JPS60149553A - 2-phenoxypropionic acid cyanamide derivative, manufacture and herbicidal composition - 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 The present invention relates to novel herbicides, 2-phenoxypropionic acid cyanamides, to processes for their production, to herbicidal compositions containing them as active ingredients, and to methods for selecting weeds in cultivated plants. The present invention relates to novel compounds and methods of using compositions containing them for the purpose of controlling insect pests. Furthermore, the invention relates to new intermediates for the synthesis of the compounds of the invention.

The 2-phenoxypropionic acid cyanamide of the present invention has the following formula: represents an alkynyl group or an alkoxyalkyl group having 2 to 4 carbon atoms, and T represents the following formula: (wherein A represents an oxygen atom or a sulfur atom, and X represents a fluorine atom, chlorine atom, bromine atom, iodine represents an atom or a trifluoromethyl group, Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge).

Herbicides containing further substituents at the para-position of the phenyl nucleus are described, for example, in West German Patent Application No. 2453067, 25
No. 31643, No. 2659796, No. 2640750
No. 3,004,770.

Surprisingly, it has now been found that the new koji compounds of the present invention are superior to such compounds described in the literature for selectively controlling weeds in crops of useful plants.

Within the scope of the present invention, the symbols R and T defined in the formula (1) are, for example, substituents such as: represents a group isomer, or allyl group, methallyl group,
2-butenyl group, 3-butenyl group, propargyl group, 2
- represents a butynyl group, 3-butynyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group or ethoxyethyl group; T generally represents a phenyl group, a 2-pyridinyl group,
It represents a group selected from the group consisting of a 2-quinolinyl group, a 2-quinoxalinyl group, a 2-benzoxasilyl group, or a 2-benzothiazolyl group, and is substituted with at least an X group. Preferably R is a hydrogen atom or a saturated group such as an alkyl group having 1 to 4 carbon atoms or R is a hydrogen atom or a saturated group having 2 to 4 carbon atoms.
and T represents a group such as 2-benzoxasilyl or 2-quinoxalinyl group.

Due to their excellent selective herbicidal action, compounds of the formula (II) are of particular interest if a) R represents a hydrogen atom or a C1 -C4 alkyl group, or in the compounds of group a) , R is C1 -C4 alkyl; in the compounds of group b), X is trifluoromethyl, Y is hydrogen and 2 is methine. represents a bridge; or X represents a trifluoromethyl group, Y represents a hydrogen atom and 2 represents a nitrogen atom; or X and Y represent a chlorine atom and 2 represents a nitrogen atom; or represents a chlorine atom, Y represents a fluorine atom, and Z represents a nitrogen atom;
For example, T consists of a 4-trifluoromethylphenyl group, a 5-trifluoromethylpyridin-2-yl group, a 3,5-dichloropyridin-2-yl group, and a 5-chloro-3-fluoropyridin-2-yl group. Preference is given to those compounds which represent groups selected from the group.

Among the compounds of group C), those compounds in which X is a fluorine atom or a chlorine atom are preferred.

A very particularly preferred group of compounds of formula 1 is one in which R is C1 -C4 alkyl and T is C4
-trifluoromethylphenyl group or 5- ) IJ
Fluoromethylpyridin-2-yl group or 3,5-dichloropyridin-2-yl group or -ri. . -3-7 Yuo. The last type is most particularly preferred, in which R represents a C1 -C4 alkyl group and T represents a 6-fluoroquinoxalin-2-yl group or 6-chloroquinoxaline-2-
or R represents an alkyl group having 1 to 4 carbon atoms and T represents a 6-chlorobenzenoxazole-2-(l group).

Preferred individual compounds are for example: 2-(4-(5-chloro-3-fluoropyridine-2-
yloxy)phenoxy]propionic acid N-cyano-N
-methylamide, 2-[4-(5-)lifluoromethylpyridin-2-yloxy)phenoxy]propionffN-cyano-N
-methylamide, 2-(4-(5-chloro-5-fluoropyridine-2-
yloxy)phenoxy]propionic acid N-cyano-N
-ethylamide, 2-(4-(6-chloroquinoxalin-2-yloxy)phenoxy)propionic acid N-cyano-N~ethylamide, 2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propion acid N-cyano-N-methylamide, 2-[4-(6-fluoroquinoxalin-2-yloxy)phenoxy]propionic acid N-cyano-N-ethylamide, 2-(4-(6-fluoroquinoxalin-2-yloxy) ) phenoxy]propionic acid N-cyano-N-methylamide or 2-(4-(6-chlorobenzoxazol-2-yloxy)propionic acid N-cyano-N-n-butylamide).

The compound represented by the formula (■) of the present invention is the following formula (■): (wherein, T
2-phenoquine propionyl halide is represented by the following formula ■: (wherein, 几 is the formula I It can be produced by reacting with ananamide represented by (representing the meaning defined in ) in the presence of an acid acceptor.

When R has a meaning other than a hydrogen atom, the following formula: (wherein T represents the meaning defined in formula I, and R
1 is an alkyl group having 11 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, and an alkenyl group having 6 to 4 carbon atoms;
represents an alkynyl group or an alkoxyalkyl group having 2 to 4 carbon atoms. ), the corresponding cyanamino compound represented by the following formula ■b= (wherein, T represents the meaning defined in Formula I) can be converted to the corresponding cyanamino compound represented by the following formula ■: Hat-R'
QV) (wherein R1 represents the meaning defined in formula 1a and H
aL represents a chlorine atom, a bromine atom or an iodine atom. ) in the presence of an acid acceptor.

According to a second method, the compounds of formula I according to the invention can also be used as phenoxypropionic acid derivatives of formula V: Formula ■: T-Hat(VD (wherein, Ta represents the meaning defined in formula l, and Ha
t represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. It can also be obtained by reacting with a halide represented by ) in the presence of an acid acceptor.

