CS214701B2 - Herbicide means and method of making the active substance - Google Patents

Abstract

1. Phenoxycarboxylic acid carbonylalkyl esters of the formula see diagramm : EP0014900,P16,F1 in which R**1, R**2, R**3 and R**4 independently of one another represent hydrogen or alkyl, R**5 represents hydroxy, alkoxy which is optionally substituted by alkoxy, alkylthio, dialkylamino, cyano or halogen, alkenoxy, alkinoxy, aralkoxy or aryloxy, or the radical see diagramm : EP0014900,P16,F2 wherein R**6 represents hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 8 carbon atoms, benzyl or phenyl which is optionally substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, akylthio with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, fluorine, chlorine, bromine, trifluoromethyl and/or nitro, and R**7 represents alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 8 carbon atoms, benzyl or phenyl which is optionally substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, fluorine, chlorine, bromine, trifluoromethyl and/or nitro, or R**6 and R**7 together with the nitrogen atom to which they are bonded, represent pyrrolidinyl or morpholinyl, in each case optionally substituted by 1 or 2 methyl groups, or piperidinyl, indolyl, tetrahydroindolyl, perhydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrothiazolyl or perhydroazepinyl, in each case optionally substituted by 1 to 3 methyl or ethyl groups, and X represents hydrogen or chlorine.

Description

The invention relates to a herbicidal composition comprising as active ingredient novel carbonylalkyl esters of phenoxycarboxylic acids, and to processes for the preparation of these novel herbicidally active compounds.

It is already known that certain phenoxycarboxylic esters have herbicidal properties. Thus, for example, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-phenoxypropionic acid methyl ester and 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-phenoxypropionic acid ethyl ester can be used for controlling weeds (cf. U.S. Pat. No. 4,093,446 and DOS 2,311,638). The effect of these substances is good both in pre-emergence and post-emergence applications. The disadvantage of these substances, however, is that some difficult to control weeds and grass weeds are not always completely controlled by these substances. Moreover, their compatibility with certain crop plants, such as cereals, is not always entirely satisfactory.

We have now found novel phenoxycarboxylic acid carbonylalkyl esters of the general formula (I) in which:

R ^{1 *} , R 2, R ^{3 *} and R 4 are each independently hydrogen or methyl,

R ⁵ is hydroxy, C 1 -C 4 alkoxy or a group of the formula

where

R ⁶ is hydrogen, C 1 -C 4 alkyl, C 1 -C 8 alkenyl, benzyl or optionally C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio 4 carbon atoms, alkoxycarbonyl having 1 to carbon atoms in the alkoxy moiety, fluorine, chlorine, bromine, trifluoromethyl and / or nitro substituted phenyl, and

R ⁷ is C 1 -C 4 alkyl, C 3 -C 8 alkenyl, benzyl or optionally C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio carbon atoms, C 1 -C 4 alkoxycarbonyl, fluoro, chloro, bromo, trifluoromethyl and / or nitro substituted phenyl, or

R @ 6 and R @ 7 together with the nitrogen atom to which they are attached in each case represent an optionally 1 or 2 methyl substituted pyrrolidinyl or morpholinyl radical, in each case optionally 1-3 methyl or ethyl substituted piperidinyl, indolyl, tetrahydroindolyl, perhydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl:, perhydroquinolyl, perhydroisoquinolyl, perhydrothiazolyl or perhydroazepinyl radical and

X is hydrogen or chlorine, has strong herbicidal properties and can therefore be used as active ingredients of the herbicidal compositions.

Accordingly, the present invention provides a herbicidal composition. characterized in that it contains at least one phenoxycarboxylic acid carbonylalkyl ester of the formula I as active ingredient.

According to the invention, the carbonylalkyl esters of the phenoxycarboxylic acids of the general formula I are prepared by reacting the chlorides. of the phenoxycarboxylic acid of formula II '

Cl oc-co-ct ^c ° - / ^no * (II) in which

R 1, R ² and X are as defined above, with α-hydroxycarboxylic acid derivatives of the general formula III

R3

HO — C — CO — R5 (III),

R4 in which

^R3, R4 and R5 -Have meaning given above, optionally in the presence vázajícíhokyselinu agent and optionally in the presence of a diluent at temperatures between 0 ° ^C - and 5ΰ ° C.

The newly found phenoxycarboxylic acid carbonylalkyl esters of general formula I have potent herbicidal properties and can therefore be used as active ingredients of herbicidal compositions.

Surprisingly, the phenoxycarboxylic acids of the present invention exhibit substantially better herbicidal activity than 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-methyl ester of the present invention. α-phenoxypropionic acid and 5- (2-fluoro-4-fluoromethylphenoxy) -2-nitro-aliphenoxypropionic acid ethyl ester, i.e. compounds known in the art, which are chemically the closest active ingredients of the same type of action. It is particularly advantageous that the compounds according to the invention, in particular for pre-emergence application, are better suited to controlling hard-to-control weeds and grassy weeds, such as bedstraw (Galium) and china (Cyperus) than the known substances. In addition, the compounds according to the invention are, in post-emergence application, better tolerated by carbohydrates than the above-mentioned known compounds.

