WO2019227771A1 - 一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途 - Google Patents

一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途 Download PDF

Info

Publication number
WO2019227771A1
WO2019227771A1 PCT/CN2018/105679 CN2018105679W WO2019227771A1 WO 2019227771 A1 WO2019227771 A1 WO 2019227771A1 CN 2018105679 W CN2018105679 W CN 2018105679W WO 2019227771 A1 WO2019227771 A1 WO 2019227771A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
substituted
halo
unsubstituted
Prior art date
Application number
PCT/CN2018/105679
Other languages
English (en)
French (fr)
Inventor
连磊
征玉荣
张辽宁
刘鹏
崔琦
王法国
刘娜
Original Assignee
青岛清原化合物有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 青岛清原化合物有限公司 filed Critical 青岛清原化合物有限公司
Publication of WO2019227771A1 publication Critical patent/WO2019227771A1/zh

Links

Classifications

    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • 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
    • C07D403/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrimidine-4-carboxylic acid derivative and a herbicidal composition and use thereof.
  • pyrimidinecarboxylic acid herbicides on the market.
  • B2 and US 7,786,044 B2 disclose certain 6-amino-2-substituted-pyrimidine-4-carboxylic acids and their derivatives and their use as herbicides.
  • CN103442570A discloses an aralkyl ester of 4-aminopyridine-2-carboxylic acid and an aralkyl ester of 6-amino-pyrimidine-4-carboxylic acid, which can be used for controlling weeds.
  • the present invention provides a substituted pyrimidine-4-carboxylic acid derivative and its herbicidal composition and use.
  • the substituted pyrimidine-4-carboxylic acid derivative and the herbicidal composition thereof have excellent herbicidal activity and crop selectivity.
  • X represents O, S, unsubstituted or substituted NH
  • Y represents unsubstituted or substituted aryl and heteroaryl
  • Z represents halogen
  • R 11 independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted aryl, Heteroaryl
  • R 12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR 31 C (O) OR 32 ;
  • R 31 represents H, alkyl or alkoxy;
  • R 32 represents H, alkyl or benzyl;
  • R 14 represents an alkyl group or a halogenated alkyl group
  • R 15 represents H, alkyl, formyl, alkyl acyl, haloalkyl acyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl, or benzyloxycarbonyl;
  • R 16 represents H, alkyl;
  • R 17 represents H, alkyl, unsubstituted or phenyl substituted with 1-3 of halogen, alkyl, or alkoxy;
  • R 18 represents H, alkyl; or
  • N CR 17 R 18 represents
  • R 21 and R 24 each independently represent H or an alkyl group
  • R 22 and R 23 each independently represent H or an alkyl group; or NR 22 R 23 represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contain an oxygen atom, a sulfur atom, or another nitrogen atom;
  • R 25 represents an alkyl group
  • X represents O, S, NR 1 ;
  • Z represents Cl or Br
  • R 11 independently represents halogen, hydroxy, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino , Di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or benzene substituted by 1-3 groups in halogen, C1-C8 alkyl, C1-C8 alkoxy, nitro Base, naphthyl,
  • R 12 represents H, C1-C18 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy, or benzyloxy;
  • R 13 represents H, C1-C8 alkyl, halo C1-C8 alkyl, phenyl, benzyl or CHR 31 C (O) OR 32 ;
  • R 31 represents H, C1-C8 alkyl or C1-C8 alkoxy
  • R 32 represents H, C1-C8 alkyl or benzyl;
  • R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl
  • R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkyl acyl, halo C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl;
  • R 16 represents H, C1-C8 alkyl;
  • R 17 represents H, C1-C8 alkyl, unsubstituted or phenyl substituted by 1-3 of halogen, C1-C8 alkyl, C1-C8 alkoxy;
  • R 18 represents H, C1- C8 alkyl; or
  • N CR 17 R 18 represents
  • R 21 and R 24 each independently represent H or C1-C8 alkyl
  • R 22 and R 23 each independently represent H or C1-C8 alkyl; or NR 22 R 23 represents
  • R 25 represents C1-C8 alkyl
  • X represents O, S, NH
  • the aryl is selected from phenyl and naphthyl; the heteroaryl is selected from
  • Z represents Cl or Br
  • R 11 independently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino , Di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or benzene substituted by 1-3 of halogen, C1-C6 alkyl, C1-C6 alkoxy, nitro Base, naphthyl,
  • R 12 represents H, C1-C14 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, C1-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR 31 C (O) OR 32 ;
  • R 31 represents H, C1-C6 alkyl or C1-C6 alkoxy
  • R 32 represents H, C1-C6 alkyl or benzyl;
  • R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl
  • R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, halo C1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl;
  • R 16 represents H, C1-C6 alkyl;
  • R 17 represents H, C1-C6 alkyl, unsubstituted or phenyl substituted with 1-3 groups of halogen, C1-C6 alkyl, C1-C6 alkoxy;
  • R 18 represents H, C1- C6 alkyl; or
  • N CR 17 R 18 represents
  • R 21 and R 24 each independently represent H or C1-C6 alkyl
  • R 22 and R 23 each independently represent H or C1-C6 alkyl; or NR 22 R 23 represents
  • R 25 represents C1-C6 alkyl
  • X represents O, S, NH
  • the aryl is selected from phenyl and naphthyl; the heteroaryl is selected from
  • Z represents Cl or Br
  • R 11 independently represents halogen, hydroxy, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkylthio, halo C1-C4 alkylthio, amino, C1-C4 alkylamino , Di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl, unsubstituted or benzene substituted by 1-3 groups of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro Base, naphthyl,
  • R 12 represents H, C1-C8 alkyl, halo C1-C4 alkyl, C1-C4 alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 represents H, C1-C4 alkyl, halo C1-C4 alkyl, phenyl, benzyl or CHR 31 C (O) OR 32 ;
  • R 31 represents H, C1-C4 alkyl or C1-C4 alkoxy
  • R 32 represents H, C1-C4 alkyl or benzyl;
  • R 14 represents C1-C4 alkyl, halogenated C1-C4 alkyl
  • R 15 represents H, C1-C4 alkyl, formyl, C1-C4 alkylacyl, halo C1-C4 alkylacyl, C1-C4 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl;
  • R 16 represents H, C1-C4 alkyl;
  • R 17 represents H, C1-C4 alkyl, unsubstituted or phenyl substituted with 1-3 of halogen, C1-C4 alkyl, C1-C4 alkoxy;
  • R 18 represents H, C1- C4 alkyl; or
  • N CR 17 R 18 represents
  • R 21 and R 24 each independently represent H or C1-C4 alkyl
  • R 22 and R 23 each independently represent H or C1-C4 alkyl; or NR 22 R 23
  • R 25 represents C1-C4 alkyl
  • X represents O
  • the aryl is selected from phenyl; the heteroaryl is selected from
  • Q represents NH 2 , NHMe, N (Me) 2 ,
  • the present invention includes a herbicidal composition
  • a herbicidal composition comprising a herbicidally effective amount of a compound of formula I mixed with an agriculturally acceptable excipient or carrier.
  • the present invention also includes using the compounds and compositions of the present invention by applying a herbicidal amount of the compound to the vegetation or to the location of the vegetation, and to the soil or to the irrigation water or floodwater before or after the emergence of the vegetation. Methods to kill or control unwanted vegetation.
  • the present invention also includes a method for controlling undesired vegetation after selective seedling in the presence of rice, wheat or forage, which comprises applying a herbicidally effective amount of a compound of the present invention or a herbicidal composition thereof to said undesired vegetation.
  • the invention also includes a method for preparing a compound of the invention.
  • the invention also relates to a method for preparing the compound of formula I, which is selected from any one of the following:
  • Hal represents halogen, preferably Cl or Br; the reaction is performed in the presence of a solvent and a base selected from one of K 2 CO 3 , Na 2 CO 3 and Cs 2 CO 3 Or two or more.
  • the solvents are all acetonitrile, DMF, dichloromethane or 1,2-dichloroethane; the reaction temperatures are all in the range of 0-40 ° C, preferably 20-30 ° C.
  • the reaction is performed in the presence of a halide and a solvent, and the halide is selected according to the type of the substituent Z in Formula I, including but not limited to NCS, NBS, Cl 2 , Br 2 or NaClO / HCl, etc .;
  • the solvent is selected from a mixture of one or more of DMF, DMSO, DCM, THF, MeCN and DCE; the reaction temperature is in the range of 0-80 ° C.
  • the A represents halogen (such as bromine, iodine, chlorine, etc.), methanesulfonyl, etc .; the reaction is performed in the presence of QH and a solvent; the solvent is selected from the group consisting of DMF, DMSO, DCM, THF, MeCN, and DCE. One or more mixtures; the reaction temperature is in the range of -10-30 ° C.
  • the reaction is performed in the presence of a catalyst, a base, and a solvent.
  • the catalyst is Pd (dppf) Cl 2 ⁇ CH 2 Cl 2 , Pd (dppf) Cl 2 or Pd (PPh 3 ) 4 ;
  • the base is CsF, K 2 CO 3 , Na 2 CO 3 , K 3 PO 4 or KF;
  • the solvent is organic solvent / water, the volume ratio of the two is 20 / 1-1 / 1, and the organic solvent is dioxane, toluene , DMF or DMSO; the temperature is in the range of 80-150 ° C.
  • herbicide is used herein to mean an active ingredient that kills, controls, or otherwise adversely alters plant growth.
  • An effective herbicidal amount or a vegetation control amount is an amount of an active ingredient that causes adverse changes and includes deviation, killing, regulation, dehydration, delay, etc. from natural development.
  • plants and vegetation includes germinated seeds, emerged seedlings, above- and below-ground plant parts such as shoots, roots, tubers, rhizomes, and the like, and established vegetation.
  • the compound of the invention exhibits herbicidal activity at any stage of growth or before planting or emergence when the compound is applied directly to the plant or plant location.
  • the measured effect depends on the plant species to be controlled, the growth stage of the plant, the application parameters of dilution and spray droplet size, the particle size of the solid components, the environmental conditions during use, and the used Specific compounds, specific excipients and carriers used, soil type, water quality, etc., and the amount of chemical applied. It is known in the art that these and other factors can be adjusted to promote selective herbicidal action. In general, it is preferred to apply a compound of formula I to relatively immature undesired vegetation after spraying via spray or water application to achieve maximum control of weeds.
  • Foliar and water-applied post-emergence operations typically use application rates of 1 to 500 grams per hectare (g / ha).
  • a preferred application rate is 10 to 300 g / ha.
  • an application rate of 5 to 500 g / ha is usually used.
  • a preferred application rate is 30 to 300 g / ha. Designed higher application rates often result in non-selective control of a wide variety of undesirable vegetation. Lower application rates typically result in selective control and can be used where the crop is located.
  • the herbicidal compounds of the present invention are often applied in combination with one or more other herbicides to control a wider variety of unwanted vegetation.
  • the compounds claimed herein may be formulated with one or more other herbicides, mixed with one or more other herbicide tanks, or with one or more other herbicides Apply one after the other.
  • the compounds of the invention are additionally useful for controlling unwanted vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or to other herbicides by genetic manipulation or by mutation and selection.
