NO814332L - propionic - Google Patents

Description

The present invention relates to propionic acid esters with the general formula

where R 1 means chlorine, bromine, iodine or trifluoromethyl,

R 2 hydrogen, chlorine, bromine or iodine i i I R"^ hydrogen or C^_^-alkyl, i

. 'R' is hydrogen; C^_^-alkyl; or phenyl, optionally substituted with halogen, C, .-alkyl and/or nitro,<

since R and R together with the carbon atom to which they are attached can also form a C,-_g-cycloalkane ring, which can optionally be substituted with 1-3 C^_^-alkyl groups,

m, n and p are the numbers 0 or 1 and

■ R"<*>means one of the following groups (a) - (f):

■<!>wherein in the above formulas with the group (a) - (f)

R 6<;> is hydrogen; C 1-6 alkyl; C^_^-haloalkyl; or<1>Ifenyl, optionally substituted with halogen, C-^_^-alkyl and/or

.nitro,

7

:R| is C 1-6 alkyl; or phenyl, optionally substituted with halo-I, C, -alkyl and/or nitro,

1 8 9

i Ri and R stand for hydrogen or together mean an eri bond,

in

.trimethylene, tetramethylene, 2-butenylene or a toconden-

I '<Rsje>^ rt bbteynr zenCr^_ingg-a,lkyl and R"''"'' trifluoromethyl, C^_g-Alkoxy, IC^_g-Alkoxy-C^_^-alkyl, C2_^-alkanoyl, C2_^-Alkoxycarbonyl-j nyl or C2_-y-Alkoxycarbonyl-C^_^-alkyl, or R"^ and R^ , form together with the carbon atom they are attached to a cyclopene-jtan ring, optionally substituted with 1-3 C, .-alkyl and/or 1

110 11

1C 1-6 alkoxy, wherein if R , R and the carbon atom form: an optionally substituted cyclopentane ring, R is chlorine, bromo<:> or trifluoromethyl,'

12 13 IR means hydrogen or C 1-6 alkyl and R C 1-6 alkyl; or 'phenyl, optionally substituted with halogen, C 1 -alkyl and/or ' 12 13 .14 nitro, or R and R formed together with the carbon atom they are l i linked ■ to a C,- 7-cycloalkane ring, and;il.' 14 15 |R and R mean C1-6-alkyl or phenyl, and I wherein when R^ 'is a group (a) , (b) or (c) jm means the number 1, n the number 0 and p the number 0 or 1; when R<5> is in a ■ group (d), m, n and p mean the number 0; when R<5>is a group (e), m means 0 and n and p means 1; and when R<5>is a group (f) m and p mean the number 0 or 1 and n the number 1. ' 'i ; i • The compound of formula I has herbicidal properties and is therefore suitable as (active substances for) weed control agent(s). Thus, the compound also includes weed control agents i which contains at least one compound of formula I as an active ingredient, a method for the production of these compounds in as well as the use of such compounds or funds for be- ! In 'control of weeds. ' ■!■ in !

1' In the above-mentioned formula I, the term "halogen" includes fluorine, ! chlorine,. bromine and iodine. Under "C 1 -alkyl" or "C 1-6 alkyl"

are meant both straight-chain and branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. tart.

> butyl, n-pentyl, isoamyl, neo-pentyl and n-hexyl. This also applies to residues containing C^_^-alkyl groups or <:>C^_g-alkyl groups, such as C^_^<-> or C^_g-Alkoxy, C2_7~Alkoxy-;carbonyl, Haloalkyl, C2_7-Alkoxycarbonyl-C^_^-

alkyl, C₁₋₋ alkoxy-C₁₋₄ alkyl and C₂₋₆ alkanoyl. When 2 or more substituents are present in a substituted phenyl residue,

the substituents may be the same or different. This also applies to the alkyl-substituted C 1-6 cycloalkane ring and the cyclopentane ring substituted with alkyl and/or alkoxy.

; The term "haloalkyl" includes one or more halogen atoms substituted with alkyl.

Since at least one asymmetric carbon atom is present in the molecule, the compound of formula I can appear in an optically active form,

■ through the presence of the nitrogen-carbon double bond, in connection with formula I, in which R 5 means a group (d)

or a group (e), occurs for those compounds in which R<1>11 * 12 13

,• and R , respectively. R and R have different meanings, in addition geometric isomerism. Such geometric isomers are denoted as

,syn and anti forms. Independently of this, an atropis.omeria also occurs in certain^ in cases. Formula I must therefore include the crude cemates as well as all these possible isomeric forms. 1;

I 1 '1 ■' Independently of each other, R preferably means iodine or trifluoromethyl and R 2 preferably hydrogen or chlorine.

: R 3 j in the sense of C 1-4 -alkyl' is preferably .methyl. ' j|>

R 1 preferably means C 1-6 alkyl.

R 1 preferably means optionally substituted phenyl.

in

:R: and R both preferably mean hydrogen.

Particularly preferred are the D forms of the compound of formula i: The preferred compounds of formula I are: D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid—succinimidomethyl ester, ethyl-N- Qd-2- [p-a , a , a-trifluoro-p-tolyloxy)phenoxy] ^-propionoxy)-acetimidate, n-butyl-N-(d-2-[p-(a,a, α-trifluoro-p-tolyloxy)phenoxy]-propionoxy)-acetimidate, D-2 - [p-a , a , α-trifluoro-p-tolyloxy)phenoxy ] ^-propionic acid- 2-:isopropylideneaminooxy-ethyl ester and D- 2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid di-ethoxyphosphinyl methyl ester.

