WO2018205048A1 - 一类土壤降解速度可控的新型绿色磺酰脲类除草剂制备方法与土壤降解的研究和应用 - Google Patents

一类土壤降解速度可控的新型绿色磺酰脲类除草剂制备方法与土壤降解的研究和应用 Download PDF

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WO2018205048A1
WO2018205048A1 PCT/CN2017/000372 CN2017000372W WO2018205048A1 WO 2018205048 A1 WO2018205048 A1 WO 2018205048A1 CN 2017000372 W CN2017000372 W CN 2017000372W WO 2018205048 A1 WO2018205048 A1 WO 2018205048A1
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sulfonylurea
group
alkyl
halogenated
compound
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PCT/CN2017/000372
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French (fr)
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李正名
周沙
周莎
王宝雷
李永红
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南开大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to a synthetic technology of agricultural chemical herbicides and a soil degradation method, in particular to the preparation of a sulfonyl urea derivative substituted with a benzene ring, soil degradation research and application thereof.
  • the object of the present invention is to provide a novel sulfonylurea herbicide which has ultra-high herbicidal activity and no residual phytotoxicity and is suitable for the unique cultivation mode of Chinese farmland.
  • the different substituents were introduced into the 5-position of the benzene ring of the sulfonylurea.
  • the preparation method of the 5-substituted derivative of the benzene ring was developed. New compounds with faster degradation rate were found, and the herbicidal activity of these new structures was maintained.
  • Z is selected from C, N;
  • R 1 is selected from the group consisting of halogen, nitro, cyano, trifluoromethyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 1 - a C 6 alkylthio group, a halogenated C 1 -C 6 alkylthio group, a C 1 -C 6 alkoxycarbonyl group, an N,N-(C 1 -C 6 alkyl)carbamoyl group;
  • R 2 is selected from the group consisting of halogen, nitro, cyano, trifluoromethyl, C 1 -C 6 alkoxycarbonyl, N,N-(C 1 -C 6 alkyl)carbamoyl, C 1 -C 6 alkane , halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkane Base, amino group, C 1 -C 6 alkylamino group, C 1 -C 6 amide group, C 1 -C 6 sulfonamide group, C 1 -C 6 imino group, C 2 -C 6 alkenyl group, halogenated C 2- C 6 alkenyl, C 2 -C 6 alkynyl, halo C 2 -C 6 alkynyl, NC 1 -C 6 alkyl-NC 1
  • Halogen is fluorine, chlorine, bromine or iodine
  • An alkyl group is a linear or branched alkyl group
  • haloalkyl group is a linear or branched alkyl group, and the hydrogen atom on these alkyl groups may be partially or completely substituted by a halogen atom; the definitions of "haloalkenyl” and “haloalkynyl” are the same as the term “haloalkyl” ;
  • alkenyl group is a straight or branched chain having 2 to 6 carbon atoms and may have a double bond at any position;
  • An alkynyl group is a straight or branched chain having 2 to 6 carbon atoms and may have a triple bond at any position.
  • the compound of the formula 11 is dissolved in acetone with ethyl chloroformate and potassium carbonate, and heated under reflux to obtain a compound of the formula 12, which is then dissolved in toluene with a substituted aromatic amine (molar ratio 1:1), and refluxed to obtain the target compound I.
  • Each group in the reaction formula is as shown above.
  • the target compound I and the sodium hydroxide were stirred and reacted in water at room temperature until the solution was pale yellow, and the title compound II was obtained by desolvation under reduced pressure.
  • the derivatives 1 to 488 prepared by using the different raw materials according to the preparation methods of Examples 1 to 2 are listed in Table 1, the partial derivative 1 H NMR (Bruker AV 400 specrometer using tetramethylsilane as the internal standard), high resolution Mass spectrometry (HRMS) and ultraviolet maximum absorption (UV) data are listed in Table 2.