  • the herbicidal compounds of the present invention can also interact with glyphosate, glufosinate, dicamba, imidazolinones, aryloxyphenoxypropionates, or 2,4- Drops (2,4-D) are used in combination on glyphosate-tolerant, glufosinate-tolerant, dicamba, imidazolinone, aryloxyphenoxypropionate, or 2,4-drop resistant crops.
  • the compounds of the present invention in combination with herbicides at an application rate that is selective for the crop to be treated and complements the spectrum of weeds controlled by these compounds. It is often further preferred to apply the compound of the invention and other supplementary herbicides simultaneously, as a combined preparation, or as a tank mixture.
  • the herbicidal compounds of the present invention can be used in combination with acetolactate synthase (ALS) inhibitors in crops resistant to acetolactate synthase inhibitors or in combination with 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors For crops resistant to 4-hydroxyphenylpyruvate dioxygenase inhibitors.
  • ALS acetolactate synthase
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • the compounds of the present invention can generally be used in combination with known herbicide safeners to enhance their selectivity, such as known herbicide safeners such as benoxacor, benthiocarb, brassin Lactone (brassinolide), cloquintocet (mexyl), cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate , Dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluofenim, and herbicide Furilazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxaphene (MG191), MON4660, naphthalene Naphthalicanhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoicacidamides.
  • the compounds of the invention are additionally useful for controlling unwanted vegetation in a variety of crops that have been made tolerant or resistant to the compounds of the invention or to other herbicides by genetic manipulation or by mutation and selection.
  • corn, wheat, rice, soybean, sugar beet, cotton, brassica, and other crops can be treated that are already resistant or resistant to compounds that act as acetolactate synthase inhibitors in susceptible plants.
  • Multiple glyphosate and glufosinate-resistant crops can also be treated alone or in combination with these herbicides.
  • Some crops have become tolerant to auxin and ACCase herbicides such as 2,4- (dichlorophenoxy) acetic acid (2,4-D) and dicamba and aryloxyphenoxypropionate. These herbicides can be used to treat such resistant crops or other auxin-resistant crops.
  • Some crops are already tolerant to herbicides that inhibit 4-hydroxyphenylpyruvate dioxygenase, and these herbicides can be used to treat such resistant crops.
  • a compound of formula I directly as a herbicide
  • Suitable excipients or carriers should not be phytotoxic to valuable crops, especially the concentrations used in the application of compositions for selective weed control in the presence of crops, and should not occur with compounds of formula I or other composition ingredients chemical reaction.
  • Such a mixture can be designed to be applied directly to the weed or its locus, or it can be a concentrate or formulation that is usually diluted with additional carriers and excipients before application.
  • They can be solids, such as powders, granules, water-dispersible granules, or wettable powders, or liquids, such as emulsifiable concentrates, solutions, emulsions, or suspensions. They can also be provided as a premix or tank mix.
  • Suitable agricultural excipients and carriers for preparing the herbicidal mixtures of the present invention are well known to those skilled in the art. Some of these excipients include, but are not limited to, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylates; benzyl cocoalkyl dimethyl quaternary ammonium salts ; Blends of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; C9-C11 alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols (C12-C16) ethoxylates; Di-sec-butylphenol EO-PO block copolymer; methyl terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethyl Oxide (8EO); tallow
  • Useful liquid carriers include water and organic solvents.
  • the organic solvents used typically include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oil, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn Oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc .; and esters of the above-mentioned vegetable oils; mono- or di-, tri-, or other lower polyols (containing 4-6 hydroxyl groups) Esters such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, diphthalate Octyl esters, etc .; Mono-, di-, and polycarboxylic acid esters.
  • organic solvents include toluene, xylene, petroleumnaphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, tetrachloroethylene, ethyl acetate, pentyl acetate, butyl acetate Esters, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, pentanol, ethylene glycol, propylene glycol, glycerol, N-methylpyrrolidin-2-one, N, N-dimethyl Alkyl amide, dimethyl sulfoxide, liquid fertilizer, etc. Water is usually the carrier of choice for concentrate dilution.
  • Suitable solid carriers include talc, pyrophylliteclay, silica, attapulgusclay, kaolin, diatomaceous earth (kieselguhr), chalk, diatomaceous earth, lime, calcium carbonate, bentonite, bleach Soil (Fuller'searth), cottonseed husk, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.
  • surfactants are beneficially used in solid and liquid compositions, especially compositions designed to be diluted with a carrier before application.
  • the surfactants can be anionic, cationic or non-ionic in nature and can be used as emulsifiers, wetting agents, suspending agents or for other purposes.
  • the surfactants commonly used in the field of formulations and also usable in this formulation are specifically "McCutcheon's Detergents and EmulsifiersAnnual," MC Publishing. Corp., Ridgewood, New Jersey, 1998, and "Encyclopedia” of Surfactants, Vol. I-III, Chemical, Publishing Co., New York, 1980-81.
  • Typical surfactants include alkyl sulfates, such as diethanolammonium laurylsulfate; alkylaryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, Examples are nonylphenol-C18 ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C16 ethoxylates; soaps, such as sodium stearate; alkylnaphthalene-sulfonates, such as di Sodium butylnaphthalenesulfonate; dialkyl esters of sulfosuccinates, such as sodium bis (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium, Examples are lauryl trimethyl-ammonium chloride; polyethylene glycol esters of fatty acids, such as poly
  • compositions commonly used in agricultural compositions include compatibilizers, defoamers, sequencing agents, neutralizers and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration aids, adhesives, dispersants Agent, thickener, antifreeze, antimicrobial agent, etc.
  • the composition may also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, pesticides, etc., and may be combined with liquid fertilizers or solid particulate fertilizer carriers such as ammonium nitrate, urea, etc. Formulated together.
  • the concentration of the active ingredient in the herbicidal composition of the present invention is usually 0.001 to 98% by weight (percent by weight). Concentrations of 0.01 to 90% by weight are often used. In compositions designed for use as concentrates, the active ingredient is usually present at a concentration of 5 to 98% by weight, preferably 10 to 90% by weight.
  • the composition is typically diluted with an inert carrier, such as water, before application.
  • the diluted composition generally applied to the weeds or weed sites generally contains 0.0001 to 1% by weight of active ingredient, and preferably contains 0.001 to 0.05% by weight of active ingredient.
  • composition of the present invention may be used by using conventional ground or air dusters, sprayers and granule applicators, by addition to irrigation water or paddy flood water, and by other known to those skilled in the art. Conventional methods are applied to weeds or their location.
  • reaction solution was poured into 20 ml of water, extracted with ethyl acetate three times, and the organic phase was dried and spin-dried. After separation and purification by column chromatography, compound 126 (0.7 g, 51% yield) was obtained (yellow solid).
  • the activity level criteria for harmful plant destruction i.e. growth control rate are as follows:
  • Level 9 The growth control rate is above 85%;
  • Level 8 The growth control rate is above 70%
  • the above growth control rate is the fresh weight control rate.
  • Post-emergence test experiment monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) are placed in plastic pots filled with soil, and then covered with 0.5-2 Centimeters of soil to grow in a good greenhouse environment. Test plants are treated at the 4-5 leaf stage after 2-3 weeks of sowing. The test compound of the invention is dissolved with acetone, and then Tween 80 is added. Water is diluted to a certain concentration and sprayed onto plants with a spray tower. After being applied in the greenhouse for 3 weeks, the experimental results of weeds after 3 weeks are listed in Table 2.
  • Control Compound A Control Compound B:
  • Control Compound C Control Compound D:
  • Control Compound E Control Compound F:
  • Control Compound G Control Compound H:
  • Control Compound I Control compound J:
  • Control compound K Control compound L:
  • Control compound M Control Compound N:
  • Wild rape, amaranth, Veronica and didyma Tenore are important weeds in major wheat fields in China and around the world. Especially after resistance to ALS inhibitors has become widespread, it is becoming increasingly difficult to control them.
  • the compound of the present invention has significantly higher control efficacy and crop selectivity than the control compound with different parent rings or different substituents.
  • the test compound of the present invention was dissolved with acetone, then Tween 80 was added, and the solution was diluted with a certain water to a certain concentration solution, and sprayed immediately after sowing. After being applied in the greenhouse for 4 weeks, the experimental results were observed after 3 weeks. It was found that most of the medicaments of the present invention had an excellent effect under the measurement of 250 g / ha, especially for weeds such as yarrow, matang, ramie, and many compounds. Good selectivity for corn, wheat, rice, soybean, rape.
  • the compounds of the present invention generally have better weed control effects, especially for the main broad-leaved weeds such as ramie, ghost needles, etc., which occur widely in corn fields, rice fields, and wheat fields. Effect, with good commercial value.
  • the broad-leaved weeds such as Maijiagong, Zhuyuan, and Stellaria, which are resistant to ALS inhibitors, have extremely high activity.
  • the seeds of yarrow, firefly, wolf grass, and wild auntie were sown, and the soil was gently covered thereon. Thereafter, it was placed in a greenhouse with a water storage depth of 0.5-1 cm, and the tubers of Ye Cigu were implanted the next day or two days later. After that, the water storage depth was kept at 3-4 cm, and the wettability of the compound of the present invention will be adjusted according to the usual preparation method at the time point when the yarrow, firefly, wolfgrass reaches 0.5 leaves, and the wild leaf aunt reaches the primary leaf stage.
  • the water or diluted solution of the powder or suspension is uniformly dropped with a pipette to achieve a predetermined amount of effective ingredients.
  • the soil was leveled to a depth of 3-4 cm, and rice (japonica rice) at the 3-leaf stage was transplanted at a transplant depth of 3 cm the next day.
  • rice japonica rice
  • the compound of the present invention was treated in the same manner as described above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

