DE4418066A1 - Substituted thiadiazolines - Google Patents

Abstract

The invention relates to novel substituted thiadiazolines of general formula (I) in which R<1>, R<2> and R<3> have the meanings given in the description, process for producing them and their use as herbicides.

Description

The invention relates to new substituted thiadiazolines, processes for their manufacture position and their use as herbicides.

It is already known that certain thiadiazolines, such as. B. the connection 2- Methylimino-3-benzyl-5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, herbicidal property have properties (cf. DE-A 27 17 742 / US-P 4020078; cf. also DE-A 42 18 157 / WO-A 93/24474). The effectiveness of the known compounds is however, especially not at low application rates and concentrations completely satisfactory in all areas of application.

The new substituted thiadiazolines of the general formula (I) found,

in which
R¹ for hydrogen, cyano, nitro, halogen or for a given, if appropriate, halogen-substituted radical of the series C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl or C₁-C₆-alkylsulfonyl stands,
R² is C₁-C₆ alkyl and
R³ is hydrogen or a radical of the series C₁-C₆- which is optionally substituted by halogen, cyano, C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl or di- (C₁-C₄-alkyl) -amino-carbonyl Is alkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl,
R³ further for an optionally substituted by halogen radical from the series C₁-C₆-alkyl-carbonyl, C₂-C₆-alkenyl-carbonyl, C₁-C₆-alkoxy-carbonyl, C₁-C₆-alkylthio-carbonyl, di- (C₁-C₄ -alkyl) -amino carbonyl or C₁-C₆-alkyl-sulfonyl,
R³ further represents C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl or C₅-C₆-cycloalkenyl, optionally substituted by halogen or C₁-C₄-alkyl, or
R³ further for an optionally substituted by nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-halogen alkoxy radical from the series phenyl, phenylcarbonyl, phenoxy carbonyl, phenylsulfonyl or Phenyl-C₁-C₄-alkyl,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl phenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4-benzyloxy-benzyl) - 5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-OS 27 17 742 / US-P 4020078 - and the compounds 2-methylimino-3- (4-methoxy-benzyl) -5- (3-trifluoromethyl phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4 -thiadiazoline and 2-methylimino-3- (4-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-A 42 18 157 / WO-A 93 / 24474 - are excluded by disclaimer.

The new substituted thiadiazolines of the general formula (I) are obtained if

• (a) thiadiazoles of the general formula (II) in which
  R¹ and R² have the meanings given above,
  with substituted benzyl halides of the general formula (III) in which
  R³ has the meaning given above and
  X represents halogen,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  or if you
• b) thiadiazolines of the general formula (I) in which R¹ and R² have the meanings given above and R³ is hydrogen,
  with electrophilic compounds of the general formula (IV) X-R³ (IV) in which R³ and X have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

The new substituted thiadiazolines of the general formula (I) stand out characterized by strong and selective herbicidal activity.

Surprisingly, the compounds of the formula (I) according to the invention show with very good tolerance to crops, such as. B. corn, significantly more effective against a number of problem weeds than the known one Compound 2-methylimino-3-benzyl-5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, wel che is a similar active ingredient with the same direction of action.

The invention preferably relates to compounds of the formula (I) in which
R¹ for hydrogen, cyano, nitro, fluorine, chlorine, bromine or for in each case optionally substituted by fluorine and / or chlorine C₁-C₄-alkyl, C₁-C₄- alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁ -C₄ alkylsulfonyl,
R² is C₁-C₄ alkyl and
R³ represents hydrogen or a radical of the series C₁- which is optionally substituted by fluorine, chlorine, cyano, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-carbonyl or di- (C₁-C₃- alkyl) -amino-carbonyl C₅-alkyl, C₂-C₅- alkenyl or C₃-C₅-alkynyl,
R³ further for a radical optionally substituted by fluorine and / or chlorine in the series C₁-C₅-alkyl-carbonyl, C₂-C₅-alkenyl-carbonyl, C₁-C₅-alkoxy-carbonyl, C₁-C₅-alkylthio-carbonyl, di - (C₁-C₃-alkyl) amino carbonyl or C₁-C₅-alkyl-sulfonyl,
R³ furthermore represents a radical of the series C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₃-alkyl or C₅-C₆-cycloalkenyl which is optionally substituted by fluorine, chlorine or C₁-C₃-alkyl, or
R³ furthermore represents a radical of the series phenyl, phenylcarbonyl, phenoxycarbonyl, phenylsulfonyl or phenyl-C₁- which is optionally substituted by nitro, cyano, fluorine, chlorine, bromine, C₁-C₃-alkyl, trifluoromethyl, C₁-C₃-alkoxy, difluoromethoxy or trifluoromethoxy C₃-alkyl is,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4-benzyloxy-benzyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-OS 27 17 742 / US-P 4020078 - and the compounds 2-methylimino-3- (4-methoxy-benzyl ) -5- (3-trifluoromethyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴- 1,3,4-thiadiazoline and 2-methylimino-3- (4-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-A 42 18 157 / WO-A 93/24474 - are excluded by disclaimers.

