IE902357A1 - New substituted pyrimidinyloxy(thio)-and¹triazinyloxy(thio)acrylic acid derivatives, processes for¹their preparation and their use as herbicides, fungicides¹and plant growth regulators - Google Patents

New substituted pyrimidinyloxy(thio)-and¹triazinyloxy(thio)acrylic acid derivatives, processes for¹their preparation and their use as herbicides, fungicides¹and plant growth regulators

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Publication number
IE902357A1
IE902357A1 IE235790A IE235790A IE902357A1 IE 902357 A1 IE902357 A1 IE 902357A1 IE 235790 A IE235790 A IE 235790A IE 235790 A IE235790 A IE 235790A IE 902357 A1 IE902357 A1 IE 902357A1
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general formula
alkyl
compound
thio
alkylamino
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IE235790A
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Schering Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/38—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Abstract

The invention relates to novel substituted pyrimidinyloxy(thio)- and triazinyloxy(thio)acrylic acid derivatives of the general formula I in which A, G, R<1>, R<2>, R<3>, X and Y have the meanings given in the description, to processes for their preparation, and to their use as agents with herbicidal, fungicidal and plant-growth-regulating activity.

Description

This invention relates to new substituted pyrimidinyloxy(thio)- and triazinyloxy(thio)acrylic acid derivatives, processes for their preparation and their use as herbicides, fungicides and plant growth regulators.
It is known that pyrimidine derivatives possess herbicidal activity (EP 223 406, 249 707, 249 708, 287 072 and 287 079). However, the herbicidal activity of these known compounds is often insufficient or selectivity problems are seen in important crops.
The object of the present invention is to make new compounds that do not have these disadvantages and have improved biological properties over the known compounds.
It has now been found that substituted pyrimidinyloxy(thio)- and 15 triazinyloxy(thio)acrylic acid derivatives of general formula I in which A is one of the groups A - 1 to A - 6 of general formula A - 3 R4 x\ A-4 A - 5 A - 6 a C^-C^-alkyl, C2~C1 θ-alkenyl or Cg-C, θ-alkynyl group (each of which is optionally substituted by one or more of the same or different C^-C^-alkoxy, C^C^-alkylthio, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, nitro, trifluoromethyl, halogen or phenyl), or a C3-C8-cycloalkyl or C4-C8~cycloalkenyl group (each of which is optionally substituted by one or more of the same or different C1-C4~alkyl, C1-C4~alkoxy, C1-C4-alkylthio, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, nitro, trifluoromethyl, halogen or phenyl); D is oxygen, sulphur or the group -NR9-; G is hydrogen or (^-Cg-alkyl; R1 is hydrogen, C1-C4~alkyl or benzyl; R2 and R3, which may be the same or different, are C1~C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino, di-C1-C4-alkylamino or halogen; R4, R5, R6, R7 and R8, which may be the same or different, are hydrogen, C^-C^-alkyl, C^-C^-alkoxy, amino, di-C^-C^-alkylamino, nitro, halogen, trifluoromethyl or phenyl; R9 is hydrogen, C1~C4-alkyl or phenyl; X is oxygen or sulphur; and Y is methine or nitrogen, as well as their alkali metal, alkaline earth metal and organic ammonium salts, and their E- and Z-isomers, show interesting herbicidal, fungicidal and plant growth regulant activity.
The expression halogen means fluorine, chlorine, bromine and iodine By the term alkali metal is meant lithium, sodium or potassium and by the term alkaline earth metal is meant calcium, strontium or barium.
The compounds of the invention of general formula I can be prepared for example by reacting a compound of general formula II / \ 1 X COOR (II) in which R1, R2 and R3, X and Y have the meanings given under general formula I, with a compound of general formula III in which A and G have the meanings given under general formula I, in a suitable solvent in the presence of a suitable base, and if desired a compound of general formula I in which R1 is hydrogen, C.,-C4-alkyl or benzyl, so obtained, is reacted with an alkali metal base, an alkaline earth metal base or an organic ammonium base, in a suitable polar solvent, to give a compound of general formula I in which R1 is an alkali metal atom, one equivalent of an alkaline earth metal atom or an organic ammonium group, and/or if desired, a compound of formula I in which R1 is C1-C4~alkyl, benzyl or an alkali metal atom, one equivalent of an alkaline earth metal atom or an organic ammonium group, is reacted with a suitable acid in a suitable solvent to give a compound of general formula I in which R1 is hydrogen.