一种取代的嘧啶-4-甲酸衍生物及其除草组合物，该嘧啶-4-甲酸衍生物及其除草组合物具有优异的除草活性和作物选择性。

Description

一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途 技术领域
本发明属于农药技术领域，具体涉及一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，目前市场上的嘧啶甲酸类除草剂种类多样，WO2005/063721A1、WO2007/082076A1、US7,863,220B2、US7,300,907B2、US7,642,220B2和US7,786,044B2公开了某些6-氨基-2-取代的-嘧啶-4-甲酸和其衍生物及其作为除草剂的用途。CN103442570A公开了一种可用于防治杂草的除草剂4-氨基吡啶-2-甲酸的芳烷基酯和6-氨基-嘧啶-4-甲酸的芳烷基酯。
由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视，需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
基于此，本发明提供了一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途。所述取代的嘧啶-4-甲酸衍生物及其除草组合物具有优异的除草活性和作物选择性。
本发明采用的技术方案如下：
一种取代的嘧啶-4-甲酸衍生物，其结构式如下：
Figure PCTCN2018105679-appb-000001
式中，
X代表O、S、未取代或取代的NH；
Y代表未取代或取代的芳基、杂芳基；
Z代表卤素；
Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的烷基、链烯基或炔基，未取代或取代的芳基、杂芳基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，烷基氨基甲酰基，二烷基氨基甲酰基，三烷基甲硅烷基或二烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2 个独立选自卤素、烷基、烷氧基、卤代烷氧基、烷硫基、卤代烷硫基、氨基、烷基氨基、二烷基氨基、烷氧基羰基中的基团所取代的不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环；
其中R 11独立地代表卤素，羟基，烷氧基，卤代烷氧基，烷硫基，卤代烷硫基，氨基、烷基氨基，二烷基氨基，烷氧基羰基，未取代或取代的芳基、杂芳基；
R 12代表H、烷基、卤代烷基、烷氧基、苯基、苯氧基或苄氧基；
R 13代表H、烷基、卤代烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、烷基或烷氧基；R 32代表H、烷基或苄基；
R 14代表烷基、卤代烷基；
R 15代表H、烷基、甲酰基、烷基酰基、卤代烷基酰基、烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、烷基；
R 17代表H、烷基、未取代或被卤素、烷基、烷氧基中的1-3个基团所取代的苯基；R 18代表H、烷基；或N＝CR 17R 18代表
Figure PCTCN2018105679-appb-000002
R 21、R 24分别独立地代表H或烷基；
R 22、R 23分别独立地代表H或烷基；或者NR 22R 23代表不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环；
R 25代表烷基；
R代表
Figure PCTCN2018105679-appb-000003
优选地，X代表O、S、NR 1；
Y代表未取代或被选自以下基团中的一种或多种取代基所取代的芳基、杂芳基：卤素，硝基，氰基，羟基，羧基，氨基，含有或不含有卤素的烷基、链烯基、炔基、环烷基、烷氧基、烷硫基、烷氧羰基、烷基磺酰基、烷基氨基、烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
Z代表Cl或Br；
Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C8烷基、C2-C8链烯基或C2-C8炔基，未取代或被卤素、C1-C8烷基、C1-C8烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
Figure PCTCN2018105679-appb-000004
-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C8烷基氨基甲酰基，二C1-C8烷基氨基甲 酰基，三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C8烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷硫基、卤代C1-C8烷硫基、氨基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基羰基中的基团所取代的
Figure PCTCN2018105679-appb-000005
其中R 11独立地代表卤素，羟基，C1-C8烷氧基，卤代C1-C8烷氧基，C1-C8烷硫基，卤代C1-C8烷硫基，氨基，C1-C8烷基氨基，二C1-C8烷基氨基，C1-C8烷氧基羰基，未取代或被卤素、C1-C8烷基、C1-C8烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
Figure PCTCN2018105679-appb-000006
Figure PCTCN2018105679-appb-000007
R 12代表H、C1-C18烷基、卤代C1-C8烷基、C1-C8烷氧基、苯基、苯氧基或苄氧基；
R 13代表H、C1-C8烷基、卤代C1-C8烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C8烷基或C1-C8烷氧基；R 32代表H、C1-C8烷基或苄基；
R 14代表C1-C8烷基、卤代C1-C8烷基；
R 15代表H、C1-C8烷基、甲酰基、C1-C8烷基酰基、卤代C1-C8烷基酰基、C1-C8烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C8烷基；
R 17代表H、C1-C8烷基、未取代或被卤素、C1-C8烷基、C1-C8烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C8烷基；或N＝CR 17R 18代表
Figure PCTCN2018105679-appb-000008
R 21、R 24分别独立地代表H或C1-C8烷基；
R 22、R 23分别独立地代表H或C1-C8烷基；或者NR 22R 23代表
Figure PCTCN2018105679-appb-000009
Figure PCTCN2018105679-appb-000010
R 25代表C1-C8烷基；
R代表
Figure PCTCN2018105679-appb-000011
更优选地，X代表O、S、NH；
Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C8烷基、C2-C8链烯基、C2-C8炔基、C3-C8环烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧羰基、C1-C8烷基磺酰基、C1-C8烷基氨基、C1-C8烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
所述芳基选自苯基、萘基；所述杂芳基选自
Figure PCTCN2018105679-appb-000012
Figure PCTCN2018105679-appb-000013
Z代表Cl或Br；
Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C6烷基、C2-C6链烯基或C2-C6炔基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C6烷基氨基甲酰基，二C1-C6烷基氨基甲酰基，三C1-C6烷基甲硅烷基或二C1-C6烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C6烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、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、二C1-C6烷基氨基、C1-C6烷氧基羰基中的基团所取代的
Figure PCTCN2018105679-appb-000014
其中R 11独立地代表卤素，羟基，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，二C1-C6烷基氨基，C1-C6烷氧基羰基，未取代或被卤素、C1-C6烷基、C1-C6烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
Figure PCTCN2018105679-appb-000015
Figure PCTCN2018105679-appb-000016
R 12代表H、C1-C14烷基、卤代C1-C6烷基、C1-C6烷氧基、苯基、苯氧基或苄氧基；
R 13代表H、C1-C6烷基、卤代C1-C6烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C6烷基或C1-C6烷氧基；R 32代表H、C1-C6烷基或苄基；
R 14代表C1-C6烷基、卤代C1-C6烷基；
R 15代表H、C1-C6烷基、甲酰基、C1-C6烷基酰基、卤代C1-C6烷基酰基、C1-C6烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C6烷基；
R 17代表H、C1-C6烷基、未取代或被卤素、C1-C6烷基、C1-C6烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C6烷基；或N＝CR 17R 18代表
Figure PCTCN2018105679-appb-000017
R 21、R 24分别独立地代表H或C1-C6烷基；
R 22、R 23分别独立地代表H或C1-C6烷基；或者NR 22R 23代表
Figure PCTCN2018105679-appb-000018
Figure PCTCN2018105679-appb-000019
R 25代表C1-C6烷基；
R代表
Figure PCTCN2018105679-appb-000020
更优选地，X代表O、S、NH；
Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧羰基、C1-C6烷基磺酰基、C1-C6烷基氨基、C1-C6烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
所述芳基选自苯基、萘基；所述杂芳基选自
Figure PCTCN2018105679-appb-000021
Figure PCTCN2018105679-appb-000022
Z代表Cl或Br；
Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C4烷基、C2-C4链烯基或C2-C4炔基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C4烷基氨基甲酰基，二C1-C4烷基氨基甲酰基，三C1-C4烷基甲硅烷基或二C1-C4烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C4烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷硫基、卤代C1-C4烷硫基、氨基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基羰基中的基团所取代的
Figure PCTCN2018105679-appb-000023
其中R 11独立地代表卤素，羟基，C1-C4烷氧基，卤代C1-C4烷氧基，C1-C4烷硫基，卤代C1-C4烷硫基，氨基，C1-C4烷基氨基，二C1-C4烷基氨基，C1-C4烷氧基羰基，未取代或被卤素、C1-C4烷基、C1-C4烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
Figure PCTCN2018105679-appb-000024
Figure PCTCN2018105679-appb-000025
