WO2015135413A1 - 一种肟醚乙酸酯类化合物及其制备方法与除草应用 - Google Patents
一种肟醚乙酸酯类化合物及其制备方法与除草应用 Download PDFInfo
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- WO2015135413A1 WO2015135413A1 PCT/CN2015/072976 CN2015072976W WO2015135413A1 WO 2015135413 A1 WO2015135413 A1 WO 2015135413A1 CN 2015072976 W CN2015072976 W CN 2015072976W WO 2015135413 A1 WO2015135413 A1 WO 2015135413A1
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/55—Acids; Esters
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Definitions
- the present invention relates to an oxime ether acetate compound, and more particularly to a phenyl ether acetate-containing oxime ether acetate compound, a preparation method thereof, and an application as an active ingredient in controlling crop weeds.
- the methoxy acrylate fungicide has been well developed and widely used as a high-efficiency, broad-spectrum and low-toxic fungicide.
- the oxime ether acetate compound is a very important one among the methoxy acrylate compounds. Types of. So far, the literature on the herbicidal activity of oxime ether acetates has rarely been reported.
- the object of the present invention is to provide a phenylpyridine group-containing oxime ether acetate compound which can effectively control harmful weeds at a small dose, and a preparation method thereof and application in crop weed control.
- X is O, S, COO or NH
- R and n represent the number of substituents and substituents on the pyridine ring, respectively, wherein 0 ⁇ n ⁇ 4, preferably 0 ⁇ n ⁇ 3, and n
- n 0
- R' and n' represent the number of substituents on the benzene ring and the number of substituents, respectively, wherein 0 ⁇ N' ⁇ 4, preferably 0 ⁇ n' ⁇ 3, and n' is a natural number.
- the substituents R' are each independently selected from CH 3 , OCH 3 , Br, Cl, F, CN, CF 3 , NO 2 or OH, and each substituent R' on the benzene ring is the same or different, as opposed to A phenyl ring, a substituted pyridyl group is ortho, meta or para to the X substituent on the phenyl ring, and the substituted phenyl group is ortho, meta or para to N on the pyridine ring relative to the pyridine ring.
- the substituted pyridyl group is located in the ortho, meta and para positions of the X substituent on the benzene ring, respectively, and the substituted phenyl group is located relative to the pyridine ring.
- the substituted pyridyl group is located adjacent to the X substituent in the ortho, meta and para positions of the phenyl ring, and the substituted phenyl group is located in the pyridine ring with respect to the pyridine ring.
- the substituted pyridyl group is located in the ortho, meta and para positions of the X substituent on the benzene ring, respectively, and the substituted phenyl group is located in the pyridine ring with respect to the pyridine ring.
- the alignment of the N is located in the ortho, meta and para positions of the X substituent on the benzene ring, respectively, and the substituted phenyl group is located in the pyridine ring with respect to the pyridine ring.
- the phenyl ether group-containing oxime ether acetate compound of the present invention is preferably a series of compounds wherein X is O in the formula (I).
- X is O
- the substituent R on the pyridine ring is selected from Br, Cl, F, CN, CF 3 or NO 2 when 0 ⁇ n ⁇ 4.
- the substituent R on the pyridine ring is the same
- the substituent R′ on the benzene ring is selected from Br, Cl, F, CN, CF 3 or NO 2 , when 0 ⁇ n′ ⁇ 4, the Each substituent R' on the phenyl ring is the same, and, with respect to the pyridine ring, the substituted phenyl group is located at the ortho, meta or para position of N on the pyridine ring, and the substituted pyridyl group is substituted on the benzene ring with respect to the benzene ring.
- the base of the base is O
- the substituent R on the pyridine ring is selected from Br, Cl, F, CN, CF 3 or NO 2 when 0 ⁇ n ⁇ 4.
- a still further preferred compound of the present invention is: in the formula (I), X is O, and at the same time, the substituent R on the pyridine ring is selected from Br, Cl, F, CN, CF 3 or NO 2 when 0 ⁇ n ⁇ 4.
- the substituent R' on the benzene ring is selected from Br, Cl, F, CN, CF 3 or NO 2 , when 0 ⁇ n' ⁇ 4,
- Each substituent R' is the same on the benzene ring, and the substituted phenyl group is ortho to N on the pyridine ring with respect to the pyridine ring, and the substituted pyridyl group is located at the meta position of the X substituent on the benzene ring with respect to the benzene ring.
- the pyridine ring and benzene ring are numbered as follows: on the pyridine ring, N is the 1 position, numbered in the order of the position of the substituted phenyl group; on the benzene ring, substituted pyridyl The position is 1 and is numbered in the order of the smallest number of X positions.
- the present invention also provides a method for preparing the phenyl ether group-containing oxime ether acetate compound, and the preparation method is carried out as follows:
- the reaction liquid A is obtained, and the reaction liquid A is post-treated to obtain a compound of the formula (II);
- the basic substance A is selected from the group consisting of carbonic acid Potassium, potassium phosphate, potassium hydroxide, potassium t-butoxide or cesium fluoride;
- the palladium catalyst is selected from the group consisting of palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, triphenylphosphine acetate palladium or [1 , 1'-bis(diphenylphosphino)ferrocene]palladium dichloride;
- the solvent A is selected from the group consisting of isopropanol, ethylene glycol, glycerol, ethanol, water, tetrahydrofuran, dioxane, One of toluene, xylene, PEG2000 or a mixed solvent of any two or more of them in any ratio;
- Liquid B is post-treated to obtain a compound of formula (I); said basic substance B is selected from the group consisting of sodium hydride, sodium methoxide, t-butyl lithium, sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate;
- the phase transfer catalyst is selected from the group consisting of n-butyl ammonium bromide or 18-crown ether-6;
- the solvent B is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetonitrile.
- the ratio of the compound of the formula (IV) to the compound of the formula (V), the basic substance A, and the palladium catalyst is recommended to be 1:1. 2:2 to 3: 0.01 to 0.2; the volume of the solvent A is preferably from 20 to 70 mL/g based on the mass of the compound represented by the formula (IV).
- reaction solution A is post-treated by the method of: after the reaction is completed, the solvent is evaporated under reduced pressure, and the residue is added with water, and then extracted with ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated and dried.
