DD154570A5 - UNKRAUTBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to weed control agents, the propionic acid esters of general formula I, wherein R is high, hydrogen, alkyl of 1-6 carbon atoms or phenyl, R is high alkyl of 1-6 carbon atoms, alkenyl of 2-6 carbon atoms, alkynyl of 2-6 carbon atoms or phenyl, or R "1" and R "tall" 2 together with the carbon atom to which they are attached form a cycloalkane ring of 4-10 carbon atoms optionally mono-, di- or tri-substituted with alkyl of 1-3 carbon atoms R 3, halogen, trifluoromethyl or nitro and R 4 and R 5 can be hydrogen or halogen, may contain active compounds, processes for the preparation of such compounds and agents, and the use of such compounds or agents to control weeds.

Description

Weed control agent Field of application of the invention

The invention relates to weed control compositions containing novel Phenoxypropionsäureestem, a process for preparing these compounds (Vorauflauf- and Nachauflauf-) herbicidal compositions, processes for preparing such agents and their use and the use of such herbicidal agents per se for weed control in horticulture and in agriculture.

Characteristic of the known technical solutions

European Patent Application No. 78.1014675 (Publication No. 2246 and -tag 13 · 6. 79) are compounds of the Pormel

0 _

OON = C <

R

'Rr

wherein R is hydrogen, C, g-alkyl or phenyl, R p C g-alkyl, Cp _- ^ alkenyl, alkynyl or phenyl Cp_g or RJ and Rg form a cyclohexane ring together with the carbon to which they are attached, which may optionally be mono-, di- or tri-substituted with Cj o-alkyl, R ^ u. a

Fluorine, chlorine, bromine, trifluoromethyl or nitro

Represent hydrogen or chlorine, known as herbicides «.

and R, and

2 2 9 7 5 1 ^{'58 48E 12}

Aim of the invention;

The aim of the invention is the provision of new agents with improved herbicidal activity, broad spectrum of activity and good plant tolerance for selective weed control in horticulture and agriculture,

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties that are suitable as an active ingredient in weedkillers and to provide methods for their preparation, »

2 2 5971

58 482/12

According to the invention, new substituted Phenoxypropionsäureester the general formula

R C00CH ₂ 0N = -c /

wherein R is hydrogen, alkyl of 1-6 carbon atoms or phenyl, R ^{2 is} alkyl of 1-6 carbon atoms, alkenyl of 2-6 carbon atoms, alkynyl of 2-6 carbon atoms or phenyl, or R and R together with the carbon atom to which they are attached form a cycloalkane ring of 4-10 carbon atoms, optionally with alkyl of 1-3 carbon atoms

3 may be mono-, di- or tri-substituted, R is halogen, trifluoromethyl or nitro and B7 and R are hydrogen or halogen.

5971 H- 58482/12

The process for the preparation of compounds of formula I is characterized in that

a) a salt of an acid of the formula T> 5

COOH II,

wherein R ^, R and R have the meaning given for formula I,

with a compound of the formula

R ¹ R ² CNOCH ² X III,

In which R and R are as defined for formula I.

"and X means a leaving group, implements, or

b) a compound of the formula _R 1

Z COOCH ₂ ON- = C /. · IV

-S

1 wherein Z is a leaving group and R and R are the

have the meaning given for formula I, with a compound of the formula

R =

^ L

-φ-

3 4 5

wherein R, R and R have the meaning given for formula I,

or an alkali metal salt thereof, if necessary in the presence of a base, or

c) a compound of the formula

COOCH ₂ -SR ⁶ O

wherein R is a lower alkyl, aryl or heteroaryl ·

3 4 group and R, R and R have the meaning given for formula I, with a compound of the formula

R ¹ R ² CNOH

VII

1 in which R and R have the meaning given for formula I,

  or an alkali metal salt thereof in the presence of a base.

2 2 5 9 7 1 - a -

The term "alkyl" having 1-6 or 1-3 carbon atoms includes, unless otherwise stated, both straight-chain and branched hydrocarbon radicals having 1-6 or 1-3 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, tert-butyl and the like. By the term "lower alkyl" are meant in particular alkyl groups having 1-6 carbon atoms.

The terms "alkenyl" and "alkynyl" having 2-6 carbon atoms include unsaturated straight and branched chain hydrocarbon radicals having up to 6 carbon atoms such as allyl, butenyl, isobutenyl, pentenyl, isopentenyl and the like as well as propargyl, butynyl, isobutinyl, pentynyl and the like preferred alkynyl groups are 1-propynyl, butynyl and isobutinyl.

The term "halogen" includes fluorine, chlorine, bromine and iodine, preferably chlorine, bromine and iodine.

The cycloalkane ring preferably contains 4-7 carbon atoms, especially 4-6 carbon atoms.

By "aryl groups" are in particular phenyl, optionally substituted by 1-3 lower alkyl groups, as well as naphthyl to understand. The alkyl groups may be the same or different.

Preferred "heteroaryl" radicals are the pyridyl, imidazolyl, thiazolyl and thiophenyl radicals

 30

Preferred compounds of the formula I are those in which

1 2

R 6 is methyl or ethyl, those in which R is methyl,

Aethyl or phenyl means those in which R is chlorine or

4 trifluoromethyl, those in which R is hydrogen and those in which R is hydrogen. Also the

'-12

Compounds of formula I wherein R and R together with the carbon atom to which they are attached form an optionally alkyl-substituted cycloalkane ring

2 2 5 9 7 1 j?

prefers.

Particularly preferred compounds of the formula I are:

the 2- / p - [(α, α, α-trifluoro-p-toiyl) oxy] phenoxy / propionic acid - / [(isopropylideneamino) oxy] methyl ester and

2- [p- (p-chlorophenoxy) phenoxy] propionic acid / [(isopropylideneamino) oxy] methyl / ester.

