JPH06505723A - Haloacetic acid derivative herbicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Haloacetic acid derivative herbicide [Field of invention] The present invention relates to a new haloacetic acid derivative having herbicidal activity, a method for preparing the same, and a method containing the same. A herbicide composition comprising:

[Conventional technology]

Certain pyrimidinyl and triazinyl acetic acid derivatives having herbicidal activity are e.g. It is described in the applicant's earlier European Patent Specification No. 410,590.

[Details of the invention]

In one embodiment, the invention provides the following formula: [wherein A is -N= or -CH=; X is halogen; R1 and R2 are the same or different and each represents alkyl, alkoxy, ha With loalkyl, haloalkoxy, halo, alkylamino or dialkylamino Yes: R3 is -CN, -COOR5, -CONR6R7, -C3N11. , -c Ho, -C)l=Z.

-C1 ((0 full kill) 2, -CII, OII, -CI+20R9 Mataha a substituted or unsubstituted 5 bonded through a ring carbon atom between two ring heteroatoms or 6-membered heterocyclic group; R4 is Hl or substituted or unsubstituted alkyl group; alkenyl, alkynyl, cycloalkyl, aryl or aralkyl group. can be; R11 is H, -N=CR'aR8b1 or substituted or unsubstituted alkyl, alkyl a kenyl, alkynyl, cycloalkyl or aralkyl group; R6 is Hl or substituted or unsubstituted alkyl, alkenyl, alkynyl, cyclo is a loalkyl, aryl, aralkyl or heteroaryl group; R7 is the group defined for R6, or -3O,R--OR1-CN1-O R”, -NO, or -NHRIO; or R6 and R7 together form a ring; R8 is -NR@aBsb, or substituted or unsubstituted alkyl, alkenyl, aryl ruquinyl, cycloalkyl, aralkyl, aryl or heteroaryl group. R9 is substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl; Kyl, aralkyl or acyl group: 11110 is a group defined by R@, or substituted or unsubstituted aryl or or a heteroaryl group: Z is =N-NR'R'2 or =NOR' R: R is as defined in R6, or is a substituted or unsubstituted acyl group. Yes; and Roll and R6b are the same or different and are each a group defined by R@. Yes, but However, if R4 is ortho-substituted phenyl or naphthyl, the ortho-substituted phenyl or naphthyl Substituents are halogen, -NO, -〇H1-OR'', -3R1-3R', -3OR8 , -3O2R', -NII, -NR'RIG, aryl or heteroaryl and salts thereof.

Any alkyl group present in the molecule preferably has from 1 to 8 carbon atoms WA, and also Preferably it has 1 to 6 pieces, particularly preferably 1 to 4 pieces. Certain preferred unsubstituted Alkyl or alkyl-containing groups include methyl, ethyl, n-propyl, isopropyl, Includes pill, n-butyl, t-butyl, methoxy, ethoxy and n-propoxy. Contains.

If the alkyl groups in the molecule are substituted, this may mean e.g. one or more halogen atoms (e.g. fluorine, chlorine or bromine), alkyl atoms of 1 to 4 carbon atoms oxy groups (e.g. methoxy or ethoxy), hydroxy, nitro, mercapto, amino, substituted amino, cyano, acyl, aryl or heteroaryl groups; may be substituted with a group of formula -3R' or -3OR''. Certain preferred substitutions Alkyl-containing groups include chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, Including dimethyl, difluoromethoxy, methoxyethyl and ethoxyethyl Ru.

Any alkenyl or alkynyl group present in a molecule has 2 to 6 carbon atoms. For example, allyl, vinyl or propargyl. like this Either alkenyl or alkynyl groups are preferably unsubstituted, but optionally For example, it may be substituted with halogen.

Any cycloalkyl group present in the molecule preferably has from 3 to 7 carbon atoms. cyclopentyl or cyclohexyl is particularly preferred. I like this or unsubstituted.

Any halogen atoms present in the molecule are preferably fluorine, chlorine or bromine. It is.

As used herein, the term "aryl" refers to an aromatic carbocycle, which is a mononuclear , for example phenyl, or polynuclear, for example naphthyl. present in molecules Any aryl group is preferably a substituted or unsubstituted phenyl group.

Therefore, any aralkyl group present in the molecule is preferably substituted or unsubstituted. It is a substituted benzyl group.

Any aryl group present in the molecule, if substituted, preferably has one or more halogen atoms (e.g. fluorine, chlorine or bromine), 1 carbon atom ~4 alkyl or alkoxy groups (e.g. methyl, ethyl, methoxy or ethoxy), hydroxy, nitro, mercapto, amino, substituted amino (e.g. alkylamino, dialkylamino or acylamino groups, especially where the alkyl part is carbon (having 1 to 4 elementary atoms), cyano, acyl, aryl or heteroaryl or a group of the formula -3R" or -3OR".

