JPS64382B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel substituted phenoxypropionate esters, processes for their production, and herbicides. More specifically, the present invention relates to a novel substituted phenoxypropionic acid ester represented by the following formula (). (In the formula, Ar is a group

[Formula] or group

[Formula], where Y represents a group selected from the group consisting of trifluoromethyl group, halogen atom, nitro group, cyano group and lower alkyl group, b represents 1, 2 or 3, and , R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, X represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, and a lower alkoxy group, a and n represents 1 or 2, respectively. ) The substituted phenoxypropionate ester of the above general formula () can be produced by the following methods) and), and the present invention also relates to these production methods.
That is, the general formula: (In the formula, Ar is the same as above. M represents a hydrogen atom or an alkali metal atom.) A compound represented by the general formula: (In the formula, R ¹ , R ² , X, a and n are the same as above. Z ¹ represents a halogen atom.) Method for producing substituted phenoxypropionate ester. General formula: (In the formula, Ar is the same as above. Z ² represents a hydroxyl group or a halogen atom.) A compound represented by the general formula: (In the formula, R ¹ , R ² , X, a and n are the same as above.) Method. Furthermore, the present invention also relates to a herbicide containing the substituted phenoxypropionate ester of the general formula () as an active ingredient. In JP-A-51-106735, which was publicly known before the application of the present invention, the following formula (A) (In the formula, X ¹ and X ² are halogen atoms, Y
is a hydrogen atom or an alkyl having 6 or less carbon atoms,
A herbicide is described which contains as an active ingredient at least one compound from the group consisting of carboxylic acids, thiocarboxylic acids, and their salts, esters, amides, or halides represented by (Z is oxygen or sulfur atom) ing. This proposal includes the groups specified in the formula () of the present invention.

Compounds having the formula are not disclosed. Also, Unexamined Japanese Patent Publication No. 1973-
In Publication No. 131545, the following formula (B) [In the above formula, R represents hydrogen or halogen,
R ₁ is (a) linear or branched (C ₁ -C ₁₂ ) alkyl (this is cyclohexyl, halogen phenyl,
Nitrophenyl, (C ₁ -C ₆ )alkyl phenyl, phenoxy (which is optionally mono- or tri-substituted by halogen and/or (C ₁ -C ₄ )alkyl), ( _C5
-C ₆ ) alkoxy, (C ₅ -C ₆ ) alkoxy-
(C ₂ - _{C 4} ) alkoxy, (C ₁ - _{C 4} ) alkoxyethoxyethoxy, (C ₁ - _{C 4} ) acyl, formula

[expression] or

(b) Cyclohexenyl or phenyl (C ₃ -
C ₄ ) alkenyl, (c) (C ₃ -C ₄ )alkynyl, which may be straight-chain or branched (C ₁ -C ₄ )alkyl,
mono- or di-substituted by halogen, phenyl, halogen phenyl or (C ₁ -C ₄ )alkylphenyl), provided that R ₁ is not an unsubstituted propargyl or butynyl group:

[expression] or

(C ₁ -C ₂ ) substituted by one of the groups of formula or (e) furyl, tetrahydrofuryl, pyridyl or oxiranyl
represents alkyl, R ₂ is hydrogen, (C ₁ -C ₄ )alkyl or (C 1 -C _{4 )} alkyl;
C ₄ ) alkoxy, R ₃ represents hydrogen, (C ₁ -C ₄ ) alkyl or phenyl, R ₂ and R ₃ together represent saturated or unsaturated alkylene having 4- or 5-ring members; represents a chain, in which case one methylene group is -O-,

[expression] or

[Formula] may be substituted by alkyl, R ₄ represents hydrogen or (C ₁ - C ₄ ) alkyl, Z represents an anion of an inorganic or organic acid,
R ₁ ' represents linear or branched (C ₁ - _{C 12} ) alkylene, R ₅ is hydrogen, (C ₁ - C ₄ ) alkyl, (C ₁ - C ₄ )
Halogenalkyl, in some cases halogen,
phenyl substituted by nitro and/or (C ₁ -C ₄ )alkyl, or of the formula or 2- _{[ 4' -} Phenoxyphenoxy]
- The fact that propionic acid derivatives have herbicidal activity;
Are listed. As mentioned above, the formula for this proposal is
R ¹ in (B) is also a group specified in the formula () of the present invention.

