DE3038635C2 - - Google Patents

Description

The invention relates to new substituted 5-phenyl-1,3,4- thiadiazol-2-yl-oxyacetic acid amides, a process for their Production and their use as herbicides.

In two previous patent applications there are certain Azolyloxycarboxamides, such as. B. 5-ethyl-1,3,4-thia diazol-2-yl-oxyacetic acid-2-methylpiperidide, a manufacturing process for this and their use as herbicides have been described (cf. DE 29 14 003 A1 and 30 04 326 A1).

The herbicidal properties of these compounds are but not in terms of the level of effectiveness and selectivity always satisfactory.

There have now been new substituted 5-phenyl-1,3,4-thiadia zol-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-alkyl, C₃- C₆- cycloalkyl or phenyl-C₁-C₂-alkyl is and
R² 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, for phenyl (with the proviso that R¹ does not represent methyl) or for phenyl substituted by methyl, chlorine, fluorine, bromine and / or nitro or - with the proviso that that R¹ then does not represent methyl - also represents phenyl substituted by trifluoromethyl or methoxy,
or in which the two remnants
R¹ and R² together with the nitrogen atom to which they are attached, for radicals optionally substituted by methyl and / or ethyl from the series pyrrolidyl, piperidyl, perhydroazepinyl, morpholinyl, indoline, perhydroindolyl, 1,2,3,4-tetrahydroquinolyl , 1,2,3,4-tetrahydroisoquinolyl, perhydroquinolyl and perhydroisoquinolyl or stand for one of the radicals below

The new compounds of formula (I) are obtained when 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 optionally in the presence of a diluent in a manner known per se.

The new 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides Formula (I) are characterized by strong herbicides Effectiveness.

The compounds of the invention surprisingly show of formula (I) a much higher herbicide Efficacy than that known from the prior art Connections of analogous constitution and the same direction of action. They show a very good effect against  monocotyledon weeds also have a good herbicidal effect dicotyledon weeds. Because of their good selectivity towards Cotton, soybeans, beets and cereals, such as e.g. B. wheat, they can be particularly advantageous in these crops be used. They thus represent a valuable one Enrichment of the state of the art. Connections of formula (I) also affect the growth of Useful plants and can be used for plant growth regulation will.

As examples of the 5-phenyl-1,3,4- thiadiazol-2-yl-oxyacetic acid amides of the formula (I) named the following connections: 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-methyl- n-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-meth yl-isopentylamide, -N-methyl-sek-pentylamide, -N-ethyl-n- propylamide, -N-ethyl-isopropylamide, -N-ethyl-n-butylamide, -N-ethyl-isobutylamide, -N-ethyl-sec- butylamide, -N-ethyl-tert-butylamide, -N-n-propyl-isopropylamide, -N-n-propyl-n-butylamide, -N-n-propyl-isobutylamide, -N-n-propyl-sec-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) -amide, -di- (2-methoxy-ethyl) -amide, -diallylamide, -dipropargyl amide, -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-methylphenyl) -, -N-methyl-N- (4- methyl-phenyl) -amide, -N-methyl-N- (2-chlorophenyl) -, -N- methyl-N- (3-chlorophenyl) -, -N-methyl-N- (4-chlorophenyl) - amide, -N-methyl-N- (3-nitro-6-methylphenyl) amide, -N- ethyl anilide, -N-ethyl-N- (2-methylphenyl) -, -N-ethyl-N- (3-methylphenyl) -, -N-ethyl-N- (4-methylphenyl) amide, -N-ethyl-N- (2-chlorophenyl) -, -N-ethyl-N- (3-chlorophenyl) -, -N-ethyl-N- (4-chlorophenyl) 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-methylphenyl) amide, -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-methylphenyl) -, -N-butyl-N- (3-methylphenyl) -, -N-butyl-N- (4-methylphenyl) amide, -N-butyl-N- (2-chlorophenyl) -, -N-butyl-N- (3-chlorophenyl) -, -N-butyl-N- (4-chlorophenyl) amide, -N-isobutyl-N- (2-methyl- phenyl) -, -N-iso-butyl-N- (3-methyl-phenyl) -, -N-iso-butyl- N- (4-methyl-phenyl) -amide, -N-iso-butyl-N- (3-nitro-6-methyl- phenyl) -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-di methyl-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-dimethyl- perhydroindolide, -1,2,3,4, tetrahydroquinolide, -2-methyl-  1,2,3,4-tetrahydroquinolide, -perhydroquinolide and -2- methyl perhydroquinolide.