  • Plate method using Brassica napus as the test object, pour 2 mL of the prepared sample solution into a petri dish (6 cm in diameter) coated with filter paper, and add 15 pieces of rapeseed seeds previously soaked in distilled water for 4 hours, then The culture dish was placed in a greenhouse (25 ⁇ 2°C) for 65 hours in the dark, and the germination of the rapeseed seeds was observed, and the corresponding embryo length was determined and compared with the blank control. The inhibition rate.
  • the measured compounds were basically in the same order of magnitude as the control drug chlorsulfuron/methanesulfuron/mesfensulfuron, and exhibited a considerable amount of rapeseed at a concentration of 0.1 ug/mL.
  • the inhibitory activity of a cyanosulfonate sodium salt having a good inhibitory activity but at the 5-position cyano group is not particularly preferable.
  • the herbicidal activity test was carried out by using the derivative provided by the present invention, and the test subjects were rapeseed, amaranth, valerian, and crabgrass, and the test methods were divided into stem and leaf treatment and soil treatment.
  • the test method is as follows:
  • Preparation of emulsified water firstly prepare an aqueous emulsion of 1 ⁇ , weigh 1g of emulsifier in a beaker, add a small amount of distilled water to dissolve it, put it into a 1000mL volumetric flask, and wash the beaker several times with distilled water, all into the volumetric flask. Finally, add to the scale with distilled water and shake well until use.
  • Preparation of mother liquor Weigh 10 mg of the test sample dissolved in 1 mL of DMF, and prepare to be 10 mg/mL of mother liquor after being fully dissolved. After calculating the dosage according to the spray area, the required volume was transferred to a 10 mL small beaker, and a corresponding volume of emulsified water was added to prepare an aqueous emulsion for use in spraying. If necessary, dilute stepwise to obtain the desired aqueous emulsion for use.
