WO2019227771A1 - Substituted pyrimidine-4-formic acid derivative, herbicidal composition and use thereof - Google Patents

Abstract

Disclosed are a substituted pyrimidine-4-formic acid derivative and an herbicidal composition thereof. The pyrimidine-4-formic acid derivative and the herbicidal composition thereof have excellent herbicidal activity and crop selectivity.

Description

Substituted pyrimidine-4-carboxylic acid derivative and herbicidal composition and use thereof Technical field

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.

Background technique

The control of weeds is a crucial link in the process of achieving efficient agriculture. At present, there are various types of 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.

Due to the ever-expanding market, resistance to weeds, the lifespan of drugs and the economics of drugs and people's increasing attention to the environment, scientists need to continue to develop new high-efficiency, safe, economic, and different functions Way of herbicide variety.

Summary of the Invention

Based on this, 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.

The technical scheme adopted by the present invention is as follows:

A substituted pyrimidine-4-carboxylic acid derivative whose structural formula is as follows:

Where

X represents O, S, unsubstituted or substituted NH;

Y represents unsubstituted or substituted aryl and heteroaryl;

Z represents halogen;

Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, alkyl, alkenyl or alkynyl optionally substituted with 1-2 R ₁₁ , unsubstituted or substituted aryl, heteroaryl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkyl Phosphono; R ₂ represents H, an alkyl optionally substituted with 1-2 R ₁₁ or -COR ₁₂ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , not Substituted or substituted by 1-2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl Substituted 5- or 6-membered saturated or unsaturated rings which do not contain or contain oxygen, sulfur or other nitrogen atoms;

Wherein 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;

R stands for

Preferably, X represents O, S, NR ₁ ;

Y represents an aryl group or a heteroaryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of: halogen, nitro, cyano, hydroxyl, carboxyl, amino, with or without halogen Alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, alkylamino, alkylacyloxy; or the Two adjacent substituents together are -O (CH ₂ ) _n O-, n = 1 or 2;

Z represents Cl or Br;

Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with 1-2 R ₁₁ , unsubstituted or Phenyl substituted with halogen, C1-C8 alkyl, C1-C8 alkoxy, 1-3 groups in nitro, naphthyl,

-COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C8 alkylcarbamoyl, di C1-C8 alkylcarbamoyl, tri-C1-C8 Alkylsilyl or di-C1-C8 alkylphosphono; R ₂ represents H, C1-C8 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C8 alkyl, 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 group substituted

Where 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;

R stands for

More preferably, X represents O, S, NH;

Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 alkylacyloxy; or wherein two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

Z represents Cl or Br;

Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, optionally substituted by 1-2 R ₁₁ , -COR ₁₂ , Nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylformyl Silane or di-C1-C6 alkylphosphono; R ₂ represents H, C1-C6 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkane Substituted by groups in thio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl

Where 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;

R stands for

More preferably, X represents O, S, NH;

Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 with or without F, Cl, Br , C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, C1-C6 alkylacyloxy; or where two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

Z represents Cl or Br;

Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, optionally substituted with 1-2 R ₁₁ , -COR ₁₂ , Nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C4 alkylcarbamoyl, di-C1-C4 alkylcarbamoyl, tri-C1-C4 alkylformyl Silane or di-C1-C4 alkylphosphono; R ₂ represents H, C1-C4 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkane Substituted by groups in thio, halo C1-C4 alkylthio, amino, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl

Where 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;

R stands for

Further preferably, X represents O;

Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 with or without F, Cl, Br , C1-C4 alkoxycarbonyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C1-C4 alkylacyloxy; or where two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

Z stands for Cl;

Q represents NH ₂ , NHMe, N (Me) ₂ ,

R stands for

The present invention includes 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:

(1) The chemical reaction equation is as follows:

When X represents O, 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.

When X represents S, Hal represents SH; when X represents unsubstituted or substituted N, Hal represents unsubstituted or correspondingly substituted NH ₂ ; the reaction is performed in the presence of a condensing agent, a base, and a solvent, and the condensing agent It is HOBt / EDCI.HCl or CDI, and the base is TEA, DIPEA, or a combination thereof.

