JPS5849364A - Substituted phenoxypropionic acid ester, its preparation and herbicide - Google Patents

Abstract

NEW MATERIAL:A substituted phenoxypropionic acid ester of formulaI(R<1> , R<2> are H, halogen lower alkyl, lower alkoxy, nitro; m,n are 1.2). EXAMPLE:2-[4-(5-trifluoromethy1-2-pyridyloxy) phenoxylpropionic 2-benzyloyethy ester. USE:Herbicide: it is low in toxicity and shows powerful selective herbicidal effect against gramineous weeds with no injury to crops. PREPARATION:For example, the reaction of a compound of formula II (M is H, alkali metal) with another compound of formula III (Y<1> is halogen) gives the compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel substituted phenoxyglopionic acid esters,
Regarding its manufacturing method and herbicide.

Ij! Specifically, the present invention relates to a novel substituted phenoxyglobionic acid ester represented by the following general formula (1).

In formula C, R1 and RIFi each represent a hydrogen atom or a lower alkyl group.

Xf-1 hydrogen atom, halogen atom, lower alkyl group, lower alkoxy group or nitro group, and wind and n each represent l or F12, respectively, the above general formula (
The substituted phenoxyglopionic acid ester of 1) can be produced by the following methods 1) and -), and the present invention relates to 4 of these production methods.

That is, 1) a compound represented by the general formula: (in the formula, 1M represents a hydrogen atom, and 1M represents an alkali gold atom); and a compound represented by the general formula: (in the formula, R", R", Same as above.

Yl represents a halogen atom. ) is defined as 1 # sign. A method for producing a substituted phenoxyglopionic acid ester represented by the general formula (1).

Heat general formula: (In the formula, Yl represents a hydroxyl group or a halogen atom.) A compound represented by General formula: (In the formula, R', R'', X, m and ntrl are the same as above.

): A method for producing a transshipment phenoxyglobionate ester of the general formula (1), which comprises carrying out a total reaction with a compound represented by C.

Furthermore, the present invention also relates to a herbicide containing the substituted phenolic siglobionic acid ester of the general formula (1) as an active ingredient.

Publication of Japanese Patent Application Publication No. 11, 1972, prior to filing of the present invention
9476 and West German Patent Publication No. 2812571, the general formula [wherein X#'i is a fluorine atom or a chlorine atom, and Yi
J hydrogen atom is chlorine 1, H is hydrogen atom, methyl group is ethyl group, g% is Of9 is 2, Zl is hydroxyl group, alkyl moiety is 1 to 3) - (CI-Cs) alkoxy group, (CI-C4) alkoxy (CI-C4) aru\koxy group, (CI-C4) alkenyloxy group, ('
1-C4) Alkynyloxy group, cycloalkyl moiety may be substituted with (CI-CJ alkyl group (Cs
-Ca) cycloalkyl group, (C, -C,) alkoxycarbonyl (CI-C4) alkoxy group, even if the phenyl moiety is open with 1 to 3 halogen atoms or (C1-C4) alkyl group Good phenoxy group, benzyloxy group, glycidyloxy group, (Ct -Cm)
Alkylthio group, (CI-Ca) 7"kenylthio group, 1 to 3 phenyl moieties, rogen atom or (C, -C
4) Phenylthio group optionally substituted with an alkyl group, amino group - (CI-C4) alkylamino group - (CI
-C4) alkoxycarbonylmethylamino group, hydroxycarbonylmethylamino group, phenyl 8 min is 1 to 3
It is described that compounds represented by an anilino group, a pyridin-2-ylamino group, an -0-cation, or a halogen atom which may be substituted with a halogen atom have herbicidal activity.

Z'' VCFI of the formula (A) of this proposal does not include the t group specified in the general formula (1) of the present invention.

The present inventors have been conducting research on the development of herbicidally active compounds based on substituted phenoxyglobionate esters.

As a result, it was found that the #-substituted phenoxyglopionic acid ester adduct represented by the above formula (1), which has not been described in any known literature, can be easily synthesized with good yield, and that the nucleic acid (1)
It has been discovered that the compound is a novel biologically active compound that exhibits selective herbicidal activity against regular weeds without causing any potential drug effects on field crops. .

