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CN109721546B - Substituted pyrimidine aryl ester derivative and preparation method, herbicidal composition and application thereof - Google Patents

Substituted pyrimidine aryl ester derivative and preparation method, herbicidal composition and application thereof Download PDF

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CN109721546B
CN109721546B CN201811641741.2A CN201811641741A CN109721546B CN 109721546 B CN109721546 B CN 109721546B CN 201811641741 A CN201811641741 A CN 201811641741A CN 109721546 B CN109721546 B CN 109721546B
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CN109721546A (en
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连磊
彭学岗
华荣保
赵德
崔琦
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Qingdao Kingagroot Chemical Compound Co Ltd
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Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrimidine aryl ester derivative, a preparation method thereof, a weeding composition and application. The substituted pyrimidine aryl ester derivative is shown as a general formula I:
Figure DDA0001931243350000011
wherein, X represents alkyl, alkoxy, alkylthio, halogen, alkenyl and alkynyl; y represents nitro or NR1R2(ii) a Z represents an unsubstituted or substituted aryl or heteroaryl group; a represents halogen and amino; b represents hydrogen, halogen, alkoxy, alkylthio, alkylamino or dialkylamino which may or may not be substituted by halogen; c represents halogen and halogenated alkyl. The compound has excellent herbicidal activity and higher crop safety, and especially establishes good selectivity for corn, wheat, rice and other key crops.

Description

Substituted pyrimidine aryl ester derivative and preparation method, herbicidal composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a substituted pyrimidine aryl ester derivative, a preparation method thereof, a weeding composition and application.
Background
The control of weeds is a crucial step in the realization of efficient agricultural processes, despite the variety of herbicides on the market, e.g. WO2005/063721a1, WO2007/082076a1, WO2005063721a1, US7863220B2, US7300907B2, US7642220B2, US7863220B2 and US7786044B2 disclose certain 6-amino-2-substituted-pyrimidine-4-carboxylic acids and derivatives thereof and their use as herbicides. However, due to the expanding market, the resistance of weeds, the life span of the drugs, and the economic nature of the drugs, and the growing environmental importance, scientists are required to research and develop new herbicide varieties with high efficiency, safety, economy, and different modes of action.
Disclosure of Invention
The invention provides a substituted pyrimidine aryl ester derivative, a preparation method thereof, a weeding composition and application thereof.
The technical scheme adopted by the invention is as follows:
a substituted aryl pyrimidinate derivative represented by the general formula I:
Figure BDA0001931243340000011
wherein,
x represents alkyl, alkoxy, alkylthio, halogen, alkenyl, alkynyl;
y represents nitro or NR1R2Wherein R is1Represents H, unsubstituted or optionally substituted by 1-2R11Substituted alkyl, alkenyl or alkynyl, -COR12Nitro, OR13，SO2R14，NR15R16，N＝CR17R18An alkylcarbamoyl group, a dialkylcarbamoyl group, a trialkylsilyl group or a dialkylphosphono group; r2Represents H, unsubstituted or 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, haloalkylPhenyl, 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, alkyl; or N ═ CR17R18Represents
Figure BDA0001931243340000021
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;
z represents an unsubstituted or substituted aryl or heteroaryl group;
a represents halogen and amino;
b represents hydrogen, halogen, alkoxy, alkylthio, alkylamino or dialkylamino which may or may not be substituted by halogen;
c represents halogen and halogenated alkyl.
Preferably, X represents C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, halogen, C2-C8 alkenyl, C2-C8 alkynyl;
y represents nitro or NR1R2Wherein R is1Represents H, unsubstituted or optionally substituted by 1-2R11Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, -COR12Nitro, OR13，SO2R14，NR15R16，N＝CR17R18C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphonyl; r2Represents H, unsubstituted or optionally substituted by 1-2R11Substituted C1-C8 alkyl or-COR12(ii) a Or NR3R4Represents 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
Figure BDA0001931243340000022
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,
Figure BDA0001931243340000031
Figure BDA0001931243340000032
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, phenyl which is unsubstituted or substituted by 1-3 of halogen, C1-C8 alkyl and C1-C8 alkoxy; r18Represents H, C1-C8 alkyl; or N ═ CR17R18Represents
Figure BDA0001931243340000033
R21、R24Each independently represents H or C1-C8 alkyl;
R22、R23each independently represents H or C1-C8 alkyl; or NR22R23Represents
Figure BDA0001931243340000034
Figure BDA0001931243340000035
R25Represents a C1-C8 alkyl group;
z represents unsubstituted or substituted aryl or heteroaryl, the "aryl" meaning phenyl, naphthyl, the "heteroaryl" meaning an aromatic cyclic group containing 3 to 6 ring atoms, of which 1 to 4 heteroatoms are selected from oxygen, nitrogen and sulfur, and which may also be fused via a benzo ring, for example,
Figure BDA0001931243340000036
Figure BDA0001931243340000037
wherein it is selected from halogen, nitro, cyano, thiocyanato, hydroxy, carboxy, mercapto, formyl, phenyl, benzyl, phenoxy, unsubstituted OR substituted by at least one group selected from halogen, alkyl, alkoxy, alkyl, alkenyl, alkynyl, cycloalkyl OR cycloalkylalkyl, OR ', SR ', alkyl-OR ', alkyl-SR ', COR COOR ', COSR ', SOR ', SO, and optionally halogen2R ', OCOR ', SCOR ', is selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl、COR”、SO2Amino OR aminocarbonyl substituted by one OR two of R ', OR', and-OCH2CH2-，-OCH2O-，-OCH2CH2At least one group of O-is substituted;
r' independently represent hydrogen, nitro, hydroxyl, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkanoyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono, with or without halogen;
r' each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl with or without halogen;
a represents halogen and amino;
b represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, di-C1-C8 alkylamino, with or without halogen substitution;
c represents halogen, halogenated C1-C8 alkyl.