The method according to the invention for the production of compounds of formula I is characterized by

a) reacts an acid with formula

12 where R and R have the meaning given above, or a reactive derivative thereof, with a compound of the ] formula

3 4 5

where R in R/ R / m/n 0<? P when the above meanings and X means a leaving group, or

b) reacts a phenol with the formula

12 ■■

where R and R have the meanings given above,

or an alkali metal salt thereof, having a compound of the formula

345

where R , R , R , m, n and p have the meanings given above and Y means a leaving group.

Method variant a) involves esterification. 1

i which can be carried out according to known methods, e.g. according to the j ' following variants a^), a^) and a^.) :

In method variant a^), the term "salt" means e.g.

an alkali metal salt, for example a sodium, potassium or lithium salt, an alkaline earth metal salt, e.g. magnesium, calcium or barium salt, a salt of an organic base, e.g. a mono-, di- or tri-alkylammonium salt, or a pyridinium salt, or ammonium salt. The term "leaving group" for X preferably stands for chlorine, bromine, mesyloxy or tosyloxy.

The esterification of the acid of formula II, preferably in the form of a salt, with the compound of formula II is preferably carried out in an inert solvent and at a temperature of approx. -20°C-100°C. A particularly preferred temperature range is between 0°C and 40°C. Solvents are preferably inert organic solvents. These preferably include ethers, e.g. diethyl ether and tetrahydrofuran, chlorinated hydrocarbons, e.g. dichloromethane and chloroform, and dimethylformamide.

: When using the free acid of formula II, the rearrangement is conveniently carried out in the presence of a base, or an acid acceptor. One can use all commonly applicable uor-'

organic or organic acid binding agents for this, to which preferably alkali metal and alkaline earth metal carbonates and bicarbonates, and tertiary amines, e.g. triethylamine, dimethylaniline and pyridine belong.

Reaction according to method variant a^) is preferably carried out in an inert solvent such as an ether, e.g. diethyl ether, a hydrocarbon, e.g. n-hexane or a chlorinated hydrocarbon, e.g. dichloromethane or chloroform, and at room temperature or higher temperature, e.g. up to the reflux temperature of the reaction mixture. A preferred temperature range is between 0°C and 40°C, especially between 10°C and 2.0°C.

When using an acid halide of the acid of formula II, the reaction is conveniently carried out in the presence of an acid binding agent. Inorganic bases, e.g. alkali metal and alkaline earth metal carbonates and bicarbonates, as well as organic bases, e.g. tertiary amine, especially triethylamine or pyridine. Acid halide is preferably acid chloride.

In method variant a^), the reaction is suitably carried out in an inert organic solvent, such as an ether,

e.g. tetrahydrofuran or a chlorinated hydrocarbon, e.g. dichloromethane or chloroform, and at temperatures between 0°C and 70°C. A preferred temperature range is between 10°C and 30°C. The conversion takes place appropriately in the presence of an acidic catalyst, or a condensing agent, such as e.g. sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, dicyclohexylcarbodiimide or carbonyl dimidazole.

Method variant a_.) is particularly suitable for those cases where the compound of formula III is an oxime, i.e. R becomes a group (d), m, n and p the number 0 and X a hydroxyl group. The acid of formula II is reacted with the oxime of formula III, preferably in the presence of dicyclohexylcarbodiimide as condensing agent. The acid is suitably dissolved in an organic solvent such as a chlorinated hydrocarbon, e.g. dichloromethane, chloroform, carbon tetrachloride or trichloroethane, an ether, e.g. diethyl ether, diisopropyl ether or dioxane, or an aromatic carbon, e.g. benzene, toluene or jxylene, and then the oxime is suspended in the solution. The dicyclohexylcarbodiimide is likewise dissolved in the same solvent and added to the reaction mixture. The reaction preferably takes place in a temperature range between 0°C and the boiling temperature of the reaction mixture, in particular between room temperature and 50°C. The reaction is normally finished after approx. 2 hours.

In method variant b) the term "departure group" means, for Y e.g. chlorine, bromine, iodine, mesyloxy or tosyloxy.

The reaction conveniently takes place in an organic inert solvent such as a hydrocarbon, e.g. benzene or toluene, an ether e.g. diethyl ether, dimethoxyethane or tetrahydrofuran, or hexamethylphosphoric acid triamide. The reaction temperature is not critical, and one preferably works at temperatures between 20°C and the reflux temperature of the reaction mixture, especially -10°C and 30°C.

In all cases, the product obtained can be isolated and purified by methods known per se.

If no targeted synthesis for the isolation of pure isomers is carried out, the product is normally formed as a mixture of three or more isomers. The isomers can be separated by methods known per se. If desired, they can also be produced through synthesis of corresponding optically active starting material.

The starting materials II, III, IV and V as well as reactive derivatives of the acid with formula II and alkali metal salts of phenols with formula IV are either known or can be prepared in a manner known per se. i The compound of formula I has herbicidal properties and is particularly suitable for the control of weeds, especially lopecurus jmyosurpides and millet species, such as e.g. echinochloa crus-galli, setaria faberii and hair-like millet. (panicum capillare) in cereals, especially barley, oat and wheat crops, as well as in rice, cotton, soya, sugar beet and • vegetable crops. In particular 1, the compounds according to the invention are suitable for the control of weeds in cotton, soya, sugar beet and vegetable crops. In general, a concentration of 0.16 kg of active ingredient of formula I/ha is sufficient, preferably 0.6-2 kg active ingredient with formula I/ha, to achieve the desired herbicidal effect.

The compounds of formula I are both preemergency and post-emergency herbicides.

The weed control agents according to the invention are characterized in that they contain an effective amount of at least one compound of formula I as stated above as well as formulation aids. The agent suitably contains at least one of the following formulation aids: solid carriers; solution, respectively dispersant; surfactants (wetting and emulsifying agents); dispersants (without surfactant effect); and stabilizers. Using such and other auxiliaries, the compound with formula I, i.e. the herbicidal active substances, can be transferred in the usual formulations such as dust, powder, granules, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like.