Further examples of compounds of the formula I are:

2- [p- (2,4-dichlorophenoxy) phenoxy] -propionic acid / [(isopropylideneamino) oxy] methyl ester,

2- [p- (2,4-dichlorophenoxy) phenoxy-3-propionic acid / C (α-methylbenzylideneamino) oxy] methyl ester,

2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid / [(sec-butylideneamino) oxy] methyl / ester,

the 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - / [(1-pentyl-1-hexyl-idenamino) oxy] -methyl ester /, the 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy phenoxy / -propionic - / [(1,3-dimethyl-2-butylidenamino) oxy] methyl / ester,

the 2- / p- [(α, α, α-trifluoro-p-tolyl) oxy) phenoxy / -propionic acid - / [(α-methyl-benzylideneamino) oxy] methyl ester / ester,

2- / ρ - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - / [(cyclohexylideneamino) oxy] methyl / ester,

2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - / [(cyclopentylideneamino) oxy] methyl / ester,

the. 2- / p- [(α, α, α-trifluoro-p-tolyDoxy] phenoxy / -propionic acid - / [(cycloheptylideneamino) oxy] methyl / ester,

2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - / [(benzylideneamino) oxy] methyl / ester,

2- [p- (p-bromophenoxy) phenoxy] propionic acid - / [(isopropylideneamino) oxy] methyl ester and

2- [p- (p-nitrophenoxy) phenoxy] propionic acid / [(isopropylideneamino) oxy] methyl ester,

and lower alkyl-substituted derivatives of the above-mentioned cyclopentylideneamino, cyclohexylideneamino and cycloheptylideneamino compounds.

2 2 5 9 7 1 .I

Particularly preferred are the D-forms of the compounds of formula I and thus the D-forms of the above individually mentioned compounds.

In one embodiment for the preparation of the compounds of the general formula I, a salt of an acid of the formula II is reacted with a compound of the formula III.

The term "salt of an acid" means, for example, an alkali metal salt, such as sodium, potassium or lithium salt, or an alkaline earth metal salt, such as magnesium, calcium or barium, a salt of an organic base, such as a mono-, di- or trialkylammonium salt or a pyridinium salt, or the ammonium salt.

The term "leaving group" for X is, for example, chlorine, bromine, iodine, tosyloxy, mesyloxy, hydroxyl in free or esterified form, or one of the following groups: 20

7 8 9

wherein R, R and R, which may be the same or different, are alkyl, in particular having 1-6 carbon atoms, or two of them together also form a C. ₇ -alkylene group and Y ^ is an anion, for example

ft "" /

a chlorine, bromine, iodine, hydroxyl or sulfate anion;

, wherein R and R, which may be the same or different, are alkyl, in particular having 1-6 carbon atoms, and Y is as defined above;

2 2 5 9 7 1 - 3 -

(Ο)

it η S - R

19

wherein R is a lower alkyl, aryl or heteroaryl group and η is 1 or 2.

The esterification of the acid of general formula II with the compound of general formula III is preferably carried out in a suitable inert solvent, at about -10 to 220 ^° C., preferably at room temperature or elevated temperature. A particularly preferred temperature range is between 20 and 70 ⁰ C. The reaction is carried out for example in the presence of an inert solvent such as benzene, toluene, petroleum ether, dimethylformamide, tetrahydrofuran, acetonitrile, N-methyl-2-pyrrolidone, tetramethylurea, dimethoxyethane, diglycol dimethyl ether, or hexamethylphosphoric.

In a further embodiment for the preparation of compounds of the formula I, a compound of the formula IV is reacted with a compound of the formula V or an alkali metal salt of a compound of the formula V in a manner known per se.

The term "leaving group" for Z is, for example, one of the leaving groups already indicated for X, or a hydroxy group activated by reaction with triphenylphosphine and azodicarboxylic acid or an ester thereof, in particular azodicarboxylic acid diethyl ester (see, for example, Bull. Chem. Soc 4_6, 2833 (1973) or Angew Chem. _88_, 111 (1976)).

The reaction according to process variant b) is conveniently carried out. in an inert organic solvent such as hydrocarbons, for example benzene or toluene, ethers, for example diethyl ether, tetrahydrofuran, dimethoxyethane or hexamethylphosphoric triamide. Temperature and pressure are not critical, and it is preferably carried out at a temperature between -20 ⁰ C and the Rückfluss.temperatur des

2 2 5 9 7 1 _ if _

Reaction mixture, preferably between -10 and 30 ⁰ C.

In a further embodiment for the preparation of compounds of the formula I, a compound of the formula VI is reacted with an oxime of the formula VII in the presence of a base, for example an alkali metal carbonate. For this purpose, the compound of the formula VI can be prepared in an inert organic solvent such as a chlorinated hydrocarbon, for example dichloromethane, chloroform, carbon tetrachloride or trichloroethane, an ether or an ethereal compound, for example tetrahydrofuran, diethyl ether, diisopropyl ether, dimethoxyethane or dioxane, an aromatic hydrocarbon. For example, benzene, toluene or xylene, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide are dissolved, and then the oxime of the formula VII, for example in the form of an alkali metal salt, is added. The reaction is generally carried out in a temperature range between 0 ° C and the boiling point of the reaction mixture, preferably between 0 ° and 50 ⁰ C. After a short time, eg a few minutes, the reaction is usually complete. The reaction mixture is conveniently poured onto water and extracted with an organic solvent, for example ethyl acetate. The residue obtained after evaporation is optionally recrystallized for purification or chromatographed.

The compounds of general formula I also include optical isomers because they have an asymmetric carbon atom in the α-position to the carbonyl group.

