Oxime ether acetate compound, preparation method therefor and weeding application thereof

{
  "publication_number": "US2017001961A1",
  "country": "US",
  "kind": "A1",
  "title": "Oxime ether acetate compound, preparation method therefor and weeding application thereof",
  "abstract": "The present invention discloses an oxime ether acetate compound containing a phenylpyridine moiety of formula (I), whose preparation method is as follows: (1) mixing a compound of formula (IV), a compound of formula (V), an alkaline substance A, a palladium catalyst and a solvent A; subjecting the mixture to a reaction at the temperature ranging from −10° C. to the reflux temperature for 0.5-20 hours to obtain a reaction solution A; post-treating the solution A to obtain a compound of formula (II); (2) mixing the compound of formula (II), an alkaline substance B, a phase transfer catalyst and a solvent B; subjecting the mixture to a reaction at the temperature ranging from −10° C. to the reflux temperature for 0.1-2 hours; then adding a compound of formula (III), continuing to react at the temperature ranging from −10° C. to the reflux temperature for 0.5-20 hours to obtain a reaction solution B; and post-treating the solution B to obtain the compound of formula (I). The oxime ether acetate compound containing a phenylpyridine moiety of formula (I) can be used for weeding in crops.",
  "claims": [
    "1. An oxime ether acetate compound containing a phenylpyridine moiety, having formula (I): wherein, X is O, S, COO or NH; R and n represent a substituent on the pyridine ring and the number of substituents respectively, wherein 0≦n≦4, preferably, 0≦n≦3, and n is a natural number, when n=0, it means that the pyridine ring does not contain R, when 0<n≦4, each of the substituents on the pyridine ring (i.e. R) is selected from the group consisting of CH 3, OCH 3, Br, Cl, F, CN, CF 3, NO 2 and OH, and the substituents on the pyridine ring are same or different; R′ and n′ represent a substituent on the benzene ring and the number of substituents, wherein 0≦n′≦4, preferably, 0≦n′≦3, and n′ is a natural number, when n′=0, it means that the benzene ring does not contain R′, when 0<n′≦4, each of the substituents on the pyridine ring independent from each other is selected from the group consisting of CH 3, OCH 3, Br, Cl, F, CN, CF 3, NO 2 and OH, and the substituents on the benzene ring are same or different; relative to the benzene ring, pyridinyl is positioned at ortho-, meta- or para-position of X on the benzene ring, and relative to the pyridine ring, the substituted phenyl is positioned at ortho-, meta- or para-position of N on the pyridine ring. 2. The oxime ether acetate compound according to claim 1 having one of formulae (I-1)˜(I-9), 3. The oxime ether acetate compound according to claim 1, wherein X is O. 4. The oxime ether acetate compound according to claim 3, wherein R on the pyridine ring is selected from the group consisting of Br, Cl, F, CN, CF 3 and NO 2; when 0<n≦4, the substituents on the pyridine ring are same; R′ on the benzene ring is selected from the group consisting of Br, Cl, F, CN, CF 3 and NO 2, when 0<n′≦4, the substituents on the benzene ring are same; and relative to the pyridine ring, the substituted phenyl group is positioned at ortho-, meta- or para-position of N on the pyridine ring, and relative to the benzene ring, the pyridinyl group is positioned at meta-position of X on the benzene ring. 5. The oxime ether acetate compound according to claim 3, wherein relative to the pyridine ring, the substituted phenyl group is positioned at ortho-position of N on the pyridine ring. 6. A method for preparing the oxime ether acetate compound containing a phenylpyridine moiety according to claim 1, comprising the following steps: (1) preparation of a compound of formula (II): mixing a compound of formula (IV), a compound of formula (V), an alkaline substance A, a palladium catalyst and a solvent A; subjecting the mixture to a reaction at the temperature ranging from −10° C. to the reflux temperature for 0.5-20 hours to obtain a reaction solution A; post-treating the solution A to obtain a compound of formula (II); in which the alkaline substance A is selected from the group consisting of potassium carbonate, potassium phosphate, potassium hydroxide, potassium t-butoxide and cesium fluoride; the palladium catalyst is selected from the group consisting of palladium chloride, palladium acetate, tetrakis (triphenyl phosphine) palladium, palladium triphenylphosphine acetate and [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium; the solvent A is selected from the group consisting of isopropyl alcohol, ethylene glycol, glycerol, ethanol, water, tetrahydrofuran, dioxane, toluene, xylene, PEG2000, and any combination thereof; (2) preparation of the compound of formula (I): mixing the compound of formula (II) obtained in step (1), an alkaline substance B, a phase transfer catalyst and a solvent B; subjecting the mixture to a reaction at the temperature ranging from −10° C. to