  • the inhibitory activities of the stem and leaf treatments of the compounds I82 and I463 at 1 g/mu were 100%; the soil treatment of I87 and I463 at 1 g/mu was also 100%.
  • I87 and I463 showed extremely high activity against four different monocotyledonous and dicotyledonous crops under 10 g/mu stem and leaf treatment and soil treatment conditions.
  • the soil degradation study was carried out by using the derivative provided by the invention.
  • the soil sample 1 was Jiangxi Ji'an red soil with pH value of 5.59 and organic matter content of 7.63 g/kg; soil sample 2 was Hebei Baoding lime soil with pH value of 8.46, organic matter content. It is 7.57 g/kg.
  • the test process is as follows:

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Abstract

提供一种土壤降解速度可控的磺酰脲除草剂，通过在磺酰脲苯环部分的5位导入给电子基团，以提高磺酰脲类除草剂的降解速率。

Description

一类土壤降解速度可控的新型绿色磺酰脲类除草剂制备方法与土壤降解的研究和应用 技术领域
本发明涉及农用化学除草剂的合成技术及土壤降解方法，具体涉及苯环5位取代的磺酰脲类衍生物的制备、土壤降解研究及其应用。
背景技术
20世纪70年代，美国杜邦公司的G.Levitt最早发现了磺酰脲类除草剂，1981年，第一个商品化品种氯磺隆问世，标志着除草剂发展进入了超高效时代，该类除草剂因为具有超高效、基本无毒、广谱、高选择性等特点受到广泛应用，目前，已有几十种商品化的品种。此类除草剂对许多一年生或多年生杂草有特效，广泛应用于防除稻田、大豆田、玉米田、麦类作物田、油菜田、草坪及其他非耕地杂草。
然而，随着磺酰脲类除草剂的广泛应用，一些问题也日益凸显，其中，最大的问题就是该类除草剂的残留药害如氯磺隆、甲磺隆、胺苯磺隆等药剂，在小麦田常规使用可在土壤中长期残留，对后茬作物玉米、油菜、棉花及某些豆科作物产生不同程度的药害，甚至死亡。在我国由于严重人多地少的国情，采取了世界独有的在同年同块土地上多茬作物密集轮种的制度，与外国发达国家普遍采用的同年同地仅种植一种作物(如小麦、玉米等)的种植制度完全不同。因此在国外普遍认为可以安全使用的某些磺酰脲除草剂在我国却时有发生残留药害的根本原因在于不同国情所致。2013年我国农业部已经禁止销售和使用国际上已广泛使用的三种著名磺酰脲类除草剂氯磺隆、甲磺隆和胺苯磺隆及其混配制剂，致使该类除草剂在国内受到广泛禁止。
1995年，英国布莱顿植保会议上杜邦公司首次报道了含位5-氟代吡啶环的磺酰脲除草剂DPX-KE459(氟吡嘧磺隆)在土壤中降解速率较快(S.R.Teaney，L.Armstrong，et al.Brighton Crop Protection Conference-Weeds，1995，1，49-56)。此报道对我们的分子设计有所启发，我们设想如果换成经典磺酰脲类中的苯环而在其5位导入不同取代基，将对其降解速率的影响如何？这些研究内容国内外从未见报道。
我们前期工作首次确定了在经典磺酰脲分子所含苯环中的5位取代基的变化 对在不同pH水质中的水解反应有明显影响；我们又将研究延伸到各类磺酰脲除草剂在不同土壤中的降解变化，经过在符合国家标准的酸性与碱性土壤中各降解反应的研究首次发现在磺酰脲苯环5位导入给电子基团加快了土壤降解速率，而导入吸电子基团则降低其降解速率，延长在土壤中的残留时间。