Other asymmetric carbon atoms can be the ester. components included. If desired, the racemic compounds may be separated into dextrorotatory and levorotatory compounds using known procedures. Such processes are described, for example, in Industrial and Engineering Chemistry 6_0_ (8) 12-28. The isomers and the racemic mixtures all have herbicidal activity, but the extent of this activity is

2 2 5 9 7 1. ΐ? _

differently. The largest activity is the D isomer, followed by the racemic mixture and then the L isomer. It has been found in connection with such investigations that, for example, in certain Ver-Suchsanordnungen the D-isomer of 2- / p - [(α, α, α, -Trifluor-ptolyl) oxy] phenoxy / -propionsäure - / [(isopropylidenamino ) -oxy] methyl] / esters has a greater activity than the racemic mixture.

The isomers may also be prepared by synthesis from corresponding optically active starting materials. The D-isomers of the compounds of the formula I are, as stated above, particularly preferred and thus also the corresponding starting materials.

Due to the nitrogen-carbon double bond in the

R ¹

Group are each given two geometric isomers (if

1 2

R and R have different meanings), which are called syn and anti form. It is possible in certain cases to isolate such isomers. These are also the subject of the invention.

The present invention also relates to herbicidal compositions containing as active ingredient one or more compounds of formula I as defined above. The herbicidal composition conveniently contains at least one of the following inert materials: carriers, wetting agents, inert diluents and solvents.

, The (pre-emergence and postemergence) herbicides according to the invention are particularly suitable for controlling grass weeds, in particular of field foxtail (Alopecurus myosuroides) and millet species such as, for example, millet

2 2 5 9 7 1

(Echinochloa crus-galli), large bristle millet (Setaria faberii) and hairy millet (panicum capillare) in cereals - especially barley, oats, wheat, rice, cotton, soybean, sugar beet and vegetable crops.

Particularly preferred are the novel (pre-emergence and Nachauflauf-) herbicides for combating üngräsern in sugar beet crops. Thus, for example, the 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionsäure- / [(isopropylideneamino) oxy] methyl / ester at a concentration of 1.25 kg / ha sufficient effectiveness against weedy grasses, without, however, damaging the sugar beet crops. In general, a concentration of 0.1-6 kg / ha, preferably 0.6-2.0 kg / ha, more preferably 1-1.5 kg / ha is sufficient to achieve the desired herbicidal effect with compounds of the formula I. ,

In the case where R represents the trifluoromethyl radical, these compounds can only be used to a limited extent in cereal cultivation since some phytotoxicity occurs. However, these compounds are particularly useful for controlling overgrass in rice, cotton, soybean, sugar beet and vegetable crops.

The compounds of formula I are generally water-insoluble and may be formulated by any of the usual methods for insoluble compounds.

If desired, the compounds of formula I can be dissolved in a water-immiscible solvent, such as a high boiling hydrocarbon, conveniently containing dissolved emulsifiers so that when added to water, it acts as a self-emulsifiable OeI.

The compounds of formula I may also be mixed with a wetting agent with or without inert diluent to form a wettable powder which is soluble or dispersible in water, or may be combined with

2 2 5 9 7 1 _ _ia _

the inert diluent to form a solid or powdery product are mixed.

Inert diluents with which the compounds of formula I can be processed are solid inert media, including powdered or finely divided solids such as clays, sands, talc, mica, fertilizers and the like, such products being either dust-like or as materials larger particle size may be present.

The wetting agents may be anionic compounds such as soaps, fatty sulfate esters such as dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate, fatty aromatic sulfonates such as alkylbenzenesulfonates or eutylnaphthalenesulfonates, more complex fatty sulfonates such as the amide condensation products of oleic acid and N-methyltaurine or the sodium sulfonate of dioctylsuccinate.

The wetting agents may also include nonionic wetting agents, such as condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide, or fatty acid esters and ethers of sugars or polyhydric alcohols, or the products obtained from the latter by condensation with ethylene oxide or the products described as Block copolymers of ethylene oxide and propylene oxide are known to be. The wetting agents may also be cationic agents such as cetyltrimethylammonium bromide and the like.

The herbicidal composition may also be in the form of an aerosol, suitably used in addition to the propellant which is suitably a polyhalogenated alkane such as dichlorodifluoromethane, a co-solvent and a co-agent.

225971 _ β.

The herbicidal compositions according to the present invention may contain, in addition to the compounds of formula I, synergists and other active substances, e.g. Insecticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilizers. Such combination agents are suitable for enhancing the activity or broadening the activity spectrum.

In their various fields of application, the compounds according to the invention can be used in different proportions.

The weed control compositions of the invention may be in a form suitable for storage and transportation. Such forms may e.g. 2-90 weight percent of one or more active compounds of formula I. These forms can then be diluted with the same or different carrier materials to concentrations suitable for practical use. In ready-to-use agent can then drug concentrations. 0.05 to 80 weight percent. However, the active ingredient concentration can also be smaller or larger. Depending on the intended use, an active compound concentration of 2-8 or 50-80 weight percent is particularly preferred.

The starting materials of the formulas II, III, IV, V and VII belong to known classes of substances.

The starting materials of the formula VI can be obtained by oxidation, for example by means of hydrogen peroxide, of compounds of the formula

, o3_ / f \ VH- / O V- O ^ / COOCHp-SR ⁶ Vl! I

2 2 5 9 7 1 as ^{58 482/12}

3 4 5 6

., wherein R, R, R and R have the meanings given above.

The compounds of the formulas VI and VIII can be prepared in analogy to the details in German Offenlegungsschrift 2,6 / 7,804. Racemates obtained in this way can be split in the usual way.

The compounds of formulas VI and VIII, wherein R represents a heteroaryl group, are novel, regardless of whether they are present as a racemate or in the form of the optical antipodes, for example the D antipodes. If R in the compounds of the formulas VI and VIII is a lower alkyl group, Z ₀ B is the methyl group, an aryl radical, z, B is the phenyl radical or a halophenyl radical, the corresponding D-isomers are likewise new.

