4-取代嘧啶基苯磺酰脲类化合物的合成与除草活性

为了探寻磺酰脲类除草剂的构效关系,以单嘧磺隆和单嘧磺酯为先导化合物,在嘧啶环上引入取代苯基,设计合成了16个新型单取代嘧啶磺酰脲衍生物,其结构均经过核磁共振氢谱、质谱和元素分析确证。盆栽试验结果表明:在1.5 kg/hm2时,大部分化合物对供试杂草具有一定的抑制活性,其中对双子叶杂草的活性高于对单子叶杂草的活性,但均不及先导化合物的活性。     

The structure-activity relationship in herbicidal monosubstituted sulfonylureas

BACKGROUND: The herbicide sulfonylurea (SU) belongs to one of the most important class of herbicides worldwide. It is well known for its ecofriendly, extreme low toxicity towards mammals and ultralow dosage application. The original inventor, G Levitt, set out structure–activity relationship (SAR) guidelines for SU structural design to attain superhigh bioactivity. A new approach to SU molecular design has been developed. RESULTS: After the analysis of scores of SU products by X‐ray diffraction methodology and after greenhouse herbicidal screening of 900 novel SU structures synthesised in the authors' laboratory, it was found that several SU structures containing a monosubstituted pyrimidine moiety retain excellent herbicidal characteristics, which has led to partial revision of the Levitt guidelines. CONCLUSIONS: Among the novel SU molecules, monosulfuron and monosulfuron‐ester have been developed into two new herbicides that have been officially approved for field application and applied in millet and wheat fields in China. A systematic structural study of the new substrate–target complex and the relative mode of action in comparison with conventional SU has been carried out. A new mode of action has been postulated. Copyright © 2011 Society of Chemical Industry     

Water and sediment dynamics of penoxsulam and molinate in paddy fields: field and lysimeter studies

BACKGROUND: In Chile, rice is cultivated under water‐seeded and continuously flooded conditions. Because herbicide dynamics in paddy fields and non‐flooded fields is different, 3 year experiments were performed to study the dissipation of molinate and penoxsulam in water and sediment. RESULTS: In field experiments, both herbicides dissipated by 45–55% from the initial applied amounts during the first 6 h after application in all crop seasons; in lysimeter experiments, dissipation amounts were approximately 10% for penoxsulam and 16% for molinate. Penoxsulam field water DT₅₀ values varied from 1.28 to 1.96 days during the three study seasons, and DT₉₀ values from 4.07 to 6.22 days. Molinate field water DT₅₀ values varied from 0.89 to 1.73 days, and DT₉₀ values from 2.82 to 5.48 days. Sediment residues were determined 2 days after herbicide application into the paddy water, and maximum concentrations were found 4–8 days after application. In sediment, DT₅₀ values varied from 20.20 to 27.66 days for penoxsulam and from 15.02 to 29.83 days for molinate. CONCLUSIONS: Results showed that penoxsulam and molinate losses under paddy conditions are dissipated rapidly from the water and then dissipate slowly from the sediment. Penoxsulam and molinate field water dissipation was facilitated by paddy water motion created by the wind. Sediment adsorption and degradation are considered to have a secondary effect on the dissipation of both herbicides in paddy fields. Copyright © 2011 Society of Chemical Industry     

Photolytic versus microbial degradation of clomazone in a flooded California rice field soil

BACKGROUND: Clomazone is a popular herbicide used on California rice fields and exhibits rapid anaerobic microbial degradation (t_1/2 = 7.9 days). To test the potential of direct and indirect photolytic degradation as a cofactor in the overall degradation rate, sacrificial time‐series microcosms were amended with water, non‐sterilized soil + water and sterilized soil + water. Clomazone was added to each microcosm, which was then exposed to natural and artificial sunlight over 35 days. Water and acetonitrile extracts were analyzed for clomazone and metabolites via LC/MS/MS. RESULTS: The calculated pseudo‐first‐order degradation rate constants (k) were k_water = 0–0.005 ± 0.003 day^?1, k_sterile = 0–0.005 ± 0.003 day^?1 and k_non?sterile = 0.010 ± 0.002–0.044 ± 0.007 day^?1, depending on light type. The formation of ring‐open clomazone, a microbial metabolite, correlated with clomazone degradation. Trace amounts of 5‐hydroxyclomazone (m/z = 256 → 125), aromatic hydroxyclomazone (m/z = 256 → 141) and an unknown product (m/z = 268 → 125) were observed. CONCLUSIONS: The photolytic degradation rate depends on both light type and the quality of the chromophores that induce indirect photolysis. Microbial degradation was found to be sensitive to temperature fluctuations. Overall, microbes are shown to be more detrimental to the environmental fate of clomazone than photolysis. Copyright © 2012 Society of Chemical Industry     

化学除草对麦田杂草群落结构的影响

１９９３－１９９７和磺酰脲类除草剂进行麦田化学除草试验。结果表明,所使用的除草剂均能有效地防治阔叶杂草,如播娘蒿,荠莱,糖芥等,除草效果大于９０％。麦杂草种类的演变为今后进行麦田化学除草提出新的课题。     

