CA1142180A - .alpha.-(PYRIDYL-2-OXY-PHENOXY)-PROPIONIC ACID DERIVATIVES, PROCESSES FOR PRODUCING THEM, AND THEIR USE AS HERBICIDES AND/OR AS REGULATORS OF PLANT GROWTH - Google Patents
.alpha.-(PYRIDYL-2-OXY-PHENOXY)-PROPIONIC ACID DERIVATIVES, PROCESSES FOR PRODUCING THEM, AND THEIR USE AS HERBICIDES AND/OR AS REGULATORS OF PLANT GROWTHInfo
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- CA1142180A CA1142180A CA000387754A CA387754A CA1142180A CA 1142180 A CA1142180 A CA 1142180A CA 000387754 A CA000387754 A CA 000387754A CA 387754 A CA387754 A CA 387754A CA 1142180 A CA1142180 A CA 1142180A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract There are described novel .alpha.-(prridyl-2-oxy-phenoxy)-propionic acid derivatives of the formula I defined herein
Description
1~4Z180 Case 5-13102/1~2 Novel a-(pyridyl-2-oxy-phenoxy2-propionic acid derivatives, processes for producin~ them, and their use as herbicides and/or as re~ulators of plant ~rowth The invention relates to compounds of the formula I
. .
. ~ ~ ~--o-cH-cooN~
wherein ....
X is hydrogen, halogen or pseudo halogen, Rl is hydrogen or a Cl-C6-alkyl or phenyl group each of which is unsubstituted or substituted by halogen, hydroxyl or Cl-C3-alkoxy, R2 is a cl-c6-alkyl, C2-C6-alkenyl, c2-C6-alkynyl or phenyl group, each of which is unsubstituted or substituted by halogen, hydroxyl or Cl-C3-alkoxy, or Rl and R2 together form a tetramethylene, pentamethylene or hexamethylene bridge, each of which is unsub-stituted or substituted by Cl-C3-alkyl, to processes for producing the novel compounds, to compo-sitîons containing them as active ingredients, and to the use thereof as herbicides and/or as regulators of plant growth.
By alkyl or by alkyl moiety of another substituent are . ~
ll~Z180 meant, depending on the given number of carbon at~ms, the following groups: methyl, ethyl, propyl, butyl, pentyl and hexyl, as well a~ isomers thereof, ~or example: i90-propyl, iso-butyl, sec-butyl, and so forth. Alkenyl i9 for example: propen-l-yl, allyl, buten-l-yl, buten-2-yl, buten-3-yl, and the like. By alkynyl is meant especially propargyl. Here and in the following, halogen denotes:
fluorine, chlorine, bromine or iodine, but preferably chlorine or bromine, particularly chlorine. And by pseudo-halogen groups are meant the cyano and thiocyano groups, in particular the cyano group.
The compounds of the formula I at room temperature are stable oils, resins or solids, which are characterised by very valuable herbicidal and plant-growth-regulating properties. They are prPferably used therefore in the agricultural and allied fields for regulating plant growth in specific ways and/or for combating weeds.
Preferred groups of active substances of the formula I
are formed by those compounds in which the substituent X
is chlorine or bromine or also hydrogen, and Rl and R2 have the meanings defined under the formula I.
Further preferred active substances of the formula I
are those wherein Rl is hydrogen or Cl-C6-alkyl while R2 is Cl-C6-alkyl, and x has the meanings defined under the formula I.
Particularly preferred a~tive substances embraced by the formula I are those wherein X is chlorine~ and Rl and R2 independently of one another are each Cl-C3-alkyl.
T~e foLlowing individual compounds are especially preferred:
a-~4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid acetoxime ester, ~421~90 - 3 ^
~-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid methyl ethyL ketoxime ester, and a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid diethyl ketoxime ester.
The novel a-(pyridyl-2-oxy-phenoxy)-propionic acid derivatives of the formula I can be produced by the following methods known per se, whereby, in the formulae II to V, the substituents X, Rl and R2 have the meanings defined under the formula I, Hal and Hal' denote a halogen atom, preferably chlorine or bromine, and M is hydrogen, or preferably an alkali metal cation or alkaline-earth metal cation, particularly a potassium or sodium cation.
One process for producing an active substance of the formula I comprises reacting a substituted acid halide of the formula II
3 ~ al - (II) with an oxime of the formula III
Ho ~2 ~ i`l (III).
~, A further procedure for producing a compound of the formula I consists in reacting a compound of the formula IV
CY3~ ~~~ -OM (IV) with an ~-halopropionic acid oxime ester of the formula V
Hal -CH-COO-N~C i, ~R2 (V).
. .
~i~2180 Finally, a compound of the formula I is obtained by reacting a 2-halo-5-trifluoromethyl-pyridine o~ the formula VI
cF3~ al tVI) with the metal salt of a hydroquinone ether with a lactic acid oxime ester of the formula VII
3 ~ (VII).
In the above formulae, Rl, R2 and X have the meanings defined under the formula I, Hal is a halogen atom, preferably chlorine or bromine, and M is hydrogen or an alkali metal cation or alkaline-earth metal cation.
These reactions are performed in an organic solvent inert to the reactants, advantageously in the presence of an acid-binding agent. Suitable acid-binding agents are organic and inorganic bases, for example tertiary amines, such as trialkylamine (trimethylamine, triethylamine, tripropylamine, and so forth), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, and the like), oxides and hydroxides, alcoholates, carbonates and hydrogen carbonates of alkali metals and alkaline-earth metals (KOH, NaOH, Na2CO3, and so forth), and also alkali salts of carboxylic acids (CH3COONa, and the like).
Formed hydrogen halide can in some cases be expelled from the reaction mixture by the passing through of inert gas, for exa~ple nitrogen, or can be adsorbed on a molecular sieve (pore si~e 3 ~ to 5 ~) [1 ~ = O.l nm~.
All the reactions are performed in the presence of solvents or diluents inert to the reactants. Suitable ~42180 in this respect are for example: aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, cyclohexane and n-hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloro-ethylene; alcohols, especially aliphatic alcohols, such as methanol, ethanol, propanol and butanol; ethers and ethereal compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert-butyl methyl ether, and so forth), anisole, dioxane or tetrahydrofuran; nitriles, such as acetonitrile, propionitrile, N,N-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; ketones, such as acetone, diethyl ketone or methyl ethyl ketone; and mixtures of solvents of this kind with one another. In some cases it is also possible for one of the reactants itself to act as solvent.