The phenoxycarboxylic acid carbonylalkyl esters which are used as active ingredients in the herbicidal composition according to the invention are generally defined by the formula I. In this formula, all the general symbols preferably have the meaning already defined above for these symbols by sub-formula I .,

When chloride is used as starting material

5- (2,6-dichloro-4-difluoromethylphenoxy) -2-nitro-phenoxypropionic acid and hydroxyacetic acid methyl ester, the process of the invention can be illustrated by the following reaction scheme:

cw

I ^ъ

O-CH-CO-Ct

Cl

+ HO-CH 2 CO-OCH 3

Cf ·

HCt

fW

O-CH-CO-o-CH 2 CO-OCH ₃

Cf ·

The phenoxycarboxylic acid chlorides required as starting materials in the process of the invention are generally defined by Formula II. · In this formula, R1, ^R2 and X preferably represent those radicals which have already been 'in context. with the description of the compounds of the formula I according to the invention are mentioned as preferred for these symbols.

Examples of phenoxycarboxylic acid chlorides of formula II include:

Target ^(T ^ of 5- (2-chloro-4-trifluoromethylphenyl ^ h ^ y ^] ^ - · phenoxy) -2-nitro-AF phenoxypropionic acid chloride of 5- (2,6-dichloro-4-phenoxy trifIuormethylf -2-nitro-α-phenoxypropionic acid.

Phenoxycarboxylic acid chlorides of formula. II are known or can be prepared by conventional methods (cf. U.S. Patent No. 4,093,446). The hitherto unknown phenoxycarboxylic acid chlorides can be synthesized by reacting the phenoxycarboxylic acids of formula IV

in which

R 1, R 2 and X are as defined above with chlorinating agents such as thionyl chloride, optionally using diluents such as benzene or ethylene chloride at temperatures between 10 ° C and 100 ° C. easily volatile components are removed by distillation at the end of the reaction.

The phenoxycarboxylic acids of formula IV are also known or can be prepared by conventional procedures [cf. U.S. Pat. file number

093,446]. Thus, compounds of formula IV are obtained by the addition of. to the phenoxycarboxylic acid esters of the formula

in which

R1, R2 and X are as defined above, and R represents an alkyl group, in particular a methyl group or an ethyl group, acting with aqueous hydroxides. alkaline. metals, preferably. sodium hydroxide or potassium hydroxide, optionally diluted with organic solvents such as methanol, ethanol or dioxane at temperatures between 20 ° and 100 ° C.

Examples of phenoxycarboxylic acids of formula V include:

5- (2-Chloro ^R-4-tri.f trifluoro-methylphenoxy) -2-nitro-fQnoxypropionovou acid and

5- (2,6-Dichloro-4-trifluoromethyl-phenoxy) -2-nitro-α-phenoxypropionic acid.

Also, the phenoxycarbonyl-esters of the first acid of formula V are known or can be prepared by conventional methods (cf. U.S. Pat. No. 4,093,446). Thus, compounds of formula V are obtained by reacting phenol derivatives of formula VI

X (VI) wherein

X is as defined above, optionally the sodium or potassium salts thereof, with the α-halo-carboxylic acid esters of formula VII

Ri

Hal — C — CO — OR [Vlij,

R ² . -. ...

in which

R1 and R2 are as defined above,

R is alkyl, especially methyl or, ethyl and

Hal represents chlorine or bromine, optionally in. the presence of an acid binding agent such as sodium methoxide or potassium carbonate and optionally using a polar diluent such as methanol, acetonitrile or sulfonate at temperatures between 20 and 100 ° C.

Examples of esters of the phenoxycarboxylic acid of formula V include:

5- (2-Chloro-4-trifluoromethyl-phenoxy) -2-nitro-α-phenoxy-propionic acid methyl ester and ethyl ester; and

5- (2,6-Dichloro-4-trifluoromethyl-phenoxy) -2-nitro-α-phenoxy-propionic acid.

Phenol derivatives of formula VI are known (cf. U.S. Patent 4,093,446). Examples of phenol derivatives of formula VI include:

5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrophenol a

5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitrophenol.

Also known are N-halocarboxylic acid esters of formula VII. Examples include:

α-chloropropionic acid methyl ester and ethyl ester as well as α-bromopropionic acid methyl ester and ethyl ester.

The .alpha.-hydroxycarboxylic acid derivatives which are required as further starting materials in the process of the invention are generally defined by formula III. In this formula, R 3, R 4 and R ⁵ preferably have those meanings which have already been mentioned as advantageous for these radicals in connection with the description of the compounds of the formula I according to the invention.

The .alpha.-hydroxycarboxylic acid derivatives of formula III are known or can be prepared by conventional methods (cf. DOS 2 200 4321.

