JPS5988459A - Herbicidal benzoic acid derivative - 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 the following σ) 7-carbon acid derivatives represented by the general formula I: [wherein B1 represents hydrogen or halodane, R2 represents halogen, nitro or cyanide, R3 represents hydrogen or methyl; 1 (4 represents 1-argyl having 1 to 6 carbon atoms; and C 11511 1-alkyl having 1 to 6 carbon atoms or 1-6 carbon atoms; 1- represents an alkoxy containing a carbon atom
Kajirutake R4 and R5 are the carbon atoms to which they are bonded and r:i
ni/, ``And, it has 5 to 7 carbon atoms to form a cycloalkyl buried flame, and m and υ・n both represent 1, 1, 11, or m.
One of and n represents O, and the other represents 1 fire, and X represents 11ii2 or 1i. L'il6 is absent, Yi mainly represents a lower alkylene containing at least 2 carbon atoms, and Fl3G, water #, or 1 to 6 carbon atoms l7i-
11.

The compounds of the formula I have algicidal properties and are therefore suitable as oleaginous substances in 4'Iy, fungicides or leather control compositions. Therefore, the present invention also provides a small number of compounds of formula I <<
Distribution containing one type of oily substance.

Pest control compositions, methods for producing these compounds, and these compounds or compositions 5, 1 (H) Used for controlling leather pests, especially 13=l-g.

In formula I, the term l-haloquine-1 includes fluorine, halogen, bromine or iodine, with chlorine being preferred. Alkynoles containing 11 to 6 carbon atoms Jb. r
lI-1. chain-like 1,1
It also means a branched alkyl radical. This also applies to alkyls containing 1 to 6 carbon atoms containing 1 to 6 carbon atoms. Terro lower-no "rukylene group is a portrait 1) It is not a scale but also a branched sword■ノ, and A
;》T1 can be used and contains 2 or 6 carbon atoms.
It is preferable.

When there is a carbon atom in the molecule, formula 1
The compound is produced in the 9′0-14-t form. Because of the element-one-carbon-two-gil bond, the R4
and also occurs in the case of compounds of formula 1 in which R5 represents a different meaning. Apart from this, in some cases atrogenic isomerism is also present. Therefore, Formula 1 includes all racemic and functional isomeric forms of the present invention.

Separately, J (1 is halogen, ・1 digit does not represent chlorine; J12 is halogen or nitro, ir:
N represents nitro, preferably one; , 1 (preferably 2 represents 7 methyl, t B4 is 1 to 6 charcoal,
Alkyl having an atom, 'I'l' has methyl
o and preferred; 1-15 and 1-6 carbon atoms 7 and 1-
Preferably, "alkyl" or "alkoxy" having 1 to 6 carbon atoms represents "alkyl having 1 to 6 carbon atoms, in particular alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms; It is preferable to represent ethylene; and it is preferable to represent ethylene.

Preferably, one of m and n represents 1, and 1. “
[The other one represents 0 '&.

When X represents -11R6-, '1-, R6 represents a water group and 1- is preferred.

Preferred compounds of formula I include the following compounds: 1-impropylideneaminooxycarbonyl-5-(0
-Chlor-p-trifluoromethyl-2
-2l-lobenzoate, 1-(1,2-dimethylpropylideneaminooxycarbonyl)-ethyl 5-(
o-chloro-p-trifluoromethyl-phenoxy)-
nitrobenzoate, 2-inderobiridine aminookine-ether 5-(o-
Chroll-p-)! J fluoromethyl-phenoxy)-2
-Nitro-benzoate, oyohi 2-(1-methylpropylideneaminooxy)-ethyl 5-(0-chloro-
p-trifluoromethyl-phenoxy)-2-nitrobenzoate.

According to the invention, the process for preparing compounds of formula I includes the following process: General formula [in the formula R3
, R4, R5, m, n and Y have the meanings given above,
and Q is reacted with a compound of the leaving group (e.g. chlorine, bromine, iodine, mesyloxy or tosyloxy) or hydroxydanase]; or and Hall represents a halogen, in particular chlorine j) an acid halide of the general formula (wherein R4, R5 and Y have no meaning as defined above, and n' represents O or 1) an alcohol of the general formula or react with an oxime; or (cl general formula, where Bl , R2 and R6 have the meanings given above)
with a compound of the general formula (wherein R3, R4, R5, Y and n' have the meanings given above and Q' represents a leaving group j); or (dl general A phenol of the formula (wherein R1 has the above-mentioned meaning) or an alkali metal salt thereof is represented by the general formula (wherein R3, R4, R5, mXHXX and Y have the above-mentioned meanings, and R2' is nitro or cyano) ,
and Ha12 represents a halogen, preferably fluorine); or re+ a compound of the general formula, in which R1, R3, R4, R5, mXn, X and Y have the meanings given above, is nitrated. .