More preferably, X represents C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, C2-C6 alkenyl, C2-C6 alkynyl;
y represents nitro or NR3R4Wherein R is3Represents H, unsubstituted or 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; r4Represents H, unsubstituted or optionally substituted by 1-2R11Substituted C1-C6 alkyl or-COR12(ii) a Or NR3R4Represents 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
Figure BDA0001931243340000041
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,
Figure BDA0001931243340000042
Figure BDA0001931243340000043
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 or benzyl;
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
Figure BDA0001931243340000051
R21、R24Each independently represents H or C1-C6 alkyl;
R22、R23each independently represents H or C1-C6 alkyl; or NR22R23Represents
Figure BDA0001931243340000052
Figure BDA0001931243340000053
R25Represents a C1-C6 alkyl group;
z represents an unsubstituted or substituted aryl or heteroaryl group, said "aryl" means phenyl, naphthyl and "heteroaryl" means
Figure BDA0001931243340000054
Figure BDA0001931243340000055
Figure BDA0001931243340000056
Wherein, it is selected from halogen, nitro, cyano, thiocyanato, hydroxyl, carboxyl, mercapto, formyl, phenyl, benzyl, phenoxy which are unsubstituted OR substituted by 1,2 OR 3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl OR C3-C6 cycloalkyl C1-C6 alkyl, OR ', SR ', C1-C6 alkyl-OR ', C1-C6 alkyl-SR ', COR COOR ', COSR ', SOR ', SO 3653922R ', OCOR ', SCOR ', is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl, COR ', SO ', and combinations thereof2Amino OR aminocarbonyl substituted by one OR two of R ', OR', and-OCH2CH2-，-OCH2O-，-OCH2CH2O-is substituted by 0, 1,2 or 3 groups;
r' independently represents hydrogen, nitro, hydroxyl, amino, C1-C6 alkyl containing or not containing fluorine, chlorine and bromine, C2-C6 alkenyl, C6-C6 alkynyl, C6-C6 cycloalkyl, C6-C6 cycloalkenyl, C6-C6 cycloalkyl C6-C6 alkyl, C6-C6 alkoxy, C6-C6 alkenyloxy, C6-C6 alkynyloxy, C6-C6 cycloalkyloxy, C6-C6 alkoxy C6-C6 alkyl, C6-C6 alkoxycarbonyl, C6-C6 alkylthio carbonyl, C6-C6 alkylsulfonyl C6-C6 alkyl, C6-C6 alkylcarbonyl, C6-C6 alkylcarbonyloxy, C6-C6 alkyl amino, C6-C6 alkyl-C6 alkyl-36, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C1-C6 alkylaminocarbonyl C1-C6 alkyl, tri-C1-C6 alkylsilyl, di-C1-C6 alkylphosphonyl;
r' respectively and independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base or C3-C6 naphthenic base C1-C6 alkyl which contains or does not contain halogen.
A represents halogen and amino;
b represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, di-C1-C6 alkylamino, with or without halogen substitution;
c represents halogen, halogenated C1-C6 alkyl.
Further preferably, X represents C1-C6 alkyl, C1-C6 alkoxy, C1-C4 alkylthio, halogen, C2-C6 alkenyl, C2-C6 alkynyl;
y represents nitro or NR3R4，
Wherein R is3Represents H, unsubstituted or substituted by 1R11Substituted C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, hydroxy, C1-C6 alkoxy, benzyloxy,
Figure BDA0001931243340000061
C1-C6 alkylsulfonyl, amino, alkylamino, dialkylamino, N ═ CR17R18；
R4Represents H, C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl;
or NR3R4Represents N ═ CHNR22R23，
Figure BDA0001931243340000062
R11Independently represent hydroxyl, C1-C6 alkoxy, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, phenyl which is unsubstituted or substituted by 1 to 3 of halogen, C1-C6 alkyl, C1-C6 alkoxy and nitro, naphthyl,
Figure BDA0001931243340000063
Figure BDA0001931243340000064
R17Represents H, C1-C6 alkyl; r18Represents H, C1-C6 alkyl;
R22、R23each independently represents a C1-C6 alkyl group;
z represents an unsubstituted or substituted aryl or heteroaryl group, said "aryl" means phenyl, naphthyl and "heteroaryl" means
Figure BDA0001931243340000071
Figure BDA0001931243340000072
Figure BDA0001931243340000073
Wherein, it is selected from halogen, nitro, cyano, thiocyanato, hydroxyl, carboxyl, mercapto, formyl, phenyl, benzyl, phenoxy which are unsubstituted OR substituted by 1,2 OR 3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl OR C3-C6 cycloalkyl C1-C2 alkyl, OR ', SR ', C1-C2 alkyl-OR ', C1-C2 alkyl-SR ', COR COOR ', COSR ', SOR ', SO 3653922R ', OCOR ', SCOR ', is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C2 alkyl, COR ', SO ', and combinations thereof2One OR two of R 'and OR'Amino or aminocarbonyl substituted with one or more groups;
r' independently represents C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl C1-C2 alkyl, C1-C6 alkoxy C1-C2 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl and C1-C6 alkylcarbonyl which contain or do not contain fluorine, chlorine and bromine;
r' respectively and independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base or C3-C6 naphthenic base C1-C2 alkyl which contains or does not contain halogen.
A represents halogen and amino;
b represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, di-C1-C6 alkylamino, with or without halogen substitution;
c represents halogen, halogenated C1-C6 alkyl.