As shown in the general formula (1), the adduct of the present invention has an ester structure tube formed between poorly converted phenoxyglobionic acid and, for example, pendyl alcohol, and in the structure, the alcohol residue of the ester. The group capendyloxyalkyl is an essential structure and has several characteristics.

According to the research of the present inventors, the novel compound of formula (1) of the present invention having such @metallic properties has excellent properties not found in other related compounds, specifically, low drug content. It has a light weeding effect in quantity, and its outstanding residual effect suppresses the regeneration of long-term weeds and perennial weeds. It was discovered that it exhibits excellent selectivity that avoids drug damage to J.

Accordingly, an object of the present invention is to provide a novel substituted phenoxyglopionic acid ester represented by the general formula (1), a method for producing the same, and its use as a substituted phenoxyglopionic acid ester.

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 good selectivity to cultivated plants, that is, it has the characteristics that there is no phytotoxicity to cultivated plants in normal use of af, so it can be used as a herbicide for weed control. It can be conveniently used to define The herbicide of the present invention exhibits excellent selective control efficacy, particularly when used as a pre-emergence soil treatment agent or a foliar treatment agent for weeds of the true family.

As described above, the compound of the present invention is excellent in safety and exhibits outstanding herbicidal activity.

As for the herbicidal spectrum, for example, Eahi
noahloa eras-galli P, Baa
uv, Mehishiba Digitalia adaaanda
*s Hunt, Ohishi p:Egg%m1ne js
dtca Ga5rtn, Enocologusa Smtaria
viridia P, Baauv, wild engineering
vgna fatua, Sparrow note A j op
s cwrusaaqsalia war, amur
gnsis Ohwi, Kineno: l a 5et
aria Lstaseans, 7/(Agi Agrap
yron rgpans, Agropyro
ntasksshiansa var, tranai
It has been shown to have a strong herbicidal effect on S. ens Ohwi and other perennial weeds, and has also shown to have an excellent herbicidal effect and regrowth-suppressing effect on other perennial weeds such as Johnsigeras and Gypsum.

The compounds of the present invention can be safely used on many crops such as beans, cotton, carrots, potatoes, beets, citrus, mustard, peanuts, radish, tobacco, tomatoes, cucumbers, etc. without causing harmful effects.

The compounds of the present invention can be produced, for example, by methods 1) and -) below.

Manufacturing method (Soju M-Y" (in the formula, Rt, B snow, X, m, s, A/ and Yl are the same as above.) In the above anti-Kiro 2, as R1 and R8, hydrogen Atoms or Fi such as methyl, ethyl, glovil, inglovir, cage-(tao-18-C-1 or tart)
-) C3-C4 low alkyl groups such as butyl and the like.

As X, a hydrogen atom, for example, a halogen atom such as fluoro, chlorine, bromo, H-do, etc., a lower alkyl group as exemplified above for R' and R'', a lower alkoxy group having the same lower alkyl association as above; Or you can raise the nitro fundamental tone.

And 1m and nVi, l or C2t- respectively.

In the method for producing compound 16 of the present invention shown by the above reaction formula,
Examples of the compound of the general formula (IT) which is a raw material include 4-(5-trifluoromethyl-2-pyridyloxine phenol and alkali metal salts thereof).

In the above reaction formula, which is also a raw material, an example of a compound of general formula (to) is #'i, 2-chloro (or bromo)
Nropionic acid 2-benzyloxyethyl ester, 2-
Kroll (also 11 Brom)! 1-methyl-2-ropionic acid
Benzyloxyethyl ester! - chlor (or bromo) 10pionic acid 3-benzyloxypropyl ester, 2-chloro (or bromo)gropion rR2-(2-
fluorobenzyloxy)ethyl ester, 2-chloro(or bromo)globioneIR$1-(4-chlorobenzyloxy)ethyl ester, 2-chloro(or 1jbromo)globiont12-C4-methoxypenzyloxy) Ethyl ester, 2-chloro(also H-bromo)prohionic acid 2-α-methylbenzyloxyethyl ester,
2-chloro(or bromo)propionic acid 2-(2-methylbenzyloxy)ethyl ester, 2-chloro(or bromopropionate 2-(2-chlorobenzyloxy)ethyl ester).

