CN113831299B - Benzoate compound and application thereof - Google Patents

Benzoate compound and application thereof Download PDF

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Publication number
CN113831299B
CN113831299B CN202010582185.7A CN202010582185A CN113831299B CN 113831299 B CN113831299 B CN 113831299B CN 202010582185 A CN202010582185 A CN 202010582185A CN 113831299 B CN113831299 B CN 113831299B
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compound
mmol
weeds
reaction
chloro
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CN113831299A (en
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陈霖
杨辉斌
马宏娟
王刚
崔东亮
李斌
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Application filed by Jiangsu Yangnong Chemical Co Ltd, Shenyang Sinochem Agrochemicals R&D Co Ltd filed Critical Jiangsu Yangnong Chemical Co Ltd
Priority to AU2021297861A priority patent/AU2021297861B2/en
Priority to PCT/CN2021/101396 priority patent/WO2021259224A1/en
Priority to EP21828024.6A priority patent/EP4169910A4/en
Priority to US18/002,421 priority patent/US20230227415A1/en
Priority to CN202180014764.4A priority patent/CN115103837B/en
Priority to BR112022026400A priority patent/BR112022026400A2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/38—Sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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

Abstract

The invention discloses a benzoate compound which has a structure shown in a general formula (I) or a stereoisomer thereof:

Description

Benzoate compound and application thereof
Technical Field
The invention belongs to the field of herbicides, and particularly relates to a benzoate compound and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of drug resistance to chemical pesticides, people continuously strengthen awareness of ecological environment protection, awareness of chemical pesticide pollution and pesticide influence on non-target organisms and importance of homing problems in pesticide ecological environments are continuously improved. With the progressive decrease in the area of cultivated land, the increasing population and the increasing demand for foodstuffs, people are forced to rapidly develop agricultural production technologies, improve and perfect cultivation systems, and there is a continuing need to invent new and improved herbicidal compounds and compositions.
CN1341105a discloses that the following compounds have herbicidal activity:
wherein R is 5 Can be carboxylic ester substituent COOR 20 。R 20 Can be selected from C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 Alkenyl or C 2 -C 6 Alkynyl groups and can be prepared from (C 1 -C 6 -alkoxy) carbonyl, (C 3 -C 6 -alkenyloxy) carbonyl, (C 3 -C 6 -alkynyloxy) carbonyl or C 1 -C 6 -alkoxy- (C) 1 -C 6 -alkoxy) carbonyl.
CN1341105a specifically discloses that the following compound KC (compound No. 30 in table 3 in the patent specification) has higher herbicidal activity:
in the prior art, the preparation and the application of the novel benzoate compound shown in the invention are not involved.
Disclosure of Invention
The invention aims to provide a benzoate compound with novel structure and good herbicidal activity and a herbicidal composition taking the benzoate compound as an active component, so as to meet the requirement of rapid production development.