The reaction temperatures are usually between -5 and +200C, preferably between O and 100C; and the duration of the reaction is between a few minutes and several days, depending on the selected reaction temperature and the solvent. The reactions are performed as a rule under normal pressure or a slight excess pressure. The presence of a reaction catalyst, for example tetraalkylammonium chloride, potassium iodide and/or crown ether, can be of advantage.
The production process forms part of the invention.
The starting materials of the formulae II to VII are known, or can be produced by methods known per se.
Substituted acid halides of the formula II are obtainable for example by reaction of a compound of the formula VIII -~- ca3 HO~ -O-CH-COOCH3 ~- (VIII) li42~80 with a trifluoromethylpyridyl derivative IX
~g .3 \ ~ -Cl (IX).
There is firstly formed, wi~h the splitting-off of HCl, an intermediate of the formula X
~_.~ ~ ~ 1 3 3 \ ~ -O~ o-c~-cooca3 (X), the ester group of which can be saponified in the customary manner, for example in an alkaline medium, to an acid group, and subsequently converted, for example with a suitable halogenating agent, such as SOC12, into an acid halide of the formula II. The symbol X in the formulae IX and X has the meanings defined under the formula I.
Compounds of the formula X exhibit herbicidal activity.
Compound VIII is obtainable from hydroquinone and
. .
. ~ ~ ~--o-cH-cooN~
wherein ....
X is hydrogen, halogen or pseudo halogen, Rl is hydrogen or a Cl-C6-alkyl or phenyl group each of which is unsubstituted or substituted by halogen, hydroxyl or Cl-C3-alkoxy, R2 is a cl-c6-alkyl, C2-C6-alkenyl, c2-C6-alkynyl or phenyl group, each of which is unsubstituted or substituted by halogen, hydroxyl or Cl-C3-alkoxy, or Rl and R2 together form a tetramethylene, pentamethylene or hexamethylene bridge, each of which is unsub-stituted or substituted by Cl-C3-alkyl, to processes for producing the novel compounds, to compo-sitîons containing them as active ingredients, and to the use thereof as herbicides and/or as regulators of plant growth.
By alkyl or by alkyl moiety of another substituent are . ~
ll~Z180 meant, depending on the given number of carbon at~ms, the following groups: methyl, ethyl, propyl, butyl, pentyl and hexyl, as well a~ isomers thereof, ~or example: i90-propyl, iso-butyl, sec-butyl, and so forth. Alkenyl i9 for example: propen-l-yl, allyl, buten-l-yl, buten-2-yl, buten-3-yl, and the like. By alkynyl is meant especially propargyl. Here and in the following, halogen denotes:
fluorine, chlorine, bromine or iodine, but preferably chlorine or bromine, particularly chlorine. And by pseudo-halogen groups are meant the cyano and thiocyano groups, in particular the cyano group.
The compounds of the formula I at room temperature are stable oils, resins or solids, which are characterised by very valuable herbicidal and plant-growth-regulating properties. They are prPferably used therefore in the agricultural and allied fields for regulating plant growth in specific ways and/or for combating weeds.
Preferred groups of active substances of the formula I
are formed by those compounds in which the substituent X
is chlorine or bromine or also hydrogen, and Rl and R2 have the meanings defined under the formula I.
Further preferred active substances of the formula I
are those wherein Rl is hydrogen or Cl-C6-alkyl while R2 is Cl-C6-alkyl, and x has the meanings defined under the formula I.
Particularly preferred a~tive substances embraced by the formula I are those wherein X is chlorine~ and Rl and R2 independently of one another are each Cl-C3-alkyl.
T~e foLlowing individual compounds are especially preferred:
a-~4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid acetoxime ester, ~421~90 - 3 ^
~-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid methyl ethyL ketoxime ester, and a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid diethyl ketoxime ester.
The novel a-(pyridyl-2-oxy-phenoxy)-propionic acid derivatives of the formula I can be produced by the following methods known per se, whereby, in the formulae II to V, the substituents X, Rl and R2 have the meanings defined under the formula I, Hal and Hal' denote a halogen atom, preferably chlorine or bromine, and M is hydrogen, or preferably an alkali metal cation or alkaline-earth metal cation, particularly a potassium or sodium cation.
One process for producing an active substance of the formula I comprises reacting a substituted acid halide of the formula II
3 ~ al - (II) with an oxime of the formula III
Ho ~2 ~ i`l (III).
~, A further procedure for producing a compound of the formula I consists in reacting a compound of the formula IV
CY3~ ~~~ -OM (IV) with an ~-halopropionic acid oxime ester of the formula V
Hal -CH-COO-N~C i, ~R2 (V).
. .
~i~2180 Finally, a compound of the formula I is obtained by reacting a 2-halo-5-trifluoromethyl-pyridine o~ the formula VI
cF3~ al tVI) with the metal salt of a hydroquinone ether with a lactic acid oxime ester of the formula VII
3 ~ (VII).
In the above formulae, Rl, R2 and X have the meanings defined under the formula I, Hal is a halogen atom, preferably chlorine or bromine, and M is hydrogen or an alkali metal cation or alkaline-earth metal cation.
These reactions are performed in an organic solvent inert to the reactants, advantageously in the presence of an acid-binding agent. Suitable acid-binding agents are organic and inorganic bases, for example tertiary amines, such as trialkylamine (trimethylamine, triethylamine, tripropylamine, and so forth), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, and the like), oxides and hydroxides, alcoholates, carbonates and hydrogen carbonates of alkali metals and alkaline-earth metals (KOH, NaOH, Na2CO3, and so forth), and also alkali salts of carboxylic acids (CH3COONa, and the like).
Formed hydrogen halide can in some cases be expelled from the reaction mixture by the passing through of inert gas, for exa~ple nitrogen, or can be adsorbed on a molecular sieve (pore si~e 3 ~ to 5 ~) [1 ~ = O.l nm~.