The compound of formula I is generally water-insoluble and can be formulated for water-insoluble compounds in the usual methods using corresponding formulation aids. Production of the agent can be carried out in a manner known per se, e.g. through mixing the individual active substances with solid carriers, by dissolving or suspending in suitable solutions or dispersing agents, possibly by using surfactants as wetting or emulsifying agents and/or from dispersing agents during dilution

IN

"of already prepared emulsifiable concentrates" with solvents or dispersants, etc.

As solid carriers mainly come into question: natural minerals such as chalk, dolomite, lime, clay and silicic acid and their salts (e.g. diatomaceous earth, kaolin, bentonite, talc, oatpulgite and montmorillonite); synthetic minerals such as highly dispersed silicic acid, aluminum oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resin; and fertilizers such as phosphates and nitrates, including such carriers e.g. can be available as powder or as granules.

Solvents and dispersants mainly include: aromatics such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffin, e.g. petroleum fractions; alcohols such as butanol and glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solutions-respectively dispersants such as dimethylformamide, N-methyl-pyrrolidone and dimethylsulfoxide, among which such solvents preferably have flash points of at least 30°C and boiling points of at least 50°C, and water. Among the solvents or the dispersants are also referred to as so-called condensers

te gaseous stretching agents or carriers, which are such products that are gaseous below room temperature and under normal pressure. Examples of such products are especially aerosol propellants, such as halogenated ones. hydrocarbons, e.g. dichlorodifluoromethane. If the weed control agent according to the invention is available in the form of a compressed gas pack, a solvent is suitably used in addition to the propellant gas.

The surfactants (wetting and emulsifying agents) can be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugar or polyhydric alcohols

'I

in

- products obtained from sugar or polyhydric alcohols

■ by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.

The surfactants can also be anionic compounds such as soaps; jfat sulfate testers, e.g. dodecyl sodium sulfate, octadecylna-yttrium sulfate and cetyl sodium sulfate; alkyl sulfonates, aryl sulfonates and fatty aromatic sulfonates such as alkylbenzene sulfonates, e.g. calcium dodecylbenzene sulfonate, and butyl naphtha-line sulfonate; and complex fatty sulfonate, e.g. amide condensation products of oleic acid and N-methyltaurine and sodium sulpho-<!>nates of dioctyl succinate.

1 ! ' . in i

! ' , ' I

The surfactants can finally be cationic compounds such as '

!alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium-

in

-i .chlorides, alkyltrimethylammonium chlorides and ethoxylated 'quaternary ammonium chlorides. IN

I<;>

■ As dispersants (without surfactant action) the following are mainly used: lignin, sodium and ammonium salts of ! jlignin sulfonic acids, sodium salts of maleic anhydride-diiso-butylene copolymers, sodium and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, and ; sulphite liquors.

i<1>

As dispersants which are particularly suitable as thickening agents. anti-sedimentation agents can be used, e.g. methyl cellulose, carboxyl ethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

!1

Examples of suitable stabilizers are acid-binding agents, cf. e.g. epichlorohydrin, phenylglycid ethers and soy epoxides; antioxidants e.g. gallic acid esters and butyl hydroxytoluene; UV absorbing agents, e.g. substituted benzophenones, diphenylacrylonitrile esters and cinnamic esters; and in

deactivators, e.g. salts of ethylenediaminotetraacetic acid !<1>|and polyglycols. In M i

In addition to the compound of formula I, the weed control agents according to the invention may contain synergists and other active substances, e.g. insecticides, acaricides, bactericides,. other herbicides, fungicides, plant growth regulators and fertilisers. Such combination agents are suitable for strengthening the activity, or to make the spectrum of action wider,

i The weed control agents according to the invention contain i

generally between 0.1 and 99 weight percent, preferably between 5 and 75 weight percent of a resp. several compounds with formula I as active ingredient(s). They can e.g. be in a form suitable for storage and transport. In such formulations, e.g. emulsifiable concentrates, the active ingredient concentration is normally in a higher range, preferably between 10 and 75 percent by weight, especially between 25 and 50 percent by weight. These formulations can then be diluted, e.g. with the same or different inert substances, to active substance concentrations that are suitable for practical use, i.e. preferably approx. 0.1 - 10 percent by weight, especially approx. 1-5 percent by weight. However, the active substance concentration can also be lower or higher.

Appropriately, the solid carriers in the weed control agents according to the invention are present in the concentration range between 1 and 99.9%, solution or the dispersing agent in the concentration range between 1 and 99.9%, the surfactants in the concentration range between 1 and 20%, the dispersing agents in the concentration range between 1 and 20%, the dispersing agents as thickeners or anti-sedimentation agents in the concentration range between 0.1 and 5% and the stabilizers in the concentration range between 0.1 and 5%, whereby these percentages refer to the agent's total weight.

As mentioned above, the production of the weed control agents according to the invention can be carried out in a manner known per se.

.For the production of powdered preparations, the active ingredient, i.e. at least one compound of formula I, can be mixed with a solid carrier, e.g. through grinding together; or one can impregnate the solid carrier with a solution or suspension of the active ingredient, and then remove the solution or the dispersant • through evaporation, heating or distillation under reduced pressure. Through the addition of surfactants or dispersants, it is possible to make such powdered agents easily wet-

only with water, so that they can be transferred in aqueous suspensions such as suitable as pesticides.

The compound of formula I can also be mixed with a surfactant and

a solid carrier to form a wettable powder that is dispersible in water, or it can be mixed with a solid pre-granulated carrier to form a granular product.