The technical scheme of the invention is as follows:
the invention provides a novel benzoate compound, which has a structure shown in a general formula (I):
wherein:
w is selected from O or S;
X 1 selected from H or F;
X 2 selected from F, cl, br, I, CN, CONH 2 Or CSNH 2 ；
R 1 Selected from CH 3 -or CH 3 CH 2 -；
R 2 Selected from CH 3 -or CH 3 CH 2 -；
R 3 Selected from H or CH 3 -；
R 4 Selected from H or C 1 -C 3 An alkyl group;
R 5 selected from CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CHCH 2 -、CH 3 CH 2 CH(CH 3 )-、(CH 3 ) 3 C-、CH 3 CH 2 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CH CH 2 CH 2 -、(CH 3 ) 3 CCH 2 -、CH 3 CH 2 CH(CH 3 )CH 2 -、CH 3 CH 2 CH 2 CH(CH 3 )-、CH 3 CH 2 C(CH 3 ) 2 -、CH 3 CH＝CHCH 2 -、CH 3 C≡CCH 2 -、C 1 -C 10 Haloalkyl, C 1 -C 6 Alkylthio C 1 -C 6 Alkyl, C 1 -C 6 Alkylsulfinyl C 1 -C 6 Alkyl, C 1 -C 6 Alkylsulfonyl C 1 -C 6 Alkyl, (C) 1 -C 6 Alkyl group 2 Amino C 1 -C 6 Alkyl, C 3 -C 10 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 3 -C 10 Halogenated cycloalkyl, C 3 -C 6 Halogenated cycloalkyl C 1 -C 6 Alkyl, C 2 -C 10 Haloalkenyl, C 1 -C 6 Alkoxy C 2 -C 6 Alkenyl, C 1 -C 6 Alkylthio C 2 -C 6 Alkenyl, C 1 -C 6 Alkylsulfinyl C 2 -C 6 Alkenyl, C 1 -C 6 Alkylsulfonyl C 2 -C 6 Alkenyl group (C) 1 -C 6 Alkyl group 2 Amino C 2 -C 6 Alkenyl, C 3 -C 10 Cycloalkenyl, C 3 -C 6 Cycloalkyl C 2 -C 6 Alkenyl, C 3 -C 6 Halogenated cycloalkyl C 2 -C 6 Alkenyl, C 2 -C 10 Haloalkynyl, C 1 -C 6 Alkoxy C 2 -C 6 Alkynyl, C 1 -C 6 Alkylthio C 2 -C 6 Alkynyl, C 1 -C 6 Alkylsulfinyl C 2 -C 6 Alkynyl, C 1 -C 6 Alkylsulfonyl C 2 -C 6 Alkynyl, (C) 1 -C 6 Alkyl group 2 Amino C 2 -C 6 Alkynyl, C 3 -C 10 Cycloalkynyl radicals, C 3 -C 6 Cycloalkyl C 2 -C 6 Alkynyl, C 3 -C 6 Halogenated cycloalkyl C 2 -C 6 Alkynyl, phenyl C 1 -C 6 Alkyl, 5-7 membered alicyclic ring having 1-4 hetero atoms, 5-7 membered aromatic heterocyclic ring having 1-4 hetero atoms, 5-7 membered alicyclic heterocyclic ring having 1-4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, hydrogen on the phenyl, alicyclic and aromatic heterocyclic ring can be substituted by one or more substituents selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkoxy radicals C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl or phenyl substituted with one or more halo;
or, stereoisomers of the compounds of formula I.
Preferred compounds of the invention are those of the general formula (I):
w is selected from O or S;
X 1 selected from H or F;
X 2 selected from Cl, br or CN;
R 1 selected from CH 3 -；
R 2 Selected from CH 3 -；
R 3 Selected from H or CH 3 -；
R 4 Selected from H or CH 3 -；
R 5 Selected from CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CHCH 2 -、CH 3 CH 2 CH(CH 3 )-、(CH 3 ) 3 C-、CH 3 CH 2 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CH CH 2 CH 2 -、(CH 3 ) 3 CCH 2 -、CH 3 CH 2 CH(CH 3 )CH 2 -、CH 3 CH 2 CH 2 CH(CH 3 )-、CH 3 CH 2 C(CH 3 ) 2 -、ClCH 2 CH 2 -、ClCH 2 CH 2 CH 2 -、CH 3 ClCHCH 2 -、CH 2 Cl(CH 3 )CH-、ClCH 2 CH 2 CH 2 CH 2 -、CH 3 ClCHCH 2 CH 2 -、CH 3 CH 2 ClCHCH 2 -、CH 3 CH 2 CH 2 ClCH-、ClCH 2 CH 2 CH(CH 3 )-、ClCH 2 (CH 3 ) 2 C-、ClCH 2 CH 2 CH 2 CH 2 CH 2 -、CH 3 CH＝CHCH 2 -、ClCH＝CHCH 2 -、Cl 2 C＝CHCH 2 -、ClCH＝CClCH 2 -、CH 3 C≡CCH 2 -、ClC≡CCH 2 -or the following substituents:
or, stereoisomers of the compounds of formula I.