The term heteroaryl as used herein refers to an aromatic heterocyclic group; It may be mononucleate or polynucleate. The mononuclear heterocyclic group is preferably 5 or 6 ring atoms and at least one nitrogen, oxygen or sulfur atom, e.g. Bafuryl, chenyl, pyrrolyl, oxacylyl, thiazolyl, imidazolyl, pyrrolyl Lazolyl, pyridinyl, pyrazinyl or thiadiazolyl.

Polynuclear heterocyclic groups are preferably benzoheterocyclic groups, such as indolyl, benzophyl ranyl, benzimidazolyl or quinolinyl. Such mononuclear or polynuclear The nuclear heterocyclic group optionally contains one or more halogen atoms, e.g. fluorine or bromine atoms, nitro groups, substituted or unsubstituted amino groups (e.g. alkylamino, dialkylamino or acylamino groups, especially where the alkyl part is carbon (having 1 to 4 elementary atoms), cyano group, or alkyl having 1 to 4 carbon atoms or substituted by an alkoxy group, e.g. methyl, ethyl, methoxy or ethoxy. It may have been replaced.

As used herein, the term "acyl" refers to carboxylic acids, sulfonic acids or phosphoric acids. Refers to residues of containing acids, such as alkanoyl, alkenoyl, alkinoyl, and loalkanoyl, aralkayl, aroyl, carbamoyl, thiocarbamoyl , alkoxycarbonyl, sulfonyl, sulfamoyl and phosphonyl groups. In these groups, alkyl, alkenyl, alkynyl or aryl groups may be substituted or unsubstituted.

Salts of compounds of formula I are preferably alkali metal (e.g. lithium, sodium or ammonium salt, or cyclohexylamide salts formed from organic amines such as chlorine or piperidine.

A is preferably -C■=.

X is preferably chlorine, fluorine or bromine, preferably fluorine.

R is preferably chloro, methyl, methoxy, difluoromethoxy or ethoxy and particularly preferably methoxy.

R1 is preferably methyl, methoxy or difluoromethoxy, particularly preferred Or methoxy.

R3 is preferably the group -COOR', where R5 optionally has 1 to 1 carbon atoms. 4 alkyl, preferably methyl, ethyl or tetrahydrofurylmethyl has been replaced.

An example of a preferred group for R3 is -C0NR'R' (wherein R8 is hydrogen and R7 is SO, CH8, SO□N(C113)2, N112, phenyl or 3-pyri or R6 and R7 together with the nitrogen atom to which they are attached. to form a ring, e.g. a morpholimo group), -cn=z (wherein Z is NNHCO CIIs or N0CHzC02CJs), -CH(OCH3)t, -C 112OR' (wherein R9 is CI'12COtCJs or so, cn3 ), or a dioxolane, thiazolyl or oxadiazolinone ring.

R4 is preferably an unsubstituted alkyl group, especially isopropyl, 5eC-butyl or is an aryl group, especially phenyl.

Specific preferred compounds of the invention are shown in the Examples below.

R3 is a group -COOR5 (wherein R5 is something other than hydrogen), and R4 is hydrogen The compound of formula (2) is a compound of the following formula: [wherein ASR' and R2 are as described above] Z is an anionic leaving group, such as a halogen group or a group of the formula -3O,Z' (in the formula 2' is alkyl or aryl having 1 to 4 carbon atoms) , in the presence of a base, the formula XCH, C00R5 (wherein R5 is as described above) , other than hydrogen, and X is a halogen) It can be prepared by any method to obtain the desired compound.

The base used is preferably lithium diisopropylamide and the reaction is as desired. or in a suitable solvent, e.g. tetrahydrofuran, e.g. cooled to about -78°C. Do it while refusing.

Is R3 a group -CN, -COOR' or -CONR'R? The compound of formula ■ is , the following formula: [In the formula, A, R1, R" and R4 are as described above, and Rsa is -CN, -COOR5 or C0NR'R' (in the formula, R5, R6 and R7 are as described above) ) is prepared by a method of halogenating the compound to form the desired compound. can be manufactured.

Halogenation can be carried out using conventional methods, depending on the nature of the halogen used. Ru. Bromination may be carried out using, for example, N-bromosuccinimide. Fluorination The compound of formula ropylamide and then the anion formed is treated with a fluorinating agent, e.g. oro-N-propyl-p-toluenesulfonamide or N-fluoro-N'- This can be done by reacting with chloromethyltriethylenediamine salt. Ru.