All the reactions are performed in the presence of solvents or diluents inert to the reactants. Suitable ~42180 in this respect are for example: aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, cyclohexane and n-hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloro-ethylene; alcohols, especially aliphatic alcohols, such as methanol, ethanol, propanol and butanol; ethers and ethereal compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert-butyl methyl ether, and so forth), anisole, dioxane or tetrahydrofuran; nitriles, such as acetonitrile, propionitrile, N,N-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; ketones, such as acetone, diethyl ketone or methyl ethyl ketone; and mixtures of solvents of this kind with one another. In some cases it is also possible for one of the reactants itself to act as solvent.
The reaction temperatures are usually between -5 and +200C, preferably between O and 100C; and the duration of the reaction is between a few minutes and several days, depending on the selected reaction temperature and the solvent. The reactions are performed as a rule under normal pressure or a slight excess pressure. The presence of a reaction catalyst, for example tetraalkylammonium chloride, potassium iodide and/or crown ether, can be of advantage.
The production process forms part of the invention.
The starting materials of the formulae II to VII are known, or can be produced by methods known per se.
Substituted acid halides of the formula II are obtainable for example by reaction of a compound of the formula VIII -~- ca3 HO~ -O-CH-COOCH3 ~- (VIII) li42~80 with a trifluoromethylpyridyl derivative IX
~g .3 \ ~ -Cl (IX).
There is firstly formed, wi~h the splitting-off of HCl, an intermediate of the formula X
~_.~ ~ ~ 1 3 3 \ ~ -O~ o-c~-cooca3 (X), the ester group of which can be saponified in the customary manner, for example in an alkaline medium, to an acid group, and subsequently converted, for example with a suitable halogenating agent, such as SOC12, into an acid halide of the formula II. The symbol X in the formulae IX and X has the meanings defined under the formula I.
Compounds of the formula X exhibit herbicidal activity.
Compound VIII is obtainable from hydroquinone and
2-chloropropionic acid methyl ester in the presence of a base.
Substituted trifluoromethylpyridyloxy-parahydroxyphenyl ethers of the formula IV can be produced according to the Belgian Patent Specification No. 862 325 and the German Offenlegungsschriften Nos. 2,847,662 and 2,732,846.
The compounds of the formula I aLways have an asymmetrical carbon atom C* in a position adjacent to the methyl group af the propionic acid radical.
Substituted trifluoromethylpyridyloxy-parahydroxyphenyl ethers of the formula IV can be produced according to the Belgian Patent Specification No. 862 325 and the German Offenlegungsschriften Nos. 2,847,662 and 2,732,846.
The compounds of the formula I aLways have an asymmetrical carbon atom C* in a position adjacent to the methyl group af the propionic acid radical.
3 \ ~~~~ o_C_Co~ ~ ~ L~ (I')-The active substances of the formula I normally occur on synthesis as racemic mixtures, and can be separated in the customary manner into their optical antipodes, for example by fractional crystallisation. Alternatively, the synthesis of an optically pure compound of the formula I is possible if, in producing the compound, an optically pure 2-halopropionic acid is used as starting material. The optical antipodes of I exhibit a varying biocidal activity, the D-form being herbicidally more effective.
Independently of the stated isomerism) unsymmetrically substituted (Rl ~`R2) active substances of the formula I
can occur in the syn or anti form.
Provided that no specific synthesis for the isolation of the pure isomers is performed, a product of the formula I is always obtained as a mixture of these possible isomeric forms.
It is already known that specific oxime esters of carboxylic acids can be used as herbicides (cp. the published European Patent Applications Nos. 2,246 and 3,114 or U.S. Patent Specification No. 4,200,587). The herbicidal effectiveness is however not always satisfactory, particularly against weeds which are difficult to control.
It has now been found that the trifluoromethylated novel pyridyloxy derivatives of the formula I according to the present invention surprisingly exhibit a herbicidal activity better than that of the cited compounds, and can be used as herbicides for pre-emergence application and for post-emergence application.
The active substances of the formul`a I according to the invention and the herbicidal compositions containing them as active ingredients are particularly applicable for selectively combating weeds difficult to control in crops -ll~Z180 ., of cultivated plants, especially in crops of cultivated dicotyledonous plants, such as soya-bean, and in all crops of leguminosae, cotton, sugar beet, sunflower, rape and further varieties of Brassica. The novel active substances can also be used to control wild grasses in perennial crops, such as grape-vines, in orchards (apples, pears, peaches, apricots, and so forth), in citrus crops, as well as in plantations of rubber trees and oil palms. The compounds according to the invention are thus compatible with many cultivated plants, and are very effective against wild grasses.
Furthermore, specific active substances according to the invention also have, when applied in suitable amounts, favourable growth-regulating effects (growth inhibition).
They inhibit in particular the growth of dicotyledonous plants. Examples of the profitable application of the compounds according to the invention are for example: the reduction of vegetative growth in the case of soya-bean plants and similar leguminosae, an effect which leads to an increase in the yields of these cultivated crops; the reduction of the undesirable growth of side shoots on tobacco plants, the leading shoots of which have been cut, an effect which promotes the formation of larger and better leaves; and the reduction of the growth of dicotyledonous plants, such as fruit trees, ornamental trees, shrubs and hedges, for the purpose of economising in the amount of cutting work.
The novel compounds of the present invention have negligible toxicity to warm-blooded animals, and application of the compounds presents no problems. The amount applied is in general between 0.005 and 5 kg of active substance per hectare, preferably between 0.05 and 2 kg of active substance per hectare.
., :~14Z180 As constituents of herbicidal compositions, the active substances of the formula I have, even in low applied amounts, an excellent herbicidal action with a high level of selectivity in crops of useful plants, particularly dicotyledonous plants, such as cotton, rape, soya-bean and sugar beet.
The compositions containing active substances of the formula I can be applied either before emergence to the sown cultivated areas or, preferably, after emergence as contact herbicides on the emerged crops.
An excellent herbicidal action is thus obtained in soya-bean crops with pre-emergence application of compositions containing an active substance of the formula I.
The present invention relates therefore also to herbicidal and/or growth-regulating compositions containing as active substance a compound of the formula 1, and to the production of these compositions, and to the use of the compositions or of the active substances for selectively combating weeds in crops of cultivated plants and/or for reducing vegetative plant growth.
The content of active substance in each commercial composition is between 0.1 and 95 per cent by weight, preferably between 1 and 80 per cent by weight. Applied concentrations can be diluted, depending on the problem presented, down to 0.001 per cent by weight.