The hydrocarbon radicals listed in the radical definitions, such as alkyl, Alkenyl and alkynyl are - also in connection with other atoms or atoms groups such as B. in alkoxy or in phenylalkyl, each straight-chain or ver branches, even if this is not expressly mentioned.

The invention relates in particular to the compounds of the formula (Ia) and the formula (Ib)

in which each
R¹ represents hydrogen, cyano, nitro, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine,
R² is methyl, ethyl, n- or i-propyl and
R³ represents hydrogen or methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, which is optionally substituted by fluorine, chlorine, cyano, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl or dimethylamino carbonyl, Propynyl or butynyl,
R³ furthermore for acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, ethenylcarbonyl, propenylcarbonyl, butenylcarbonyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl or optionally substituted by fluorine and / or chlorine Dimethylaminocar bonyl,
R³ further represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexyl methyl, cyclopentenyl or cyclohexenyl, each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or
R³ furthermore represents phenyl, phenylcarbonyl, in each case optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy, Phenoxycarbonyl or benzyl,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4-benzyloxy-benzyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-OS 27 17 742 / US-P 4020078 - and the compounds 2-methylimino-3- (4-methoxy-benzyl ) -5- (3-trifluoromethyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴- 1,3,4-thiadiazoline and 2-methylimino-3- (4-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline - known from DE-A 42 18 157 / WO-A 93/24474 - are excluded by disclaimers.

The radicals listed above or specified in preferred ranges definitions apply to both the end products of the formula (I) and ent speaking for the respective starting materials or Intermediates. These residual definitions can be among each other, that is, also between the specified ranges of preferred connections, any combination become.

If, for example, 2- (3-chlorophenyl) -5-methylamino-1,3,4-thiadiazole is used and 3-ethoxy-benzyl chloride as starting materials, so the course of the reaction can Methods according to the invention are outlined by the following formula:

The process (a) according to the invention for the preparation of the compounds of general formula (I) thiadiazoles to be used as starting materials generally defined by formula (II). In formula (II), R¹ and R² have preferably or in particular those meanings which have already been mentioned above in Zu in connection with the description of the compounds of formula (I) as preferred or as particularly preferred for R¹ and R².  

The starting materials of formula (II) are known and / or can be per se known processes can be produced (cf. US-P 3522267, DE-A 18 16 696, DE- A 21 00 057, DE-A 22 31 664, DE-A 22 47 330, DE-A 24 40 922, DE-A 25 41 115, DE-A 25 45 142, US-P 4028090, US-P 4092148, US-P 4283543, US-P 4686294, EP-A 296864, WO-A 93/24474).

The process (a) according to the invention for the preparation of the compounds of general formula (I) further substituted starting materials to be used Formula (III) generally defines benzyl halides. In the formula (III) R³ preferably or in particular has the meaning that already above in connection with the description of the compounds of the formula (I) was specified as preferred or as particularly preferred for R³; X stands preferably for fluorine, chlorine, bromine or iodine, in particular for chlorine, bromine or Iodine.

The starting materials of the formula (III) are known and / or per se known processes can be prepared (cf. J. Org. Chem. 46 (1981), 3029- 3035; DE-OS 25 56 474; US-P 4221919).