The individual process variants are preferably carried out in the presence of a diluent. For this, a solvent which is inert to the reactants is used.
Suitable solvents include water, aliphatic, alicyclic and aromatic hydrocarbons, that can be optionally chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; ketones, such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol and ethylene glycol, esters, such as for example ethyl acetate and amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, sulphones and sulphoxides, such as for example dimethyl sulphoxide, and bases, such as for example pyridine.
The presence of a catalyst can be an advantage. Suitable catalysts include potassium iodide and onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds as well as sulphonium compounds. Also suitable are polyglycol ethers, especially cyclic ethers, such as 18-crown-6, and tertiary amines, such as for example tributylamine. Preferred compounds are quaternary ammonium compounds, such as for example benzyltriethylammonium chloride and tetrabutylammonium bromide.
The reactions can be carried out under atmospheric pressure but if desired higher or lower pressures can be used.
The main process variant is preferably carried out in an aprotic solvent such as benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, dimethylformamide or dimethyl sulphoxide.
Bases that can be used include sodium hydride, potassium tert-butylate or lithium diisopropylamide.
The reactions are suitably carried out between -78°C and the boiling point of the particular solvent or solvent mixture.
The reaction usually takes 5 minutes to 48 hours, preferably 0.5 to 24 hours.
Compounds of general formula II are described in the literature or can be prepared by methods analogous to those described in the literature. (Khim.-Farm. Zh. 16 (8), 931-4 [1982]; Ukr. Khim. Zh. (Russ. Ed) 49 (11), 1205-8 [1983]; Fizol. Akt. Veshchestva 18. 75-9 [1986]; and USSR Patent 791746).
For the optional subsequent processes there is preferably used as a solvent an alcohol, such as ethanol, propanol or isopropanol, a ketone, such as acetone or methyl ethyl ketone, dimethylformamide or dimethyl sulphoxide, water or solvent/water mixtures.
Alkaline metal bases, alkaline earth metal bases or organic ammonium bases that can be used include for example, carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, metal hydroxides, such as sodium hydroxide, potassium hydroxide, barium hydroxide or strontium hydroxide and as organic ammonium bases, ammonium derivatives, alkylamines (primary amines), dialkylamines (secondary amines) or trialkylamines (tertiary amines).
Examples of acids are hydrochloric or sulphuric acid.
The reaction temperature lies between room temperature and the boiling point of the particular solvent. The reaction time lies between 0.5 to 48 hours. When converting an ester in which R1 is benzyl to the free acid a catalytic reduction (hydrogenation) can also be used.
The compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced pressure, by precipitation with water or by extraction.
A higher level of purity can be achieved as a rule by column chromatography as well as by fractional distillation or crystallisation.
The compounds of the invention are, as a rule, colourless and odourless liquids or crystals that are soluble in water, slightly soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxane, nitriles, such as acetonitrile, alcohols, such as methanol and ethanol, amides, such as dimethylformamide, and sulphoxides, such as dimethyl sulphoxide.
The compounds of the invention show a good herbicidal activity in broad leaved weeds and grasses. A selective use in various crops is possible, for example in such as rape, beets, soya beans, cotton, rice, barley, wheat and other cereals. Individual active substances are particularly suitable as selective herbicides in beet, cotton, soya and cereals. However the compounds can be used for control of weeds in permanent crops, such as for example forestry, ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations and for the selective control of weeds in annual crops.
The compounds of the invention can used for example against the following plant species: Dicotyledonous weeds of the species Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.
Monocotyledonous weeds of the species Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ischaemum and Apera.