The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of active substances of the general formula I
with suitable carriers and/or distributing agents, optionally with the addition of antifoaming agents, wetting agents, dispersing agents and/or solvents, all inert to the active substances. The active substances can be obtained and used in the following forms:
l~Z1~30 solid preparations: dusts, scattering agents, granules (coated granules, impre~nated granules and homogeneous granules);
ater-dispersible concentrates of active substance:
wettable powders, pastes, emulsions and emulsion concentrates; and liquid preParations: solutions.
The preferred form of preparation is the emulsion concentrate.
Other biocidal active substances or compositions can be added to the compositions according to the invention.
For broadening their sphere of activity, the novel compositions can thus contain, besides the stated compounds of the general formula I, for example: insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematocides, or further herbicides.
The Examples which follow serve to further illustrate the invention without limiting its scope. Temperature values are given in degrees Centigrade, and percentages and parts are by weight. E~cept where otherwise stated, the racemic mixture is meant when reference is made to 'an active substance of the formula I'.
Production ExamPles Example 1: Production of Cl C~3 CF3~ O-CH-~COON-C~
a-~4-(3-Chloro-5-trifluoromethyl-pyrLdyl-2-oxy)-phenoxy]-proeionic acid acetoxime ester a) Production of the intermediate:
~14Z~
/Cl _ C~
CF3~ .-0~ .-0-CH-C~OCX3 a-[4-(3-ChLoro-5-trifl~oromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid_methyl ester 53 g (0.27 mol) of a-(4-hydroxy-phenoxy)-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 +40C; there are subsequently added 2 g of benzyltriethylammonium chloride and 58.3 g (0.27 mol) of 2,3-dichloro-5-trif~uoromethylpyridine, and the reaction mixture is refluxed for 10 hours. Salt which has formed is filtered off, and the filtrate is concentrated by evaporation. The yield is 85.5 g (85% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy~-propionic acid methyl ester.
b) Production of a further intermediate: -cooa a-[4-(3-Chloro-5-trifluoromethYl-pyridyl-2-oxy)-phenoxy3-propionic acid 37.5 g of the ester produced according to a) are stirred in 120 ml of 2 N sodium hydroxide solution at +70C 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 is removed in vacuo to thus obtain 33 g (91.3% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid, m.p. 104-L06C.
1~42i~30 c) Production of the intermediate:
Cl CF ~ -0-~ O-C~-COCl a-[4-(3-Chloro-5-trifluoromethyl-pYridyl-2-oxy)-phenoxy]-propionic acid chloride 18.1 g (0.05 mol) of the acid produced according to b) and 15 ml of thionyl chloride are stirred at ~60C for 5 hours. Unreacted thionyl chloride is removed in vacuo, and the residue is subsequently taken up in toluene and evaporated to dryness. The yield is 19.8 g of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid chloride in the form of yellow oil.
d) Production of the final product:
11.8 g ~0.03 mol) of the acid chloride produced according to c) are dissolved in 40 ml of toluene, and at 0C is added dropwise a solution of 2.4 g (0.034 mol) of acetoxime and 4 g ~0.04 mol) of triethylamine.
The mixture is stirred for 2 hours at room temperature;
the salt which has precipitated is filtered off, and the filtrate is concentrated by evaporation. The residue is taken up in ethyl acetate/hexane (1:1), and filtered through silica gel. The yield is 9.2 g (73% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid acetoxime ester, melting point 59-62C
(compound No. 2).
The following compounds of the formula I can be produced in an analogous nner.
:
,~
;
~4Z1~30 Table 1: Compounds of the formula I
_ !~ ~ ~ 'c~n~C~I
2 ClC~3 ca3 m . p . 59-62C .
3 BrC~3 c~3
Independently of the stated isomerism) unsymmetrically substituted (Rl ~`R2) active substances of the formula I
can occur in the syn or anti form.
Provided that no specific synthesis for the isolation of the pure isomers is performed, a product of the formula I is always obtained as a mixture of these possible isomeric forms.
It is already known that specific oxime esters of carboxylic acids can be used as herbicides (cp. the published European Patent Applications Nos. 2,246 and 3,114 or U.S. Patent Specification No. 4,200,587). The herbicidal effectiveness is however not always satisfactory, particularly against weeds which are difficult to control.
It has now been found that the trifluoromethylated novel pyridyloxy derivatives of the formula I according to the present invention surprisingly exhibit a herbicidal activity better than that of the cited compounds, and can be used as herbicides for pre-emergence application and for post-emergence application.
The active substances of the formul`a I according to the invention and the herbicidal compositions containing them as active ingredients are particularly applicable for selectively combating weeds difficult to control in crops -ll~Z180 ., of cultivated plants, especially in crops of cultivated dicotyledonous plants, such as soya-bean, and in all crops of leguminosae, cotton, sugar beet, sunflower, rape and further varieties of Brassica. The novel active substances can also be used to control wild grasses in perennial crops, such as grape-vines, in orchards (apples, pears, peaches, apricots, and so forth), in citrus crops, as well as in plantations of rubber trees and oil palms. The compounds according to the invention are thus compatible with many cultivated plants, and are very effective against wild grasses.
Furthermore, specific active substances according to the invention also have, when applied in suitable amounts, favourable growth-regulating effects (growth inhibition).
They inhibit in particular the growth of dicotyledonous plants. Examples of the profitable application of the compounds according to the invention are for example: the reduction of vegetative growth in the case of soya-bean plants and similar leguminosae, an effect which leads to an increase in the yields of these cultivated crops; the reduction of the undesirable growth of side shoots on tobacco plants, the leading shoots of which have been cut, an effect which promotes the formation of larger and better leaves; and the reduction of the growth of dicotyledonous plants, such as fruit trees, ornamental trees, shrubs and hedges, for the purpose of economising in the amount of cutting work.
The novel compounds of the present invention have negligible toxicity to warm-blooded animals, and application of the compounds presents no problems. The amount applied is in general between 0.005 and 5 kg of active substance per hectare, preferably between 0.05 and 2 kg of active substance per hectare.
., :~14Z180 As constituents of herbicidal compositions, the active substances of the formula I have, even in low applied amounts, an excellent herbicidal action with a high level of selectivity in crops of useful plants, particularly dicotyledonous plants, such as cotton, rape, soya-bean and sugar beet.