Some of the yet unknown α-hydroxycarboxylic acid amides of formula IIIa

(lilac) in which

R 3, R ⁴ , R 6 and R ⁷ are as defined above, e.g.

R3 R5

I /

Hal-C-CO-N (viiii,

R4 \ R7 wherein

R3, R4, ^R and. R7 have ·. the above meaning. and ... · '- ·. ·:

Hal is chlorine or bromine, reacted in the first step with an excess of sodium acetate or potassium acetate, optionally in the presence of a catalyst such as tetrabutylammonium bromide and optionally using a diluent such as acetic acid or toluene at temperatures between 20 and 200 ° C and in the second step the acetoxycarboxylic acid amides of the formula IX are formed

R3 R ⁶

I /

CH 3 —CO — O — C — CO — N (IXi,

R4

in which

R 3, R 4, R e and R 7 are as defined above, deacylated by reaction with dilute aqueous-alcoholic sodium hydroxide at temperatures between 20 and 150 ° C.

Examples of α-hydroxycarboxylic acid derivatives of formula III include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, benzyl, phenyl, methylamide, ethylamide, n-propylamide, isopropylamide, n-butylamide, isobutylamide, dimethylamide, diethylamide, di-n-propylamide, di-isopropylamide, N-methyl-N-isopropylamide, N-methyl-N-isobutylamide, N-methyl-N-sec-butylamide, diallylamide, · anilide,

2-nitro-, 3-nitro- and 4-nitrophenylamide,

2-chloro-, 3-chloro- and 4-chlorophenylamide,

2,4-dichloro-, 2,5-dichloro-, 3,4-dichloro- and 3,5-dichlorophenyl amide,

2-methyl-, 3-methyl- and 4-methylphenylamide,

N-methylanilide, N-methyl-N- (2-methylphenyl Jamid),

N-methyl-N- [2-nitrophenyl]

N-methyl-N- (3-nitrophenyl.) - a

N-methyl-N- (4-nitrophenyl) amide,

N-methyl-N- (2-chlorophenyl)

N-methyl-N- (3-chlorophenyl) -a

N-methyl-N- (4-chlorophenyl) amide

N-methyl-N-4-nitro-G-methylphenyl Jamid,

N-ethylanilide,

N-ethyl-N- (2-nitrophenyl) -, N-ethyl-N- (3-nitrophenyl) -,

N-ethyl-N- (4-nitrophenyl) amide,

N-ethyl-N- (2-chlorophenyl)

N-ethyl-N- (3-chlorophenyl) -,

N-ethyl-N- (4-chlorophenyl) amide

N-ethyl-N- (3-nitro-6-methylphenyl) amide, N-propylarlidide,

N-Propyl 1-N- (2-nitrophenyl) -,

N-propyl-N- (3-nitrophenyl) -,

N-propyl-N- (4-nitrophenyl) amide,

N-propyl-N- (2-chlorophenyl) -,

N-propyl-N- (3-chlorophenyl) -a

N-propyl-N- (4-chlorophenyl) amide

N-propyl-N- (2-methylphenyl),

N-propyl-N- (3-methylphenyl) -,

N-propyl-N- (4-methylphenyl) amide,

N-propyl-N- (3-nitro-6-methylphenyl jamide),

N-butylanilide,

N-butyl-N- (2-nitrophenyl) -,

N-butyl-N-3-mirophenyl-a

N-butyl-N-. (4-mtrophenyl) amide,

N-butyl-N- (2-chlorophenyl)

N-butyl-1'-3-chlorophenyl-a

N-butyl-N- (4-chlorophenyl jamide),

N-butyl-N- (2-nitro-1) -,

N-butyl-N- (3-methylphenyl) -a

N-butyl-N- [4-nitrophenyl] amide,

N-butyl-N- (3-nitro-6-methylphenyl) amide, N-isobutylanilide,

N-isobutyl-N- (2-nitrophenyl) -,

N-isobutyl-N- (3-nitrophenyl) - a

N-isobutyl-N- (4-nitrophenyl) amide,

N-isobutyl-N- (2-chlorophenyl) -,

N-isobutyl-N- (3-chlorophenyl) and N-isobutyl-N- (4-chlorophenyl) amide,

N-isobutyl-N- (2-chlorobutyl) -,

N-isobutyl-N- (3-methylphenyl) -a

N-isobutyl-N- (4-methylphenyl jamide),

N-isobutyl-N- (3-nitro-6-methylphenyl Jamid, benzylamide, Dibenzylamide, N-methyl-N-butylamide, N-ethyl-N-benzylamide, ^N-propyl-N-i beiiz ylamide, N-butyl N-benzylamide, pyrrolidide, 2-methylpyrrolidide, morpholide, plperidide, 2-methylpiperidide,