The compound of formula ■ and the method for its preparation are described in European Patent Specification No. 410,590. ing. Any compound 2■ that is not listed there can be treated in the same manner as described above. and prepare the vine.

R3 is a group -CN, -COOR', -CIIO or -CI-1. OR, R1 and R1 are each alkyl, alkoxy, amino or alkylamino Compounds of formula l have the formula: [wherein R1, R2, R4, X and A are as defined above] ) is reacted with an appropriate electrophilic substance in the presence of a strong base to form the desired compound. It can be prepared by the following method.

The strong base used is, for example, butyllithium or lithium diisopropylamide. The reaction is preferably carried out at a low temperature, e.g. -78°C, in a suitable solvent, e.g. Carry out in lahydrofuran.

Suitable electrophiles include cyanates (e.g. phenyl cyanate), chloroforme salts (e.g. alkyl chloroformates), aldehydes (e.g. formaldehyde), ) and formamide (e.g. formdimethylamide).

Compounds of formula (1) where R1 and R2 are alkyl are prepared by standard methods. R Compounds of formula (1) where 1 and R2 are alkoxy, amino or alkylamino are , formula R'-CIl(X)-f (wherein R4 and X are as described above, and W is an acid, ester, acid chloride, amide or nitrile group] carboxylic acid The derivative has the formula R'-C(=NH)-^-C(=NH)-R" [wherein R1, R2 and and A are as described above].

Compounds of formula I, in which R4 is other than hydrogen, also include corresponding compounds in which R4 is hydrogen. by alkylation or arylation methods known per se or by those skilled in the art. It can be prepared by similar methods well known in the art.

Is R3 -CN, -COOR' and -CONR6R? of formula I that is other than Compounds can be prepared from such compounds by conventional methods well known to those skilled in the art.

In particular, compounds of formula (3) in which R3 is carboxy can be prepared from the corresponding ester by hydrolysis. and the acid or ester functionality can be prepared by known methods. can be further converted into various other groups.

For example, a compound of formula I in which R3 is the group -COOR5 may be R3 is a group -cHO (use equivalent to 1 molar ratio of hydride) or - Reduce to the corresponding compound which is CII, OH (using 2 molar ratio equivalent of hydride) be able to. The reduction is conveniently carried out in a suitable solvent such as tetrahydrofuran. For example, this is carried out while cooling to 5°C.

The compound of formula (1) in which R3 is -C1l, OR is acylated or etherified to form R Corresponding compounds in which 3 is the group -CII, OR' can be obtained.

Compounds of formula 1 in which R3 is -C■0 can be prepared in a known manner by the corresponding hydrazone 11. in a suitable solvent such as an alcohol. Reaction with N-NR’R” compound ), oxime (II, NOR' in a suitable solvent such as alcohol) ), ketal, 1,3-dioxolane, 1,3-dithiola 1,3-dioxane, 3-dithiane or imidazolidine (e.g. acid catalyst) In the presence of a medium, 2RQI (or ■Q-(Cut)z where Q is OlS or NH -s-QH compound).

Furthermore, the compound of formula (■) in which R3 is carboxy can be obtained by first reacting an acid with thionyl chloride. to give the corresponding acyl chloride, which is then converted into a compound of formula NaNH302R' A two-step process in which R3 is a group -CONH3O2R ” can be converted into the corresponding compound.

Salts of compounds of formula I can be prepared by preparing the corresponding non-chlorinated compounds of formula I by methods known per se. prepared by reacting the compound with a suitable salt-forming base.

Compounds of formula (3) in which R3 is -CN can be prepared by known methods (e.g. pyridine, (reaction with hydrogen sulfide in a suitable solvent) for the corresponding thioa Can be converted to mido.

Compounds of formula I where R3 is a heterocycle, wherein R3 is -CN.

-C3NR, or -CONR'R' for the corresponding compound of formula I. It can be prepared by ring closure methods which are well known per se. For example, R A compound of formula I in which 3 is -CN can be converted into a compound of formula I in which R3 is -C (=NH ) Nl! , which can further be converted to the corresponding compound which is α-halo by reacting with ketones, α-haloacid chlorides, or β-diketones, respectively. imidazoles, imidasilones and pyrimidines can be obtained. similarly , the ring-closing reaction is performed when R3 is -C3N11. For a compound of formula ■ which is, for example, di or by reaction with bromoethane of formula I, wherein R3 is -CONR'R' For compounds, this can be done, for example, by reaction with acid chlorides or anhydrides. can.

