hydrolysis reaction was determined to be 23.9 kcal mol?1 deg?1. One hydrolysis product was formed during the course of the study and was identified by co-chrornatography with analytical standards, using h.p.l.c., to be 3-chloroallyl alcohol. The alcohol appeared to be stable to further hydrolytic conversion and was formed in the same cis: trans ratio as in the initial 1, 3-D starting material, indicating essentially identical rates of hydrolysis for the cis and trans isomers of 1, 3-D.  相似文献   

18.
为优化旱地小麦高效施氮管理,实现高效生产目标,通过2 a(2019—2020年度和2020—2021年度)田间试验,设不施肥(CK)、不施氮(T1)、300 kg·hm-2尿素N(T2,常规施氮处理)、300 kg·hm-2缓释尿素N(T3)、195 kg·hm-2缓释尿素N(T4)和90 kg·hm-2缓释尿素N(T5)6个处理,分析不同缓释尿素减施量对农田土壤硝态氮分布及累积、氮素吸收与转运、冬小麦产量和氮素利用效率的影响。结果表明,缓释尿素减施处理(T4和T5)显著降低收获期0~200 cm土层的土壤NO-3-N累积量,同时提高0~40 cm土层NO-3-N占比。施用缓释尿素显著提高冬小麦氮素转运量和花后氮素吸收量,T3处理较当地常规施氮处理分别提高12.9%和13.6%。氮素转运对籽粒的贡献率随缓释尿素减施比例的增加呈先增后降的变化趋势,T4处理最大,较其他施氮处理提高0.2%~50.0%。施用缓释尿素可不同程度地改善冬小麦产量构成因素和提高产量;T4处理两年产量分别为8 434、9 060 kg·hm-2,2019—2020年度较T2和T3处理分别提高19.7%和13.9%,2020—2021年度分别提高17.3%和10.4%,其经济效益2019—2020年度较T2和T3处理分别提高33.3%和34.0%,2020—2021年度分别提高26.8%和23.2%。缓释尿素减施显著降低氮素表观损失,提高了氮素利用效率和氮肥偏生产力。通过拟合分析发现,缓释尿素施用量为208.7 kg·hm-2时,两年产量分别为8 054、8 806 kg·hm-2,净效益分别为6 890、8 475 CNY·hm-2NHI分别为78.2%和78.9%,可实现西北旱区冬小麦高产高效。  相似文献   

19.
为探讨不同秸秆还田模式下,氮肥管理对夏玉米产量和氮素利用的影响,试验设置施氮措施和秸秆还田模式2个因素。施氮措施设稳定性氮肥施氮量F1(180 kg·hm-2)、尿素减量施氮量F2(180 kg·hm-2)和尿素农户传统施氮量F3(270 kg·hm-2)3个水平;秸秆还田模式设秸秆不还田(N)和秸秆还田(S)2个水平,共6个处理。结果表明:在不同秸秆还田模式下,各施氮措施的玉米产量在8 708.16~9 626.71 kg·hm-2之间,处理间无显著性差异(P>0.05)。在不同施氮措施下,秸秆还田(S)的产量均高于秸秆不还田(N),增幅为4.96%~8.94%(P>0.05)。施氮措施对土壤N2O排放量有显著影响(P<0.05),在不同秸秆还田模式下,稳定性氮肥措施F1和尿素减量措施F2的土壤N2O排放量显著低于F3尿素农户施氮措施,降幅为29.26%~68.52%,且F1和F2之间存在显著差异(P<0.05)。在不同施氮措施下,除了SF2和NF2处理之间的N2O排放量有显著性差异(1.53 kg·hm-2和1.91 kg·hm-2),其他秸秆还田模式处理之间均无显著性差异(P>0.05)。不同秸秆还田模式下,各施氮措施的氨挥发累积量在1.61~15.40 kg·hm-2之间,表现为:F3氨挥发累积量最高(14.37 kg·hm-2和15.40 kg·hm-2),F2氨挥发累积量次之(11.80 kg·hm-2和12.49 kg·hm-2),F1氨挥发累积量最低(1.61 kg·hm-2和1.79 kg·hm-2),各施氮措施间达到显著水平(P<0.05)。在不同施氮措施下,秸秆还田(S)的氨挥发累积量较秸秆不还田(N)提高5.85%~11.18%,但除了SF3和NF3的氨排放量有显著性差异,其他处理间均无显著性差异。不同秸秆还田模式下,各施氮措施0~100 cm土层硝态氮含量均表现出F3>F2>F1;秸秆还田处理(SF1、SF2和SF3)的土壤硝态氮含量显著低于无秸秆还田(NF1、NF2和NF3),分别显著降低了65.65%、144.79%和128.48%。因此,综合考虑作物产量和农田氮素损失,秸秆还田+稳定性氮肥处理(SF1)是本研究地区夏玉米稳产减排的最优试验处理组合。  相似文献   

20.
刘长春 《农药学学报》2015,17(1):97-100
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。  相似文献   

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