The compositions containing active substances of the formula I can be applied either before emergence to the sown cultivated areas or, preferably, after emergence as contact herbicides on the emerged crops.
An excellent herbicidal action is thus obtained in soya-bean crops with pre-emergence application of compositions containing an active substance of the formula I.
The present invention relates therefore also to herbicidal and/or growth-regulating compositions containing as active substance a compound of the formula 1, and to the production of these compositions, and to the use of the compositions or of the active substances for selectively combating weeds in crops of cultivated plants and/or for reducing vegetative plant growth.
The content of active substance in each commercial composition is between 0.1 and 95 per cent by weight, preferably between 1 and 80 per cent by weight. Applied concentrations can be diluted, depending on the problem presented, down to 0.001 per cent by weight.
The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of active substances of the general formula I
with suitable carriers and/or distributing agents, optionally with the addition of antifoaming agents, wetting agents, dispersing agents and/or solvents, all inert to the active substances. The active substances can be obtained and used in the following forms:
l~Z1~30 solid preparations: dusts, scattering agents, granules (coated granules, impre~nated granules and homogeneous granules);
ater-dispersible concentrates of active substance:
wettable powders, pastes, emulsions and emulsion concentrates; and liquid preParations: solutions.
The preferred form of preparation is the emulsion concentrate.
Other biocidal active substances or compositions can be added to the compositions according to the invention.
For broadening their sphere of activity, the novel compositions can thus contain, besides the stated compounds of the general formula I, for example: insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematocides, or further herbicides.
The Examples which follow serve to further illustrate the invention without limiting its scope. Temperature values are given in degrees Centigrade, and percentages and parts are by weight. E~cept where otherwise stated, the racemic mixture is meant when reference is made to 'an active substance of the formula I'.
Production ExamPles Example 1: Production of Cl C~3 CF3~ O-CH-~COON-C~
a-~4-(3-Chloro-5-trifluoromethyl-pyrLdyl-2-oxy)-phenoxy]-proeionic acid acetoxime ester a) Production of the intermediate:
~14Z~
/Cl _ C~
CF3~ .-0~ .-0-CH-C~OCX3 a-[4-(3-ChLoro-5-trifl~oromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid_methyl ester 53 g (0.27 mol) of a-(4-hydroxy-phenoxy)-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 +40C; there are subsequently added 2 g of benzyltriethylammonium chloride and 58.3 g (0.27 mol) of 2,3-dichloro-5-trif~uoromethylpyridine, and the reaction mixture is refluxed for 10 hours. Salt which has formed is filtered off, and the filtrate is concentrated by evaporation. The yield is 85.5 g (85% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy~-propionic acid methyl ester.
b) Production of a further intermediate: -cooa a-[4-(3-Chloro-5-trifluoromethYl-pyridyl-2-oxy)-phenoxy3-propionic acid 37.5 g of the ester produced according to a) are stirred in 120 ml of 2 N sodium hydroxide solution at +70C 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 is removed in vacuo to thus obtain 33 g (91.3% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid, m.p. 104-L06C.
1~42i~30 c) Production of the intermediate:
Cl CF ~ -0-~ O-C~-COCl a-[4-(3-Chloro-5-trifluoromethyl-pYridyl-2-oxy)-phenoxy]-propionic acid chloride 18.1 g (0.05 mol) of the acid produced according to b) and 15 ml of thionyl chloride are stirred at ~60C for 5 hours. Unreacted thionyl chloride is removed in vacuo, and the residue is subsequently taken up in toluene and evaporated to dryness. The yield is 19.8 g of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid chloride in the form of yellow oil.
d) Production of the final product:
11.8 g ~0.03 mol) of the acid chloride produced according to c) are dissolved in 40 ml of toluene, and at 0C is added dropwise a solution of 2.4 g (0.034 mol) of acetoxime and 4 g ~0.04 mol) of triethylamine.
The mixture is stirred for 2 hours at room temperature;
the salt which has precipitated is filtered off, and the filtrate is concentrated by evaporation. The residue is taken up in ethyl acetate/hexane (1:1), and filtered through silica gel. The yield is 9.2 g (73% of theory) of a-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionic acid acetoxime ester, melting point 59-62C
(compound No. 2).
The following compounds of the formula I can be produced in an analogous nner.
:
,~
;
~4Z1~30 Table 1: Compounds of the formula I
_ !~ ~ ~ 'c~n~C~I
2 ClC~3 ca3 m . p . 59-62C .
3 BrC~3 c~3
4 Cl H C2H5 56 CNC~3H~ 3 ~D5 1.5250 8 cClC~3 C2~5 ~ 1.5220 9 Br(i) C3H7 (i) C3H7 .
l CclC~a C6~5 ~5 1.5620 12 ¦ Cl H i C6a4Cl (4) 13 I Cl (n) C3H7 ¦ (n) C3 7 14 ClCa3 I C6H5 Clca3 ll C6H4Cl (3) 16 BrCH3 '~ C6a5 17 Clca3 ll (n) C4a9 18 Clca3 l -ca-ca-ca3 19 Cl I Ca3 1 -CH=C (Ca3) 2 HH H I tert .C~Xg ~ 1.5165 22 HCa3 C2H5 ~ 1.5135 23 H C2H5 L _ _ ______~____ l . 24 Cl ! -(ca2)4- ~ 1.5320 Cl I -(CX2)5- ~ 1.5327 26 Cl - (CH2) 6 27 H -(Ca2) 4-~4Zl~O
_ .
Comp. No. ~ Rl R2 Physical . constants --_ 28 ~: C~3 C~3 29 F 3 C2~5 F C2~5 C2~s 31 Cl CH3 C(C~3)3 32 Cl 3 cH2c~(cH3)2 -Formulation Examples Example 2: Emulsion concentrates The following substances are used to produce emulsion concentrates a), b) and c) having concen~rations of active substance of 10%, 25% and 50%, respectively:
. a) b) c) active substance of the formula I 10% 25% 50%
calcium dodecylbenzenesulfonate 5% 3% 4%
castor oil polyethylene glycol ether 5% 7%
(36 mols of ethylene oxide) tributylphenoyL-polyethylene glycol - - 6%
ether (30 mols of ethylene oxide) mineral oil having a high content 10% - -of paraffin cyclohexanone - ~ 15%
xylene mixture 70% 65% 25%
Emulsions of any required concentration can be produced from such concentrates by dilution with- water.
