DD202373A5 - HERBIC AND / OR PLANT GROWTH-CONTROLLING AGENT - Google Patents

Abstract

New alpha (pyridyl-2-oxy-phenoxy) -propionic acid derivatives of the formula I defined herein and their preparation and their use are described. The novel compounds of the formula I can be used in the form of appropriate agents for regulating plant growth and / or for combating weeds in crop plants.

Description

O & 4 * + J J Berlin, the 3.3.1982

Δ? G 07 C / 234 045/5 J 59 343/11)

Field of application of the invention

The invention relates to a process for the preparation of new

^Q ^ - (pyridyl-2-o3: y-phenoxy) -propionic acid derivatives for use in agriculture, for example as herbicides and / or plant growth regulators,

Characteristic of the known technical solutions

It has already become known that certain oxime esters of carboxylic acids can be used as herbicides (cf., European Patent Applications Laid Open ♦ 2,246 and 3,114 and British Patent Specification 4,200,587, respectively). However, the herbicidal activity is not always satisfactory especially against hard-to-control weeds.

Object of the invention

The aim of the invention is the provision of herbicides, which are particularly suitable for controlling weeds in cultivated crops, as well as plant growth-regulating substances in order to increase the yield per unit area in agricultural üTutzpflanzenanbau or reducing the amount of work.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

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According to the invention, compounds of the formula I

manufactured,

X is hydrogen, halogen or pseudohalogen;

R 1 represents hydrogen or a grafted or substituted by halogen, hydroxy or C 1 -C 3 -alkoxy carboxy-G 1 -C 4 -aryl or phenyl group

R _{2 represents} unsubstituted or halogen, hydroxy, or G, G, alkoxy-substituted C 1 -C 6 -alkyl, G ₂ -alkyl, alkenyl, Gp-Gg-alkynyl or phenyl;

R and R ₂ together for an unsubstituted or a through

j substituted tetramethylene, pentamethylene, or hexamethylene bridge,

Processes for their preparation, agents containing them as active substances and their use as herbicides 125ide and / or as plant growth regulators,

Alkyl or alkyl moiety of another substituent, depending on the number of carbon atoms given, are understood as meaning the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers, eg. Iso-propyl, isobutyl, sec-butyl, etc.) Alkenyl is exemplified by propenyl (1), allyl, butenyl (1), 3-silyl (2), butenyl (3), etc .; By alkynyl is meant in particular propargyl. Halogen is available

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here and below for fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, in particular chlorine. Pseudohalogen groups are to be understood as meaning the cyano and rhodano groups, in particular the cyano group.

The compounds of formula I are stable at room temperature oils, resins or solids, which are characterized by very valuable herbicidal and plant growth-regulating properties. They can therefore be used preferably in the agricultural sector .or related fields for the targeted influencing of plant growth and / or for the control of weeds.

Preferred groups of active compounds of the formula I are those compounds in which the substituent X is chlorine, bromine or else hydrogen, and R and R have the meanings given under formula I.

Furthermore, those active compounds of the formula I are preferred in which R is hydrogen or C -C -alkyl and R is C -C -alkyl while X has the meanings given under formula I.

Particularly preferred in the scope of the formula I are active ingredients in which X is chlorine, R and R "independently of one another are C -C -alkyl.

The following individual compounds are particularly preferred:

a- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenoxy] -propionsäureacetonoximester

ct- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) -phenoxy] -propionic acid methyl ethyl ketone oxime ester

a- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenoxy] -propionsäurediethylketonoximester.

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The novel α- (pyridyl-2-oxy-phenoxy) -propionsäurederivate of formula I can be prepared by the following methods known per se, wherein in the formulas II to V, the substituents X, R and R "mean the meanings given under formula I. have Hai and Hai 'is a halogen atom, preferably chlorine or bromine and M is hydrogen or preferably an alkali or alkaline earth metal cation, in particular a potassium or sodium cation.

One way of preparing the active compounds of the formula I consists in the reaction of a substituted acid halide of the formula II

XCH

c -. (\ -o -. (Win- / ^(II)

with an oxime of the formula III

HO-N = C ^ I. (III)

Next one comes to the compounds of formula I by reaction of a compound of formula IV

· - ·

) -0- () · -0Μ (IV)

with an α-Halogenpropxonsäureoximester of formula V

^CH 3

¹ A

Hal'-CH-COO-N = C) (V).

