CN108774179B

CN108774179B - Substituted pyrimidine-4-formic acid derivative and weeding composition and application thereof

Info

Publication number: CN108774179B
Application number: CN201810529799.1A
Authority: CN
Inventors: 连磊; 征玉荣; 张辽宁; 刘鹏; 崔琦; 王法国; 刘娜
Original assignee: Qingdao Qing Yuan Compound Co Ltd
Current assignee: Qingdao Qing Yuan Compound Co Ltd
Priority date: 2018-05-29
Filing date: 2018-05-29
Publication date: 2020-01-21
Anticipated expiration: 2038-05-29
Also published as: WO2019227771A1; CN108774179A

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrimidine-4-formic acid derivative, a weeding composition thereof and application thereof. The substituted pyrimidine-4-carboxylic acid derivative has the following structural formula:

wherein, X represents O, S, unsubstituted or substituted NH; y represents an unsubstituted or substituted aryl, heteroaryl; z represents halogen; q represents nitro or NR₁R₂R represents

Description

Substituted pyrimidine-4-formic acid derivative and weeding composition and application thereof

Technical Field

The invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrimidine-4-formic acid derivative, a weeding composition thereof and application thereof.

Background

The control of weeds is a crucial link in the process of realizing high-efficiency agriculture, the current pyrimidine formic acid herbicides in the market are various, and WO2005/063721A1, WO2007/082076A1, US7,863,220B2, US7,300,907B2, US7,642,220B2 and US7,786,044B2 disclose certain 6-amino-2-substituted-pyrimidine-4-formic acid and derivatives thereof and application thereof as the herbicide. CN103442570A discloses a herbicide aralkyl ester of 4-aminopyridine-2-carboxylic acid and aralkyl ester of 6-amino-pyrimidine-4-carboxylic acid which can be used for controlling weeds.

Due to the ever-expanding market, the problems of weed resistance, the life span of the drugs and the economic efficiency of the drugs, and the increasing attention of people to the environment, scientists are required to continuously research and develop new herbicide varieties with high efficiency, safety, economy and different action modes.

Disclosure of Invention

Based on the above, the invention provides a substituted pyrimidine-4-formic acid derivative, a weeding composition and application thereof. The substituted pyrimidine-4-carboxylic acid derivatives and herbicidal compositions thereof have excellent herbicidal activity and crop selectivity.

The technical scheme adopted by the invention is as follows:

a substituted pyrimidine-4-carboxylic acid derivative having the formula:

in the formula (I), the compound is shown in the specification,

x represents O, S, unsubstituted or substituted NH;

y represents an unsubstituted or substituted aryl, heteroaryl;

z represents halogen;

q represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted alkyl, alkenyl or alkynyl, unsubstituted or substituted aryl, heteroaryl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈An alkylcarbamoyl group, a dialkylcarbamoyl group, a trialkylsilyl group or a dialkylphosphono group; r₂Represents H, optionally substituted by 1-2R₁₁Substituted alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅A 5-or 6-membered saturated or unsaturated ring which is unsubstituted or substituted by 1 to 2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, which ring contains no or no oxygen, sulfur or other nitrogen atom;

wherein R is₁₁Independently represent halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;

R₁₂represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, alkyl, haloalkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, alkyl or alkoxy; r₃₂Represents H, alkyl or benzyl;

R₁₄represents alkyl, haloalkyl;

R₁₅represents H, alkyl, formyl, alkanoyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, alkyl;

R₁₇represents H, alkyl, phenyl which is unsubstituted or substituted by 1 to 3 groups of halogen, alkyl and alkoxy; r₁₈Represents H,An alkyl group; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or alkyl;

R₂₂、R₂₃each independently represents H or alkyl; or NR₂₂R₂₃Represents a 5-or 6-membered saturated or unsaturated ring which contains no or no oxygen, sulfur or other nitrogen atoms;

R₂₅represents an alkyl group;

r represents

Preferably, X represents O, S, NR₁；

Y represents aryl, heteroaryl, unsubstituted or substituted by one or more substituents selected from the group consisting of: halogen, nitro, cyano, hydroxyl, carboxyl, amino, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, alkylamino, alkanoyloxy, which may or may not contain halogen; or wherein two adjacent substituents on the phenyl ring portion of the aryl group taken together are-O (CH)₂)_nO-, n-1 or 2;

z represents Cl or Br;

q represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, phenyl which is unsubstituted or substituted by 1 to 3 of halogen, C1-C8 alkyl, C1-C8 alkoxy and nitro, naphthyl,

-COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphineAn acyl group; r₂Represents H, optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅Unsubstituted or substituted by 1 to 2 radicals independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, phenyl, naphthyl, unsubstituted or substituted by 1-3 of halogen, C1-C8 alkyl, C1-C8 alkoxy and nitro,

R₁₂Represents H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, C1-C8 alkyl, halogeno-C1-C8 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, C1-C8 alkyl or C1-C8 alkoxy; r₃₂Represents H, C1-C8 alkyl or benzyl;

R₁₄represents C1-C8 alkyl, halogenated C1-C8 alkyl;

R₁₅represents H, C1-C8 alkyl, formyl, C1-C8 alkanoyl, halogeno-C1-C8 alkanoyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, C1-C8 alkyl;