作物保护剂对磺酰脲类除草剂解毒效应述评

结合国内外学者以及作者自己对作物保护剂和磺酰脲类除草剂的研究,概述了保护剂对磺酰脲类除草剂的解毒作用。不同环境条件对保护剂的解毒作用有一定的影响,并从理论上证明保护剂通过抑制核苷二磷酸（RDP）,并间接抑制乙酰乳酸合成酶（ALS）的活性,从而对磺酰脲类除草剂进行解毒效应．     

Applicability of ELISA for determination of metsulfuron‐methyl in soil samples

An immunoassay (ELISA) for analysis of metsulfuron‐methyl was evaluated as a method for quantifying residues in soil. Soil samples were extracted with phosphate buffered saline (PBS), PBS + acetone (80 + 20 by volume) or ammonium carbonate and were analyzed with both ELISA and LC‐MS. A tendency for the ELISA to overstimate the metsulfuron‐methyl content was noted and matrix effects were pronounced, particularly in PBS + acetone or ammonium carbonate extracts. Dilution of extracts before analysis improved the situation but reduced the sensitivity of the assay. Using light standard concentrations it was shown that the extracts in PBS on dilutions exhibited a curve parallel with the standard curve, indicating no significant interference due to matrix effects. A working range of 10–250 ng litre⁻¹ was found for ELISA on this type of extracts. © 2000 Society of Chemical Industry     

Phytotoxic sites of action for molecular design of modern herbicides (Part 1): The photosynthetic electron transport system

A bird's eye review was tried to select the bio‐rational targets from known and novel plant‐specific ones for the molecular design of modern herbicides, which exhibit efficient phytotoxicity at a low‐use rate and preserve a good environment in the 21st century. In phytotoxic sites in the photosynthetic electron transport (PET) system discussed in the present article (Part 1), the generally called bleaching herbicides interfering with the biosynthesis of photosynthetic pigments, chlorophylls and carotenoids, and the biosynthesis of plastoquinone, were considered to be good models for the molecular design of modern herbicides. The PET itself was still considered as an interesting target site for new herbicides, although they need to exert their action in all green leaves of weeds to achieve herbicidal efficacy. Because these herbicides never form a tight binding with D1‐protein, their use‐rate cannot be expected to be as low as the herbicides inhibiting chlorophyll or branched amino‐acid biosynthesis. Other herbicidal targets found in chloroplasts, namely ATP and NADPH formations, have already been omitted from the worldwide biorational molecular design program of herbicides targeting the PET system.     

Release of atrazine and alachlor from clay-oxamide controlled-release formulations

Controlled-release herbicide formulations have been shown to decrease the leaching potential of several herbicides under laboratory and field conditions. The utility and efficacy of these formulations may be improved by combining several herbicides and a fertilizer source in a single formulation. The objective of these studies was to develop granular alginate formulations that were composed of a combination of the herbicides atrazine and alachlor with the slow-release nitrogen source oxamide (ethanediamide). Controlled release of the herbicides was obtained by addition of selected minerals, including calcium bentonite, fine-grind bentonite, montmorillonite K10, kaolinite and iron (III) oxide. A formulation without clay was used as a comparison. The formulations tested had herbicide active ingredient contents ranging from ∽0·02 to 0·54% and a nitrogen content of 21%. Release of the herbicides was studied by equilibrating the formulations with deionized water on a rotary shaker at 200 rev min^-1 and sampling at regular time intervals up to 104 hours. The minerals used in the different formulations influenced the herbicide active ingredient composition, as well as the release properties of the individual formulations. The atrazine content of the formulations decreased in the order calcium bentonite>fine-grind bentonite>kaolinite>montmorillonite=iron oxide>no clay. For alachlor the content decreased in the order of calcium bentonite>fine-grind bentonite>montmorillonite>iron oxide>kaolinite>no clay. Controlled release of atrazine (i.e. reduction in release rate) varied in the order calcium bentonite>iron oxide>montmorillonite>fine-grind bentonite= kaolinite>no clay, and for alachlor fine-grind bentonite>calcium bentonite>montmorillonite>no clay=kaolinite=iron oxide. A certain percentage of the applied active ingredient of both alachlor and atrazine was not recovered. From 5 to 27% of the active ingredient was not released, with the greatest retention by the bentonite formulations. Release of nitrogen was not strongly influenced by mineral type, although a trend indicated greater release with formulations containing kaolinite. © 1998 SCI     

Communication to the Editor Degradation of Bromoxynil,Ioxynil, Dichlobenil and their Mixtures by Agrobacterium radiobacter 8/4

Degradation of three benzonitrile herbicides, bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), ioxynil (3,5-diiodo-4-hydroxybenzonitrile), dichlobenil (2,6-dichlorobenzonitrile), and their mixtures by the soil micro-organism Agrobacterium radiobacter 8/4 was studied in batch cultures. Bromoxynil was found to be most rapidly degraded, while dichlobenil had the lowest toxicity to our strain. All transformations of studied benzonitriles were performed by the nitrile hydratase which has been shown to act on a broad range of substituted aromatic nitriles. © 1997 SCI.