4-methyiyipeгidid,

2.4- dtmethylpipertdid,

2.4.6-triethylpiperidide, 2-ethylpiperidide, ethylpiperidine,

2.4- dieteylyiyeridid,

2.4.6-triethylyl peroxide, 2-methyl-4-methylpiperidine, 2-ethyl-4-methyl-piperidine, 2-methyl-5-ethyl-piperidine, 2-ethyl-5-meteyl-glyceride, 2-methyl-6-ethylpiperidine, 1,2,3-tetrahydroindole, 2-methyl-11,2,3,4-tetragallydinoindolide, perhydroindolide, 2-methylyerhydreindolide, 2,2-dimethylperhydroindolide,

1.2.3.4- tΌtraeydrochl nO'ltd ·, · 2-methyl -l, second, 3,4-tetraeydrocemolid, yereydrochtnoIid _l 2-methylyerh.ydrochiinoltd,

4-methylpethydrecninolid,

1.2.3.4- tetrahydroisoquinolide and yereydrothisoquinolide of hydroxyacetic acid, α-hydroxydroyroyonic acid and α-hydroxyisobutyric acid,

The α-halocarboxylic acid amides of the formula VII are known or can be prepared analogously to known processes. They are obtained, for example, by reacting α-halocarboxylic acid halides such as chloroacetyl chloride with ammonia, optionally with primary or secondary amines, optionally in the presence of an acid binder, as. for example potassium hydroxide (cf. J, Agric, Food Chem, 4 (1S56), 5: 52-252).

Examples of halocarboxylic acid amides of formula VIII include:

methylamide, ethylamide, n-propylamide, tsoproyylamtd, n-butylamide, isobutylamide, dimethylamide, diethylamide, di-n-propylamide, dttsoyreyylamide, N-methyl-N-isopropyl-amide, N-methyl-N-isobutyl amide, N-methyl-amide sec, butylamide, diallylamtd,

14 7 (JI

anilide, i

2-nitro-, 3-nitro- and 4-nitrophenylamide, 2-chloro, 3-chloro- and 4-chlorophenylamide,

2,4-dichloro-, 2,5-dlchloro-, 3,4-dichloro- and

3,5-dichlorophenylamine,

2-methyl-, 3-methyl- and 4-methylphenylamide, N-methylanilide,

N-methyl-N- [2-methylphenyl] amide, N-methyl-N- (2-nitro-phenyl) -,

N-methyl N- (3-nitrophenyl) - and N-methyl-N- (4-nitrophenyl) amide, N-methyl-N- (2-chlorophenyl) N-methyl-N- (3-chlorophenyl) - N-methyl-N- (4-chlorophenyl) amide, N-methyl-N- (3-nitro-6-methylphenyl) amide,

N-ethylanilide,

N-ethyl-N- (2-methylphenyl)

N-ethyl-N- (3-nitrophenyl) - and N-ethyl-N- (4-nitrophenyl) amide, N-ethyl-N- (2-chlorophenyl) N-ethyl-N- (3-chlorophenyl) enyl) - and N-ethyl-N- (4-chlorophenyl) amide, N-ethyl-N- (3-nitro-6-methylphenyl) amide, N-propylanilide,

N-propyl-N- (2-nitrophenyl) -, N-propyl-N- (3-nitrophenyl) - and N-propyl-N- (4-nitrophenyl) amide, N-propyl-N- (2- chlorophenyl) -, N-propyl-N- (3-chlorophenyl) - and N-propyl-N- (4-chlorophenyl) amide, N-propyl-N- (2-methylphenyl) -, N-propyl-N - (3-methylphenyl) - and N-propyl-N- (4-methylphenyl) amide, N-propyl-N- (3-nitro-G-methylphenyl) amide, N-butylanilide,

N-butyl-N- (2-nitrophenyl) -, N-butyl-N- (3-nitrophenyl) - and N-butyl-N- (4-nitrophenyl) amide, N-butyl-N - ( 2-chlorophenyl 1) N-butyl-N- (3-chlorophenyl) - and N-butyl-N- (4-chlorophenyl) amide, N-butyl-N- (2-methylphenyl) -, N-butyl-N - (3-methylphenyl) - and N-butyl-N- (4-methylphenyl) amide, N-butyl-N- (3-nitro-6-methylphenyl) amide, N-isobutylanilide,

N-isobutyl-N- (2-nitrophenyl) N-isobutyl-N- (3-nitrophenyl) - and N-isobutyl-N- (4-nitrophenyl) amide, N-isobutyl-N (2-chlorophenyl) -, N-isobutyl-N- (3-chlorophenyl) - and N-isobutyl-N- (4-chlorophenyl) amide, N-isobutyl-N- (2-methylphenyl) -, N-isobutyl-N- (3- methylphenyl) - and N-isobutyl-N- (4-methylphenyl) amide, N-isobutyl-N- (3-nitro-6-methyl ifenyl) amide, benzylamide, dibenzylamide,

N-methyl-N-benzylamide, N-ethyl-N-benzylamide, N-propyl-N-benzylamide, N-butyl-N-benzylamide, pyrrolidide,

2-methylpyrrole did, morpholide, piperidide,

2-methylpiperidide,

4-methylpiperidide,

2,4-dimethyipiperidide, <

2.4.6-trimethylpiperidide, L '