Compounds having the formula are not included. Furthermore, in JP-A-52-144637, the following general formula (C) [In the above formula, R means the same or different substituents selected from the group consisting of halogen, (C ₁ - C ₄ ) alkyl or (C ₁ - _{C 4} ) alkoxy, and Y means O or S. , n is a number of 1 or 2, and R ₁ is (a) straight-chain or branched (C ₁ -C ₁₂ ) alkyl, which is cyclohexyl, halogen phenyl, nitrophenyl, (C ₁ - _C4 ) Alkylphenyl, formula

【formula】

【formula】 or

By the group represented by the formula:
halogen, rhodane or phenyl), (b) mono- or di-(C ₁ -C ₄ )alkylcyclohexyl, (c) cyclohexenyl or (C (d) naphthyl or phenyl, which may be substituted by halogen, hydroxy, phenyl, halogen phenyl _or ((C ₁ -C _{4 )} alkyl phenyl); Therefore, (C ₁ - _{C 4} ) alkyl, (C ₁ - _{C 3} ) halogen alkyl, CF ₃ , NO ₂ , CN, SCN, CHO,
(C ₁ - C ₃ ) alkoxy, (C ₁ - _{C 3} ) alkoxycarbonyl, aminocarbonyl, di- (C ₁ -
C ₄ )alkylamino, substituted one or more times by (C ₁ -C ₄ )alkylthio and may further contain halogen), or in the case of Y=O, ( e) straight-chain or branched (C ₃ -C ₆ )alkynyl, which may also be (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, halogen, phenyl, halogen; phenyl or (C ₁ -C ₄ )alkylphenyl), (f) cyclohexyl halogen optionally substituted by (C ₁ -C ₄ )alkyl; , Formula (g)-R ₁ ′-O-R ₃ ,

[Formula] -R ₁ ′-O-CO-R ₆ , -R ₁ ′-O-CO-O-R ₇ ,

[Formula]-R ₁ ′-CO-R ₉ ,

[Formula] or a group represented by -R ₁ '-S(O) _p -R ₇ XII, (h) (C ₁ -C ₂ alkyl, (i) 3 to (C ₂ - C ₄ ) alkyl substituted by 7 to 7 chlorine and/or fluorine atoms, or (k) (C ₃ - C ₄ ) alkenyl if Y=S and R ₂ is hydrogen, (C ₁ - C ₄ ) alkyl, (C ₁ - _{C 4} )
means alkoxy, hydroxyethyl or chloroethyl, R ₃ is hydrogen, (C ₁ - _{C 4} ) alkyl, chloroethyl, phenyl, halogen phenyl, (C ₁ - _{C 4} )
means alkylphenyl, hydroxyethyl or aliphatic (C ₁ -C ₄ )acyl, R ₂ and R ₃ together and optionally one carbon atom -O-, -CO-, - N=,-
NH—or

[Formula] means a saturated or unsaturated hydrocarbon chain having 2, 4 or 5 members optionally substituted by alkyl, R ₄ means hydrogen or (C ₁ - C ₄ ) alkyl, Z means an anion of an inorganic or organic acid;
R ₁ ' means linear or branched (C ₁ - _{C 12} ) alkylene, R ₅ means (C ₁ - _{C 6} ) alkyl, (C ₁ - C ₄ ) halogen alkyl, (C ₂ - _C8 ) alkoxyalkyl,
(C ₃ -C ₁₂ )alkoxyalkoxyalkyl, hydroxyethyl or phenyl optionally substituted once or twice with halogen and/or (C ₁ -C ₃ )alkyl, R ₆ is hydrogen, (C ₁ ―C ₄ ) alkyl, (C ₁ ―C ₄ )
halogenalkyl, phenyl optionally substituted with halogen, nitro and/or (C ₁ -C ₄ )alkyl or of the formula or R ₇ is (C ₁ -C ₄ )alkyl, phenyl, halogen phenyl, nitrophenyl or (C _{1 -C 4} ).
_C4 ) means alkylphenyl, ^R8 is hydrogen,
( _C1 - _C4 )alkyl or ( _C1 - _C4 )alkoxy, _R9 means ( _C1 - _C4 )alkyl, and p means 0, 1 or 2] 2-[4′-phenoxyphenoxy]-
It is stated that propionic acid derivatives have herbicidal activity. As mentioned above, the formula (C) of this proposal is
R′ is also the group specified in the formula () of the present invention.

Compounds having the formula are not included. Furthermore, in JP-A-54-119479, the following general formula (D) [Wherein, X is a fluorine atom or a chlorine atom,
Y is a hydrogen atom or a chlorine atom, R is a hydrogen atom, a methyl group or an ethyl group, n is 0 or 2, Z ¹ is a hydroxyl group, and the alkyl moiety is 1 to 3
may be substituted with a halogen atom (C ₁ -
C ₆ ) alkoxy group, (C ₁ - _{C 4} ) alkoxy (C ₁ -
C ₄ ) alkoxy group, (C ₂ - _{C 4} ) alkenyloxy group, (C ₂ - _{C 4} ) alkynyloxy group, cycloalkyl moiety may be substituted with (C ₁ - _{C 4} ) alkyl group (C ₃ - C ₆ ) cycloalkyl group, (C ₁ -
_C4 ) alkoxycarbonyl ( _C1 - _C4 ) alkoxy group, phenoxy group in which the phenyl moiety may be substituted with 1 to 3 halogen atoms or ( _C1 - _C4 ) alkyl group, benzyloxy group, glycidyloxy group, (C ₁ - C ₄ ) alkylthio group, (C ₂ - _{C 4} )
alkenylthio group, phenylthio group in which the phenyl moiety may be substituted with 1 to 3 halogen atoms or (C ₁ -C ₄ ) alkyl group, amino group, (C ₁
-C ₄ ) alkylamino group, (C ₁ -C ₄ ) alkoxycarbonylmethylamino group, hydroxycarbonylmethylamino group, anilino group in which the phenyl moiety may be substituted with 1 to 3 halogen atoms, pyridine-2- ylamino group, -O-cation, or halogen atom] is described as having herbicidal activity. Z ¹ in this proposed formula (D) includes the group specified in the formula () of the present invention.