Still more preferably, X represents fluorine, chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, allyl, ethynyl;
y represents NH2，NHMe，N(Me)2，N(Et)2，NO2，
Figure BDA0001931243340000074
Figure BDA0001931243340000075
Figure BDA0001931243340000081
Figure BDA0001931243340000082
And unsubstituted or substituted by at least one group selected from methoxy, nitro, fluoro
Figure BDA0001931243340000083
Unsubstituted or substituted by methyl
Figure BDA0001931243340000084
Z represents unsubstituted or substituted fluorine,Chlorine, bromine, iodine, methyl, ethyl, isopropyl, vinyl, ethynyl, cyclopropyl, trifluoromethyl, methoxy, vinyloxy, methylthioethylthio, methoxymethyl, methoxycarbonyl, methylthiocarbonyl, methylsulfonyl, amino, dimethylamino, nitro, cyano, thiocyano, hydroxy, formyl, acetyl, trifluoromethyl,
Figure BDA0001931243340000085
Figure BDA0001931243340000086
Figure BDA0001931243340000087
Phenyl, phenoxy, benzyl substituted by chlorine, phenyl substituted by 1 to 3 of the benzyloxy groups substituted by methyl, naphthyl,
Figure BDA0001931243340000088
Figure BDA0001931243340000089
R' independently represents methyl, ethyl, isopropyl, vinyl, cyclopropylmethyl, methylsulfonyl, methoxycarbonyl, acetyl, methoxymethyl;
Figure BDA0001931243340000091
represents
Figure BDA0001931243340000092
Figure BDA0001931243340000093
In the definition of the compounds of the general formula I above and in all the formulae below, the terms used, whether used alone or in compound words, represent the following substituents: alkyl groups having more than two carbon atoms may be straight chain or branched. Such as the compound "-alkyl-OR" ", where alkyl may be-CH2-、-CH2CH2-、-CH(CH3)-、-C(CH3)2-and the like. Alkyl groups are, for example, methyl; an ethyl group; n-propyl or isopropyl; n-butyl, isobutyl, tert-butyl or 2-butyl; a pentyl group; hexyl radicals, such as the n-hexyl radical, the isohexyl radical and the 1, 3-dimethylbutyl radical. Halogen is fluorine, chlorine, bromine or iodine.
If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different radicals selected from those mentioned. The same or different substitution characters contained in the same or different substituents are independently selected and may be the same or different.
The preparation method of the substituted pyrimidine aryl ester derivative comprises the following steps: carrying out esterification reaction on the compound shown in the general formula III and the compound shown in the general formula II to obtain a compound shown in the general formula I; the chemical reaction equation is as follows:
Figure BDA0001931243340000094
preferably, the reaction is carried out in the presence of triethylamine, PyBOP and a solvent selected from one or a combination of more of acetonitrile, DMF, dichloromethane and 1, 2-dichloroethane; the reaction temperature is 0-50 ℃.
A herbicidal composition comprising a herbicidally effective amount of at least one of said substituted aryl pyrimidinium derivatives and preferably further comprising a formulation adjuvant.
A method of controlling weeds which comprises applying a herbicidally effective amount of at least one of said substituted pyrimidinylaryl ester derivatives or said herbicidal composition on a plant or a weed area.
The use of at least one of said substituted pyrimidinylaryl ester derivatives or said herbicidal composition for controlling weeds, preferably the use of said substituted pyrimidinylaryl ester derivatives for controlling weeds in crops of useful plants, said crops of useful plants being transgenic or treated with genome editing techniques.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substance is used before sowing, before germination or after germination. Mention is made in particular of representative examples of the monocotyledonous and dicotyledonous weed groups which the compounds of the invention can control, without being restricted to a defined species. Examples of weed species for which the active substance acts effectively include monocotyledons: annual avena, rye, grass, alopecurus, farris, barnyard grass, digitaria, setaria and sedge, and perennial agropyron, bermudagrass, cogongrass and sorghum, and perennial sedge.
With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are effective in controlling harmful plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing of rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. The compounds of the invention are particularly active against plants such as, for example, alpinia, sesamum indicum, polygonum convolvulus, chickweed, veronica vinifera, veronica albo, viola tricolor and amaranth, cleavers and kochia.
Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not at all harmful or only insignificantly harmful to the important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Especially good compatibility with cereal crops such as wheat, barley and maize, especially wheat. The compounds according to the invention are therefore very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants.
Due to their herbicidal properties, these active substances can be used for controlling harmful plants in the cultivation of genetically engineered plants which are known or are to occur. Transgenic plants often have advantageous traits, such as resistance to specific insecticides, particularly to specific herbicides, resistance to plant diseases or to microorganisms pathogenic to plant diseases, such as specific insects or microorganisms of fungi, bacteria or viruses. Other specific traits are related to the conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients. Thus, it is known that the resulting transgenic plant products have an increased starch content or an improved starch quality or a different fatty acid composition.
The compounds of the formula I according to the invention or their salts are preferably used for economically important transgenic crops and ornamentals, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable plants. The compounds of the formula I are preferably used as herbicides for cultivating useful plants which are resistant to the action of the herbicide or which are resistant to the toxic action of the herbicide by genetic engineering.
Conventional methods for breeding plants having improved shape over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits may be obtained by means of methods of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:
to improve starch synthesis in plants, crop plants are altered by genetic engineering (e.g. WO 92/11376, WO 92/14827, WO 91/19806);
transgenic crop plants which are resistant to particular herbicides, to glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or to glyphosate-type herbicides (WO 92/00377), or to sulfonylurea-type herbicides (EP-0257993A, US-5013659A);
transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) which protect against attack on plants by specific pests (EP-0142924A, EP-0193259A);
-transgenic crop plants with improved fatty acid composition (WO 91/13972).