More preferred compounds of the invention are those of formula (I):
w is selected from S;
X 1 selected from F;
X 2 selected from Cl;
R 1 selected from CH 3 -；
R 2 Selected from CH 3 -；
R 3 Selected from H or CH 3 -；
R 4 Selected from H or CH 3 -；
R 5 Selected from CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CHCH 2 -、CH 3 CH 2 CH(CH 3 )-、(CH 3 ) 3 C-、CH 3 CH 2 CH 2 CH 2 CH 2 -、(CH 3 ) 2 CH CH 2 CH 2 -、(CH 3 ) 3 CCH 2 -、CH 3 CH 2 CH(CH 3 )CH 2 -、CH 3 CH 2 CH 2 CH(CH 3 )-、CH 3 CH 2 C(CH 3 ) 2 -、ClCH 2 CH 2 -、ClCH 2 CH 2 CH 2 -、CH 3 ClCHCH 2 -、CH 2 Cl(CH 3 )CH-、ClCH 2 CH 2 CH 2 CH 2 -、CH 3 ClCHCH 2 CH 2 -、CH 3 CH 2 ClCHCH 2 -、CH 3 CH 2 CH 2 ClCH-、ClCH 2 CH 2 CH(CH 3 )-、ClCH 2 (CH 3 ) 2 C-、ClCH 2 CH 2 CH 2 CH 2 CH 2 -、CH 3 CH＝CHCH 2 -、ClCH＝CHCH 2 -、Cl 2 C＝CHCH 2 -、ClCH＝CClCH 2 -、CH 3 C≡CCH 2 -、ClC≡CCH 2 -or substituents as follows：
Or, stereoisomers of the compounds of formula I.
The stereoisomers described in formula I refer to: when R is 3 And R is R 4 When the carbon atoms are different, i.e. the carbon atoms connected with the compound are chiral carbon atoms, the compound in the general formula I can be an R body or an S body or a mixture of the R body and the S body in different proportions.
In the definition of compounds of the general formula I given above, the terms used in the collection are defined as follows:
halogen means fluorine, chlorine, bromine, iodine. Alkyl refers to straight or branched chain forms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms, such as chloroethyl, trifluoromethyl, and the like. Cycloalkyl is meant to include groups in the form of cyclic chains such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl refers to straight or branched alkenyl groups such as 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl and the like. When the compound substituent is alkenyl, it also includes Z-type or E-type configurational isomer formed when two sides of the carbon-carbon double bond are connected with different atoms. Alkynyl refers to straight or branched chain alkynyl groups such as 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl and the like. Alkoxy refers to a group having an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. Alkylthio means a group having a sulfur atom attached to the end of an alkyl group, such as methylthio, ethylthio, n-propylthio, isopropylthio, terbutathio and the like. The alkylsulfinyl group means a group having a sulfinyl group attached to the terminal of the alkyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, an isopropylsulfinyl group, a tert-butylsulfinyl group and the like. Alkylsulfonyl refers to a group having a sulfonyl group attached to the end of the alkyl group, such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, tert-butylsulfonyl, and the like. By 5-7 membered alicyclic ring containing 1-4 hetero atoms is meant a 5-7 membered heterocyclic ring containing 1-4 hetero atoms without aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, etc. A5-7 membered aromatic heterocycle having 1 to 4 hetero atoms means a 5-7 membered heterocyclic compound having 1 to 4 hetero atoms and having an aromatic character, such as furan, thiophene, pyridine, etc.
The compounds of the general formula (I) according to the invention can be prepared by the following processes, in which the other radicals, unless otherwise indicated, are as defined above:
reacting the intermediate aminobenzoate (II) with a carbonylation reagent to form isocyanate (III), and reacting with 1, 3-disubstituted urea or 1, 3-disubstituted thiourea in an organic solvent at a temperature of between-10 ℃ and the boiling point of the organic solvent for 0.5 to 48 hours to obtain the general formula compound (I). The organic solvent may be selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, THF, dioxane, etc. The addition of basic substances, such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium bicarbonate, is advantageous for the reaction.
The carbonylation reagent is selected from triphosgene, carbonyl Diimidazole (DCI), phosgene, diphosgene, chloroformate, and the like.
Intermediate nitrobenzoate (IV) is reacted with a suitable reducing agent at a temperature of-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to prepare intermediate aminobenzoate (II). The solvent can be selected from alcohols such as methanol, ethanol, isopropanol, etc., ethers such as diethyl ether, tetrahydrofuran, dioxane, etc.