R₁₇represents H, C1-C8 alkyl, unsubstituted or substituted by halogen, C1-C8Phenyl substituted by 1-3 of alkyl and C1-C8 alkoxy; r₁₈Represents H, C1-C8 alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or C1-C8 alkyl;

R₂₂、R₂₃each independently represents H or C1-C8 alkyl; or NR₂₂R₂₃Represents

R₂₅Represents a C1-C8 alkyl group;

r represents

More preferably, X represents O, S, NH;

y represents aryl, heteroaryl, unsubstituted or substituted by 1,2 or 3 substituents selected from: f, Cl, Br, nitro, cyano, hydroxyl, carboxyl, amino, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, C1-C8 alkanoyloxy with or without F, Cl, Br; or wherein two adjacent substituents on the phenyl ring portion of the aryl group taken together are-O (CH)₂)_nO-, n-1 or 2;

the aryl is selected from phenyl and naphthyl; the heteroaryl group is selected from

Z represents Cl or Br;

q represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphonyl; r₂Represents H, optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅Unsubstituted or substituted by 1 to 2 radicals independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, phenyl, naphthyl, unsubstituted or substituted by 1-3 of halogen, C1-C6 alkyl, C1-C6 alkoxy and nitro,

R₁₂Represents H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, C1-C6 alkyl, halogeno-C1-C6 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, C1-C6 alkyl or C1-C6 alkoxy; r₃₂Represents H, C1-C6 alkyl orA benzyl group;

R₁₄represents C1-C6 alkyl, halogenated C1-C6 alkyl;

R₁₅represents H, C1-C6 alkyl, formyl, C1-C6 alkanoyl, halogeno-C1-C6 alkanoyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, C1-C6 alkyl;

R₁₇represents H, C1-C6 alkyl, phenyl which is unsubstituted or substituted by 1-3 of halogen, C1-C6 alkyl and C1-C6 alkoxy; r₁₈Represents H, C1-C6 alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or C1-C6 alkyl;

R₂₂、R₂₃each independently represents H or C1-C6 alkyl; or NR₂₂R₂₃Represents

R₂₅Represents a C1-C6 alkyl group;

r represents

More preferably, X represents O, S, NH;

y represents aryl, heteroaryl, unsubstituted or substituted by 1,2 or 3 substituents selected from: f, Cl, Br, nitro, cyano, hydroxyl, carboxyl, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, C1-C6 alkanoyloxy with or without F, Cl, Br; or wherein two adjacent substituents on the phenyl ring portion of the aryl group taken together are-O (CH)₂)_nO-, n-1 or 2;

Z represents Cl or Br;

q represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C4 alkylcarbamoyl, di-C1-C4 alkylcarbamoyl, tri-C1-C4 alkylsilyl or di-C1-C4 alkylphosphonyl; r₂Represents H, optionally substituted by 1-2R₁₁Substituted C1-C4 alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅Unsubstituted or substituted by 1 to 2 radicals independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylthio, halogenated C1-C4 alkylthio, amino, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylthio, halogenated C1-C4 alkylthio, amino, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl, phenyl, naphthyl, unsubstituted or substituted by 1-3 of halogen, C1-C4 alkyl, C1-C4 alkoxy and nitro,

R₁₂Represents H, C1-C8 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, C1-C4 alkyl, halogeno-C1-C4 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, C1-C4 alkyl or C1-C4 alkoxy; r₃₂Represents H, C1-C4 alkyl or benzyl;

R₁₄represents C1-C4 alkyl, halogenated C1-C4 alkyl;

R₁₅represents H, C1-C4 alkyl, formyl, C1-C4 alkanoyl, halogeno-C1-C4 alkanoyl, C1-C4 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, C1-C4 alkyl;

R₁₇represents H, C1-C4 alkyl, phenyl which is unsubstituted or substituted by 1-3 of halogen, C1-C4 alkyl and C1-C4 alkoxy; r₁₈Represents H, C1-C4 alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or C1-C4 alkyl;

R₂₂、R₂₃each independently represents H or C1-C4 alkyl; or NR₂₂R₂₃Represents

R₂₅Represents a C1-C4 alkyl group;

r represents

Further preferably, X represents O;

y represents unsubstitutedOr aryl, heteroaryl substituted with 1,2 or 3 substituents selected from: f, Cl, Br, nitro, cyano, hydroxyl, carboxyl, amino, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkoxycarbonyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C1-C4 alkanoyloxy with or without F, Cl, Br; or wherein two adjacent substituents on the phenyl ring portion of the aryl group taken together are-O (CH)₂)_nO-, n-1 or 2;

the aryl group is selected from phenyl; the heteroaryl group is selected from

Z represents Cl;

q represents NH₂、NHMe、N(Me)₂、

R represents

The present invention includes herbicidal compositions comprising a herbicidally effective amount of a compound of formula I in admixture with an agriculturally acceptable adjuvant or carrier.

The invention also includes methods of using the compounds and compositions of the invention to kill or control undesirable vegetation by applying a herbicidal amount of the compound to the vegetation or to the locus of the vegetation, and to the soil before or after emergence of the vegetation or to irrigation or flooding water (flodwater).