A number of molecular biotechnologies are known which enable the production of transgenic plants with improved traits (see, for example, Sambrook et al, 1989, molecular amplification, second edition of the laboratory Manual, Cold spring harbor laboratory publications in USA, Cold spring harbor, New York; or Winnacker "Gene und Klone" [ genes and clones ], VCH Weinheim, second edition 1996 or Christou, "trends in plant science" 1(1996)423- "431)). In order to carry out the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, which undergo mutations or sequence changes by recombination of DNA sequences. Using standard methods as described above, it is possible, for example, to exchange substrates, remove partial sequences or add natural or synthetic sequences. In order to ligate the DNA fragments to each other, it is possible to attach a binder or a linker to the fragments.
Plant cells of reduced activity gene products can be prepared, for example, by expressing at least one suitable antisense-RNA, sense-RNA to achieve a cosuppression effect, or by expressing at least one suitably configured ribozyme which specifically cleaves transcripts of the gene products.
For this purpose, it is possible to use DNA molecules which contain the entire coding sequence of the gene product, including any flanking sequences which may be present, and to use DNA molecules which contain only a part of the coding sequence which has to be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous but not identical to the coding sequence of the gene product may also be used.
When expressing the nucleic acid molecule in a plant, the synthetic protein can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to link the coding region to a DNA sequence in order to ensure localization in a specific location. These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J.11(1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85(1988), 846-850; Sonnewald et al Plant J.1(1991), 95-106).
Transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plant may be of any desired plant variety, i.e., monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (═ natural) genes or gene sequences, or by expressing heterologous (═ external) genes or gene sequences.
When the active substances according to the invention are used on transgenic crops, in addition to the harmful-plant-inhibiting effects observed on other crops, special effects are often observed on the corresponding transgenic crops, for example an improved or enlarged spectrum of weed control, improved application rates in the application, preferably a good combination of resistance of the transgenic crop and herbicide performance, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds as herbicides for controlling harmful plants in transgenic crop plants.
In addition, the compound of the invention can obviously regulate the growth of crop plants. These compounds are used to target the control of plant components and to promote harvesting, such as desiccation and stunting of plants, by regulating the metabolism of plants involved. They are also suitable for regulating and inhibiting undesirable vegetation without destroying the growth of the crop plants. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crop plants, since this reduces or completely prevents lodging.
The compounds of the present invention can be applied using general formulations, and wettable powders, concentrated emulsions, sprayable solutions, powders or granules can be used. Thus the present invention also provides herbicidal compositions comprising compounds of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), water Soluble Powders (SP), water soluble concentrates, Emulsion Concentrates (EC), emulsions dispersed in water (EW), for example, oil-in-water and water-in-oil (EW), sprayable solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluent, solutions of miscible oils, powders (DP), Capsule Suspensions (CS), core (cutting) compositions, granules for spreading and soil application, spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), ULV (ultra low volume) formulations, microcapsules and wax preparations. These individual formulation types are known and described in, for example, Winnacker-Kuchler, "Chemische Techologie" [ Chemicals Process ], Vol.7, C.Hauser Verlag Munich, 4 th edition 1986; wade van Valkenburg, "Pesticide Formulations," Marcel Dekker, n.y., 1973; martens, "Spray Drying" handbook, 3 rd edition 1979, g.
The necessary formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described in the documents mentioned below, for example in Watkins, "handbook of powdered diluents pesticides and carriers", second edition, Darland book Caldwell n.j.; h.v.01phen, "entry to clay colloid chemistry," second edition, j.wiley and Sons, n.y.; marsden, second edition "solvent guide", Interscience, n.y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issues, Ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964;
Figure BDA0001931243340000121
is/are as follows
Figure BDA0001931243340000122
[ ethylene oxide adduct surfactant]Uss.verlagageell.stuttgart 1976; "Chemische technology" by Winnacker-Kuchler [ chemical Process]Volume 7, c.hauser Verlag Munich, 4 th edition 1986.
Wettable powders can be uniformly dispersed in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary instruments, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of the adjuvants.
Emulsions are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or higher boiling aromatics or hydrocarbons or mixtures of solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are calcium alkylarylsulfonates, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers, for example polyglycol esters of fatty acids, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
The active substance and finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Water or oil based suspensions may be prepared, for example, by wet milling using a commercially available bead mill, with or without the addition of a surfactant of the other formulation type described above.
For preparing emulsions, for example oil-in-water Emulsions (EW), it is possible to use aqueous organic solvents, using stirrers, colloid mills and/or static mixers, and, if desired, to add surfactants of another formulation type as described above.
Granules are prepared by spraying the active substance onto the adsorbate, granulating with inert material, or concentrating the active substance onto the surface of a carrier, for example sand, kaolinite, and granulating the inert material with a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the process for preparing fertilizer granules, if desired mixed with fertilizers. The preparation of water-suspendable granules is carried out by customary methods, for example spray-drying, fluidized-bed granulation, millstone granulation, mixing using high-speed mixers and extrusion without solid inert materials.
For the preparation of granules using a millstone, a fluidized bed, an extruder and Spray coating, see the following processes, for example "Spray Drying handbook", third edition 1979, g.goodwin ltd, london; browning, "Agglomeration", chemical and engineering 1967, page 147 ff; "Perry's handbook of Engineers of chemistry", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If preparations for crop protection products are to be known, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, New York, pages 196181-96 and J.D. Freyer, S.A. Evans, "Weed Control Manual", fifth edition, Blackwell Scientific rules, Oxford university 1968, page 101-.
Agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95% by weight of active substance of formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, with usual formulation components making up the remainder to 100% by weight. The concentration of the active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. Powder formulations contain from 1 to 30% by weight of active, usually preferably from 5 to 20% by weight of active, whereas sprayable solutions contain from about 0.05 to 80%, preferably from 2 to 50% by weight of active. The content of active substance in the aqueous suspension granules depends primarily on whether the active substance is liquid or solid, and the auxiliaries, fillers and the like used in granulation. The content of active substance in the water-suspendable granule formulation is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
The active substance formulations mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and generally customary pH and viscosity regulators in all cases.