If desired, the compound of formula I can be dissolved in a solvent which. is not miscible with water such as e.g. a high-boiling hydrocarbon which preferably contains dissolved emulsifiers, so that the solution acts as a self-emulsifier when water is added. Otherwise, the active ingredient can be mixed with an emulsifier and the mixture then diluted with water to the desired concentration. In addition, the active substance can be dissolved in a solvent and then mixed with an emulsifier. Such a mixture can also be diluted with water to the desired concentration. In this way, emulsifiable concentrates or ready-to-use emulsions.

The use of weed control agent according to the invention

can occur by various application methods, such as spraying, spreading, with dust, pouring or scattering. The method according to the invention for combating weeds is characterized by treating the material to be protected against weeds and/or the weeds with a compound according to the invention or a weed control agent according to the invention.

Subsequent examples serve to illuminate the invention in more detail.

. EXAMPLES

I. Preparation of the active substance of formula I:

Example 1

To a 5°C cooled solution of <1>,72 g of D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 0.58 g of 2-isopropylideneaminooxy-ethanol in 40 ml of benzene is added dropwise to 0.47 g of pyridine. The reaction product is stirred for 1 hour at room temperature and then evaporated under reduced pressure to dryness. The residue is then dissolved in diethyl ether/n-hexane (1:1) and the solution is shaken out with water and dilute sodium bicarbonate solution, dried over a desiccant and finally evaporated to dryness. ,

The liquid residue is purified chromatographically on silica gel with acetone/n-hexane (1:7). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]propionic acid-2-isopropylideneaminooxyethyl ester is obtained;

n 20 1.5088; [a] 00 + 13.0° (c = 1.0% in CHC1 ).

D

In an analogous way, you get from

D-2-[pia/a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride

and N-hydroxymethyl-acetamide D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]propionic acid acetamide methyl ester; mp 103-105°C; [α]22 + 13.5° (c = 1.1% in CHCl3).

D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]propionic acid chloride and N-hydroxymethyl-chloroacetamide., - D-2-[p-(a ,a ,a-trifluoro-p -tolyloxy)phenoxy]propionic acid chloroacetamide methyl ester, m.p. 98-99°C; [a]<22>+.19.8° (c•= 0.7% in CHCl-j). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]propionic acid chloride and N-hydroxymethyl-trichloroacetamide - D-2[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy ]propionic acid trichloroacetamide methyl ester; n<20>1.532 0; [α] 20 + 14.8° (c = 0.6% in CHCl 3 ). D-2-[p-(a,a,a-trifluoro--p-tolyloxy)phenoxy]propionic acid chloride and 2-methanesulfonamido-ethanol, D-2-[p-(a,a,a-trifluoro-t >- ;tolyloxy)phenoxy]-propionic acid-2-methanesulfonamido-ethyl ester; ; m.p. 65-68°C; [α]22 + 24.6° (c = 1.1% in CHCl3). D-2-[p-(a ,a ,a-trifluoro-p-tolyloxy)phenoxy]propionic acid chloride and N-hydroxymethyl-succinimide, - D-2-[p-(a,a,a-trifluoro-p -tolyloxy)phenoxy]-propionic acid succinimidomethyl ester; m.p. 74-76°C; la^ 2+ 13.5° (c = 1.3% in CHCl 3 ). D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloro rid and N-hydroxymethyl-phthalimide, - D-2-[p-(α,α,α-trifluoro-, p-tolyloxy)phenoxyl-propionic acid phthalimidomethyl ester; m.p. 99-100°C; [α]22-4.9° (c = 0.7% in CHCl 3 ). D-2- [p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride aydiethoxyph osphinylmethanol,. - D-2-[p-(α,α,α-trifluoro-p-tolyl-20oxy)phenoxy]propionic acid diethoxy-phosphinyl methyl ester; n^ 1.5008; [a^2+ 27'5° (c = 1'0% 1 CHC13)..D-2 - [p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 2-diethoxyphosphinyl- ethanol, - D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propion sy r e-a-die toc sy f phosphinyl ethyl ester; n<20>1.5001; [a]<22>+ 20.7° (c = 0.7% in CKC13). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 1-diethoxyphosphinyl-ethanol, - D-2-[p-(a,a,a-trifluoro-p- tolyloxy.) phenoxy]-propionic acid 1-diethoxyphosphinyl ethyl ester; n<20>1.4963; [a]<22>+ 20.3° (c 1.3% in CHCl 3 ). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 1-diethoxyphosphinyl-n-butanol, - D-2-[p-(a,a,a-trifluoro- p-tolyloxy)phenoxy]-propionic acid 1-diethoxy-phosphinyl-n-butyl ester; n<20>1.4945; [α] 22 + 23.0° (c = 1.4% in CHCl 3 ). ' D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and α-diethoxyphosphinyl-benzyl alcohol, - D-2-[p-(α ,α ,α-trifluoro-p -tolyloxy)phenoxy]-propionic acid α-diethoxyphosphinyl benzyl ester; n<20>1.5228 ; [a] 22 +25 .5° . (c 0.7% in CHCl-j)'... D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid chloride and 2-isopropylideneaminooxy-ethanol, - D-2-[p-(p-iodophenoxy) )phenoxy]-. propionic acid 2-isopropylideneaminooxyethyl ester; [α]22+12.6° (c = 1.2% in CHCl 3 ). D D-2-[p-(p-iodophenoxy)phenoxy]propionic acid chloride and 2-methanesulfonamide ethanol, - D-2-[p-(p-iodophenoxy)-phenoxy]-propionic acid-2- methanesulfonamido-ethyl ester; m.p. 84-67°C; [α] 22 + 23.2° (c = 1.0% in CHCl 3 ). D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid chloride and N-hydroxymethyl-succinimide, - D-2-[p-(p-iodophenoxy)-phenoxy]-propionic acid succinimide methyl ester; [a]^2 + 11/5° (c = 0.8% in CHCl3). D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid chloride and diethoxy-phosphinyl methanol, - D-2-[p-(p-iodophenoxy)-phenoxy]-propionic acid diethoxy phosphinyl methyl ester; tet]<22>+ 23.7° (c = 1.7% in CHCl 3 ). D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid chloride and 2-diethoxyphosphinyl ethanol, - D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid 2-diethoxyphosphinyl ethyl ester; t0!^2 + 19.7° (c = 1.3% in CHCl3). D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid chloride and 2-isopropylideneaminooxy-ethanol, - D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid -2-isopropylideneaminooxy- ■ ethyl ester; ta]20 + 11.7° (c = 0.9% in CHCl3>.