2-Chlor(bromo)gropion 122-(4-bromobenzyloxy)ethyl ester, 2-chlor(also habrom)gropion ltl & 2-(B-nitropenzyloxy)ethyl ester, 2-/lol(also hablom) )1
#2-(2,4-dichlorobenzyloxy)ethyl ester, etc. can be used.

Next, we will give a representative flJ and specifically explain the Joki splitting method.

The method for producing a chemical compound of the present invention can be carried out preferably using a solvent or a diluent. All inert solvents and diluents can be used in this method.

Such solvents or diluents include water: aliphatic resin l1
Group 7i and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride.

Chloroform, carbon tetrachloride, ethylene chloride and trichlorethylene, chlorobenzene; ethers such as diethyl ether.

Methyl ethyl ether, carbonyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl is.

-Globylketone, methyl-1sO-butylketone-nitrile such as acetonitrile, gropionitrile,
Acrylonitrile; alcohols e.g.

methanol, ethanol, 1so-gropanol,
.

Butanol, ethylene glycol; esters @ e.g.
Ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacedoide; sulfones, sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as pyridine.

Further, as described above, the reaction of the VC of the present invention can be carried out in the presence of a labeled binding agent. Such hard binders include commonly used alkali metal hydroxides, carbonates, monobicarbonates, alcolades, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. can.

The method of the invention has a wide tM! Make sure that it is implemented within the scope. It can generally be carried out between -20°C and the boiling point of the mixture, preferably between 0 and about 100°C. In addition, it is preferable to carry out the reaction under normal pressure.
It is also possible to operate under reduced pressure.

Production method 1 (IV) (V) (In the formula, R1, R concentration %X1m, n and Y"u are the same as above.) ), for example, 2-(a-(Is-)ripuromethyl-2-
Instead of pyridyloxy[7)phenoxy]globionyl chloride and the chloride, compounds in the form of bromide or free globionyl chloride can be used.

Also, same a! Specific examples of the compound of general formula (V) which is a raw material include, for example, 2-benzylox7ethanol,
l-benzyloxy-2-7'rotsuknol, 3-benzyloxygulo/fonol, 2-(2-fluorobenzyloxy)ethanol, 2-(4-chlorobenzyloxy)ethanol, 2-(4-methoxybenzyl) Oxy)
Ethanol, 2-α-methylbenzyloxyethanol, 2-(2-methylbenzyloxy)ethanol, 2-
(Ll-chlorobenzyloxy)ethanol, 2-(4
-Brombenzyloxy7) Ethanol, 2-(3-nitrobenzyloxy)ethanol, 2-(2,4-dinitrobenzyloxy), etc.? I can give it to you.

Next, the above-mentioned manufacturing method will be specifically explained with reference to a typical example.

In carrying out all of the above methods, it is preferable to use the same inert bath additives and secondary diluents as described above, and the desired vIJ1ft can be obtained with high purity and high yield.

The active compounds of the present invention may be manufactured within a wide temperature range. Generally, about -20
°C and the boiling point of the mixture.

Preferably, it can be carried out at a temperature of about 0 to about 100°C.

It is preferable to carry out the reaction under normal pressure, but it is also possible to operate under elevated or reduced pressure.

When the compound of the present invention is used as a herbicide, it can be used in the form of various formulations using methods commonly practiced in the agricultural manufacturing field using a negative mulberry adjuvant. . In actual use, these various preparations can be used directly as is or diluted with 1fC#'i water as desired.

j & Pharmaceutical auxiliary agents are 1. For example, diluents (solvents, fillers, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents)
, stabilizers, fixing agents, aerosol propellants.

Examples include synergistic agents.

As a science agent, water: organic solvent; hydrocarbons [moth, tri
, n-hexane, petroleum neal, naphtha, petroleum 1 minute (paraffin wax, kerosene, light oil, medium oil, heavy oil) benzene, toluene, xylenes], halogenated hydrocarbons [for example,
Chlormethylene, carbon tetrachloride 1)! l Chlormethylene ethylene chloride.

Ethylene tribromide, chlorobenzene, chloroform].

7"Co-7'm (% Jjiij, 1 thyl alcohol, ethyl alcohol % globyl alcohol, ethylene glycol], ether [e.g. ethyl ether, ethylene oxide, dioxane], alcohol ether [1 (N
Examples include ethylene glycol, monomethyl ether], ketones [e.g. aceto/isophorone], and esters [e.g.
For example, ethyl acetate.