On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.
Suitable active substances which can be mixed with the active substances according to the invention in a compounded or tank-mixed formulation are, for example, the substances known from "the world Wide Specification of New agricultural chemical products", from the national agricultural science and technology Press, 2010.9 and the documents cited therein. For example, the herbicidal active substances mentioned below may be mixed with the mixtures of the formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, buta, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naphazel, thiachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamidam, flupiram, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineone-flumetsulam, ciprofloxacin, glycazine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, clonazine, atrazine, metribuzin, cyanuric acid, indaziflazaflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl, sulfometuron, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenflur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazol, Thiobencarb, merthiolane, diclofop, triallate, penoxsulam, pyributicarb, dichlorfon, edifenphos, ethiofen, prosulfocarb, clenbuterol, prosulfocarb, dichotomene, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chlorobutyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-d propionic acid, 2-d propionic acid, 2-cloroprionic acid, triclocarb, triclopyr, triclop, Aminodiclofenac, metocloprofenac, diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-p-butyl, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-ethyl, clodinafop-ethyl, benazolin, clodinafop-ethyl, haloxyfop-methyl, benazolin, propalaxyl, butyfen-ethyl, chloroethafloxacin, aminofluanid, benazolin, dichlofop-ethyl, methamphetalin, propamocarb-ethyl, benfop-methyl, thiophosphine, pirimiphos-methyl, benfop-ethyl, benazolin, benfop-methyl, imax-methyl, mefenofos, mefeno, Imazamox ammonium salt, imazapic acid, imazamethabenz ester, fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyril, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, clethodim, topramezone, Buthidazole, metribuzin, hexazinone, metamitron, metribuzin, amitridione, Amibuzin, bromoxynil, octanoyl ioxynil, dichlobenitrile, pyraclonil, hydroxybensulam, Iodobonil, flumetsulam, penoxsulam, clofenapyr, pyraclonil, pyraflufen-ethyl, pyraoxystrobin, flumetsulam, pyraclonil, pyraoxystrobin, isoxathion, pyriftalid, pyriminobac-methyl, pyrithiobac-methyl, benzobicylon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, isoxaclomazone, fenoxasulfofone, methiozoline, isopyrafen, pyraflufen, pyrazote, difenzoquat, pyrazoxazole, pyroxaflutole, pyroxsulam, pyraclofos, pyraclonil, amicarbazone, carfentrazone, flumiclone, sulfentrazone, bencarane, bisphenomezone, butafenacil, isoxaflutole, cyclam, triclopyr, fluroxypyr, flumethazine, parnaprox, flumiclone, flumethol, carfentrazone, carzone, carfentrazone, car, Fluazifop-methyl, pyriminostrobin, bromopicrin, didaphylm, pyridaben, Pyridafol, quinclorac, chloroquine, bentazon, pyridate, oxaziclomefone, benazolin, clomazone, isoprox, isoproxypyrim, propyribac, cumylfen, clomazone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, mesotrione, ethofumesate, pyrimethanil, clodinafop-methyl, clodinium, pyributaine, benfurazolin, meton, metamitron, metolachlor, dichlorvofen, triclopyr, aloac, Dietmquat, Etpronil, ipriflam, iprimazam, iprodione, Trizopyr, Thiaclonifen, chlorpyrifos, pyradifquat, chlorpyrifos, propiram, pyradifurone, pyradifon, pyradifurone, pyrazone, thion, pyrazone, clomazone, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, DOWFAUC, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.
When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
Detailed Description
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.
In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, a selection of which are listed in table 1 below. Specific compound structures and corresponding compound information are shown in table 1. The compounds in table 1 are only for better illustrating the present invention, but not for limiting the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.
Table 1 Structure of Compounds and methods of use thereof1HNMR data
Figure BDA0001931243340000171
Figure BDA0001931243340000172
Figure BDA0001931243340000181
Figure BDA0001931243340000191
Figure BDA0001931243340000201
Figure BDA0001931243340000211
Figure BDA0001931243340000221
Figure BDA0001931243340000231
Figure BDA0001931243340000241
Figure BDA0001931243340000251
Figure BDA0001931243340000261
Figure BDA0001931243340000271
Figure BDA0001931243340000281
Figure BDA0001931243340000291
Figure BDA0001931243340000301
Figure BDA0001931243340000311
Figure BDA0001931243340000321
Figure BDA0001931243340000331
Figure BDA0001931243340000341
Figure BDA0001931243340000351
Figure BDA0001931243340000361
Figure BDA0001931243340000371
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 present 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 given below, and the synthesis of other compounds is similar and will not be described in detail herein.
1. Preparation of compound 2:
Figure BDA0001931243340000381
to 10mL of DCM was added a (0.5g), Et in sequence3N (1.2eq) and b (1.2eq) were then added to PyBOP (1.2eq) at 20 ℃ and the reaction stirred for 4 hours at 20 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 10ml of water, separated, the aqueous phase was extracted once with 20 ml of ethyl acetate, and the organic phase was washed once with saturated brine (10ml), dried, spin-dried, and separated by column chromatography to give compound 2(0.45g, 73% yield) (white solid).
2. Preparation of compound 10:
Figure BDA0001931243340000382
to 10ml of DMF was added c (0.5g), Et in sequence3N (1.2eq) and b (1.2eq) were then added to PyBOP (1.2eq) at 30 ℃ and the reaction stirred for 4 hours at 30 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 10ml of water, followed by liquid separation, extraction of the aqueous phase once with 20 ml of ethyl acetate, washing of the organic phase once with saturated brine (10ml), drying, spin-drying, and column chromatography to give compound 10(0.37g, 62% yield) (white solid).