The compound of formula ■ and its salts have herbicidal activity against a wide range of broad-leaved trees and weeds. However, it is relatively safe for certain crop types. In other words, these are herbicides. as a selective herbicide, especially for cereals such as corn, wheat or Effective on rice, beet crops, such as sugarcane, soybeans or cotton.

Therefore, in another aspect, the present invention provides Provided are herbicidal compositions containing one or more compounds of formula I or salts thereof in do.

Compositions of the invention typically contain from 0.01 to 99% by weight of a compound of the invention, and , usually initially from 0.5 to 99% by weight, preferably from 0.5 to 85% by weight, particularly preferably It is prepared as a concentrate containing 10-50% by weight. If necessary, like this Before applying the concentrate to the area to be treated, the active ingredient should be added to 0.0% of the application formulation. Dilute to 1-5% by weight.

The carrier may be water, in which case an organic solvent may also be present, although it is not usually used. good. Flowable suspension concentrates are prepared by combining the compound with water, a wetting agent, and a suspending agent such as xane. It may be prepared by grinding with tan gum.

The carrier can also be a water-immiscible organic solvent, such as carbon having a boiling point of 130-270°C. hydrogen chloride, such as xylene (in which the compound is dissolved or suspended; water Emulsifiable concentrates containing immiscible solvents may be prepared using surfactants; As a result, the concentrate acts as a self-emulsifying part in water.

The carrier can also be a water-miscible organic solvent, such as 2-methoxyethanol, methanol , propylene glycol, diethylene glycol, diethylene glycol monoester It may be thyl ether, methylformamide or dimethylformamide.

The carrier can also be a finely divided or granular solid. Appropriate Examples of solids are limestone, viscosity, sand, mica, chalk, acpurguide, diatomite. perlite, seviolite, silica, silicates, lignosulfonates and It is a solid fertilizer. The carrier can be natural or synthetic, or modified natural It can be a substance.

Wettable powders that are soluble or dispersible in water are used to combine particulate compounds with particulate carriers. Mix or spray the molten compound onto the granular carrier to form a wetting agent and dispersant. may be formed by mixing the powder mixture and finally milling the entire powder mixture. .

Aerosol compositions can be used to transport the compound into a propellant gas, such as a polyhalogenated alkane, e.g. e.g. by mixing with dichlorofluoromethane and, suitably, with a solvent. It can be done.

The term "surfactant" is used in a broad sense and includes emulsifiers, dispersants, etc., which have various names. agents and wetting agents.

Such reagents are well known to those skilled in the art.

The surfactants used are anionic surfactants, such as phosphoric acid and aliphatic alcohols. Monoesters or diesters of ethoxylates or such esters salts, aliphatic alcoholates, e.g. sodium dodecyl sulfate, ethoxyl aliphatic alcohol sulfate, ethoxylated alkylphenol sulfate lignin sulfate, petroleum sulfonate, alkylaryl sulfonate , such as alkylbenzene sulfonates or lower alkylnaphthalene sulfones. salts of sulfonated naphthalene formaldehyde condensates, sulfonated phenols salts of formaldehyde condensates, or more complex sulfonates, e.g. amides Sulfonates, such as sulfonated condensation products of oleic acid and N-methyltaurine , or a dialkyl sulfosuccinate, such as dioctyl succinate. Contains thorium sulfonate.

Surfactants also include non-ionic substances such as fatty acid esters, fatty alcohols, etc. condensation of fatty acid amide or alkyl-substituted phenol with ethylene oxide aliphatic esters of polyhydric alcohol ethers, such as sorbitan fatty acid esters condensation products of such esters with ethylene oxide, e.g. Ethylene sorbitan fatty acid ester, ethylene oxide and propylene oxide Block copolymers, acetylenic glycols such as 2.4.7.9-tetramethane Tyl-5-decyne-4,7-diol or ethoxylated acetylenic glycosyl Contains

Surfactants can also contain cationic substances, such as alkyl- and/or aryl -Substituted quaternary ammonium compounds, such as cetyltrimethylammonium bromide , or an ethoxylated tertiary aliphatic amine.

Preferred surfactants include ethoxylated fatty alcohol sulfates, lignin, sulfonates, alkyl-aryl sulfonates, sulfonated naphthalene sulfonates salts of formaldehyde condensates, salts of sulfonated phenol formaldehyde condensates, Sodium oleyl N-methyltauride, dialkyl sulfosuccinate, alkaline There are kylphenol ethoxylates, and aliphatic alkyl ethoxylates.