[Formula] is not included. The present inventors have been conducting research and development on herbicidally active compounds based on substituted phenoxypropionic esters. As a result, it was found that the substituted phenoxypropionic acid ester compound represented by the above formula (), which has not been described in any known literature, can be easily synthesized with good yield, and that the compound of formula () can be used in field crops. The inventors have discovered that this is a novel biologically active compound that exhibits selective and excellent herbicidal activity against weeds of the family Helicoptera, without causing any substantial phytotoxicity. As shown in the general formula (), the compound of the present invention forms an ester structure of substituted phenoxypropionic acid and, for example, benzyloxyalcohol, and in this structure, the alcohol residue of the ester is benzyloxyalkyl. That,
This is an essential structure and feature. According to the research conducted by the present inventors, the novel compound of formula () of the present invention having such a structure has excellent properties not seen in other related compounds, specifically, at low doses. It has been discovered that it exhibits sufficient herbicidal effects, has excellent residual potency, suppresses the long-term regeneration of weeds, especially perennial weeds, and exhibits excellent selectivity, making it possible to avoid chemical damage to crops. Therefore, an object of the present invention is to provide a novel substituted phenoxypropionic acid ester represented by the general formula (), a method for producing the same, and its use as a herbicide. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The herbicide of the present invention has low toxicity to warm-blooded animals and has good selectivity for cultivated plants, that is, it does not cause harm to cultivated plants at normal concentrations, so it can be used as a herbicide for weed control. It can be conveniently used for. In particular, the herbicide of the present invention exhibits excellent selective control efficacy when used as a pre-emergence soil treatment agent or a foliage and foliage soil treatment agent for weeds of the true family. As described above, the compound of the present invention is excellent in safety and exhibits excellent herbicidal activity. As for the herbicidal spectrum, for example,
Echinochloa crus-galli P.Beauv, crabgrass
Digitaria adscendens Henr, Eleusine
indica Gaertn, Setaria viridis P.
Beauv, Wild Oat Avena fatua, Alopecurus aequalis var.amurensis
Ohwi, Setaria lutescens, Agropyron repens, Agropyron
It has a strong herbicidal effect on tsukushiense var.
Excellent herbicidal and regeneration inhibiting effects are recognized. The compounds of the present invention can be safely used on a number of crops such as beans, cotton, carrots, potatoes, beets, citrus, mustard, mustard, peanuts, radish, tobacco, tomatoes, and cucumbers without causing any harmful effects. The compounds of the present invention include, for example, the following) and)
It can be manufactured by the following method. Manufacturing method (In the formula, Ar, R ¹ , R ² , X, a, n, M, and Z ¹ are the same as above.) In the above reaction formula, the group