In process (al), this esterification can be carried out according to methods known per se and leads to compounds of formula (I) in which the symbol X (if present) represents oxygen (.Thus, for example, an acid of formula Salts contain leaving groups, especially chlorine, bromine,
Formula representing iodine, mesyloxy or tosyloxy (
1), preferably in an inert diluent, at about -20
Temperature from 0c to 15a'c, preferably from 0c to 1ooo
React at a temperature of °C. Salts of acids of formula ■ include in particular alkali metal salts (e.g. sodium, potassium or lithium salts), alkaline earth metal salts (e.g. magnesium, calcium or barium salts), salts with organic bases (e.g. mono-, di- or tri-alkyl salts), ammonium salts or pyridinium salts), or ammonium salts, with alkali metal salts being preferred. Diluents that can be used are aliphatic and cyclic ethers (e.g. diethyl ether,
Inert organic solvents such as tetrahydrofuran, aromatic (eg benzene and toluene), dimethylformamide, dimethylsulfoxide and hexamethylphosphoric triamide are preferred.

When using the free acid of formula (1), it is convenient to carry out the reaction in the presence of a base or an acid acceptor.

All conventional inorganic and organic acid binders can be used for this purpose, including alkali metal and alkaline earth metal carbonates and bicarbonates, 6-ary amines (such as triethylamine, dimethylaniline and pyridine) and 1,8 −
Ciazubicyclo[5.4.O]undec-7-ene is preferred.

When a reactive derivative of the acid of formula II is used, Q in formula II represents hydroxy. The reactive derivative of the acid of formula (1) is preferably a halide, especially a chloride, but can also be, for example, an imidazolide or an anhydride. The reaction is carried out with aliphatic or cyclic ethers (e.g. diethyl ether, tetrahydrofuran or dioxane), aliphatic or aromatic hydrocarbons (e.g. n-hexane, benzene or toluene), or halogenated, especially chlorinated hydrocarbons (e.g. methylene chloride or chloroform). ) at a temperature of about -206C to iso'C, preferably from 0C to 50C.

When using acid halides of acids of formula (1), the reaction is conveniently carried out in the presence of an acid binder. Inorganic bases (eg alkali metal and alkaline earth metal carbonates and bicarbonates) and organic bases (eg 6-ary amines, especially triethylamine or 15-lysine) have been found suitable. The acid halide is preferably an acid chloride.

Method (bl is m represents 1, and X is -NR'-
This leads to a compound of formula I represented by Y. This process is conveniently carried out under the conditions described above for the reaction of a reactive derivative of an acid of formula (1) with a compound of formula (2) in which Q represents hydroxy.

Method (cl also represents m is 1 and X is -NR6
A compound of the formula (■) representing - is derived. In formula (2), Q' particularly represents chlorine, bromine, iodine, mesyloxy or tosyloxy, with bromine being preferred.

The reaction with Cl is conveniently carried out in the presence of an inert solvent, especially an organic solvent, and in the presence of an acid binder. Particularly suitable organic solvents are aliphatic or cyclic ethers, such as diethyl ether, tetrahydrofuran and dioxane), aromatics (e.g. penze/and toluene), and dimethylformamide, with toluene and dimethylformamide being particularly preferred solvents. Preferred acid binders are lower tertiary alkyl amines (e.g. triethylamine) and dimethylformamide. -Siazu-Bicyclo [4.3
・0] Non-5-ene, 1,8-cyazu-bicyclo[4
・5@0) Undec-7-ene and 1,4-siazu-
Pinkro [2.2.2] octane. Instead of such acid binders, sodium hydride can also be used as a base.

In carrying out this process, the reaction temperature is generally between -20°C.
~12 [J°C, preferably 20°C to 80°C.

Method (dl leads to compounds of formula l in which R2 represents nitro or cyano. This method involves the azeotroping of water using IJium or potassium hydroxide. Conversion is preferably carried out by removal and then reaction of this salt with a halide of formula (1).

This last reaction step is performed using a bipolar approach solvent (e.g. dimethylformamide or dimethyl sulfoxide).
Or conveniently in pyridine at a temperature of 500C to 150C, preferably 70C to 110C. This process is preferably used for the preparation of nitro- or cyano-substituted compounds of formula I in which m and n are 1 or m represents O and n represents 1.

The nitration is conveniently carried out using nitric acid or a mixture or solution containing nitric acid.

Examples of such mixtures or solutions include mixtures of nitric acid and sulfuric acid, solutions of nitric acid in glacial acetic acid, and solutions of concentrated nitric acid in chlorinated hydrocarbons (eg methylene chloride). The nitration is preferably carried out at a temperature between U.degree. C. and room temperature. This process is preferably used to prepare compounds of formula I in which m and n both represent 17 or m represents O and n represents 1.