[Amyl acetate], idos [for example, dimethylformamide, dimethylacedo], sulfoxides [the tip can be shown as dimethyl sulfoxide 3].

As a violet thickening agent or carrier, inorganic powder: sulfur, slaked lime, magnesium lime 1 gypsum, calcium carbonate, silica,
) minerals such as stone, calcite, quartzite, amorphous silicon oxide, aluminum, zeolite, clay minerals (e.g.
non-ilophyllite, talc, montmorillonite, beidellite, bar-culite, kaolinite, granite): vegetable granules; grain flour, starch, processed dengue, sugar, grape shield, crushed plant stems: synthetic resin granules body; examples include phenol resin, urea resin, and vinyl chloride resin.

Examples of surfactants include anionic surfactants; alkyl sulfate esters [e.g., sodium lauryl sulfate], aryl sulfonic acids [fp4, alkylaryl sulfone #salt, sodium alkylnaphthalene sulfonate]; Huccinates, polyethylene glycol, arylnylene-yl@@techxfkN: cationic (II) (one) surfactant;
For example, lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride], boroxyethylene alkyl t7
tA: Nonionic surfactant; polyoxyethylene glycol ethers [for example, polyoxyethylene alkylaryl ether and condensates thereof] diethylene glycol esters in polio [for example, polyoxyethylene fatty acid ester].

Polyhydric alcohol esters [e.g., polyoxyethylene sorbitan monolaurate] diampholytic surfactants, etc.
can be exemplified.

In addition, antistatic agents, fixing agents [e.g., agricultural chemical river soap, casein lime, sodium alginate, polyvinyl alcohol (
PV, 4), vinyl hexate adhesive, acrylic adhesive]
, efficacy prolonging agents: dispersion stabilizers (casein, tragacanth, carboquine methylcellulose (CMC), /vinyl alcohol (PVA)): synergists, etc.

The compound of the present invention can be produced in the form of cedar wood by a method generally practiced in the field of manufacturing Mk drugs. For example, the form of the preparation is as follows.

Emulsions: Oils: Wettable powders: Bathing agents: Suspension agents: Powders, two-grain preparations: Powder preparations, etc.

The herbicide of the present invention contains about (LOOI ~ 10
01iii9G, preferably from about CLO5 to about 95wt-
It can contain.

In actual use, the various formulations and spray preparations described above (rmady-to-usa-prm
The active compound in the par-ratio solution generally contains from about aO1 to about 95 wt -1, preferably from about α05 to about 60
A range of weight and arrogance is appropriate.

The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, time, place, occurrence of miscellaneous vehicles, etc.

In addition to the compound of the present invention, if necessary, other drugs may be added, such as insecticides, decontaminants, acaricides, and nematicides.

Antiviral agents, descaling, plant growth, 1jliJ renal agents, attractants, [For example, organophosphate compounds, carbamate thread compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro Compounds based on organic sulfur compounds are metal-based chemical compounds and antibiotic compounds.

M-converted diphenyl ether compounds, urea compounds, triazine compounds) teri/, fertilizers, etc. can also be present.

1141R4712) (ready-to-us)
e-prapara-tionl is applied by application methods and spraying [e.g., liquid spraying (spraying), misting], which are commonly used in the drug manufacturing field.
, atomizing (αtomig (%g), powder, powder, water surface application, pouring)
: Soil application [for example, mixing, sprinkling
nkling )]. Mayu so-called super, I! 6-density low-perishability cloth method (sltra-1 part w-voluna) It can also be used from yc to j. In this way, 100% active ingredient content is possible.

Application per unit area is generally about (LOI-fJ2Kf, preferably about α05 to
Approximately IK41 can be used. However, in special cases VC
It is possible, and sometimes even necessary, to increase or decrease these ranges tHi.

According to the present invention, the compound of the general formula (1) is included as an active ingredient, and a diluent (an feI agent and/or a thickening agent and/or a carrier) and/or a surfactant, and if necessary, For example, herbicidal compositions containing stabilizers, fixing agents, synergists, etc. can be provided.

Furthermore, the present invention provides a method for controlling weeds and/or their growth by applying the compound of the general formula (1) alone or to
Weed control by applying a thickening agent and/or a carrier or a surfactant to bath additives and/or dermis, and/or surfactants, if necessary, with stabilizers, fixing agents, synergists, etc., mixed with gold. method can be provided.