According to the third method, the compound of the present invention represented by the formula
t represents a chlorine atom, a bromine atom, a tosyl group or a mesyl group. ) and a hydroquinone derivative represented by the following formula ■; (wherein T represents the meaning defined in Formula I) in the presence of an acid acceptor. It will be done.

The different reactions to obtain the compounds of formula I or of formulas Ia to Ib are conveniently carried out in neutral, inert organic solvents. Example B of such a solvent: Hydrocarbons such as benzene, toluene, quinrane or cyclohexane; Chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, or chlorobenzene; Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether ethers such as , tetrahydrone or dioxane; nitriles such as acetonitrile or propionitrile; and more amides of dimethylformamide, diethylformamide or N-methyl-pyrrolidinone. The reaction temperature is preferably 120
℃ to +120℃. Preferred bases are trimethylamine, triethylamine, quinuclidine,
1,4-diazabicyclo(2,2,2)octane, 1,
A 6th amine such as 5-diazabicyclo(4,3,0)-non-5-ene or 1,8-diazabicyclo(s,4.0)undec-7-ene. However, the bases used can also be hydrides, such as sodium urea and calcium hydride, hydroxides, such as sodium hydroxide and potassium hydroxide, carbonate salts, such as sodium and potassium carbonate, etc. Inorganic bases such as potassium carbonate and bicarbonates such as sodium chloride may also be used.

Many of the formulas (1, 2, 2, 2, and Vl) are known or can be produced by the method of 31 (μ).

Among the compounds represented by the formulas ■and
It was developed and manufactured. As a result, they are admonishing another ten points of the present invention.

The fluorionic acid derivative represented by the following formula CHC-Ha, 4 (wherein, Hat represents the filthiness defined in formula ■, and H
atl represents a chlorine atom or a bromine atom. ) is the propionylreno-ride represented by the following formula: X-N-R 1(X) N It can be obtained by reacting in the presence of the body.

According to a modification of the above method, a compound of the following formula (a) can also be prepared by combining a glopionyllide of the formula (1) with a cyanamino of the following formula (X): H2N-0N (M); These compounds of formula (a) are reacted in the presence of an acid acceptor and optionally with an alkylating agent which introduces an R1 group having the meaning fC, which is defined by fC. It is also possible to produce rainbows.

The intermediate represented by the formula ■ is prepared by reacting the compound represented by the following formula ■: N with 4-benzyloxyphenol in the presence of a base, and the intermediate represented by the following formula M: (wherein R is the formula ■). Reaction production 4F represented by
t=can be prepared from a compound of formula (1) by treatment with hydrogen in the presence of a hydrogenation catalyst such as palladium on carbon.

The starting materials represented by formula (1), X or X are known or can be prepared by known methods. A novel intermediate represented by formula I was specifically developed and prepared for the synthesis of compounds of formula I. They likewise constitute another object of the invention.

The novel intermediates of formulas V and (2) are prepared according to known methods. The reaction conditions are selected in each case according to the requirements of the reagents used.

A compound represented by the following formula ■C; (wherein R and X represent the meanings defined in formula I) is a) a compound represented by the following formula (Ha L2 represents a fluorine atom, a chlorine atom or a bromine atom) is reacted with hydroquinone in the presence of a base to give a compound represented by the following formula XIv: , this intermediate is reduced in the presence of a metal catalyst to give an amine compound of the formula and convert this fluorinated intermediate into a compound of the formula ■: N, where R represents the meaning defined in formula ■, and Ha
t represents a chlorine atom, a bromine atom, a tosyl group or a mesyl group 0) A propionic acid derivative represented by the formula 0) is reacted in the presence of a base, or b) a nitropyridine represented by the formula ■ is reacted with the following formula ■ : (In the formula, alkyl represents an alkyl group having 1 to 4 carbon atoms.) is reacted with a propionate ester represented by the following formula X The body is reduced in the presence of a metal catalyst to form the following formula
x: give an amino compound of formula XX:, diazotize this intermediate and convert it with a fluorinating agent to a compound of formula XX:, saponify the ester and convert it to a rotanizing agent. The following formula: (In the formula, Hat and X have the meanings defined in the formula ■.

), and the above 2-phenoxyprovinyl halide is reacted with a cyanamino represented by formula (■) at the lower right of the base i. be able to.

According to a modification of the above method, the intermediate of formula
(2) A propionate ester of the compound represented by the following formula: (In the formula, Hat represents a chlorine atom or a bromine atom, and alkyl f@represents an alkyl group having 1 to 4 carbon atoms.) It can also be obtained by reacting with in the presence of a base.

The reaction conditions for these known reaction steps, such as catalysts, solvents and reaction temperatures, are known from the literature and the starting materials of the following formulas are known: The intermediates represented by X■ and ■ are new and have the formula I
It was specifically developed for the synthesis of compounds represented by C. Along with the above intermediates and variants a and b, the new process is
The purpose of the present invention is p? It consists of Compounds of the formula...a in which X represents a hydrogen atom are also novel and constitute another object of the invention.

The compound represented by formula 1 is obtained as a racemate. Expression ■
Both the optical antipodes of the compounds represented by and mixtures thereof constitute the object of the present invention. Unless the specific isomer is specified, what is described in the specification refers to the racemate.

The compounds of formula I are stable compounds and no protective measures are required in their handling.

When used in low rate applications, the compounds of formula 1 are particularly useful against monocotyledonous weeds, especially against dicotyledonous crops, especially cotton, soybean, radish, sugar beet, forage radish and sunflower. It has good selective herbicidal properties that make it very suitable for use in. Some of the compounds of formula I according to the invention can also be used as selective herbicides in monocotyledonous crops such as cereals such as wheat and barley. In some cases, damage also occurs to weeds previously controlled only with general herbicides.

When used in high rate applications, the compounds of formula I act as general herbicides.

Selective herbicidal action of the compounds of the invention is seen in both pre-emergence and post-emergence applications. These compounds can therefore be used with equally good results for selectively controlling weeds, especially weeds, before and after emergence.