The present invention also includes a method for selective post-emergence control of undesirable vegetation in the presence of rice, wheat or forage which comprises applying to the undesirable vegetation a herbicidally effective amount of a compound of the present invention or a herbicidal composition thereof. The invention also includes processes for preparing the compounds of the invention.

The invention also relates to a preparation method of the compound of the formula I, which is selected from any one of the following:

(1) the chemical reaction equation is as follows:

when X represents O, Hal represents halogen, preferably Cl or Br; the reaction is carried out in the presence of a solvent and a base selected from K₂CO₃、Na₂CO₃And Cs₂CO₃One or more than two of them.

When X represents S, Hal represents SH; when X represents unsubstituted or substituted N, Hal represents unsubstituted or correspondingly substituted NH₂(ii) a The reaction is carried out in the presence of a condensing agent, which is HOBt/edci. hcl or CDI, a base, which is TEA, DIPEA, or a combination thereof, and a solvent.

The solvent is acetonitrile, DMF, dichloromethane or 1, 2-dichloroethane; the reaction temperature is within the range of 0-40 ℃, and preferably 20-30 ℃.

(2) The chemical reaction equation is as follows:

the reaction is carried out in the presence of a halide and a solvent, the halide being selected according to the type of substituent Z in formula I, including but not limited to NCS, NBS, Cl₂、Br₂Or NaClO/HCl, etc.; the solvent is one or more of DMF, DMSO, DCM, THF, MeCN and DCE; the reaction temperature is in the range of 0-80 ℃.

(3) The chemical reaction equation is as follows:

a represents halogen (e.g., bromine, iodine, chlorine, etc.), methanesulfonyl, etc.; the reaction is carried out in the presence of Q-H and a solvent; the solvent is one or more of DMF, DMSO, DCM, THF, MeCN and DCE; the reaction temperature is in the range of-10 to 30 ℃.

(4) The chemical reaction equation is as follows:

the reaction is carried out in the presence of a catalyst, a base and a solvent, the catalyst being Pd (dppf) Cl₂·CH₂Cl₂、Pd(dppf)Cl₂Or Pd (PPh)₃)₄(ii) a The alkali is CsF and K₂CO₃、Na₂CO₃、K₃PO₄Or KF; the solvent is organic solvent/water, the volume ratio of the organic solvent to the water is 20/1-1/1, and the organic solvent is dioxane, toluene, DMF or DMSO; the temperature is in the range of 80-150 ℃.

The compounds of formula I have been found to be useful as pre-and post-emergence herbicides for rice and cereal planting regimes and pasture management programs. The term herbicide is used herein to mean an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. An herbicidally effective or vegetation controlling amount is an amount of active ingredient which causes an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation, and the like. The terms plants and vegetation include germinating seeds, emerging seedlings, above ground and below ground plant parts such as shoots, roots, tubers (tubers), rhizomes (rhizomes) and the like and established vegetation.

The compounds of the present invention exhibit herbicidal activity when applied directly to the plant or to the locus of the plant at any stage of growth or prior to planting or emergence. The effect measured depends on the plant species to be controlled, the stage of growth of the plant, the application parameters (the application parameters of dilution and spray droplet size), the particle size of the solid components, the environmental conditions at the time of use, the specific compounds used, the specific adjuvants and carriers used, the soil type, the water quality, etc., and the amount of chemicals 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 the compounds of formula I to relatively immature undesirable vegetation post-emergence 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). Preferred application rates are from 10 to 300 g/ha. For pre-emergence application, application rates of from 5 to 500g/ha are generally used. A preferred application rate is from 30 to 300 g/ha. Higher application rates are designed to generally produce non-selective control of a wide variety of undesirable vegetation. Lower rates of application typically produce selective control and can be used at the locus of the crop.