The active compound according to the invention may be another pesticide, such as a herbicide, fungicide or insecticide, or It may be mixed with plant growth regulators, especially other herbicides. Another suitable herbicide is Torie Tazine, Linuron, MCP^, dichlorprop, isoxaben, diflufeny Can, Metrafluor, Fluometuron, Oxyfluorfen, Fuomesafen , Pentacine, Promethrin, Norflurazone, Crocin, EPTC, Imaza and especially isoproturon, metabenzthiazuron, trifluralin, Soquinil, bromoxynil, benazoline, mecoprop, fluroxivir, a LaCroix, Atifluorofene, Lactofen, Metribuzin, Bendimethalin , etofumesate, penfresate, fenmedipham, penzofenap, bu tachloro, clomethoxyfene, dimepiperate, mefenacet, molinate , nabroanilide, oxacyacin, biperofos, promethrin, biladix Phen, pyrazosulfuron-ethyl, bensulfuron, cystrin, virazole t, pretilacroa, thiobencarb, and pyributicarb.

The compounds of the invention can be used in plants, soil, land or aquatic areas, especially where crops are grown. It may be applied to land that is The compound shows both pre- and post-developmental activity and 1 g It may be used at a rate of ~2 kq/ha.

〔Example〕

The invention is illustrated by the following examples. In the examples, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, 5-Bu is 1-methylpropyl, Oct is octyl , cyhex is cyclohexyl, THF is tetrahydrofuranmo, Ph is phenate. It's Niru.

Example 1 Ethyl 2-fluoro-2-(4,6-cymethoxypyrimidin-2-yl)acetate root Butyllithium (1.6M solution 2b+/ in hexane) was added in a dry oven under nitrogen at -78°C. Diisopropylamine (4,94t/) in trihydrofuran (Loom/) was added and the mixture was stirred for 30 minutes. in dry tetrahydrofuran (20s+/) of ethyl fluoroacetate (2,519) was added at -60°C and the mixture was stirred for 1 hour. Hexamethylphosphoric triamide (5,12++/) was added and the mixture was stirred for an additional 10 minutes. Next, 4,6-simethoxy-2-methoxy Rusulfonylpyrimidine (5,09) was added in portions and the temperature of the reaction mixture was 2. ．． The temperature rose to room temperature within 5 hours. Saturate the reaction mixture with ammonium chloride and salt The aqueous phase was extracted with ethyl acetate and the combined organic layers were washed with sulfuric acid solution. Dry with magnesium and evaporate. The obtained product was dissolved in hexane/ethyl acetate. Chromatography on silica gel using (0-20% ethyl acetate) The desired compound (0.56q) was obtained as a colored oil. Refractive index at 20°C = 1, 4 829 Example 2 Ethyl 2-(4,6-cymethoxypyrimidin-2-yl)-2-fluoro-3- Butyl lithium methylbutanoate (12.8 g of a 1.6 M solution in hexane + 7 liters) diisopropyl in tetrahydrofuran (120 mJ) dried under nitrogen at -78 °C. Amine (3.05 t/) was added and the mixture was stirred for 30 minutes. dry tetrahydride The product of Example 1 (3,49) in Lofuran (20t/) was added at -65°C; The mixture was stirred for 1 hour, during which time the temperature rose to -30°C. Cool to -60℃ After that, 3.189 g of hexamethylphosphoric triamide was added and the mixture was heated to 15 g. Stir for a minute. Next, 2-iodopropane (3,49) is added and the mixture is Stir at room temperature for an hour, then dilute it with diethyl ether Loom/ and saturate. Washed with ammonium chloride and sodium chloride solutions.

The aqueous phase was extracted with diethyl ether and the organic layer was dried over magnesium sulfate and evaporated. I set it. The resulting yellow oil was finally diluted with hexane/ethyl acetate (0-5% acetic acid). Chromatography on silica gel using (ethyl) yields the desired product 1.4 I got 69. Refractive index at 20°C = 1.4756 Example 3 Methyl 2-(4,6-cymethoxypyrimidin-2-yl)-2-fluoro-2- Phenyl acetate method A Methyl 2-(4,6-cymethoxypyrimidin-2-yl)-2-phenylacete -) (1,29) dissolved in tetrahydrofuran (25 mA') and the solution brought to 5 °C. Cool and add n-butyllithium (2.5M in hexane; 1.7 μl) dropwise. added.

The solution was stirred for 20 minutes and then diluted with toluene (14t/).

N-Fluoro-N-propyltoluenesulfonamide (1,59) was added and the solution The solution was stirred at room temperature under nitrogen for 20 hours and then treated with saturated ammonium chloride solution (300,z ).

Extracted with ether, washed the organic layer, dried and then evaporated to dryness. the residue, Column on silica using 15% ether in Vetrol 60-80 as eluent Purification by chromatography gave the desired product 0.959 as a yellow oil. Obtained.