[expression] or base

Specific examples of Y in Ar represented by the formula include trifluoromethyl group, halogen atoms such as fluoro, chloro, bromine, and iodine;
Mention may be made of a nitro group, a cyano group, or a lower alkyl group such as methyl, ethyl, propyl, isopropyl, n-(iso-, sec-, or tert-)butyl, and the like. b represents 1, 2 or 3. R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and examples of such alkyl groups include the same lower alkyl groups as exemplified above. Further, X specifically represents a hydrogen atom, a halogen atom similar to the above-mentioned examples, a nitro group, a lower alkyl group similar to the above-mentioned examples, or a lower alkoxy group having a lower alkyl group similar to the above-mentioned examples. a and n represent 1 or 2. In the method for producing the compound of the present invention represented by the above reaction formula, specific examples of the compound of general formula () as a raw material include 4-(4-trifluoromethylphenoxy)phenol, 4-(2- trifluoromethylphenoxy)phenol, 4-
(4-fluorophenoxy)phenol, 4-
(2,4 dichlorophenoxy)phenol, 4(2
-chloro-4-nitrophenoxy)phenol,
4-(2-trifluoromethyl-4-chlorophenoxy)phenol, 4-(4-trifluoromethyl-2-chlorophenoxy)phenol, 4-
(3,5-dichloro-2-pyridyloxy)phenol, 4-(5-nitro-2-pyridyloxy)phenol, 4-(4-nitrophenoxy)
Phenol, 4-(4-bromo-2-chlorophenoxy)phenol, 4-(4-trifluoromethyl-2-nitrophenoxy)phenol, 4-
(2,6-dichloro-4-trifluoromethylphenoxy)phenol, 4-(2-cyano-4-
trifluoromethylphenoxy)phenol, 4
-(2-chloro-4-cyanophenoxy)phenol, 4-(3-chloro-5-nitro-2-pyridyloxy)phenol, 4-(5-trifluoromethyl-2-pyridyloxy)phenol, 4
-(3-chloro-5-trifluoromethyl-2-
pyridyloxy)phenol, 4-(5-bromo-3-chloro-2-pyridyloxy)phenol, 4-(4-chloro-2-methylphenoxy)
Examples include phenols, and alkali metal salts thereof such as Li, Na, and K salts. In the above reaction formula, which is also a raw material, the general formula ()
Specific examples of the compounds include, for example, 2-chloro(or bromo)propionic acid 2-benzyloxyethyl ester, 2-chloro(or bromo)propionic acid 3-benzyloxypropyl ester,
2-chloro(or bromo)propionic acid 1-methyl-2-benzyloxyethyl ester, 2-chloro(or bromo)propionic acid 2-α-methylbenzyloxyethyl ester, 2-chloro(or bromo)propionic acid 2- (2-fluorobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(4-fluorobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(2-chlorobenzyloxy) ) Ethyl ester, 2-chloro(or bromo)propionic acid 2-(4-chlorobenzyloxy)ethyl ester, 2-chloro(or bromo)
Propionic acid 2-(2,4-dichlorobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(3,4-dichlorobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(2,6-dichlorobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(2-methylbenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(3-) nitrobenzyloxy)ethyl ester, 2-chloro (or brome)
Propionic acid 2-(4-methoxybenzyloxy)ethyl ester, 2-chloro (or brome)
2-(4-brombenzyloxy) propionate
Ethyl ester, 2-chloro(or bromo)propionate 1-methyl-2-α-methylbenzyloxyethyl ester, 2-chloro(or bromo)
2-(3-chlorobenzyloxy) propionate
Ethyl ester, 2-chloro(or bromo)propionic acid 2-(2-bromobenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(3-fluorobenzyloxy)ethyl ester, 2-chloro( or bromo) propionic acid 1-methyl-2-(2-fluorobenzyloxy)ethyl ester, 2-chloro(or bromo)
Propionic acid 3-(2-fluorobenzyloxy)propyl ester, 2-chloro(or bromo)propionic acid 2-(2-nitrobenzyloxy)ethyl ester, 2-chloro(or bromo)
2-(4-nitrobenzyloxy) propionate
Ethyl ester, 2-chloro(or bromo)propionic acid 2-(4-methylbenzyloxy)ethyl ester, 2-chloro(or bromo)propionic acid 2-(2-methoxybenzyloxy)ethyl ester, 2-chloro(or Examples include bromo)propionic acid 3-(4-fluorobenzyloxy)propyl ester. Next, the above manufacturing method will be specifically explained using representative examples. The method for producing the compounds of the present invention can be carried out desirably using a solvent or diluent. All inert solvents and diluents can be used for this purpose. Such solvents or diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as hexane,
Cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso- Propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso-butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol , ethanol, iso-propanol, butanol, ethylene glycol; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as
Dimethyl sulfoxide, sulfolane; and bases such as pyridine can be mentioned. Furthermore, as described above, the reaction of the present invention can be carried out in the presence of an acid binder. Such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholates, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. . The method of the invention can be carried out within a wide temperature range. It can generally be carried out between about -20°C and the boiling point of the mixture, preferably between 0 and about 100°C.
It can be carried out between Further, although the reaction is preferably carried out under normal pressure, it is also possible to operate under increased pressure or reduced pressure. Manufacturing method (In the formula, Ar, R ¹ , R ² , X, a, n and Z ² are the same as above.) In the method for producing the compound of the present invention represented by the above reaction formula, the starting compound of the general formula () is Specific examples include 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionyl chloride, 2-[4-(2-trifluoromethylphenoxy)phenoxy]propionyl chloride, 2-[ 4-(4-fluorophenoxy)phenoxy]propionyl chloride, 2-[4-
(2,4-dichlorophenoxy)phenoxy]propionyl chloride, 2-[4-(2-chloro-