The herbicidal compounds of the present invention are often applied in combination with one or more other herbicides to control a wider variety of undesirable vegetation. When used in combination with other herbicides, the claimed compounds can be formulated with the other herbicide or herbicides, tank mixed with the other herbicide or herbicides or applied sequentially with the other herbicide or herbicides. Some herbicides that may be used in combination with the compounds of the present invention include: 2,4-D salts, esters and amines (2,4-Dsalts, esterands), acetochlor (acetochlor), acifluorfen (acifluorfen), alachlor (alchlor), amidosulfuron (amidosulfuron), aminopyralid (aminopyralid), aminotriazole (aminotriazole), ammonium thiocyanate (ammonium thiocyanide), aniliprifos, atrazine (atrazine), azimsulfuron (azimsulfuron), benfuresate (benfururon), bensulfuron-methyl (bensuluron-methyl), bentazone (bentazon), benthiacarb (benthiocarb), benzobicyclon (bentazone), pyraflufenap (bentazon), butachlor (butachlor), butachlor (fenamidosulfuron), fenacet (butachlor), fenamidosulfuron (fenamidosulfuron), fenamidosulfuron (fenfluridone), butafenacetron (fenamidosulfuron), butachlor (fenamidosulfuron-methyl), butachlor (fenamidosulfuron), butachlor (fenamidosulfuron (fenac), butachlor (fenamidosulfuron), fenamidosulfuron (fenamidopropyl (butachlor), butachlor (fenamidosulfuron (butachlor), butachlor (fenamidosulfuron), butachlor (fenamidosulfuron-methyl), butachlor (fenamidosulfuron), butachlor (fenamidopropyl (butachlor), butachlor (butachlor), butachlor (fenamidopropyl (butachlor), butachlor (butachlor), butachlor (fenamidopropyl (butachlor, Clomeprop (clomeprop), clopyralid (clopyralid), cloransulam-methyl (cloransulam), cyclosulfamuron (cyclosulfamuron), cycloxydim (cycloxydim), cyhalofop-butyl (cyhalofop-butyl), cumyluron (cumyluron), cumyluron (daimuron), flumetsulam (diclosulam), diflufenican (diflufenican), difluron (diflufenzopyr), dimerate (dimepiperate), metribuzin (dimethyron), diquat (diquat), dithiopyr (dithiopyr), EK2612, EPTC), penflufen (esprocarb), ET-751, ethoferon (ethysoferon), flumetfenuron (diethylflufen), pyrazofen (pyraflufen-ethyl), fenoxaprop-ethyl (flufen-ethyl), fenoxaprop-ethyl (isoxaprop-P), fenoxaprop-ethyl (isoxaprop-ethyl), fenoxaprop-P-ethyl (isoxaprop-ethyl), fenoxaprop-ethyl (fenoxaprop-P-ethyl), fenoxaprop-ethyl (fenoxaprop-ethyl), fenoxaprop-P), fenoxaprop-ethyl (fenoxaprop-ethyl), fenoxaprop-ethyl (fenoxaprop-ethyl), fenoxaprop-ethyl (fenoxaprop-ethyl, fenoxaprop, Flupyrosulfuron (flufenpyr), flufenacet (flufenacet), flupyridaphenthyl-ethyl (flufenpyr-ethyl), flumetsulam (flumetsulam), flumioxazin (flumioxazin), flupyrsulfuron-methyl (flupyrsulfuron), fluroxypyr (fluoxypyr), fomesafen (fomesafen), foramsulfuron (foralfuron), glufosinate (glufosinate), glufosinate-P (glufosinate-P), glyphosate (glyphosate), halosulfuron-methyl (halosulfuron-methyl), haloxyfop (haloxyfop-R), haloxyfop (R-methyl), imazaquin (imazaquin), imazamox (imazamox), imazapyr (imazamox), imazamox (imaz), imazapyr (imazamox (imaz), imazamox (imazamox) and imazamox-P (imazamox) are provided in a, Isoxaben (isoxaben), 2-methyl-4-chloro (MCPA), 2-methyl-4-chlorobutyric acid (MCPB), mefenacet (mefenacet), mesosulfuron-methyl-amino acid (mesosulfuron), mesotrione (mesotrione), metamifop (metamifop), diether-clopyrazosulfuron (metazosulfuron), metolachlor (metolachlor), metsulfuron-methyl-amino acid (metsuluron), molinate (molinate), monosulfuron (monosulfuron), arsonium monosodium (MSMA), orthosulfamuron (orthosulfamuron), oryzalin (oryzalin), oxadiargyl (oxadiargyl), oxaziclomefone (oxaziclomefon), ethoxyfurazafen (ethoxyfen), metoclopramide (oxyphenbutazone), penoxsulam (metosulam), penoxsulam (penoxsulam), pen, Propachlor, propanil, propisochlor, propyzamide, pyrazosulfuron (propazamide), azimilion (propylisulfuron), prosulfuron (prosulfuron), pyrabuticarb, pyraclonil (pyraclonil), pyrazosulfuron (pyrazogyl), pyrazosulfuron (pyrazosulfuron-ethyl), pyrazoxazole (pyrazosulfuron), pyribenzoxim (pyribenzoxim), pyridate (pyribenzonate), pyrithiobac-methyl (pyrithiobac-methyl), pyriminosulf-fen, flusulfuron-methyl (pyrithion-methyl), pyrithiobac-sodium (pyrithiobac-methyl), pyrithiobac-methyl (pyrithion-methyl), pyrithion (pyrithion-ethyl), pyrithion (S-ethyl), pyrithion (S-methyl), pyrithiobac-sodium (pyrithion-ethyl), pyrithiobac (pyrithion-methyl), pyrithion (pyrithion-ethyl), pyrithion (S-ethyl-sodium (S-methyl), pyrithion (pyrithion, pyrithion-ethyl), pyrithion (pyrithion, pyrithiobac (pyrithion, pyrithion (S-methyl), pyrithion (pyrithion, pyrithion (S-methyl), pyrithion (pyrithion, pyrithiobac (pyrithio, Thiazopyr, thiobencarb, triclopyr and amines, trifluralin, trinexapac-ethyl, triflusulfuron and other 4-amino-6- (substituted phenyl) pyridine-2-carboxylic acids and 6-amino-2- (substituted phenyl) -pyrimidine-4-carboxylic acids and salts and esters thereof.

