DE3038635A1 - Substd. 5-phenyl-1,3,4-thiadiazol-2-yl oxy:acetic acid amide derivs. - selective herbicides for use in cotton, soya beet and cereal crops against dicotyled on weeds - Google Patents

Abstract

Substd. 5-phenyl-1,3,4-thiadiazol-2-yl- oxy-acetic acid amide derivs. of formula (I) are new. R1 is opt. halosubstd. 1-5C alkyl, 3-5C alkenyl, 3-5C alkinyl, cyano-(1-4C)alkyl, 1-4C alkoxy (1-4C) alkyl, 3-6C cycloalkyl or phenyl (1-2C) alkyl; R2 is opt. halosubstd. 1-5C alkyl, 3-5C alkenyl, 3-5C alkinyl, cyano-(1-4C)alkyl, 1-4C alkoxy (1-4C) alkyl, 3-6C cycloalkyl or phenyl (1-2C) alkyl, Ph, opt. substd. by Me, Cl, F, Br and/or NO2 (provided R1 is not Me) or Ph substd. by CF3 or MeO; or R1 and R2 together with the N atom to which they are attached (Nm opt. Me and/or Et substd. pyrrolidyl, piperidyl, perhydroazepinyl, morpholinyl, indolinyl, perhydroindolyl, 1,2,3,4-tetrahydro-quinolyl, 1,2,3,4-tetrahydro- isoquinolyl, perhydro-quinolyl or perhydro-isoquinolyl or form a gp. of formula (II) or (III). (I) are herbicides with a very good effect against dicotyledonous weeds. (I) are highly selective and can be esp. used in cotton, soya, beet and cereal crops.

Description

Substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic

Acid amides, process for their preparation and their use as Herbicides The invention relates to new substituted 5-phenyl-1,3-thiadiazol-2-yl-oxyacetic acid amides, a process for their preparation and their use as herbicides.

In two previous patent applications, certain azolyloxycarboxamides, such as 5-ethyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-2-methylpiperidide, a manufacturing method have been described for this and their use as Herb Izide (see. DE patent applications P 29 14 003.2 and P 30 04 326).

However, the herbicidal properties of these compounds are in respect of Effect level and selectivity nmcYt always satisfactory.

There were now new substituted 5-phenyl-1,3,4-thidiazol-2-yl-oxyacetic acid amides of the formula found, in which R1 for optionally halogen-substituted radicals from the series C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4- alkly, C3-C6-cycl.oalkyl or phenyl-C1-C2-alkyl and R2 represents optionally halogen-substituted radicals from the series C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, cyano-C1 -C4-alkly, C1-C4-alkoxy-C-C4-alkly, C3-C6-cycloalkyl. Or phenyl-C1-C2-alkyl, for phenyl (with the proviso that R1 then does not stand for methyl) or for through Methyl, chlorine, fluorine, bromine and / or nitro-substituted phenyl is powder - with the proviso that R1 then does not represent methyl - also represents phenyl substituted by trifluoromethyl or methoxy, or in which the two radicals R1 and R2- together with the nitrogen atom to which they are bonded for radicals from the series pyrrolidyl, piperidyl, perhydroazepinyl, morpholinyl, indolinyl, perhydroindolyl, 1,2,3,4-tetrahydroquinolyl, optionally substituted by methyl and / or methyl, 1 , 2,3,4-tetrahydroisoquinolyl, perhydroquinolyl and perhydroisoquinolyl or represent one of the following radicals The new compounds of the formula (I) are obtained if hydroxyacetic acid amides of the formula in which R1 and R2 have the meanings given above, with 2-chloro-5-phenyl-1,3,4-thiadiazole of the formula optionally in the presence of an acid acceptor and, where appropriate, show reaction in the presence of a diluent.

The new 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides of the formula (I) are distinguished by a strong herbicidal activity.

Surprisingly, the compounds according to the invention show the Formula (I) a much higher herbicidal effectiveness than that from the prior Technique known compounds of analogous constitution and the same direction of action. In addition to having a very good effect, they show them monocot weeds also has a good herbicidal effect on dicotyledon weeds. Because of their good selectivity against cotton, soybeans, beets and cereals such as wheat they are used particularly advantageously in these cultures. So you pose a valuable addition to the state of the art. Connect the formula (I) also influence the growth of useful plants and can be used to regulate plant growth can be used.