- a compound represented by the formula (II) is obtained.
- the ratio of the compound represented by the formula (II) to the compound of the formula (III), the basic substance B, and the phase transfer catalyst is recommended to be 1:1. ⁇ 2:1 to 3: 0.01 to 0.2; the volume of the solvent B is preferably from 20 to 30 mL/g based on the mass of the compound represented by the formula (II).
- the reaction liquid B is post-treated by the following steps: after the reaction is completed, water is added to the reaction liquid B, ethyl acetate is extracted, and the combined ethyl acetate layer is back-extracted with saturated brine, the aqueous phase is discarded, and the organic phase is dried. Filtration and de-solubilization, the obtained concentrate is subjected to silica gel column chromatography, and the eluent containing the target compound is collected by using a petroleum ether/acetone mixed solvent having a volume ratio of 1 to 30:1 as an eluent, and concentrated and dried to obtain a compound of the formula (I).
- L represents a leaving group, which is Cl or Br
- the substituents R on the pyridine ring are each independently selected from CH 3 , OCH 3 , Br, Cl, F, CN, CF 3 , NO 2 or OH, on the pyridine ring
- Each substituent R is the same or different;
- each substituent R' on the benzene ring is the same or different; in the formula (II) or (V), X is O, S, COO or NH; in the formula (II), relative to a benzene ring, a substituted pyridyl group located at the ortho, meta or para position of the XH substituent on the phenyl ring, Pyridyl ring, a phenyl group substituted in the ortho position on the pyridine ring N, meta or para position.
- the basic substance A, the solvent A, the letter A in the reaction liquid A, and the basic substance B, the solvent B, and the letter B in the reaction liquid B have no particular meaning, and are only used to identify or distinguish between different reaction steps. Alkaline substances, solvents or reaction solutions to avoid confusion.
- the phenylpyridyl group-containing oxime ether acetate compound of the present invention can be applied to crop weeding, and the application is as follows: using the phenylpyridyl group-containing oxime ether acetate compound of the present invention as herbicide activity Ingredients for controlling broadleaf weeds and grass weeds.
- the phenylpyridyl group-containing oxime ether acetate compound of the present invention may further be formulated into a certain preparation, such as a wettable powder, a suspending agent, an emulsifiable concentrate or a water-dispersible granule, etc., using a dish method and a living body.
- phenyl ether acetate-containing oxime ether acetate compound is particularly suitable for use in crop fields such as corn and wheat, and is particularly suitable for inhibiting mustard, alfalfa, sorghum, bluegrass, and small carp in farmland.
- mustard, alfalfa, sorghum, bluegrass, and small carp in farmland The growth of weeds such as the head grass, ramie, crabgrass, anti-twig, valerian, calf, and dogtail.
- the experimental results of the herbicidal activity assay of the present invention showed that the compound 19, 27, 83, 85, 98, 99, 101, 112, 120, 133 of the sprayed stem and leaf treatment at the dose of 150 g ai/ha was compared with the clear water control. After 30 days, it has certain inhibitory activity on the growth of broadleaf weed target mustard, sorghum, ramie, amaranthus and scorpion, but these compounds have no activity on grasses such as crabgrass and dogtail. Among them, compounds 101 and 133 showed up to 100% inhibition of growth of broadleaf weed target mustard, sorghum, ramie, amaranthus and scorpion at 150 g a.i./ha.
- the preliminary screening test results of herbicidal activity of compounds 101 and 133 showed that the compound 101, 133 had the control effect against the anti-branched scorpion and the sputum as high as 97.5-100% under the conditions of 150, 75 and 37.5 g ai/ha.
- Compound 133 has 100% control effect against ramie, and has no or no activity on crabgrass, valerian and dog tail; pre-emergence soil blocking treatment dose 150g ai/ha, compound 101 and 133 are also broad-leaved weeds It has good activity and is generally active against grass weeds. After reducing the dose, the activity of 6 weed targets is significantly reduced or inactive.
- 3-Hydroxybenzeneboronic acid (86-A, 12 mmol, 1.66 g), 2-bromo-5-trifluoromethylpyridine (86-B, 10 mmol, 2.26 g), potassium carbonate (25 mmol, 3.45 g), acetic acid Palladium (0.5 mmol, 110 mg), dioxane (50 ml) and water (50 ml) were added to a 250 ml three-neck reaction flask, and the mixture was warmed to reflux for 6 hours.
- 3-Hydroxybenzeneboronic acid (87-A, 12 mmol, 1.66 g), 2-bromo-5-trifluoromethylpyridine (87-B, 10 mmol, 2.26 g), cesium fluoride (25 mmol, 3.80 g), Palladium acetate (0.2 mmol, 45 mg) and toluene (50 ml) were placed in a 250 ml three-neck reaction flask, and reacted at room temperature (25 ° C) for 6 hours.
- 3-Hydroxybenzeneboronic acid (101-A, 10 mmol, 1.38 g), 2-bromo-5-trifluoromethylpyridine (101-B, 10 mmol, 2.26 g), cesium fluoride (20 mmol, 3.04 g), Palladium acetate (0.2 mmol, 45 mg) and xylene (50 ml) were placed in a 250 ml three-neck reaction flask, and reacted at room temperature (25 ° C) for 6 hours.
- Example 8 60% wettable powder
- Component content Compound 48 60% Sodium dodecyl benzene sulfonate 1% Sodium lignosulfonate 6% Diffusion agent NNO 5% diatomite 28%
- Example 9 35% emulsifiable concentrate
- Component content Compound 48 35% Cyclohexanone 20% Emulsifier OP-10 (Emulsifier A) 7% Sodium dodecylbenzene sulfonate (emulsifier B) 5% Solvent oil 33%
- Compound 48 was dissolved in cyclohexanone and mineral spirits, and then emulsifier A and emulsifier B were added and mixed uniformly to obtain a transparent homogeneous solution, that is, an emulsifiable concentrate containing 35% of the active ingredient (Compound 48).