The compounds of the invention can additionally be used to control undesirable vegetation in a wide variety of crops which have been rendered tolerant or resistant to the compounds of the invention or to other herbicides by genetic manipulation (geneticanipulation) or by mutation and selection. The herbicidal compounds according to the invention can also be used in combination with glyphosate (glyphosate), glufosinate (glufosinate), dicamba (dicamba), imidazolinones (imidazolinones), aryloxyphenoxypropionates (aryloxyphenopionates) or 2,4-D on glyphosate-, glufosinate-, dicamba-, imidazolinone-, aryloxyphenoxypropionates-or 2, 4-D-tolerant crops. It is generally preferred to use the compounds of the invention in combination with herbicides which are selective for the crop to be treated at the application rates employed and which complement the spectrum of weeds controlled by these compounds. It is generally further preferred to apply the compounds of the invention and other supplementary herbicides simultaneously, either as a combined preparation or as a tank mix. Similarly, the herbicidal compounds of the present invention may be used in acetolactate synthase inhibitor-tolerant crops in combination with acetolactate synthase (ALS) inhibitors or in 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors.

The compounds of the invention can generally be used in combination with known herbicide safeners, to enhance their selectivity, such known herbicide safeners are, for example, benoxacor (benoxacor), benthiazole (benthiaecarb), brassinolide (brassinolide), cloquintocet (mexyl), chloracetearonitrile (cyclotrinil), cyprosulfamide (cyprosulfamide), cumarone (daimuron), dichlormid (dichlormid), dicyclonon, dietholate, dimepiperate (dimepiperate), disulfoton (disulphoton), fenchlorazole-ethyl (fenchlorazole-ethyl), fenpropidin (fenclorim), fluquinate (fluxazole), fluxofenamate (fluxofenim), furazolate (furilazole), hypersensitive proteins (proteazoles), isoxadifen-ethyl (isoxadifen-ethyl), pyraclostrobin (pyrazolate), pyraclonil (phthalazinone), benzofenapyr-60, benzofenapyr-ethyl (benzoxazole-ethyl), benzofenamate (isoxadifenox-ethyl), benzofenamate (phthalic anhydride (benzoxazole, benzofenamate, naphyl-60, naphthalimide (benzoxazole, benzofenate (benzoxazole, naphalonil (naphthalene-48). The compounds of the invention are additionally useful for controlling undesirable vegetation in a wide variety of crops which have been rendered tolerant or resistant to the compounds of the invention or to other herbicides by genetic manipulation or by mutation and selection. For example, corn, wheat, rice, soybean, sugar beet, cotton, canola and other crops that have been tolerant or resistant to compounds that are acetolactate synthase inhibitors in susceptible plants may be treated. Various glyphosate-and glufosinate-resistant crops may also be treated, either alone or in combination with these herbicides. Some crops have developed tolerance to auxinic 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 have been tolerant to herbicides that inhibit 4-hydroxyphenylpyruvate dioxygenase, and these herbicides can be used to treat such resistant crops.

Although it is possible to employ the compounds of formula I directly as herbicides, it is preferred to use them in the form of mixtures comprising a herbicidally effective amount of the compound and at least one agriculturally acceptable adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to the valuable crop, in particular at the concentrations used in the application of the compositions for selective weed control in the presence of the crop, and should not react chemically with the compounds of the formula I or with other composition constituents. Such mixtures may be designed for direct application to the weeds or their locus, or may be concentrates or formulations which are normally diluted with additional carriers and adjuvants prior to application. They may be solids, such as dusts, granules, water-dispersible granules or wettable powders, or liquids, such as emulsifiable concentrates, solutions, emulsions or suspensions. They may also be provided as a pre-mix or tank mix.

Suitable agriculturally acceptable adjuvants and carriers for preparing the herbicidal mixtures of the present invention are well known to those skilled in the art. Some of these adjuvants include, but are not limited to, crop oil concentrate (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylate; benzyl cocoalkyl dimethyl quaternary ammonium salt; a blend of petroleum hydrocarbon, alkyl ester, organic acid and anionic surfactant; C9-C11 alkyl polyglycoside; a phosphorylated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylates; di-sec-butylphenol EO-PO block copolymers; a methyl terminated polysiloxane; nonylphenol ethoxylate + urea ammonium nitrate; an emulsified methylated seed oil; tridecanol (synthetic) ethoxylate (8 EO); tallow amine ethoxylate (15 EO); PEG (400) dioleate-99.

Liquid carriers that can be used include water and organic solvents. The organic solvent used typically includes, but is 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 and the like; and esters of the above vegetable oils; esters of monohydric alcohols or dihydric, trihydric or other lower polyhydric alcohols (containing 4 to 6 hydroxyl groups), such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, dioctyl succinate, dibutyl adipate, dioctyl phthalate, etc.; esters of mono-, di-, and polycarboxylic acids, and the like. Specific organic solvents include toluene, xylene, naphtha (petrolemma), crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, tetrachloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerol, N-methylpyrrolidin-2-one, N-dimethyl alkylamide, dimethyl sulfoxide, liquid fertilizers, and the like. Water is generally the carrier of choice for dilution of the concentrate.

Suitable solid carriers include talc, pyrophyllite clay (pyrophyllite), silica, activated clay (attapulgus), kaolin, diatomaceous earth (kieselguhr), chalk, diatomaceous earth (diatomous earth), lime, calcium carbonate, bentonite, Fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice (pumice), wood flour, walnut shell flour, lignin, and the like.