Method B (a) 4.6-Simethoxy 2-(α-fluorobenzyl)pyrimidine Dimethylmalonimidate dihydrochloride (11,09) was dissolved in dichloromethane at -40°C. (10 To/). Ethyldiisopropylamine (38,9111) was lubricated for 15 min at -40°C and then quenched in dichloromethane (15 ml). -Fluoro-2-phenylacetyl chloride (11,09) at -40°C for 10 minutes It dripped over time. The reaction mixture was allowed to warm to room temperature and was incubated overnight. Then dichlorometh further diluted with ammonium chloride solution, then washed with water and magnesium sulfate. Dry. The cyclomethane solution was evaporated to dryness to give the desired product 13.99 .

(b) Methyl 2-(4,6-simethoxypyrimidin-2-yl)-2-fluoro -2-phenylacetate n-butyllithium (2.5M in hexane, 1. 7 mA') was di-distilled under nitrogen in dry tetrahydrofuran (15 ml) at -78°C. Added to sopropylamine (0,59w+1). Stir this solution for 30 minutes, Next, the product of step (a) above (1,09 ) solution was added over 20 minutes. meadow in dry tetrahydrofuran (10ml) Add methyl chloroformate (0,49) over 15 minutes at -78°C and mix the reaction. The material was slowly brought to room temperature and then added to an aqueous ammonium chloride solution. blend was extracted with ether, the extract was washed with water, dried over magnesium sulfate, and evaporated to dryness. Solidification yielded 1.08 q of desired product similar to Method A above.

Example 4 Methyl 2-chloro-2-(4,6-cymethoxypyrimidin-2-yl)-2-ph phenyl acetate Methyl 2-(4,6-cymethoxypyrimidin-2-yl)-2-phenylacete (2,09) and N-chlorosuccinimide (2,09) for 18 hours. The mixture was stirred under reflux in carbon tetrachloride (25 ml) under low lighting. Filter the reaction mixture and evaporated to dryness, and the residue was eluted with ether:hexane (1:1). It was purified by column chromatography on silica, and the product was purified as a pale yellow oil. The desired product (2,169) was obtained.

Example 5 2-Fluoro-3-methyl-2-(4,6-cystoxyl,3,5-triazid (2-yl)butan-1-olethyl 2-fluoro-3-methyl-2-(4 ,6-Simethoxy1.3.5-)riazin-2-yl)butanoate (1,5 9) (see Example 11 below) was dissolved in tetrahydrofuran (40ml), The solution was cooled to 5°C under nitrogen. Diisobutylaluminum hydride (hexa 1.0M during operation.

118/) was added and the mixture was stirred at room temperature for 24 hours, after which it was mixed with water (51/ 1/) was added dropwise. The solution was stirred for an additional 30 min and silica (Log) was added. Ta. The suspension was filtered and the solution was dried and evaporated. Chromatography of the residue The desired compound (0,229) was obtained as a white solid. Melting point 72 ~75℃ Example 6 2-Fluoro-3-methyl-2-(4,6-cystoxyl,3,5-triazid (2-yl)butyl acetate The product of Example 5 (0,609) was triturated at 5°C. Dissolved in dry ether (40++1) with ethylamine (0,35ml) , acetyl chloride (0,18 m/) in dry ether (1 (1+1)) Ta. The solution was left at room temperature for 2 days, then filtered, and the organic layer was washed with water and dried. . The residue was purified by chromatography to give the desired product as a clear oil. 0.35q was obtained.

Example 7 2-Fluoro-3-methyl-2-(4,6-simethoxypyrimidin-2-yl) butanoic acid Methyl 2-fluoro-3-methyl-2-(4,6-diphtoquine pyrimidine-2- ) butanoate (1,09) (see Example 9 below) was dissolved in methanol (7 m /) and treated with 5N sodium hydroxide solution (1,5++ l) at 5-10°C. I understood. Methanol was evaporated off, the residue was treated with water and acidified with 5N hydrochloric acid, Saturated with sodium chloride and extracted with ether. Saturated sodium chloride solution in ether and dried over magnesium sulfate. obtained by evaporating ether The product was triturated with pentane to give the desired product (0,879).

Examples 8-48 A compound of formula (2) in which R1 and R2 are both methoxy is prepared as in the above example. It was prepared as follows.