发明内容
本发明的目的在于提供一类具有超高除草活性、无残留药害的适用于中国农田独特耕种模式的新型磺酰脲类除草剂。将不同取代基团引入磺酰脲苯环部分的5位，开发了苯环5位取代衍生物的制备方法，发现了降解速率较快的新化合物，确认了这些新结构的除草活性仍能维持原磺酰脲类商品的超高效除草活性，总结了新的构效关系及土壤降解规律。
本发明提供的苯环5位取代的磺酰脲类衍生物通式见式I和II：
Figure PCTCN2017000372-appb-000001
式中
Z选自C，N；
R1选自卤素、硝基、氰基、三氟甲基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、C1-C6烷氧基羰基、N，N-(C1-C6烷基)氨基甲酰基；
R2选自卤素、硝基、氰基、三氟甲基、C1-C6烷氧基羰基、N，N-(C1-C6烷基)氨基甲酰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、氨基、C1-C6烷基氨基、C1-C6酰胺基、C1-C6磺酰胺基、C1-C6亚胺基、C2-C6烯基，卤代C2-C6烯基，C2-C6炔基，卤代C2-C6炔基，，N-C1-C6烷基-N-C1-C9烷氧基羰基，N-C1-C6烷基-N-C1-C6氟代烷氧基羰基，N-氟代烷氧基羰基，含N，O，S三元-五元杂环，C1-C6烷基取代的含N，O，S三元-五元杂环
R3、R4选自H、F、Cl、CH3、OCH3、OC2H5、OCH2CH2CH3、CF3、OCF3、 OCHF2、OCH2CF3、NHCH3、N(CH3)2、SCH3、CH＝CHCH3。
在上述衍生物的定义中，所用术语不论单独使用还是用在复合词中，代表如下取代基：
卤素为氟、氯、溴或碘；
烷基为直链或支链烷基；
卤代烷基为直链或支链烷基，在这些烷基上的氢原子可以部分或全部被卤原子取代；“卤代烯基”、“卤代炔基”的定义与术语“卤代烷基”相同；
烯基为有2-6个碳原子的直链或支链并可在任何位置上存在有双键；
炔基为有2-6个碳原子的直链或支链并可在任何位置上存在有三键。
本发明苯环5位取代的磺酰脲类化合物I按Scheme-1所示合成方法：
Figure PCTCN2017000372-appb-000002
Scheme-1苯环5位取代磺酰脲类化合物I合成路线
通式化合物11与氯甲酸乙酯、碳酸钾溶于丙酮中，加热回流得到通式化合物12，然后与取代的芳香胺(摩尔比1∶1)溶于甲苯中，回流制得目标化合物I，反应式中各基团如上所示。
苯环5-位取代的磺酰脲钠盐类化合物II按Scheme-2所示方法合成：
Figure PCTCN2017000372-appb-000003
Scheme-2苯环5位取代磺酰脲类化合物II合成路线
目标化合物I与氢氧化钠在水中室温搅拌反应至溶液呈淡黄色，减压脱溶即得到目标化合物II。
附图说明
图1部分目标化合物I的土壤降解一级动力学曲线(pH＝5.59)
图2部分目标化合物I的土壤降解一级动力学曲线(pH＝8.46)
具体实施方式
以下结合实施例来进一步说明本发明，其目的是能更好的理解本发明的内容及体现本发明的实质性特点，因此所举之例不应视为对本发明保护范围的限制。
实施例1
2-甲氧羰基-5-氰基苯磺酰胺基甲酸乙酯的合成：
Figure PCTCN2017000372-appb-000004
在100mL单口圆底烧瓶中，将2-甲氧羰基-5-氰基苯磺酰胺(2.37g，0.01mol)、碳酸钾(2.76g，0.02mol)溶到30mL丙酮中，然后加入氯甲酸乙酯(1.30g，0.012mol)，加热回流6小时，减压浓缩除去溶剂丙酮，剩余物加入乙醚与水的混合溶剂(50mL，v/v＝1∶1)溶解，分液去掉乙醚层，水层用盐酸调节pH至3左右，有固体析出，抽滤，干燥得到白色固体，直接用于下一步反应。
实施例2
1-(2-甲氧羰基-5-氰基苯基磺酰基)-3-(4-甲氧基-6-甲基-1，3，5-三嗪-2-基)脲的合成：
Figure PCTCN2017000372-appb-000005
在100mL单口圆底烧瓶中，将2-甲氧羰基-5-氰基苯磺酰胺基甲酸乙酯(2.94g，0.01mol)、4-甲基-6-甲氧基-2-氨基-1，3，5-三嗪(0.14g，0.01mol)溶到40mL甲苯中，加热回流8小时。反应完毕后冷却至室温，将反应液脱溶，残余物经柱色谱纯化得到目标化合物。