R 12代表H、C1-C8烷基、卤代C1-C4烷基、C1-C4烷氧基、苯基、苯氧基或苄氧基；
R 13代表H、C1-C4烷基、卤代C1-C4烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C4烷基或C1-C4烷氧基；R 32代表H、C1-C4烷基或苄基；
R 14代表C1-C4烷基、卤代C1-C4烷基；
R 15代表H、C1-C4烷基、甲酰基、C1-C4烷基酰基、卤代C1-C4烷基酰基、C1-C4烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C4烷基；
R 17代表H、C1-C4烷基、未取代或被卤素、C1-C4烷基、C1-C4烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C4烷基；或N＝CR 17R 18代表
Figure PCTCN2018105679-appb-000026
R 21、R 24分别独立地代表H或C1-C4烷基；
R 22、R 23分别独立地代表H或C1-C4烷基；或者NR 22R 23代表
Figure PCTCN2018105679-appb-000027
Figure PCTCN2018105679-appb-000028
R 25代表C1-C4烷基；
R代表
Figure PCTCN2018105679-appb-000029
进一步优选地，X代表O；
Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧羰基、C1-C4烷基磺酰基、C1-C4烷基氨基、C1-C4烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
所述芳基选自苯基；所述杂芳基选自
Figure PCTCN2018105679-appb-000030
Z代表Cl；
Q代表NH 2、NHMe、N(Me) 2、
Figure PCTCN2018105679-appb-000031
Figure PCTCN2018105679-appb-000032
R代表
Figure PCTCN2018105679-appb-000033
本发明包括除草组合物，其包含与可农用辅料或载体混合的除草有效量的式I化合物。
本发明还包括通过向植被或者向植被的所在地，以及在植被出苗之前向土壤或者在出苗之前或之后向灌溉水或淹灌水(floodwater)施用除草量的化合物，使用本发明的化合物和组合物来杀死或防治不期望植被的方法。
本发明还包括在稻、小麦或饲草存在下选择性苗后防治不期望植被的方法，其包括向所述不期望植被施用除草有效量的本发明化合物或其除草组合物。本发明还包括制备本发明化合物的方法。
本发明还涉及所述式I化合物的制备方法，其选自以下任意一种：
(1)化学反应方程式如下：
Figure PCTCN2018105679-appb-000034
当X代表O时，Hal代表卤素，优选Cl或Br；所述反应在溶剂和碱的存在下进行，所述碱选自K 2CO 3、Na 2CO 3和Cs 2CO 3中的一种或两种以上。
当X代表S时，Hal代表SH；X代表未取代或取代的N时，Hal代表未取代或相应取代的NH 2；所述反应在缩合剂、碱和溶剂的存在下进行，所述缩合剂为HOBt/EDCI.HCl或CDI，所述碱为TEA、DIPEA或其组合。
所述溶剂均为乙腈、DMF、二氯甲烷或1,2-二氯乙烷；所述反应温度均在0～40℃范围内，优选20～30℃。
(2)化学反应方程式如下：
Figure PCTCN2018105679-appb-000035
所述反应在卤化物和溶剂的存在下进行，根据式I中取代基Z的类型选择所述卤化物，包括但不限定于NCS、NBS、Cl 2、Br 2或NaClO/HCl等；所述溶剂选自DMF、DMSO、DCM、THF、MeCN和DCE中的一种或多种混合；所述反应温度在0-80℃范围内。
(3)化学反应方程式如下：
Figure PCTCN2018105679-appb-000036
所述A代表卤素(如溴、碘、氯等)、甲磺酰基等；所述反应在Q-H和溶剂的存在下进行；所述溶剂选自DMF、DMSO、DCM、THF、MeCN和DCE中的一种或多种混合；所述反应温度在-10-30℃范围内。
(4)化学反应方程式如下：
Figure PCTCN2018105679-appb-000037
所述反应在催化剂、碱和溶剂的存在下进行，所述催化剂为Pd(dppf)Cl 2·CH 2Cl 2、Pd(dppf)Cl 2或Pd(PPh 3) 4；所述碱为CsF、K 2CO 3、Na 2CO 3、K 3PO 4或KF；所述溶剂为有机溶剂/水，二者体积比为20/1-1/1，所述有机溶剂为二氧六环、甲苯、DMF或DMSO；所述温度在80-150℃范围内。
已经发现，式I的化合物作为稻和谷类种植制度和牧草管理规划的苗前和苗后除草剂是有用的。术语除草剂用在本文中意思是杀死、防治或其它不利地改变植物生长的活性成分。除草有效量或植被防治量是引起不利改变作用和包括从自然发育中偏离、杀死、调节、脱水、延迟等的活性成分的量。术语植物和植被包括发芽的种子、出苗的苗、地上和地下植物部分例如枝条、根、块茎(tubers)、根茎(rhizomes)等和已长成的植被。
在生长的任何阶段或者在种植或出苗前，当将化合物直接施用于植物或植物的所在地时，本发明的化合物表现出除草活性。实测效果取决于所要防治的植物物种、植物的生长阶段、稀释和喷雾液滴大小的施用参数(the application parameters of dilution and spray drop size)、固体组分的粒度、使用时的环境状况、所用的具体化合物、所用的具体辅料和载体、土壤类型、 水质等，以及所施用化学品的量。本领域已知的是，这些及其它因素可进行调整以促进选择性的除草作用。通常，优选在苗后经由喷雾或水施用向相对不成熟的不期望的植被施用式I的化合物以实现对杂草的最大防治。
叶面施用的和水施用的苗后操作通常使用1至500克每公顷(g/ha)的施用率。优选的施用率是10至300g/ha。对于苗前施用，通常使用5至500g/ha的施用率。优选的施用率是30至300g/ha。所设计的较高施用率通常产生宽广种类不期望的植被的非选择性防治。较低的施用率典型地产生选择性防治并且可以在作物的所在地使用。
本发明的除草化合物常与一种或更多种其它除草剂联合施用以防治更广种类的不期望的植被。当与其它除草剂联合使用时，可将本发明要求保护的化合物与其它一种或多种除草剂一起配制，与其它一种或多种除草剂罐混合或者与其它一种或多种除草剂先后施用。一些可与本发明的化合物联合使用的除草剂包括：2,4-滴盐、酯和胺(2,4-Dsalts、estersandamines)、乙草胺(acetochlor)、三氟羧草醚(acifluorfen)、甲草胺(alachlor)、酰嘧磺隆(amidosulfuron)、氯氨基吡啶酸(aminopyralid)、氨基***(aminotriazole)、硫氰酸铵(ammoniumthiocyanate)、anilifos、莠去津(atrazine)、四唑嘧磺隆(azimsulfuron)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron-methyl)、灭草松(bentazon)、禾草丹(benthiocarb)、苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、甲羧除草醚(bifenox)、双草醚-钠(bispyribac-sodium)、溴丁酰草胺(bromobutide)、丁草胺(butachlor)、唑草胺(cafenstrole)、唑草酮-乙基(carfentrazone-ethyl)、chlodinafop-propyrgyl、氯嘧磺隆脱乙基酸(chlorimuron)、氯苯胺灵(chlorpropham)、醚磺隆(cinosulfuron)、烯草酮(clethodim)、异噁草酮(clomazone)、稗草胺(clomeprop)、二氯吡啶酸(clopyralid)、氯酯磺草胺(cloransulam-methyl)、环丙嘧磺隆(cyclosulfamuron)、噻草酮(cycloxydim)、氰氟草酯-丁基(cyhalofop-butyl)、苄草隆(cumyluron)、香草隆(daimuron)、唑嘧磺胺(diclosulam)、吡氟酰草胺(diflufenican)、二氟吡隆(diflufenzopyr)、哌草丹(dimepiperate)、戊草津(dimethametryn)、敌草快(diquat)、氟硫草定(dithiopyr)、EK2612、茵草敌(EPTC)、戊草丹(esprocarb)、ET-751、乙氧嘧磺隆(ethoxysulfuron)、ethbenzanid、噁唑禾草灵(fenoxaprop)、噁唑禾草灵-乙基(fenoxaprop-ethyl)、噁唑禾草灵-乙基(fenoxaprop-ethyl)+isoxadifen-ethyl、四唑草胺(fentrazamide)、啶嘧磺隆(flazasulfuron)、双氟磷草胺(florasulam)、吡氟禾草灵(fluazifop)、精吡氟禾草灵-丁基(fluazifop-P-butyl)、氟吡磺隆(flucetosulfuron)、氟噻草胺(flufenacet)、氟哒嗪草酯-乙基(flufenpyr-ethyl)、唑嘧磺草胺(flumetsulam)、丙炔氟草胺(flumioxazin)、氟啶嘧磺隆脱甲基酸(flupyrsulfuron)、氯氟吡氧乙酸(fluroxypyr)、氟磺胺草醚(fomesafen)、甲酰胺磺隆(foramsulfuron)、草铵膦(glufosinate)、精草铵膦(glufosinate-P)、草甘膦(glyphosate)、氯吡嘧磺隆(halosulfuron-methyl)、氟吡甲禾灵(haloxyfop-methyl)、高效氟吡禾灵(haloxyfop-R)、高效 氟吡甲禾灵(haloxyfop-R-methyl)、咪草酯(imazamethabenz)、甲氧咪草烟(imazamox)、甲咪唑烟酸(imazapic)、咪唑烟酸(imazapyr)、咪唑喹啉酸(imazaquin)、咪唑乙烟酸(imazethapyr)、唑吡嘧磺隆(imazosulfuron)、茚草酮(indanofan)、碘苯腈(ioxynil)、卤苯胺唑(ipfencarbazone)、异噁酰草胺(isoxaben)、2甲4氯(MCPA)、2甲4氯丁酸(MCPB)、苯噻酰草胺(mefenacet)、甲磺胺磺隆脱甲基酸(mesosulfuron)、硝磺草酮(mesotrione)、噁唑酰草胺(metamifop)、双醚氯吡嘧磺隆(metazosulfuron)、异丙甲草胺(metolachlor)、磺草唑胺(metosulam)、甲磺隆脱甲基酸(metsulfuron)、禾草敌(molinate)、单嘧磺隆(monosulfuron)、甲胂一钠(MSMA)、嘧苯胺磺隆(orthosulfamuron)、氨磺乐灵(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、噁嗪草酮(oxazichlomefone)、乙氧呋草醚(oxyfluorfen)、百草枯(paraquat)、二甲戊灵(pendimethalin)、五氟磺草胺(penoxsulam)、戊噁唑草(pentoxazone)、烯草胺(pethoxamid)、氨氯吡啶酸(picloram)、哌草磷(piperophos)、丙草胺(pretilachlor)、环苯草酮(profoxydim)、调环酸-钙(prohexadione-calcium)、毒草胺(propachlor)、敌稗(propanil)、异丙草胺(propisochlor)、炔苯酰草胺(propyzamide)、嗪咪唑嘧磺隆(propyrisulfuron)、氟磺隆(prosulfuron)、pyrabuticarb、双唑草腈(pyraclonil)、双唑草腈(pyrazogyl)、吡唑特(pyrazolynate)、吡嘧磺隆(pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、嘧啶肟草醚(pyribenzoxim)、哒草特(pyridate)、环酯草醚(pyriftalid)、嘧草醚-甲基(pyriminobac-methyl)、pyrimisulfan、氟嘧磺隆脱甲基酸(primisulfuron)、啶磺草胺(pyroxsulam)、灭藻醌(quinoclamine)、二氯喹啉酸(quinclorac)、精喹禾灵-乙基(quizalofop-P-ethyl)、S-3252、烯禾啶(sethoxydim)、西玛津(simazine)、西草净(simetryne)、精异丙甲草胺(s-metolachlor)、磺草酮(sulcotrione)、甲磺草胺(sulfentrazone)、草硫膦(sulfosate)、tefuryltrione、噻吩草胺(thenylchlor)、噻唑烟酸(thiazopyr)、禾草丹(thiobencarb)、绿草定(triclopyr)、三氯吡氧乙酸酯和胺(triclopyr-estersand amines)、氟乐灵(trifluralin)、抗倒酯(trinexapac-ethyl)、三氟甲磺隆(tritosulfuron)及其它4-氨基-6-(取代的苯基)吡啶-2-甲酸和6-氨基-2-(取代的苯基)-嘧啶-4-甲酸及其盐和酯。