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Finally, compounds of the formula I are also obtained by reaction of a. Z-halo-S-trifluoromethyl-pyridine of the formula VI

CI " ₃ - \ J) -HAI (VI)

with the metal salt of a hydroquinone ether with a lactic acid oxime ester of the formula VII

MO- <> -OCH-COON = C '(VII)

In the above formulas, R, R and X have the meaning given under formula I, Hal represents a halogen atom, preferably chlorine or bromine while M is hydrogen or an alkali metal or alkaline earth metal cation.

These reactions are advantageously carried out in an organic solvent inert to the reactants in the presence of an acid-binding agent. As an acid-binding agent

suitable organic and inorganic bases, for example tertiary amines such as trialkylamine (trimethylamine, triethylamine, tripropylamine, etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, etc.), oxides and hydroxides, alcoholates, carbonates and bicarbonates of alkali - And alkaline earth metals (KOH, NaOH, Na ₉ CO., etc.) and alkali metal salts of carboxylic acids (CELCOONa, etc.).

Hydrogen halide which is produced may in some cases also be conveyed by passing inert gas, e.g. Nitrogen, be expelled from the reaction mixture or molecular sieve (pore size 3A to 5a)

adsorbed [IA = 0.1 am].

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All reactions are carried out in the presence of reaction-inert solvents or diluents. For example, aromatic and aliphatic hydrocarbons, such as benzene, toluene, are suitable. Xylenes, petroleum ether, cyclohexane, η-hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachlorethylene; Alcohols, in particular aliphatic alcohols such as methanol, ethanol, propanol, butanol; Ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; Nitriles such as acetonitrile, propionitrile, Ν, Ν-dialkylated amides such as dimethylformamide; dimethyl sulfoxide; Ketones such as acetone, diethyl ketone, methyl ethyl ketone and mixtures of such solvents with one another. In some cases, one of the reactants may also be used as solvent.

The reaction temperature response are usually between -5 and +200 ⁰ C, preferably between 0 and 100 ⁰ C, the reaction time is depending on the selected reaction temperature and solvent of between a few minutes and several days. In general, the reactions are carried out at atmospheric pressure or slight overpressure. The presence of a reaction catalyst, for example tetraalkylammonium chloride, potassium iodide and / or crown ether may be advantageous.

The manufacturing process is part of the invention.

The starting materials of the formulas II to VLI are known or can be prepared by methods known per se.

Substituted acid halides of formula II are e.g. by reaction of a compound of formula VIII

CH,

3 -O-CH-COOCH-, (VIII)

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with a trifluoromethylpyridyl derivative IX

accessible., Ss initially formed with HCl elimination an intermediate of the formula X.

- ^CH 3

^ .- 0-CH-COOGH ₃ (X),

the ester group can be saponified in the customary manner, for example in an alkaline medium, to give an acid group and then be converted into an acid halide of the formula II, for example using a suitable halogenating agent such as SOCloj. In the formulas IX and X, X has the meanings given under formula I ·

Compounds of formula X show herbicidal activity »

Compound VIII is accessible from hydroquinone and 2-chloro-propionic acid methyl ester in the presence of a base *

Substituted trifluoromethylpyridyloxy-parahydroxyphenyl ethers of the formula IV can be prepared in accordance with BE-PS 862 325 and DE-OS 2,847,662 or 2,732,846.

The compounds of the formula I always have an asymmetric carbon atom G ^z in apparent position relative to the methyl group of the propionic acid ester.

In the synthesis the active substances of the formula I fall normally

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example as racemic.es mixture and can be cleaved in the usual way in their optical antipodes, z. B. by fractional crystallization "On the other hand, the synthesis of an optically pure compound of formula I is possible if one of their optical production pure 2-halopropionic acid "The optical antipodes of I have different biocidal activity, whereby the D-form is more herbicidally effective."

Regardless of the mentioned isomerism can asymmetrically substituted (H .. ^ ^ o ^ ^ ir ^ ³ ^ ⁰ ^ ^{0 he} formula I are in the synoder anti form ·

If no specific synthesis is carried out to isolate pure isomers, a product of the formula I is always obtained as a mixture of these possible isomeric forms.

It has now surprisingly been found that the trifluoromethylated new pyridyloxy derivatives of the formula I according to the present invention have a better herbicidal action than the known oxime esters of carboxylic acids cited in European patent applications Ur 2 246 and 3 114 and in US Pat. No. 4,200,587 pre- and post-emergent use as weed killers can be used «

The active compounds of the formula I according to the invention and the herbicidal compositions containing them as active component are particularly useful for the selective control of difficult-to-control grasses in cultivated plant stands, especially in dicotyledonous crops such as soybean and all cultured legumes, cotton, sugar beets, sunflowers, rapeseed and other Brassica Types "You can also enter

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cultures such as vines, orchards, (apple, pears, peaches, apricots), citrus crops and plantations of rubber or Glpalmen for combating ennobles. The erfindungagemäßen connections

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are thus well tolerated by many crops and very effective against grass weeds.