These novel compounds of the formulas VI and VIII can be obtained, for example, by reacting the racemate or the D-form of a compound of the formula II with a compound of the formula

HO-CH ₂ -SR ⁶ IX

implements. This reaction can be advantageously carried out in an inert organic solvent, for example in chloroform or dimethyl sulfoxide, and in the presence of dicyclohexylcarbodiimide in a conventional manner. A compound of the formula VIII thus obtained can then be oxidized, for example with hydrogen peroxide, to form a compound of the formula VI.

Particularly preferred starting materials of the formulas VI and VIII are:.

225971 * ^58482/12

the 0-2 - [[(P-Cp-BrOmPiIe] IOXy) phenoxy J -propionic acid methyl thiomethyl ester,

the D-2- ^ p-Cp-PIuorphenoxy) phenoxy-1-propionic acid methylthiomethyl ester,

"the D-2-Q ρ- (p-nitrophenoxy) phenoxy-1-propionic acid methylthiomethyl ester and

the D-2- [p- (p-trifluoromethylphenoxy) phenoxy] -propionic acid methylthiomethyl ester or the corresponding sulfonyl compounds.

The above-indicated starting materials of the formulas VI and VIII, in particular the D forms thereof, are additionally valuable as herbicides since they have a similar spectrum of activity as the compounds of the formula I. They can therefore be used in the same way as described for the compounds of formula I for the preparation of herbicidal agents. The D-antipodes have the advantage that, for example, they have a lower phytotoxicity on cotton and soybeans compared to the particular racemate *,

embodiment

The following examples are intended to illustrate the present invention. All temperatures are given in ⁰ C *

2 2 5971

I. Preparation of the active compounds of the formula I :

example 1

36 g of 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylsulfonyl) methyl] ester are dissolved in 20 ml of tetrahydrofuran. To this solution is added a mixture of 0.35 g of acetone oxime sodium salt dissolved in 20 ml of dimethylformamide, and the reaction mixture is stirred for 2 minutes at room temperature. The mixture is poured into water, extracted with ethyl acetate and washed neutral with water. The ethyl acetate is evaporated and the residue is then chromatographed on 100 g of silica gel with hexane / ethyl acetate 8: 2. The eluate is evaporated and the residue recrystallized from ether / hexane. The resulting 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid / [(isopropylideneamino) oxy] methyl ester melts at 76-77 °.

In an analogous manner is obtained when using 20

D-2- / p- [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylsulfonyl) methyl] ester and acetone oxime sodium salt containing D-2- / p - [(α , α, α-trifluoro-p-tolyl) oxy] phenoxy / propionic acid / [(isopropylideneamino) oxy] methyl / ester; Mp 80-85 °; Ca] ²² + 11.62 ° (c = 1.25% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid [(methylsulfonyl) methyl] ester and acetophenone oxime sodium salt the D-2- / p - [(α, α , α-trifluoro-p-tolyl) oxy] phenoxy / -propionic - / [(a-methyl-benzylideneamino) oxyjmethyl / ester; Mp 63-64 °; Ca] ²² -13.64 ° (c = 0.75% in CHCl ₃ ).

D-2- [p- (p-Chlorophenoxy) phenoxy] -propionic acid [(methylsulfonyl) methyl] ester and acetone oxime sodium salt give the D-2- [p- (p-chlorophenoxy) phenoxy] -propionic acid / [(isopropylidene amino) oxy methyl / ester; n ²⁰ 1.5480; CaJ ²² + 13.58 ° (c = 1.93% in CHCl ₃ ). , ·

2 2 5 9 7 1 _n_

2- [p- (o, p-Dichlorophenoxy) phenoxy] -propionic acid [(methylsulfonyl) methyl] ester and acetone oxime sodium salt

2- [ρ (o, p-dichlorophenoxy) phenoxy! -Propionic acid / [(isopropyl-20-denominino) oxy! Methyl] ester; η 1.5557.

2- [p- (o, p-Dichlorophenoxy) phenoxy! -Propionic acid [(methylsulfonyl) methyl] ester and acetophenone oxime sodium salt ···. ^C A is the 2- [ρ (o, p-dichlorophenoxy) phenoxy! -Propionic acid - / [(α-methylbenzylideneamino) oxy! Methyl] ester; Mp 66-67 °. 10

D-2- [p- (p-Bromopherioxy) phenoxy! -Propionic acid [(methylsulfonyl) methyl] ester and acetone oxime sodium salt give the D-2-Cp (p-bromophenoxy) phenoxy! -Propionic acid / [(isopropylidene amino) oxy! methyl, 1.15% in CHCl ₃ ).

amino) oxy methyl / ethyl ester; n ^ 1.5598; [α] "+ 11,92 ° (c =

D-2- [ρ- (p-iodophenoxy) phenoxy! -Propionic acid C (methylsulfonyl) methyl! Ester and acetone oxime sodium salt) the D-2- [p- (p-iodophenoxy) phenoxy! -Propionic acid / [(isopropylideneamino) oxy ! methyl / ester; Mp 40-43 °, Ca ²² + 8.60 ° (c = 0.90% in CHCl ₃ ).

D-2- / p - [(a, a, a-trifluoro-p-tolyl) oxy! Phenoxy / -propionic acid [(methylsulfonyl) methyl] ester and cyclopentanone oxime sodium salt the D-2- / p - [(α, α , α-trifluoro-p-tolyl) oxy! phenoxy / -propionic acid - / [(cyclopentyideneamino) oxy] methyl / ester; Mp 43-45 °; Ca! ²² + 7.52 ° (c = 2.28% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy! Phenoxy / propionic acid [(methylsulfonyl) methyl] ester and cyclohexanone oxime sodium salt. the D-2- / p- [(a, a, ct-trifluoro-p-tolyl) oxy! phenoxy / propionic acid / [(cyclohexylideneamino) oxy] methyl / ester; Mp 71-73 °; [α! ^ ² + 5.55 ° (c = 1.49% in CHCl ₃ ).