2-ethylpiperidide,, 4-ethylpiperidide,

2.4- diethylpiperidide,

2.4.6- triethylpiperidine,

2-methyl-4-ethylpiperidide,

2-ethyl-4-methylpiperidide, 2-methyl-5-ethylpiperidide, 2-ethyl-5-methylpiperidide, 2-methyl-6-ethylpiperidide, 1,2,3,4-tetrahydroindolide, 2-methyl 1-1,2,3,4-tetrahydroindolide, perhydroindolide, 2-methylperhydroindolide, 2,2-dimethylperhydromidolide,

1.2.3.4-tetrahydroquinolide, 2-methyl-1,2,3,4-tetrahydroquinoline, perhydroquinolide,

- methу 1 p e r hyd оo hi no 1 i d,

4-methylperhydroquinolide,

1.2.3.4-Tetrahydro-isoquinolide and perhydroisoquinolide of chloiroacetic acid, α-chloropropionic acid and α-chloroisobutyric acid.

The process according to the invention is preferably carried out using suitable solvents or diluents. As such, virtually all inert organic solvents are suitable.

These include, in particular, aliphatic and aromatic and / or chlorinated hydrocarbons, such as petrol, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, as well as aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, sulfolane and hexamethyltriophosphoric triamide.

All conventional acid binding agents can be used as acid binding agents. Of particular note are alkali metal carbonates and alkoxides such as sodium carbonate and potassium carbonate, sodium and potassium methoxide, sodium and potassium ethoxide, and aliphatic, aromatic or heterocyclic amines such as triethylamine, trimethylamine, dimethylanilide, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a wide range. In general, the reaction is carried out at temperatures between -20 and 100 ° C, preferably between 0 and 100 ° C

5 ° C.

The process according to the invention is generally carried out at atmospheric pressure.

In order to carry out the process according to the invention, generally 1 to 2 moles of phenoxycarboxylic acid chloride of the formula II are used

1.5 mol, preferably 1 to 1.2 mol of the α-hydroxycarboxylic acid derivative of the formula (III) is 1 to 5 mol of the acid-binding agent. The reaction is generally carried out in a suitable diluent and the reaction mixture is stirred for several hours at the desired temperature. Then, an organic solvent such as toluene is added and the organic phase is worked up in the usual manner by washing, drying and distilling off the solvent.

The novel compounds are obtained in part in the form of oils, which in part cannot be distilled without decomposition, but by so-called "distillation", i.e. by prolonged heating under reduced pressure to slightly elevated temperatures, they are freed of the last volatiles and can be purified in this way. Refractive index is used to characterize them.

If the products are formed in solid form, they can be purified by recrystallization. The melting point is used to characterize them.

The active compounds according to the invention influence the growth of plants and can therefore be used as defoliants, desiccants, weed control agents, germination inhibiting agents and in particular as weed control agents. In the broadest sense, weeds are understood to mean all plants that grow where they are undesirable. Whether the compounds of the invention act as total or selective herbicides depends essentially on the amount applied.

The active compounds according to the invention can be used, for example, in the following plants:

Double-uterine weeds of genera:

mustard (Si.napis), watercress (Adhesives), bedstraw (Galium), chickweed (Stellaria), chamomile (Ma-tricaria), chamomile (Anthemis), chamois (Galinsoga), goosefoot (Chenopodium), nettle (Urtica), ragwort (Senecio ·), Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Thistle (Carduus), Milk (Sonchus), Eggplant (Solanum), Mustard (Rorippa), Rotala, Lindernia, Deadnettle (Lamium), Speedwell (Veronica), Abutilon (Abutilon), Emex, Durman (Datura), Violet (Viola) , cannabis (Galeopsis), poppy (Papaver), cornflower (Ccntaurea),

Dicotyledonous plants of genera:

cotton (Go-ssypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (rhasedlus), peas (Pisum), potato (Socanum), flax (linum), mulberry (Ipomoea), vetch ( Vicia), tobacco (Nicotiana), tomato (Lycopersioon), peanut (Arachis), kale (Brassica), lettuce (Lactuca ·), cucumber (Cucumis), gourd

Monocotyledonous weeds of genera:

is-harvest (Echinochloa), shear (Setaria), millet (Panicum), tree frog (Digitaria), timothy (Phleum), meadow-grass (Poa), fescue (Eestuca), eleusine (Eleusine), Brachiaria,

Lolium, Bromus,.

oats (Avena), flathead (Cyperus), sorghum (Sorghum), wheatgrass (Agropyron), wreckage (Cynodon),

Monocharia, Fi-mbristylis, arrowhead (Sagiitaria),

Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea

Dactyloctenium, Agrostis, Alope .curus, Apera.

Monocotyledonous plants of the genera: rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Aven-a), rye (Secale), sorghum (Sorghum), millet (Panicum), sugarcane ( Saccharurn), pineapple (Asparagus), garlic (Allium).