D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid chloride and

in

2-methanesulfonamide-ethanol, D-2-[p-(o-chloro-p-iodophenoxy)

.phenoxy]-<p>ro<p>ionic acid 2-methanesulfonamide ethyl ester; [Q]D<20>

+ 19.4° (c = 0.8% in CHCl 3 ).

D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid chloride and diethoxyphenylmethanol, - D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid diethoxyphenyl methyl ester; t01]^ + 19.7°

(c = 1.6% in CHCl 3 ).

D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and dibutoxyphosphinyl methanol, - D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]- propionic acid dibutoxy phosphinyl methyl ester; n<20>1.4932 ; [a]<2>°+ 23.2° ( c = 0.60% in CHCiy . D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 1-diphenoxyphosphinyl -ethanol, - D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid-1-diphenoxyphosphinyl ethyl ester; n<20>1.5449; [a]<22>+ 7.3° (c 1.1% in CHCl 3 ).D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-<p>ropionic acid chloride and l-isopropylideneaminooxy-2- propanol, - D-2-[p<->

(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid 1-isopropylideneaminooxy-2-propyl ester; n<2>^ 1.5026; ta]22<+><1>9.0°

(c = 1.1% in CHCl 3 ).

D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and l-isopropylideneaminooxy-2-butanol, - D-2-[p-(a,a,a-trifluoro- p-tolyloxy)phenoxy]-propionic acid 1-isopropylideneaminooxy-2-butyl ester; nD 1.5023; [<*]D + 20.7°

(c = 1.0% in CHCl 3 ).

D-2-[p-(a-, a , a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 2-isopropylideneaminooxy-l-phenyl-ethanol, - D-2-[p-(a,a, α-trifluoro-p-tolyloxy)phenoxy]-propionic acid-2-isopro-2 2 o pylideneaminooxy-1-phenylethyl ester; ta]D + 19.8

(c = .0.9% in CHCl 3 ).

In D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 2-(2-butylideneamtnoxy)--ethanol, - D-2- [p- (a ,a , α-,trifluoro-p-tolyloxy)phenoxy]T-propionic acid 2-(2-butylideneaminooxy)ethyl ester; n<20>1.5072; [a]<22>+ 13.7° (c = 1.1% in CHCl 3 ).

D-2- tp-(a , a ,.a-trifluoro-p-tolyloxy)phenoxy]-propionic acid chloride and 2-(a-methylbenzylideneaminooxy)-ethanol, - D-2-[p<->

(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid 2-(α-methylbenzylideneaminooxy)-ethyl ester; n 2 0 1.5456;

ta]^+ 7.6° (c = 1.0% in CHCl 3 ).

D-2-[p-(a,a,a-trifluoro-p<->tolyloxy)phenoxy]-propionic acid chloride and 2-cyclohexyl idenaminooxy-ethanol, - "D-2- [p-(a,a,a- Trifluoro-p-tolyloxy)phenoxy]-propionic acid-2-cyclohexylideneaminooxyethyl ester; nQ1.5201; [<*]D + 11.7°

(c = 1.1% in CHCl 3 ).

Example 2

3.0 g of D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid was suspended in 10 ml of dichloromethane and at room temperature 1.3 g of acetoacetic acid ethyl ester oxime was added. The suspension was added dropwise over 10 min. a solution of 1.9 g of dicyclohexylcarbodiimide in 10 ml. dichloromethane. Then the reaction mixture temperature rose to 40°C. The mixture was stirred for 2 hours at room temperature and then filtered and evaporated to dryness under reduced pressure.

3-(D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionoxyimino}butyric acid ethyl ester was obtained; [a]<2>^+39.8°

(c = 1.0% in CHCl 3 ).

In an analogous way, you get from

D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and 1,1,1-trifluoroacetonoxime, - D-2-[p-(a,a,a-trifluoro- p-tolyloxy)phenoxy]-propionic acid 1,1,1-trifluoroacetonoxime ester; [α]<20>+ 39.5° (c 1.0% in CHCl 3 ). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and 1-hydroxyimino-diethyl ether, - ethy 1-N-fD-2-[p-(a ,a ,a -trifluoro-p-tolyloxy)phenoxy]-propionoxy)-acetimidate; n Q 20 1.5087; [α]22+ 53° (c = 0.9% in CHCl 3 ). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and n-butyl-(1-hydroxyiminoethyl)-ether, - n-butyl-N-(d-2-[ p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionoxy)-acetimidate; n<20>1, 5036 ; [a] 22 + 49 .87° (c = 1.2% in CHCl-j). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl-(1-hydroxyimino-n-butyl)-ether, - ethyl-N-(b-2-[ p-(α,α,α-trifluoro-p-tolyloxy)phenoxy)-propionoxy]-n-butyrimidate;

n<20>1.5058; [a]<20>+ 52.58° (c = 1.0% in CHCl-j)."

D-2- [p-(a , a', a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and methoxyacetonoxime, - D-2-[p-(a,a,a-trifluoro-p-tolyloxy) -phenoxy]-propionic acid methoxyacetone oxy ester; [a]<2>^+ 48.77°

(c = 1.9% in CHCl 3 ).