Isolation and purification of the compounds of formula I thus prepared can be carried out according to methods known per se.

If an asymmetric carbon atom is present in a molecule of formula I and no systematic synthesis is performed to isolate the pure optical isomer, the product will usually be produced as a racemate.

Isomers can be separated according to methods known per se.

Of course, if desired, optical isomers can also be produced by synthesis from corresponding optically active raw materials.

The starting materials of formulas 1 to 1 and the salts and reactive derivatives of acids of formula 2 and the alkali metal salts of phenols of formula 2 are known or can be prepared by methods known per se.

The compound of formula ■ has herbicidal properties and is effective against weeds in cereal crops, especially barley, oats, wheat, maize, rice and soybean farms, especially Gallium aparine.
), Amaranth retroflexus (Amaran
thus retroflexuθ), 177 species of warts (
Ipomea day pp,), Abutilontheophrasti (A
butilon theophrasti), Sesbania exalta (5esbania exalta)
ta), Thienopodium album (Ohenopo
Xantium album), Xantium pensylvanicum
), Dauaus carota
, Fagopyrum esculentum
esculentum), synapsis alpensis (
Elinapsis arvensis ) and Daturastramonium
) is suitable for controlling. The compounds according to the invention include wheat,
Particularly suitable for weed control in corn, rice and soybean farms.

In general, in order to obtain the desired herbicidal effect, 0.05 to 2 kg of active substance of formula 1 per hectare, preferably 0.
．． A concentration of 2-1 kg is sufficient.

The compounds of formula I are not only pre-emergent herbicides but also post-emergent herbicides and are preferably used as post-emergent herbicides.

The weed control composition according to the present invention has the formula ■ as defined above.
and a formulation aid. Preferably, the composition contains at least one of the following formulation aids: a solid carrier material; a solvent or dispersion medium;
Surface-active agents (wetting and emulsifying agents); dispersing agents (without surface-active action); and stabilizing agents. By using these and other auxiliaries, compounds of formula I,
In other words, herbicidal active substances are fine powders, powders, granules, solutions,
It can be converted into conventional formulations such as emulsions, suspensions, emulsifiable concentrates, and yeasts.

Compounds of formula 1 are generally water-insoluble and can be formulated according to methods customary for water-insoluble compounds using suitable formulation aids. The compositions are prepared in a manner known per se, for example by mixing the respective active substance with a solid carrier substance in a suitable solvent or dispersion medium, if necessary as a wetting or emulsifying agent, a surfactant and/or a dispersing agent. This can be carried out, for example, by diluting a previously prepared emulsifiable concentrate with a solvent or dispersion medium.

As solid support materials, the following materials can basically be considered: chalk, dolomite, limestone, alumina and silicic acids and their salts (for example diatomaceous earth, kaolin, bentonite, talc, attapulgite, and montmorillonite). natural mineral substances such as highly dispersed silicates, synthetic mineral substances such as aluminum oxides and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and nitrates; In this case, such carrier substances can be present, for example, as a powder or as granules.

As solvents or dispersion media, the following substances can basically be considered: aromatics such as benzene, toluene, xylene and alkylnaphthalenes; chlorinated aromatics and chlorinated fats such as chlorobenzene, chlorethylene and methylene chloride. aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. petroleum distillates); alcohols and their ethers and esters such as butanol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and Strong polar solvents or dispersion media such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide (such solvents are
(preferably has a flash point of 0°C and a boiling point of at least 50°C), and water. in a solvent or dispersion medium,
Also possible are so-called liquefied gaseous spreading agents or carrier substances, which are products that are gaseous at room temperature and normal pressure. Examples of such products are essentially aerosol propellants such as halogenated hydrocarbons (eg dichlorodifluoromethane). When the weed control composition according to the invention is provided in the form of a vacuum pack, it is advantageous to use a solvent in addition to the propellant.

Surfactants (wetting and emulsifying agents) are condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide; fatty acid esters or ethers of sugars or polyhydric alcohols; products obtained from sugars or polyhydric alcohols by condensation with ethylene oxide a block 1 combination of ethylene oxide and propylene oxide; or a nonionic compound such as an alkyldimethylamine oxide.

Surfactants also include soaps; fatty sulfate esters (e.g. sodium dodecyl sulfate, sodium octadecyl sulfate and sodium cetyl sulfate); alkyl sulfonates, aryl sulfonates and alkylbenzene sulfonates (e.g. calcium dodecylbenzene sulfonate) and butylnaphthalene sulfonate. Anionic compounds such as aromatic sulfonates; and even complex fatty sulfonates (eg, the combination product of oleic acid and N-methyltaurine and the sodium sulfonate of dioctyl succinate) may also be used.

Furthermore, the surfactant can be a cationic compound such as alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride and ethoxylated quaternary ammonium chloride.