As examples of the 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides according to the invention of the formula (I) the following compounds may be mentioned: 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid dimethylamide, -diethylamide, -di-n-propylamide, -di-isopropylamide, -di-n-butylamide, -di-isobutylamide, -N-methyl-ethylamide, -N-methyln-propylamide, -N-methyl-isopropylamide, -N-methyl-n-butylamide, -N-methyl-isobutylamide, -N-methyl-sec-butylamide, -N-methyl-tert-butylamide, -N-methyl-n-pentyl-amide, -N-methyl-isopentylamide, -N-methyl-sec-pentylamide, -N-ethyl-npropylamide, -N-ethyl-i-sopropylamide, -N-ethyl-n-butylamide, -N-ethyl-isobutylamide, -N-ethyl- secbutylamide, -N-ethyl-tert-butylamide, -N-n-propyl-isopropylamide, -N-n-propyl-n-butylamide, -N-n-propyl-isobutylamide, -N-n-propyl-se'-butylamide, -N-n-propyl-tert-butylamide, -N-isopropyl-N-isobutylamide, -N-n-butyl-iso-butylamide, -N- n-butyl- sec-butylamide, -N-n-butyl-tert-butylamide, -N-methyl- (2-cyano-ethyl) -amide, -di (2-cyano-ethyl) -amid, -.di- (2-methoxy-ethyl) -amid, -diallylamide, -dipropargylamid, -N-methyl-propargylamide, -N-methyl- (1-methyl-propargyl) -amide, -N-methyl- (1,1, -dimethyl-propargyl) -amide, -N-methyl-cyclopentylamide, -N-methyl-cyclohexylamide, -N-ethyl-cyclohexylamide, -N-methyl-N- (2-methyl-phenyl) amide, -N-methyl-N- (3-methyl-phenyl) -, -N-methyl-N- (4-methyl-pehnyl) -amid, -N-methyl-N- (2-chlorophenyl) - , -N-methyl-N- (3-chloro-phenyl) -, -N-methyl-N- (4-chloro-phenyl) -amide, -N-methyl-i6- ( 3-nitro-6-met; hyl-phenul) -amid, -N-ethyl-anilide, -N-ethyl-N- (2-methyl-phenyl) -, -N-ethyl-N- (3-methyl-phenyl) -, -N-ethyl-N- (4-methyl-phenyl) -amid, -N-ethyl-N- (2-chlorophenyl) -, -N-ethyl-N- (3-chloro-phenyl) -, -N-ethyl-N- (4-chloro-phenyl) -amide, -N-ethyl-N- (3-nitro-6-methyl-phenyl ) -amide, -N-propylanilide, -N-propyl-N- (2-methyl-phenyl) -, -N-propyl-N- (3-methyl-phenyl) -, -N-propyl-N- (4-methyl-phenyl) -amid, -N-propyl-N- (2-chlorophenyl) -, -N-propyl-N- (3-chlorophenyl) -, -N-propyl-N- (4-chlorophenyl) amide, -N-iso-propyl-N- (2-methyl-phenyl) -, N-iso-propyl-N- (3-methyl-phenyl) -, -N-iso-propyl-N- (4-methyl-phenyl) -amide, N-iso-propyl-N- (3-nitro-6-methyl-phenyl) -amide, -N-butyl-anilide, -N-butyl-N- (2-methyl-pheyl) -, -N-butyl-N- (3-methyl-phenyl) -, -N-butyl-N- (4-methyl -phenyl) -amid, -N-butyl-N- (2-chloro-phenyl) -, -N- (butyl-N- (3-chloro-phenyl) -, -N-butyl-N- (4-chloro-phenyl) -amide, -N-isobutyl-N- (2-methylphenyl) -, -N-iso-butyl-N- (3-methyl-phenyl) -, -N-iso-butyl-N- (4-methyl-phenyl) -amide , -N-iso-butyl-N- (3-nitro-6-methylphenyl) -amide, -N-methyl-N- (4-chloro-3-methyl-phenyl) -amide, -dibenzylamide, -N-methyl-N-benzylamide, -N-ethyl-N-benzylamide, -N-propyl-N-benzylamide, -N-propargyl-N-benzyl-amide, -pyrrolidide, -2-methyl-pyrrolidide, -morpholide, -3,5-dimethyl-morpholide, -piperidide, -2-methyl-piperidide, -3-methyl-piperidide, -4-methyl-piperidide, 2,4-dimethyl-piperidide, -2,4,6-trimethyl-piperidide, -2-ethyl-piperidide, -4-ethyl-piperidide, -indolinide, -2-methyl-indolinide, -perhydroindolide, -2-methyl-perhydroindolide, -2,2-dimethylperhydroindolide, -1,2,3,4, tetrahydroquinolide, -2-methyl- 1,2,3,4-tetrahydroquinolide, -perhydroquinolide and -2-methyl-perhydroquinolide.

If, for example, X, yaroxyacetic acid dimethylamide and 2-chloro-5-phenyl-1,3,4-thiadiazole are used as starting materials, the course of the reaction according to the process according to the invention can be represented by the following equation: The hydroxyacetic acid amides of the formula (II) to be used as starting materials are already known (cf. DE-OS 29 04 490 and EP-OS 5501).