现将根据实施例1～2的制备方法而采用不同的原料制备的该类衍生物1～488，列入表1，部分衍生物1H NMR(Bruker AV400spectrometer using tetramethylsilane as the internal standard)、高分辨质谱(HRMS)、紫外最大吸收值(UV)数据列入表2。
表1 目标化合物I和II的结构
Figure PCTCN2017000372-appb-000006
Figure PCTCN2017000372-appb-000007
Figure PCTCN2017000372-appb-000008
Figure PCTCN2017000372-appb-000009
Figure PCTCN2017000372-appb-000010
Figure PCTCN2017000372-appb-000011
Figure PCTCN2017000372-appb-000012
Figure PCTCN2017000372-appb-000013
Figure PCTCN2017000372-appb-000014
Figure PCTCN2017000372-appb-000015
Figure PCTCN2017000372-appb-000016
Figure PCTCN2017000372-appb-000017
Figure PCTCN2017000372-appb-000018
Figure PCTCN2017000372-appb-000019
Figure PCTCN2017000372-appb-000020
Figure PCTCN2017000372-appb-000021
Figure PCTCN2017000372-appb-000022
Figure PCTCN2017000372-appb-000023
Figure PCTCN2017000372-appb-000024
Figure PCTCN2017000372-appb-000025
Figure PCTCN2017000372-appb-000026
Figure PCTCN2017000372-appb-000027
Figure PCTCN2017000372-appb-000028
Figure PCTCN2017000372-appb-000029
Figure PCTCN2017000372-appb-000030
Figure PCTCN2017000372-appb-000031
Figure PCTCN2017000372-appb-000032
表2 部分目标化合物I和II的核磁、高分辨质谱/元素分析及紫外数据
Figure PCTCN2017000372-appb-000033
Figure PCTCN2017000372-appb-000034
Figure PCTCN2017000372-appb-000035
Figure PCTCN2017000372-appb-000036
实施例3
平皿法：以油菜(Brassicanapus)作为测试对象，将2mL配置好的样品溶液倒入铺有滤纸的培养皿(直径6cm)中，向其中加入15粒事先在蒸馏水中浸泡4小时的油菜种子，然后将培养皿放入温室(25±2℃)中避光培养65小时，观察油菜种子的萌发情况，并测定相应的胚胎长度，与空白对照进行比较，得出相应 的抑制率。
上述平皿法所得部分化合物对油菜抑制率的结果如表3所示：
表3部分目标化合物I及II的油菜抑制率
Figure PCTCN2017000372-appb-000037
从表3所示油菜抑制结果来看，所测化合物基本与对照药氯磺隆/甲磺隆/胺苯磺隆的活性在同一数量级，而且在0.1ug/mL的浓度下对油菜展现了相当好的抑制活性但5位氰基取代的氯磺隆钠盐的抑制活性则不是特别理想。
实施例4
利用本发明提供的衍生物进行除草活性测试，测试对象为油菜、苋菜、稗草、马唐，测试方式分为茎叶处理与土壤处理。测试方法如下：
1)药液配制
乳化水的配制：首先配制含量1‰的水乳液，用烧杯称取1g乳化剂，加少量蒸馏水充分溶解后，装入1000mL的容量瓶中，并用蒸馏水多次清洗烧杯，全部倒入容量瓶中，最后用蒸馏加到刻度，充分摇匀待用。
母液配制：称取10mg供试样品溶于1mL的DMF中，待充分溶解后配制成10mg/mL的母液。按照喷雾面积计算用药量后，移取所需体积至10mL小烧杯中，加入相应体积的乳化水配制成水乳液以备喷雾使用。如果需要，逐级稀释得到所需水乳液备用。
2)盆栽法(土壤处理)