4-Nitrophenoxy)phenoxy]propionyl chloride, 2-[4-(2-trifluoromethyl-4-chlorophenoxy)phenoxy]propionyl chloride, 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl Chloride, 2-[4-(4-trifluoromethyl-2-chlorophenoxy)phenoxy]propionyl chloride, 2-[4-(5-nitro-2-
pyridyloxy)phenoxy]propionyl chloride, 2-[4-(4-nitrophenoxy)phenoxy]propionyl chloride, 2-[4-(4
-bromo-2-chlorophenoxy) phenoxy]
Propionyl chloride, 2-[4-(4-trifluoromethyl-2-nitrophenoxy)phenoxy]propionyl chloride, 2-[4-(2,6
-Dichloro-4-trifluoromethylphenoxy)phenoxy]propionyl chloride, 2-
[4-(2-cyano-4-trifluoromethylphenoxy)phenoxy]propionyl chloride,
2-[4-(2-chloro-4-cyanophenoxy)phenoxy]propionyl chloride, 2-
[4-(3-chloro-5-nitro-2-pyridyloxy)phenoxy]propionyl chloride, 2
-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionyl chloride,
2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionyl chloride, 2-[4-(5-bromo-3-
Chlor-2-pyridyloxy)phenoxy]propionyl chloride, 2-[4-(4-chloro-2
-methylphenoxy)phenoxy]propionyl chloride and the like, and instead of these chlorides, their bromides or their free propionic acid forms can also be mentioned. Further, as specific examples of the compound of general formula () which is also a raw material, for example, 2-benzyloxyethanol, 3-benzyloxypropanol,
1-benzyloxy-2-propanol, 2-α
-Methylbenzyloxyethanol, 2-(2-
fluorobenzyloxy)ethanol, 2-(4
-fluorobenzyloxy)ethanol, 2-
(2-chlorobenzyloxy)ethanol, 2-
(4-chlorobenzyloxy)ethanol, 2-
(2,4-dichlorobenzyloxy)ethanol,
2-(3,4-dichlorobenzyloxy)ethanol, 2-(2,6-dichlorobenzyloxy)
Ethanol, 2-(2-methylbenzyloxy)
Ethanol, 2-(3-nitrobenzyloxy)
Ethanol, 2-(4-methoxybenzyloxy)ethanol, 2-(4-brombenzyloxy)ethanol, 1-(α-methylbenzyloxy)-2-propanol, 2-(3-chlorobenzyloxy)ethanol, 2 -(2-bromobenzyloxy)ethanol, 2-(3-fluorobenzyloxy)ethanol, 1-(2-fluorobenzyloxy)-2-propanol, 3-(2
-Fluorobenzyloxy)propanol, 2-
(2-nitrobenzyloxy)ethanol, 2-
(4-nitrobenzyloxy)ethanol, 2-
(4-methylbenzyloxy)ethanol, 2-
(2-methoxybenzyloxy)ethanol, 3
-(4-fluorobenzyloxy)propanol and the like. Next, the above manufacturing method will be specifically explained using representative examples. To carry out the above method, preferably the same inert solvent or diluent as described above is used, and the desired product can be obtained with high purity and high yield. To prepare the active compounds of the invention, it is possible to carry out within a wide temperature range. Generally carried out between about -20°C and the boiling point of the mixture,
Preferably it is carried out at a temperature between about 0 and about 100°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. When the compound of the present invention is used as a herbicide, it can be used in various formulations using methods commonly used in the agricultural chemical manufacturing field using agricultural chemical adjuvants. In actual use, these various formulations can be used directly or diluted with water to a desired concentration. Examples of pesticide adjuvants include diluents (solvents,
fillers, carriers), surfactants (solubilizers, emulsifiers,
Examples include dispersants, wetting agents), stabilizers, fixing agents, propellants for aerosols, synergists, and the like. Solvents include water: organic solvent; hydrocarbons [e.g., n-hexane, petroleum ether, naphtha, petroleum fractions (paraffin wax, kerosene, light oil, middle oil, heavy oil), benzene, toluene, xylenes], halogenated Hydrocarbons (e.g. chlormethylene, carbon tetrachloride, trichlorethylene, ethylene chloride, ethylene dibromide, chlorobenzene, chloroform), alcohols [e.g. methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol], Ethers [e.g. ethyl ether, ethylene oxide, dioxane], alcohol ethers [e.g. ethylene glycol, monomethyl ether], ketones [e.g.
acetone, isophorone], esters [e.g. ethyl acetate, amyl acetate], amides [e.g. dimethylformamide, dimethylacetamide],
Examples include sulfoxides, such as dimethyl sulfoxide. As fillers or carriers, inorganic powders such as slaked lime, magnesium lime, gypsum, calcium carbonate, silicon, perlite, pumice, calcite, diatomaceous earth,
Amorphous silicon oxide, alumina, zeolite, clay minerals (e.g. pyrophyllite, talc, montmorillonite, beidellite, vermiculite,
Kaolinite, mica): Vegetable granules; Grain flour, starch, modified starch, sugar, glucose, crushed plant stems: Synthetic resin granules; Examples include phenolic resins, urea resins, vinyl chloride resins, etc. can. Examples of the surfactant include anionic surfactants; alkyl sulfates, [e.g. sodium lauryl sulfate], arylsulfonic acids,
[e.g. alkylaryl sulfonates, sodium alkylnaphthalene sulfonates], succinates, polyethylene glycol alkyl aryl ether sulfate salts: cationic surfactants; alkylamines, [e.g.
laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride], polyoxyethylene alkyl amines: nonionic surfactants; polyoxyethylene glycol ethers, [e.g., polyoxyethylene alkylaryl ether and condensates thereof] polyoxyethylene glycol esters,
[For example, polyoxyethylene fatty acid ester],
Examples include polyhydric alcohol esters [for example, polyoxyethylene sorbitan monolaurate]: amphoteric surfactants, and the like. In addition, stabilizers, fixing agents [e.g., agricultural soap, casein lime, sodium alginate, polyvinyl alcohol (PVA), vinyl acetate adhesives, acrylic adhesives], potency extenders, dispersion stabilizers [e.g., casein, tragacanth, carboxymethylcellulose (CMC), polyvinyl alcohol (PVA)] and synergists. The compound of the present invention can be manufactured into various formulations by methods generally practiced in the agricultural chemical manufacturing field. Examples of formulation forms include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, and powders. The herbicide of the present invention contains the active ingredient from about 0.001 to