In addition, certain active compounds according to the invention, at a suitable application rate, also have favorable growth-regulating effects (growth inhibition). In particular, they also inhibit the growth of dicotyledonous plants. Examples of the beneficial application of the compounds of the invention are e.g. the reduction of vegetative growth in soya and similar legumes, which leads to an increase in the yield of this crop, the inhibition of the unwanted growth of tobacco stings, whose main instinct has been cut, which benefits the formation of larger and more beautiful leaves, or inhibition the growth of dicotyledonous plants, such as fruit trees, ornamental trees, bushes and hedges, in order to save on cutting work.

The novel compounds of the present invention are not very toxic to warm-blooded animals and their application poses no problems. The application rate is generally between 0.005 and 5 kg of active ingredient per hectare, preferably between 0.05 and 2 kg of active ingredient per hectare.

The active compounds of the formula I as constituents of herbicidal compositions have pronounced herbicidal activity even at low application rates with high selectivity in crops of useful plants, especially dicotyledons such as cotton, oilseed rape, soybean and sugarbeet.

The agents with active ingredients of the formula I can be administered pre-emergently on cultivated cultivated surfaces, or preferably as post-emergent agents in the mentioned cultures as contact herbicides.

Thus, in soybean crops, pre-emergent use of agents containing an active ingredient of formula I achieves excellent selective herbicidal action.

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The present invention thus also relates to herbicidal and / or growth-regulating agents containing as active ingredient a compound of formula I, as well as the preparation of these Mittal and the use of the agents or active substances for selective control of weeds in crops and / or for the inhibition of vegetative plant growth.

The content of active substance in the marketable agent is between 0.1 to 95 weight percent, preferably between 1 to 80 weight percent. Application concentrations can be diluted down to 0.001% by weight, depending on the problem.

The preparation according to the invention is carried out in a manner known per se by intimately mixing and grinding active substances. general formula I with suitable carriers and / or distribution agents, optionally with the addition of active ingredients to the inert antifoam, wetting, dispersing and / or solvents. _# The active substances can be present and used in the following reprocessing forms:

Solid reprocessing forms: dusts, litter, granules,

Coating granules, impregnation granules and homogenous granules;

Water dispersible

Active substance concentrates: wettable powder, pastes,

emulsions; Emulsion concentrates;

Liquid reprocessing forms: solutions.

Preferably, emulsion concentrates are used as the preparation form.

The described inventive compositions can be mixed with other biocidal agents or agents. Thus, in addition to the compounds of the general formula I mentioned, the new agents can be used e.g. Insecticides,

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Fungicides, bactericides, fungistats, bacteriostats, nematocidal or other herbicides to broaden the spectrum of action included.

embodiment

The following examples serve to illustrate the invention without limiting it. Temperatures are given in gelai degrees. Percentages and parts are by weight. Unless otherwise stated, the term "active compound of formula I" always refers to the racemic mixture.

Preparation Examples: Example 1: Preparation of

3 3

propionaäure.acetonosimester

a) Preparation of the intermediate:

/ X CH.

N ^. -0- CH-

COOOCH-

- \ A- ( 3-Chloro-5-trifluoromethyl-2-pyridyl-2-o3: y) -phenoxy-4-propionic acid

53 g (0.27 mol) of oC- (4-hydroxy-pheno2: y) -propionic acid methyl ester and 47 g (0.34 mol) of potassium carbonate are stirred in 300 ml of ethyl methyl ketone for 1 hour at +40 ⁰ C, then 2 g of benzyltriethylammonium chloride and 58.3 g (0.27 mol) of 2,3-dichloro-5-trifluoromethylpyridine was added and the reaction mixture was heated under reflux for 10 hours, the salt formed was filtered off and the filtrate was evaporated, to give 85.5 g (85 % of Theory) 06- 4- (3-chloro-5-trifluoro-

234U4D ο

- 11 methyl-pyridy1-2-hydroxy-phenoxy] propionate.

b) Preparation of another intermediate:

Cr - ^ s ~ ° ~ \ / O-CH-COOH

α- (4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy -) - phenoxy] propionic acid