本发明的化合物另外可用来防治多种作物中的不期望的植被，所述作物已经通过遗传操作(geneticmanipulation)或通过突变和选择使其对本发明的化合物或对其它除草剂耐受或耐药。本发明的除草化合物还可以与草甘膦(glyphosate)、草铵膦(glufosinate)、麦草畏(dicamba)、咪唑啉酮(imidazolinones)、芳氧苯氧丙酸酯(aryloxyphenoxypropionates)或2,4-滴(2,4-D)联合用在耐草甘膦、耐草铵膦、耐麦草畏、耐咪唑啉酮、耐芳氧苯氧丙酸酯或耐2,4-滴的作物上。通常优选将本发明的化合物与除草剂联合使用，所述除草剂在所用的施用率对于待处理的作物具有选择性，并且对这些化合物所防治的杂草的谱进行了补充。通常进一步优选同时施用本发明的化合物和其它补充除草剂，作为组合制剂，或者作为罐混合物。类似地，本发明的 除草化合物可与乙酰乳酸合酶(ALS)抑制剂联合用于耐乙酰乳酸合酶抑制剂的作物或者与4-羟基苯基丙酮酸双加氧酶(HPPD)抑制剂联合用于耐4-羟基苯基丙酮酸双加氧酶抑制剂的作物。
本发明的化合物通常可与已知的除草剂安全剂组合使用，以增强其选择性，所述已知的除草剂安全剂例如解草嗪(benoxacor)、禾草丹(benthiocarb)、芸薹素内酯(brassinolide)、解草酯(cloquintocet(mexyl))、解草胺腈(cyometrinil)、环丙磺酰胺(cyprosulfamide)、香草隆(daimuron)、烯丙酰草胺(dichlormid)、dicyclonon、dietholate、哌草丹(dimepiperate)、乙拌磷(disulfoton)、解草唑-乙基(fenchlorazole-ethyl)、解草啶(fenclorim)、解草胺(flurazole)、氟草肟(fluxofenim)、解草噁唑(furilazole)、超敏蛋白(harpin proteins)、双苯噁唑酸乙酯(isoxadifen-ethyl)、吡唑解草酯(mefenpyr-diethyl)、mephenate、解草烷(MG191)、MON4660、萘二甲酸酐(naphthalicanhydride,NA)、解草腈(oxabetrinil)、R29148和N-苯基-磺酰基苯甲酸酰胺(N-phenyl-sulfonylbenzoicacidamides)。本发明的化合物另外可用来防治多种作物中的不期望的植被，所述作物已经通过遗传操作或通过突变和选择使其对本发明的化合物或对其它除草剂耐受或耐药。例如，可以处理玉米、小麦、稻、大豆、甜菜、棉花、芸苔和其它作物，所述作物已经对在易感植物中作为乙酰乳酸合酶抑制剂的化合物耐受或耐药。还可以单独或与这些除草剂组合处理多种耐草甘膦和耐草铵膦的作物。一些作物已经对植物生长素除草剂和ACCase除草剂如2,4-(二氯苯氧基)乙酸(2,4-D)和麦草畏和芳氧苯氧丙酸酯产生耐受。这些除草剂可以用来处理这样的耐药作物或其它耐植物生长素的作物。一些作物已经对抑制4-羟基苯基丙酮酸双加氧酶的除草剂耐受，而这些除草剂可用来处理这样的耐药作物。
尽管有可能直接采用式I化合物作为除草剂，但优选的是以混合物的形式使用，所述混合物含有除草有效量的化合物以及至少一种可农用的辅料或载体。适合的辅料或载体不应对有价值作物有植物毒性，特别是在作物存在时在施用用于选择性杂草防治的组合物中所用的浓度，且不应与式I化合物或者其它组合物成分发生化学反应。这样的混合物可以设计成直接施用于杂草或其所在地，或者可以是通常在施用前以另外的载体和辅料来稀释的浓缩物或制剂。它们可以是固体，例如粉剂、颗粒剂、水分散颗粒剂或可湿性粉末剂，或者液体，例如乳油(emulsifiable concentrates)、溶液、乳液或混悬液。它们还可以作为预先混合物或罐混合物来提供。
用于制备本发明的除草混合物的适合农用辅料和载体为本领域技术人员所熟知。这些辅料中的一些包括，但不限于，作物油浓缩物(矿物油(85％)+乳化剂(15％))；壬基苯酚乙氧基化物；苄基可可烷基二甲基季铵盐；石油烃、烷基酯、有机酸和阴离子表面活性剂的共混物；C9-C11烷基多聚糖苷；磷酸化醇乙氧基化物；天然伯醇(C12-C16)乙氧基化物；二仲丁基苯 酚EO-PO嵌段共聚物；甲基封端的聚硅氧烷；壬基苯酚乙氧基化物+脲硝酸铵；乳化的甲基化种子油；十三醇(合成的)乙氧基化物(8EO)；牛脂胺乙氧基化物(15EO)；PEG(400)二油酸酯-99。
可使用的液体载体包括水和有机溶剂。所用的有机溶剂典型地包括，但不限于，石油馏分或烃例如矿物油、芳香族溶剂、石蜡油等；植物油例如大豆油、菜籽油、橄榄油、蓖麻油、葵花子油、椰子油、玉米油、棉籽油、亚麻子油、棕榈油、花生油、红花油、麻油、桐油等；以及上述植物油的酯；一元醇或者二元、三元或者其它低级多元醇(含有4-6个羟基)的酯，例如硬脂酸2-乙基己酯、油酸正丁酯、十四烷酸异丙酯、丙二醇二油酸酯、琥珀酸二辛酯、己二酸二丁酯、酞酸二辛酯等；单、二和多羧酸的酯等。具体的有机溶剂包括甲苯、二甲苯、石脑油(petroleumnaphtha)、作物油、丙酮、甲基乙基酮、环己酮、三氯乙烯、四氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇单甲醚和二甘醇单甲醚、甲醇、乙醇、异丙醇、戊醇、乙二醇、丙二醇、甘油、N-甲基吡咯烷-2-酮、N,N-二甲基烷基酰胺、二甲基亚砜、液体肥料等。水通常是浓缩物稀释所选择的载体。
适合的固体载体包括滑石、叶蜡石粘土(pyrophylliteclay)、硅石、活性白土(attapulgusclay)、高岭土、硅藻土(kieselguhr)、白垩、硅藻土(diatomaceous earth)、石灰、碳酸钙、膨润土、漂白土(Fuller′searth)、棉子壳、小麦粉、大豆粉、浮石粉(pumice)、木粉、胡桃壳粉、木质素等。
通常期望的是将一种或更多种表面活性剂引入本发明的组合物中。这种表面活性剂有益地在固体和液体组合物中使用，尤其是设计成在施用前用载体稀释的组合物。所述表面活性剂的性质可以是阴离子的、阳离子的或非离子的，并可用作乳化剂、润湿剂、助悬剂或用于其它目的。通常在制剂领域中使用的且也可在本制剂中使用的表面活性剂特别地(interalia)在“Mc Cutcheon’s Detergents and Emulsifiers Annual,”MC Publishing Corp.,Ridgewood,NewJersey,1998and in“Encyclopedia of Surfactants,”Vol.I-III,Chemical Publishing Co.,NewYork,1980-81中有述。典型的表面活性剂包括烷基硫酸盐，例如月桂基硫酸二乙醇铵(diethanolammoniumlaurylsulfate)；烷基芳基磺酸盐，如十二烷基苯磺酸钙；烷基苯酚-氧化烯加成产物，例如壬基苯酚-C18乙氧基化物；醇-氧化烯加成产物，例如十三烷基醇-C16乙氧基化物；皂，例如硬脂酸钠；烷基萘-磺酸盐，例如二丁基萘磺酸钠；磺基琥珀酸盐的二烷基酯，例如磺基琥珀酸二(2-乙基己基)酯钠；山梨糖醇酯，例如油酸山梨糖醇酯；季铵，例如月桂基三甲基-氯化铵；脂肪酸的聚乙二醇酯，例如硬脂酸聚乙二醇酯；环氧乙烷和环氧丙烷的嵌段共聚物；磷酸单烷基酯的盐和磷酸二烷基酯的盐；植物油或种子油，例如大豆油、菜籽油/芸苔油、橄榄油、蓖麻油、葵花子油、椰子油、玉米油、棉籽油、亚麻子油、棕榈油、花生油、红花油、麻油、桐油等；以及上述植物油的酯，特别是甲酯。
通常，这些物质中的一些，例如植物油或种子油以及其酯，可互换地作为农用辅料、作为液体载体或者作为表面活性剂使用。
常用于农用组合物的其它辅料包括相容剂、消泡剂、掩蔽剂(sequesteringagent)、中和剂和缓冲剂、缓蚀剂、染料、芳香剂、铺展剂、渗透助剂、粘着剂、分散剂、增稠剂、防冻剂、抗微生物剂等。所述组合物还可以含有其它相容性组分，例如，其它除草剂、植物生长调节剂、杀真菌剂、杀虫剂等，并可与液体肥料或者固体颗粒肥料载体例如硝酸铵、脲等一起配制。
本发明除草组合物中活性成分的浓度通常在0.001至98wt％(重量百分数)。常使用0.01至90wt％的浓度。在设计用作浓缩物的组合物中，活性成分通常以5至98wt％，优选以10至90wt％的浓度存在。在施用前将所述组合物典型地用惰性载体(例如水)稀释。通常施用至杂草或杂草所在地的稀释的组合物一般含有0.0001至1wt％活性成分，并优选含有0.001至0.05wt％活性成分。
本发明组合物可通过使用常规的地面或空气撒粉器、喷雾器和颗粒施用器(granule applicators)，通过添加至灌溉水或稻田淹灌水(paddy flood water)以及通过本领域技术人员已知的其它常规手段施用于杂草或其所在地。
具体实施方式
提出下列实施例是来说明本发明的各个方面而不应被视作对权利要求的限制。
表1.化合物的结构及其 1HNMR数据
Figure PCTCN2018105679-appb-000038
Figure PCTCN2018105679-appb-000039
Figure PCTCN2018105679-appb-000040
Figure PCTCN2018105679-appb-000041
Figure PCTCN2018105679-appb-000042
Figure PCTCN2018105679-appb-000043
Figure PCTCN2018105679-appb-000044
Figure PCTCN2018105679-appb-000045
Figure PCTCN2018105679-appb-000046
Figure PCTCN2018105679-appb-000047
Figure PCTCN2018105679-appb-000048
Figure PCTCN2018105679-appb-000049
Figure PCTCN2018105679-appb-000050
Figure PCTCN2018105679-appb-000051
Figure PCTCN2018105679-appb-000052
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下：
1、化合物1的合成
Figure PCTCN2018105679-appb-000053
于室温下，在一个10mL的单口茄形瓶中加入化合物Ⅱ-1(1当量)、
Figure PCTCN2018105679-appb-000054
(1.1当量)、碳酸钾(1.5当量)和DMF(10V，V代表每克底物对应1mL溶剂DMF，下同)，室温条件下，搅拌过夜。TLC检测反应已经完成，将反应体系加水后用乙酸乙酯萃取，有机相浓缩后通过柱层析硅胶(100目到200目)分离，得到产物，收率为80％。
2、化合物6的合成
Figure PCTCN2018105679-appb-000055
在50毫升单口瓶中加入20毫升的DMF，然后依次加入化合物Ⅱ-2(1g，2.4mmol，1eq)和NCS(481.7mg，3.61mmol，1.5eq)并在室温下搅拌4小时。TLC检测反应进行完全。将反应液倒入20毫升的水中，乙酸乙酯萃取三次，饱和食盐水洗涤有机相三次，有机相干燥后旋干，经柱层析分离纯化后得到化合物6(0.9g，83％收率)(白色固体)。
3、化合物15的合成
Figure PCTCN2018105679-appb-000056
在20毫升的DCM中依次加入Ⅱ-1(1g，3.0mmol 1.0eq)，HOBt(0.53g，3.9mmol，1.3eq)，EDCI.HCl(0.75g，3.9mmol，1.3eq)，TEA(0.60g，6.0mmol，2.0eq)并在室温搅拌30min后加入
Figure PCTCN2018105679-appb-000057
(0.51g，3.6mmol，1.2eq)，然后反应液搅拌12小时。TLC检测，反应完成。将反应液倒入20毫升水中，分液，水相用20毫升DCM萃取三次，有机相干燥，旋干，柱层析分离得到化合物15(1.1g，80％收率)(白色固体)。
4、化合物51的合成
Figure PCTCN2018105679-appb-000058
在20毫升的DMF中加入Ⅱ-3(1g,3.0mmol 1.0eq)和CDI(0.84g,6.0mmol,2.0eq)，在室温搅拌30min后加入
Figure PCTCN2018105679-appb-000059
(0.75g,3.6mmol,1.2eq)，然后反应液搅拌12小时。TLC检测，反应完成。将反应液倒入20毫升水中，加入30毫升乙酸乙酯萃取，水相再用30毫升乙酸乙酯萃取两次，有机相干燥，旋干，柱层析分离得到化合物51(1.4g,85％收率)(白色固体)。