- Example 10 50% water dispersible granules
- Component content Compound 48 50% Sorbitan sulfate 1% Polyvinylpyrrolidone 3% Sodium lignosulfonate 10% diatomite 36%
- An analytical balance (0.0001 g) was used to weigh a certain amount of the original drug (selected from the compound in Table 1), and dissolved in DMF containing 1 wt% Tween-80 emulsifier to prepare a mother liquor having a mass concentration of 1.0 to 5.0%. Then, after dilution with distilled water, the formulation of the desired concentration was prepared according to the group distribution ratio of Examples 8, 9, and 10.
- Petri dish method pre-screening: The target is radish, cucumber, rape, wheat, sorghum and valerian, in which wheat, sorghum and radish seeds are pre-germinated, and uniform white seeds are taken for testing, and the above targets are placed.
- the inner diameter of the double-layer filter paper is 9cm culture dish, and 9mL of each new compound solution with the concentration of 100mg/L is added; after dip-coating, the number is marked separately, and it is placed in the artificial climate chamber to set the temperature at 28°C; the illumination is 3000Lux, and the illumination time is 16h. /8h dark, RH 75%, after 7 days, the growth inhibition rate (%) of roots and stems of each target was visually investigated.
- Potted method (dish high activity compound): the target is for mustard, small scorpion, ramie, sorghum, scorpion, horse stalk, dog tail, take the inner diameter 7.5cm flower pot, and install compound soil (garden soil: seedling The substrate, 1:2, v/v) to 3/4, directly sown the above six weed targets (bud rate ⁇ 85%), cover soil 0.2cm, wait until the weeds grow to around 3 leaves, reserve, pre-emergence soil Closed treatment is used for spray treatment after planting weeds. Each compound was applied at a dose of 150, 75, 37.5 g ai/ha in an automatic spray tower (model: 3WPSH-700E), and the weed leaf foliar solution was dried and transferred to a greenhouse for cultivation. After 30 days, the weeds were visually investigated. Comprehensive inhibition rate (%).
- compounds 101 and 133 showed up to 100% inhibition of the growth of broadleaf weed target mustard, sorghum, ramie, amaranthus and scorpion at 150g ai/ha, therefore, continue to the two compounds Further herbicidal activity screening is carried out.
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Abstract
本发明公开了一种式(I)所示含苯基吡啶基团的肟醚乙酸酯类化合物,其制备方法为:(1)将式(IV)所示化合物、式(V)所示化合物、碱性物质A、钯催化剂和溶剂A混合,于-10℃至回流温度反应0.5~20小时,反应结束后,得反应液A,后处理得式(II)所示化合物;(2)将所得式(II)所示化合物、碱性物质B、相转移催化剂和溶剂B混合,于-10℃至回流温度反应0.1~2小时,再加入式(III)所示化合物,继续于-10℃至回流温度反应0.5~20小时,反应结束后,得反应液B,后处理得式(I)所示化合物;本发明式(I)所示化合物可应用于农作物除草。
Description
本发明涉及肟醚乙酸酯类化合物,具体涉及含苯基吡啶基团的肟醚乙酸酯类化合物及其制备方法,以及作为活性成分在防治农作物杂草中的应用。
甲氧基丙烯酸酯类杀菌剂作为高效、广谱、低毒的杀菌剂已得到了很好的开发和广泛应用,肟醚乙酸酯类化合物是甲氧基丙烯酸酯类化合物中非常重要的一种类型。到目前为止,关于肟醚乙酸酯类化合物除草活性的文献鲜见报道。
(三)发明内容
本发明的目的在于提供一种在较小剂量下就可以有效控制有害杂草的含苯基吡啶基团的肟醚乙酸酯类化合物,并提供其制备方法以及在农作物除草中的应用。
为实现上述目的,本发明的技术方案如下:
一种含苯基吡啶基团的肟醚乙酸酯类化合物,如通式(I)所示:
式(I)中,X为O、S、COO或NH;R和n分别代表吡啶环上的取代基及取代基的个数,其中0≤n≤4,优选0≤n≤3,且n为自然数,当n=0时表示吡啶环上只有氢没有取代基R,当0<n≤4时,所述吡啶环上的取代基R各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的吡啶环上每个取代基R相同或不同;R'和n'分别代表苯环上的取代基及取代基的个数,其中0≤n'≤4,优选0≤n'≤3,且n'为自然数,当n'=0时表示苯环上只有氢没有取代基R',当0<n'≤4时,所述苯环上的取代基R'各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的苯环上每个取代基R'相同或不同,相对于苯环,取代吡啶基位于苯环上X取代基的邻位、间位或对位,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位。