The reducing agent is selected from hydrogen, a catalytic amount of a transition metal or a catalytic amount of a transition metal compound; among them, transition metals are particularly selected from group VIII compounds, preferably Ni, pd, pt, etc. (used directly or supported via media such as activated carbon, aluminum oxide, silica, etc.); the hydrogen can be provided by a hydrogen storage steel cylinder, or can be generated in situ by active metals (such as reduced iron powder, reduced zinc powder and the like) under acidic conditions (such as hydrochloric acid and sulfuric acid) and participate in the reduction reaction.
Suitable reducing agents also include metal hydrides, semi-metal hydrides and derivatives thereof such as lithium aluminum hydride, diisobutylaluminum hydride, sodium borohydride, borane, etc.
Intermediate IV can be prepared by the following three routes:
route one:
intermediate nitrobenzoic acid (V, commercially available) and substituted hydroxycarboxylic acid ester (VI, commercially available) are dissolved in a suitable solvent and reacted at a temperature of-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours, and intermediate nitrobenzoic acid ester (IV) is prepared under the action of a dehydrating agent. The solvent may be selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane, etc. The dehydrating agent may be Dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl), etc. The addition of bases such as triethylamine, pyridine, 4-Dimethylaminopyridine (DMAP) and the like is advantageous for the reaction.
Route two:
the intermediate nitrobenzoate (IV) can also be prepared by reacting the intermediate nitrobenzoic acid (V) with the corresponding substituted carboxylic acid ester (VII, commercially available) having an easily leaving group in a suitable solvent at a temperature of from-10℃to the boiling point of the solvent for a period of from 0.5 to 48 hours. The solvent may be selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane, etc. The addition of basic substances, such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium bicarbonate, is advantageous for the reaction.
In the substituted carboxylic acid ester (VII), L is a leaving group such as chlorine, bromine, iodine, methylsulfonate group, p-toluenesulfonate group and the like.
Route three:
the intermediate nitrobenzoate (IV) can also be prepared by reacting the intermediate nitrobenzoic acid (V) with oxalyl chloride, thionyl chloride, phosphorus trichloride or phosphorus pentachloride in a proper solvent at the temperature of minus 10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to prepare acyl chloride (VIII), and then carrying out alcoholysis reaction with the substituted hydroxy carboxylic acid ester (V). Suitable solvents for preparing the acid chloride are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, THF, dioxane or dimethyl sulfoxide and the like. Suitable solvents for the alcoholysis reaction are selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc. The addition of a suitable base selected from organic bases such as DMF, triethylamine, N-dimethylaniline or pyridine is advantageous for the reaction.
In the compound, carboxylate groups are further introduced, and after the carboxylate groups are introduced, the whole molecule has larger difference in electronegativity, space structure and the like, so that the conductivity of the whole molecule in organisms such as plants is greatly different. The proper conductivity of bioactive molecules plays an important role in the exertion of drug effects. The suitability of bioactive molecule transduction properties is unpredictable and requires significant inventive effort to learn.
Compared with the known benzoate compounds, the compound containing two carboxylic ester structures simultaneously has unexpectedly high herbicidal activity, can effectively control dicotyledonous weeds after being used at a lower dosage, and has unexpectedly satisfactory effect on broadleaf weeds.
The technical solution of the present invention therefore also includes the use of the compounds of general formula (I) for controlling weeds.
The invention also relates to herbicidal agents containing the compounds of formula (I) as active ingredient. The weight percentage of the active components in the weeding composition is 5-90%. The herbicidal composition also includes an agriculturally acceptable carrier.
The herbicidal composition of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated in a formulation dissolved or dispersed in a carrier for easier dispersion when used as herbicides. For example: these chemicals may be formulated as wettable powders or emulsifiable concentrates. Thus, in these compositions, at least one liquid or solid carrier is added, and it is often necessary to add an appropriate surfactant.
A further embodiment of the present invention is a method of controlling weeds, which comprises applying a herbicidally effective amount of a herbicidal composition of the invention to the weeds or to the locus of the weeds or to the surface of the growth medium thereof. A more suitable effective amount is typically selected from 1 gram to 500 grams per hectare, with an effective amount of 2 grams to 250 grams per hectare being preferred. For certain applications, one or more other herbicides may be added to the herbicidal compositions of the present invention, thereby producing additional advantages and effects.