5、化合物105的合成
Figure PCTCN2018105679-appb-000060
室温下在100毫升的三口瓶中加入20毫升的DMSO，再加入化合物Ⅱ-4(1g，2.0mmol，1eq)，搅拌使其溶解。然后向溶液中慢慢鼓入NH 3。TLC检测原料基本反应完全后停止通入NH 3。将反应液倒入20毫升的水中，乙酸乙酯萃取三次，饱和食盐水洗涤有机相三次，有机相干燥后旋干，经柱层析分离纯化后得到化合物105(0.75g，78％收率)(白色固体)。
6、化合物126的合成
Figure PCTCN2018105679-appb-000061
室温下在50毫升的单口瓶中依次加入化合物Ⅱ-5(1g，3.0mmol，1eq)，
Figure PCTCN2018105679-appb-000062
(674mg，3.30mmol，1.1eq)，CsF(911mg，6mmol，2eq)，1,4-二氧六环和水(V/V＝4/1)。N 2置换三次后加入Pd(dppf)Cl 2·CH 2Cl 2(122mg，0.15mmol，0.05eq)，然后加热至120℃搅拌12小时。TLC检测原料基本反应完全。将反应液倒入20毫升的水中，乙酸乙酯萃取三次，有机相干燥后旋干，经柱层析分离纯化后得到化合物126(0.7g，51％收率)(黄色固体)。
7、化合物131的合成
Figure PCTCN2018105679-appb-000063
在20毫升的DMF中加入Ⅱ-6(1.0g,3.0mmol 1.0eq),
Figure PCTCN2018105679-appb-000064
(0.5g,3.0mmol 1.0eq)和K 2CO 3(0.67g,6.0mmol,2.0eq)，室温搅拌12小时。TLC检测，反应完成。将反应液倒入20毫升水中，加入30毫升乙酸乙酯萃取，水相再用30毫升乙酸乙酯萃取两次，有机相干燥，旋干，柱层析分离得到化合物131(1.4g,87％收率)(白色固体)。
生物活性评价：
有害植物破坏(即生长控制率)的活性级别标准如下：
10级：完全死亡；
9级：生长控制率在85％以上；
8级：生长控制率在70％以上；
7级：生长控制率在60％以上；
6级：生长控制率在50％以上；
5级：生长控制率在40％以上；
4级：生长控制率在30％以上；
3级：生长控制率在20％以上；
2级：生长控制率在5-20％；
1级：生长控制率在5％以下；
0级：无效果。
以上生长控制率为鲜重控制率。
苗后测试实验：将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2-3周后在4-5叶期处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养3周，3周后杂草的实验效果列于表2。
表2.苗后杂草试验(15克/公顷)
化合物序号 播娘蒿 荠菜 猪殃殃 宝盖草 小麦
1 10 10 10 10 0
2 10 10 10 10 0
3 10 10 10 10 0
4 10 10 10 10 0
5 10 10 10 10 0
6 10 10 10 10 0
7 10 10 10 10 0
8 10 10 10 10 0
9 10 10 10 10 0
10 10 10 10 10 0
11 10 10 10 10 0
12 10 10 10 10 0
13 10 10 10 10 0
14 10 10 10 10 0
15 10 10 10 10 0
16 10 10 10 10 0
17 10 10 10 10 0
18 10 10 10 10 0
19 10 10 10 10 0
20 10 10 10 10 0
21 10 10 10 10 0
22 10 10 10 10 0
23 10 10 10 10 0
24 10 10 10 10 0
25 10 10 10 10 0
26 10 10 10 10 0
27 10 10 10 10 0
28 10 10 10 10 0
29 10 10 10 10 0
30 10 10 10 10 0
31 10 10 10 10 0
32 10 10 10 10 0
33 10 10 10 10 0
34 10 10 10 10 0
35 10 10 10 10 0
36 10 10 10 10 0
37 10 10 10 10 0
38 10 10 10 10 0
39 10 10 10 10 0
40 10 10 10 10 0
41 10 10 10 10 0
42 10 10 10 10 0
43 10 10 10 10 0
44 10 10 10 10 0
45 10 10 10 10 0
46 10 10 10 10 0
47 10 10 10 10 0
48 10 10 10 10 0
49 10 10 10 10 0
50 10 10 10 10 0
51 10 10 10 10 0
52 10 10 10 10 0
53 10 10 10 10 0
54 10 10 10 10 0
55 10 10 10 10 0
56 10 10 10 10 0
57 10 10 10 10 0
58 10 10 10 10 0
59 10 10 10 10 0
60 10 10 10 10 0
61 10 10 10 10 0
62 10 10 10 10 0
63 10 10 10 10 0
64 10 10 10 10 0
65 10 10 10 10 0
66 10 10 10 10 0
67 10 10 10 10 0
68 10 10 10 10 0
69 10 10 10 10 0
70 10 10 10 10 0
71 10 10 10 10 0
72 10 10 10 10 0
73 10 10 10 10 0
74 10 10 10 10 0
75 10 10 10 10 0
76 10 10 10 10 0
77 10 10 10 10 0
78 10 10 10 10 0
79 10 10 10 10 0
80 10 10 10 10 0
81 10 10 10 10 0
82 10 10 10 10 0
83 10 10 10 10 0
84 10 10 10 10 0
85 10 10 10 10 0
86 10 10 10 10 0
87 10 10 10 10 0
88 10 10 10 10 0
89 10 10 10 10 0
90 10 10 10 10 0
91 10 10 10 10 0
92 10 10 10 10 0
93 10 10 10 10 0
94 10 10 10 10 0
95 10 10 10 10 0
96 10 10 10 10 0
97 10 10 10 10 0
98 10 10 10 10 0
99 10 10 10 10 0
100 10 10 10 10 0
101 10 10 10 10 0
102 10 10 10 10 0
103 10 10 10 10 0
104 10 10 10 10 0
105 10 10 10 10 0
106 10 10 10 10 0
107 10 10 10 10 0
108 10 10 10 10 0
109 10 10 10 10 0
110 10 10 10 10 0
111 10 10 10 10 0
112 10 10 10 10 0
113 10 10 10 10 0
114 10 10 10 10 0
115 10 10 10 10 0
116 10 10 10 10 0
117 10 10 10 10 0
118 10 10 10 10 0
119 10 10 10 10 0
120 10 10 10 10 0
121 10 10 10 10 0
122 10 10 10 10 0
123 10 10 10 10 0
124 10 10 10 10 0
125 10 10 10 10 0
126 10 10 10 10 0
127 10 10 10 10 0
128 10 10 10 10 0
129 10 10 10 10 0
130 10 10 10 10 0
131 10 10 10 10 0
132 10 10 10 10 0
对比实验：
(1)苗后测试条件同上，实验结果如表3-4所示。
对照化合物A：
Figure PCTCN2018105679-appb-000065
对照化合物B：
Figure PCTCN2018105679-appb-000066
对照化合物C：
Figure PCTCN2018105679-appb-000067
对照化合物D：
Figure PCTCN2018105679-appb-000068
对照化合物E：
Figure PCTCN2018105679-appb-000069
对照化合物F：
Figure PCTCN2018105679-appb-000070
对照化合物G：
Figure PCTCN2018105679-appb-000071
对照化合物H：
Figure PCTCN2018105679-appb-000072
对照化合物I：
Figure PCTCN2018105679-appb-000073
对照化合物J：
Figure PCTCN2018105679-appb-000074
对照化合物K：
Figure PCTCN2018105679-appb-000075
对照化合物L：
Figure PCTCN2018105679-appb-000076
对照化合物M：
Figure PCTCN2018105679-appb-000077
对照化合物N：
Figure PCTCN2018105679-appb-000078
表3.对比实验结果(3克/公顷)
化合物序号 猪殃殃 荠菜 播娘蒿 Veronica didyma Tenore
1 10 9 10 10
2 9 9 10 9
3 8 7 10 8
A 2 2 4 4
B 1 2 3 3
C 2 2 4 3
D 3 2 5 4
E 0 0 0 0
F 0 0 0 0
G 2 1 3 2
H 0 1 2 2
I 2 2 2 2
J 2 1 3 2
表4.对比实验(5克/公顷)
化合物序号 野油菜 蔊菜 Veronica didyma Tenore 通泉草
1 10 9 10 10
K 1 3 3 2
注：野油菜、蔊菜、Veronica didyma Tenore是中国和全球主要麦田的重要难防除杂草，尤其是对ALS抑制剂普遍产生了抗药性之后，防除难度日益加大。
(2)直播水稻2-3叶期，玉米2-3叶期，稗草3叶期茎叶喷雾安全性与活性测试，结果如表5所示。
表5.安全性与活性测试结果(30克/公顷)
化合物序号 水稻 玉米 小麦 稗草
1 1 3 0 10
124 0 1 0 10
129 1 2 0 10
131 0 1 0 9
L 5 9 3 9
M 6 7 1 9
N 2 8 2 10
由以上表格可知，本发明化合物与母环或取代基不同的对照化合物相比，明显具有更高的防效和作物选择性。
苗前测试实验：
将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，播种后立即喷施。施药后在温室中培养4周，3周后观察实验结果，发现本发明的药剂多数在250克/公顷计量下效果出众，尤其对稗草、马塘、苘麻等杂草，且很多化合物对玉米、小麦、水稻、大豆、油菜有良好的选择性。
通过实验我们发现本发明所述化合物普遍具有较好的杂草防效，尤其对于玉米田、水稻田、小麦田广泛发生的杂草苘麻、鬼针草等主要的阔叶杂草有良好的效果，具备良好的商业价值。尤其是我们注意到对于ALS抑制剂有抗性的麦家公、猪殃殃、繁缕等阔叶杂草有极高的活性。
移栽水稻安全性评价与水田杂草防效评价：
在1/1,000,000公顷罐中装入水田土壤后，播种稗草、萤蔺、狼把草、野慈姑的种子，在其上轻轻地覆盖土。其后以蓄水深0.5-1厘米的状态静置于温室内，第二天或者2天后植入野慈姑的块茎。其后保持蓄水深3-4厘米，在稗草、萤蔺、狼把草达到0.5叶，野慈姑达到初生叶期的时间点，将按照通常的制剂方法调制本发明化合物而成的可湿性粉剂或者悬浮剂的水稀释液，用吸液管进行均匀的滴下处理以达到规定的有效成分量。
另外，在1/1,000,000公顷罐中装入水田土壤后，进行平整，使蓄水深3-4厘米，第二天以移栽深度3厘米来移植3叶期的水稻(粳稻)。移植后第5天与上述同样地处理本发明化合物。
分别用肉眼观察药剂处理后第14天稗草、萤蔺、狼把草及野慈姑的生育状态，药剂处理后第21天水稻的生育状态，以1-10的活性标准级别评价除草效果，试验发现很多本发明的化合物有优秀的活性和选择性，尤其对于野慈姑和稗草。
注：稗草、萤蔺、野慈姑、狼把草种子均采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
同时经过很多测试发现，本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的小麦、玉米、水稻、甘蔗、大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (10)