The rates of use vary depending on the manner of pre- and postemergent use between 0.001 and 5 kg/ha.
The compounds of the invention can also be used as defoliants, desiccants and as total herbicides. They also influence plant growth and can thus be used to influence plant growth of crops. Some compounds also show fungicidal activity.
The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for the treatment. When it is desired to broaden the spectrum of activity, other herbicides can also be added. Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 38, No.3 (1989) under the heading Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts.
An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.
The designated active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.
Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil fractions and plant oils.
Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ethers, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.
The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.
The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 1/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.
Formulations can be prepared, for example, from the following ingredients.
A) Wettable Powder 1) 25 percent by weight active ingredient 60 percent by weight kaolin percent by weight silicic acid 5 percent by weight of a mixture of calcium lignosulphonate and the sodium salt of N-methyl-N-oleyltaurine 2) 40 percent by weight active ingredient percent by weight bentonite 25 percent by weight colloidal silicic acid 10 percent by weight of a mixture of calcium lignosulphonate and alkylphenyl polyglycol ether B) Paste percent by weight active ingredient 5 percent by weight sodium aluminium silicate percent by weight cetyl polyglycol ether with 8 mol of ethylene oxide percent by weight spindle oil percent by weight polyethylene glycol 23 percent by weight water C) Emulsifiable Concentrate percent by weight active ingredient percent by weight cyclohexanone 55 percent by weight xylene percent by weight of a mixture of calcium dodecylbenzenesulphonate and nonylphenolpolyoxyethylene.
The following Examples illustrate the preparation of compounds of the invention.
Example 1 Methyl 2-(4,6-dimethoxy-2-pyrimidinylthio)-3-phenylacrylate 2.8 g (28.7 mmol) Diisopropylamine was dissolved in 80 ml tetrahydrofuran under nitrogen and treated with 11.5 ml (28.7 mmol) 2.5 M n-butyllithium in hexane at a temperature between -78 and -50*C.
The mixture was stirred for 10 minutes and then a solution of 7 g (28.7 mmol) methyl 2-(4,6-dimethoxy-2-pyrimidinylthio)acetate in 80 ml tetrahydrofuran was added to the reaction mixture and the mixture then stirred for 20 minutes. 2.8 g (28.7 mmol) Benzaldehyde was added, dropwise, to the solution. The reaction mixture was slowly allowed to reach room temperature, with stirring, and then stirred for 16 hours. The precipitate was treated with 500 ml water and extracted with ethyl acetate. The ethyl acetate phase, after drying over magnesium sulphate, was evaporated and then purified by medium pressure chromatography using hexane/ethyl acetate as eluent.
Yield: 6.1 g = 63.9% of theory r^20: 1.5926 Preparation of the Starting Material Methyl 2-(4,6-dimethoxy-2-pyrimidinylthio)acetate g (230 mmol) Methyl thioglycolate was dissolved in 250 ml dimethylformamide and treated with 16.3 g (115 mmol) potassium carbonate.
After 20 minutes stirring at room temperature, 50 g (2.3 mmol) 4,6-dimethoxy-2-methylsulphonylpyrimidine was added and the mixture heated for 3 hours at 90 °C. The reaction mixture was then poured into water and extracted with ethyl acetate. The organic phase was washed with water and dried over magnesium sulphate. The solvent was distilled and the resulting crude product was recrystallised from diisopropyl ether.
Yield: 44.6 g = 79.4% of theory mp: 67-69 °C Example 2 2-(4,6-dimethoxy-2-pyrimidinylthio)-3-phenylacrylic acid 0.5 g (1.5 mmol) Methyl 2-(4,6-dimethoxy-2-pyrimidinylthio)3-phenylacrylate and 95 mg (1.7 mmol) potassium hydroxide were added to a mixture of 5 ml water and 5 ml ethanol and the mixture heated at 50°C for 8 hours. It was then diluted with about 100 ml water and extracted with ethyl acetate. The aqueous phase was acidified with 10% hydrochloric acid until it was pH 2 and extracted with ethyl acetate. After drying the ethyl acetate phase over magnesium sulphate, the solvent was evaporated under reduced pressure and the residue recrystallised from diisopropyl ether.