D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid

and diacetone monoxime, - D-2-[p-(α,α,α-trifluoro-p-tolyloxy)-phenoxy]-propionic acid diacetone monoximester; [a]2(^+ 30.7°

(c 1.0% in CHC13). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-pro<p>ionic acid and pyruvic acid ethyl ester oxime, - 2- (d-2- [p- (a,a ,α-trifluoro-p-tolyloxy)phenoxy]-propionoxyimino}"-propionic acid ethyl ester; [α]20+ 45.01° (c = 2.0% in -CHCl-j) .

D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy-propionic acid

and α-methyl-acetoacetic acid ethyl ester oxime, - 2-methyl-3-(d-2-tp-(α,α,α-trifluoro-p-folyloxy)phenoxy-propionoxy-imino-butyric acid ethyl ester; [a ]<20>+ 41.07° (c 0.9% in CHCl 3 ).

D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and levulinic acid ethyl ester oxime, - 4-(d-2-[p-(a,a,a-trifluoro -p-tolyloxy)phenoxy]-propionoxyimine-n-valeric acid ethyl ester; [α]20 + 37.4° (c = 1.2% in CHCl 3 ). D-2-[p-(o-chloro-p-trifluoromethyl-phenoxy)phenoxy]-propionic acid and 2-isopropylideneaminooxy-ethanol, - D-2-[p-(o-chloro-p-tri-1 fluoromethyl-phenoxy )phenoxy]-propionic acid 2-isopropylideneaminooxyethyl ester; ^- a^° + 12.3° (c = 0.69% in GHC13). D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy!-propionic acid and cyclopentanone oxime, - D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy] -propionic acid- cyclopentanone oxy ester; f0!^ + 40.8°'c = 1.0% in CHCl3).

Example 3

A solution of 1.79 g of D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid, 1.30 g of 1-diethoxyphosphinyl-cyclohexanol and 0.06 g of 4- dimethylaminopyridine in 20 ml of dichloromethane

1.13 g of dicyclohexylcarbodiimide was added at room temperature and stirred for 24 hours. The reaction mixture was evaporated under reduced pressure to dryness, the residue was dissolved in diethyl ether/n-hexane (1:1) and the insoluble part of the residue filtered off. Finally, the filtrate is washed twice with 30 ml of 5% acetic acid and three times with 30 ml of water, dried over a desiccant and evaporated to dryness. The liquid residue was chromatographically purified on silica gel with dichloromethane/diethyl ether (1:1). D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid-1-diethoxyphosphinyl-cyclohexyl ester was obtained;

20

n^ 1.5073.

In an analogous way, one obtains from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and 2-dimethoxyphosphinyl-2-propanol, - D-2-[p-(a ,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid 2-dimethoxyphosphinyl-2-propyl ester; n20 1.5019; [α]22+ 7.6° (c = 1.2% in CHCl3).

r

. Example. 4

A mixture of 1/89 g of D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid, 1.43 g of 3-diethoxyphosphinylpropyl bromide, 0.40 g of potassium carbonate and 50 ml of absolute acetone was heated'

for 15 hours at reflux temperature. The reaction mixture was then evaporated under reduced pressure and the residue dissolved in diethyl ether. The solution was washed twice with 25 ml of water and twice shaken with 25 ml of sodium bicarbonate solution, dried over a desiccant and evaporated to dryness.

The liquid residue was chromatographically purified on silica gel

with dichloromethane. D-2-[p-(a,a,a-trifluoro-p<->tolyloxy)-phenoxy]-propionic acid-3-diethoxy-phosphinyl-propyl ester is obtained; n^ 1.4986; [a]<22>+ 20.52° (c = 0.9% in CHCl 3 ).

In an analogous way, you get from

D-2-[p-(p-iodophenoxy)phenoxy]propionic acid and 3-diethoxyphosphinylpropyl bromide, - D-2-[p-(p-iodophenoxy)phenoxy]propionic acid 3-diethoxyphosphinyl propyl ester; [a]^<2>+ 20.4° (c = 1.2%

in CHC13).

II. Formulation examples

Example 5

To prepare an emulsifiable concentrate, the following ingredients are mixed with each other:

This mixture is filled up with jxylene to 1 liter,

The concentrate thus obtained emulsifies spontaneously in water. The resulting emulsion is suitable as a ready-to-use spray liquid.

Example 6

To prepare an emulsifiable concentrate, the following ingredients are mixed with each other:

Solvent mixture of the alkylbenzene in 1000 ml.

■^Emulsifier A: Emulsifier consisting of 60 parts of a block polymer of ethylene oxide and propylene oxide, 20 parts of calcium salt of a branched dodecylbenzenesulfonic acid and 20 parts of a solvent mixture of isobutanol and C^n-alkylbenzenes.<2>)Emulsifier B : Mixture of 70 parts of the calcium salt of a branched dodecylbenzenesulfonic acid and 30 parts of a solvent mixture of isobutanol and C 2 -alkylbenzenes.

The concentrate thus obtained emulsifies spontaneously in water. The emulsion that is formed is suitable as a ready-to-use spray liquid.

III. Biological results:

Example 7

The formulation from example 6 is sprayed under constant dilution with water containing 0.5% by volume nonoxynol (condensation product of nonylphenol and ethylene oxide) on the experimental plant (lolium multiflorum or bromus inermis). The spraying takes place using a logarithmic spraying device which makes it possible to automatically halve the concentration of the active substance after certain distances. The syringe volume is 500 l/ha. 33 days after spraying, the weeds are examined with regard to the effect that has occurred, i.e. the dosage is determined by which a sufficient control of the weeds;

is achieved. The results are summarized in the following table I.

Example 8

The active substance is tested in the formulation from example 6. Short

before the start of the experiment, dilute with water containing 0.5 volume percent nonoxynol as wetting agent to the desired concentration.