2-chloro-5-phenyl-1,3,4-thiadiazole, which is used as a further starting compound is to be used is also already known (see. J.Org.Chem. 31 (1966), 3528-3531).

The method of the invention is preferably used suitable solvents or diluents carried out. As such come next Water practically all organic solvents in question. This includes in particular Alcohols such as methanol, ethanol, n- tiiid iso-propanol, n-, iso-, sec- and tert-butanol, Ethers such as dipropyl and dibutyl ethers, glycol dimethyl ether and diglycol dimethyl ether, Tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isopropyiketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile and carboxamides, such as dimethylformamide and dimethylacetamide.

In the process according to the invention, practical acid acceptors can be used all commonly used acid binders are used: these include in particular alkali and alkaline earth hydroxides or oxides such as sodium and potassium hydroxide as well as calcium oxide or calcium hydroxide, alkali and alkaline earth carbonates such as sodium, Potassium and calcium carbonate, alkali metal alcoholates, such as sodium methylate, ethylate and tert-butoxide, potassium methylate, -ethylate and -tert-butoxide, also aliphatic, aromatic or heterocyclic amines such as triethylamine, dimethylaniline, dimethylbenzylamine, Pyridine, diazabicyclooctane and diazabicycloundecene.

The reaction temperature can vary within a relatively wide range will. In general, one works between 0 and 80 ° C, preferably at 10 to 5o 0C.

The process according to the invention is generally carried out at normal pressure carried out.

The starting compounds are used to carry out the process according to the invention of the formulas (II) and (III) and the acid binder in general approximated Equal molar amounts are used. The reaction is generally carried out in a suitable Verdünnurgsmitt.el carried out and the reaction mixture is at the required stirred for a few hours.

Working up can be carried out by customary methods: Crystalline products are obtained after pouring the reaction mixture into water, if necessary, neutralization with hydrochloric acid, sulfuric acid or acetic acid and suction, In a purer form by recrystallization. So much for the products at room temperature Are oils, they can be obtained in relatively pure form by mixing the reaction mixture, optionally after concentration, with an organic which is practically immiscible with water Solvent, like. e.g., methylene chloride diluted with dilute acid and with Washed water, dried, filtered and the filtrate the solvent under reduced Pressure carefully distilled off. The melting point or the refractive index.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, sprout inhibitors unci can be used in particular as a herbicide. Under weeds in the broadest sense all plants are to be understood that grow in places where they are undesirable. Whether the substances according to the invention as total or selective The effect of herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants are used: Dikotvleweeds of the genera: sinapis, Lepidioum, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecior Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicot cultures of the genera: Gossypiuni, Glycine, Acta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.

Monocot weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Isachaemum, Sphenoclea, Dailoctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium The use However, the active ingredients according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control zXs. on industrial and rail systems and on paths and Places with and without trees. Likewise, the compounds can be used for weed control in permanent crops e.g. forest, ornamental wood, fruit, wine, citrus, nut, banana, Coffee, tea, rubber, oil palm, cocoa, berry fruit and hops plants and for selective weed control can be used in annual crops.

The active compounds according to the invention show not only very good herbicidal properties Effect against monocotyledonous (grassy) weeds also good selectivity in various important cultures. A selective use of the invention according to Active ingredients is possible; e.g. in cotton, soybeans, beets and grain, e.g. in wheat.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granulates, suspension-emulsion concentrates, impregnated with active ingredients Natural and synthetic materials, finest encapsulation in polymer materials.

These formulations are prepared in a known manner, e.g. Mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally with the use of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: Aromas, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic raw hydrogen, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following can be used as solid carriers: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as high- dispersed silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g.

broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-producing agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo, metal phthalocyanine dyes and trace nutrients such as salts of Iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90% u The invention Active ingredients, as such or in their formulations, can also be used as a mixture with known ones Herbicides for weed control are used, with finished formulation or Tank mixing is possible.

Also a mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, growth substances, Plant nutrients and soil structure improvers are possible.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by watering, squirting, atomizing, Scattering or dusting.

The active ingredients according to the invention can both before and after Emergence of the plants are applied.

The application is preferably before the emergence of the plants, that is Made in the pre-emergence process, you can also pre-sow in the. floor The amount of active ingredients used can vary over a wide range. It essentially depends on the type of effect you want. In general lie the Application rates between 0.1 and 10 kg of active ingredient per hectare, preferably between 0.1 and 5 kg / ha.

Some of the active ingredients according to the invention have certain application concentrations also have a growth-regulating effect on the following examples are used for Explanation of the invention.