The invention also relates to herbicidal compositions containing the novel compounds of formula I and to methods for the pre- and post-emergence control of monocotyledonous weeds, in particular weeds of the weed family.

The compounds of the formula I are used in unmodified form or preferably together with the auxiliaries customary in formulation technology and can also be used as emulsion concentrates, directly sprayable or dilutable solutions, powder emulsions. , hydrated powders, soluble powders, dusts, granules, and encapsulated, for example in polymeric materials, in a known manner. Depending on the nature of the composition, application methods such as jetting, spraying, dusting, sprinkling, pouring, etc. are selected according to the purpose of application and the given situation.

The formulations, i.e. compositions containing the compound of formula I (active ingredient) and optionally solid or liquid auxiliaries, can be prepared in a known manner, e.g. by combining the active ingredient with fillers such as solvents or solid carriers and optionally with Surfactant (5urfactan)
ts) by uniformly mixing and/or grinding.

Suitable solvents include aromatic hydrocarbons, preferably those having 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalates such as diptyl- or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and Glycols and their ethers and esters such as ethanol, ethylene glycol, monomethyl or monoethyl ether of ethylene glycol, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylforphogide or dimethylformamide, and vegetable oils, Mention may be made of epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

Solid carriers used, for example for dusts and dispersible powders, include in general natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acids or highly dispersed absorbent polymers can also be used to improve the physical properties.

Suitable granular adsorptive carriers include porous carriers such as pumice, crushed brick, sepiolite or bentonite; non-adsorbent carriers include materials such as calcite or sand. Furthermore, most pre-granulated materials of inorganic or organic nature can be used, such as in particular dolomite or powdered plant residues.

Suitable surface-active compounds are nonionic, cationically active and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the compound of formula I to be incorporated. In this case, "surfactant" is also understood to mean mixtures of surfactants.

Suitable anionic surfactants include both water-soluble soaps and water-soluble synthetic surfactant compounds.

Suitable soaps include alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids having 10 to 22 carbon atoms, such as the sodium or potassium salts of oleic acid or stearic acid or, for example, coconut. Examples include natural fatty acid mixtures obtained from oil or beef tallow, and potassium salts. Also included are fatty acid methyltaurine salts.

However, more often so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

The fatty sulfonates or fatty sulfates are usually in the form of alkali gold salts, alkaline earth metal salts or -unsubstituted or substituted ammonium salts and contain 8 carbon atoms.
to 22 alkyl groups, but this alkyl group also includes the alkyl group moiety in the acyl group,
Examples include the sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or fatty alcohol sulfate mixtures obtained from natural fatty acids. These compounds also include sulfate ester salts and sulfonate salts of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivative preferably has two sulfonic acid groups and one C8-C22 fatty acid group. Examples of the alkylaryl sulfonates include the sodium, calcium or triethanolamine salts of dodecyl benzene sulfonic acid, dibutylnaphthalene sulfonic acid or the 7talenes sulfonic acid-formaldehyde condensation product. Also, the corresponding phosphate, for example 4 to 14 moles of ethylene oxide and p
- salts of phosphoric acid esters of adducts with nonylphenol;
Alternatively, lipids are also suitable.

Preferred nonionic surfactants are aliphatic or linear cycloaliphatic alcohols, or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkylphenols, which ether derivatives contain 3 to 10 glycol ether groups and (aliphatic ) 8 carbon atoms in the hydrocarbon group
The alkylphenol contains 6 to 20 carbon atoms and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Further suitable nonionic surfactants include polypropylene glycols having t-1 to 10 carbon atoms in the alkyl chain, ethylene diaminopropylene glycols and polyethylene oxide adducts with polypropylene glycols. This adduct contains 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually have 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of the above-mentioned nonionic surfactants include nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene/polyethyleneoxy adduct, tributylphenoxy7-bolyethoxyethanol,
Mention may be made of polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty esters of polyoxyethylene sorbitol, such as polyoxyethylene sorbitan trioleate, are also treated with a suitable nonionic surfactant.

The cationic surfactants include at least one alkyl group having 8 to 22 carbon atoms as an N substituent, and optionally a dihalogenated lower alkyl group, a benzyl group, or a lower alkyl group as an N substituent. Quaternary ammonium salts having an alkyl group are preferred. The ammonium salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, such as stearyltrimethylammonium chloride or hahenzyldi<2-chloroethyl)ethylammonium bromide.

Surfactants used in conventional formulation techniques are described in the following literature: Me Cutcheon's Detergents and Emulsifiers Annual.
and Emulsifers Annual)
”, xA MePublishing Corp., Ringe-wood, New Chassis 1981 edition;
), “Ten5id Taschenpuch (Ten5id
-Taschenbuch)” 2nd edition, Sea Hanser Verlag (C, Hanser Verlag),
Munich&T (-7, 1981;
J.A. (M, andJ.

Asc h ) + “Encyclopedia of
Surfactants (Encyclopedia of
5urfactantJ#.

Volumes 1-3, Chemical Bubbling Campa = (
Chemical Publishing Co.)
, = New York, 1980-81.

Herbicidal compositions usually contain from 0.1 to 95% of a compound of formula I, preferably from 0.1 to 80%, from 1 to 99% of a solid or liquid additive and from 25% to 25% of a surfactant.
, preferably 1 to 25% of Q.

Preferred formulations consist in particular of the following components (%=% by weight):

Active ingredients 1-20% preferably 5-10% surfactant 5-30% preferably 10-20% liquid carrier
50-94% preferably 70-85% powder active ingredient 01-10% preferably 01-1% solid carrier 999-90% preferably 999-99% suspension concentrate active ingredient 5-75% preferably 10 ~50% water 94
~25% preferably 90-60% surfactant 1-40
% Preferably 2-30% Wettable powder active ingredient 05-90% Preferably 1-80% Surfactant 05-20% Preferably, 1-15% Solids Key Viya 5-95% Preferably 15-90% 90% Granules Active Ingredients 0.5-30% Preference 3-15% Solid Carrier 995-70% Preferably 97-bAlthough the product is preferably formulated as a concentrate, the end consumer typically Use dilute formulations. Formulation iQ, 001% can be diluted to a low concentration. The application rate is usually 0.
01 to 1°Kfa,j,/ha, preferably 0o2
5 to 5Kga, r,/hB.