The novel 4-pyridyloxy-phenoxy-propionic acids and their derivatives of the formula I, as well as compositions containing them, have an excellent selective-herbicidal action against weeds in the various crops of cultivated plants. Some of these compounds likewise have an action i~4Z180 regulating plant growth.
The novel active substances of the formula I are effective both with the pre-emergence and with the post-emergence forms of application, whereby the effect obtained with the pre-emergence application is excellent compared with that resuLting from the use of many known phenoxy-phenoxy herbicides.
The novel active substances are preferably formulated for example as 50% and i5% emulsifiable concentrates and, diluted with water, applied to the crops after emergence, or directly to the soil or incorporated with it before emergence of the crops.
The following test methods serve to demonstrate the suitability of the novel active substances for use as herbicides (pre-emergence) and as growth inhibitors:
ExamPle 3: Pre-emer~ence herbicidal action Immediately after sowing of the test plants in pots of 11 cm diameter in a greenhouse, the surface of the soil is treated with an aqueous suspension of the respective i active substance, obtained from a 25% emulsion concentrate.
Two different concentration series are used, corresponding to 1 and 0.5 kg of active substance per hectare. The pots are left in the greenhouse at 22-25C with 50-70%
relative humidity, and the test is evaluated after 3 weeks, , the results being assessed according to the following scale of ratings (9 ratings):
, 1 = plants have not germinated or have fully died off, 2-8 - intermedi~te stages of impairment of growth, 9 - plants unimpaired (as untreated control plants).
The test results are summarised in the Table which follows.
;
1~ 4 ~ D
,Compound No. 2 ~ 21 22 applied amounts 1 0.5 1 0.5 1 0.5 1 0.5 k~/hectare plant Avena fatua 2 2 1 2 7 9 3 9 ,Bromus tectorum 1 1 1 2 2 2 1 6 ~Lolium perenne 1 1 1 1 1 2 1 '1 Alopecurus 2 2 i 1 1 1 1 2 myosuroides Digitaria 1 1 l 1 1 2 1 2 sanguinalis Echinochloa 1 L
crus galli Sorghum halepense 1 Rottboellia 1 l 1 1 1 2 exaltata soya bean 8 8 9 9 9 9 9 9 sugar beet 9 9 9 9 9 9 9 9 cotton 9 9 9 9 9 9 9 9 ~_ ExamPle 4: Herbicidal action with application of the active substances after emer~ence of the plants (Post-emer~ence) Various cultivated plants and weeds are grown from seeds in pots in a greenhouse until they have reached the 4- to 6-leaf stage. The plants are then sprayed with an aqueous active-substance emulsion, the amount corresponding to 0.25 kg per hectare. The plants are subsequently kept under optimum conditions with regard to light, watering, temperature (22-25C) and relative humidity (50-70%). An evaluation of the test results is made 15 days after the treatment, the scale of ratings given in the foregoing being taken as a basis for assessment. The results are summarised in the following Table.
~ ~ 4 2 1~D
Compound No. ~ 2 8 21 22 plant Avena fatua 1 1 6 7 Bromus tectorum 2 2 3 4 Lolium perenne 1 1 3 3 Alopecurus myosuroides 1 1 4- 2 Digitaria sanguinalis 1 1 2 Echinochlora crus galli Sorghum halepense Rottboellia exaltata 1 1 5 2 soya bean 9 9 9 9 sugar beet 7 8 9 9 cotton 9 9 9 9 ExamPle_5: Increase in Y _ld of soYa beans Soya beans of the i'Hark" variety are sown in a soil/peat/
sand mixture (6:3:1) in plastics containers in a controlled-atmosphere chamber. As a result of optimum choice of temperature, illumination, supply of fertiliser and watering, the plants are able to develop during about 5 weeks to the ~ 5 - 6 trifoliate leaf-stage. The plants at this point of j time are sprayed with the aqueous spray liquor of the active substance until they are fully wetted. The active-substance concentrations are 10, 50, 100 and 500 ppm of active sub-stance. An evaluation is-made about 5 weeks after treatment.
The compound No. 2 at concentrations of 50 and 500 ppm results in a slight reduction in the length of growth, whilst the pod setting increases by about 4 - 7% compared with that of control plants which have not been treated.
l CclC~a C6~5 ~5 1.5620 12 ¦ Cl H i C6a4Cl (4) 13 I Cl (n) C3H7 ¦ (n) C3 7 14 ClCa3 I C6H5 Clca3 ll C6H4Cl (3) 16 BrCH3 '~ C6a5 17 Clca3 ll (n) C4a9 18 Clca3 l -ca-ca-ca3 19 Cl I Ca3 1 -CH=C (Ca3) 2 HH H I tert .C~Xg ~ 1.5165 22 HCa3 C2H5 ~ 1.5135 23 H C2H5 L _ _ ______~____ l . 24 Cl ! -(ca2)4- ~ 1.5320 Cl I -(CX2)5- ~ 1.5327 26 Cl - (CH2) 6 27 H -(Ca2) 4-~4Zl~O
_ .
Comp. No. ~ Rl R2 Physical . constants --_ 28 ~: C~3 C~3 29 F 3 C2~5 F C2~5 C2~s 31 Cl CH3 C(C~3)3 32 Cl 3 cH2c~(cH3)2 -Formulation Examples Example 2: Emulsion concentrates The following substances are used to produce emulsion concentrates a), b) and c) having concen~rations of active substance of 10%, 25% and 50%, respectively:
. a) b) c) active substance of the formula I 10% 25% 50%
calcium dodecylbenzenesulfonate 5% 3% 4%
castor oil polyethylene glycol ether 5% 7%
(36 mols of ethylene oxide) tributylphenoyL-polyethylene glycol - - 6%
ether (30 mols of ethylene oxide) mineral oil having a high content 10% - -of paraffin cyclohexanone - ~ 15%
xylene mixture 70% 65% 25%
Emulsions of any required concentration can be produced from such concentrates by dilution with- water.
The novel 4-pyridyloxy-phenoxy-propionic acids and their derivatives of the formula I, as well as compositions containing them, have an excellent selective-herbicidal action against weeds in the various crops of cultivated plants. Some of these compounds likewise have an action i~4Z180 regulating plant growth.