It is generally desirable to incorporate one or more surfactants into the compositions of the present invention. Such surfactants are beneficially used in solid and liquid compositions, especially compositions designed to be diluted with a carrier prior to application. The surfactants may be anionic, cationic or nonionic in nature and may be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants which are commonly used in the field of formulations and which can also be used in the present formulations are described in particular (interpallia) in "Mc Cutcheon's Detergents and Emulsifiers Annual," MC Publishing Corp., Ridgewood, New Jersey,1998and in "Encyclopedia of Surfactants," Vol.I-III, Chemical Publishing Co., NewYork, 1980-81. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate (diethanolammonium lauryl sulfate); alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C16 ethoxylate; soaps, such as sodium stearate; alkyl naphthalene-sulfonates, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl-ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of monoalkyl phosphates and salts of dialkyl phosphates; vegetable or seed oils, such as soybean oil, rapeseed/canola 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 and the like; and esters, especially methyl esters, of the above vegetable oils.

Typically, some of these materials, such as vegetable or seed oils and esters thereof, are used interchangeably as an agriculturally acceptable adjuvant, as a liquid carrier, or as a surfactant.

Other adjuvants commonly used in agricultural compositions include compatibilizers, defoamers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration aids, stickers, dispersants, thickeners, antifreeze, biocides, and the like. The compositions may also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides, and the like, and may be formulated with liquid fertilizers or solid particulate fertilizer carriers such as ammonium nitrate, urea, and the like.

The concentration of the active ingredient in the herbicidal compositions of the present invention is generally from 0.001 to 98% by weight. Concentrations of 0.01 to 90 wt.% are often used. In compositions designed for use as concentrates, the active ingredient is generally present at a concentration of from 5 to 98% by weight, preferably from 10 to 90% by weight. The composition is typically diluted with an inert carrier (e.g., water) prior to administration. The diluted compositions which are usually applied to the weeds or to the locus of the weeds generally contain from 0.0001 to 1% by weight of active ingredient and preferably contain from 0.001 to 0.05% by weight of active ingredient.

The compositions of the present invention may be applied to weeds or their locus by the use of conventional ground or air dusters, sprayers and granule applicators (grannuleapplicators), by addition to irrigation or paddy flooding water (paddy flood water) and by other conventional means known to those skilled in the art.

Detailed Description

The following examples are presented to illustrate various aspects of the invention and should not be viewed as limiting the claims.

TABLE 1 Structure of Compounds and their uses¹HNMR data

Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic route are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.

The following process examples are provided to facilitate a further understanding of the methods of preparation of the invention, and the particular materials, species and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. The reagents used in the synthesis of the compounds indicated in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.

Examples of representative compounds are as follows:

1. synthesis of Compound 1

At room temperature, a 10mL single-mouth eggplant-shaped bottle is added with a compound II-1 (1 equivalent),

(1.1 equiv.), potassium carbonate (1.5 equiv.) and DMF (10V, 1mL DMF solvent per g substrate, see below), were stirred at room temperature overnight. TLC detection reaction is completed, water is added into the reaction system, ethyl acetate is used for extraction, organic phase is concentrated and is separated by column chromatography silica gel (100 meshes to 200 meshes), and the product is obtained with the yield of 80%.

2. Synthesis of Compound 6

In a 50 ml single neck flask was added 20 ml of DMF followed by the addition of compound II-2 (1g, 2.4mmol, 1eq) and NCS (481.7mg, 3.61mmol, 1.5eq) in that order and stirring at room temperature for 4 hours. The TLC detection reaction was complete. The reaction solution was poured into 20 ml of water, extracted three times with ethyl acetate, the organic phase was washed three times with saturated saline, dried and then spin-dried, and purified by column chromatography to give compound 6(0.9g, 83% yield) (white solid).

3. Synthesis of Compound 15

To 20 mL of DCM were added 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) in that order, and after stirring at room temperature for 30min, the mixture was added

(0.51g, 3.6mmol,1.2eq), and the reaction was stirred for 12 hours. And (5) detecting by TLC, and finishing the reaction. The reaction was poured into 20 ml of water, separated, the aqueous phase extracted three times with 20 ml of DCM, the organic phase dried, spun dried and isolated by column chromatography to give compound 15(1.1g, 80% yield) (white solid).

4. Synthesis of Compound 51

To 20 ml of DMF were added II-3 (1g,3.0mmol, 1.0eq) and CDI (0.84g,6.0mmol,2.0eq), and the mixture was stirred at room temperature for 30min and then added

(0.75g,3.6mmol,1.2eq), and the reaction was stirred for 12 hours. And (5) detecting by TLC, and finishing the reaction. The reaction solution was poured into 20 ml of water, extracted with 30 ml of ethyl acetate, the aqueous phase was extracted twice with 30 ml of ethyl acetate, the organic phase was dried, spun-dried and isolated by column chromatography to give compound 51(1.4g, 85% yield) (white solid).

5. Synthesis of Compound 105

20 ml of DMSO was added to a 100 ml three-necked flask at room temperature, followed by addition of Compound II-4 (1g, 2.0mmol, 1eq)And stirred to dissolve. Then slowly bubbling NH into the solution₃. Stopping introducing NH after TLC detection of complete reaction of raw materials₃. The reaction solution was poured into 20 ml of water, extracted three times with ethyl acetate, the organic phase was washed three times with saturated saline, dried and then spin-dried, and separated and purified by column chromatography to give compound 105(0.75g, 78% yield) (white solid).