For example, hydroxy is used as the starting material acetic acid dimethylamide and 2-chloro-5-phenyl-1,3,4-thiadiazole, so can the course of the reaction according to the invention Process represented by the following formula will:

The hydroxyacetic acid amides to be used as starting materials of the formula (II) are already known (cf. DE 29 04 490 A1 and EP 5 501 A2).

2-chloro-5-phenyl-1,3,4-thiadiazole, which as another Output connection to use is also already known (see J. Org. Chem. 31 (1966), 3528-3531).

The inventive method is preferably under Use of suitable solvents or diluents carried out. As such come in handy in addition to water all organic solvents in question. These include especially alcohols, such as methanol, ethanol, n- and iso-propanol, n-, iso-, sec- and tert-butanol, ether such as dipropyl and dibutyl ether, glycol dimethyl ether  and diglycol dimethyl ether, tetrahydrofuran and dioxane, Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile and carboxamides, such as. B. Dimethyl formamide and dimethylacetamide.

As acid acceptors in the invention Practically all commonly used methods Acid binders are used: these include especially alkali and alkaline earth metal hydroxides or oxides such as sodium and potassium hydroxide and calcium oxide or Calcium hydroxide, alkali and alkaline earth carbonates such as Sodium, potassium and calcium carbonate, alkali 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, diazabicyclo octane and diazabicycloundecene.

The reaction temperature can be within a larger Range can be varied. Generally you work between 0 and 80 ° C, preferably at 10 to 50 ° C.

The process according to the invention is generally described in Normal pressure carried out.

To carry out the method according to the invention the starting compounds of the formulas (II) and (III) and the acid binder is generally in approximately equimolar Amounts used. The implementation is general carried out in a suitable diluent and the reaction mixture is at the required temperature stirred for a few hours.  

The processing can be carried out according to customary methods:
Crystalline products are obtained after pouring the reaction mixture into water, optionally neutralization with hydrochloric acid, sulfuric acid or acetic acid and suction, in a purer form by recrystallization. Insofar as the products are oils at room temperature, they are obtained in relatively pure form by the reaction mixture, if appropriate after concentration, with an organic solvent which is practically immiscible with water, such as, for. B. diluted methylene chloride, washed with dilute acid and with water, dried, filtered and the solvent carefully distilled off from the filtrate under reduced pressure. The melting point or refractive index is used for characterization.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, Haulm killers, germ inhibitors and in particular can be used as a weed killer. Under Weeds are to be understood in the broadest sense, all plants, who grow up in places where they are undesirable. If she Substances according to the invention as total or selective herbicides act essentially depends on the amount used.

The active compounds according to the invention can, for. B. in the following Plants are used:

Dicotyledon weeds of the genera:
Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippernia, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyle cultures of the genera:
Gossypium, Glycine, Beta, 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, Spochhenium, Ischatenumum, Ischaeaeaum Agrostis, Alopecurus, Apera.

Monocot cultures of the genera:
Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these genres, but extends affect other plants in the same way.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and Track systems and on paths and squares with and without tree cover. Likewise, weed control compounds in permanent crops e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, Cocoa, berry fruit and hop plants and for selective Weed control can be used in annual crops.

The active ingredients according to the invention show a very good herbicidal activity against monocot (grass-like) Weeds also have good selectivity in various important cultures. A selective use of the fiction  Appropriate active ingredients is possible, e.g. B. in cotton, soybeans, Beets and cereals, e.g. B. in wheat.

The active ingredients can be converted into the usual formulations like solutions, emulsions, wettable powders, Suspensions, powders, dusts, pastes, soluble Powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances, Fine encapsulation in polymeric substances.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, So liquid solvents and / or solid Carriers, optionally using upper surfactants, i.e. emulsifiers and / or Dispersing agents and / or foaming agents. If water is used as an extender can e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. 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, as well as water.