It can contain 100% by weight, preferably about 0.005 to about 95% by weight. In actual use, the various formulations and spray preparations described above (ready-to-use)
The active compound content in the preparation is generally approximately
A range of 0.01 to about 95% by weight, preferably about 0.005 to about 60% by weight is suitable. The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, and weed growth status. The compound of the present invention may also be used, if necessary, with other agricultural chemicals, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants [e.g. Organic phosphoric acid ester compounds, carbamate compounds, dithio (or thiol)
Carbamate-based compounds, organic chlorine-based compounds, dinitro-based compounds, organic sulfur or metal-based compounds, antibiotics, substituted diphenyl ether-based compounds, urea-based compounds, triazine-based compounds] or/and fertilizers, etc. may be present or used in combination. You can also do it. Various formulations or spray preparations (ready-to-use) containing the active ingredients of the invention are available.
Preparation) refers to the application methods commonly used in the field of agrochemical manufacturing, such as spraying, misting, atomizing, dusting, powdering, water surface application, and pouring. ]: Can be carried out by soil application [for example, soil mixing, sprinkling], etc. It can also be used by what is called an ultra-low-volume spraying method. In this way it is possible to have 100% active ingredient content. The application rate per unit area is from about 0.01 to about 2 Kg of active compound per hectare, preferably about
0.05 to about 1 kg is used. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges. According to the present invention, the compound of the general formula () is included as an active ingredient, and a diluent (solvent and/or filler and/or carrier) and/or
Alternatively, a herbicidal composition containing a surfactant and, if necessary, a stabilizer, a fixing agent, a synergist, etc., can be provided. Furthermore, according to the present invention, weeds and/or their growing areas are treated with the compound of the general formula () alone, or with a diluent (solvent and/or filler and/or carrier) and/or surfactant,
Furthermore, if necessary, a weed control method can be provided in which a stabilizer, a fixing agent, and a synergist are mixed and applied. EXAMPLES Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. Example 1 (Wettable powder) Compound No. 1 of the present invention, 15 parts, 80 parts of a mixture (0:5) of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay, sodium alkylbenzenesulfonate, 2 parts , 3 parts of sodium alkylnaphthalene sulfonate formalin condensate were ground and mixed to prepare a wettable powder. This is diluted with water and sprayed onto weeds and/or their growing areas. Example 2 (Emulsion) Compound No. 11 of the present invention, 30 parts, xylene, 55 parts, polyoxyethylene alkyl phenyl ether, 8
part, calcium alkylbenzenesulfonate, 7
Mix and stir to form an emulsion. This is diluted with water and sprayed onto weeds and/or their growing areas. Example 3 (Powder) 2 parts of Compound No. 12 of the present invention and 98 parts of powdered clay were pulverized and mixed to prepare a powder. Sprinkle this on weeds and/or their growing areas. Example 4 (Powder) 1.5 parts of the compound No. 13 of the present invention, 0.5 parts of isopropyl hydrogen phosphate (PAP), and 98 parts of powdered clay were pulverized and mixed to make a powder.
Or sprinkle powder on the growing areas. Example 5 (Granules) To a mixture of 10 parts of the present compound No. 14, 30 parts of bentonite (montmorillonite), 58 parts of talc, and 2 parts of lignin sulfonate, 25 parts of water was added, It is well granulated and extruded using an extrusion type granulator.
Form into granules of 10 to 40 mesh and dry at 40 to 50°C to make granules. Sprinkle this on weeds and/or their growing areas. Example 6 (Granules) Clay mineral particles having a particle size distribution of 0.2 to 2 mm, 95
1 part was placed in a rotary mixer, and while rotating, oily compounds of the present invention No. 2 and 5 parts were sprayed and evenly absorbed to form granules. Sprinkle this on weeds and/or their growing areas. The excellent results of the compounds of the present invention can be recognized from the test results below. Test Example 1 Pre-emergence Soil Treatment Test on Upland Weeds and Crops Preparation of Active Compounds Carrier: 5 parts by weight of acetone Emulsifier: 1 part by weight of benzyloxypolyglycol ether The preparation of the active compound consists of 1 part by weight of active compound and the amounts specified above. A carrier and an emulsifier are mixed to obtain an emulsion. A predetermined dose of the preparation is prepared by diluting it with water. Test method Peanut, pea, soybean, and cotton seeds were sown in ^two 1000 cm pots filled with field soil in a greenhouse.
The soil was then covered with soil mixed with seeds of Shibagi, Japanese cabbage, and Golden cabbage to a depth of 1 cm. One day after sowing, 500ppm of the above preparation,
10 ml of each chemical solution of 200 ppm, 100 ppm, and 50 ppm was uniformly sprayed on the soil surface layer of each test pot. Four weeks after spraying, the herbicidal effect and the degree of chemical damage to crops were investigated. Weeding evaluation