Yield: 0.25 g = 52% of theory mp: 162-164°C In a similar manner, the following compounds of formula I were prepared: Example No. A 6 R1 R2 R3 X Y Physical constant 3 2-Furyl HCH3 och3 och3 s CH mp. : 106-108°C 4 2-Furyl H H och3 och3 s CH mp. : 133-136°C 5 2-Thienyl HCH3 och3 och3 s CH mp. : 106-109°C 6 2-Thienyl H H och3 och3 s CH mp. : 176°C (dec.) 7 2-Nitro- phenyl HCH3 och3 och3 s CH mp. : 162-164°C 8 2-Nitro- phenyl H H och3 och3 s CH mp. : 215°C (dec.I 9 1-Naphthyl HCH3 och3 och3 s CH mp. : 95-96°C 10 2-Naphthyl HCH3 ocn30CH3 s CH mp. : 98-99°C 11 ch3ch=ch- HCH30CH3 och3 s CH mp. : 40-42°C 12CH3CK2- HCH3 0CH3 och3 s CH 20 % : 1,5431 13 2-Naphthyl H H och3 och3 s CH mp. : 159-161°C 14 1-Naphthyl H H och3 och3 s CH mp. : 180-182°C 15 h2c=ch- HCK3 och3 och3 s CH mp. : 40-43°C 16 HCH3 ocn30CH3 s CH 20 % : 1.5381 17 Phenyl H och3 N ( CH3 2 S N mp. : 107-108°C 18 (ch3)2ch- HCH3 0Ch30CH3 s CH mp. 20 : 50-53°C 19 2-Phenylethyl HCH3 ocn30CH3 s CHno : 1.5711 20 Phenyl H H och3 N ( CH3 2 S N mp. : 156-158°C 21ch3ch2ch2- H H och3 och3 s CH mp. : 108-111°C 22 (CH3)2CH- H H °CH3 och3 s CH mp. : 100-103°C 23CH3- HCH3 och3 och3 0 CH mp. : 70-71°C 24CH3- H H 0CH3 och3 0 CH Rf: 0,26 (ethyl acetate) 25 3-Thienyl HCH3 °ch3 och3 s CH mp. : 81°C 26 3-Furyl HCH30CH30CH3 s CH mp. : 115°C 27 N-Methyl- 2-pyrrolyl HCH30CH30CH3 s CH mp. : 109°C Example No. A 6 R1 R2 R3 X Y Physical constant 28 4-Nitro- phenyl HCH3 och30CH3 s CH mp. : 148°C 29 2-Pyrrolyl HCH30CH30CH3 s CH mp. : 137°C 30 2-Pyridyl HCH3 och3 och3 s CH mp. : 110°C 31 3-Pyridyl HCH3 och3 0Ch3 s CH mp. : 100°C 32 2-Chloro- phenyl HCH3 oCh30CH3 s CH mp. : 100°C 33 3-Chloro- phenyl HCH3 OCH3 och3 s CH mp. : 110°C 34 2-Methoxy- phenyl HCH3 OCH3 0CH3 s CH mp. : 110°C 35 2-Methyl- phenyl HCH30CH30CH3 s CH mp. : 94°C 36 3-Pyridyl H H och30CH3 s CH mp. : 190°C (dec.) (x HCl) 37 3-Methyl- phenyl HCH3 oCh3 och3 s CH mp. : 90°C 38 4-Fluoro- phenyl HCH3 oCh3 och3 s CH 20 nD : 1.5618 39 3-Chloro- phenyl H H0CH3 och3 s CH mp. : 147°C 40 4-Methyl- phenyl HCH30CH3 och3 s CH mp. : 95°C 4 1 2-Methyl- phenyl H H och30CH3 s CH mp. : 200-210°C (dec.I 42 3-Methyl- phenyl H H0CH3 och3 s CH mp. : 212°C (dec .) 43 2-Fluorophenyl HCH3 och3 0CH3 s CH mp. : 85°C 44 2-Fluoro- phenyl H H och3 och3 s CH mp. : 1 82°C (dec .) 45 4-Methoxy- H H0CH3 och3 s CH mp. : 195°C (dec.) phenyl Example No. A 6 R1 R2 R3 X Y Physical constant 46 4-Fluoro- phenyl H H och3 och3 s CH mp.: 188°C ( 47 4-Methoxy- phenyl HCH3 och3 och3 s CH mp.: 80°C 48 4-Pyridyl HCH3och3 och3 s CH mp.: 81 °C 49 Cyclohexyl HCH3 °ch3 och3 s CH mp.: 76-81°C 20 50 ich3i3c- H ch3 °ch3 och3 s CH n‘ : 1.5308 51 2-Phenyl- ethyl H H och3 och3 s CH 0 (ethyl a 52 Phenyl HCH3CH3CH3 s CH 20 πθ : 1.5978 53 Phenyl HCH2CH3 °ch3 och3 s CH ηθ : 1.5974 54 Phenyl HCH3 °ch3 och3 s N 55 Phenyl H H0CH3 och3 s N 56 Phenyl HCH30CH3 och3 0 CH 57 Phenyl H H och3 och3 0 CH 58 Phenyl H ch3 och3 0CH3 0 N 59 Phenyl H H0CH3 och3 0 N The following examples illustrate the possibilities for use of the compounds of the invention.
Example A In a greenhouse, the noted plant species were treated post-emergently 5 with the noted compounds of the invention, at a rate of 0.1 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed a high crop selectivity in wheat and maize with excellent activity against the weeds. The comparison material did not show similar high efficacy.
In the following table: = no damage 1 = 1 - 24% damage 2 = 25 - 74% damage 3=75— 89% damage 4 = 90 - 100% damage TRZAX - Triticum aestivum ZEAMX = Zea mays GALAP = Galium aparine SEBEX - Sesbania exaltata SOLSS = Solanum sp.
Compounds of invention T Z R E Z A A M X_X G S S A E 0 L B L AES P X S Example 1 0 3 3 3 Untreated Comparison Methyl 2-(4-iso.propyl- 0 q 4-methyl-5-oxo-2-imidazolin2-yl)-4(5)-methylbenzoate Example B In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invention, at a rate of 0.1 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the soil as emulsions or suspensions in 500 litres water/ha. Three weeks after the treatment, the compounds of the invention showed a high crop selectivity in wheat and maize with excellent activity against the weeds. The comparison material did not show similar high efficacy.
In the following table: = no damage = 1 - 24% damage = 25 - 74% damage = 75 - 89% damage 4 = 90 - 100% damage TRZAX - Triticum aestivum VERPE = Veronica persica VIOSS = Viola sp τ V V R Ε I Ζ R 0 Compounds of A invention X P S t_S. Example 13 0 Example 25 0 3 3 3 5 Untreated 0 0 0 Comparison Methyl 2-(4-isopropyl- o 4-methyl-5-oxo-2-imidazolin2-yl)-4(5)-methylbenzoate 1 2