The compounds of the present invention may be used alone or in combination with other known pesticides, fungicides, plant growth regulators or fertilizers.
It should be understood that various changes and modifications can be made within the scope of the invention as defined in the appended claims.
Detailed description of the preferred embodiments
The following synthetic examples, as well as the results of the green test, are intended to further illustrate the invention and are not meant to limit the invention.
Synthetic examples
Example 1: 1-ethoxycarbonyl) benzoic acid (1-ethoxycarbonyl) ethyl ester of compound 241 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl)
Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-nitrobenzoic acid (1-ethoxycarbonyl) ethyl ester
A250 mL reaction flask was charged with 2-chloro-4-fluoro-5-nitrobenzoic acid (4.40 g,20.0 mmol), toluene (20 mL), thionyl chloride (3.0 mL,41.1 mmol), and the reaction was refluxed for 3h. The reaction system is changed from suspension to clear solution. The solvent and excess thionyl chloride were distilled off under reduced pressure and the residue was diluted with 10mL of dichloromethane for further use.
To a further 250mL reaction flask, methylene chloride (20 mL), ethyl lactate (2.65 g,22.4 mmol) and triethylamine (3.0 mL,21.5 mmol) were successively added, and the above-prepared acid chloride methylene chloride solution was added dropwise thereto at room temperature, and stirring was continued at room temperature for 2 hours after completion of the addition. The reaction solution was poured into 50mL of water, extracted with 50mL of methylene chloride, and the combined organic layers were washed with 30mL of saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 6.16g of a yellow liquid in 96% crude yield. The obtained (1-ethoxycarbonyl) ethyl 2-chloro-4-fluoro-5-nitrobenzoate is directly used in the next synthesis without further purification.
Step b) Synthesis of intermediate 5-amino-2-chloro-4-fluorobenzoic acid (1-ethoxycarbonyl) ethyl ester
In a 250mL reaction flask, 2-chloro-4-fluoro-5-nitrobenzoic acid (1-ethoxy-1-oxo-2-propanol) ester (6.16 g,19.3 mmol) was dissolved in a mixed solvent of 20mL ethanol and 20mL tetrahydrofuran, reduced iron powder (4.00 g,71.6 mmol) was added, concentrated hydrochloric acid (15.0 mL, about 180 mmol) was added dropwise thereto in an ice-water bath, and the reaction was resumed at room temperature for 1h after the completion of the addition. The solvent was distilled off under reduced pressure, and 50mL of water was added to the residue, which was extracted with ethyl acetate (30 mL. Times.3), and the combined organic layers were washed with 50mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 4.00g of a yellow liquid in a crude yield of 72%. The obtained 5-amino-2-chloro-4-fluorobenzoic acid (1-ethoxycarbonyl) ethyl ester is directly used in the next synthesis without further purification.
Step c) Synthesis of (1-ethoxycarbonyl) ethyl 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thio-1, 3, 5-triazin-1-yl) benzoate as Compound 241
To a 250mL reaction flask, 30mL ethyl acetate was added, followed by 5-amino-2-chloro-4-fluorobenzoic acid (1-ethoxycarbonyl) ethyl ester (4.00 g,13.8 mmol), triethylamine (2.5 mL,18.0 mmol) and carbonyldiimidazole (DCI, 5.60g,34.5 mmol) to form a solution, and the solution was heated to 50℃for 30min. 1, 3-dimethylthiourea (1.75 g,16.8 mmol) was added thereto, followed by heating to reflux and reacting for 2 hours. After completion of the reaction, 60mL of ethyl acetate was added thereto, and the mixture was washed with saturated brine (30 mL. Times.2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a brown viscous liquid. Column chromatography Separation (SiO) 2 EtOAc: p.e. =1:9, then 1:4) to give compound 241 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) ethyl benzoate 4.20g (1-ethoxycarbonyl) as a yellow liquid in 68% yield.