The compositions can also contain other ingredients, such as stabilizers, defoamers, viscosity modifiers, binders, adhesives and fertilizers and other compounds for obtaining special effects.

Production Examples Example P1: 2-(4-(4-trifluoromethylphenoxy)phenoxy)globionic acid N-cyanamide (compound 1.4) 85% water mizing power 1) U A 1 a4r (u157s
% Le) in 75 dlC of water. Cyanamid engineering 5th floor (
α0825 mol) is added at 20°C and the clear, colorless solution is cooled to 10°C. Then 2-(4-(4-
25.8f (11075 mol) of acetate of 78noxy]propionyl chloride 15. 1 of the solution is added dropwise so that its temperature does not exceed 15°C. After stirring the reaction mixture at this temperature for 45 minutes, 37% hydrochloric acid? P ((109 mol)) is added dropwise at 5° C. The product precipitates as an oil which crystallizes if left for more than 50 minutes. Colorless crystals are isolated by filtration, washed with water and purified over phosphorus pentoxide. 2-(4-(4-trifluoromethylphenoxy)phenoxy)propionic acid N-cyanamide having a melting point of 125-127°C when dried at 24.
9t (theoretical value of 95.0chi) is obtained.

Example P2: 2-(4-(4-)lifluoromethylphenoxy)phenoxy]globio/acid N-cyano-N-methylamide (compound 1.3) 2-(4-(4-)lifluoromethylphenoxy) Phenoxy]propionic acid N-
Cyanamide 17.5P (α05 moles) is dissolved in methyl ethyl ketone 60- and potassium carbonate 7.69P (
Heat to reflux temperature for 50 minutes with α055 mol).

Then, methyl iodide &6d (α057 mol) was added at 30°C.
to the colorless suspension and the mixture is stirred at the same temperature for 2 hours. The reaction mixture is then filtered and the filtrate is concentrated by evaporation.

The oily residue was eluted with petroleum ether/ethylacetate (
s: 1) Separate by chromatography on silica gel using e and concentrate the main fraction by evaporation to obtain a refractive index nl,
: 1.522 B as a colorless and transparent oily substance 2-(
4-(4-)Refluoromethylphenoxy)phenoxypropionic acid N-cyano-N-methylamide is obtained.

Example P3: 2-(4-(6-chlorobenzoxazol-2-ylox)phenoxy)p-pionic acid N-cyano-N-butyramide (compound 2.4) a) 2-bromopropionic acid N-cyano- N-Methylamidosiftmil'1 (L5F (125 mol) is dissolved in 250° C. of 2N potassium hydroxide solution and the solution so obtained is cooled to 10.degree.

At this temperature 2-glomopropionyl bromide 26.5
d (125 mol) is added dropwise and the reaction mixture is stirred for 1 hour at the same temperature. Then 1 tar of sodium bicarbonate (
12 mol) Wokayoru.

Continue with dimethyl sal 7ate 65? (α5 mol) to 20
C. and the reaction mixture is stirred for 4 hours and extracted with methylene chloride. The combined organic phases are dried over sodium sulfate and concentrated by evaporation to yield 27.5 f of crude product as a residue. The crude product was distilled under a vacuum lid to give 2-bromopropionic acid N-cyano-N-methylamide 156f (2a5% of theory) with a boiling point of 45/-/47 DEG C. at 008 mbar.

b) 2-(4-benzyloxyphenoxy)furopionic acid N-cyano-N-methylamide With thorough stirring,
2-Bromopropionic acid N-cyano-N-methylamide was dissolved in hydroxynonmonobenzyl ether (11
mol) and potassium carbonate (α12 mol) in 200 d of dimethylformamide solution.

After the mildly exothermic reaction has subsided, the reaction mixture is heated to 40° C. for 3 hours. The precipitated salts are then removed by filtration and the filtrate is concentrated by evaporation. The afterflame is dissolved in ether and the ether solution is extracted with dilute sodium hydroxide solution. The organic phase was dried over sodium sulfate, the solvent was evaporated off and the residue was distilled under vacuum to 56-58°C.
2-(4-benzyloxyphenoxy) with a melting point of
Propionic acid N-cyano-N-butylamide 19.5
t (the 63rd coefficient of the theoretical value) is obtained.

c) 2-(4-hydroxyphenoxy)propionic acid N
- Cyano-N-butyramide 2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-butyramide prepared according to example b) 1&5SF (α047 mol) 5thipalladium on carbon catalyst in dioxane 170- Hydrogenate with hydrogen in the presence of 1.71. The catalyst is then removed by filtration, the filtrate is concentrated by evaporation. The residue was separated and purified by chromatography on silica gel using ethyl acetate/hexane (1:3) as an eluent to obtain 2-(4-hydroxyphenoxy)propionic acid N as a colorless oil.
-cyano-N-butyramide 7,59 (theoretical value 61
h). n”D: 1-5152°d) 2-(hydroxyphenoxy)propionic acid N-cyano-N-butyramide 4.41cα017 mol), z,6-cyclobenzo*?:/-X58f (0.02 mol) and potassium carbonate &51 (α025 mol) in acetonitrile 5
Stir in 01111 at room temperature for 10 hours. The salts are then removed by filtration, and the filtrate is concentrated by distillation.

The residue was eluted with ethyl acetate/hexane (1:3).
Separate and purify by chromatography on silica gel using 91. 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propio/acid N-cyano-N-butyramide having a melting point of -92 DEG C. is obtained.

Example P4: 2-bromopropionic acid N-cyano-N-
butyramide 2-bromopropionylpromy)” 29.57 (0
, 137 mol) with butyl cyanamide 114f (α 157 mol) and triethylamine 11B in ether 150d.
f (57 mol of OA) at 15°C.