Claims (8)

1. Substituted pyrimidinyloxy(thio)- and triazinyloxy(thio)acrylic acid derivatives of general formula I in which 5 A is one of the groups A - 1 to A - 6 of general formula A - 4 A - 5 A - 6 a C^C^-alkyl, C 2 ~C 10 -alkenyl or C 2 -C 10 ~alkynyl group (each of which is optionally substituted by one or more of the same or different C 1 -C 4 ~alkoxy, C 1 ~C 4 -alkylthio, amino, C 1 -C 4 -alkylamino, di-C 1 ~C 4 -alkylamino, nitro, trifluoromethyl, halogen or phenyl), 10 or a Cj-Cg-cycloalkyl or C 4 ~Cg-cycloalkenyl group (each of which is optionally substituted by one or more of the same or different C 1 -C 4 -alkyl, C 1 ~C 4 -alkoxy, C 1 -C 4 -alkylthio, amino, C 1 -C 4 -alkylamino, di-C.pC^-alkylamino, nitro, trifluoromethyl,» halogen or phenyl); D is oxygen, sulphur or the group -NR 9 -; G is hydrogen or C^Cg-alkyl; 5 R 1 is hydrogen, C^C^alkyl or benzyl; R 2 and R 3 , which may be the same or different, are C 1 -C 4 -alkyl, C 1 -C 4 ~alkoxy, C 1 ~C 4 -alkylthio, C^-C^-alkylamino, di-C.pC^-alkylamino or halogen; R 4 , R 5 , R 6 , R 7 and R 8 , which may be the same or different, are 10 hydrogen, C 1 ~C 4 -alkyl, C 1 -C 4 ~alkoxy, amino, di-C 1 -C 4 -alkylamino, nitro, halogen, trifluoromethyl or phenyl; R 9 is hydrogen, C 1 -C 4 ~alkyl or phenyl; X is oxygen or sulphur; and Y is methine or nitrogen, 15 as well as their alkali metal, alkaline earth metal and organic ammonium salts, and their E- and Z-isomers
2. A herbicidal composition which comprises a compound according to claim 1, in admixture with in admixture with agriculturally 20 acceptable carriers or diluents.
3. A method of combating weeds which comprises applying to the weeds or their locus a compound according to claim 1. -224.
4.A process for preparing a compound of formula I as defined in claim I by reacting a compound of general formula II in which R 1 , R 2 and R 3 , X and Y have the meanings given under general formula I, with a compound of general formula III G A in which A and G have the meanings given under general formula I, in a suitable solvent in the presence of a suitable base, and if desired a compound of general formula I in which R 1 is hydrogen, C 1 -C 4 -alkyl or benzyl, so obtained, is reacted with an alkali metal base, an alkaline earth metal base or an organic ammonium base, in a suitable polar solvent, to give a compound of general formula I in which R 1 is an alkali metal atom, one equivalent of an alkaline earth metal atom or an organic ammonium group, and/or if desired, a compound of formula I in which R 1 is C^C^-alkyl, benzyl or an alkali metal atom, one equivalent of an alkaline earth metal atom or an organic ammonium group, is reacted with a suitable acid in a suitable solvent to give a compound of general formula I in which R 1 is hydrogen.
5. A compound substantially as hereinbefore described with reference to the Examples.
6. A composition substantially as hereinbefore described with reference to the Examples.
7. A method substantially as hereinbefore described with reference to the Examples.
8. A process substantially as hereinbefore described with reference to the Examples.
IE235790A 1989-07-19 1990-06-29 New substituted pyrimidinyloxy(thio)-and¹triazinyloxy(thio)acrylic acid derivatives, processes for¹their preparation and their use as herbicides, fungicides¹and plant growth regulators IE902357A1 (en)