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.

(2) The chemical reaction equation is as follows:

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.

(3) The chemical reaction equation is as follows:

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.

(4) The chemical reaction equation is as follows:

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.

Compounds of formula I have been found to be useful as pre-emergent and post-emergent herbicides for rice and cereal planting systems and forage management programs. The term 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. The term 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. For pre-emergence application, 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. When used in combination with other herbicides, 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. Some herbicides that can be used in combination with the compounds of the present invention include: 2,4-Dip salts, esters and amines (2,4-Dsalts, estersandamines), acetochlor, acifluorfen, Alachlor, amidosulfuron, aminopyralid, aminotriazole, ammoniumthiocyanate, anilifos, atrazine, tetrazolidine Azimsulfuron, benfuresate, bensulfuron-methyl, bentazon, benthiocarb, benzobicyclon, benzofenap ), Bifenox, bispyribac-sodium, bromobutide, butachlor, cafenstrole, oxamethoxone-ethyl (carfentrazone-ethyl), chlodinafop-propyrgyl, chlorimuron, chlorpropham, cinosulfuron, clethodim, clomazone , Clomeprop, clopyralid, cloransulam-methyl, Cyclosulfamuron, cycloxydim, cyhalofop-butyl, cumyluron, daimuron, diclosulam, pyridoflurane Diflufenican, diflufenzopyr, dimepiperate, dimethametryn, diquat, dithiopyr, EK26112, ephedrine (EPTC) ), Esprocarb, ET-751, ethoxysulfuron, ethbenzanid, fenoxaprop, fenoxaprop-ethyl, oxazol Fenoxaprop-ethyl + isoxadifen-ethyl, fentrazamide, flazasulfuron, florasulam, fluazifop, essence Fluazifop-P-butyl, flucetosulfuron, flufenacet, flufenpyr-ethyl, fluoxafop-P-butyl Flumetsulam, flumioxazin, flupyrsulfuron, fluroxypyr, fomesafe n), foramsulfuron, glufosinate, glufosinate-P, glyphosate, halosulfuron-methyl, flupiron Haloxyfop-methyl, haloxyfop-R, haloxyfop-R-methyl, imazamethabenz, imazamox, memidazole Imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, ioxynil, halogen Ipfencarbazone, isoxaben, 2 methyl 4 chloride (MCPA), 2 methyl 4 chlorobutyric acid (MCPB), mefenacet, mesosulfuron demethyl acid (mesosulfuron), mesotrione, metamifop, metazosulfuron, metolachlor, metosulam, formazan Metsulfuron, molinate, monosulfuron, monosodium monosodium (MSMA), orthosulfamuron, alfsulfuron (o ryzalin), oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, paraquat, pendimethalin, Penoxsulam, penoxsulam, pentoxazone, pethoxamid, picloram, piperophos, pretilachlor, mesotrione (profoxydim), prohexadione-calcium, propachlor, propanil, propisochlor, propyzamide, imazasulfuron ( propyrisulfuron, prosulfuron, pyrabuticarb, pyraclonil, pyrazogyl, pyrazolilynate, pyrazosulfuron-ethyl, pyrazoxyfen ), Pyribenzoxim, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, primisulfuron , Pyroxsulam, quinoclamine, quinclorac, quinclorac- (Quizalofop-P-ethyl), S-3252, sethoxydim, simazine, simetryne, s-metolachlor, sulcotrione ( sulcotrione, sulfentrazone, sulfosate, tefuryltrione, thenylchlor, thiazopyr, thiobencarb, triclopyr, trichlor Triclopyr-esters and amines, trifluralin, trinexapac-ethyl, tritosulfuron, and other 4-amino-6- (substituted benzenes) ) Pyridine-2-carboxylic acid and 6-amino-2- (substituted phenyl) -pyrimidine-4-carboxylic acid and salts and esters thereof.

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. It is generally preferred to use 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. Similarly, 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.