As dispersants (without associated surface-active effect), the following compounds can in principle be considered: lignin, sodium and ammonium salts of geninsulfonic acid, sodium salts of maleic anhydride-diisobutylene copolymer. , sodium and ammonium salts of sulfonated polycondensation products of naphthalene and formamide, and sulfite alkaline solutions.

Dispersants which are particularly suitable as thickeners or antisettling agents include, for example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, holvinyl alcohol, alginates, caseinates and blood albumin.

Examples of suitable stabilizers include acid binders (e.g. epichlorohydrin, phenylglycidyl ether and soybean epoxide); antioxidants (e.g. gallic acid esters and butyl hydroxy); UV absorbers (e.g. substituted benzophenones, diphenyl acrylonitrile); acid esters and cinnamate esters); and deactivators (e.g. salts of ethylenediaminotetraacetic acid and polyglycols).

The weed control composition according to the invention, in addition to the compound of formula I,
Synergists and other active substances (e.g. pesticides,
Acaricides, fungicides, other herbicides, fungicides, plant growth regulators, and fertilizers)'ff: Can be contained. Such combination compositions are suitable for enhancing the activity or for broadening the spectrum of activity.

Weed control compositions according to the invention generally contain 0.005 to 95% by weight, preferably 5 to 80% by weight of one or more compounds of formula (1) as active substance(s).
Contained in an amount of 1%. These can be provided in a form suitable for storage and transport, for example. The active ingredient concentration in such formulations (e.g. emulsifiable concentrates) is in the upper range of the usual ranges, preferably 10-80], especially 25
~75M quantity. These formulations can be subsequently diluted (e.g. using the same or a different inert substance) to a practical active substance concentration, i.e. preferably about 0.0
0.05 to 2 mfl, especially about 0.05 to 1 Ni'. However, the active substance concentration may be lower or higher.

As mentioned above, the weed control composition according to the invention can be produced by methods known per se.

When preparing finely divided powders, the active substance, i.e. a small amount (at least one compound of formula I) can be mixed with a solid carrier material.
For example - by grinding together), or the solid support material can be impregnated with a solution or suspension of the active substance and then the solvent or dispersion medium removed by evaporation, heating or suction under reduced pressure. By adding surfactants or dispersants to such finely divided powders, they can be made easily wettable with water and thus converted into aqueous suspensions suitable, for example, as spray compositions. can.

The compounds of formula I can also be mixed with a surfactant and a solid carrier material to form a wettable powder dispersible in water, or mixed with a solid pre-milled carrier material to form a granule. Products can also be formed.

If desired, the compound of formula I can also be dissolved in a water-immiscible solvent, for example a high-boiling hydrocarbon, in which case it may be advantageous to contain a dissolved emulsifier, so that the solution self-emulsifies when added to water. Become sexual. Alternatively,
It is also possible to mix the active substance with an emulsifier and then dilute the mixture with water to the desired concentration. Furthermore, it is also possible to dissolve the active substance in a solvent and then mix the solution with an emulsifier. Such mixtures can also be diluted with water to the desired concentration. In this way emulsifiable concentrates or ready-to-use emulsions are obtained.

The use of the weed control composition according to the invention can be carried out according to conventional application methods such as watering, spraying, scattering, injection or scattering. The method according to the invention for controlling weeds comprises treating the area to be protected from weeds and/or the weeds with a compound according to the invention or with a weed control composition according to the invention.

The following section describes the invention.

■ Preparation example of active substance of formula I 1 3.1 g of 5-(o-chloro-p-trifluoromethyl-phenoxy)-2-nitro-benzoic acid was added to 5 Qm of toluene.
Dissolve in l. To this solution, 1.8-cyazu-bicyclo[5.4.0]undec-7-nin 1.53,! i'
and 2.11 g of acetone 0-(2-bromozolopionyl)oxime are then added.

The mixture is then heated at reflux temperature for 18 hours.

Let the mixture cool to room temperature and add 1 ooml diethyl ether.
The organic phase is washed with 2N hydrochloric acid and water, dried over anhydrous sodium sulfate and then concentrated. The residue is purified by chromatography on silica del using n-hexane/diethyl ether (42I).