The mixture is stirred at 20°C to 25°C for 3 hours and then filtered to remove precipitated salts.

The filtrate is extracted with dilute hydrochloric acid and the extracts are dried over sodium sulfate and concentrated by evaporation.

The oil was distilled under high vacuum to give 2-bromopropionic acid N having a boiling point of 53-54°C at 0.0052 mbar.
-Cyano-N-butyramide 22.6 f (708 f of theory) are obtained.

Example P5: 2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)propionic acid N
-Cyano-N-butyramide (compound 1.26) a) 4-(5-chloro-6-nitopyridin-2-yloxy)phenolhydrokilanone 85.9 (α 78 mol), acetonitrile 1200 m4' and potassium carbonate 519 f ( α39 mol) was heated to 60°C, then 500 d of acetonitrile
2,5-dichloro-5-nitroviridine in 115.8
2 (α60 mol) is added dropwise over a period of 6 hours and the mixture is stirred for 36 hours. The solvent is distilled off and the residue is poured into a mixture of ice water and hydrochloric acid. After extraction with methylene chloride, the combined organic phases are dried over magnesium sulfate, treated with activated charcoal, filtered and concentrated. The residue was purified by recrystallization in a mixture of hexane and ethyl acetate to give 4-(5-chloro-3-nitroberidin-2-yloxy)phenol 991 (theoretical) with a melting point of 125-126°C. 62 pieces).

b) 4-(3-Amino-5-chloropyridin-2-yloxy)phenol 4-(5-chloro-5-nitropyridin-2-yloxy)phenol 11α7fCα415 mol) is dissolved in dioxane 1200- and 2 nickel Solvent 22.
After addition of Of, hydrogenate with hydrogen at 20-25°C. The desolvent was then removed by filtration, the solution was concentrated and the residue was stirred in hexane and the product was filtered and dried to give 4-(3-
96.0 tC of amino-5-chloropyridin-2-yloxy)phenol (theoretical value 98 t) is obtained.

c) 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol 122.5t (α518 mol) of 4-(3-amino-5-chloropyridin-2-yloxy)phenol was dissolved in hydrogen fluoride 400F ( -8 to 0 in a container containing 20 moles)
Introduce at °C. Then sodium nitrite 57.39 (
α540 mol) Add little by little over t1 hour. The mixture is stirred for 2 hours at 0°C and slowly heated to 55°C in an autoclave. Excess hydrogen heptafluoride was removed by distillation and the residue was taken up in methylene chloride and the solution was neutralized with ice water and ammonia, the organic phase was dried and concentrated by evaporation to 97-98°C. 4-(5-dichloro3-fluoropyridine-2-
yloxy)phenol 112r'i is obtained.

d) 4-(5-chloro-3-fluorobiricin-2-y/l/oxy) 7 z / k 4aOf((12
0 mol) and 2-bromopropionic acid N-cyano-N-)
20 mol of f amide 5a2fCrL) is dissolved in 400 d of acetonitrile. Potassium carbonate 5hqy (α26
mole) and potassium iodide IIL3! ilO,002 mol) is added to the solution and the reaction mixture is heated to 80° C. for 13 hours.

The precipitate is removed by filtration, the filtrate is concentrated by evaporation and the residue is taken up in 500 methylene chloride. The solution is purified by treatment with activated carbon and filtration through silica gel. The filtrate was concentrated by evaporation and the residue was crystallized from a mixture of hexane and ethyl acetate to give 2-
(4-(5-chloro-5-fluoropyridin-2-yloxy)phenoxy)propion 1llN-cyano-N
-Methylamide 61t is obtained.

Example P6: 2-(4-(5-ritsuguchi-3-fluoropyridin-2-yloxy)phenoxy)propionic acid N
-n-Butyl-N-cyanamide (compound 1.28) a) Methyl 2-(4-(5-chloro-3-nitropyridin-2-yloxy)phenoxy)gropionate 2.5-dichloro-3-nitropyridine 5 & 6t (0,
20 mol), methyl 2-(4-hydroxyphenoxy)
Gropionate 41. Sl (α21 mol), acetonitrile 400 tries, potassium carbonate 55.99CCL2
6 mol) and potassium halide CL55f (α002 mol) are heated to 80° C. for 13 hours. Filter the reaction mixture and wash the filter cake with acetonitrile. The filtrate was concentrated by evaporation and the residue was dissolved in methylene chloride.
〇-Take it inside. After treating the solution with 15 t of activated carbon, it is filtered through a layer of silica gel and the filtrate is concentrated by evaporation. The residue was crystallized from a mixture of hexane and ethyl acetate to give 91. Methyl 2- with a melting point of -92 °C
65.79 (951% of theory) of (4-(5-chloro-3-nitropyridin-2-yloxy)phenoxyfupyrobionate) are obtained.

b) Methyl 2-(4-(5-amino-5-ripropyridin-2-yloxy)phenoxy)globionate Methyl 2-(4-(5-chloro-3-nidotetrapyridin-2-yloxy)phenoxy)propionate 1918
1 (α541 mol) is dissolved in 1.9 t of dioxane.

Raney nickel decomposer 401 was added and hydrogen was applied at 20S and 25°C. The catalyst is then filtered off, the solution is distilled off and the still warm oily residue is crystallized by stirring in hexane. The crystalline precipitate was isolated by filtration and dried 92. Methyl 2-(4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]globione-)16 with a melting point of -94°C
7.1' (96% of the theoretical value) is obtained.