Same method as in Example 1 NoAR’ R’ X 8 N C00Et HF Yellow oil Same method as Example 2 NoAR’ R’ X 9 COO1le 1-Pr F rdl, 476210 CHC00Et 5 -Bu　F　Colorless oily substance 11　N　C00Et　1-Pr　F　mp48~49 ℃12 N C00Et 5-Bu F Yellow oily substance 13 N C00Et C 1(Et)z　F　bp160℃/Q, 1mwHg14　N　C00Et　CH lCOt-Bu　F Pale yellow gum-like substance 15　N C00Et　n-Pr　F Pale Yellow gum-like substance 16 N C00Et CHole) Ph F Pale yellow gum-like substance 1 7 N C00Et (jl(llie) COOEt F pale yellow gum-like substance 18 N C00Et C1 ((Iris e) CN F Pale yellow gum-like substance 19 N C00 Et　CO(Me)COIIe　F Light orange oil Method of Example 3 (Method B) and similar No　A　　　R”　R’　X 20 CHCoon-Pentyl Ph F Yellow oil Same method as Example 4 No　A　　　R”　R’　X 21 CI COO1le HBr a+p74~76℃22 COCOOMe Ph Br Pale yellow moth-like substance Various suitable methods No　A　　　R”　R’　X 23　COCoon-Oat　5-Bu　F24　CI　C00N’C(Me) z　Ph　F25　COC0NR30,Me　Ph　F26　CI　COONC 00N=C(2-MePh　F27　CH2-COoCH, TFIF　3-11 ePh　F28　C1’l　C1’lOPh　F 29 CO1,3-dioxolan-2-yl Ph F32 C1'I C)1 20+1 Ph F33 CHCH20C1'12COOEt 1-Pr F3 4 CI CH, 03O211e 5-Bu F35 N C00n-Bu 1 -Pr　F36NCN　PhF 37　N　CR=NNHCOMe　Ph　F38　N　C0NHltH,Ph　 F 39 N C00n-Bu Ph C140Cl (JI=NOCH2COOE tn-Pr F41 N C0NHPh cyhex F42 CI C00 n-Bu　1-Pr　of formula I where both FRl and R2 are methyl The compound was prepared in a manner similar to that described above.

No　A　R3R’　X 43　CHC0NH30tile　1-Pr　F44　CI　CONHC0NH 30zN(Ph) of formula I where FlI is chloro and R1 is methoxy The compound was prepared in a manner similar to that described above.

No　A　　　R”　R’　X 45CHC00Et C old CCH, F The following compounds of formula 1, where Rl and R1 are both difluoromethoxy, It was prepared in the same manner as described above.

No　A　　　R”　R’　X 46　C1l　C00Et　2-C/Ph　F47　Cl’l　COOC1’l , Ph　3-C4'Ph　F48　CHC0NH-3-pyridyl　Ph　F　 Herbicide Example A (before emergence)] Seeds of the test plants listed below were filled with sterilized loam soil to within 2 cm of the top. The seeds were sown in 8.5 cm square pots and covered with 2 to 5 layers of loam. pot water, then acetone and wetting agent polyoxyethylene (20 mol) monomer. The following was formulated as a solution/suspension in a volume ratio of 3:1 in urate solution (lh/l): The example compounds shown were applied to the soil surface in a spray cabinet. gave. The concentration and application volume of each test compound was 200I! compound in /ha calculated to obtain the desired ratio of application.

Greenhouse (minimum temperature 16℃ for temperate species, 21℃ for non-temperate species, lighting time - After 3-4 weeks of growth (16 hours per day), visually assess plant response to herbicides. did. All differences from the unsprayed control group are as follows: 0 = no effect, 1 = 1-24% effect, 2 = 2 5-69% effect, 3 = 70-89% effect, and 4 = 90-100% effect index Scores were given according to the following. In the table below, plant species are indicated using the following letters: .

e-^1 opeculus 1Iyosuroides (black grass) f -＾vena fatua (oat) g -Elymus repens (Jinoku wheat) j -5 tellaria media (chickweed) m -P oligonum lapathifolium n-Ver onica persica The following results were obtained.

Yin Ag/ha Midantanwadanko (to ±1k1mdan2 0.125 4 4 4 4 4 4 4 4 4 4 4 4 43 0.125 4344444 4 4344410 0.125 3 4 4 4 4 3 4 4 4 4 4 4 4 411 0.125 4424434424414412 0.1 25 4 3 3 4 4 3 4 4 3 4 3 1 4 413 0.1 25 2234414334334415 0.125 3423424413 304416 0.125 2 2 1 1 2 2 4 2 1 0 3 1 3 3 [Herbicide Example B (after emergence)] The following plant species are grown in a greenhouse (minimum temperature is 16°C for temperate species and 16°C for non-temperate species). 8.5 cm square with sterilized loam at 21℃, lighting time - 16 hours per day) grown in pots with acetone and a wetting agent polyoxyethylene (20 mol). Formulated as a 3:1 solution/suspension by volume of nolaurate solution (109/1) The following example compounds were administered in a spray cabinet at the 2-3 leaf stage. . The concentration and application volume of each test compound was 2001/ha for compound application. Calculations were made to obtain the desired ratio.