【table】

【table】 The test results are shown in Table 1.

【table】

【table】

【table】

[Table] Test Example 2 Stalk treatment test for field weeds and crops In a greenhouse, seeds of soybean, radish, and beet were sown in ^two 2000cm pots filled with field soil, and on top of the seeds were seeded with grasshopper, Japanese grasshopper, blackberry grass, foxtail grass, and other seeds.
The soil was covered to a depth of 1 cm with soil mixed with seeds of wild oat and sycamore. 10 days after sowing and covering the soil (average 2-leaf stage for weeds, early stage of true leaf development for radish, soybean, beet), 500ppm, 200ppm, 100ppm, 50ppm prepared in the same manner as Test Example 1.
20 ml of each chemical solution was uniformly sprayed on the stems and leaves of the test plants in each test pot. Three weeks after spraying, the herbicidal effect and the degree of chemical damage to crops were investigated in the same manner as in Test Example 1. The test results are shown in Table 2.

【table】

【table】

【table】

【table】

【table】

[Table] Test Example 3 Weeding test and regeneration suppression test on staghorn grass The staghorn grass colony on the rice field ridge was divided into 1 m ² sections, and 1000ppm, 500ppm, 200ppm, 100ppm, 200ppm,
100 ml of each 100 ppm chemical solution was sprayed on the stems and leaves of the grasshopper. 20 days after spraying, the herbicidal effect was investigated in the same manner as in Test Example 1. Furthermore, 40 and 60 days after spraying, the effect of suppressing the regeneration of staghorn grass was investigated. Evaluation of regeneration inhibitory effect

[Table] Regulation rate

【table】 The test results are shown in Table 3.

【table】

[Table] Test Example 4 Weeding test and regeneration suppression test against Aspergillus elegans In a field where erect grass grows in clusters, erect grass was sprayed at the same dosage as in Test Example 3 in each test plot divided into 1 m ² sections. The herbicidal effect was investigated 20 days after spraying, and the regeneration suppressing effect was investigated 40 and 60 days after spraying. Evaluation of herbicidal effect and regeneration suppressing effect was the same as in the above test. The test results are shown in Table 4.

【table】

【table】

【table】

[Table] Similar to the test results above, the compounds of the present invention that were not listed in the test examples above also exhibited excellent herbicidal effects at low dosages, and also exhibited long-term regrowth-suppressing effects on perennial weeds. It was confirmed that it appears. Next, a synthesis example will be shown and a method for producing the compound of the present invention will be specifically described. Synthesis example 1 Add 25.4 g of 4-(4-trifluoromethylphenoxy)phenol to 150 ml of dry acetonitrile, then add 28.7 g of 2-bromopropionic acid 2-benzyloxyethyl ester and 14.5 g of anhydrous potassium carbonate, and dissolve the contents. While stirring well, 4
Reflux for an hour. After the reaction was completed, acetonitrile was distilled off under reduced pressure, toluene was added to the residue, and the toluene layer was treated with a 1% aqueous sodium hydroxide solution and water in order.
Wash. The toluene was distilled off under reduced pressure to obtain 41 g of the desired colorless and viscous 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionic acid-2-benzyloxyethyl ester.
n ²⁰ _D 1.5300 Synthesis example 2 Add 30.6 g of 4-(3,5-dichloro-2-pyridyloxy)phenol sodium salt and 30.5 g of 2-chloropropionic acid 2-(4-fluorobenzyloxy)ethyl ester to 100 ml of dimethylformamide, and reduce the contents to 70 ml. Heat and stir at ~80°C for 3 hours. After cooling to room temperature, the contents are poured into 300 ml of water and extracted with ether. 1% ether layer
After washing with an aqueous sodium hydroxide solution and then water, and after dehydration, the ether was distilled off, resulting in the desired pale yellow, viscous oil, 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid. -2-
(4-fluorobenzyloxy)ethyl ester,
38g is obtained. n ²⁰ _D 1.5643. Synthesis example 3 22.1 g of 2-(2,6-dichlorobenzyloxy)ethanol and 10.1 g of triethylamine are dissolved in 200 ml of toluene and cooled to 0°C. A solution of 34.5 g of 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionyl chloride in 50 ml of toluene is added dropwise to this solution at 0 to 10°C. After the addition, the contents were gradually warmed and stirred at 40°C for 1 hour to complete the reaction. After cooling to room temperature, it is washed successively with a 1% aqueous sodium hydroxide solution and water, and then dehydrated. After distilling off the toluene under reduced pressure, the colorless viscous oil is left at room temperature for about a month, and crystals of 2-[4-
49.2 g of (4-trifluoromethylphenoxy)phenoxy]propionic acid 2-(2,6-dichlorobenzyloxy)ethyl ester is obtained. m.
p.51-53℃. Synthesis example 4 1-benzyloxy-2-propanol 16.6
Dissolve 10.6 g of triethylamine in 200 ml of toluene and cool to 0°C. Add 2-[4-
(3,5-dichloro-2-pyridyloxy)phenoxypropionyl chloride 34.7g toluene
Add 80 ml of the solution dropwise at 0-5° C. with stirring. After dropping, the contents were gradually warmed and stirred at 40-50°C for 1 hour to complete the reaction. After cooling to room temperature, it is washed successively with a 1% aqueous sodium hydroxide solution and water and dried. By distilling off the toluene under reduced pressure, 43.3 g of 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid 1-methyl-2-benzyloxyethyl ester was obtained as a pale yellow viscous oil. It will be done. n ²⁰ _D 1.5710. Synthesis Example 5 The compounds of the present invention shown in the table below were synthesized in the same manner as in Synthesis Example 1 or 2 above, except that the synthesis raw materials shown in the table below were used.