, D_2- / p - [(α, α, cc-trifluoro-p-tolyl) oxy! PhenoxyZ-propionic acid-1 (methylsulfonyl) methyl! Ester and cycloheptanonoxime sodium salt, the D-2- / p - [(α, α, α- trifluoro-p-tolyl) oxy] phenoxy / -propionsaure - / [(cycloheptylidenamino) oxy methyl /! -

2 2 5 9 7 1. _ί9 _

ester; Mp. About 30 °; [ct] β ² + 6.00 ° (c = 1.96% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid! (methylsulfonyl) methyl] ester and 3,3,5-trimethylcyclohexanone oxime sodium salt the D-2- / p - [(α, α, α-trifluoro-ptolyl) oxy] phenoxy / -propionic acid / [(3,3, 5 trimethylcyclo-

20 22

hexylidenamino) oxy] methyl / ester; η 1.5062; Ca] + 6.86 °

(c = 2.73% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylsulfonyl) methyl] ester and benzaldoxime sodium salt of D-2- / p - [(α, α , α-trifluoro-p-tolyl) oxy] phenoxy / -propionic - / [(benzylideneamino) oxy] methyl / ester; Mp 65-66 '

[a] ²² -16.34 ° (c = 1.60% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylsulfonyl) methyl] ester and ethyl methyl ketoxime natriurase salt containing D-2- / p - [(α, α , α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(sec-butylideneamino) oxy] methyl / ester; Mp 38-40 °; [cc] ²² + 10.34 ° (c = 2.36% in CHCl ₃ ).

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxyphenoxy / -propionic acid C (methylsulfonyl) methyl ester and dipentyl ketoxime sodium salt, the D-2- / pC (a, a, a-trifluoro) p-tolyl) oxy] phenoxy / -propionic - / [(1-penty1-hexylidenamino) oxy] -

on ο o

methyl / ester; η ^ ^υ 1.4913; Ca] ^ + 11.71 ° (c = 3.27% in CHCl ₃ )

D-2- / p - [(a, a, a-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid [(methylsulfonyl) methyl] ester and methyl (2-methyl-1-propenyl) -ketoxime sodium salt D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic - / [(1,3-dimethyl-2-butene

22

ylideneamino) oxy] methyl / ester; Mp 52-54 °; [cül "-5.75 ° (c =

0.78% in CHCl ₃ )

Example 2

A solution of 10 g <0.0307 mol) D-2- / p- (α, α, α-γ-fluoro-p-tolyl) oxy] phenoxy / -propionic acid in 100 ml of dimethyl

2 2 5 9 7 1. g.

Formamide is added dropwise to a suspension of 1.5 g of 55% (0.0307 mol) sodium hydride dispersion in 20 ml of dimethylformamide with stirring. After the addition, stirring is continued at room temperature until the evolution of hydrogen has ceased. The reaction mixture is stirred for a further 15 minutes and 15 g (0.048 mol) of NC (isopropylideneamino) -oxy] -N-methyl-piperidinium iodide and 0.5 g of 15-crown-5 (the polyether-crown compound having a 15-oxygen atom containing 15 Ring) too. After 2 hours of stirring at 110 °, the reaction's mixture is poured into 500 ml of water and extracted three times with 300 ml of ethyl acetate. The entire ethyl acetate solution is then washed twice with 200 ml of water each time and evaporated, and the residue is recrystallized from diethyl ether / n-hexane. This gives 8.0 g of D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy! Phenoxy / -propionsäure- /! (isopropylideneamino) oxy methyl ester which melts at 85-86 °; [a] £ + 11.3 ° (c = 1.2% in CHCl ₃ ).

Example 3

1.75 g of L (-) - lactic acid - / ^ (isopropylideneamino) oxy] methyl ester, 2.65 g of triphenylphosphine and 2.54 g of ρ - [(α, α, α-trifluoro-p-tolyl) oxy ] -phenol are dissolved at 0 ° in 10 ml of absolute tetrahydrofuran. 1.75 g of azodicarboxylic acid diethyl ether are added dropwise to the solution while cooling. After the addition is stirred for one half an hour, then the reaction mixture is poured into 100 ml of water, extracted twice with 50 ml of water, dried over anhydrous sodium sulfate and evaporated. The residue is chromatographed on 20 times the amount of silica gel with n-hexane / ethyl acetate (4: 1) and the eluate is evaporated. It is crystallized from diethyl ether / n-hexane and receives D-2- / p - [(α, α, α-trifluorop-tolyl) oxy] phenoxy / -propionsäure- / [(isopropylideneamino) -

on

oxylmethyl / ester; Mp. 85 °; [a] * + 10.9 ° (c = 1.33% in CHCl ₃ ).

225971

II. Preparation of the starting materials :

Example 4

100 g of 2- / p - [(a, a, a-trifluoro-p-tolyl) oxy] phenoxy / propionic acid (0.03 mol) and 252 g of sodium bicarbonate (3.0 mol) are dissolved in 2.5 l of dimethylsulfoxide suspended and then slowly with 336.5 ml tert. Butyl bromide (3.0 mol) was added. The mixture is stirred at room temperature overnight and the whole mixture, including the precipitated thick precipitate, is taken up in 5 l of ethyl acetate. The Essigesterlösung is • twice with 1 1 water washed out via sodium sulphate "dried and evaporated and the residue is chromatographed on a 10-fold amount of silica gel with hexane / Essigester in the ratio ^7:.. Chromatograph 1 and the eluate is evaporated, giving 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylthio) methyl] ester in the form of an oil.