式(I)中,吡啶环与苯环连接位置的9种情况,如式(I-1)~式(I-9)所示:
其中,式(I-1)~式(I-3)中,相对于苯环,取代吡啶基分别位于苯环上X取代基的邻、间、对位,相对于吡啶环,取代苯基位于吡啶环上N的邻位;
式(I-4)~式(I-6)中,相对于苯环,取代吡啶基分别位于苯环上X取代基的邻、间、对位,相对于吡啶环,取代苯基位于吡啶环上N的间位;
式(I-7)~式(I-9)中,相对于苯环,取代吡啶基分别位于苯环上X取代基的邻、间、对位,相对于吡啶环,取代苯基位于吡啶环上N的对位。
本发明含苯基吡啶基团的肟醚乙酸酯类化合物,优选式(I)中,X为O的一系列化合物。
本发明进一步优选的化合物为:式(I)中,X为O,同时,吡啶环上的取代基R选自Br、Cl、F、CN、CF3或NO2,当0<n≤4时,所述的吡啶环上每个取代基R相同,苯环上的取代基R'选自Br、Cl、F、CN、CF3或NO2,当0<n'≤4时,所述的苯环上每个取代基R'相同,并且,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位,相对于苯环,取代吡啶基位于苯环上X取代基的间位。
本发明更进一步优选的化合物为:式(I)中,X为O,同时,吡啶环上的取代基R选自Br、Cl、F、CN、CF3或NO2,当0<n≤4时,所述的吡啶环上每个取代基R相同,苯环上的取代基R'选自Br、Cl、F、CN、CF3或NO2,当0<n'≤4时,所述的苯环上每个取代基R'相同,并且,相对于吡啶环,取代苯基位于吡啶环上N的邻位,相对于苯环,取代吡啶基位于苯环上X取代基的间位。
表1中列出了部分具体的化合物,可以用表1来说明本发明,但并不限定本发明。
表1合成化合物详表
注:表1中,吡啶环和苯环的编号规则如下:吡啶环上,以N为1号位,按照使取代苯基的位置具有最小数的顺序进行编号;苯环上,以取代吡啶基所在的位置为1号位,按照使X的位置具有最小数的顺序进行编号。
本发明还提供了一种制备所述含苯基吡啶基团的肟醚乙酸酯类化合物的方法,所述的制备方法按如下步骤进行:
(1)式(II)所示的化合物的制备(如反应式2所示):将式(IV)所示化合物、式(V)所示化合物、碱性物质A、钯催化剂和溶剂A混合,于-10℃至回流温度反应0.5~20小时,反应结束后,得反应液A,所述反应液A经后处理得式(II)所示化合物;所述的碱性物质A选自碳酸钾、磷酸钾、氢氧化钾、叔丁醇钾或氟化铯;所述的钯催化剂选自氯化钯、醋酸钯、四(三苯基膦)钯、三苯基膦醋酸钯或[1,1'-双(二苯基膦基)二茂铁]二氯化钯;所述的溶剂A选自异丙醇、乙二醇、丙三醇、乙醇、水、四氢呋喃、二噁烷、甲苯、二甲苯、PEG2000中的一种或者其中两种以上任意比例的混合溶剂;
(2)式(I)所示的化合物的制备(如反应式1所示):将步骤(1)中所得的式(II)所示化合物、碱性物质B、相转移催化剂和溶剂B混合,于-10℃至回流温度反应0.1~2小时,再加入式(III)所示化合物,继续-10℃至回流温度下反应0.5~20小时,反应结束后,得反应液B,所述反应液B经后处理得式(I)所示化合物;所述的碱性物质B选自氢化钠、甲醇钠、叔丁基锂、氢氧化钠、氢氧化钾、碳酸钾或碳酸钠;所述的相转移催化剂选自正丁基溴化铵或18-冠醚-6;所述的溶剂B选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、乙腈、丙酮、二氯甲烷、二甲基亚砜中的一种或者其中两种以上任意比例的混合溶剂。
本发明所述的制备方法步骤(1)中,推荐所述式(IV)所示化合物与式(V)所示化合物、碱性物质A、钯催化剂的投料物质的量比为1:1~2:2~3:0.01~0.2;推荐所述溶剂A的体积用量以式(IV)所示化合物的质量计为20~70mL/g。
所述的反应液A后处理的方法为:反应结束后,反应液A减压蒸除溶剂,残余物中加入水,再用乙酸乙酯萃取,无水硫酸镁干燥,过滤,滤液浓缩干燥即得式(II)所示的化合物。
本发明所述的制备方法步骤(2)中,推荐所述式(II)所示化合物与式(III)所示化合物、碱性物质B、相转移催化剂的投料物质的量比为1:1~2:1~3:0.01~0.2;推荐所述溶剂B的体积用量以式(II)所示化合物的质量计为20~30mL/g。
所述的反应液B后处理的方法为:反应结束后,反应液B中加入水,乙酸乙酯萃取,合并的乙酸乙酯层再用饱和食盐水反萃,弃水相,有机相经干燥、过滤、脱溶,所得浓缩物进行硅胶柱层析,以体积比为1~30:1的石油醚/丙酮混合溶剂为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥后即得式(I)所示的化合物。
反应式1
反应式2
式(III)中,L表示离去基团,为Cl或Br,化合物(III)可以采用现有已知方法制备(参见DE10017724,CN1793115A,CN101941921A,CN100357263C);式(II)、(IV)或(V)中,R和n分别代表吡啶环上的取代基及取代基的个数,其中0≤n≤4,且n为自然数,当n=0时表示吡啶环上只有H没有取代基R,当0<n≤4时,所述吡啶环上的取代基R各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的吡啶环上每个取代基R相同或不同;R'和n'分别代表苯环上的取代基及取代基的个数,其中0≤n'≤4,且n'为自然数,当n'=0时表示苯环上只有H没有取代基R',当0<n'≤4时,所述苯环上的取代基R'各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的苯环上每个取代基R'相同或不同;式(II)或(V)中,X为O、S、COO或NH;式(II)中,相对于苯环,取代吡啶基位于苯环上XH取代基的邻位、间位或对位,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位。
碱性物质A、溶剂A、反应液A中的字母A,以及碱性物质B、溶剂B、反应液B中的字母B,都没有特别的含意,只是用来标识或区分不同反应步骤中的碱性物质、溶剂或反应液,以避免混淆。
本发明所述的含苯基吡啶基团的肟醚乙酸酯类化合物可以应用于农作物除草,所述的应用为:将本发明含苯基吡啶基团的肟醚乙酸酯类化合物作为除草剂活性成分,用于防除阔叶杂草和禾本科杂草。本发明所述的含苯基吡啶基团的肟醚乙酸酯类化合物还可以进一步制成一定的制剂,如:可湿性粉剂、悬浮剂、乳油或水分散粒剂等,使用皿测法和活体盆栽法,评价这类化合物的除草活性。结果揭示所述含苯基吡啶基团的肟醚乙酸酯类化合物特别适合应用于玉米、麦类等农作物田间,尤其适合用于抑制农田里的芥菜、菵草、繁缕、早熟禾、小藜、棒头草、苘麻、马唐、反枝苋、稗草、鳢肠、狗尾等杂草的生长。
本发明除草活性测定的实验结果表明:与清水对照相比,150g a.i./ha剂量下苗后茎叶喷雾处理的化合物19、27、83、85、98、99、101、112、120、133药后30天对阔叶杂草靶标芥菜、小藜、苘麻、反枝苋和鳢肠的生长具有一定的抑制活性,但这些化合物对马唐、狗尾等禾本科靶标基本无活性。其中化合物101和133在150g a.i./ha下对阔叶杂草靶标芥菜、小藜、苘麻、反枝苋和鳢肠的生长表现出了高达100%的抑制率。