The present invention will be specifically explained below using VC implementation, but the present invention should not be limited to this only.

Example 1 (Irrigation agent) 111ills of the present compound A1.15, white carbon (water-containing non-rotating silicon oxide fine powder) and powdered clay
80 parts of soybean paste (1:5), 2 parts of alkylbenzene sulfone-plated sodium, and 3 parts of alkylnaphthalene sulfone-plated sodium formalin condensate were pulverized and mixed to prepare an irrigation agent.

This was diluted with social water, and F9'rVC was sprayed dropwise onto M males and/or males.

Implementation example 2 (emulsion) Compound A of the present invention 2, 30 parts, xylene, 55 parts.

Polyoxyethylene alkylphenyl ether.

8 parts and 7 parts of calcium alkylbenzenesulfonate were mixed and stirred to form an emulsion. This is diluted with water and sprayed onto weeds and/or their growing areas.

Example 3 (Powder) 0.2 parts of the compound of the present invention AI, 98 parts of powdered clay [pulverized and mixed to form a powder]. Sprinkle dust on the growing areas of this material and grass.

Examples Reef (powder) Compound A8 of the present invention, 5 parts L, isoglopyrnohydrogen phosphatide (PIP), 0.5 part, powdered clay,
Grind and mix 98 parts to make a powder and sprinkle it on weeds and/or weeds and their growing areas.

Implementation flJ 5 (granules) 4-Genming Compound A3.10, bentonite (montmorillonite I, 30 parts, talcum, 58 parts, lignin sulfonic acid, 2 parts), water, 25 add part,
The mixture is thoroughly kneaded and made into granules of % 1O to 40 mesh using an extrusion type granulator and dried at % 40 to 50''C to form granules.The resulting granules are sprinkled on weeds and/or weeds or their growing areas.

Row 6 (granules) From 0.2 to 2111: clay mineral particles with a particle size distribution.

Put the ssg'15' into a rotary mixer and squirt 5 parts of the oily version under rotation to absorb it evenly.

Take the form of granules. Sprinkle this on male and female plants and/or their growing areas.

The excellent effects of the compounds of the present invention can be recognized from the following test results.

Test row 1 Pre-emergence soil damage treatment test for upland weeds and crops Preparation of active compounds Carrier: Acetone 5 Violet Emulsifier: Benzyl oxy 7 Polyglycol ether 1
1[-1 part of active compound 04 & octopus with l subpart of active compound.

What about the above-mentioned electrical distribution carrier and emulsifier? Mix and obtain an emulsion. The prescribed drug t of the preparation is prepared by diluting it with water.

Test method: In a greenhouse, seeds of peanuts, peas, daisies, and cotton were sown in field soil Ls Kanazumetomo 1000:d pots, and on top of the seeds, 13 seeds of each of grasshoppers, chinese wheat, and goldenrod were sown. Covered to depth.

Sooppm prepared above one day after sowing.

ROOppm, 1100pp% 50ppm each chemical solution 1
0mjQ was uniformly sprayed on the ±4 surface layer of 4 ts for each test.

The herbicidal effect and the degree of placement on crops after 4 weeks of spraying [1
-I prepared a meal.

Evaluation of herbicidal effect lO: Weed killing rate 100 g (complete death) for untreated area
: I' 90% or more and less than 1oos 8: # 80%l 90
% 17: # 7G11 8
0% #6: #60 whisper 1
70 arrogant 15: # 50 arrogant #
60chi 14: I 40
%I 50chi 13: #
30% 1 40% 12: #
20cs1 30%11: 1
10 regrets # 20% #0: #
Less than 10% * (no herbicidal effect) The test results are shown in the first panel.

[Note] L Compound I6 is the same as that described in the synthesis example and Table 5 below.

2' The "-" in "#&Harm" indicates that there is no chemical harm.

Test Example 2 Grave collection treatment test for upland weeds and crops In a greenhouse, each seed of soybean, radish, and Bee F was sown at 2000 at/plant packed in field soil, and on top of that, Japanese millet,
Mix 1 seed each of crabgrass, hackberry, wild oat, and sparrow gnome to a depth of 1 cm.
It was soil.