Example 2: compound 283 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) benzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester
Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-nitrobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester
To a 250mL reaction flask were added 2-chloro-4-fluoro-5-nitrobenzoic acid (5.49 g,25.0 mmol), ethyl α -hydroxyisobutyrate (4.00 g,30.0 mmol), 4- (N, N-dimethylamino) pyridine (DMAP, 0.30g,2.5 mmol) and methylene chloride (50 mL), and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl,9.60g,50.0 mmol) was added portionwise thereto with stirring at room temperature, and the reaction system was changed from suspension to a clear solution. After the addition was completed, stirring was continued at room temperature for 2 hours. The reaction solution was poured into 50mL of water, extracted with 50mL of methylene chloride, and the combined organic layers were washed with 30mL of saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2.70g of a yellow liquid in 33% crude yield. The intermediate 2-chloro-4-fluoro-5-nitrobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester obtained is directly used in the next synthesis without further purification.
Step b) Synthesis of intermediate 5-amino-2-chloro-4-fluorobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester
In a 100mL reaction flask, 2-chloro-4-fluoro-5-nitrobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester (2.70 g,8.10 mmol) was mixed with 20mL of methanol to prepare a solution, and 10% palladium on charcoal catalyst (0.25 g) was added thereto, and the reaction was carried out at room temperature for 2 hours with a hydrogen stream. After completion of the reaction by TLC, the catalyst was removed by filtration. The solvent was distilled off from the filtrate under reduced pressure to obtain 1.80g of a yellow liquid in a crude yield of 73%. The obtained 5-amino-2-chloro-4-fluorobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester is directly used in the next synthesis without further purification.
Step c) Synthesis of (1-methyl-1-ethoxycarbonyl) ethyl 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) benzoate as Compound 283
To a 100mL reaction flask, 15mL of toluene was added, followed by 5-amino-2-chloro-4-fluorobenzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester (1.80 g,6.0 mmol) and triphosgene (0.90 g,3.0 mmol) were added sequentially, heated to reflux and the reaction was kept under reflux for 2 hours. After returning to room temperature, a toluene solution of isocyanate was obtained for use.
15mL of toluene, 1, 3-dimethylthiourea (1.75 g,16.8 mmol) and triethylamine (1.0 mL,7.2 mmol) were sequentially added to a 100mL reaction flask, and the above-prepared toluene isocyanate solution was dropwise added thereto at room temperature, and after the completion of the dropwise addition, carbonyldiimidazole (DCI, 1.45g,9.0 mmol) was further added thereto, and the mixture was heated to reflux and kept under reflux for 2 hours. After completion of the reaction, 30mL of toluene was added thereto, and the mixture was washed with saturated brine (15 mL. Times.2), dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a brown viscous liquid. Column chromatography Separation (SiO) 2 EtOAc: p.e. =1:9, then 1:4) to give compound 283 2-chloro-4-fluoro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) benzoic acid (1-methyl-1-ethoxycarbonyl) ethyl ester 1.80g, as a white solid (m.p. 98-100 ℃) in 66% yield.
Other compounds of formula I, the structure and physical properties of which are shown in Table 1, can be obtained by replacing the starting materials according to the above-described method.
TABLE 1
Of part of the compounds 1 H NMR(CDCl 3 600 MHz) delta (ppm) data are as follows:
compound 241.01 (d, 1H, j=7.2 Hz), 7.41 (d, 1H, j=9.0 Hz), 5.32 (q, 1H, j=7.2 Hz), 4.24 (q, 2H, j=7.2 Hz), 3.78 (s, 6H), 1.61 (d, 3H, j=7.2 Hz), 1.26 (t, 3H, j=7.2 Hz).
Compound 242.02 (d, 1H, j=8.4 Hz), 7.41 (d, 1H, j=9.0 Hz), 5.32 (q, 1H, j=7.2 Hz), 4.30 (q, 2H, j=7.2 Hz), 3.78 (s, 6H), 1.61 (d, 3H, j=6.6 Hz), 1.29 (t, 3H, j=7.2 Hz).
Compound 243.8.02 (d, 1H, j=7.8 Hz), 7.41 (d, 1H, j=9.0 Hz), 5.32 (q, 1H, j=7.2 Hz), 4.23 (q, 2H, j=7.2 Hz), 3.78 (s, 6H), 1.61 (d, 3H, j=6.6 Hz), 1.29 (t, 3H, j=7.2 Hz).