1-isopropylideneamineoxycarbonyl-ethyl 5-(0-chloro-p-to!7fluoromethyl-phenoxy)-2-nitro-benzoate is obtained; n
20=1.5387° In a similar manner, 5-(o-chloro-1)-)lifluoromethyl-phenoxy)-2-nitrobenzoic acid and 2-methyl-3-
From butanone 0-(2-bromozolopionyl)oxime to 1-(1,2-dimethylzolobylideneamineoxycarbonyl)-ethyl 5-(0-chloro-p-)! J Fluoromethyl-phenoxy)-2-nitro-benzoate is obtained; n” = L5122;
3-7" tanone 0-(2-7" lomozolobionyl)oxime to 1-(1,2,2-)dimethylzolobylideneamineoxycarbonyl)-ethyl 5-(0〒chloro-p-)lifluoromethyl -phenoxy)-2-nitrobenzoate is obtained: nBo = 1.4960.
5-(0-chloro-X)-)lifluoromethyl-phenoxy)-2-nitrobenzoic acid and 3-hexanone 0-
From (2-bromopropionyl)oxime, 1-(1-
Ethyl butylidene aminooxycarbonyl)-ethyl
5-(0-chloro-p-trifluoromethyl-phenoxy)-2-nitrobenzoate is obtained: n also '=1,
5032: and 5-(0-1t=+ru p-)! J Fluoromethyl-phenoxy)-2-nitro-benzoic acid and ethyl acetate-)0-(2-bromopropionyl)oxime, 1
-(1-ethoxyethylideneaminooxycarbonyl)
-Ethyl 5-(0-chloro-p-trifluoromethyl-phenoxy)-2=nitro-benzoate is obtained: mp 107-108<0>C.

Example 2 5-(0-10 ru p-)! 2.7 g of Jfluoromethyl-phenoxy)-2-nitro-benzamide and 0.361 g of sodium hydride (50% in oil) are placed in 5 Ornl of dimethylformamide and the mixture is stirred for 1 hour. Acetone 0-(
2-bromozolopionyl) oxime 1.56,! i'
solution is then added dropwise at 25°C.

The mixture is stirred at 25°C for 2 hours. 20ON diethyl ether is added to the mixture, the organic phase is washed neutral with water, dried over anhydrous sodium sulfate and then concentrated.

5-(0-chloro-p-trifluoromethyl-phenoxy)-2-nitro-N-(1-isozolobylideneaminooxycarbonylethyl)-benzamide is obtained.

Mass spectrum m/Z: 56 (100%), 10
0 (23%), 207 (25%), 344 (52%),
34 (S (18%), 441 (43%) and 443 (
15ch).

Example 6 5-(O-chloro-p in thionyl chloride 41.3, F
-11fluoromethyl-phenoxy)-2-nitro-benzoic acid30. The solution of OII is heated at reflux temperature for 2.5 hours. After distilling off the excess thionyl chloride and drying under high vacuum, the 5-(0-chloro-p-)lifluoromethyl-phenoxy)-2-nitro- -benzoyl chloride 31.8F is obtained.

Dissolve 6 g of the above benzoyl chloride in 40 ml of methylene chloride, and mix the solution with 1 Q ml of methylene chloride and 1 ml of pyridine.
．． Add dropwise to a water-cooled solution of 2 g of 2-isopropylideneaminooxy-ethanol in 4 g. .

The mixture is left to react for 2 hours at room temperature. For working up, the solution is concentrated under reduced pressure, the residue is taken up in diethyl ether, the ether solution is washed with water, dried over anhydrous sodium 51te and evaporated under reduced pressure. The oily residue is finally passed through silica gel and then crystallized from n-hexane. 2-isopropylideneamineoxy-ethyl'5-(o-chloro-p-trifluoromethyl-phenoxy)-2-nitrobenzoate is obtained; melting point 53-54<0>C.

In a similar manner, 5-(0-chloro-p-)IJfluoromethyl-phenoxy)-2-nitro-benzoyl chloride and 2-
(1-methylpropylideneaminooxy)-ethanol to 2-(1-methylpropylideneaminooxy)-
Ethyl 5-(0-chloro-1-)lifluoromethyl-phenoxy)-2-nitro-benzoate is obtained: lH-NMR (aDa13): 8.2-6.9 (
m, 6B > 4.7~4.2 (m, 4)1
), 2.4-2.0 (m, 2H), 1.8 (
s, 3H) and 1.3-0.9 (t, 3H);
From 5-(o-chloro-p-tolynefluoromethyl-phenoxy)-2-ditho-hundred-penzoyl chloride and 1-(isopropylideneaminooxy)-2-propatol, 2-isozolobylideneamineoxy -1-Methyl-ethyl 5-(o-chloro-p-1lifluoromethyl-
Obtain phenoxy)-2-nitrobenzoate; lHNMR (ODO persimmon>: 8.04 (d, 1) 1
), 7.82 (d.