37.5 g of the estar prepared according to a) are stirred in 120 ml of 2 N sodium hydroxide solution at + 7o ³ C for 2 hours. After cooling to room temperature, the mixture is acidified with concentrated hydrochloric acid and extracted with diethyl ether. The combined extracts are dried over magnesium sulfate, filtered and the solvent removed in vacuo. This gives 33 g (91.3% of theory) of a- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-öxy-) phenoxy] propionic acid having a melting point of 104-106 ⁰ C.

c) Preparation of the intermediate:

α- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy -) - phenoxy] propionic acid chloride

18.1 g (0.05 mol) of the acid prepared according to b) and 15 ml of thionyl chloride are stirred at + 60 ⁰ C for 5 hours. Excess thionyl chloride is removed in vacuo, the residue taken up in toluene and evaporated to dryness. This gives 19.8 g of α- [4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenoxy-[-propionic acid chloride as a yellow oil.

d) Preparation of the final product:

11.8 g (0.03 mol) of the acid chloride prepared according to c) are dissolved in

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Dissolved 40 ml of toluene. A solution of 2.4 g (0.034 mol) of acetone oxime and 4 g (0.04 mol) of triethylamine is added dropwise to O ⁰ C. The mixture is stirred for 2 hours at room temperature, the precipitated salt is filtered off and the filtrate is evaporated. The residue is taken up in ethyl acetate / hexane (1: 1) and filtered through silica gel. This gives 9.2 g (73% of theory) of a- { 4-O-chloro-j-trifluoromethyl-pyridyl ^ -oxy-) - phenoxy -] - propionic acid acetone oxime ester having a melting point of 59-62 ⁰ C. . (Compound No. 2)

In an analogous manner, the following compounds of formula I can be prepared.

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Table 1: Compounds of the formula I

Verb no. V A, H CH ! -CCH ₂ ) ₄ --CCH ₂ ) ₅ - ^ ₂ V ^R 2 Physik.Konstante 59-62 ° C 5250 I 5165 1 Cl. H CH ₃ -CCH ₂ ) ₆ CH ₃ 5220 5135 2 Cl CH ₃ ^C 2 ^H 5 I - ( CH ₃ Mp. 3 • 3r CH ₃ CH ₃ 1. 5620 .5320 .5327 4 Cl H C ₂ H ₅ 1 5 6 CN Cl CH ₃ CH ₃ C ₂ H ₅ 25 7 8 Cl Cl CH ₃ ' Cn) C ₃ H ₇ C ₂ H ₅ 30 1 9 3r Ci) C ₃ H ₇ Ci) C ₃ H ₇ 10 11 CN Cl CH ₃ H Ci) C ₃ H ₇ ^C 6 ^H 5 35 ¹¹ D 12 Cl H- CH, Cl (4) 0 4 13 Cl Cn) C ₃ H ₇ Cn) C ₃ H ₇ 14 Cl CH ₃ CH_ 6 2 15 Cl CH ₃ C ₅ H ₄ Cl (3) 16 br CH ₃ ^C 6 ^H 5 17 Cl CH ₃ (n) C ₄ H _g 18 Cl CH ₃ -CH = CH-CH 19 Cl CH ₃ -CH = C (CH ₃ ) ₂ 1 20 H H tert, C ₄ H ₉ r-1 21 H CH 3 30 22 H C ₂ H ₅ XY 30 1 1 23 H C ₂ H ₅ 24 25 Cl Cl 30 \ ¹¹ D 26 Cl 27 H

L ö

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Verb no. X ^R i • ^R 2 Physik.Konstante 28 F- CH ₃ CH ₃ 29 F CH ₃ ^C 2 ^H 5 30 F C ₂ H ₅ C ₂ H ₅ 31 ,egg CH ₃ C (CH ₃ ) ₃ 32 Cl CH ₃ CH ₂ CH (CH ₃ ) ₂

Formalization examples: Example. 2: emulsion concentrates

To prepare a) 10% and b) 25% and c) 50% emulsion concentrate, the following substances are used:

Active substance of the formula I Ca-dodecylbenzenesulfonate Castor oil polyethylene glycol ether (36 moles of AeO) Tributylphenoyl polyethylene glycol ether (30 moles of AeO) Mineral oil with high paraffin content Cyclohexanone XyIo!

a) b) c) 10% 25%   50% 5% 3% 4% 5% 7%

10%

70%

65%

6%

15% 25%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

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The new 4-pyridyloxy-phenoxy-propionic acid and its derivatives of the formula I, as well as the agents containing them have an excellent selective herbicidal activity against weeds in various crops. Some of them also have a plant growth regulating effect.