【table】

【table】

[Table] Synthesis Example 6 The compounds of the present invention shown in Table 5 below were obtained by substantially the same method as in the above Synthesis Example.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula: (In the formula, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group. , b represents 1, 2 or 3, and R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X represents a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, or a lower alkoxy group. (a and n each represent 1 or 2) A substituted phenoxypropionate ester represented by the following. 2 formula: 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
Phenoxy]-propionic acid-2-(4-chlorobenzyloxy-ethyl ester. 3 Formula: 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
Phenoxy]-propionic acid-2-benzyloxyethyl ester. 4 formula: 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
Phenoxy]-propionic acid-3-benzyloxypropyl ester. 5 formula 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
phenoxy]-propionic acid-2-α-methylbenzyloxyethyl ester. 6 formula 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
phenoxy]-propionic acid-2-(2-fluorobenzyloxy)-ethyl ester. 7 formula 2-- of Claim 1 expressed as
[4-(4-trifluoromethylphenoxy)-
Phenoxy]-propionic acid-1-methyl-2-
Benzyloxyethyl ester. 8 Formula: 2-- of Claim 1 expressed as
[4-(3,5-dichloropyridyloxy)-phenoxy]-propionic acid-2-(2-fluorobenzyloxy)-ethyl ester. 9 Formula: 2-- of Claim 1 expressed as
[4-(3,5-dichloropyridyloxy)-phenoxy]-propionic acid-2-benzyloxyethyl ester. 10 Formula: 2-- of Claim 1 expressed as
[4-(3,5-dichloropyridyloxy)-phenoxy]-propionic acid-1-methyl-2-benzyloxyethyl ester. 11 Formula: 2-- of Claim 1 expressed as
[4-(3,5-dichloropyridyloxy)-phenoxy]-propionic acid-2-(4-chlorobenzyloxy)-ethyl ester. 12 General formula: (In the formula, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group. , b represents 1, 2 or 3, and M represents a hydrogen atom or an alkali metal atom.) and a compound represented by the general formula: (In the formula, R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, and a lower alkoxy group. , a and n each represent 1 or 2, and Z ¹ represents a halogen atom.) (wherein, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group, b represents 1, 2 or 3, and R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X consists of a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, and a lower alkoxy group a group selected from the group, a and n each represent 1 or 2. 13 General formula: (In the formula, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group. , b represents 1, 2 or 3, and Z ² represents a hydroxyl group or a halogen atom.) and the general formula: (In the formula, R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X is a group selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, and a lower alkoxy group. and a and n each represent 1 or 2.) A general formula characterized by reacting with a compound represented by: (In the formula, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group. , b represents 1, 2 or 3, and R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X consists of a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, and a lower alkoxy group. a group selected from the group, a and n each represent 1 or 2. 14 General formula: (In the formula, Ar represents a group [formula] or a group [formula], where Y represents a group selected from the group consisting of a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, and a lower alkyl group. , b represents 1, 2, or 3, and R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, and X represents a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, or a lower alkoxy group. A herbicide containing a substituted phenoxypropionate ester represented by the following as an active ingredient: a group selected from the group consisting of: a and n each represent 1 or 2.