化合物101和133的除草活性初筛试验结果表明,苗后茎叶处理剂量150、75、37.5g a.i./ha条件下,化合物101、133对反枝苋、鳢肠防效高达97.5~100%,化合物133对苘麻防效均为100%,对马唐、稗草、狗尾活性一般或无活性;苗前土壤封闭处理剂量150g a.i./ha条件下,化合物101和133同样对阔叶杂草活性较好,对禾本科杂草活性一般,降低剂量后,对6种杂草靶标活性明显降低或无活性。
安全性实验表明,化合物101和133苗后茎叶喷雾处理时,对玉米、大麦较为安全。
以下为本发明的有代表性的具体实施例,但它们不应解释为对本发明范围的限制。
以下产物含量均为HPLC含量,检测条件如下:
仪器:岛津LC-10AT;色谱柱:Hypersil BDS C18,4.6mm×150mm,5μm;流动相:甲醇/水=60:40;流速:0.8ml/min;检测波长:254nm;进样量:2μL。
实施例1:表1中化合物4的制备
反应式:
3-(2-吡啶基)苯酚(4-C)的合成:
依次将3-羟基苯硼酸(4-A,20mmol,2.77g)、2-溴吡啶(4-B,10mmol,1.58g)、磷酸钾(30mmol,6.39g)、醋酸钯(0.2mmol,45mg)、异丙醇(50ml)和水(50ml)加入到250ml三口反应瓶中,升温至80℃反应6小时。待反应完成,旋蒸脱除异丙醇后加乙酸乙酯(40ml×3)萃取,干燥、过滤、脱溶、结晶,烘干得1.32g淡黄色固体,即化合物4-C,含量98.6%(HPLC),收率76.1%。
化合物(4)的合成:
将3-(2-吡啶基)苯酚(4-C,2mmol,342mg)、NaH(60wt%,2mmol,80mg)、正丁基溴化铵(0.02mmol,6.4mg)和乙腈(10ml)加入100ml三口反应瓶中,升温至64℃搅拌反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),升温至回流反应3~6小时。待反应结束,旋蒸脱除乙腈后,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,无水硫酸镁干燥2小时以上。再抽滤、脱溶,用石油醚和丙酮的混合液(V/V=10:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥得0.40g淡黄色油状液体,即为目标化合物4,含量96.5%(HPLC),收率51.7%。
1H NMR(500MHz,CDCl3)δ8.70(m,1H),7.76(td,J=7.7,1.8Hz,1H),7.71(d,J=8.0Hz,1H),7.61–7.57(m,3H),7.49–7.34(m,3H),7.26–7.23(m,2H),6.96(ddd,J=8.2,2.6,0.8Hz,1H),5.06(s,2H),4.04(s,3H);IR(KBr):νmax(cm-1)2943,1729,1586,1456,1300,1212,1069,1018,956,771,740,693;MS(ESI):m/z(%)=377.20[M+1].
实施例2:表1中化合物47的制备
反应式:
3-(2-硝基-5-吡啶基)苯酚(47-C)的合成:
依次将3-羟基苯硼酸(47-A,15mmol,2.08g)、3-溴-5-硝基吡啶(47-B,10mmol,2.03g)、磷酸钾(25mmol,5.33g)、醋酸钯(0.2mmol,45mg)、乙二醇(50ml)和水(50ml)加入到250ml三口反应瓶中,在-10℃下反应6小时。待反应完成,加乙酸乙酯(40ml×3)萃取,后用饱和食盐水(40ml×3)反萃,干燥、过滤、脱溶、结晶,烘干得1.67g淡黄色固体,即化合物47-C,含量96.5%(HPLC),收率74.6%。
化合物(47)的合成:
将3-(2-硝基-5-吡啶基)苯酚(47-C,2mmol,432mg)、NaH(60wt%,2.4mmol,96mg)、18-冠醚-6(0.1mmol,27mg)和10ml DMF(10ml)加入100ml三口反应瓶中,在-10℃下搅拌反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),继续保温反应3~6小时。待反应结束,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,合并的有机相再用饱和食盐水(30ml×3)反萃,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=15:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥得0.52g淡黄色固体,即为目标化合物47,含量99.2%(HPLC),收率61.2%。
1H NMR(500MHz,CDCl3)δ8.38–8.34(m,2H),7.59–7.54(m,2H),7.50–7.49(m,1H),7.39(d,J=1.7Hz,1H),7.33(td,J=8.1,2.4Hz,2H),7.22(s,1H),7.14–7.11(m,1H),6.89(ddd,J=8.2,2.5,0.9Hz,1H),5.01(s,2H),4.02(s,3H),3.83(s,3H);MS(ESI):m/z(%)=421.96[M+1].
实施例3:表1中化合物48的制备
反应式:
3-(2-三氟甲基-5-吡啶基)苯酚(48-C)的合成:
依次将3-羟基苯硼酸(48-A,12mmol,1.66g)、2-溴-5-三氟甲基吡啶(48-B,10mmol,2.26g)、磷酸钾(25mmol,5.33g)、醋酸钯(0.1mmol,23mg)、THF(50ml)和水(50ml)加入到250ml三口反应瓶中,升温至回流反应6小时。待反应完成,旋蒸脱除THF后加乙酸乙酯(40ml×3)萃取,干燥、过滤、脱溶、结晶,烘干得2.10g淡黄色固体,即化合物
48-C,含量98.2%(HPLC),收率86.6%。
化合物(48)的合成:
将3-(2-三氟甲基-5-吡啶基)苯酚(48-C,2mmol,478mg)、NaOH(3mmol,120mg)、18-冠醚-6(0.2mmol,53mg)和丙酮(10ml)加入100ml三口反应瓶中,升温至回流反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),降温至60℃反应3~6小时。待反应结束,旋蒸脱除乙腈后加乙酸乙酯(30ml×3)和水(30ml)进行萃取,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=18:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥后得0.58g淡黄色固体,即为目标化合物48,含量98.8%(HPLC),收率64.5%。
1H NMR(500MHz,CDCl3)δ8.91(s,1H),8.01(d,J=8.0Hz,1H),7.76(d,J=8.1Hz,1H),7.57(d,J=7.4Hz,1H),7.47(td,J=7.5,1.4Hz,1H),7.43(ddd,J=13.8,9.1,4.6Hz,2H),7.24(dd,J=7.5,1.3Hz,1H),7.19(d,J=7.6Hz,1H),7.11(s,1H),7.00(dd,J=8.3,2.1Hz,1H),5.05(s,2H),4.03(s,3H),3.84(s,3H);MS(ESI):m/z(%)=445.11[M+1].