Although the new compounds of formula I are effective in pre- and post-emergent application, in pre-emergent administration, as opposed to. many known Phenoxyphenoxy herbicides achieved an excellent effect.

Preferably, the new agents are used as e.g. 50% or. Formulated 25% emulsifiable concentrates and diluted with water, applied to plant populations post-emergent or pre-emergent or incorporated directly onto the soil.

To demonstrate their usefulness as herbicides (pre-emergent) and as growth inhibitors, the following test methods were used:

Example 3: Pre-eminent herbicidal action Immediately after sowing, the test plants in pots of 11 cm diameter, the soil surface is treated in the greenhouse with an aqueous suspension of the active ingredients obtained from a 25% strength emulsion concentrate. Two different concentration ranges were used, corresponding to 1 and 0.5 kg of active substance per hectare. The pots are kept in the greenhouse at 22.-25 ^o C and 50-70 Z relative humidity and evaluated the test after 3 weeks and the results scored according to the following grading scale (9-index):

1 = plants not germinated or totally dead 2-8 = intermediate stages of injury

9 = plants undamaged (like untreated control).

234134b

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The experimental results are summarized below:

Compound No. 1 2 1 8th 1 21 1 22 Application rates kg / ha 0.5 0.5 0.5 0.5 plant 2 1 7 3 avena fatua 1 2 1 2 2 9 1 9 bromus tectcrum. 1 1 1 2 1 2 1 6 lolium perenne 2 1 1 1 1 2 1 1 alopecurus myosuroides 1 2 1 1 1 1 1 2 digitaria sanguinalis 1 1 1 1 1 2 1 2 echinochloa crus galli 1 1 1 1 1 1 1 1 Sorghum halepense 1 1 1 1 1 1 1 1 rottboellia exaltata 8th 1 9 1 9 2 9 1 soy 9 8th Q 9 9 9 9 9 sugar beet 9 9 9 9 9 9 9 9 cotton 9 9 9 9

Example 4 Herbicidal Action on Application of the Active Substances After Emergence of the Plants (Post-emergent) . Various crops and weeds are grown from the seeds in pots in the greenhouse until they reach the 4- to 6-leaf stage. Then the plants are sprayed with an aqueous emulsion of active substance corresponding to 0.25 kg per hectare. The treated plants are then kept in optimal conditions of light, flowering, temperature (22-25 ° C) and humidity (50-70% relative). 15 days after treatment, the evaluation of the experiments at the top index was carried out. The results are summarized below:

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Compound No. 2 8th 21 22 plant avena fatua 1 1 6 7 bromus tectorum 2 2 3 4 lolium perenne r-l r-l 3 3 alopecurus myosuroides r-l r-l 4 2 digitaria sanguinalis 1 1 2 r-l echinochloa crus galli 1 1 1 1 Sorghum halepense 1 1 r-l 1 rottboellia exaltata 1 1 5 2 soy 9 9 9 9 sugar beet 7 8th 9 9 cotton 9 9 9 9

Example 5: Yield increase in soybeans

Soybeans of the "Hark" variety were sown in the climate chamber in plastic containers containing soil peat-sand mixture (6: 3: 1). Optimal temperature selection, lighting, fertilizer application and irrigation allowed the plants to develop to the 5-6 trifoliate leaf stage after approximately 5 weeks. At this time, the plants were sprayed with the aqueous spray mixture of an active ingredient until the wetting was good. The active ingredient concentration was .10, 50, 100 and 500 ppm of active substance

 The evaluation took place about 5 weeks after the application.

The compound No .. 2 achieved at drug concentrations of 50 and 500 ppm compared to untreated control plants a small reduction in the length of growth while the pods approach was increased by about 4-7%.

Claims (1)

Erf indungsansprucn A herbicidal and / or plant growth-regulating agent, characterized in that, in addition to inert carriers and excipients, it contains as active component a pyridyloxyphenoxypropionic acid derivative of the formula I CH. I ³ 0 GH GOOET = C wherein S is hydrogen, halogen or pseudohalogen; R _{1 is} hydrogen or an unsubstituted or substituted by halogen, hydroxy or G ₁ -Qo-AIkOXy G ^ -Cg alkyl or phenyl group; R _{2 represents} an unsubstituted or halogen substituted by a halogen, hydroxy or C ..- G., - Alkoxy G.-Cg-alkyl, Q ~ -G _r - alkenyl, Gp-Gg-alkynyl * or phenyl group; or R ₁ and Rp together represent an unsubstituted or substituted by C.-C-3-alkyl tetramethylene, pentamethylene or hexamethylene bridge contains.