6. Synthesis of Compound 126

Compound II-5 (1g,3.0mmol, 1eq) was added sequentially at room temperature in a 50 ml single-necked flask,

(674mg, 3.30mmol, 1.1eq), CsF (911mg, 6mmol, 2eq), 1, 4-dioxane and water (V/V ═ 4/1). N is a radical of₂After three replacements Pd (dppf) Cl was added₂·CH₂Cl₂(122mg, 0.15mmol, 0.05eq) and then heated to 120 ℃ with stirring for 12 hours. The TLC detection raw material basically completely reacts. The reaction solution was poured into 20 ml of water, extracted three times with ethyl acetate, the organic phase was dried and then spin-dried, and purified by column chromatography to give compound 126(0.7g, 51% yield) (yellow solid).

7. Synthesis of Compound 131

To 20 ml of DMF was added II-6 (1.0g,3.0mmol, 1.0eq),

(0.5g,3.0 mmole 1.0eq) and K₂CO₃(0.67g,6.0mmol,2.0eq), and stirred at room temperature for 12 hours. And (5) detecting by TLC, and finishing the reaction. Pouring the reaction solution into 20 ml of water, adding 30 ml of ethyl acetate for extraction, extracting the water phase twice with 30 ml of ethyl acetate, drying the organic phase, spin-drying, and separating by column chromatography to obtain the compound 131(1.4g, 87% yield)Rate) (white solid).

Evaluation of biological Activity:

the activity level criteria for harmful plant destruction (i.e. growth control rate) are as follows:

10 level: death is complete;

and 9, stage: the growth control rate is more than 85 percent;

and 8, stage: the growth control rate is more than 70%;

and 7, stage: the growth control rate is more than 60 percent;

and 6, level: the growth control rate is more than 50%;

and 5, stage: the growth control rate is more than 40%;

4, level: the growth control rate is more than 30 percent;

and 3, level: the growth control rate is more than 20 percent;

and 2, stage: the growth control rate is 5-20%;

level 1: the growth control rate is below 5%;

level 0: no effect is produced.

The growth control rate is the fresh weight control rate.

Post-emergence test experiments: placing monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil to make the plastic pot grow in a good greenhouse environment, treating test plants in a 4-5 leaf period after sowing for 2-3 weeks, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with certain water to a certain concentration, and spraying the solution onto the plants by a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in Table 2.

TABLE 2 post emergence weed test (15 g/hectare)

Comparative experiment:

(1) the test conditions after seedling stage were the same as above, and the results are shown in tables 3 to 4.

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 CompoundsSubstance J:

control compound K:

control compound L:

control compound M:control compound N:

TABLE 3 comparative experimental results (3 g/hectare)

Number of Compounds	Galium aparine	Capsella bursa-pastoris	Descurainia sophia	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

TABLE 4 comparative experiment (5 g/hectare)

Number of Compounds	Wild rape	Indian rorippa herb	Veronica didyma Tenore	Herb of Japanese Galium
					1	10	9	10	10
K	1	3	3	2

Note: rape, rorippa and Veronica didyma Tenore are important weeds which are difficult to control in China and main wheat fields all over the world, and particularly, the difficulty of control is increased after the ALS inhibitor generally generates drug resistance.

(2) The stem and leaf spraying safety and activity test results of the direct seeding rice at the 2-3 leaf stage, the corn at the 2-3 leaf stage and the barnyard grass at the 3 leaf stage are shown in the table 5.

TABLE 5 safety and Activity test results (30 g/ha)

Number of Compounds	Rice (Oryza sativa L.) with improved resistance to stress	Corn (corn)	Wheat (Triticum aestivum L.)	Barnyard grass
					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

As can be seen from the above table, the compounds of the present invention have significantly higher control effect and crop selectivity than the control compounds with different parent rings or substituents.

Pre-emergence test experiment:

placing the monocotyledon and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into solution with a certain concentration by using a certain amount of water, and immediately spraying the solution after sowing. After the application, the mixture is cultured in a greenhouse for 4 weeks, and after 3 weeks, experimental results are observed, so that the medicament has a superior effect under the measurement of 250 g/hectare, particularly on weeds such as cockspur grass, kukukuh, piemarker and the like, and a plurality of compounds have good selectivity on corn, wheat, rice, soybean and rape.

Experiments show that the compound generally has better weed control effect, particularly has good effect on main broadleaf weeds such as abutilon, bidens bipinnata and the like widely occurring in corn fields, paddy fields and wheat fields, and has good commercial value. In particular, we pay attention to the extremely high activity of broadleaf weeds such as maidenhair, cleavers, chickweed and the like which have resistance to ALS inhibitors.

Evaluating the safety of transplanted rice and the weed control effect of paddy field:

after the paddy field soil was filled in a tank of 1/1,000,000 hectare, seeds of barnyard grass, japanese iris, bidens tripartita and edible tulip were sown, and soil was lightly covered thereon. Standing in a state of water storage depth of 0.5-1 cm in a greenhouse, and implanting tuber of Pseudobulbus Cremastrae seu pleiones in the next or 2 days. Thereafter, the water storage depth was maintained at 3 to 4 cm, and an aqueous dilution of a wettable powder or a suspension, which was prepared by a usual formulation method, was dropped uniformly by a pipette at a time point when barnyard grass, japanese iris, or burley reached 0.5 leaf and the bulb reached the primary leaf stage to obtain a predetermined amount of active ingredient.