实施例4:表1中化合物86的制备
反应式:
3-(2-三氟甲基-5-吡啶基)苯酚(86-C)的合成:
依次将3-羟基苯硼酸(86-A,12mmol,1.66g)、2-溴-5-三氟甲基吡啶(86-B,10mmol,2.26g)、碳酸钾(25mmol,3.45g)、醋酸钯(0.5mmol,110mg)、二噁烷(50ml)和水(50ml)加入到250ml三口反应瓶中,升温至回流反应6小时。待反应完成,旋蒸脱除二噁烷后加乙酸乙酯(40ml×3)萃取,干燥、过滤、脱溶、结晶,烘干得1.94g淡黄色固体,即化合物86-C,含量99.1%(HPLC),收率80.6%。
化合物(86)的合成:
将3-(2-三氟甲基-5-吡啶基)苯酚(86-C,2mmol,478mg)、K2CO3(4mmol,552mg)、18-冠醚-6(0.2mmol,53mg)和THF(10ml)加入100ml三口反应瓶中,升温至回流反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),继续回流反应3~6小时。待反应结束,旋蒸脱除THF后,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=18:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥后得0.48g淡黄色固体,即为目标化合物86,含量99.1%(HPLC),收率53.7%。
1H NMR(500MHz,CDCl3)δ7.57(s,1H),7.46(d,J=1.3Hz,1H),7.41(d,J=1.1Hz,1H),7.31(s,1H),7.26–7.24(m,1H),7.16(s,1H),7.13(s,1H),7.05(s,1H),7.00(d,J=1.9Hz,1H),6.89(dd,J=8.3,2.3Hz,1H),6.81(dd,J=8.0,2.4Hz,1H),5.03(s,2H),4.03(s,3H),3.84(s,
3H);MS(ESI):m/z(%)=445.17[M+1].
实施例5:表1中化合物87的制备
反应式:
3-(2-三氟甲基-5-吡啶基)苯酚(87-C)的合成:
依次将3-羟基苯硼酸(87-A,12mmol,1.66g)、2-溴-5-三氟甲基吡啶(87-B,10mmol,2.26g)、氟化铯(25mmol,3.80g)、醋酸钯(0.2mmol,45mg)、甲苯(50ml)加入到250ml三口反应瓶中,室温(25℃)反应6小时。待反应完成,加乙酸乙酯(40ml×3)和水(40ml)萃取,干燥、过滤、脱溶、结晶,烘干得2.09g淡黄色固体,即化合物87-C,含量97.8%(HPLC),收率85.5%。
化合物(87)的合成:
将3-(2-三氟甲基-5-吡啶基)苯酚(87-C,2mmol,478mg)、NaH(60wt%,3mmol,120mg)、18-冠醚-6(0.05mmol,13mg)和N'N-二甲基乙酰胺(10ml)加入100ml三口反应瓶中,在-10℃下搅拌反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),继续于-10℃保温反应3~6小时。待反应结束,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,合并的有机相再用饱和食盐水(30ml×3)反萃,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=18:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥后得0.64g淡黄色固体,即为目标化合物87,含量99.5%(HPLC),收率71.2%。
1H NMR(500MHz,CDCl3)δ8.92(d,J=5.2Hz,1H),7.97(s,1H),7.69–7.53(m,4H),7.48–7.39(m,3H),7.23(dd,J=7.5,1.3Hz,1H),7.07–6.99(m,1H),5.10(s,2H),4.04(s,3H),3.86(s,3H);MS(ESI):m/z(%)=445.12[M+1].
实施例6:表1中化合物101的制备
3-(2-三氟甲基-5-吡啶基)苯酚(101-C)的合成:
依次将3-羟基苯硼酸(101-A,10mmol,1.38g)、2-溴-5-三氟甲基吡啶(101-B,10mmol,2.26g)、氟化铯(20mmol,3.04g)、醋酸钯(0.2mmol,45mg)、二甲苯(50ml)加入到250ml三口反应瓶中,室温(25℃)反应6小时。待反应完成,加乙酸乙酯(40ml×3)和水(40ml)萃取,干燥、过滤、脱溶、结晶,烘干得2.09g淡黄色固体,即化合物101-C,含量97.8%(HPLC),收率85.5%。
化合物(101)的合成:
将3-(2-三氟甲基-5-吡啶基)苯酚(101-C,2mmol,478mg)、NaH(60wt%,3mmol,120mg)、18-冠醚-6(0.2mmol,53mg)和CH2Cl2(10ml)加入100ml三口反应瓶中,在-10℃下搅拌反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),继续于-10℃保温反应3~6小时。待反应结束,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,合并的有机相再用饱和食盐水(30ml×3)反萃,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=18:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥后得0.64g淡黄色固体,即为目标化合物101,含量99.5%(HPLC),收率71.2%。
1H NMR(500MHz,CDCl3)δ8.85(d,J=1.1Hz,2H),8.05(d,J=1.5Hz,2H),7.58(d,J=7.5Hz,2H),7.46(dd,J=7.6,1.4Hz,2H),7.44–7.37(m,4H),7.36(dd,J=5.1,3.9Hz,2H),7.31–7.28(m,3H),7.23(dd,J=7.5,1.2Hz,2H),7.03(ddd,J=8.2,2.6,1.0Hz,2H),5.03(s,4H),4.02(s,6H),3.84(s,6H);MS(ESI):m/z(%)=478.87[M+1].