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. For example, 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.

Although it is possible to use a compound of formula I directly as a herbicide, it is preferred to use it as a mixture containing a herbicidally effective amount of the compound and at least one agriculturally acceptable excipient or carrier. 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); tallowamine ethoxylate (15EO); PEG (400) dioleate-99.

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. Specific 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.

It is generally desirable to incorporate one or more surfactants into the composition of the invention. Such 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 polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of monoalkyl phosphates And dialkyl phosphate salts; vegetable or seed oils such as soybean oil, rapeseed / brassica 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, especially methyl esters.

Generally, some of these materials, such as vegetable or seed oils and their esters, are used interchangeably as agricultural adjuvants, as liquid carriers, or as surfactants.

Other excipients 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.

The 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.

Detailed ways

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

Table 1. Compound structures and their ¹ HNMR data

Several methods of preparing the compounds of the invention are illustrated in the following schemes and examples. The starting materials can be purchased on the market or can be prepared by methods known in the literature or as shown in the detailed description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar raw materials and conditions, such as the compounds produced by the modification or variation of the preparation method of the present invention. Various isomers and the like are included in the scope of the present invention. In addition, the preparation method described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, and the like.

The method examples provided below are used to promote a further understanding of the preparation method of the present invention. The specific substances, types, and conditions used are determined to further explain the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds indicated in the table below are either commercially available or can be easily prepared by one of ordinary skill in the art.

Examples of representative compounds are as follows:

1. Synthesis of compound 1

At room temperature, add compound II-1 (1 equivalent),

(1.1 equivalents), potassium carbonate (1.5 equivalents), and DMF (10 V, V represents 1 mL of solvent DMF per gram of substrate, the same below), and stirred overnight at room temperature. The reaction was detected to be complete by TLC. The reaction system was added with water and extracted with ethyl acetate. The organic phase was concentrated and separated by column chromatography on silica gel (100 mesh to 200 mesh) to obtain the product with a yield of 80%.

2. Synthesis of compound 6

20 ml of DMF was added to a 50 ml single-necked flask, followed by compound II-2 (1 g, 2.4 mmol, 1 eq) and NCS (481.7 mg, 3.61 mmol, 1.5 eq) in this order and stirred at room temperature for 4 hours. The TLC detection reaction went to completion. The reaction solution was poured into 20 ml of water, extracted three times with ethyl acetate, and the organic phase was washed three times with saturated brine. The organic phase was dried and spin-dried, and purified by column chromatography to obtain compound 6 (0.9 g, 83% yield). (White solid).

3. Synthesis of compound 15

To 20 ml of DCM were added II-1 (1 g, 3.0 mmol 1.0 eq), HOBt (0.53 g, 3.9 mmol, 1.3 eq), EDCI.HCl (0.75 g, 3.9 mmol, 1.3 eq), and TEA (0.60 g). , 6.0 mmol, 2.0 eq) and stirred at room temperature for 30 min and added

(0.51 g, 3.6 mmol, 1.2 eq), then the reaction was stirred for 12 hours. TLC detection, the reaction is complete. The reaction solution was poured into 20 ml of water and the layers were separated. The aqueous phase was extracted three times with 20 ml of DCM. The organic phase was dried, spin-dried, and separated by column chromatography to obtain compound 15 (1.1 g, 80% yield) (white solid).

4. Synthesis of compound 51

In 20 ml of DMF, add II-3 (1 g, 3.0 mmol 1.0 eq) and CDI (0.84 g, 6.0 mmol, 2.0 eq), and stir at room temperature for 30 min.

(0.75 g, 3.6 mmol, 1.2 eq), then the reaction was stirred for 12 hours. TLC detection, the reaction is complete. The reaction solution was poured into 20 ml of water, and extracted with 30 ml of ethyl acetate. The aqueous phase was extracted twice with 30 ml of ethyl acetate. The organic phase was dried and spin-dried. Yield) (white solid).