将固定量的土壤放入直径为7.0cm的塑料小杯中，同时加一定量水，以喷施法对土壤施以不同剂量的药剂，之后播种，在其上面翻盖固定厚度的土壤，于温室中培养，并以塑料布覆盖直至幼苗出土，每天施以定量清水保持植物的正常生长。待施药处理21天后测量地上部分鲜重，与未施药组进行对比计算出鲜重抑制百分率。测试材料为：油菜(Brassicanapus)、反枝苋(Amaranthusretroflexus)、稗草(Echinochloacrusgalli)以及马唐(Digitariaadscendens)。
3)盆栽法(茎叶处理)
将固定量的土壤放入直径为7.0cm的塑料小杯中，同时加一定量水，之后播种，在其上面翻盖固定厚度的土壤，于温室中培养，并以塑料布覆盖直至幼苗出土，每天施以定量清水保持植物的正常生长。幼苗出土后，以喷施法施以不同剂量的药剂，待施药处理21天后测量地上部分鲜重，与未施药组进行对比计算出鲜重抑制百分率。测试材料同盆栽法(土壤处理)。
上述盆栽试验的除草活性的测试结果如表4所示：
表4部分目标化合物I的除草活性抑制率(％)
Figure PCTCN2017000372-appb-000038
Figure PCTCN2017000372-appb-000039
结果表明，所测目标化合物中氯磺隆和甲磺隆的改造表现出与商品化的除草剂氯磺隆/甲磺隆/胺苯磺隆相当的除草活性。例如化合物I82和I463在1g/亩使用量下的茎叶处理对油菜的抑制活性均为100％；I87和I463在1g/亩使用量下土壤处理对油菜抑制活性也为100％。I87和I463在10g/亩茎叶处理和土壤处理条件下，对四类不同的单子叶和双子叶作物都表现出超高活性。
实施例5
利用本发明提供的衍生物进行土壤降解研究，供试土壤样品1为江西吉安红壤，pH值为5.59，有机质含量为7.63g/kg；土壤样品2为河北保定灰土，pH值为8.46，有机质含量为7.57g/kg。测试流程如下：
首先对空白和施药的土壤分别分析，对比各新结构的HPLC谱图，选择个性化液相分析条件，然后在特定分析条件下，建立各新结构的标准曲线，随后采用不同的浸取方法，分别测定在土壤中的添加回收率，计算实验误差，最后，测定各新结构在土壤中的降解半衰期。酸性土壤降解测试结果见表5：
表5部分目标化合物I酸性土壤降解动力学测定结果(pH＝5.59)
No. 一级动力学方程 R2 半衰期(DT50)/天
I6 Ct＝4.4083e-0.4323t 0.9938 1.60
I82 Ct＝4.7637e-0.033t 0.9852 21.32
I87 Ct＝4.20899e-0.136t 0.9945 5.11
I91 Ct＝4.5571e-0 021t 0.8006 32.39
I497 Ct＝4.1498e-0.243t 0.992 2.85
I509 Ct＝4.0341e-1.6117t 0.9955 0.43
I527 Ct＝4.284e-0.0621t 0.9978 11.16
I530 Ct＝4.466e-0.0878t 0.9975 7.89
I533 Ct＝4.392e-0.0737t 0.9973 9.40
I539 Ct＝4.0179e-0.0644t 0.9991 10.76
I542 Ct＝3.8828e-0.0474t 0.9976 14.62
I545 Ct＝4.5170e-0.0636t 0.9990 10.90
甲磺隆 Ct＝4.8674e-0.126t 0.9965 5.50
胺苯磺隆 Ct＝4.921e-0.057t 0.9944 12.24
氯磺隆 Ct＝4.2798e-0.0537t 0.9995 12.91
碱性降解结果见表6：
表6部分目标化合物I碱性土壤降解动力学测定结果(pH＝8.46)
No. 一级动力学方程 R2 半衰期(DT50)/天
I6 Ct＝4.9111e-0.1108t 0.9936 6.25
I497 Ct＝4.9253e-0.082t 0.9734 8.40
I509 Ct＝4.6814e-0.2062t 0.9918 3.36
氯磺隆 Ct＝4.1900e-0.0082t 0.9992 84.53
甲磺隆 Ct＝4.7002e-0.009t 0.9998 75.34