The test weeds (oryza sativa) in 2 leaf stages are sprayed in greenhouses with the active ingredient thus formulated. During the subsequent period, a 16-hour day is simulated by mercury-silver vapor lamps. 3 weeks after spraying, the weeds are examined with regard to the effect that has occurred, i.e. the percentage necrosis is determined, as 100% necrosis corresponds to a complete destruction of the weeds. The results are summarized in the following table II.

Claims (15)

IN 1. Compound character.ested by the general formula where R means chlorine, bromine, iodine or trifluoromethyl, 2 R hydrogen, chlorine, bromine or iodine, R<3> hydrogen or C, .-alkyl, R 4 hydrogen; C 1 -C 4 -alkyl; or phenol, optionally substituted with halogen, C 1 -alkyl and/or nitro, since R and R together with the carbon atom to which they are attached can also form a C,-_g-cycloalkane ring, which may optionally be substituted with 1-3 C^ _^ -alkyl groups, m, n and p are the numbers 0 or 1 and R^ one of the following groups (2) - (f) :' wherein in the above formulas with the groups (a) - (f) R 6 means hydrogen; C 1-6 alkyl; C 1 -C 4 -haloalkyl; or phenyl, optionally substituted with halogen, C 1 -alkyl and/or nitro, R 7 C 1-6 alkyl; or phenyl, optionally substituted with halogen, C 1-6 alkyl and/or nitro, 8 9 • R and R stand for hydrogen or together mean a bond, trimethylene, tetramethylene, 2-butenylene or a fused benzene ring, R"^ C₁_g-alkyl and R₂ trifluoromethyl, C₁_g₂-alkoxy, C₁_₂-₂ alkoxy-C₁ _₂ -alkyl, C₂ _7₂ alkanoyl, C₂ _₆ -alkoxycarbonyl or C₂ _₆₂ alkoxycarbonyl-G₂_ ^-alkyl, or R"^ and R^^~ together with the carbon atom to which they are attached form a cyclopentane ring, which may optionally be substituted with 1- 3 C, .-alkyl and/or 1 C, .-alkoxy, under which, if 10 II R and R and the carbon atom form an optionally substituted cyclopentane ring, R" <*> " is chlorine, bromine or trifluoromethyl, 12 13 R means hydrogen or C1-6-alkyl and R C1-6-alkyl; or phenyl, optionally substituted with halogen, C 1 -C 2 -alkyl and/or nitro, or 12 13 R and R form together with the carbon atom to which they are attached. to a C[ -_7 -cycloalkane ring, 14 15 R • and R means C, .--alkyl or phenyl, and wherein, when R 5 is a group (a), (b) or (c), m means the number 1, n the number 0 and p the number 0 or 1; when • is a group (d), m, n and p mean the number 0; when R^. is a group (e), m means the number 0 and n and p the number 1; and when 5 R is a group (f) means m and p the number 0 or 1 and n the number 1. '2. Compounds according to claim 1, characterized in that R means iodine or trifluoromethyl. ' 3: Compound according to claim 1 or 2, characterized in that R <2.> means hydrogen or chlorine. 4. Compounds according to one of claims 1-3, characterized in that they are D-isomeric compounds. 5. Compound according to claim 1, characterized in that it is D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]- .propionic acid succinimide methyl ester. 6. Compound according to claim 1, characterized in that it is ethyl N-Jh-2-[p-(a,a,a-trifluoro-p-tolyloxy)-phenoxy]-propionoxyj-acetmidate. 7. Compound according to claim 1, characterized in that it is n-butyl-N-[p-2-[p-(a,a,a-trifluoro-p-tolyloxy)-phenoxy]-propionoxy7-acetimidate. 8. Compound according to claim 1, characterized in that it is D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid-2-isopropylideneaminooxy-ethyl ester. 9. Compound according to claim 1, characterized in that it is D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-. propionic acid diethoxyphosphinyl methyl ester. 10. Compound according to claim 1, characterized in that it is selected from D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid-2-isopropylideneaminooxy-ethyl ester, D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid-2-methanesulfonamide ethyl ester, D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid succinimide methyl ester, D-2-[p-(p-iodophenoxy). phenoxy ].-propionsyphen-diethoxy-phosphinyl-methyl ester, D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid 2-diethoxyphosphinyl ethyl ester, D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]*-propionic acid-2~isoprO"-pyridenemonooxyethyl ester, D-2-[p-o.-chloro-p-iodophenoxy)phenoxy]-propionic acid-2*-methanesulfonamide ethyl ester, D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionic acid diethoxyphosphinyl methyl ester, D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]^ propionic acid dibutoxyphosphinyl methyl ester, D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid-1-diphenoxyphosphinyl ethyl ester, D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-^propionic acid-1-isopropylideneaminooxy-2-=-propyl ester, D-2-[p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]-propionic acid 1-isopropylideneaminooxy-2-butyl ester, D-2- [p-(α,α,α-trifluoro-p-tolyloxy)phenoxy]'-propionic acid-1-iso*-propylideneaminooxy-1-phenylethyl ester, D-2- [p-(a, a, a-trifluoro-p-tolyloxy) phenoxy] *-propionic acid 2-(2-butylidenam±nooxy)-ethyl ester, D-2- [p- (a, a , α-trifluoro-p-tolyloxy)phenoxy]-propionic acid->2-(α-methylbenzylideneaminooxy)ethyl ester, D-2-[p-(α,α,α-trifluoro-p-tolylox/)phenoxy]-propionic acid-2-cyclohexylideneaminooxyethyl ester and D-2-[p-(iodophenoxy)phenoxy]-propionic acid-3 -diethoxyphosphinyl propyl ester. 