IH), 7.61 ((1, IH), 7.24(di
H), 7.14 ((1, I H), 7.0j(q,
IH), 5.45 (m, IH), 4.11
(d, 2B), 1.85 (s, 3a), 1.81
(s, 3H) and L37C(1,3)i); from 5-(0-chloro-p-)lifluoromethyl-phenoxy)-2-nitrobenzoyl chloride and 2-cyclohexylideneaminooxy-ethanol , 2-cyclohexylideneaminooxy-ethyl 5-(Q-chloro-p-fluoromethyl-phenoxy)-2-nitro-benzoate; melting point 92-94 °C; 5-(o-chloro-p −)! J Fluoromethyl-phenoxy)-2-chloro-benzoyl chloride and 2-inzolobylideneaminooxy-ethanol to 2-inzolobylideneaminooxy-ethyl 5-(0-chloro-p-trifluoromethyl-phenoxy) Obtain ~2-chlorobenzoate; nj0=1.5347° Microanalysis: Calculated value: 0%50.69 N%3.58 N%6.
11c+7+%15.75 Actual value=C%50.72 Hchi3.58 N%3.
from 11c7%15.61 and 5-(o-chloro-1)-)+7fluoromethyl-phenoxy)-2-iodo-benzoylquaride and 2-isozolobylideneamineoxy-ethanol,
2-isozolobylideneamineoxyethyl 5-(0-
Chlor-p-1!7 fluoromethyl-phenoxy)-2
-Iodo-benzoate is obtained; melting point 60-62°C.

Example 4 3.95 pyridine in 50 WLt of methylene chloride,! i
' solution of 2-isopropylideneaminooxy-ethanol in 1001 nl of methylene chloride, 5.85,! i'
and 2-promopropionylpromi)' 10.75
, F (7) is added dropwise to the solution cooled to −40° C. with stirring. The mixture is stirred for 1 hour at room temperature and then evaporated to dryness under reduced pressure. The residue is then dissolved in n-hexane, the salt remaining behind (pyridine hydrobromide) is filtered off with suction and the filtrate is evaporated to dryness. The 2-impropylideneaminooxy-ethyl 2-bromopropionate required for the last step of the manufacturing process (below) is obtained; n
%'= 1.4710゜5-(o in 60ml of toluene
-chloro-p-1 (lifluoromethyl-phenoxy)-2
-Nitro-benzoic acid 7.22. ! i', 2-isozolobylideneaminooxy-ethyl 2-bromozolopione-
)5.04I and 1,8-diazarbisict-(5.
4.O]Undec-7-nin 3.04.9 solution was kept at room temperature for 60 hours with stirring. The mixture is then evaporated to dryness under reduced pressure, the residue is dissolved in n-hexane, the solution is washed with water, dried over anhydrous sodium sulfate and then evaporated to dryness under reduced pressure. The viscous residue is purified by chromatography on silica gel with n-hexane/diethyl ether (5:1).

1-((2-isopropylideneaminooxy-ethoxy)carbonylcyethyl 5-(o-chloro-p-trifluoromethyl-phenoxy)-2-nitrobenzoate is obtained; LH-NMR (ODO!3): 8.C16 (d, IH)
, 7.82 (d, 1H), 7.62 (q, IH), 7.
32 (d, IH), 7.26' (d, IH), 7.08
(q, IH), 5.40 (q, IH), 4.40 (m
, 2H), 4.21 (t, 2H), 1.85(
BI3H), 1.82(2,3H), and 160
(d, 3H).

In a similar manner, 5-(0-10 p-trifluoromethyl-phenoxy)-2-ditorobenzoic acid and 2-(1-methylzolobylideneaminooxy)-ethyl 2-bromozolobionate (2 -(2-(1-methylzolobylideneaminooxy)-ethoxy]carbonyl)-ethyl 5 -(○-chlorop-)lifluoromethylphenoquine)-2-nitro-benzoate is obtained; in-NM
R(aDcII3): 8.06 (d*IH)
, 7.81 (d, IH), 7.62 (ddllH), 7
．． 31 (d, IH), 7.25 (d.

1H), 7.04 (aa, 1H), 5.4 (
(11・1H), 4.48-4.32 (m, 2H), 4
．． 23-4.18 (m, 2H), 2.35-2. ．． 13
(m.

2H), 1.83 and 1.80 (each e, 3H), 1
．． 59 (d, 3H) and J: and 1.1 to 1.0 (tt
.

(6H).

■ Formulation Example 5 The ingredients listed below are mixed together to form an emulsifiable concentrate (
1, 2, 3, 4, 5 or 6): emulsifiable concentrate 1 active substance of formula 1 250. FN-methyl-2-biolidoy300,! i2 emulsifier Al
100. ! li' emulsifier B2
25 j9 Emulsifier 1 is ethylene oxide-propylene oxyto floc copolymer 60
part, calcium dodecylbenzenesulfone) and 20 parts of isobutanol/C1o-alkylbenzene mixture.

Emulsifier 2 is calcium dodecylbenzene sulfonate 7
0 parts and 30 parts of an insitanol/clo-alkylbenzene mixture.