C) Methyl 2-(4-5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionate Place 400 g (20 moles) of hydrogen fluoride in a container and add methyl 2-(4-(5-amino-5- Chloropyridine-2-
yloxy)phenoxy]sodium 37.3 y((
540 mol) is added over 1 hour and the mixture is stirred for 2 hours under VC before being slowly heated to 55° C. in an autoclave. Excess hydrogen fluoride is removed by distillation, the residue is taken up in a mixture of 200 d of methylene chloride and ice water, and the solution is neutralized with concentrated ammonia. The neutralized solution was extracted six times with methylene chloride and the organic extracts were washed with water, dried and concentrated by evaporation to give 63. −
Methyl 2-(4-(5-10rho-3-fluoropyridin-2-yloxy)phenoxy) having a melting point of 64°C
Propionate 81. Of (48% of theory) d) 2-(4-(5-chloro-3-fluoropyridine-
Methyl 2-yloxy)phenoxypropionate 2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)gropionate 67.
Of (α206 mol), dioxane 350d and IN
A mixture of 250 d of sodium hydroxide solution is stirred at 40° C. for 2 hours.

The reaction mixture is poured into a mixture of ice and 150 d of 2N hydrochloric acid and extracted twice with ethyl acetate. The extract is washed with a saturated solution of sodium chloride, dried over magnesium sulfate, filtered and concentrated by evaporation to 2-(4-(5-chloro-3- Fluoropyridin-2-yloxy)phenoxitapropionic acid 656
1 (99% of the theoretical value).

e) 2-(4-(5-chloro-6-fluoropyridin-2-yloxy)phenoxy)propionyl chloride 2-(4-(5-chloro-3-fluoropyridin-2-
656 t of phenoxytapropionic acid are dissolved in 700 g of toluene and 200 g of toluene are then removed from this solution by distillation. After cooling to 90°C,
Thionyl chloride 25d (4 mol OJ) is added dropwise and the solution is stirred at this temperature for 14 hours. The reaction mixture was then diluted with 2
The resulting solution of 2-(4-(5-10-5-fluoropyridin-2-yloxy)phenoxy)propionyl chloride is used directly in the next reaction step.

f) 2-(4-
(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride9.99 (10
30 mol) solution to k x 740a! 'Naka (iri)
) Add dropwise to a solution of ethylamine &5t (α035 mol) and n-butylcyanamine 5.2t (1033 mol). After 5 hours, the precipitate is filtered off and purified by chromatography through silica gel. The eluent was concentrated by evaporation to give 2-(4-(s) as a yellow oil.
-Chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid N-n-butyl-N~cyanamide is obtained. n”: 1.5482° Example P7: 2R-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxypropionate N-ethyl-N-cyanamide in 10 sl of acetonitrile with cooling with ice) 1,8-diazabicyclo(5,4
, 0) Undese-7'-xn (97%) (i') 443
A solution of P(a030-v-le) was mixed with ethylcyanamiy2.1f (α030 mol) and 2R in acetonitrile 50 ml.
-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxyfupropionyl chloride (melting point 4
7, -48°C) into a solution of 9.91F (0,030 mol). After 4 hours, the reaction mixture is concentrated. Purpose 2
R-(4-(5-chloro-3-fluoropyridine-2
-yloxy)phenoxy]gropionate N-ethyl-
The N-cyanamide is obtained by chromatographically separating the residue through silica gel and concentrating the eluent (mixed solvent: ethyl acetate/hexane 1:1) by evaporation.

Example P8: 2-(4-(6-fluoroquinoxaline-
2-yloxy)phenoxyfupropionic acid N-cyano-N-ethylamide (compound 5.18) 4-(6-fluoro-tetraquinoxalin-2-yloxy)phenol 10t (α039 mol), 2-p-tetramobrobion [N-cyano- N-ethylamide 9.6t (0.04
7 mol) and potassium carbonate B & 1F (α058 mol) were stirred in 100 g of acetonitrile at room temperature for 14 hours. The precipitated salts are removed by filtration, and the filtrate is concentrated by evaporation. The residue was eluted with ethyl acetate/hexane (1
2-(4-
(6-fluoroquinoxalin-2-yloxy)phenoxyfupropionic acid N-cyano-N-ethylamide is obtained.

The compounds of formula I and intermediates listed in the table below are obtained in a similar manner.

Table 2. : Table 2: (continued) Table 3 = Table 3: (continued) Table 4 = H3 Hat-CI-1-CO-C-R ■ N Table 5: Table 6: Table 7: Table 8: Table 11: Formulation example Example F1: Examples of formulations of liquid active ingredients of formula I (all
(Percentages are by weight) Compound of the formula ■ 20% 40% 50% cyclohexanone -15% 20 thixylene mixture 70 t 25% 20 t An emulsion of the required concentration is diluted with water from a concentrate of this type. It can be prepared by:

b) Solution a) b) c) d) Compound represented by formula ■ 80% 10 5 95%
Ethylene glycol monomethyl ether 20 parts --- Polyethylene glycol (M0400) -70% -- N-methyl-2-pyrrolidone - 20 parts -- Epoxidized coconut oil -- 1 part 5% petroleum distillate (boiling point range 160-190 '0) --94CH - The solution is suitable for application in the form of fine drops.

C) Granules a) b) Compound of formula I 5% 10% Kaolin 94% - Highly dispersed silicic acid 10% - Attapulgide - 90% The active ingredient was dissolved in methylene chloride and the resulting solution was dissolved. vtitm onto the support and then evaporate the solvent under reduced pressure.

d) Powders a) b) Compound of formula I 2% 5% Highly dispersed silicic acid 1% 5% Talc 97% - Kaolin 90% Ready-to-use powders can be prepared by mixing the active ingredient with a carrier. You can get good results.

Example F2: (All percentages are by weight) a) Irrigation agent a) b) c) Compound of formula 1 2o 6o 5 α5 sodium tirigutsulfonate 5 5% 5 thi diuryl sodium sulfate Highly Dispersed Silicic Acid 5% 27% Thikaolin 67% Sodium Chloride - 59.5% The active ingredient is thoroughly mixed with the auxiliaries and the mixture is thoroughly ground in a suitable mill. By diluting with water, a water-based agent can be obtained which can be made into a suspension at a desired concentration.

Compound of formula (■) 10% 1% Cyclohexanone 3oIs 1oIs Xylene mixture 50% 79% An emulsion of the required concentration can be obtained by diluting this concentrate with water.