40 g of 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid C (methylthio) methyl] ester (0.096 mol) are dissolved in 120 ml of acetone / water in a ratio of 5: 1 and slowly added 192 ml of hydrogen peroxide (30% solution). 9 ml of ammonium molybdate solution (35.2 g of ammonium molybdate in 96 ml of water) are added dropwise to the mixture, cooling with an ice-bath. Thereafter, the mixture is stirred for 2 hours at room temperature. It is shaken out repeatedly with ether, the ether extract washed with Natriumd.ithionitlösung and then the solution washed eight more times with 100 ml of saturated sodium chloride solution and then five times with 100 ml of water until neutral. The mixture is treated with charcoal, filtered and evaporated. The residue is recrystallized from methylene chloride / n-hexane. Is obtained 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid - [(methylsulfonyl) methyl] ester, which melts at 87-88 °.

Analogous d-em in the first paragraph of this example described method is obtained when using

2 2 597 1 _ «_

D-2- / pC (α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid the D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy ! / propionic acid - [(methylthio) methyl ester; Mp 47-48 °; [Cc! ²² + 31.24 ° (c = 1.58% in CHCl ₃ )

 - '

D-2- [p- (p-chlorophenoxy) phenoxy! -Propionic acid the D-2-.Cp- (p-chlorophenoxy) phenoxy] propionic acid [(methylthio) methyl] ester; Mp 75 °; [Cc! ²² + 50.54 ° (c = 1.34% in CHCl ₃ ).

2- [p- (o, p-Dichlorophenoxy) phenoxy! -Propionic acid 2- [p- (o, p-dichlorophenoxy) phenoxy! -Propionic acid C (methylthio) methyl! Ester; Mp 54 °.

D-2- [p- (p-Bromophenoxy) phenoxy! -Propionic acid 2- [p- (o, p-dichlorophenoxy) phenoxy! -Propionic acid C (methylthio) -

methyl] ester; Mp 83-87 °; Ca! ²² + 45.52 ° (c = 1.81% in CHCl ₃ ),

D-2- [p- (p-iodophenoxy) phenoxy! -Propionic acid the D-2-Cp- (p-iodophenoxy) phenoxy! -Propionic acid [(methylthio) methyl 3-ester; Mp 71-74 °; Ca! ²² + 41.39 ° (c = 1.43% in CHCl ₃ ).

Analogously to the process described in the second paragraph of this example, the use of

D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy! PhenoxyZ-propionic acid C (methylthio) methyl! Ester, the D-2- / p - [(a, cc, a-) Trifluoro-p-tolyl) oxy! Phenoxy / -propionic acid - [(methylsulfonyl) -methoxyester; Mp. 79-82 °; [Α! ²⁰ + 40.77 ° (c = 1.66% in GHCl ₃ ).

,

2- / p - [(α, α, α-trifluoro-p-tolyl) oxy! Phenoxy / -propionic acid - [(phenylthio) methyl] ester the 2- / p - [(α, α, a- Trifluoro- _r- p-tolyl) oxy! Phenoxy / -propionic acid - [(phenylsulfonyl) methyl ester; Mp 89-92 °

 ,

D-2-Cp- (p-chlorophenoxy) phenoxy! -Propionic acid C (methylthio) methyl ester C-methyl (methylsulfonyl) -methyl D-2-Cp- (p-chlorophenoxy) phenoxy-3-propionate, mp 81-83 °;

2 2 597 1

Ca] ²² + 43.42 ° (c = 1.02% in CHCl ₃ ).

-C (methyl thio) methyl] ester, the 2-Cp- (o, p-dichlorophenoxy) phenoxy] -propionic acid C (methylsulfonyl) methyl] ester; Mp 95 °.

D-2-Cp- (p-Bromophenoxy) phenoxy] -propionic acid C (methylthio) methyl! Ester C-methyl (methylsulfonyl) -methyl D-2-Cp- (p-bromophenoxy) phenoxy] propionate; Mp 84-87 °; Ca] ²² + 39.20 ° (c = 1.43% in CHCl ₃ ).

-; D-2-Cp- (p-iodophenoxy) phenoxy] -propionic acid C (methylthio) methyl] ester C-methyl (D-2-Cp- (p-iodophenoxy) phenoxy] propionate (methylsulfonyl) methyl] ester; Mp 121-123 °; Ccx3 ^ + 37.91 ° (c = 2.66% in CHCl _3).

Example 5

To a suspension of 10 g (0.11 mol) of L (+) - lactic acid and 94.2 g (1.1 mol) of sodium bicarbonate in 200 ml of dimethyl sulfoxide are 153 ml (1.1 mol) of tert. Butylbromide slowly added dropwise. The reaction mixture is stirred for 48 hours, then poured into 1 1 of water and extracted twice with 100 ml of ethyl acetate. The organic phase is washed three times with 200 ml of water and then evaporated. The crude product is chromatographed on 20 times the amount of silica gel with n-hexane / ethyl acetate (4: 1) and the eluate evaporated. This gives 5.7 g of L (-) - lactic acid C (me (c = 1.3% in CHCl ₃ ).

L (-) - lactic acid C (methylthio) methyl ester, Ca] ^ -39,27 '

The above product can also be obtained by heating 11.2 g of L (+) - sodium lactate, 0.5 g of 15-crown-5 and 9.25 g of chlorodimethylsulfide and a trace of sodium iodide in 100 ml of absolute acetonitrile at reflux temperature. After 6 hours pour the reaction mixture onto water and continue working as above. This gives 6.1 g of Ll -) -

Hydrochloric acid C (methylthio) methyl Jester, Ca] -38.5 ° (c =

2 2 5 9 7 1

0.69% in CHCl ₃ ).