After 3-4 weeks, plants were visually assessed for herbicide response. Difference from unsprayed control group are all 0 = no effect, 1-1 to 24% effect, 2 = 25 to 69% effect, 3; 70 to It was scored according to the index of 89% efficacy and 4 = 90-100% efficacy.

In the tables below, the letters used indicate the same plant species as in Herbicide Example A. Point.

The results obtained are shown below.

Parking kg/ha 0.125 4 4 4 4 4 4 4 4 4 4 2 4 23 0.25 4 4 4 4 3 4 4 3 4 4 4 2 4 49 0.125 444444444 4444410 0.125 1 1 2 2 2 0 2 2 3 4 2 0 2 011 0.125 4 4 2 3 4 4 4 4 2 4 4 0 4 212 0.125 2 4 2 3 4 4 4 3 2 4 4 1 3 213 0.25 2 2 2 3 4 3 4 4 1 1 4 0 3 315 0.25 4 4 3 4 4 4 3 4 3 4 4 1 4 316 0.25 2 2 2 3 4 3 3 3 2 1 3 0 3 219 0.125 2 2 2 2 2 2 2 3 1 2 3 0 3 　4 Amendment translation submission form (Article 184-8 of the Patent Act) September 10, 1993

Claims (10)

[Claims] 1. The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein A is -N= or -CH=; X is halogen; R1 and R2 are the same or different and each represents alkyl, alkoxy, ha With loalkyl, haloalkoxy, halo, alkylamino or dialkylamino can be; R3ma-CN, -COOR5, -CONR6R7, -CSNH2, -CHO, - CH=Z, -CH(Oalkyl)2, -CH2OH, -CH2OR9 or ring Substituted or unsubstituted 5-membered or or a 6-membered heterocyclic group; R4 is H, or substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl group ; R5 is H, -N=CR6aR6b, or substituted or unsubstituted alkyl, alke is a nyl, alkynyl, cycloalkyl or aralkyl group; R6 is H, or substituted or unsubstituted alkyl, alkenyl, alkynyl, cyclo is a loalkyl, aryl, aralkyl or heteroaryl group; R7 is R6 or -SO2R8, -OH, -CN, -OR10, -NH2 or -NHR10; or R6 and R7 together ring R8 is -NR6R8b, or substituted or unsubstituted alkyl, alkyl; Nyl, alkynyl, cycloalkyl, aralkyl, aryl or heteroaryl R9 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, is a chloroalkyl, aralkyl or acyl group; R10 is the group defined for R9, or substituted or unsubstituted aryl or is a heteroaryl group; Z is =N-NR6R12 or =NOR6; R 12 is the group defined for R6 or a substituted or unsubstituted acyl group; and R6a and Rb are the same or different and each is a group defined for R6 but, However, if R4 is ortho-substituted phenyl or naphthyl, the ortho-substituted phenyl or naphthyl Substituents are halogen, -NO2, -OH, -OR10, -SH, -SR8, -SOR 8, -SO2R8, -NH2, -NR6R10, aryl or heteroaryl haloacetic acid derivatives and salts thereof. 2. R1 is chloro, methyl, methoxy, difluoromethoxy or ethoxy 2. The compound according to claim 1. 3. Claim 1 or 2, wherein R2 is methyl, methoxy or difluoromethoxy. Compounds described. 4. 4. A compound according to claim 1, wherein X is chlorine, bromine or fluorine. 5. R3 is a group -COOR5 and R5 is alkyl having 1 to 4 carbon atoms; A compound according to any one of claims 1 to 4. 6. Claim 1 wherein R4 is hydrogen, alkyl having 1 to 4 carbon atoms, or phenyl. The compound according to any one of -5. 7. Methyl 2-(4,6-dimethoxypyrimidine-2-fluoro-2-phenyl acetate. 8. According to any one of claims 1 to 7, together with a suitable carrier and/or surfactant. A herbicidal composition containing 0.01 to 99% by weight of one or more compounds. 9. An effective amount of one or more compounds according to any one of claims 1 to 7 is applied to a weed colony. or to control weeds in such areas by applying them to areas where they are likely to grow. How to kill. 10. The method according to claim 9, wherein the applied amount is 0.001 to 2 kg/ha.