The following are suitable as solid carriers: e.g. B. natural rock flour, such as kaolins, clays, Talc, chalk, quartz, attapulgite, montmorillonite or Diatomaceous earth and synthetic rock powder, how high  disperse silica, aluminum oxide and silicates; as solid carriers for granules are possible: z. B. broken and fractionated natural rocks like Calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules from organic materials such as Sawdust, coconut shells, corn cobs and tobacco stalks; come as emulsifying and / or foam-generating agents in question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fat alcohol ether, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxy can be used in the formulations methylcellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. B. 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 are used will.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.  

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known ones Find herbicides for weed control, wherein Ready formulation or tank mix is possible. Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, Protection against bird feed, growth substances, plant nutrients and soil structure improvers possible.

The active ingredients as such, in the form of their formulations or those prepared from it by further dilution Application forms, such as ready-to-use solutions, Suspensions, emulsions, powders, pastes and granules be applied. The application is done in the usual way Way, e.g. B. by pouring, spraying, spraying, scattering or dusts.

The active compounds according to the invention can be used both before and can also be applied after the plants have emerged. The application is preferably made before the emergence of the Plants, i.e. in the pre-emergence process. They can also be worked into the soil before sowing will.

The amount of active ingredient used can be in larger ranges vary. It essentially depends on the type the desired effect. In general, the  Application rates between 0.1 and 10 kg of active ingredient per ha, preferably between 0.1 and 5 kg / ha.

Some of the active ingredients according to the invention certain application concentrations also a growth-regulating Effect on.

The following examples serve to explain the Invention.

Manufacturing examples Example 1

9.8 g (0.05 mol) of 2-chloro-5-phenyl-1,3,4-thiadiazole at room temperature (20 ± 10 ° C) to a mixture of 8.5 g (0.05 mol) Hydroxyacetic acid 2,4-dimethylpiperidide, 5.6 g (0.05 mol) potassium tert-butoxide and 100 ml tert-butanol given. The mixture is 3 hours at room temperature stirred, diluted with 200 ml of methylene chloride, with 2 n Hydrochloric acid and then washed with water, dried and filtered. The solvent is reduced from the filtrate Pressure carefully distilled off. 11 g are obtained 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid-2,4-dimethyl- piperidide as an oily residue from the refractive index: 1.5812.

Analogous to Example 1, the table below Compounds of formula (I) listed are prepared:  

table

Examples of the compounds of the formula (I)

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount Emulsifier and dilute the concentrate with water the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the active ingredient preparation after 24 hours. It is useful to keep the amount of water per unit area constant. The drug concentration in the Preparation is irrelevant, only that is decisive Application rate of the active ingredient per unit area. After three The degree of damage to the plants is rated for weeks in% damage compared to the development of the untreated Control. It means:

0% = no effect (like untreated control)
100% = total annihilation

In this test, e.g. B. the following compounds excellent effectiveness according to manufacturing examples: 1, 2, 3.

Claims (6)

1. Substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides of the formula 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-alkyl, C₃- C₆-cycloalkyl or phenyl-C₁-C₂-alkyl and
R² 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, for phenyl (with the proviso that R¹ does not represent methyl) or for phenyl substituted by methyl, chlorine, fluorine, bromine and / or nitro or - with the proviso that that R¹ then does not represent methyl - also represents phenyl substituted by trifluoromethyl or methoxy,
or in which the two remnants
R¹ and R² together with the nitrogen atom to which they are attached, for radicals from the series pyrrolidyl, piperidyl, perhydroazepinyl, morpholinyl, indolinyl, perhydroindolyl, 1,2,3,4-tetrahydroquinolyl, optionally substituted by methyl and / or ethyl, 1,2,3,4-tetrahydroisoquinolyl, perhydroquinolyl and perhydroisoquinolyl or stand for 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. A process for the preparation of substituted 5-phenyl-1,3,4-thiadiazol-2-yl-oxyacetic acid amides of the formula (I) according to claim 1, characterized in that 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. Use of substituted 5-phenyl-1,3,4-thia diazol-2-yl-oxyacetic acid amides of the formula (I) according to Claim 1 to combat plant growth.