5. Synthesis of compound 105

20 ml of DMSO was added to a 100 ml three-necked flask at room temperature, and then compound II-4 (1 g, 2.0 mmol, 1 eq) was added, and the mixture was stirred to dissolve. Then NH ₃ was slowly bubbled into the solution. After the basic reaction of the raw materials was detected by TLC, the introduction of NH ₃ was stopped. The reaction solution was poured into 20 ml of water, extracted three times with ethyl acetate, and the organic phase was washed three times with saturated brine. The organic phase was dried and spin-dried. After separation and purification by column chromatography, compound 105 was obtained (0.75 g, 78% yield). (White solid).

6. Synthesis of compound 126

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

(674 mg, 3.30 mmol, 1.1 eq), CsF (911 mg, 6 mmol, 2 eq), 1,4-dioxane and water (V / V = 4/1). After replacing N ₂ three times, Pd (dppf) Cl ₂ · CH ₂ Cl ₂ (122 mg, 0.15 mmol, 0.05 eq) was added, and then heated to 120 ° C. and stirred for 12 hours. The basic reaction of the raw materials by TLC was complete. The 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).

7. Synthesis of compound 131

Add Ⅱ-6 (1.0g, 3.0mmol 1.0eq) to 20ml of DMF,

(0.5 g, 3.0 mmol 1.0 eq) and K ₂ CO ₃ (0.67 g, 6.0 mmol, 2.0 eq), and stirred at room temperature for 12 hours. TLC detection, the reaction is complete. The reaction solution was poured into 20 ml of water, and extracted with 30 ml of ethyl acetate. The aqueous phase was extracted twice with 30 ml of ethyl acetate. The organic phase was dried, spin-dried, and separated by column chromatography to obtain compound 131 (1.4 g, 87%). Yield) (white solid).

Evaluation of biological activity:

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

Level 10: Complete death;

Level 9: The growth control rate is above 85%;

Level 8: The growth control rate is above 70%;

Level 7: Growth control rate is above 60%;

Level 6: Growth control rate is above 50%;

Level 5: Growth control rate is above 40%;

Level 4: Growth control rate is above 30%;

Level 3: Growth control rate is above 20%;

Level 2: Growth control rate is 5-20%;

Level 1: Growth control rate is below 5%;

Level 0: No effect.

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.

Table 2. Post-emergence weed tests (15 g / ha)

Compound number

Artemisia sojae

Amaranth

Pig

Sorrel

wheat

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
twenty one	10	10	10	10	0
twenty two	10	10	10	10	0
twenty three	10	10	10	10	0
twenty four	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

Comparative Experiment:

(1) Post-emergence test conditions are the same as above, and the experimental results are shown in Table 3-4.

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 compound J:

Control compound K:

Control compound L:

Control compound M:

Control Compound N:

Table 3. Comparative experimental results (3 g / ha)

Compound number	Pig	Amaranth	Artemisia sojae	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 experiments (5 g / ha)

Compound number	Wild rape	Amaranth	Veronica Didyma Tenore	Tongquan
1	10	9	10	10
K	1	3	3	2

Note: 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.

(2) The spraying safety and activity test of the direct seedling rice 2-3 leaf stage, corn 2-3 leaf stage, and yarrow grass 3-leaf stage are shown in Table 5.

Table 5. Safety and activity test results (30 g / ha)

Compound number	Rice	corn	wheat	Yarrow
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 compound of the present invention has significantly higher control efficacy and crop selectivity than the control compound with different parent rings or different substituents.

Pre-emergence test experiment:

Place monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in plastic pots filled with soil, and then cover 0.5-2 cm of soil. 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.

Through experiments, we found that 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. In particular, we have noticed that the broad-leaved weeds, such as Maijiagong, Zhuyuan, and Stellaria, which are resistant to ALS inhibitors, have extremely high activity.

Evaluation of safety of transplanted rice and evaluation of weed control in paddy field:

After filling the paddy field soil in 1 / 1,000,000 hectare pots, 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.