2.55 g (0.01 mol) of p - [(α, α, α-trifluoro-p-tolyl) oxy] phenol, 1.5 g (0.01 mol) of L (-) - lactic acid - [( Methylthio) -methylüester and 2.63 g (0.01 mol) of triphenylphosphine are placed in 10 ml of absolute tetrahydrofuran and the whole cooled to 0 °. While cooling, 0.011 mol of diethyl azodicarboxylate are added dropwise, during which time the yellow color of this ester disappears. The reaction mixture is then stirred for 30 minutes at room temperature, poured into 100 ml of water, extracted twice with 50 ml of ethyl acetate and the organic phase washed neutral with water. Thereafter, the ethyl acetate solution is evaporated, the residue chromatographed on the 20-fold amount of silica gel with n-hexane / ethyl acetate (9: 1) and the eluate evaporated. After crystallization from diethyl ether / n-hexane gives 2.1 g of D-2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / -

20% propionic acid - [(methylthio) methyl] ester; Mp 52 °; [ot3 _n

+ 46.87 ° (c = 0.65% in CHCl ₃ )

 20

Example 6

To 100 ml of 36% formalin 100 ml of piperidine are added dropwise with cooling at 10 ° and then added 73 g of acetone oxime and 75 g of potassium carbonate. The reaction mixture is stirred overnight at room temperature, then taken up in ethyl acetate and the aqueous phase separated. The organic phase is evaporated, taken up in acetone and treated dropwise with cooling with 65 ml of methyl iodide, after which the product crystallizes out slowly. After a further 10 hours, the product is filtered off. This gives 291 g of N-C (isopropylideneamino) oxy] -N-methyl-piperidiniumjodid; Mp 132-133 ° ..

Example 7

1.1 g of sodium lactate, 3.5 g of N - [(isopropylideneamino) -oxy] -N-methyl-piperidinium iodide and 0.1 g of 15-crown-5 in

225971

10 ml of diglycol dimethyl ether are heated for 4 hours at 110 ° under nitrogen. Thereafter, the reaction mixture is poured into 50 ml of water and extracted three times with ethyl acetate. The organic phase is washed four times with water and then 'evaporated. After the residue is chromatographed on 10 times the amount of silica gel with n-hexane / ethyl acetate (1: 1) and evaporation of the eluate, 0.35 g of L (-) - lactic acid (isopropylideneamino) oxy] methyl ester are obtained; Ca] * -1.2 ° (c = 1.50% in CHCl ₃ ).

III. Formulation examples :

Example 8

To prepare an emulsifiable concentrate, the ingredients listed below are mixed together:

Compound of the formula I 500 g

Condensation products of an alkylphenol and ethylene oxide / dodecylbenzenesulfonic acid calcium 100 g Epoxidized soya oil with an oxirane oxygen content of approx. 6% 25 g

Butylated hydroxytoluene 10 g

This mixture is made up to 1 liter with xylene.

Example 9

The active ingredient, for example, 2- / p - [(α, α, α-trifluorop-tolyl) oxy] phenoxy / propionic acid / [(isopropylideneamino) oxy] methyl ester (compound A in the table below), becomes so dissolved in acetone to give a 2% solution of active ingredient. Shortly before the start of the test, it is diluted with water to the desired concentration, which in the present experiment is 312 g / ha. (When using "insoluble" active ingredients, spray powders containing kaolin as an inert diluent are formulated.

2 2 5 9 7 1 _ gj _

The test plants are sprayed in the greenhouse with the formulated active ingredient; using mercury vapor lamps simulates a 16-hour day. 3 weeks after spraying, the plants are examined for the effect that has occurred, i. % necrosis is determined with 100% necrosis of a complete necrosis. Destruction of the plant corresponds. Solvent effects - if present - are compensated by the "Abbott formula". The results are summarized in the table below.

Table I (% necrosis)

Active substance dosage Alipecurus Digitaria Avena

g / ha myosuroides floridana fatua

Compound A 312 100 100 100

A = 2- / p - [(α, α, α-trifluoro-p-tolyl) oxy] phenoxy / ~ propionic acid - / [(isopropylideneamino) oxy] methyl / ester

Example 10 Table II

% Necrosis in cotton cv. Stoneville 7A

Dosage compound A. Connection H

kg / ha ·

22

250 g / l

300 g / l

100 g / l

25 g / l

to 1000 ml

1.25 0 0.62 0 30 Formulation: • active ingredient NMP Tensiofix B 7425 Phenylsulfonate CA 35 Shellsol AB fill up. Wetting agent: 0.08% nonoxynol

22 5 9 7 1 ^2? '- - fts - Turn wax stage at treatment: 2 leaf stage spray volume: 1000 l / ha Scoring: 10 days after treatment 5 place: Glasshouse

Compound A see Example 9

Compound H = D-2- [p- (p-trifluoromethylphenoxy) phenoxy] ·

Propionic acid methyl ester 10

example

Table III 15 % necrosis in soybean cv. Hood

dosage 25 Wetting agent: Connection A active substance 250 g / l kg / ha growth stage NMP 300 g / l 1.25 30 at treatment: 0 Tensiofix B 7425 100 g / l 20 0.62 spray volume: 0 Phenylsulfonate CA 25 g / l Formulation: Scoring: Shellsol AB on 1000 ml Place: fill up. 0.08% nonoxynol 2 three-part leaves 1000 l / ha 2 weeks after treatment Glasshouse

35 Compound A see Example 9

2 2 5 9 7 1 _ g _

The terms NMP, Tensiofix 7425, phenylsulfonate CA, Shellsol AB and nonoxynol used in Examples 10 and 11 above have the following meanings:

NMP: N-methyl-2-pyrrolidone

Tensiofix B 7425: emulsifier consisting of 60 parts of a block polymer of ethylene oxide and propylene oxide, 20 parts of the calcium salt of a branched chain dodecylbenzenesulfonic acid and 20 parts of a solvent mixture of isobutanol and C ₁₀ -alkylbenzenes.

Phenylsulfonate CA: Mixture of 70 parts of the calcium salt of a branched-chain dodecylbenzenesulfonic acid and 30 parts of a solvent mixture of isobutanol and C ₁ "-alkylbenzenes.

Shellsol AB: solvent consisting of a mixture of C ₁ Q-alkylbenzenes.