实施例7:表1中化合物133的制备
3-(2-三氟甲基-5-吡啶基)苯酚(133-C)的合成:
依次将3-羟基苯硼酸(133-A,12mmol,1.66g)、2-溴-5-三氟甲基吡啶(133-B,10mmol,2.26g)、氟化铯(25mmol,3.80g)、醋酸钯(0.2mmol,45mg)、PEG2000(50ml)加入到250ml三口反应瓶中,室温(25℃)反应6小时。待反应完成,加乙酸乙酯(40ml×3)和水(40ml)萃取,干燥、过滤、脱溶、结晶,烘干得2.09g淡黄色固体,即化合物133-C,含量97.8%(HPLC),收率85.5%。
化合物(133)的合成:
将3-(2-三氟甲基-5-吡啶基)苯酚(133-C,2mmol,478mg)、NaH(60wt%,3mmol,120mg)、18-冠醚-6(0.2mmol,53mg)和DMSO(10ml)加入100ml三口反应瓶中,在-10℃下搅拌反应半小时,然后加入(E)-2-(2’-氯甲基苯基)-2-羰基乙酸甲酯-O-甲基酮肟(2.4mmol,580mg),继续于-10℃保温反应3~6小时。待反应结束,加乙酸乙酯(30ml×3)和水(30ml)进行萃取,合并的有机相再用饱和食盐水(30ml×3)反萃,干燥、抽滤、脱溶,用石油醚和丙酮的混合液(V/V=18:1)为流动相,进行硅胶柱层析,收集含目标化合物的洗脱液,浓缩干燥后得0.64g淡黄色固体,即为目标化合物133,含量99.5%(HPLC),收率71.2%。
1H NMR(500MHz,CDCl3)δ8.54(d,J=2.2Hz,1H),7.83(d,J=2.2Hz,1H),7.72–7.66(m,2H),7.61–7.53(m,1H),7.47–7.39(m,2H),7.24(dd,J=7.5,1.3Hz,1H),7.02–6.97(m,2H),5.03(s,2H),4.05(s,3H),3.86(s,3H);MS(ESI):m/z(%)=444.88[M+1].
实施例8~10为制剂实施例
以下各组分均以质量百分含量计,活性组分均选自表1中的化合物。
实施例8:60%可湿性粉剂
表2 60%可湿性粉剂组分表
组分 | 含量 |
化合物48 | 60% |
十二烷基苯磺酸钠 | 1% |
木质素磺酸钠 | 6% |
扩散剂NNO | 5% |
硅藻土 | 28% |
各组分均匀混合在一起,在粉碎机中粉碎,直到细度达到标准(≤44μm),得到含有效成分(化合物48)60%的可湿性粉剂。
实施例9:35%乳油
表3 35%乳油组分表
组分 | 含量 |
化合物48 | 35% |
环己酮 | 20% |
乳化剂OP-10(乳化剂A) | 7% |
十二烷基苯磺酸钠(乳化剂B) | 5% |
溶剂油 | 33% |
将化合物48溶解在环己酮和溶剂油中,然后加入乳化剂A和乳化剂B混合均匀,得到透明的均相溶液,即为含有效成分(化合物48)35%的乳油。
实施例10:50%水分散粒剂
表4 50%水分散粒剂
组分 | 含量 |
化合物48 | 50% |
失水山梨醇硫酸酯 | 1% |
聚乙烯吡咯烷酮 | 3% |
木质素磺酸钠 | 10% |
硅藻土 | 36% |
将以上各组分混合均匀后研磨,加少量水捏合、造粒、烘干,得到含有效成分(化合物48)50%的水分散粒剂。
实施例11:除草活性测定
化合物配制
用分析天平(0.0001g)称取一定质量的原药(选自表1中的化合物),用含1wt%吐温-80乳化剂的DMF溶解配制成原药质量浓度为1.0~5.0%的母液,然后用蒸馏水稀释后按实施例8、9、10的组分配比制成所需浓度的制剂。
试验方法
培养皿法(普筛):供试靶标为萝卜、黄瓜、油菜、小麦、高粱和稗草,其中小麦、高粱和萝卜种子预先进行催芽,取均匀一致的露白种子进行试验,将上述靶标放入铺双层滤纸的内径9cm培养皿,加入浓度100mg/L的各新化合物溶液9mL;浸药均匀后分别编号标记,置于人工气候箱中培养,设置温度28℃;光照3000Lux,光照时间16h光照/8h黑暗,RH 75%,7天后目测调查对各靶标的根、茎生长抑制率(%)。
盆栽法(皿测高活性化合物):供试靶标为芥菜、小藜、苘麻、反枝苋、鳢肠、马唐、狗尾,取内径7.5cm花盆,装复合土(菜园土:育苗基质,1:2,v/v)至3/4处,直接播种上述六种杂草靶标(芽率≥85%),覆土0.2cm,待杂草长至3叶期左右备用,苗前土壤封闭处理种植好杂草后即用于喷雾处理。各化合物按照150,75,37.5g a.i./ha剂量在自动喷雾塔(型号:3WPSH-700E)施药后,待杂草叶面药液晾干后移入温室培养,30天后目测调查对杂草的综合抑制率(%)。
试验结果
表8部分化合物除草活性皿测试验结果(抑制率/%,100mg/L)
除草活性皿测试验结果表明(表8),处理剂量100mg/L条件下,化合物19、27、83、85、98、99、101、112、120、133对3种或以上试验靶标的根/茎生长有较强抑制作用(≥60%),对上述10个化合物进行盆栽普筛以进一步明确其除草活性。
表9部分化合物的除草活性普筛试验结果(防效/%,150g a.i./ha)
盆栽普筛试验结果(表9)表明,与清水对照相比,150g a.i./ha剂量下的化合物19、27、83、85、98、99、101、112、120、133药后30天对阔叶杂草靶标芥菜、小藜、苘麻、反枝苋和鳢肠生长具有一定的除草活性,而对禾本科靶标马唐、狗尾的活性较差。通常情况下,经苗后茎叶喷雾处理的化合物活性优于苗前土壤处理的相应化合物活性。其中化合物101和133在150g a.i./ha下对阔叶杂草靶标芥菜、小藜、苘麻、反枝苋和鳢肠的生长表现出了高达100%的抑制率,因此,继续对这两化合物进行进一步的除草活性复筛。
表10化合物101和133除草活性复筛试验结果(防效/%)
化合物101和133的除草活性初筛试验结果表明(表10),苗后茎叶处理剂量150、75、37.5g a.i./ha条件下,化合物101、133对反枝苋、鳢肠防效高达97.5~100%,化合物133对苘麻防效高达100%,对马唐、稗草、狗尾活性一般或无活性;苗前土壤封闭处理剂量150g a.i./ha条件下,对阔叶杂草活性较好,对禾本科杂草活性一般,降低剂量后,对6种杂草靶标活性明显降低或无活性。
表11化合物101和133的作物抑制率(%)
安全性实验表明(表11),化合物101和133苗后茎叶喷雾处理时,对玉米、大麦较为安全。
Claims (10)