In addition, after filling the 1/1,000,000 hectare pot with paddy field soil, leveling is carried out to ensure that the water storage depth is 3-4 cm, and the rice (japonica rice) at the 3-leaf stage is transplanted with the transplanting depth of 3 cm on the next day. The compound of the present invention was treated on the 5 th day after transplantation in the same manner as described above.

The growth states of barnyard grass, Chinese iris, bidens tripartita and edible tulip on the 14 th day after the treatment with the medicament and the growth states of rice on the 21 th day after the treatment with the medicament are respectively observed by naked eyes, the weeding effect is evaluated according to the activity standard level of 1-10, and tests show that a plurality of compounds of the invention have excellent activity and selectivity, particularly for the edible tulip and the barnyard grass.

Note: the seeds of barnyard grass, Chinese iris, edible tulip and bidens tripartita are all collected from Heilongjiang in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.

Meanwhile, a plurality of tests show that the compound and the composition thereof have good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, festuca arundinacea, bluegrass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims

1. A substituted pyrimidine-4-carboxylic acid derivative having the formula:

wherein X represents O;

y represents a phenyl group unsubstituted or substituted with 1 or 2 substituents selected from the group consisting of: halogen;

z represents halogen;

q represents NH₂Or

R represents

2. A substituted pyrimidine-4-carboxylic acid derivative according to claim 1,

y represents a phenyl group unsubstituted or substituted with 1 or 2 substituents selected from the group consisting of: F. cl or Br;

z represents Cl or Br.

3. A substituted pyrimidine-4-carboxylic acid derivative according to claim 1 or 2,

q represents NH₂。

4. A substituted pyrimidine-4-carboxylic acid derivative selected from any one of:

5. a process for the preparation of substituted pyrimidine-4-carboxylic acid derivatives as claimed in any one of claims 1 to 4, selected from any one of the following:

(1) the chemical reaction equation is as follows:

when X represents O, Hal represents halogen; the reaction is carried out in the presence of a solvent and a base selected from K₂CO₃、Na₂CO₃And Cs₂CO₃One or more than two of the above;

when X represents S, Hal represents SH;

when X represents NH, Hal represents NH₂(ii) a The reaction is carried out in the presence of a condensing agent, a base and a solvent, wherein the condensing agent is HOBt/EDCI.HCl or CDI, and the base is TEA, DIPEA or a combination thereof;

(2) the chemical reaction equation is as follows:

the reaction is carried out in the presence of a halide and a solvent;

(3) the chemical reaction equation is as follows:

a represents bromine, iodine, chlorine, methylsulfonyl; the reaction is carried out in the presence of Q-H and a solvent;

(4) the chemical reaction equation is as follows:

the reaction is carried out in the presence of a catalyst, a base and a solvent;

wherein the group X, Y, Z, Q, R is as defined in any one of claims 1 to 4.

6. The process for preparing substituted pyrimidine-4-carboxylic acid derivatives according to claim 5,

in the step (1), when X represents O, Hal represents Cl or Br; the reaction temperature is within the range of 0-40 ℃; or the solvents are acetonitrile, DMF, dichloromethane or 1, 2-dichloroethane;

in the step (2), the halide is NCS, NBS, Cl₂、Br₂Or NaClO/HCl; the solvent is one or more of DMF, DMSO, DCM, THF, MeCN and DCE; or the reaction temperature is in the range of 0-80 ℃;

the solvent in the step (3) is one or more selected from DMF, DMSO, DCM, THF, MeCN and DCE; or the reaction temperature is in the range of-10 to 30 ℃;

in the step (4), the catalyst is Pd (dppf) Cl₂·CH₂Cl₂、Pd(dppf)Cl₂Or Pd (PPh)₃)₄(ii) a The alkali is CsF and K₂CO₃、Na₂CO₃、K₃PO₄Or KF; the solvent is organic solvent/water; or the temperature is in the range of 80-150 ℃.

7. The process for preparing a substituted pyrimidine-4-carboxylic acid derivative according to claim 6, wherein the reaction temperature in step (1) is in the range of 20 to 30 ℃; the volume ratio of the organic solvent to the water in the step (4) is 20/1-1/1, and the organic solvent is dioxane, toluene, DMF or DMSO.

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 4 in admixture with an agriculturally acceptable adjuvant or carrier.

9. A method of controlling undesirable vegetation which comprises contacting vegetation with an herbicidally effective amount of a compound according to any one of claims 1 to 4 or an herbicidal composition according to claim 8, or applying to soil or water an herbicidally effective amount of a compound according to any one of claims 1 to 4 or an herbicidal composition according to claim 8, via foliar or water application or locus application of vegetation, thereby preventing emergence of vegetation.

10. A method for the selective postemergence control of undesirable vegetation in the presence of rice, wheat or forage, which comprises applying to the undesirable vegetation an herbicidally effective amount of a compound according to any one of claims 1 to 4 or an herbicidal composition according to claim 8.