Nonoxynol: Condensation product of nonylphenol and ethylene oxide.

Claims (7)

invention claim A weed control composition, characterized in that it contains an effective amount of at least one compound of the general formula RS '. , wherein R is hydrogen, alkyl of 1-6 carbon atoms or phenyl, R is alkyl of 1-6 carbon atoms, alkenyl of 2-6 carbon atoms, alkynyl of 2-6 1 2 Carbon atoms or phenyl, or R and R together with the carbon atom to which they are attached form a cycloalkane ring of 4-10 carbon atoms, which may optionally be mono-, di- or tri-substituted with alkyl of 1-3 carbon atoms, R , Halogen, trifluoromethyl or nitro and R ^ and R ^ represent hydrogen or halogen, and contains inert carrier material. 2 # Weed control composition according to item 1, characterized in that the cycloalkane ring contains 4-6 carbon atoms. 3. Weedkiller according to item 2, marked ι
in that R denotes methyl or ethyl 4 · weed control products according to item 2 or 3, identified characterized in that R represents methyl, ethyl or phenyl · 2 2 5 9 7 1 3o 58 482/12 5 · Weed control products according to one of the items 2 to 4 »marked c
methyl means characterized in that R 1 is chlorine or trifluoro- 6. weed control agent according to one of the items 2 to 5, characterized in that R is hydrogen. 7 * weed control agent according to any one of items 2 to 6, characterized in that R is hydrogen. Weed control composition according to item 2, characterized in that it contains an effective amount of 2- / p- [(&, <*, "* a.-trifluoro-p-tolyl) oxy-phenoxy / -propionic acid / ε-isopropylideneamino) oxy-methyl ester and inert carrier material 9 · weed control composition according to item 2, characterized in that it contains an effective amount of 2-jjp- (p-chlorophenoxy) phenoxyJ-propionic acid / C (isopropylideneamino) oxyjmethyl ester and inert carrier material. 10 © weed control composition according to item 2, characterized in that it comprises an effective amount of at least one compound selected from: D-2- / p- £ (c *, α, Ο-trifluoro-p-tolyl) oxyj phenoxy / propionic acid / f (isopropylideneamino) oxy-methyl ester, D-2- / p- [l <y., I * -, ciy-trifluoro-p-tolyZoxy] phenoxy / -propionic acid / C (cc-methyl-benzylideneamino) oxy! methyl / ester, D-2-FP (p-chlorophenoxy) phenoxyJ propionic acid-/ £ '(isopropylideneamino) oxy] methyl / ester, 2- [p- (ο, ρ-dichlorophenoxy) phenoxy] -propionic acid / ε (iso-propylideneamino) oxy-3-methyl-ester, 2 2 5 9 7 1 31 ^{58 482/12} - KOt - 2- [ρ (o, p-dichlorophenoxy) phenoxy] propionic acid / LC ⁰⁵ · methyl-benzylideneamino) oxy / methyl ester, D-2- fp- (p-Bromophenoxy) phenoxy] -propionic acid / L (isopropylideneamino) oxy] methyl ester, D-2- / p-L (fc, a ,, <* - trifluoro-p-tolyl) oxyJ phenoxy / -propionic acid - / ^ cyclopentylideneamino) oxyj methyl / ester, D-2- / p- f (> -, a,! X.-trifluoro-p-tolyl) oxyJ phenoxy / -propionic acid / C (cyclohexylidenaraino) oxy) methyl / ester, D-2- / P-LCoi ' jOi.jQi.-trifluoro-p-tolyl) oxy] phenoxy / -propionic acid / fCbenzylidenaraino) oxy] methyl / ester, D-2- / p-KOijOUjOt-trifluoro-p-tolyl) oxy] phenoxyZ-propionic acid Z ^ Csec. butylideneamino) oxyj methyl / ester and D-2 / p-quolyl, trifluoro-p-tolyl) oxy-phenoxy / -propionic acid / f (1-pentyl-hexylideneamino) oxy-methyl ester, and inert carrier material. 11 »weed control agent according to item 1, characterized in that it comprises an effective amount of at least one compound selected from: D-2-p * p- (p-iodophenoxy) phenoxy-1-propionic acid / (isopropylideneamino) oxy] methyl / ester, D ~ 2- / p- | _ (fc, a-, ou.T _r ifluor-p-tolyl) oxyj phenoxy / -propionic acid / ε (3,3 »S-trimethylcyclohexylidehamino) oxy3 methyl / ester and D-2- / p - ^^, Ä-trifluoro-p-tolyl) oxyj phenoxy / -propionic acid - / (_ (1 ', 3-dimethyl-1-2-butenylideneamino) oxyj methyl / ester, and inert carrier material. 12 ", weed control agent according to item 1, characterized in that as connection or. Compounds of formula I, the D-isomers are used. 07 C 07 C / 225 971 58 482 12 2 2 5 9 7 1 13. weed control agent according to one of the items 2 to 7, characterized in that are used as the compound or compounds of formula I, the D-isomers · 14. A process for the preparation of a weed control agent, characterized in that at least one of the compounds mentioned in item 1, 11 or 12 mixed with an inert carrier material » Process for the preparation of a herbicidal composition, characterized in that at least one of the compounds mentioned in points 2 to 10 and 13 is mixed with an inert carrier material. Method for combating weeds, characterized in that the product to be protected against weeds and / or the weeds is treated with an effective amount of an agent mentioned in items 1, 11 or 12 17. A method of controlling weeds, characterized in that treating the weeds to be protected against weeds and / or the weeds with an effective amount of one of the means mentioned in the points 2 to 10 and 14. 58 482 12 2 2 5 9 7 1 _ g. 18. Use of a compound or agent mentioned in items 1, 11 or 12, characterized in that it is used for combating weeds. 19. Use of a or one of the mentioned in points 2 to 10 and 13 V _e rbindungen or compositions, characterized in that they are used for combating weeds.