C) Powder a) b) c) Compound represented by formula I 5% 8% 11 Talc
95% - 999 Thikaolin - 92 Thi - The ready-to-use powder is obtained by mixing the active ingredient with the carrier and milling the mixture in a suitable mill.

d) Extruded granules a> b) Compound of formula I 1% 1% Sodium lignosulfonate 2% Carboxymethyl cellulose 1% 1% cacao 7 87% 969
6. Mix and mill the active ingredient with the auxiliaries and subsequently moisten the mixture with water. The mixture is extruded and dried in a stream of air.

Compound of formula (■) 5% Polyethylene glycol (MG200) 5% Kaolin 94% The pulverized active ingredient is uniformly applied to the kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

f) Suspension concentrates a) b) Compound of formula I 40% 5 ethylene glycol 10% 10% Sodium lignosulfonate 10% 5qb carboxymethyl cellulose 1% 1% 57% formaldehyde aqueous solution 0.2% 0 .2% Water 52q6 77% The finely divided active ingredient is homogeneously mixed with the auxiliaries. A suspension concentrate is obtained in this way, from which a suspension of the desired concentration is obtained by dilution with water.

Biological Examples: For comparison, test results obtained from a compound of the following formula A: from West German Patent Publication No. 5004770, page 12, number 58, were used as biological examples B1 and B2.
Add a note to the results.

Example B1: Pre-emergence herbicidal activity As soon as the seeds of the test plants were sown in seedlings in the greenhouse, the soil surface was coated with 25% emulsion concentrate or milk due to insufficient solubility of the test compound. If formulation as a suspension concentrate is not possible, an aqueous dispersion of the test compound prepared from a 25% aqueous solution is sprayed. Two different concentration series were used, containing 1 and 0 of the test compound per hectare, respectively.
．． 5. We responded immediately. The seedlings are placed in a greenhouse at a temperature of 22-25°C and a relative humidity of 50-70°C. The test result is 5
After a week, evaluation was made according to the following evaluation criteria.

1: The plant does not germinate or dies completely.

2-5: Very strong effect 4-6: Average effect 7-8 - Weak effect 9: No effect In this test, the test compound represented by formula i was the most effective against monocotyledonous weeds. there were. However, cultivated plants such as wheat, barley, sugar beet, soybeans, and cotton suffered little or no damage at the given application rates. Comparative Compound A had virtually no effect.

Results: Many weeds and cultivated plants, both monocotyledonous and dicotyledonous plants, were treated with an aqueous dispersion containing the active ingredient at a rate of 25,05 and 1 mark per hectare at the 4th to 6th leaf stage after germination. is sprayed and maintained at 24-26° C. and relative temperature 45-609 g. Test results were evaluated at least 15 days after treatment according to the evaluation criteria used in the pre-emergence test.

In this test as well, the compound represented by formula (■) was also the most effective against monocot weeds.

Cultivated plants such as wheat, barley, sugar beet, cotton and soybean were not damaged or were damaged only when the compound was applied at high rates. Comparative Compound A had virtually no effect.

Result: Patent applicant Civer Geigy Akchengeselzoyaft agent Yumi Kaede and one other personContinued from page 1 ■ I nt , CI , 4 identification symbol priority claim 01g8 April 18th Office docket number

Claims (1)