The novel active substances of the formula I are effective both with the pre-emergence and with the post-emergence forms of application, whereby the effect obtained with the pre-emergence application is excellent compared with that resuLting from the use of many known phenoxy-phenoxy herbicides.
The novel active substances are preferably formulated for example as 50% and i5% emulsifiable concentrates and, diluted with water, applied to the crops after emergence, or directly to the soil or incorporated with it before emergence of the crops.
The following test methods serve to demonstrate the suitability of the novel active substances for use as herbicides (pre-emergence) and as growth inhibitors:
ExamPle 3: Pre-emer~ence herbicidal action Immediately after sowing of the test plants in pots of 11 cm diameter in a greenhouse, the surface of the soil is treated with an aqueous suspension of the respective i active substance, obtained from a 25% emulsion concentrate.
Two different concentration series are used, corresponding to 1 and 0.5 kg of active substance per hectare. The pots are left in the greenhouse at 22-25C with 50-70%
relative humidity, and the test is evaluated after 3 weeks, , the results being assessed according to the following scale of ratings (9 ratings):
, 1 = plants have not germinated or have fully died off, 2-8 - intermedi~te stages of impairment of growth, 9 - plants unimpaired (as untreated control plants).
The test results are summarised in the Table which follows.
;
1~ 4 ~ D
,Compound No. 2 ~ 21 22 applied amounts 1 0.5 1 0.5 1 0.5 1 0.5 k~/hectare plant Avena fatua 2 2 1 2 7 9 3 9 ,Bromus tectorum 1 1 1 2 2 2 1 6 ~Lolium perenne 1 1 1 1 1 2 1 '1 Alopecurus 2 2 i 1 1 1 1 2 myosuroides Digitaria 1 1 l 1 1 2 1 2 sanguinalis Echinochloa 1 L
crus galli Sorghum halepense 1 Rottboellia 1 l 1 1 1 2 exaltata soya bean 8 8 9 9 9 9 9 9 sugar beet 9 9 9 9 9 9 9 9 cotton 9 9 9 9 9 9 9 9 ~_ ExamPle 4: Herbicidal action with application of the active substances after emer~ence of the plants (Post-emer~ence) Various cultivated plants and weeds are grown from seeds in pots in a greenhouse until they have reached the 4- to 6-leaf stage. The plants are then sprayed with an aqueous active-substance emulsion, the amount corresponding to 0.25 kg per hectare. The plants are subsequently kept under optimum conditions with regard to light, watering, temperature (22-25C) and relative humidity (50-70%). An evaluation of the test results is made 15 days after the treatment, the scale of ratings given in the foregoing being taken as a basis for assessment. The results are summarised in the following Table.
~ ~ 4 2 1~D
Compound No. ~ 2 8 21 22 plant Avena fatua 1 1 6 7 Bromus tectorum 2 2 3 4 Lolium perenne 1 1 3 3 Alopecurus myosuroides 1 1 4- 2 Digitaria sanguinalis 1 1 2 Echinochlora crus galli Sorghum halepense Rottboellia exaltata 1 1 5 2 soya bean 9 9 9 9 sugar beet 7 8 9 9 cotton 9 9 9 9 ExamPle_5: Increase in Y _ld of soYa beans Soya beans of the i'Hark" variety are sown in a soil/peat/
sand mixture (6:3:1) in plastics containers in a controlled-atmosphere chamber. As a result of optimum choice of temperature, illumination, supply of fertiliser and watering, the plants are able to develop during about 5 weeks to the ~ 5 - 6 trifoliate leaf-stage. The plants at this point of j time are sprayed with the aqueous spray liquor of the active substance until they are fully wetted. The active-substance concentrations are 10, 50, 100 and 500 ppm of active sub-stance. An evaluation is-made about 5 weeks after treatment.
The compound No. 2 at concentrations of 50 and 500 ppm results in a slight reduction in the length of growth, whilst the pod setting increases by about 4 - 7% compared with that of control plants which have not been treated.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formuIa I
(I) wherein X is hydrogen, halogen or pseudo halogen, R1 is hydrogen or a C1-C6-alkyl or phenyl group each of which is unsubstituted or substituted by halogen, hydroxyl or C1-C3-alkoxy, R2 is a C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or phenyl group, each of which is unsubstituted or sub-stituted by halogen, hydroxyl or C1-C3-alkoxy, or R1 and R2 together form a tetramethylene, pentamethylene or hexamethylene bridge, each of which is unsub-stituted or substituted by C1-C3-alkyl.
(I) wherein X is hydrogen, halogen or pseudo halogen, R1 is hydrogen or a C1-C6-alkyl or phenyl group each of which is unsubstituted or substituted by halogen, hydroxyl or C1-C3-alkoxy, R2 is a C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or phenyl group, each of which is unsubstituted or sub-stituted by halogen, hydroxyl or C1-C3-alkoxy, or R1 and R2 together form a tetramethylene, pentamethylene or hexamethylene bridge, each of which is unsub-stituted or substituted by C1-C3-alkyl.
2. A compound of the formula I according to Claim 1, wherein X is chlorine or bromine, and R1 and R2 have the meanings defined under the formula I.
3. A compound of the formula I according to Claim 1, wherein X is hydrogen, and R1 and R2 have the meanings defined under the formula I.
4. A compound of the formula I according to Claim 1, wherein X is chlorine, and R1 and R2 independently of one another are each C1-C3-alkyl.
5. .alpha.-[4-(3-Chloro-5-trifluoromethyl-pyridyl-2-oxy)-phen-oxy]-propionic acid acetoxime ester, according to Claim 1.
6. .alpha.-[4-(3-Chloro-5-trifluoromethyl-pyridyl-2-oxy)-phen-oxy]-propionic acid methyl ethyl ketoxime ester, according to Claim 1.
7. .alpha.-[4-(3-Chloro-5-trifluoromethyl-pyridyl-2-oxy)-phen-oxy]-propionic acid diethyl ketoxime ester, according to Claim 1.
8. A process for producing a compound of the formula I, Claim 1, which process comprises reacting in an inert organic solvent, optionally in the presence of an acid-binding agent, a) a substituted acid halide of the formula II
(II) with an oxime of the formula III
(III), b) a compound of the formula IV
(IV), with an .alpha.-halopropionic acid oxime ester of the formula V
(V) or c) a compound of the formula VI
(V) with a lactic acid oxime ester of the formula VII
(VII) wherein in formulae II-VII R1, R2 and X have the meanings defined in Claim 1, Hal is a halogen atom and M is hydrogen or an alkali metal cation or alkaline-earth metal cation.