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DE3924259A DE3924259A1 (en) 1989-07-19 1989-07-19 SUBSTITUTED (ALPHA) -PYRIMIDINYLOXY (THIO) AND (ALPHA) -TRIAZINYLOXY (THIO) CARBONIC ACID DERIVATIVES, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDES, FUNGALIZING AGENTS AND PLANTING AGENTS

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CA2053603A1 (en) * 1990-10-19 1992-04-20 Katsumasa Harada 3-alkoxyalkanoic acid derivative, process for preparing the same and herbicide using the same
DE4108029A1 (en) * 1991-03-13 1992-09-17 Bayer Ag TRIAZINYL-SUBSTITUTED ACRYLIC ACID ESTERS
EP0517215B1 (en) * 1991-06-07 1998-09-02 Ube Industries, Ltd. Pyrimidine or triazine derivative, process for preparing the same and herbicide using the same
PT100941A (en) * 1991-10-11 1993-10-29 Ciba Geigy Ag HERBICIDES BASED ON PYRIMIDYLENIC OR TRIAZYNILIC ETEREYS OR TIOETERES, AND PROCESS FOR THEIR PREPARATION
TW211581B (en) * 1991-11-07 1993-08-21 Hoechst Ag
CA2110500A1 (en) * 1992-06-17 1993-12-23 Christoph Luthy Pyrimidinyl- and tetrazinyl compounds with herbicidal activity
US5541148A (en) * 1992-07-08 1996-07-30 Ciba-Geigy Corporation Selective safened herbicidal composition comprising 2-ethoxycarbonyl-3-(4,6-dimethoxypyrimidine-2-yl) oxy-pyridine and an acylsulfamoylphenyl-urea safener
MX9708552A (en) * 1995-05-09 1997-12-31 Basf Ag (het)aryloxy-, -thio-, aminocrotonates, methods of preparing them and their use as insecticides and fungicides.

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EP0223406B1 (en) * 1985-10-15 1990-08-29 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives and herbicidal uses thereof
GB8912700D0 (en) * 1989-06-02 1989-07-19 Shell Int Research Herbicidal compounds

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