Emulsifiable Concentrate 2 Active Substances 250.9 Zomethylformamide 300g Fatty Alcohols
(10)-Ethoxylate 75. F Calcium Dodecylbenzene Sulfonate 25. Active substances of formula I 500. ! i'Castor oil-
(30)-Ethoxylate 50g Calcium dodecylbenzenesulfonate 25. F Cyclohexanone Amount to bring the total volume to 1 oooy Emulsifiable concentrate 4 Active substance of formula I 750. F alkylbenzene-(8)-ethoxyle) 50. F
Ammonium alkylbenzene sulfonate 25
．． ! 7 xylene solvent mixture total volume 1000ml
Precious emulsifying concentrate 5 Active substance of formula I 250 g Castor oil-(20)-ethoxylate 50.9
Calcium dodecylbenzene sulfonate 251! i1
7 alkylbenzene solvent mixture 15
0g active substance of formula ■ 250I castor oil-(20)-ethoxylate 50g calcium dodecylbenzenesulfone) 25.
F cyclohexanone 20
0I The concentrate thus obtained (1,2,3°4.
5 or 6) spontaneously emulsifies in water and the resulting emulsion is ready for use. Suitable as Jfi liquid.

Example 6 The components listed below are mixed with each other and the mixture is finely ground to produce a spray powder (1 or 2): Spray powder 1 Active substance by weight 1 silicic acid hydrate
Pentasodium lauryl sulfate
Monosodium Liku7 Sulfonate
2 kaolin
42 Spray ring powder 2 □View.

Active substance of formula ■ 25-hydrated silicic acid
30 polycarboxylic acid sodium salt
4 kaolin
37 Powder thus obtained (1
or 2) can be wetted with water. The resulting suspension is concentrated as a ready-to-use spray liquid 7.

Example 7 The following ingredients are mixed together, the mixture is finely ground,
Produce a fine powder composition: % by weight Active substance of formula ■ decahydrated silicic acid
7.5 talc
82.5 Example 8 The following ingredients are mixed with each other to produce granules.

Weight % Active substance of formula ■ 5 Dipfubilene glycol 5 Pumice granules
90 Agent Akira AsamuraContinued from page 1Priority claim @July 8, 1983 ■Switzerland (CH)■
3768783-4 0 Inventor Paul Reincil Nirala, Greifense am Fuisterhorsli, Switzerland 50

Claims (1)