  1. 一种取代的嘧啶-4-甲酸衍生物，其结构式如下：
    Figure PCTCN2018105679-appb-100001
    式中，
    X代表O、S、未取代或取代的NH；
    Y代表未取代或取代的芳基、杂芳基；
    Z代表卤素；
    Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的烷基、链烯基或炔基，未取代或取代的芳基、杂芳基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，烷基氨基甲酰基，二烷基氨基甲酰基，三烷基甲硅烷基或二烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、烷基、烷氧基、卤代烷氧基、烷硫基、卤代烷硫基、氨基、烷基氨基、二烷基氨基、烷氧基羰基中的基团所取代的不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环；
    其中R 11独立地代表卤素，羟基，烷氧基，卤代烷氧基，烷硫基，卤代烷硫基，氨基、烷基氨基，二烷基氨基，烷氧基羰基，未取代或取代的芳基、杂芳基；
    R 12代表H、烷基、卤代烷基、烷氧基、苯基、苯氧基或苄氧基；
    R 13代表H、烷基、卤代烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、烷基或烷氧基；R 32代表H、烷基或苄基；
    R 14代表烷基、卤代烷基；
    R 15代表H、烷基、甲酰基、烷基酰基、卤代烷基酰基、烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、烷基；
    R 17代表H、烷基、未取代或被卤素、烷基、烷氧基中的1-3个基团所取代的苯基；R 18代表H、烷基；或N＝CR 17R 18代表
    Figure PCTCN2018105679-appb-100002
    R 21、R 24分别独立地代表H或烷基；
    R 22、R 23分别独立地代表H或烷基；或者NR 22R 23代表不含有或含有氧原子、硫原子或其它氮原子的5-或6-元饱和或不饱和环；
    R 25代表烷基；
    R代表
    Figure PCTCN2018105679-appb-100003
  2. 根据权利要求1所述的一种取代的嘧啶-4-甲酸衍生物，其特征在于，
    X代表O、S、NR 1；
    Y代表未取代或被选自以下基团中的一种或多种取代基所取代的芳基、杂芳基：卤素，硝基，氰基，羟基，羧基，氨基，含有或不含有卤素的烷基、链烯基、炔基、环烷基、烷氧基、烷硫基、烷氧羰基、烷基磺酰基、烷基氨基、烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
    Z代表Cl或Br；
    Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C8烷基、C2-C8链烯基或C2-C8炔基，未取代或被卤素、C1-C8烷基、C1-C8烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
    Figure PCTCN2018105679-appb-100004
    -COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C8烷基氨基甲酰基，二C1-C8烷基氨基甲酰基，三C1-C8烷基甲硅烷基或二C1-C8烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C8烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷硫基、卤代C1-C8烷硫基、氨基、C1-C8烷基氨基、二C1-C8烷基氨基、C1-C8烷氧基羰基中的基团所取代的
    Figure PCTCN2018105679-appb-100005
    其中R 11独立地代表卤素，羟基，C1-C8烷氧基，卤代C1-C8烷氧基，C1-C8烷硫基，卤代C1-C8烷硫基，氨基，C1-C8烷基氨基，二C1-C8烷基氨基，C1-C8烷氧基羰基，未取代或被卤素、C1-C8烷基、C1-C8烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
    Figure PCTCN2018105679-appb-100006
    Figure PCTCN2018105679-appb-100007
    R 12代表H、C1-C18烷基、卤代C1-C8烷基、C1-C8烷氧基、苯基、苯氧基或苄氧基；
    R 13代表H、C1-C8烷基、卤代C1-C8烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C8烷基或C1-C8烷氧基；R 32代表H、C1-C8烷基或苄基；
    R 14代表C1-C8烷基、卤代C1-C8烷基；
    R 15代表H、C1-C8烷基、甲酰基、C1-C8烷基酰基、卤代C1-C8烷基酰基、C1-C8烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C8烷基；
    R 17代表H、C1-C8烷基、未取代或被卤素、C1-C8烷基、C1-C8烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C8烷基；或N＝CR 17R 18代表
    Figure PCTCN2018105679-appb-100008
    R 21、R 24分别独立地代表H或C1-C8烷基；
    R 22、R 23分别独立地代表H或C1-C8烷基；或者NR 22R 23代表
    Figure PCTCN2018105679-appb-100009
    Figure PCTCN2018105679-appb-100010
    R 25代表C1-C8烷基；
    R代表
    Figure PCTCN2018105679-appb-100011
  3. 根据权利要求1或2所述的一种取代的嘧啶-4-甲酸衍生物，其特征在于，
    X代表O、S、NH；
    Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C8烷基、C2-C8链烯基、C2-C8炔基、C3-C8环烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷氧羰基、C1-C8烷基磺酰基、C1-C8烷基氨基、C1-C8烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
    所述芳基选自苯基、萘基；所述杂芳基选自
    Figure PCTCN2018105679-appb-100012
    Figure PCTCN2018105679-appb-100013
    Z代表Cl或Br；
    Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C6烷基、C2-C6链烯基或C2-C6炔基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C6烷基氨基甲酰基，二C1-C6烷基氨基甲酰基，三C1-C6烷基甲硅烷基或二C1-C6烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C6烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、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、二C1-C6烷基氨基、C1-C6烷氧基羰基中的基团所取代的
    Figure PCTCN2018105679-appb-100014
    其中R 11独立地代表卤素，羟基，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，二C1-C6烷基氨基，C1-C6烷氧基羰基，未取代或被卤素、C1-C6烷基、C1-C6烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
    Figure PCTCN2018105679-appb-100015
    Figure PCTCN2018105679-appb-100016
    R 12代表H、C1-C14烷基、卤代C1-C6烷基、C1-C6烷氧基、苯基、苯氧基或苄氧基；
    R 13代表H、C1-C6烷基、卤代C1-C6烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C6烷基或C1-C6烷氧基；R 32代表H、C1-C6烷基或苄基；
    R 14代表C1-C6烷基、卤代C1-C6烷基；
    R 15代表H、C1-C6烷基、甲酰基、C1-C6烷基酰基、卤代C1-C6烷基酰基、C1-C6烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C6烷基；
    R 17代表H、C1-C6烷基、未取代或被卤素、C1-C6烷基、C1-C6烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C6烷基；或N＝CR 17R 18代表
    Figure PCTCN2018105679-appb-100017
    R 21、R 24分别独立地代表H或C1-C6烷基；
    R 22、R 23分别独立地代表H或C1-C6烷基；或者NR 22R 23代表
    Figure PCTCN2018105679-appb-100018
    Figure PCTCN2018105679-appb-100019
    R 25代表C1-C6烷基；
    R代表
    Figure PCTCN2018105679-appb-100020
  4. 根据权利要求1-3任意一项所述的一种取代的嘧啶-4-甲酸衍生物，其特征在于，
    X代表O、S、NH；
    Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷氧羰基、C1-C6 烷基磺酰基、C1-C6烷基氨基、C1-C6烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
    所述芳基选自苯基、萘基；所述杂芳基选自
    Figure PCTCN2018105679-appb-100021
    Figure PCTCN2018105679-appb-100022
    Z代表Cl或Br；
    Q代表硝基或NR 1R 2，其中R 1代表H，任选地被1-2个R 11取代的C1-C4烷基、C2-C4链烯基或C2-C4炔基，-COR 12，硝基，OR 13，SO 2R 14，NR 15R 16，N＝CR 17R 18，C1-C4烷基氨基甲酰基，二C1-C4烷基氨基甲酰基，三C1-C4烷基甲硅烷基或二C1-C4烷基膦酰基；R 2代表H，任选地被1-2个R 11取代的C1-C4烷基或-COR 12；或者NR 1R 2代表N＝CR 21NR 22R 23，N＝CR 24OR 25，未取代或被1-2个独立选自卤素、C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷硫基、卤代C1-C4烷硫基、氨基、C1-C4烷基氨基、二C1-C4烷基氨基、C1-C4烷氧基羰基中的基团所取代的
    Figure PCTCN2018105679-appb-100023
    其中R 11独立地代表卤素，羟基，C1-C4烷氧基，卤代C1-C4烷氧基，C1-C4烷硫基，卤代C1-C4烷硫基，氨基，C1-C4烷基氨基，二C1-C4烷基氨基，C1-C4烷氧基羰基，未取代或被卤素、C1-C4烷基、C1-C4烷氧基、硝基中的1-3个基团所取代的苯基、萘基、
    Figure PCTCN2018105679-appb-100024
    Figure PCTCN2018105679-appb-100025
    R 12代表H、C1-C8烷基、卤代C1-C4烷基、C1-C4烷氧基、苯基、苯氧基或苄氧基；
    R 13代表H、C1-C4烷基、卤代C1-C4烷基、苯基、苄基或CHR 31C(O)OR 32；R 31代表H、C1-C4烷基或C1-C4烷氧基；R 32代表H、C1-C4烷基或苄基；
    R 14代表C1-C4烷基、卤代C1-C4烷基；
    R 15代表H、C1-C4烷基、甲酰基、C1-C4烷基酰基、卤代C1-C4烷基酰基、C1-C4烷氧基羰基、苯基羰基、苯氧基羰基或苄氧基羰基；R 16代表H、C1-C4烷基；
    R 17代表H、C1-C4烷基、未取代或被卤素、C1-C4烷基、C1-C4烷氧基中的1-3个基团所取代的苯基；R 18代表H、C1-C4烷基；或N＝CR 17R 18代表
    Figure PCTCN2018105679-appb-100026
    R 21、R 24分别独立地代表H或C1-C4烷基；
    R 22、R 23分别独立地代表H或C1-C4烷基；或者NR 22R 23代表
    Figure PCTCN2018105679-appb-100027
    Figure PCTCN2018105679-appb-100028
    R 25代表C1-C4烷基；
    R代表
    Figure PCTCN2018105679-appb-100029
  5. 根据权利要求1-4任意一项所述的一种取代的嘧啶-4-甲酸衍生物，其特征在于，
    X代表O；
    Y代表未取代或被选自以下基团中的1种、2种或3种取代基所取代的芳基、杂芳基：F，Cl，Br，硝基，氰基，羟基，羧基，氨基，含有或不含有F、Cl、Br的C1-C4烷基、C2-C4链烯基、C2-C4炔基、C3-C6环烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷氧羰基、C1-C4烷基磺酰基、C1-C4烷基氨基、C1-C4烷基酰氧基；或者其中芳基苯环部分上的两个相邻取代基一起为-O(CH 2) nO-，n＝1或2；
    所述芳基选自苯基；所述杂芳基选自
    Figure PCTCN2018105679-appb-100030
    Z代表Cl；
    Q代表NH 2、NHMe、N(Me) 2、
    Figure PCTCN2018105679-appb-100031
    Figure PCTCN2018105679-appb-100032
    R代表
    Figure PCTCN2018105679-appb-100033
  6. 根据权利要求1-5任意一项所述的一种取代的嘧啶-4-甲酸衍生物，其特征在于，其结构式如下任意一种：
    Figure PCTCN2018105679-appb-100034
    Figure PCTCN2018105679-appb-100035
    Figure PCTCN2018105679-appb-100036
    Figure PCTCN2018105679-appb-100037
    Figure PCTCN2018105679-appb-100038
    Figure PCTCN2018105679-appb-100039
    Figure PCTCN2018105679-appb-100040
  7. 一种如权利要求1-6任意一项所述的取代的嘧啶-4-甲酸衍生物的制备方法，其特征在于，选自以下任意一种：
    (1)化学反应方程式如下：
    Figure PCTCN2018105679-appb-100041
    当X代表O时，Hal代表卤素，优选Cl或Br；所述反应在溶剂和碱的存在下进行，所述碱选自K 2CO 3、Na 2CO 3和Cs 2CO 3中的一种或两种以上；
    当X代表S时，Hal代表SH；X代表未取代或取代的N时，Hal代表未取代或相应取代的NH 2；所述反应在缩合剂、碱和溶剂的存在下进行，所述缩合剂为HOBt/EDCI.HCl或CDI，所述碱为TEA、DIPEA或其组合；
    优选地，所述反应温度均在0～40℃范围内，更优选20～30℃；或所述溶剂均为乙腈、DMF、二氯甲烷或1,2-二氯乙烷；
    (2)化学反应方程式如下：
    Figure PCTCN2018105679-appb-100042
    所述反应在卤化物和溶剂的存在下进行；优选地，所述卤化物为NCS、NBS、Cl 2、Br 2或NaClO/HCl；所述溶剂选自DMF、DMSO、DCM、THF、MeCN和DCE中的一种或多种混合；或所述反应温度在0-80℃范围内；
    (3)化学反应方程式如下：
    Figure PCTCN2018105679-appb-100043
    所述A代表溴、碘、氯、甲磺酰基；所述反应在Q-H和溶剂的存在下进行；优选地，所述溶剂选自DMF、DMSO、DCM、THF、MeCN和DCE中的一种或多种混合；或所述反应温度在-10-30℃范围内；
    (4)化学反应方程式如下：
    Figure PCTCN2018105679-appb-100044
    所述反应在催化剂、碱和溶剂的存在下进行；优选地，所述催化剂为Pd(dppf)Cl 2·CH 2Cl 2、 Pd(dppf)Cl 2或Pd(PPh 3) 4；所述碱为CsF、K 2CO 3、Na 2CO 3、K 3PO 4或KF；所述溶剂为有机溶剂/水，二者体积比优选为20/1-1/1，所述有机溶剂为二氧六环、甲苯、DMF或DMSO；或所述温度在80-150℃范围内。
  8. 一种除草组合物，其特征在于，包含与可农用辅料或载体混合的除草有效量的根据权利要求1-6任意一项所述的式I化合物。
  9. 一种防治不期望的植被的方法，其特征在于，包括经由叶面施用或水施用或者植被所在地施用使植被与除草有效量的根据权利要求1-6任意一项所述的式I化合物或者根据权利要求8所述的除草组合物接触，或者向土壤或水施用除草有效量的根据权利要求1-6任意一项所述的式I化合物或者根据权利要求8所述的除草组合物，从而防止植被出苗。
  10. 在稻、小麦或饲草存在条件下选择性苗后防治不期望的植被的方法，其特征在于，包括向所述不期望的植被施用除草有效量的根据权利要求1-6任意一项所述的式I化合物或者根据权利要求8所述的除草组合物。
PCT/CN2018/105679 2018-05-29 2018-09-14 一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途 WO2019227771A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810529799.1 2018-05-29
CN201810529799.1A CN108774179B (zh) 2018-05-29 2018-05-29 一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途