Preparation examples Example 1 9.8 g (0.05 mol) of 2-chloro-5-phenyl-1,3,4-thiadiazole become a mixture of 8.5 g (0.05 mol) 2-hydroxyacetic acid at room temperature (20 + 10 ° C.) 4-dimethylpiperidide, 5.6 g (0.05 mol) of potassium tert-butoxide and io-o ml of tert-butanol were added. The mixture is stirred for 3 hours at room temperature, diluted with 200 ml of methylene chloride, washed with 2N hydrochloric acid and then with water, dried and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure. 11 g of 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-2,4-dimethylpiperidide are obtained as an oily residue with a refractive index nD20: 1.5812.

The compounds of the formula (I) listed in the table below can be prepared analogously to Example 1 ~: Table: Examples of the compounds of the formula (I) R1 refractive index (n0 with refractive inverse or melting game -N 2 point melting- r. R point (OC) 2 -nT H) -C, H, 1.5829 3 -N 9 1.5639 C2H5 4 N / C2H5 66 C 3H7-iso 3 5 -N ß -CH3 32 CH3 3 6 -N 9 1.5615 Ü 7 -Ü; 1 1.6075 Bei- / R1 refractive index (S0) game -N or ScEameXz- No. R2 point (OC) C3 CH, Cn 8 -ti <) 97 / C2H5 80 C4H9-n 10 Nm% H 1.5932 CH3 ii -D 96 12 N / CH3 58 C4H9-n / CH2-CnCH 13 -N CH2-C- = CH \ 1.61251.6125 CH2 CH 14 -Nt) 118 14 -ru \ f 15 -N 1 96 C4H9-iso Bei- / R1 refractive index 1 20 play -N2 or melting- No. \ R point (oC) . , C2H5 16 -N-CH2- O 1.5440 17 -N (CH2CH20CH3) 2 73-75 C12H5 18 -N 133 / C3H, -iso 19 -N / 3 7 96 \ C4Hg.-iso zCH 2o / CH3 N \ C'H iso 1.56o2 49 21 -N g 78 c2ps5 Example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after Doused with the active ingredient preparation for 24 hours.

The amount of water per unit area is expediently kept constant. The concentration of the active substance in the preparation does not matter, it is decisive is only the amount of active ingredient applied per unit area. After three weeks it will the degree of damage to the plants is rated in% damage in comparison to development the untreated control. It means: 0% = no effect (like untreated Control) 100% = total destruction In this test, for example, the following compounds show according to production examples an excellent effectiveness: 1, 2, 3.

Claims (1)

Claims 1) Substituted 5-phenyl-1, 3,4-thiadiazol-2-yloxyacetic acid amides of the formula in which R stands for optionally halogen-substituted radicals from the series C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkyl or phenyl-C1-C2-alkyl and R2 represents optionally halogen-substituted radicals from the series C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, cyano-C1-C4-alkyl , C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkyl or phenyl-C1 -C2-alkyl, for phenyl (with the proviso that R then does not represent methyl) or for by methyl, chlorine, fluorine , Bromine and / or nitro-substituted phenyl or - with the proviso that R¹ is not methyl - also stands for phenyl substituted by trifluoromethyl or methoxy, or in which the two radicals R1 and R2 together with the nitrogen atom to which they are attached are bound, for radicals from the series pyrrolidyl, piperidyl, perhydroazepinyl, morpholinyl, indolinyl, perhydroindolyl, 1,2,3,4 tetrahydroquinolyl, 1,2,3,4-tetrahy which are optionally substituted by methyl and / or ethyl droisoquinolyl, perhydroquinolyl and perhydroisoquinolyl or represent one of the following radicals: 2) 5-Phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-2,4-dimethyl-piperidide of the formula according to claim 1. 3) 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-4-. ethyl piperidide of the formula according to claim 1. 4) 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-2-ethyl-piperidide of the formula according to claim 1. 5) Process for the preparation of substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxiacetic acid amides of the formula (I) according to claim 1, characterized in that one hydroxyacetic acid amides of the formula in which R1 and R2 have the meanings given above, with 2-chloro-5-phenyl-1,3,4-thiadiazole of the formula if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent. 6) Herbicidal agents, characterized by a content of substituted 5-Phenyl-1,3,4-thiadiazol-2-yloxyacetic acid amides of the formula (I) according to Claim 1. 7) method of controlling unwanted plant growth, thereby characterized in that substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides of formula (I) according to claim 1 on the undesired plants or their habitat can act. 8.) Use of substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides Formula (I) according to Claim 1 for combating plant growth. 9) Process for the preparation of herbicidal agents, characterized in that that substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides of the formula (I) according to claim 1 mixed with extenders and / or surface-active agents.