However, the use of the active compounds according to the invention is by no means restricted to these genera, but applies equally to other plants.

The compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial and railway surfaces and on roads and squares, possibly with trees. The compounds of the invention may also be used to control weeds in long-term crops such as forest crops, ornamental trees, fruit trees, vineyards, citrus, butternut, banana, coffee, tea, rubber, coconut, cocoa, also in crops - berries and hop gardens, selective control of weeds in annual crops.

The active compounds according to the invention show a very good action against weeds and grass weeds. In particular, they can be used to remove hard-to-control herbal weeds and grassy weeds such as Galium and Cyperus. Combinations with other herbicides, especially N-benzthiazod-2-yl-N, N‘-dimethylurea, are possible to further improve the activity spectrum.

The active substances may be converted into. customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, natural and synthetic substances impregnated with active substances and fine capsules in polymeric substances.

These compositions are prepared in a manner known per se, for example by mixing the active ingredients with fillers, i.e. liquid solvents and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a carrier, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffinic hydrocarbons such as petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone ^1, -methylethylketon, -or · methyl cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulphoxide, as well as water.

Suitable solid carriers are: for example, natural stone meal, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoimite, and synthetic stone meal, such as highly disperse silica, alumina and silicates; Suitable solid carriers for the granulates are: for example, crushed and fractionated natural stone materials, such as limestone, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and -organic flours, as well as granules - organic material such as sawdust, coconut shells, corn sticks and tobacco stems; suitable emulsifiers and / or foaming agents are, for example: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example lignin from sulphite waste liquors and methylcellulose.

The compositions of the invention may comprise adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Furthermore, the compositions may contain colorants such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and -organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes, as well as trace elements, such as iron salts, of manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates contain - generally between 0.1 and 95% by weight, preferably - between -0.5 and 90% by weight, of the active ingredient.

The active compounds according to the invention can be used in weed control alone or in the form of compositions and also in admixture with known herbicides, and these can be added to the finished compositions or immediately before application. Mixing is also possible with other known active ingredients, such as fungicides, insecticides, acaricides, nematocides, bird ozone control agents, growth agents, plant nutrients and soil conditioners.

The active compounds can be applied as such, in the form of concentrates or in the form of application preparations obtained from these concentrates by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in the usual manner, for example by watering, spraying, dusting or sprinkling.

The active compounds according to the invention can be used both before and after emergence of the plants. The application is preferably carried out before emergence of the plants, i.e. pre-emergence. The substances according to the invention can also be incorporated into the soil before sowing.

The application rate of the active compounds can vary within wide limits. This amount depends - essentially on the type of effect desired. In general, the application rate is between 0.05 and 10 kg of active ingredient per ha, preferably between 0.1 and -5 kg / ha.

The herbicidal activity of the compounds according to the invention is illustrated by the following examples. ⁱⁿ

In these examples, the following substances are used as reference substances:

CH ₃ ct-O-CH-COOC 2 S (A)

(B)

Example A

Preemergence test>

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkyl aryl polyglycoil ether

To make a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent, the said amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the same plant are sown in normal soil and, after 24 hours, watered with the active agent. The amount of water per unit area is expediently kept constant. The concentration of active ingredient in the composition is of no importance, only the amount of active ingredient used per unit area is critical. After 3 weeks, the degree of plant damage was evaluated and expressed as% damage compared to the development of untreated control plants. It means:

% = no effect (as untreated control)

100% = total destruction

In this test, for example, the compound of the invention as described in Example 14 shows a significantly better activity against cyperus than the known comparator A.

The test results are shown in Table A below:

TABLE A

Pre-emergence test

Amount used kg / ha

Cyperus

Active substance number ·

A (known substance) 2.5 14 2.5 12 2.5 1 2.5 15 Dec 2.5 4 2.5 5 2.5 6 2.5 7 2.5 8 2.5 9 2.5 10 2.5 17 2.5 18 2.5 11 2.5 21 2.5 22nd 2.5

100 ALIGN!

Example В

Preemergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the said amount of emulsifier is added, and the concentrate is diluted to the desired concentration with water.

The seeds of the test plants are sown in normal soil and, after 24 hours, are covered with the active ingredient. The amount of water per unit area is expediently kept constant. The concentration of active ingredient in the composition is of no importance, only the amount of active ingredient used per unit area is critical. After three weeks, the degree of plant damage in% was evaluated.

damage compared to the development of untreated control plants. It means:

% = no effect (as untreated control)

100% = complete destruction of plants.

In this test, the following compounds of the invention show a significantly better effect against Galium than the known comparator B.