In addition, after paddy field soil was filled in 1 / 1,000,000 hectare pots, 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. On the 5th day after transplantation, the compound of the present invention was treated in the same manner as described above.

Observe the reproductive status of yarrow, firefly, wolf grass, and wild auntie on the 14th day after the treatment with the naked eye, and evaluate the herbicidal effect on the basis of the activity level of 1-10 on the 21st day after the treatment. Many of the compounds of the present invention have been found to have excellent activity and selectivity, especially for A. citricola and Yarrow.

Note: The seeds of Yarrow, Firefly, Yeci, and Wolf are all collected from Heilongjiang, China, and have been tested for resistance to conventional doses of pyrimisulfuron.

At the same time, after many tests, it has been found that many of the compounds and compositions of the present invention have good selectivity to grasses such as zoysiagrass, dogtooth root, tall fescue, bluegrass, ryegrass, seashore paspalum and can control Many key grass weeds as well as broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, fruit trees, vegetables under different application methods also showed excellent selectivity and commercial value.

Claims (10)

1. A substituted pyrimidine-4-carboxylic acid derivative whose structural formula is as follows:

   

   Where

   X represents O, S, unsubstituted or substituted NH;

   Y represents unsubstituted or substituted aryl and heteroaryl;

   Z represents halogen;

   Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, alkyl, alkenyl or alkynyl optionally substituted with 1-2 R ₁₁ , unsubstituted or substituted aryl, heteroaryl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkyl Phosphono; R ₂ represents H, an alkyl optionally substituted by 1-2 R ₁₁ or -COR ₁₂ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , un Substituted or substituted by 1-2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl Substituted 5- or 6-membered saturated or unsaturated rings which do not contain or contain oxygen, sulfur or other nitrogen atoms;

   Wherein 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;

   R stands for

   
2. The substituted pyrimidine-4-carboxylic acid derivative according to claim 1, wherein:

   X stands for O, S, NR ₁ ;

   Y represents an aryl group or a heteroaryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of: halogen, nitro, cyano, hydroxyl, carboxyl, amino, with or without halogen Alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, alkylamino, alkylacyloxy; or the Two adjacent substituents together are -O (CH ₂ ) _n O-, n = 1 or 2;

   Z represents Cl or Br;

   Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with 1-2 R ₁₁ , unsubstituted or Phenyl substituted with halogen, C1-C8 alkyl, C1-C8 alkoxy, 1-3 groups in nitro, naphthyl,

   

   -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 Alkylsilyl or di-C1-C8 alkylphosphono; R ₂ represents H, C1-C8 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C8 alkyl, 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 group substituted

   

   Where 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;

   R stands for

   
3. The substituted pyrimidine-4-carboxylic acid derivative according to claim 1 or 2, characterized in that:

   X stands for O, S, NH;

   Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 with or without F, Cl, Br , C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl, C1-C8 alkylamino, C1-C8 alkylacyloxy; or wherein two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

   

   

   Z represents Cl or Br;

   Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, optionally substituted by 1-2 R ₁₁ , -COR ₁₂ , Nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylformyl Silane or di-C1-C6 alkylphosphono; R ₂ represents H, C1-C6 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkane Substituted by groups in thio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl

   

   Where 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;

   R stands for

   
4. A substituted pyrimidine-4-carboxylic acid derivative according to any one of claims 1-3, characterized in that:

   X stands for O, S, NH;

   Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 with or without F, Cl, Br , C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylamino, C1-C6 alkylacyloxy; or where two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

   

   

   Z represents Cl or Br;

   Q represents nitro or NR ₁ R ₂ , wherein R ₁ represents H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, optionally substituted with 1-2 R ₁₁ , -COR ₁₂ , Nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N = CR ₁₇ R ₁₈ , C1-C4 alkylcarbamoyl, di-C1-C4 alkylcarbamoyl, tri-C1-C4 alkylformyl Silane or di-C1-C4 alkylphosphono; R ₂ represents H, C1-C4 alkyl or -COR ₁₂ optionally substituted with 1-2 R ₁₁ ; or NR ₁ R ₂ represents N = CR ₂₁ NR ₂₂ R ₂₃ , N = CR ₂₄ OR ₂₅ , unsubstituted or 1-2 independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkane Substituted by groups in thio, halo C1-C4 alkylthio, amino, C1-C4 alkylamino, di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl

   

   Where 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;

   R stands for

   
5. A substituted pyrimidine-4-carboxylic acid derivative according to any one of claims 1-4, characterized in that:

   X stands for O;

   Y represents an aryl or heteroaryl group which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: 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 with or without F, Cl, Br , C1-C4 alkoxycarbonyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C1-C4 alkylacyloxy; or where two adjacent substituents on the arylbenzene ring portion together are- O (CH ₂ ) _n O-, n = 1 or 2;

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

   

   Z stands for Cl;

   Q represents NH ₂ , NHMe, N (Me) ₂ ,

   

   

   R stands for

   
6. The substituted pyrimidine-4-carboxylic acid derivative according to any one of claims 1-5, wherein the structural formula is any one of the following:

   

   

   

   

   

   

   
7. A method for preparing a substituted pyrimidine-4-carboxylic acid derivative according to any one of claims 1-6, characterized in that it 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 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 more than two

   When X represents S, Hal represents SH; when X represents unsubstituted or substituted N, Hal represents unsubstituted or correspondingly substituted NH ₂ ; the reaction is performed in the presence of a condensing agent, a base, and a solvent, and the condensing agent HOBt / EDCI.HCl or CDI, and the base is TEA, DIPEA, or a combination thereof;

   Preferably, the reaction temperatures are all in the range of 0-40 ° C, more preferably 20-30 ° C; or the solvents are all acetonitrile, DMF, dichloromethane, or 1,2-dichloroethane;

   (2) The chemical reaction equation is as follows:

   

   The reaction is performed in the presence of a halide and a solvent; preferably, the halide is NCS, NBS, Cl ₂ , Br ₂ or NaClO / HCl; the solvent is selected from DMF, DMSO, DCM, THF, MeCN and One or more kinds of DCE are mixed; or the reaction temperature is in the range of 0-80 ° C;

   (3) The chemical reaction equation is as follows:

   

   The A represents bromine, iodine, chlorine, methanesulfonyl; the reaction is performed in the presence of QH and a solvent; preferably, the solvent is selected from one of DMF, DMSO, DCM, THF, MeCN, and DCE, or Multiple mixing; or the reaction temperature is in the range of -10-30 ° C;

   (4) The chemical reaction equation is as follows:

   

   The reaction is performed in the presence of a catalyst, a base and a solvent; preferably, the catalyst is Pd (dppf) Cl ₂ · CH ₂ Cl ₂ , Pd (dppf) Cl ₂ or Pd (PPh ₃ ) ₄ ; the base It is CsF, K ₂ CO ₃ , Na ₂ CO ₃ , K ₃ PO ₄ or KF; the solvent is an organic solvent / water, and the volume ratio between the two is preferably 20 / 1-1 / 1, and the organic solvent is dioxygen. Hexacyclic, toluene, DMF or DMSO; or the temperature is in the range of 80-150 ° C.
8. A herbicidal composition comprising a herbicidally effective amount of a compound of formula I according to any one of claims 1-6, mixed with an agricultural adjuvant or a carrier.
9. A method for controlling undesired vegetation, which comprises foliar application or water application or application of a vegetation location to make vegetation and weeding an effective amount of a compound of formula I according to any one of claims 1-6 or according to The herbicidal composition according to claim 8 is contacted, or a herbicidally effective amount of a compound of formula I according to any one of claims 1-6 or a herbicidal composition according to claim 8 is applied to soil or water, thereby preventing Vegetation emerges.
10. Method for selectively controlling unwanted vegetation after seedling in the presence of rice, wheat or forage, characterized in that it comprises applying a herbicidally effective amount according to any one of claims 1-6 to said unwanted vegetation A compound of formula I or a herbicidal composition according to claim 8.