the reflux temperature for 0.1-2 hours; then adding a compound of formula (III), continuing to react at the temperature ranging from −10° C. to the reflux temperature for 0.5-20 hours to obtain a reaction solution B; and post-treating the solution B to obtain the compound of formula (I); in which, the alkaline substance B is selected from the group consisting of sodium hydride, sodium methoxide, tert-butyllithium, sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate; the phase transfer catalyst is selected from the group consisting of n-butyl ammonium bromide and 18-crown-6; and the solvent B is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetonitrile, acetone, methylene chloride, dimethyl sulfoxide, and any combination thereof; in the formula (III), L represents a leaving group and is Cl or Br, in the formula (II), (IV) or (V), R, n, R′, and n′ are as defined in claim 1, in the formula (II) or (V), X is as defined in claim 1, in the formula (II), relative to the benzene ring, pyridinyl is positioned at ortho-, meta- or para-position of XH on the benzene ring, and relative to the pyridine ring, the substituted phenyl is positioned at ortho-, meta- or para-position of N on the pyridine ring. 7. The method according to claim 6, wherein in step (1), the mole ratio of the compound of formula (IV) to the compound of formula (V) ranges from 1:1 to 1:2, the mole ratio of the compound of formula (IV) to the alkaline substance A ranges from 1:2 to 1:3, the mole ratio of the compound of formula (IV) to the palladium catalyst ranges from 1:0.01 to 1:0.2; and the ration of the solvent A to the compound of formula (IV) ranges from 20 mL/g to 70 mL/g. 8. The method according to claim 6, wherein in step (2), the mole ratio of the compound of formula (II) to the compound of formula (III) ranges from 1:1 to 1:2, the mole ratio of the compound of formula (II) to the alkaline substance B ranges from 1:1 to 1:3, the mole ratio of the compound of formula (II) to the phase transfer catalyst ranges from 1:0.01 to 1:0.2; and the ratio of the solvent B to the compound of formula (II) ranges from 20 mL/g to 30 mL/g. 9. A method of using the oxime ether acetate compound containing a phenylpyridine moiety according to claim 1 for controlling and killing broadleaf weeds and grass weeds, comprising the step of applying a herbicide in which the oxime ether acetate compound is used as an active ingredient. 10. The method according to claim 9, wherein the oxime ether acetate compound containing a phenylpyridine moiety is prepared into wettable powders, suspensions, emulsifiable concentrates or water-dispersible granules, and used for controlling and killing mustard, Beckmannia syzigachne, chickweed, bluegrass, small quinoa, Polypogon grass, abutilon, crabgrass, Amaranthus retroflexus, barnyard grass, Eclipta, and dog point."
  ],
  "description_excerpt": "The present invention relates to oxime ether acetate compounds, and in particular, to oxime ether acetate compounds containing phenylpyridine moieties, preparation method therefor and use thereof as an active ingredient in controlling weeds in crops.\n\nStrobilurin fungicides, as a type of highly effective, broad-spectrum, low-toxicity fungicides, have been well developed and applied widely. Oxime ether acetate compounds are a very important type of strobilurins. But till now, the herbicidal activity of oxime ether acetate compounds has been rarely reported.\n\nAn object of the present invention is to provide oxime ether acetate compounds containing a phenylpyridine moieties that can be used to effectively control noxious weeds at a low dose, preparation method thereof and use thereof in weeding.\n\nTo achieve the above object, the present invention adopts the following technical solutions:\n\nAn oxime ether acetate compound containing a phenylpyridine moiety, having formula (I):\n\nwherein, X is O, S, COO or NH; R and n represent a substituent on the pyridine ring and the number of substituents respectively, wherein 0≦n≦4, preferably, 0≦n≦3, and n is a natural number, when n=0, it means that the pyridine ring does not contain R, when 0<n≦4, each of the substituents on the pyridine ring (i.e. R) is selected from the group consisting of CH 3, OCH 3, Br, Cl, F, CN, CF 3, NO 2 and OH, and the substituents (i.e.",
  "cpc": [
    "C07D 213/55",
    "A01N 43/40",
    "C07D 213/30",
    "C07D 213/57",
    "C07D 213/61",
    "C07D 213/64",
    "C07D 213/65",
    "C07D 213/76",
    "C07D 213/84",
    "C07D 213/85"
  ],
  "ipc": [
    "A01N 43/40",
    "C07D 213/55",
    "C07D 213/76",
    "C07D 213/30",
    "C07D 213/57",
    "C07D 213/61",
    "C07D 213/64",
    "C07D 213/65",
    "C07D 213/84",
    "C07D 213/85"
  ],
  "assignees": [
    "Zhejiang University of Technology ZJUT"
  ],
  "inventors": [
    "Xiaohua Du",
    "Dajie Mao",
    "Zhenyuan Xu"
  ],
  "filing_date": "2015-02-13",
  "publication_date": "2017-01-05",
  "priority_date": "2014-03-11",
  "application_number": "US-201515125540-A",
  "family_id": "51328995",
  "cited_by_count": 1
}