The test results are shown in Table B below:

TABLE В

Pre-emergence test

Active substance number Amount used kg / ha Galium В (known substance) 1,25 20 May 13 1,25 100 ALIGN! 2 1,25 90 12 2.5 100 ALIGN! 1 2.5 100 ALIGN! 15 Dec 2.5 100 ALIGN! 4 2.5 70 5 2.5 50 6 2.5 60 7 2.5 50 8 2.5 80 9 2.5 90 10 2.5 10 17 2.5 80 18 2.5 90 11 2.5 90 21 2.5 80 22nd 2.5 100 ’

Example C

Postemergence test

Solvent ·: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

К produce a suitable active agent ¹ were mixed 1 part by weight of active compound with the stated amount of solvent added the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Test plants which are 5 to 15 cm high are sprayed with the active agent in such a way that the required amount of active substance per unit area is always applied. The concentration of the spray suspension is chosen so that the required amount of active substance is always applied in 2000 liters / ha. After 3 weeks, the degree of damage to the plants was evaluated as% damage compared to the development of untreated control plants. It means:

0% no effect (as untreated control)

100% complete destruction of plants.

In this test, the compounds according to the invention show a significantly better wheat tolerance than the known comparative substance A. with an equally good action against chickweed (Stellaria) and chamomile (Matricaria).

The test results are shown in Table C below:

TABLE C

Post-emergence test Active substance Quantity used S.tellaria Matricaria Wheat number active substance kg / ha

A (known) 0.5 100 ALIGN! 100 ALIGN! 60 ' 14 0.5 100 ALIGN! 100 ALIGN! 0 12 0.5 100 ALIGN! 100 ALIGN! 20 ' 1 0.5 100 ALIGN! 100 ALIGN! 60 15 Dec 0.5 100 ALIGN! 100 ALIGN! 80 4 0.5 - Í100 60 5 0.5 90 100 ALIGN! 70 6 0.5 90 100 ALIGN! 40 7 0.5 80 100 ALIGN! 60 8 0.5 90 100 ALIGN! 60 9 0.5 80 100 ALIGN! 60 10 0.5 - 20 May 20 May 17 0.5 100 · • 10 » 40 18 0.5 100 ALIGN! 100 ALIGN! 40 11 0.5 1.00 100 ALIGN! 80 21 0.5 100 ALIGN! 100 ALIGN! 40 22nd 0.5 100 ALIGN! 100 ALIGN! 60 ·

Example 1 d

Defoliation and drying of leaves in cotton

Solvent: 30 parts by weight of dimethylformamide

Emulsifier; 1 part by weight of polyoxyethylene sorbitan monoururate

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Cotton plants are grown in the greenhouse until the fifth assimilation leaf unfolds. At this stage, the plants are sprayed with the active ingredients until moistened. After one week, the degree of fallen leaves and drying is evaluated in comparison with the control plants. In doing so, it means:

no drying of leaves, no falling 'of leaves. + weak. Drying of leaves, slight dropping of leaves + + strong drying of leaves, strong dropping of leaves + + + very strong drying of leaves, very strong dropping of leaves.

In this test, the compounds described in Examples 5, 12 and 14 show very good activity, as shown in Table D below:

TABLE D

Defoliation and drying of leaves in cotton

Active substance number Active substance concentration in ppm Effect - (control) - 0 5 500 + - + - + 250 + - + '+ 12) 5 + 12 500 + + + 14 500 + + +

Example E

Suppression of cotton growth

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Cotton plants are grown in the greenhouse until the fifth-assimilation leaf unfolds. At this stage, the plants are sprayed with the active ingredients until moistened. After 3 weeks, the plant growth is measured and growth inhibition is calculated as a percentage of the control plant growth. 100% growth inhibition means no growth and 0% growth corresponds to the growth of control plants.

In this test, the compound described in Example 12 shows very potent growth retardant activity.

The test result is shown in Table E below:

TABLE E

Cotton growth suppression:

Active substance number

Active substance concentration in ppm

Deceleration of growth in% - (control)

500

100 ALIGN!

Examples illustrating a method of producing an active Example 1 component:

A solution of 12.5 g (27 mmol) of 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-α-phenoxypropionic acid chloride in 30 ml of toluene was added dropwise to a solution of 5 g (30 mmol) of N- of hydroxyacetic acid methylanilide and 10 ml of pyridine in 70 ml of toluene, cooled to 0-5 ° C. The reaction mixture is stirred overnight at room temperature, then diluted with 300 ml of toluene, washed neutral, dried, filtered and concentrated. 13 g (81% of theory) of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy-propionic acid (N-methyl-N-phenylcarbamoylmethyl)-ester are obtained as a yellowish oil having a refractive index n _D ²⁴ = 1.5607.