3. Preparation of compound 42:
Figure BDA0001931243340000391
to 10ml of acetonitrile were added d (0.5g), Et in sequence3N (1.2eq) and b (1.2eq) were then added to PyBOP (1.2eq) at 40 ℃ and the reaction stirred for 4 hours at 40 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 10ml of water, separated, the aqueous phase was extracted once with 20 ml of ethyl acetate, and the organic phase was washed once with saturated brine (10ml), dried, spin-dried, and separated by column chromatography to give compound 42(0.40g, 65% yield) (white solid).
4. Preparation of compound 68:
Figure BDA0001931243340000392
to 10ml of 1, 2-dichloroethane were added e (0.5g), Et in that order3N (1.2eq) and b (1.2eq) were then charged to PyBOP (1.2eq) at 50 ℃ and the reaction stirred at 50 ℃ for 4 hours. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 10ml of water, followed by liquid separation, extraction of the aqueous phase with 20 ml of ethyl acetate once, washing of the organic phase with saturated brine (10ml) once, drying, spin-drying, and column chromatography to give compound 68(0.47g, 81% yield) (white solid).
5. Preparation of compound 202:
Figure BDA0001931243340000393
to 10mL of DCM was added a (0.5g), Et in sequence3N (1.2eq) and f (1.2eq) were then added to PyBOP (1.2eq) at 25 ℃ and the reaction stirred for 4 hours at 25 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 10ml of water, separated, the aqueous phase was extracted once with 20 ml of ethyl acetate, and the organic phase was washed once with saturated brine (10ml), dried, spin-dried, and separated by column chromatography to give compound 202(0.32g, 59% yield) (white solid).
Evaluation of biological Activity:
the activity level criteria for plant disruption (i.e. growth control rate) are as follows:
and 5, stage: the growth control rate is more than 85 percent;
4, level: the growth control rate is more than or equal to 60 percent and less than 85 percent;
and 3, level: the growth control rate is more than or equal to 40% and less than 60%;
and 2, stage: the growth control rate is more than or equal to 20% and less than 40%;
level 1: the growth control rate is more than or equal to 5% and less than 20%;
level 0: the growth control rate is less than 5%.
The growth control rate is the fresh weight control rate.
(1) 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, sowing the plastic pot for 2-3 weeks, then treating test plants, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with a certain concentration by using a certain amount of water, and spraying the solution onto the plants by using 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 tables 2-3.
TABLE 2 post-emergence weed test (weeds 4-5 leaves stage)
Figure BDA0001931243340000401
Figure BDA0001931243340000411
Figure BDA0001931243340000421
Figure BDA0001931243340000431
Figure BDA0001931243340000441
Figure BDA0001931243340000451
Figure BDA0001931243340000461
Figure BDA0001931243340000471
Note: the application dosage is 45 g/hectare of the active ingredient, and the water adding amount is 450 kg/hectare.
TABLE 3 post-emergence weed test (applied dose of 30 g/ha active ingredient, 3-leaf stage of weeds, 3-leaf stage of rice)
Figure BDA0001931243340000472
Figure BDA0001931243340000481
(2) The safety and activity of stem and leaf spray at the 2-3 leaf stage of direct seeding rice and the 3 leaf stage of barnyard grass are tested, and the results are shown in Table 5. The ratio of the average of the doses of the two compounds inhibiting 10% in rice to the dose inhibiting 90% in barnyard grass was used as the selection index for the crop, and it was generally considered that the selection index was at least greater than 2 to make it possible to use them safely in production, with higher selection indexes being better.
TABLE 4 safety and Activity test results (application dose of 30 g/ha of active ingredient)
Number of Compounds Japonica rice Indica rice Barnyard grass Selection index
2 1 0 5 2.1
84 0 0 5 2.5
86 0 0 5 3
Control Compound B 4 4 5 0.9
Control Compound C 3 3 5 1.2
(3) The stem and leaf spray safety and activity of wheat in the 3-leaf stage and the 4-5-leaf stage of the Veronica are tested, and the results are shown in Table 6. The ratio of the average number of doses of compound inhibiting 10% in wheat to the 90% in veronica is used as the selection index for crops, it is generally accepted that a selection index at least greater than 2 makes it possible to use it safely in production, the higher the selection index the better.
TABLE 5 safety and Activity test results (application dose of 30 g/ha of active ingredient)
Number of Compounds Wheat (Triticum aestivum L.) Herb of veronica Selection index
78 0 5 6.2
79 0 5 5.5
84 0 5 5.4
132 0 5 6.4
Control Compound D 2 3 0.5
(4) The safety and activity of the stem and leaf sprays at the 3-leaf stage of corn, the abutilon and the 4-5-leaf stage of Chenopodium quinoa are tested, and the results are shown in Table 6. The ratio of the average dose of 10% corn inhibition compounds to the average 90% broadleaf inhibition doses is used as the selection index for the crop, and it is generally considered that the selection index is at least greater than 2 to ensure safe use in production, with higher selection indexes being better.
TABLE 6 safety and Activity test results (application dose of 30 g/ha of active ingredient)
Number of Compounds Corn (corn) Chenopodium quinoa (L.) Merr Abutilon Selection index
81 0 5 5 6.2
132 0 5 5 5.5
Control Compound B 4 5 5 1.2
Control Compound C 4 5 5 1.5
Control Compound D 3 5 5 1.7
Note: control compound a:
Figure BDA0001931243340000491
(from patent WO2005063721A 1);
control compound B:
Figure BDA0001931243340000492
control compound C:
Figure BDA0001931243340000493
control compound D: fluorochloropyridine esters
Figure BDA0001931243340000494
As can be seen from the above tables, compared with the control compound, the compound of the present invention significantly improves the safety and herbicidal activity of crops by changing the structure of the mother ring, the type of the substituent, and the type of the carboxyl derivative, and particularly establishes good selectivity for key crops such as corn, rice, wheat, etc., whereas the control compound has poor selectivity for major crops, which indicates that the present invention achieves excellent unexpected technical effects.