- 一种含苯基吡啶基团的肟醚乙酸酯类化合物,如通式(I)所示:式(I)中,X为O、S、COO或NH;R和n分别代表吡啶环上的取代基及取代基的个数,其中0≤n≤4,且n为自然数,当n=0时表示吡啶环上只有H没有取代基R,当0<n≤4时,所述吡啶环上的取代基R各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的吡啶环上每个取代基R相同或不同;R'和n'分别代表苯环上的取代基及取代基的个数,其中0≤n'≤4,且n'为自然数,当n'=0时表示苯环上只有H没有取代基R',当0<n'≤4时,所述苯环上的取代基R'各自独立选自CH3、OCH3、Br、Cl、F、CN、CF3、NO2或OH,所述的苯环上每个取代基R'相同或不同;相对于苯环,取代吡啶基位于苯环上X取代基的邻位、间位或对位,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位。
- 如权利要求1所述的含苯基吡啶基团的肟醚乙酸酯类化合物,其特征在于式(I)中,X为O。
- 如权利要求3所述的含苯基吡啶基团的肟醚乙酸酯类化合物,其特征在于,吡啶环上的取代基R选自Br、Cl、F、CN、CF3或NO2,当0<n≤4时,所述的吡啶环上每个取代基R相同;苯环上的取代基R'选自Br、Cl、F、CN、CF3或NO2,当0<n'≤4时,所述的苯环上每个取代基R'相同;并且,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位,相对于苯环,取代吡啶基位于苯环上X取代基的间位。
- 如权利要求4所述的含苯基吡啶基团的肟醚乙酸酯类化合物,其特征在于,相对于吡啶环,取代苯基位于吡啶环上N的邻位。
- 一种制备如权利要求1所述的含苯基吡啶基团的肟醚乙酸酯类化合物的方法,其特 征在于所述方法按如下步骤进行:(1)式(II)所示化合物的制备:将式(IV)所示化合物、式(V)所示化合物、碱性物质A、钯催化剂和溶剂A混合,于-10℃至回流温度反应0.5~20小时,反应结束后,得反应液A,所述反应液A经后处理得式(II)所示化合物;所述的碱性物质A选自碳酸钾、磷酸钾、氢氧化钾、叔丁醇钾或氟化铯;所述的钯催化剂选自氯化钯、醋酸钯、四(三苯基膦)钯、三苯基膦醋酸钯或[1,1'-双(二苯基膦基)二茂铁]二氯化钯;所述的溶剂A选自异丙醇、乙二醇、丙三醇、乙醇、水、四氢呋喃、二噁烷、甲苯、二甲苯、PEG2000中的一种或者其中两种以上任意比例的混合溶剂;(2)式(I)所示化合物的制备:将步骤(1)中所得的式(II)所示化合物、碱性物质B、相转移催化剂和溶剂B混合,于-10℃至回流温度反应0.1~2小时,再加入式(III)所示化合物,继续于-10℃至回流温度反应0.5~20小时,反应结束后,得反应液B,所述反应液B经后处理得式(I)所示化合物;所述的碱性物质B选自氢化钠、甲醇钠、叔丁基锂、氢氧化钠、氢氧化钾、碳酸钾或碳酸钠;所述的相转移催化剂选自正丁基溴化铵或18-冠醚-6;所述的溶剂B选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、乙腈、丙酮、二氯甲烷、二甲基亚砜中的一种或者其中两种以上任意比例的混合溶剂;式(III)中,L表示离去基团,为Cl或Br;式(II)、(IV)和或(V)中,R、n、R’、n’的定义与式(I)中R、n、R'、n'各自相同;式(II)或式(V)中,X的定义与式(I)中X相同;式(II)中,相对于苯环,取代吡啶基位于苯环上XH取代基的邻位、间位或对位,相对于吡啶环,取代苯基位于吡啶环上N的邻位、间位或对位。
- 如权利要求6所述的含苯基吡啶基团的肟醚乙酸酯类化合物的制备方法,其特征在于步骤(1)中,所述式(IV)所示化合物与式(V)所示化合物、碱性物质A、钯催化剂的投料物质的量比为1:1~2:2~3:0.01~0.2;所述溶剂A的体积用量以式(IV)所示化合物的质量计为20~70mL/g。
- 如权利要求6所述的含苯基吡啶基团的肟醚乙酸酯类化合物的制备方法,其特征在于步骤(2)中,所述式(II)所示化合物与式(III)所示化合物、碱性物质B、相转移催化剂的投料物质的量比为1:1~2:1~3:0.01~0.2;所述溶剂B的体积用量以式(II)所示化合物的质量计为20~30mL/g。
- 如权利要求1~5之一所述的含苯基吡啶基团的肟醚乙酸酯类化合物作为除草剂活性成分,在防除阔叶杂草和禾本科杂草中的应用。
- 如权利要求1~5之一所述的含苯基吡啶基团的肟醚乙酸酯类化合物在农作物除草中的应用,所述的应用为将含苯基吡啶基团的肟醚乙酸酯类化合物制成可湿性粉剂、悬浮剂、乳油或水分散粒剂,用于防除芥菜、菵草、繁缕、早熟禾、小藜、棒头草、苘麻、马唐、反枝苋、稗草、鳢肠、狗尾草。
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US5145980A (en) * | 1989-05-27 | 1992-09-08 | Basf Aktiengesellschaft | Oxime ethers, and fungicides containing same |
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US6583090B1 (en) * | 1998-03-09 | 2003-06-24 | Basf Aktiengesellschaft | Hetaryl-substituted benzyl phenyl ethers, method for the production thereof, and their use for combating harmful fungi and animal pests |
WO2002092581A1 (de) * | 2001-05-15 | 2002-11-21 | Bayer Cropscience Ag | Heterocyclylphenyl-benzylether als fungizide |
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US5145980A (en) * | 1989-05-27 | 1992-09-08 | Basf Aktiengesellschaft | Oxime ethers, and fungicides containing same |
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CN103951612A (zh) * | 2014-03-11 | 2014-07-30 | 浙江工业大学 | 一种肟醚乙酸酯类化合物及其制备方法与应用 |
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