[Scope of Claims] (1) The following formula ■: [In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkynyl group having 6 to 4 carbon atoms. or an alkoxyalkyl group having 2 to 4 carbon atoms, and T represents the following formula: (wherein A represents an oxygen atom or a sulfur atom, and represents a trifluoromethyl group, Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge). ] 2-phenoxypropionic acid cyanamide. (2) The compound according to claim 1, in which %R in formula (2) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. (3) The compound according to claim 2, wherein in formula 1, R represents an alkyl group having 1 to 4 carbon atoms. (4) In formula I, T represents a group represented by the following formula: (wherein, X, Y, and 2 have the meanings defined in claim 1) Compound according to item 1. (5) In formula 1, T represents a group represented by the following formula: (wherein, X represents the meaning defined in claim 1). Compound. (6) The compound according to claim 5, in which X represents a fluorine atom or a chlorine atom. (7) The compound according to claim 1, wherein in formula (2), T represents a group represented by the following formula: (8) The compound according to claim 4, wherein X represents a chlorine atom, Y represents a fluorine atom, and 2 represents a nitrogen atom. (9) In formula (■), R represents an alkyl group having 1 to 4 carbon atoms, and T is 6-fluoroquinoxaline-2
A compound according to claim 1, which represents -yl. αQ The compound according to claim 1, in which R represents an alkyl group having 1 to 4 carbon atoms and T represents 6-chloroxal>-2-yl. (6) The compound according to claim 1, in which R represents an alkyl group having 1 to 4 carbon atoms and T represents 6-chlorobenzoxazol-2-yl in formula (1). υ The compound according to claim 1, in which R represents an alkyl group having 1 to 4 carbon atoms and T represents 5-chloro-3-fluoropyridin-2-yl. Q3 The compound according to claim 1, which is 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxyfupropionic acid N-cyano-N-methylamide. Q41 The compound according to claim 1, which is 2-(4-(5-)lifluoromethylpyridin-2-yloxy)phenoxy]propionic acid N-cyano-N-methylamide. The compound according to claim 1, which is α$ 2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)propionic acid N-cyano-N-ethylamide. (a) 2- (4-(6-chloroquinoxalin-2-yloxy)phenoxy)propionic acid N-cyano-N-
The compound according to claim 1, which is ethylamide. Q71 2- (4-(6-chlorogytukizarin-2-
yloxy)phenoxy]propionic acid N-cyano-N
The compound according to claim 1, which is -methylamide. (to) 2-[4-(6-fluoroquinoxaline-2-
yloxy]phenoxy]propionic acid N-cyano-N
The compound according to claim 1, which is -ethylamide. 01 2- (4-(6-fluoroquinoxaline-2-
yloxy)phenoxy]propionic acid N-cyano-N
- The compound according to claim 1, which is methylamide. m 2-[4-(6-chloropenzoxasol-2-
yloxy) phenoxyfupropionic acid N-cyano-N
The compound according to claim 1, which is -n-butylamide. (C) The following formula■: [In the formula, T is the following formula: (In the formula, A represents an oxygen atom or a sulfur atom, and X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethyl group. , YFi represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom or trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge), and HaA! represents a chlorine atom or a bromine atom. ] 2-phenoxy-propionyl halide represented by the following formula ■: (wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or a 2-phenoxy-propionyl halide group having 3 carbon atoms) 2 to 4 alkynyl group or C2 to C4 alkoxyalkyl group) in the presence of an acid acceptor. and T represents the meaning defined in formula (2). Stem The following formula ■b = (In the formula, T represents the following formula: (In the formula, A represents an oxygen atom or a sulfur atom, and X represents a heptad atom, a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethyl group. % hydrogen atom, Y represents a fluorine atom, chlorine atom, bromine atom, or trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge.) The corresponding cyanoamino compound represented by the following formula!■=HaJ −
R'' (IV) (wherein R1 is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 6 to 4 carbon atoms, an alkynyl group having 5 to 4 carbon atoms, or an alkoxy group having 2 to 4 carbon atoms; (wherein R1 is the formula ■ represents the meaning defined by T
represents the meaning defined in 21b. ) A method for producing a compound represented by The phenoxypropionic acid spinner represented by the following formula ■: (wherein R represents the meaning defined in formula l) is expressed by the following formula ■: T -Hal(Vl) (wherein T is the formula ■ represents the meaning defined by and Ha
l represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ) in the presence of an acid acceptor to form a reaction with a halide represented by the following formula ■: [In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 5 to 4 carbon atoms] represents an alkenyl group having 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 4 carbon atoms, and T is the following formula: (wherein A is an oxygen atom or 1-1 is a sulfur atom) , XtIi represents a fluorine atom, chlorine atom, bromine atom, iodine atom or trifluoromethyl group, Y represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom or trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge). ] A method for producing a compound represented by (c) The following formula ■: N (In the formula, R represents the meaning defined by the formula r, and Ha
l represents a chlorine atom, a bromine atom, a tosyl group or a mesyl group. ) and a hydroquinone derivative represented by propionic acid salt (wherein T represents the meaning defined in formula ■) in the presence of an acid acceptor, the following formula ■:
[In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 4 carbon atoms. and T represents the following formula: (wherein, A represents an oxygen atom or a sulfur atom, X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethyl group, and Y represents a hydrogen atom , represents a fluorine atom, a chlorine atom, a bromine atom, or a trifluoromethyl group, and 2 represents a nitrogen atom or a methine bridge). ] A method for producing a compound represented by (c) As an active ingredient, the following formula ■: [wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or represents an alkoxyalkyl group having 2 to 4 carbon atoms, and T represents the following formula: (wherein A represents an oxygen atom or a sulfur atom; It represents a methyl group, Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a J4 atom or a +7 fluoromethyl group, and represents a nitrogen atom or a methine bridge. ) represents a group represented by A herbicidal composition containing at least one 2-phenoxypropionic acid amide represented by the following formula together with a carrier and/or other auxiliary agents. (a) The following formula ■: [wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or a carbon atom represents an alkoxyalkyl group of numbers 2 to 4, and T represents the following formula: (wherein, A represents an oxygen atom or a negative sulfur atom, and Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a trifluoromethyl group, and Z represents a nitrogen atom or a methine bridge. A method for controlling weeds, which comprises using a herbicide-effective amount of a compound represented by the following formula or a composition containing such a compound. (Incorporated) The method according to claim 26 for selectively controlling weeds. b) The method according to claim 27 for selectively controlling monocot weeds. 29. The method according to claim 28 for selectively controlling monocot weeds in crops of useful plants before or after germination. ■ Claim 2 in which the crops of useful plants are dicotyledonous plants such as soybean, oil, sugar beet, cotton, etc.
The method described in Section 9. 01) The following formula ■: N (wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or 2 carbon atoms) -4 alkoxyalkyl group, and Had represents a chlorine atom, a bromine atom, a tosyl group or a mesyl group). (2) The following formula V: (wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 6 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or 2 carbon atoms) Represents an alkoxyalkyl group of Kaishi 4). ) The following formula 2 to 4 alkoxyalkyl groups). (B) a) The following formula x■: (In the formula, React with hydroquinone in the presence of a base to obtain a compound represented by the following formula: This intermediate is reduced in the presence of a metal catalyst to obtain an amino compound represented by the following formula xv: This amino compound is diazotized and converted into a compound of the following formula x with a fluorinating agent, and this fluorinated intermediate is converted into a compound of the formula R, (vnlN, where R has the meaning defined in formula Ic, and H
al represents a chlorine atom, a bromine atom, a tosyl group or a mesyl group. ) with a propionic acid derivative represented by the following formula xvn: (wherein alkyl is an alkyl group having 1 to 4 carbon atoms). ) in the presence of a base, and the resulting intermediate represented by the following formula xm: is reduced in the presence of a metal catalyst to form the following formula : Obtain an amino compound of the following formula, diazotize this intermediate and convert it with a fluorinating agent into a compound of the following formula XX2, saponify the ester and convert it with a halogenating agent to a compound of the following formula : (In the formula, Hal represents a chlorine atom or a bromine atom, and 6X represents the meaning defined in the formula fc.) and the 2-phenoxypropionyl halide is The following formula ■c consists of reacting cyanamino represented by ■ in the presence of a base:
(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 4 carbon atoms. , and X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethyl group. ) A compound represented by the following formula xrv: (wherein, X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and X represents a trifluoromethyl group). (To) A compound represented by the following formula Xv: (wherein 'X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a trifluoromethyl group). (b) Expressed by the following formula compound. ) A compound represented by the following formula (a): (wherein, Hal represents a chlorine atom or a bromine atom, and X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).