[Claims] (1) General formula [in the formula, H1 represents hydrogen or halogen; B2 represents halogen, nitro or cyano; B3 represents 1゛hydrogen or methyl as shown in Table 1]; n'&-J : represents 1-roargyl having 1 to 6 carbon atoms: and H5 & 1. represents alkyl having 1 to 6 carbon atoms or 1-roalkoxy having 1 to 6 carbon atoms;
Alternatively, R4 and R5 form a cycloalkyl ring having 5 to 7 carbon atoms when bonded with the carbon atom to which they are bonded; m and n both represent 1; -, or one of m and n represents U and the other represents 1; or represents oxygen or -NR6-; Y represents lower alkylene having at least 2 carbon atoms; and B6 represents hydrogen or alkyl having 1 to 6 carbon atoms; a compound represented by i-J; (21Hl represents chlorine, B2 represents nitro, [
73 and R4 each represent methyl; R5 is 1-
represents 1-alkyl having 3 carbon atoms or alkoxy having 1 to 0 carbon atoms, one of m and n represents 1 and the other represents O, and X represents oxygen , and Y is ethylene'+? Table 1 - Compounds of Claim 1. (3) 1-isopropylideneaminookinecarbo-ruethyl 5-(o-chloro-T)-)IJfluoromethyl-phenoxy)-2-nitropenzoate, Claim 1 (4) 1-(1,2-dimethylpropylideneaminooxycarbonyl)-ethyl 5-(o-chloro-p-)!
The compound of claim 1 which is J fluoromethyl-phenoxy)-2-nitro-benzoate. (5) 2-isopropylideneaminooxy-ethyl 5
-(0-chloro-p-trifluoromethyl-phenoki/
)-2-nitro-benzony 1. (612-(1--methylzolobylideneamino/oxy)
-Ethyl 5-(0-chloro-p-)lifluoromenalufenoquine)-2-nitrobenzoate. ('71 1-(1,2.2-)dimethylpropylideneaminooxycarbonyl)-ethyl 5-(o-chloro-p-trifluoromethyl-phenoquine)-2-nitrobenzoate, 1-(1-ethyl butylidene aminooxycarbonyl)
-ethyl 5(0-chloro-p-) IJ fluoromethyl-phenoxy)-2-nitrobenzoate, 1-(1-ethoxyethylideneaminooxycarbonyl)-ethyl 5-(o-chloro-p-)lifluoromethyl -phenoxy)-2-nitro-benzoate, 5-(0-chloro-p-trifluoromethyl-phenoxy)-2-nitro-N-(1-isopropylideneaminooxycarbonyl-ethyl)-benzamide, 2-isozolo Pylideneaminooxy-1-methyl-ethyl 5-(o-chloro-p-trifluoromethyl-phenoxy)-2-nitrobenzoate, 2-cyanohexylideneaminooxy-ethyl 5-(0
-Chlor-p-trifluoromethyl-2
-nitrobenzoate, 1-[:(2-isopropylideneaminooxy-ethquine)carbonylkuethyl
5-(0-chloro-p-trifluoromethyl-phenoxy)-2-nitrobenzoate, and 1=((2'-(1-methylpropylidene aminookine)-ethoxy]carbonyl)-ethyl 5-( 0-chloro-p-) IJ fluoromethyl-phenoxy)-
2-Nitrobenzoate, a compound according to claim 1 comprising: (8) 2-isopropylideneaminooxy-ethyl 5
+-(0-chloro-p-)lifluoromethyl-benzony)-2-chloro-benzony 1-, t+; and 2--
Isofu 0 Loviridin Aminoogin-Ejiri-(0-
A compound according to claim 1 selected from chloro-p-) IJ fluoromethyl-phenoxy)-2-iodo-benzoate. (9) As a weed control agent! Claim 1
Jy+σ) Compound, 1 (Il++ General formula [wherein R1 represents hydrogen or halogen, P2 represents halogen, nitro or cyanone, R3 represents hydrogen or methyl, R4 has 1 to 6 carbon atoms -J - represents alkyl having 1 to 6 carbon atoms, and R5 represents 1-3-alkyl having 1 to 6 carbon atoms or 1-3 alkoxy having 1 to 6 carbon atoms.
3- or R4 and 1-5 are bonded together with the carbon atom C to form a cycloargyl ring having 5 to 7 carbon atoms, InoJ:birl both represent 1, or one of m and n represents O and the other represents 1; lower alkylene 2 and R6 is hydrogen or alkyl having 1 to 6 carbon atoms; Composition. 01) 1-isopropylideneaminooxycarbonyl-
Ethyl 5-(0-chloro-p-trifluoromethyl-
phenoxy)-2-nitro-benzoate, or 1-
(1,”2-dimethylpropylideneaminooxycarbonyl)-ethyl 5-(0-chloro-p-trifluoromethyl-phenoxy)-2-nitro-benzoate, or 2-isozolobylideneamineoxy-ethyl 5-
(0-chloro-p-trifluoromethyl-phenoxy)
-2-nitro-benzoate, ff is 2-(1-methylpropy'lideneaminooxy)-ethyl 5-(o-
Chlor-p-trifluoromethyl-phenoxy)-2-
2) The weed control composition according to claim 10, characterized by the effectiveness of low benzoate and formulation auxiliaries. (12) General formula [wherein R1 represents hydrogen or halodane, R2 represents halogen, nitro or cyano1, R3 represents hydrogen or methyl, R4 represents alkyl having 1 to 6 carbon atoms,
and R5 is alkyl having 1 to 6 carbon atoms or 1 to
represents alkoxy having 6 carbon atoms, or R4 and R5 together with the carbon atoms to which they are attached form a cycloargyl ring having 5 to 7 carbon atoms, m and n Both represent 1", or one of m and n represents [ ] and the other represents 1, X represents oxygen or -NR6-, and Y represents at least 2 carbon atoms and R6 represents hydrogen or alkyl having 1 to 6 carbon atoms. ', the light, the taste: I
i-ru)'s acid 2r is the most active or its reactive 2N
, body general formula (in the formula R3, R4, Fl, 5, IIIXn
and Y is one of f'ffl He, <(1 taste Kei J'
L , and Q represent a leaving group or OL hydroxy and are reacted with a compound of the general formula (1)) (in which B, 1 , R2, and R6, the above-mentioned The acid halide fire general formula (wherein ++4, r+5 and Y have the above-mentioned appearance and taste)
, and n' is the alcohol of Omabuko (Table 49-'3-). , R2 O', BiR6 ke the above 10 attraction request 1-
benzamide of the general formula (wherein R3, R4, R5, Y: and n' are as defined in the above report,
It has a taste, and Q,′ has a taste. (representing an sIE group), or ((1) a phenol of the general formula (having the meaning of the preceding R''& J in the formula),
The alkali metal base is expressed by the general formula (in the formula R3, R
4, R5, m, n, X and Y have the meanings given above, R
2' is nitro or cyan, and (7 is Ha'+
2 represents halogen -) Let's react with the halide,
or (θ) A method comprising kenitration of a compound of the general formula (wherein R1, R3, R4, R5, mX nX X and Y have the above meanings). θ3) IV 1611↑Question 1li1) Places where the compound described in section 1611↑ or in an effective amount within the scope of the claims should be used to protect against weeds. Control method on the left. (141% ii'l・Compounds described in claims 1 and 4 or 'IN'l in claim 1U)
Use of one of the compositions listed in L+ (difficult to control).
f request! 1) Compounds of general formula I as described in box 1, top 1.