(5) 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 has better weed control effect generally, has good effect on main gramineous weeds such as cockspur grass, digitaria sanguinalis and setaria viridis and main broadleaf weeds such as piemarker, rorippa rorifolia and sponish needles herb which are widely generated in corn fields, paddy fields and wheat fields, and has good commercial value. Particularly, the broadleaf weeds such as rorippa rorifolia, descurainia sophia, capsella bursa-pastoris, ophiopogon japonicus, cleavers and chickweed which have resistance to ALS inhibitors have extremely high activity.
(6) 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 cockspur grass, Chinese iris, bidens tripartita and edible tulip on 14 th day after the treatment with the medicament and the growth state of rice on 21 th day after the treatment with the medicament are respectively observed by naked eyes, and the weeding effect is evaluated according to the activity standard grade of the grade 1-5, and a plurality of compounds show excellent activity and selectivity.
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 has good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, tall fescue, blue grass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims (12)

1. A substituted aryl pyrimidinate derivative represented by the general formula I:
Figure FDA0002673819350000011
wherein,
x represents C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, halogen, C2-C8 alkenyl or C2-C8 alkynyl;
y represents nitro or NR1R2，
Wherein R is1Represents H, unsubstituted or optionally substituted by 1R11Substituted C1-C8 alkyl, -COR12、OR13、SO2R14、NR15R16Or N ═ CR17R18；
R2Represents H, C1-C8 alkyl or-COR12；
Or NR1R2Represents N ═ CR21NR22R23、
Figure FDA0002673819350000012
Wherein R is11Independently represent hydroxyl, C1-C8 alkoxy, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, phenyl which is unsubstituted or substituted by 1 to 3 of halogen, C1-C8 alkyl, C1-C8 alkoxy, nitro, naphthyl,
Figure FDA0002673819350000013
R12Represents H, C1-C18 alkyl or C1-C8 alkoxy;
R13represents H, C1-C8 alkyl, benzyl or CHR31C(O)OR32；R31Represents H or C1-C8 alkyl; r32Represents H or C1-C8 alkyl;
R14represents a C1-C8 alkyl group;
R15represents H, C1-C8 alkyl, formyl or C1-C8 alkylacyl; r16Represents H or C1-C8 alkyl;
R17represents H or C1-C8 alkyl; r18Represents H or C1-C8 alkyl;
R21represents H or C1-C8 alkyl;
R22、R23each independently represents H or C1-C8 alkyl;
z represents an unsubstituted or substituted aryl or heteroaryl group, said "aryl" being phenyl or naphthyl, and "heteroaryl" being phenyl or naphthyl
Figure FDA0002673819350000014
Figure FDA0002673819350000015
Figure FDA0002673819350000021
Figure FDA0002673819350000022
Wherein, it is selected from halogen, nitro, cyano, thiocyanato, phenyl, benzyl OR phenoxy which are unsubstituted OR substituted by 1,2 OR 3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl OR C3-C6 cycloalkyl C1-C6 alkyl, OR ', SR ', C1-C6 alkyl-OR ', C1-C6 alkyl-SR ', COR COOR ', COSR ', SOR ', SO, and2r ', OCOR ', SCOR ', and substituted by a group selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C66 alkyl substituted by 0, 1,2 or 3 groups in amino or aminocarbonyl;
r' independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl or C1-C6 alkylcarbonyl with or without fluorine, chlorine or bromine;
r' respectively and independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base or C3-C6 naphthenic base C1-C6 alkyl which contains or does not contain halogen;
a represents halogen or amino;
b represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino or di-C1-C8 alkylamino, with or without halogen substitution;
c represents halogen or halogenated C1-C8 alkyl.
2. A substituted pyrimidinearyl ester derivative according to claim 1,
x represents C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, C2-C6 alkenyl or C2-C6 alkynyl;
y represents nitro or NR1R2，
Wherein R is1Represents H, unsubstituted or optionally substituted by 1R11Substituted C1-C6 alkyl, -COR12、OR13、SO2R14、NR15R16Or N ═ CR17R18；
R2Represents H, C1-C6 alkyl or-COR12；
Or NR1R2Represents N ═ CR21NR22R23、
Figure FDA0002673819350000023
Wherein R is11Independently represents hydroxy, C1-C6 alkoxy, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or substituted by halogen, C1-C6 alkyl, C1-C1Phenyl, naphthyl, substituted by 1-3 of the 6 alkoxy and nitro groups,
Figure FDA0002673819350000031
R12Represents H, C1-C14 alkyl or C1-C6 alkoxy;
R13represents H, C1-C6 alkyl, benzyl or CHR31C(O)OR32；R31Represents H or C1-C6 alkyl; r32Represents H or C1-C6 alkyl;
R14represents a C1-C6 alkyl group;
R15represents H, C1-C6 alkyl, formyl or C1-C6 alkylacyl; r16Represents H or C1-C6 alkyl;
R17represents H or C1-C6 alkyl; r18Represents H or C1-C6 alkyl;
R21represents H or C1-C6 alkyl;
R22、R23each independently represents H or C1-C6 alkyl;
a represents halogen or amino;
b represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino or di-C1-C6 alkylamino, with or without halogen substitution;
c represents halogen or halogenated C1-C6 alkyl.