从表5和表6中结果可以看出出5位不同烷基等取代的氨基等结构的引入可以大大加快氯磺隆、甲磺隆等的在不同的酸碱性土壤中的降解速率。例如：5位二乙氨基引入代表化合物I6在pH＝5.59酸性土壤降解中半衰期相对原化合物氯磺隆来说，DT50加快了接近10倍。而在pH＝8.46的碱性土壤中，DT50也加快了13倍之多。而二甲氨基在氯磺隆上的引入I509无论在酸性土壤还是碱性土壤，其降解速率都加快了30倍。5位二甲氨基在甲磺隆上的引入代表化合物I497在pH＝5.59酸性土壤中，降解半衰期加快了2倍，而在pH＝8.46的碱性土壤中，降解半衰期加快了接近10倍。由此可以发现5位不同基团的引入可以不同程度地加快磺酰脲化合物的土壤降解速率，同时不同结构的化合物在同一种土壤中的土壤降解加快比例也有所差异。另外，同一化合物在pH值不同的土壤中，土壤降解加快比例也有所不同，而且在碱性土壤中降解速率相对原始商品化药品来说加快比例更大。此项研究对于解决磺酰脲类除草剂难降解，尤其在碱性土壤中残留期更长的问题 的解决提供了有效的方法。通过此项技术的研究可以创制开发符合中国国情多茬轮种模式所需要的各种新型降解可控的绿色环保除草剂。

Claims (7)

  1. 一类如下通式I和II表示的磺酰脲类衍生物：
    Figure PCTCN2017000372-appb-100001
    式中：
    Z选自C或N；
    R1选自卤素、硝基、氰基、三氟甲基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、C1-C6烷氧基羰基、卤代C3-C6环烷基或N，N-(C1-C6烷基)氨基甲酰基；
    R2R2选自卤素、硝基、氰基、三氟甲基、C1-C6烷氧基羰基、N，N-(C1-C6烷基)氨基甲酰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、氨基、C1-C6烷基氨基、C1-C6酰胺基、C1-C6磺酰胺基、C1-C6亚胺基、C2-C6烯基，卤代C2-C6烯基，C2-C6炔基，卤代C2-C6炔基，，N-C1-C6烷基-N-C1-C9烷氧基羰基，N-C1-C6烷基-N-C1-C6氟代烷氧基羰基，N-氟代烷氧基羰基，含N，O，S三元-五元杂环，C1-C6烷基取代的含N，O，S三元-五元杂环；
    R3、R4选自H、F、Cl、CH3、OCH3、OC2H5、OCH2CH2CH3、CF3、OCF3、OCHF2、OCH2CF3、NHCH3、N(CH3)2、SCH3或CH＝CHCH3。
  2. 根据权利要求1所述磺酰脲类衍生物，其特征在于：所述衍生物中的卤素为氟、氯、溴或碘；C1-C6烷基为直链或支链烷基；卤代C1-C6烷基为直链或支链烷基，卤代C1-C6烷基上的氢原子可以部分或全部被卤原子取代；“卤代C2-C6烯基”、“卤代C2-C6炔基”和“卤代C3-C6环烷基”的定义与术语“卤代C1-C6烷基”相同；C2-C6烯基为有2-6个碳原子的直链或支链并可在任何位置上存在有双键；C2-C6炔基为有2-6个碳原子的直链或支链并可在任何位置上存在有三 键。
  3. 一类如权利要求1所述磺酰脲类衍生物的制备方法，磺酰脲类化合物I的特征合成按Scheme-1所示的方法合成：
    Figure PCTCN2017000372-appb-100002
    制备步骤如下：
    通式化合物10与氯甲酸乙酯、碳酸钾溶于有机溶剂中，加热回流得到通式化合物11，然后与取代的芳香胺溶于有机溶剂中，回流制得目标化合物I，反应式中各基团如权利要求1中的定义。
    磺酰脲钠盐类化合物II的特征合成按Scheme-2所示方法合成：
    Figure PCTCN2017000372-appb-100003
    目标化合物I与氢氧化钠在水中室温搅拌反应至溶液呈淡黄色，减压脱溶即得到目标化合物II，反应式中各基团如权利要求1中的定义。
  4. 如权利要求3所述的磺酰脲类衍生物的制备方法，其特征在于所述的有机溶剂选自丙酮、氯仿、四氯化碳、苯、甲苯、甲醇、乙醇、乙酸乙酯、四氢呋喃、乙腈、1，4-二氧六环、N，N-二甲基甲酰胺或二甲基亚砜。
  5. 一类根据权利要求1所述取代磺酰脲类衍生物的应用，其特征在于：用于制备农用化学除草剂。
  6. 如权利要求5所述的的应用，其特征在于防除一年生或多年生杂草；还可以作为活性成分配以农业可以接受的助剂组成的农药组合物用于杂草的防治。
  7. 一类根据权利要求1所述取代磺酰脲类衍生物的土壤降解行为，其特征在于：在磺酰脲苯环5位引入不同的取代基团会影响化合物的土壤降解行为，但 当磺酰脲杂环胺结构发生变化时，降解速率和除草活性同样也受到影响。
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