10 days after sowing the soil (average zs stage for weeds, early leaf development for radish, soybean, and beet), WrOOppm% 200ppm, 100FF & sOνp prepared in the same manner as test QI.
Each chemical solution of tx gos/i was uniformly sprayed on the grave leaves wA of the test plants in each test wax 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.

Test ``!Fi1m Weeding test and regeneration suppression test for kamojigusa ``Kamojiga'' on the rice field ridge?# Fabric t-1-.

Each test group [1000pps, 600ppm,! G.

100aJ of each chemical solution p p vm, i 009 j-
'i Sprayed on the xsm of Kamojigusa. Twenty days after the spraying, the herbicidal effect was investigated in the same manner as in Test Example 1. Further spraying 40
After 60 days and 60 days, the effect of suppressing the regeneration of Physcomitrella japonica was investigated.

Evaluation of regeneration suppression effect lO: Regeneration suppression rate relative to untreated area 100- (Complete suppression of regeneration @: II 1ie- or more and less than tooLs IB; t
80S# 9011#7: y
'1041 80%11i:
I fio%z 70jl#6
: I 50 pieces 1 g
Dfk14: #4G4
1 m09113: #
30 yam 140% 12: #
-flO@1 3091#l:
z 1o@z 2o@zQ:
The results of the I less than 10 (no regeneration inhibition) test are shown in Table 3.

□ [Note] Compounds are the same as those listed in the synthesis examples and Table 1 below.

2 Comparison? mA-1: ('#Kaisei 54-1194-64II period compound) Test 91j4 Weeding test and regeneration inhibition test on A. nigra.The test was carried out in each test plot divided into % 1 m'' in a field where a colony of A. a. Use the same dosage as in step 3 to spray and treat Gigatsu Gishipa.

Scatter! After O days, weeding effect t% spraying 4 mouths Evaluation of unveiling effect and regeneration suppressing effect was the same as above.

The test results are shown in Table 4.

Next, a synthesis example will be shown and a method for producing the compound of the present invention will be specifically described.

Synthesis Ip41 (Compound '4I! JI611 4-i-) Rialomethyl-2-pyridyloxy)phenol 21L5 f, anhydrous potassium carbonate 141F,!
-bromo-10-2-benzylodiethyl ester28. A mixture of Tf and 15G of dry acetonitrile is allowed to flow for S hours while stirring well.

After the reaction was completed, acetonitrile was distilled off under reduced pressure to leave the remaining ff1K.
, ) Luen 1! ! 0111@processing, this toluene layer t
i1g sodium hydroxide aqueous solution and water, sequentially.

Wash. If toluene is distilled off under reduced pressure, the target product 3-
[Reef-(S-trifluoromethyl=8-elysyloxy)phenoxy]globion cough 2-benzyloxyethyl ester 429f is obtained.

", 9.44-47℃ Synthetic alcohol (compound 2) 2-(4-chlorobenzyloxy)ethanol 11L7
F.) Lithylamine in 1air is dissolved in 200% of total toluene and cooled to O'CK. Add 2-[reef-(5-
A solution of 346 tons of trifluoromethyl-2-pyridyloxy) phenol chloride in toluene was added dropwise at O-6°C. After the addition, the contents were gradually warmed and stirred at 40°C for 1 hour. Complete the reaction. Cool apparatus to room temperature.

Wash with water, 1g & sodium hydroxide aqueous solution, water clay,
Dehydrate. When the toluene was removed under reduced pressure, a colorless oily heavy-[reef-(b-trifluoromethyl-2-pyridyloxyphenol)]gropionic acid!-(4-chlorobenzyloxy)ethyl ester 4?, 1f was obtained. can get.

S'1585G Typical examples of the compounds of the present invention synthesized by a method similar to those in Synthesis Examples 1 and 2 above are specifically shown in Table t@5.

Procedural Amendment November 25, 1980 Director General of the Patent Office Shima 1) Harukan 1, Indication of the Case 1986'FPIIl ai m+h 1447?
8 %2, Renamed invention phenoxyprobionic acid ester, its manufacturing process, and relation to the herbicide 3 amendment case Patent applicant address 4th generation, 2-8 Rekimachi, Nihonbashi, Chuo-ku, Higashibunto
107 556- [I] Kusunoki Of Co., Ltd. in the “Claims” of the specification,
The following corrections are made.