Publications (1)

Publication Number Publication Date
WO2019227771A1 true WO2019227771A1 (zh) 2019-12-05

Family

ID=64027929

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/105679 WO2019227771A1 (zh) 2018-05-29 2018-09-14 一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途

Country Status (2)

Country Link
CN (1) CN108774179B (zh)
WO (1) WO2019227771A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023010192A1 (pt) * 2021-08-02 2023-02-09 Eurofarma Laboratórios S.A. Compostos n-acilidrazônicos inibidores de nav 1.7 e/ou nav 1.8, seus processos de obtenção, composições, usos, métodos de tratamento destes e kits

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721546B (zh) * 2018-12-29 2020-11-20 青岛清原化合物有限公司 取代的嘧啶芳酯衍生物及其制备方法、除草组合物和应用
CN109942498A (zh) * 2019-05-07 2019-06-28 湖南省农业生物技术研究所 含腙结构的苯基嘧啶衍生物及其制备方法和应用
WO2020253696A1 (zh) * 2019-06-20 2020-12-24 青岛清原化合物有限公司 取代的吡啶甲酸吡啶亚甲基酯衍生物及其制备方法、除草组合物和应用
CN112841195B (zh) * 2019-11-12 2021-11-05 江苏清原农冠杂草防治有限公司 包含嘧啶羧酸苄酯类化合物的除草组合物及其应用
CN113273575B (zh) * 2020-02-19 2022-02-11 江苏清原农冠杂草防治有限公司 包含嘧啶羧酸苄酯类化合物的三元除草组合物及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1894220A (zh) * 2003-12-19 2007-01-10 纳幕尔杜邦公司 除草的嘧啶
CN102977036A (zh) * 2006-01-13 2013-03-20 美国陶氏益农公司 2-（多取代芳基）-6-氨基-5-卤代-4-嘧啶甲酸及其作为除草剂的用途
CN103254137A (zh) * 2007-08-30 2013-08-21 陶氏益农公司 2-(取代的苯基)-6-氨基-5-烷氧基、硫代烷氧基和氨基烷基嘧啶-4-羧酸衍生物及其作为除草剂的用途
CN103442570A (zh) * 2011-01-25 2013-12-11 陶氏益农公司 4-氨基-6-(取代的苯基)吡啶-2-甲酸的芳基烷基酯和6-氨基-2-(取代的苯基)-嘧啶-4-甲酸的芳基烷基酯及其作为除草剂的用途

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5847146A (en) * 1992-02-14 1998-12-08 Hoechst Schering Agrevo Gmbh N-heteroartyl-n'-(pyrid-2yl-sulfonyl) ureas, processes for their preparation, and their use as herbicides and plant growth regulators

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1894220A (zh) * 2003-12-19 2007-01-10 纳幕尔杜邦公司 除草的嘧啶
CN102977036A (zh) * 2006-01-13 2013-03-20 美国陶氏益农公司 2-（多取代芳基）-6-氨基-5-卤代-4-嘧啶甲酸及其作为除草剂的用途
CN103254137A (zh) * 2007-08-30 2013-08-21 陶氏益农公司 2-(取代的苯基)-6-氨基-5-烷氧基、硫代烷氧基和氨基烷基嘧啶-4-羧酸衍生物及其作为除草剂的用途
CN103442570A (zh) * 2011-01-25 2013-12-11 陶氏益农公司 4-氨基-6-(取代的苯基)吡啶-2-甲酸的芳基烷基酯和6-氨基-2-(取代的苯基)-嘧啶-4-甲酸的芳基烷基酯及其作为除草剂的用途

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023010192A1 (pt) * 2021-08-02 2023-02-09 Eurofarma Laboratórios S.A. Compostos n-acilidrazônicos inibidores de nav 1.7 e/ou nav 1.8, seus processos de obtenção, composições, usos, métodos de tratamento destes e kits

Also Published As

Publication number Publication date
CN108774179B (zh) 2020-01-21
CN108774179A (zh) 2018-11-09

Similar Documents

Publication Publication Date Title
WO2019227771A1 (zh) 一种取代的嘧啶-4-甲酸衍生物及其除草组合物和用途
KR102102067B1 (ko) 피라졸 화합물 또는 그의 염, 그의 제조 방법, 제초제 조성물 및 그의 용도
CN107629035B (zh) 一种吡唑酮类化合物或其盐、除草剂组合物及用途
RU2566760C2 (ru) Сложные арилалкиловые эфиры 4-амино-6-(замещенный фенил)пиколинатов и 6-амино-2-(замещенный фенил)-4-пиримидинкарбоксилатов и их применение в качестве гербицидов
CN109535070B (zh) 吡啶氧基羧酸酯衍生物及其制备方法、除草组合物和应用
CN109293640B (zh) 一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途
CN113402510B (zh) 一种稠环取代的芳香类化合物及其制备方法、除草组合物和应用
CN108586357B (zh) 取代的嘧啶甲酰基肟衍生物及其制备方法、除草组合物和应用
CN112778289B (zh) 一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用
CN109438333B (zh) 一种吡啶氧基羧酸酯衍生物及其制备方法、除草组合物和应用
KR102276572B1 (ko) 피라졸 화합물 또는 그의 염, 및 제조 방법, 제초제 조성물 및 그의 용도
CN111253333A (zh) N-(1,3,4-噁二唑-2-基)芳基甲酰胺类或其盐、制备方法、除草组合物和应用
CN107759581B (zh) 取代的苯甲酰基异恶唑类化合物或其互变异构体、盐、制备方法、除草组合物及应用
CN107674025B (zh) 一种4-苯甲酰吡唑类化合物及其制备方法和应用
CN113149975B (zh) 一种异噁唑啉甲酸肟酯类化合物及其制备方法、除草组合物和应用
JP2023551870A (ja) 除草性誘導体
JP2023139056A (ja) Ｒ－ピリジルオキシカルボン酸、その塩、そのエステル誘導体、その調製方法、その除草組成物及びその用途
CN109721546B (zh) 取代的嘧啶芳酯衍生物及其制备方法、除草组合物和应用
CN113024531B (zh) 一种含异噁唑啉的化合物及其制备方法、除草组合物和应用
CN112390759B (zh) 一种哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用
CN109400526B (zh) 吡啶氧基硫酯衍生物及其制备方法、除草组合物和应用
CN112441993B (zh) 一种取代的噻二嗪酮二氧化物及其制备方法、除草组合物和应用
RU2777594C2 (ru) Замещенное производное пиримидинилформилоксима, способ его получения, его гербицидная композиция и применение
CN109832277B (zh) 取代的含氮杂芳环甲酸亚胺酯衍生物及其制备方法、除草组合物和应用
CN107629046B (zh) 吡唑酮类化合物或其盐、除草剂组合物及用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18920926

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18920926

Country of ref document: EP

Kind code of ref document: A1