11. Weed control agent characterized in that it contains an effective amount of at least one compound with the general formula where R"*" means chlorine, bromine, iodine or trifluoromethyl, R 2 hydrogen, chlorine, bromine or iodine 3 R 4 hydrogen or C 1-6 alkyl, R is hydrogen; C 1 -C 4 -alkyl; or phenyl, optionally substituted with halogen, C 1 -C 2 -alkyl and/or nitro, wherein R <3> and R^ together with the carbon atom. they are linked to can also form a C,-_g-cycloalkane ring, which may optionally be substituted with a 1-3 C^_^ -alkyl group, m, n and p mean the number 0 or 1, and R^ one of the following groups (a)' - (f): wherein in the above formulas with the groups (a) - (f) hydrogen means C^__g-alkyl j C-^_^-haloalkyl; or phenyl, optionally substituted with halogen, C 1 -alkyl and/or nitro, R 7 C 1 -alkyl; or phenyl, optionally substituted with halogen, C 1-6 alkyl and/or nitro, R and R 9 mean hydrogen or together are a bond, trimethylene, tetramethylene, 2-butenylene or a fused benzene ring, R"^ means C^ _g-alkyl and R" <*> "" <*> " trifluoromethyl, C- C 1 -C 6 -Alkoxy, C 1 -C 6 -Alkoxy-C 1 -C 1 -Alkyl, C 1 -C 1 -Alkanoyl, C 2 -C 1 -Alkoxycarbonyl or C 1 -C 3 -Alkoxycarbonyl-C 1 -C 3 -Alkyl, 1011 or R and R form, together with the carbon atom to which they are attached, a cyclopentane ring, which may optionally be substituted with 1-3 C,_.-alkyl and/or 1 C,-.-alkyl, 10 ■ II wherein if R and R and the carbon atom form an optionally substituted cyclopenta.n ring, R is chlorine, bromine or trifluoromethyl, 12 '13 R . means hydrogen or C 1 -C 6 -alkyl and R C 1 -C 6 -alkyl; or phenyl, optionally substituted with halogen, C, .-alkyl 12 13 and/or nitro, or R and R form together with the carbon atom they are attached to a CV 7-cycloalkane ring, and 14 15 ■' R and R mean ° C^ _5 g-alkyl or phenyl, and wherein, when R is a group (a) or (c), m is 1, n is 0 and p is 0 or 1; when R~ <*> is a group (d), m, n and p mean the number 0; when R is a group (e), m means 0 and n and p means 1; and when R<5> is a group (f), m and p mean the number 0 or 1 and n the number 1, as well as formulation aids. 12. Weed control agent according to claim 11, characterized in that it contains an effective amount of one of the compounds mentioned in claims 5-9. 13. Procedure for making compounds with • the general formula where R"*" means chlorine, bromine, iodine or trifluoromethyl, 2 R hydrogen, chlorine, bromine or iodine, R is hydrogen or C 1 -alkyl R 4 hydrogen; C 1 -C 4 -alkyl; or phenyl, optionally substituted is with halogen, C 1 -alkyl and/or nitro, where R 3 and R <4> together with the carbon atom to which they are attached can also form a C,-_g-cycloalkane ring, which may optionally be substituted with a 1-3 C^^-alkyl group, m, n and p mean the number 0 or 1 and R^ one of the following groups (a) - (f): wherein in the above formulas with the groups (a) - (f) R 6 means hydrogen; C 1 -C 6 alkyl; C 1 -C 4 -haloalkyl; or phenyl, optionally substituted with halogen, C 1 -alkyl and/or nitro, R 7 C 1-6 alkyl; or phenyl, optionally substituted with halogen, C 1-6 alkyl and/or nitro, 8 '9 R and R stand for hydrogen or together mean a bond, trimethylene, tetramethylene, 2-butenylene or a fused benzene ring, R means C 1 -g -alkyl and R is trifluoromethyl, C 1 -g - alkoxy, C 1 -g - alkoxy-C 1 -4 -alkyl, C 2 -7 -alkanoyl, C 2 -7 -alkyloxycarbonyl or C 9 -7 -alkoxycarbonyl-C 1 -alkyl, or 10 11 R and R together with the carbon atom to which they are attached form a cyclopentane ring, which may optionally be substituted with 1-3 C,_.-alkyl and/or 1 C,_i,-alkoxy, under which, if 10 11 R , R and the carbon atom forms an optionally substituted cy chloropentane ring, R^ is chlorine, bromine or trifluoromethyl, 12 13 R means hydrogen or C₁₋₋ alkyl and R₋₋₋₋ alkyl; or phenyl, optionally substituted with halogen, C^_^-alkyl and/or nitro, or 12 13 R and R form together with the carbon atom they are attached to CV7 _cycloalkane ring and R and R 15 mean C 1-6 alkyl or phenyl, and wherein, when R 1 is a group (a), (b) or (c), m is 1, n is 0 and p is 0 or 1; when 5 " 5 R is a group (d), m, n and p mean the number 0; when R is a group (e) m means the number 0 and n and p the number 1; and when R~ <*> is a group (f), m and p mean the number 0 or 1 and n the number 1, characterized in that one ■ a) reacts an acid with formula 12 where R and R have the meanings given above, or a reactive derivative thereof, with a compound with formula 3 4 5 where R , R , R , m, n and p have the meanings given above and X means a leaving group, orb) reacts a phenol with the formula 12 where R and R have the meanings given above, or an alkali metal salt thereof, with a compound of the formula 3 4 5 where R , R , R , m, n and p have the meanings given above and Y means a leaving group. 14. Method for combating weeds, characterized by treating the material to be protected against weeds and/or the weeds with an effective amount of one of the compounds mentioned in claims 1-9, respectively. et.in claim 11 or 12 said agent. 15. Application of one of the compounds mentioned in claims 1 9, respectively a weed control agent mentioned in claim 11 or 12.