"1) General formula (wherein R1 and R8 each represent a hydrogen atom or a lower alkyl group, XL hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a nitro group, and

Dai and % indicate 1 or 2 meetings, respectively. ) Substituted phenoxypropionic acid ester.

2) Formula: 2-(4-(
5-Trifluoromethyl-2-pyridyloxy)phenoxyfuzolopionic acid-2-benzyloxyethyl ester.

3) Formula: 2-(4-(
5-Trifluoromethyl-2-pyridyloxy)phenoxy]gropion &-2-(2-fluorobenzyloxy)ethyl ester.

4) Formula: 2-[4-
(5-) Rialomethyl-2-pyridyloxy)phenoxy]zolopionic acid-2-(4-chlorobenzyloxy)ethyl ester.

5) Formula; 2-(4-(
5-Trifluoromethyl-2-pyridyloxy)phenoxy]propio/acid-3-benzyloxypropyl ester.

6) General formula: (In the formula, Mit represents a hydrogen atom or an alkali metal atom.) A compound represented by the general formula: (In the formula, R1 and R1 each represent a hydrogen atom or a lower alkyl group.

X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a nitro group, ηI and n each represent 1 or 2, and Yl represents a halogen atom. ) wherein R', R'', X, m and n are the same as above.

) A method for producing #-substituted phenoxyzolopionic acid ester.

7) General formula: (In formula 1, Yl represents a hydroxyl group or a halogen atom.) and the contained compounds represented by.

General formula: (In the formula, R1 and RI B each represent a hydrogen atom or a lower alkyl group.

X represents a hydrogen atom, a halog/atom, a lower alkyl group, a lower alkoxy group, or a nitro group; A method for producing a substituted phenoxypropionate ester represented by the general formula:

8) General formula: (In the formula, R1 and R3 each represent a hydrogen atom or a lower alkyl group.

Xd represents a hydroxyl atom, a halogen atom, a lower alkyl group, a lower alkoxy group' or a nitro group, and indium and n represent 1 or 2, respectively) A seal characterized by containing stone as an active ingredient.
4 of Kuren's "Ile".牟++ F, 1”・Ariya 1
b[shisoft 1. It is suspended as follows.

+11 19j In the 39th line of the detailed text, 8th line, ``Ohishiba,'' is added after ``Mehishiba.''

Claims (1)

[Claims] l) General formula (wherein R1 and R1a each represent a hydrogen atom or a lower alkyl group, , and m and 龟respectively represent 1 or 2, respectively. 2) Formula: 2-[4-(
5-Trifluoromethyl-2-pyridyloxy)phenoxy]gropionic acid-2-benzyloxyethyl ester. 3.) Formula: 2-[reef-(
5-Trifluoromethyl-2-pyridyloxy)phenoxy]glot-2-(2-fluoropenzyloxy)ethyl ester. 4) Take: 2-[<-(
5-Trifluoromethyl-2-pyridyloxy)phenoxy]gropion $-2-(4-chlorobenzyloxy)ethyl ester. 5) Formula: 2-(4-(
S-)lipromethyl-2-pyridyloxy)phenoxy]globionic acid-3-penzyloxyglobil ester. 6) General formula: In formula C, M represents an alkali metal atom in a hydrogen atom box. ) and the general formula: In formula 1, R' and Rlh each represent a hydrogen atom or a lower alkyl group, and xB represents a hydrogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group or a nitro group. Show. Washing and nu, respectively, on one side! and Yl represents a halogen atom. ) and the compound represented by ? To make it react? Patented general formula: (wherein R1, R1, X, m and nFi are the same as above,
) A method for producing a substituted phenoxyglogionate ester represented by (In the formula, Y8 represents a hydroxyl group or )・Rogen I Toyo. General formula: In formula 1, 81 and 82 are each a hydrogen atom or a lower alkyl group? Show. XF'i all represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a nitro group, and the door and n represent 1 or 2, respectively. ) General formula: (where h', R'', X% m and nra are the same as above,
) A method for producing a cyclopionic acid ester represented by: 8) General formula: (In the formula, 81 and R3 each represent a hydrogen atom or a lower alkyl group. Containing substituted phenoxyglopionic acid esters represented by (151 and 2) as an active ingredient? Characteristic herbicide.