The compounds of the formula I shown in Table 1 were prepared in an analogous manner to that of Example 1:

Table 1

Qi-U Qe

’Ίΐηίο t>

LO CM LO CM O CO 'CM WHAT rd R FROM CM vd rH cM what 00 9 uo LO L0_ uo 1П C ° rd E | R t— < R R x II II II II II II + "· f Tb Tb 10 Those T < CN CN CN CN CN CN 0 O 0 0 0 0 ň ň and β q and

it it ДЕЕ £ .it it it к ω o ω O 0 ω

5CSS! Sa ssa ж

ОО 05

CH 3 H CH 3 -OC 2 H 5 n _D 21 = 1.5221

CH3-H -ОС4Н9-П n _D ²⁴ = 1.5006 жж

Vdо vd CN

R rd

Example X R 1 R 3 R 3 <Melting point (° C)

No. R ⁵ refractive index ь - O CTI CO CM CQ ΙΓ ^ ΙΩ ^ xjl

H H

Q Q Д Д

AND

o o

it ssg Ж д д to д о it SSĚ к ® ac Д д к X it Я ж д о

it it it iirc £ £ it К it Д To do it хдд ООО о о О о ООО К Д Д д Д К Д Д Д Д

Д o o 5 3 o

^r_ ^ Ш o oul

Phenoxycarboxylic acid chlorides which are used as starting materials can be prepared, for example, as follows:

Example II —1

9.7 g (82 mmol) of thionyl chloride are added dropwise at room temperature to a solution of 30 g (68 mmol) of 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-af enoxypropionic acid and 0.5 ml of dimethylformamide. in 100 ml 1,2-dichloroethane. The mixture was heated at reflux for 4 hours. Activated carbon is then added to the mixture, the mixture is filtered and the filtrate is concentrated. After digesting the oily residue with 100 ml of ligroin, 26.2 g (84% of theory) of 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-α-phenoxypropionic acid chloride are obtained in the form of yellow crystals, m.p. 92 ° C.

The phenoxycarboxylic acids required as starting materials for the above-mentioned substances are prepared as follows:

Example I V - 1

135 g (0.3 mol) of methyl 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-n-phenoxypropionic acid methyl ester and 3.0 ml of concentrated sodium hydroxide are stirred in 400 ml of acetonitrile and 150 ml of water. hours at 20 ° C. The solution is concentrated, the residue is taken up in 500 ml of water and acidified with 50 ml of concentrated hydrochloric acid. 93 g (71%) of 5- ^{(2,6-dichlorobenzoyl!} R-4-trifluoromethylphenoxy) -2-f ni.tro-phenoxypropionic acid ethyl ester as light yellow crystals, m.p. 146 ° C (recrystallized from mixture of toluene and cyclohexane).

Phenoxycarboxylic acid esters which are required as precursors can be prepared as follows:

Example V - 1

CWj

Cl O'CHCO'0 ^CH 5

Cl g (0.24 mol) of α-bromopropionic acid methyl ester was added dropwise to a mixture of 73.6 g (0.2 mol) of 5- (6-dichloro-6-trifluoromethylphenoxy) -2-nitro-phenol, 32 g of potassium carbonate and 200 ml of acetonitrile and heated to 50 ^o C. the reaction mixture was heated for 5 hours under reflux, then poured into 1 liter of water and extracted with 1 liter toluene. The toluene phase is washed with 300 ml of 1 N aqueous sodium hydroxide solution and then with 500 ml of water. After distilling off the solvent in vacuo, 74 g (81% of theory) of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-%-phenoxy-propionic acid methyl ester are obtained in the form of an oil which crystallizes when methanol is added. mp 78 ° C.

Claims (2)

SUBJECT OF THE INVENTION A herbicidal composition, characterized in that it contains at least one phenoxycarboxylic acid carbomylalkyl ester of the formula I as active ingredient. X in which R ^1, R ^2, R ³ and R ⁴ are independently hydrogen or methyl, R ⁵ is hydroxy, C 1 -C 4 alkoxy or a group of the formula R ^G / where R ⁶ is hydrogen, alkyl of 1-4 carbon atoms, alkenyl C 3 -C 8 -alkyl, benzyl or optionally C 1 -C 8 -alkyl (C 4 -C 4), (C 1 -C 4) alkoxy, (C 1 -C 4) alkylthio, (C 1 -C 4) alkoxycarbonyl, fluorine, chlorine, bromine, trifluoromethyl and / or nitro substituted phenyl, and R ⁷ is C 1 -C 4 alkyl, C 3 -C 8 alkenyl, benzyl or optionally C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio carbon atoms, C 1 -C 4 alkoxycarbonyl, fluoro, chloro, bromo, trifluoromethyl and / or nitro substituted phenyl, or R ⁶ and R ⁷ together with the nitrogen atom to which they are attached represent in each case 1 or 2 methyl-substituted pynrolidinyl or morpholinyl residues, further optionally 1 to 3 methyl or ethyl-substituted piperidinyl, indolyl, tetrahydroindolyl, perhydroindolyl, a tetrahydroquinolyl, tetrahydroisoquinolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrothiazolyl or perhydroazepinyl radical, and X is hydrogen or chlorine. 2. A process for the preparation of an active ingredient according to claim 1, which comprises reacting the phenoxycarboxylic acid chlorides of the formula II in which: R ¹ , R ² and X are as defined above, with the N-hydroxycarboxylic acid derivatives of the general formula III R ³ AND HO — C — CO — R ⁵ (III), R ⁴ in which R ^3, R ⁴ and R ⁵ have the meaning given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent at temperatures between O and 50 ° C.