Compound 257 8.04 (d, 1H, j=7.8 Hz), 7.42 (d, 1H, j=9.0 Hz), 5.37 (q, 1H, j=7.2 Hz), 4.39-4.48 (m, 2H), 3.78 (d, 6H, j=3.0 Hz), 3.71 (t, 2H, j=6.0 Hz), 1.65 (d, 3H, j=7.2 Hz).
Compound 283 7.91 (d, 1H, j=7.8 Hz), 7.39 (d, 1H, j=9.0 Hz), 4.22 (q, 2H, j=7.2 Hz), 3.78 (s, 6H), 1.68 (s, 6H), 1.26 (t, 3H, j=7.2 Hz).
Example of biological measurement
Example 3: determination of herbicidal Activity
Sowing broadleaf weeds (zinnia, abutilon) or grassy weeds (green bristlegrass and barnyard grass) seeds into paper cups with 7cm diameter and containing nutrient soil, covering 1cm after sowing, compacting, watering, culturing in a greenhouse according to a conventional method, and carrying out stem and leaf spraying treatment after 2-3 leaf periods of weeds.
After the raw material is dissolved in acetone, the solution to be tested with the required concentration is prepared by using 1 per mill of Tween 80 to stand tap water according to the test requirement. Spraying treatment (spraying pressure 1.95 kg/cm) on crawler-type crop spraying machine (manufactured by UK Engineer Research Ltd.) according to the experimental design dose 2 The spraying amount of the spray liquid is 500L/hm 2 Track speed 1.48km/h). The test was repeated 3 times. After the test materials are treated, the test materials are placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test materials are placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the chemical agents is observed and recorded, after the test materials are treated, the control effect of the test materials to the weeds is visually detected at regular intervals, the test materials are expressed by 0-100%, and 0 represents no control effect and 100 represents complete killing.
The test results show that the compound of the general formula I has high prevention effect on various weeds. Of the compounds tested, compounds 241, 242, 243, 283 were administered at a dose of 150g a.i./hm 2 Has better control effect on the zinnia, the abutilon and the barnyard grass, and the inhibition rate is 100 percent.
According to the above test method, a parallel test of herbicidal activity was carried out by selecting a part of the compound of the general formula I and the following compound KC specifically disclosed in patent CN1341105A (compound No. 30 in Table 3 of the specification) at an application dose of 37.5g a.i./hm 2 And 9.375g a.i./hm 2 . The results are shown in Table 2.
Table 2: herbicidal activity of a part of the compounds of the general formula (I) (post-emergence inhibition%)

Claims (4)

1. A benzoate-type compound, which is prepared from the compound,
。
2. use of the benzoate compound according to claim 1 for controlling weeds.
3. A herbicidal composition characterized in that: the weeding composition is an active substance and an acceptable carrier, the active component is the benzoate compound in claim 1, and the weight percentage of the active component in the composition is 1-99%.
4. A method of controlling weeds in a herbicidal composition according to claim 3, wherein: a herbicidal composition according to claim 3 in a herbicidally effective amount applied to weeds or to a growth medium or locus of weeds.
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DE4228000A1 (en) * 1992-08-24 1994-03-03 Bayer Ag 3-aryl-triazine-2,4-diones
CN1341105A (en) * 1999-02-23 2002-03-20 巴斯福股份公司 1-aryl-1,3,5-triazine-4-thione-2,6-diones, production thereof and use thereof as herbicides
WO2019162702A1 (en) * 2018-02-26 2019-08-29 AlzeCure Pharma AB Triazine derivatives for treating diseases relating to neurotrophins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4228000A1 (en) * 1992-08-24 1994-03-03 Bayer Ag 3-aryl-triazine-2,4-diones
CN1341105A (en) * 1999-02-23 2002-03-20 巴斯福股份公司 1-aryl-1,3,5-triazine-4-thione-2,6-diones, production thereof and use thereof as herbicides
WO2019162702A1 (en) * 2018-02-26 2019-08-29 AlzeCure Pharma AB Triazine derivatives for treating diseases relating to neurotrophins

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