3. A substituted pyrimidinearyl ester derivative according to claim 2,
x represents C1-C6 alkyl, C1-C6 alkoxy, C1-C4 alkylthio, halogen, C2-C6 alkenyl or C2-C6 alkynyl;
y represents nitro or NR1R2，
Wherein R is1Represents H, unsubstituted or substituted by 1R11Substituted C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, hydroxy, C1-C6 alkoxy, benzyloxy, phenyloxy,
Figure FDA0002673819350000032
C1-C6 alkylsulfonyl, amino, C1-C6 alkylamino, di-C1-C6 alkylamino or N ═ CR17R18；
R2Represents H, C1-C6 alkyl, C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl;
or NR1R2Represents N ═ CHNR22R23、
Figure FDA0002673819350000033
R11Independently represent hydroxyl, C1-C6 alkoxy, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, phenyl which is unsubstituted or substituted by 1 to 3 of halogen, C1-C6 alkyl, C1-C6 alkoxy and nitro, naphthyl,
Figure FDA0002673819350000034
Figure FDA0002673819350000035
R17Represents H or C1-C6 alkyl; r18Represents H or C1-C6 alkyl;
R22、R23each independently represents a C1-C6 alkyl group;
z represents an unsubstituted or substituted aryl or heteroaryl group, said "aryl" being phenyl or naphthyl, and "heteroaryl" being phenyl or naphthyl
Figure FDA0002673819350000041
Figure FDA0002673819350000042
Figure FDA0002673819350000043
Wherein, it is selected from halogen, nitro, cyano, thiocyanato, phenyl, benzyl or phenoxy which are unsubstituted or substituted by 1,2 or 3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C2 alkyl, with or without halogenOR ', SR', - (C1-C2) alkyl-OR ', - (C1-C2) alkyl-SR', COR ', COOR', COSR ', SOR', SO2R ', OCOR ', SCOR ', and 0, 1,2 or 3 of the amino or aminocarbonyl groups substituted by one or two groups selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C2 alkyl;
r' independently represents C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl C1-C2 alkyl, C1-C6 alkoxy C1-C2 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl or C1-C6 alkylcarbonyl which contains or does not contain fluorine, chlorine or bromine;
r' respectively and independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base or C3-C6 naphthenic base C1-C2 alkyl which contains or does not contain halogen;
a represents halogen or amino;
b represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino or di-C1-C6 alkylamino, with or without halogen substitution;
c represents halogen or halogenated C1-C6 alkyl.
4. A substituted pyrimidinearyl ester derivative according to claim 2,
x represents fluorine, chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, allyl or ethynyl;
y represents NH2，NHMe，N(Me)2，N(Et)2，NO2，
Figure FDA0002673819350000044
Figure FDA0002673819350000051
Figure FDA0002673819350000052
And unsubstituted or substituted by at least one group selected from methoxy, nitro, fluoro
Figure FDA0002673819350000053
Unsubstituted or substituted by methyl
Figure FDA0002673819350000054
Z represents an unsubstituted or substituted group selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, vinyl, ethynyl, cyclopropyl, trifluoromethyl, methoxy, vinyloxy, methylthio, ethylthio, methoxymethyl, methoxycarbonyl, methylthiocarbonyl, methylsulfonyl, amino, dimethylamino, nitro, cyano, thiocyanato, hydroxy, formyl, acetyl, cyano, amino, cyano, nitro, cyano, amino, nitro, cyano, amino, nitro, cyano,
Figure FDA0002673819350000055
Figure FDA0002673819350000056
Figure FDA0002673819350000057
Phenyl, naphthyl substituted by 1 to 3 groups of phenyl, phenoxy, benzyl or benzyl substituted by chlorine,
Figure FDA0002673819350000058
Figure FDA0002673819350000059
R' independently represents methyl, ethyl, isopropyl, vinyl, cyclopropylmethyl, methylsulfonyl, methoxycarbonyl, acetyl or methoxymethyl;
Figure FDA0002673819350000061
represents
Figure FDA0002673819350000062
Figure FDA0002673819350000063
5. A substituted pyrimidinylaryl ester derivative selected from any one of the following compounds:
Figure FDA0002673819350000064
Figure FDA0002673819350000065
Figure FDA0002673819350000071
Figure FDA0002673819350000081
Figure FDA0002673819350000091
Figure FDA0002673819350000101
Figure FDA0002673819350000111
Figure FDA0002673819350000121
Figure FDA0002673819350000131
Figure FDA0002673819350000141
Figure FDA0002673819350000151
Figure FDA0002673819350000161
Figure FDA0002673819350000171
Figure FDA0002673819350000181
Figure FDA0002673819350000191
Figure FDA0002673819350000201
6. a process for the preparation of substituted aryl pyrimidinate derivatives according to any of the claims 1 to 5, characterized by the following steps: carrying out esterification reaction on the compound shown in the general formula III and the compound shown in the general formula II to obtain a compound shown in the general formula I; the chemical reaction equation is as follows:
Figure FDA0002673819350000202
7. the process according to claim 6, wherein the reaction is carried out in the presence of triethylamine, PyBOP and a solvent selected from the group consisting of acetonitrile, DMF, dichloromethane and 1, 2-dichloroethane in combination with one or more solvents; the reaction temperature is 0-50 ℃.
8. A herbicidal composition comprising a herbicidally effective amount of at least one of the substituted aryl pyrimidineester derivatives defined in any one of claims 1 to 5.
9. A herbicidal composition according to claim 8, characterized by further comprising formulation adjuvants.
10. A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of the substituted aryl pyrimidineates derivatives defined in any one of claims 1 to 5 or a herbicidal composition defined in claim 8 or 9 to a plant or to a weed area.
11. Use of at least one of the substituted aryl pyrimidinederivatives as claimed in any of claims 1 to 5 or the herbicidal composition as claimed in claim 8 or 9 for controlling weeds.
12. Use according to claim 11, wherein the substituted pyrimidinylaryl ester derivative is used for controlling weeds in crops of useful plants, which are transgenic or genome editing technology treated crops.
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