(II) with an oxime of the formula III
(III), b) a compound of the formula IV
(IV), with an .alpha.-halopropionic acid oxime ester of the formula V
(V) or c) a compound of the formula VI
(V) with a lactic acid oxime ester of the formula VII
(VII) wherein in formulae II-VII R1, R2 and X have the meanings defined in Claim 1, Hal is a halogen atom and M is hydrogen or an alkali metal cation or alkaline-earth metal cation.
9. A method of selectivity combating weeds in crops of cultivated plants which method comprises applying thereto or to the locus thereof a herbicidally effective amount of a pyridyloxy-phenoxy-alkanecarboxylic acid derivative of the formula I according to Claim 1, or of a composition containing it.
10. A method of selectively combating weeds in cultivated crops of soya-bean and sugar beet, which method comprises applying thereto or to the locus thereof a herbicidally effective amount of a pyridyloxy-phenoxy-propionic acid derivative of the formula I, Claim 1, or of a composition containing it.
11. A method of increasing the yields in cultivated crops of soya-bean, which method comprises applying thereto or to the locus thereof an effective amount of a pyridyloxy-phenoxy-propionic acid derivative of the formula I, Claim 1, or of a composition containing it.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH769980 | 1980-10-15 | ||
| CH7699/80-0 | 1980-10-15 | ||
| CH5720/81-5 | 1981-09-04 | ||
| CH572081 | 1981-09-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142180A true CA1142180A (en) | 1983-03-01 |
Family
ID=25698270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000387754A Expired CA1142180A (en) | 1980-10-15 | 1981-10-13 | .alpha.-(PYRIDYL-2-OXY-PHENOXY)-PROPIONIC ACID DERIVATIVES, PROCESSES FOR PRODUCING THEM, AND THEIR USE AS HERBICIDES AND/OR AS REGULATORS OF PLANT GROWTH |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0050097B1 (en) |
| AR (1) | AR231280A1 (en) |
| AU (1) | AU549804B2 (en) |
| BR (1) | BR8106635A (en) |
| CA (1) | CA1142180A (en) |
| DD (1) | DD202373A5 (en) |
| DE (1) | DE3167651D1 (en) |
| ES (1) | ES8301921A1 (en) |
| IL (1) | IL64037A (en) |
| NZ (1) | NZ198641A (en) |
| PH (1) | PH17279A (en) |
| RO (1) | RO82503A (en) |
| TR (1) | TR21448A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3170423D1 (en) * | 1980-11-26 | 1985-06-13 | Hoffmann La Roche | Oxime esters, processes for their preparation, their use and compositions containing these esters |
| US4505743A (en) * | 1981-12-31 | 1985-03-19 | Ciba-Geigy Corporation | α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity |
| IL68822A (en) * | 1982-06-18 | 1990-07-12 | Dow Chemical Co | Pyridyl(oxy/thio)phenoxy compounds,herbicidal compositions and methods of using them |
| US4480102A (en) * | 1982-07-23 | 1984-10-30 | The Dow Chemical Company | 2,3-Difluoro-5-(trifluoromethyl)pyridine and methods of making and using the same |
| HU208311B (en) * | 1989-11-02 | 1993-09-28 | Alkaloida Vegyeszeti Gyar | Resolving process for producing enantiomers of 2-/4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy/-propanoic acid |
| CN107176950B (en) * | 2017-06-01 | 2019-12-31 | 赣州市正畅塑胶有限公司 | Aryloxy phenoxy propionate compound and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0028870B1 (en) * | 1977-08-12 | 1988-03-16 | Imperial Chemical Industries Plc | Phenoxypyridine compound |
| US4200587A (en) * | 1977-11-28 | 1980-04-29 | Hoffmann-La Roche Inc. | 2-[P-(p-Substituted phenoxy)phenoxy]propionyl oximes |
| DE2961917D1 (en) * | 1978-01-18 | 1982-03-11 | Ciba Geigy Ag | Herbicidal active unsaturated esters of 4- (3',5'-dihalogenpyridyl-(2')-oxy)-alpha-phenoxy propionic acids, process for their preparation, herbicidal compositions containing them and their use |
-
1981
- 1981-10-06 PH PH26325A patent/PH17279A/en unknown
- 1981-10-09 DE DE8181810405T patent/DE3167651D1/en not_active Expired
- 1981-10-09 EP EP81810405A patent/EP0050097B1/en not_active Expired
- 1981-10-12 IL IL64037A patent/IL64037A/en unknown
- 1981-10-13 RO RO81105547A patent/RO82503A/en unknown
- 1981-10-13 AR AR287079A patent/AR231280A1/en active
- 1981-10-13 CA CA000387754A patent/CA1142180A/en not_active Expired
- 1981-10-13 DD DD81234045A patent/DD202373A5/en unknown
- 1981-10-14 NZ NZ198641A patent/NZ198641A/en unknown
- 1981-10-14 ES ES506235A patent/ES8301921A1/en not_active Expired
- 1981-10-14 BR BR8106635A patent/BR8106635A/en unknown
- 1981-10-14 TR TR21448A patent/TR21448A/en unknown
- 1981-10-15 AU AU76386/81A patent/AU549804B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| TR21448A (en) | 1984-06-04 |
| ES506235A0 (en) | 1983-01-01 |
| AU7638681A (en) | 1982-04-22 |
| RO82503B (en) | 1983-08-30 |
| PH17279A (en) | 1984-07-06 |
| DD202373A5 (en) | 1983-09-14 |
| IL64037A0 (en) | 1982-01-31 |
| BR8106635A (en) | 1982-06-29 |
| AR231280A1 (en) | 1984-10-31 |
| DE3167651D1 (en) | 1985-01-17 |
| NZ198641A (en) | 1984-04-27 |
| IL64037A (en) | 1986-03-31 |
| AU549804B2 (en) | 1986-02-13 |
| EP0050097A1 (en) | 1982-04-21 |
| RO82503A (en) | 1983-09-26 |
| ES8301921A1 (en) | 1983-01-01 |
| EP0050097B1 (en) | 1984-12-05 |
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