The process (b) according to the invention for the preparation of the compounds of general formula (I) to be used as starting materials electrophilic Ver Bonds are generally defined by the formula (IV). In formula (IV) R³ preferably or in particular that meaning already mentioned above in Zu in connection with the description of the compounds of formula (I) as preferred or was specified as particularly preferred for R³; X is preferably for fluorine, chlorine, bromine or iodine, especially for chlorine, bromine or iodine.

The starting materials of the formula (IV) are known synthetic chemicals.

As a diluent for carrying out process (a) according to the invention and (b) the usual organic solvents are suitable. For this include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, Xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloro methane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether,  Dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propio nitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacet amide, N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamid; Esters such as methyl acetate or ethyl acetate, sulfoxides such as Dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono methyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Processes (a) and (b) according to the invention are optionally described in In the presence of a suitable reaction auxiliary. As such all common inorganic or organic bases are suitable. For this include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as, for example Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert.- butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, Potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, Potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and basic organic nitrogen compounds, such as trimethylamine, triethyl amine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-di methylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or Diazabicycloundecene (DBU).

The reaction temperatures can be carried out when carrying out the inventive Processes (a) and (b) can be varied over a wide range. In general one works at temperatures between 0 ° C and 150 ° C, preferably at tem temperatures between 10 ° C and 120 ° C.

Processes (a) and (b) according to the invention are generally described under Normal pressure carried out. However, it is also possible to increase or decrease reduced pressure - generally between 0.1 bar and 10 bar.

To carry out processes (a) and (b) according to the invention, the starting materials required in each case generally in approximately equimolar  Amounts used. However, it is also possible to switch one of the two on put components to use in a larger excess. The reactions are generally in a suitable diluent, optionally in In the presence of a reaction auxiliary, and the reaction mixture is stirred for several hours at the temperature required in each case. The on work takes place in the method according to the invention in each case according to the usual Methods (see the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, herb kills Means and especially used as a weed killer. Weeds in the broadest sense are understood to mean all plants that are in places grow up where they are undesirable. Whether the substances according to the invention as total or selective herbicides act essentially depends on the applied Amount off.

The active compounds according to the invention can, for. B. in the following plants be 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, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous 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, Ischaemum, Sphenoclea, Dactyloctenium, 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 limited to these genera, but also extends in the same way other plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hops, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The compounds of formula (I) according to the invention are particularly suitable for selective control of monocot and dicot weeds in monocot Cultures such as cereals and maize, especially in the post-emergence process.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-imp gnated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Vermi the active ingredients with extenders, i.e. liquid solvents and / or fe Most carriers, optionally using surface-active agents agents, i.e. emulsifiers and / or dispersants and / or foam-producing agents Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaph thalines, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as  Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic Hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, 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 are suitable as solid carriers:
For example, ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine 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 Weight percent active ingredient, preferably between 0.5 and 90%.  

The active compounds according to the invention can be used as such or in their form also mixed with known herbicides for weed control Find use, where ready formulations or tank mixes possible are.

Known herbicides are suitable for the mixtures, for example anilides, such as B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. dichlor picolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, butachlor, Metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines such as e.g. B. Oryzalin, pendimethalin and trifluralin; Diphenyl ether, such as. B. Acifluorfen, Bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and Methabenzthiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cyclo xydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromoxynil, Dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Printisulfuron, Pyrazosulfuron ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, such as B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, Thiobencarb and triallates; Triazines, e.g. B. atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone, Metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, Bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, Ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.  

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after Emergence of the plants can be applied. You can also sow before sowing Be incorporated into the floor.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 10 g and 10 kg of active ingredient per hectare of soil area, preferably between 50 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1

A mixture of 3.0 g (13 mmol) of 5- (3-chlorophenyl) -2-methylamino-1,3,4-thia diazole, 4.5 g (26 mmol) of 4-ethoxybenzyl chloride and 100 ml of dioxane turn 14 Heated under reflux for hours. After cooling with 200 ml of hexane diluted and filtered off. The filter cake is washed twice with 50 ml of diethyl ether washed and 2 hours in 25 ml of 10% methanolic potassium hydroxide Solution stirred. The product obtained in crystalline form is isolated by filtration, washed with water and dried.

2.8 g (59% of theory) of 5- (3-chlorophenyl) -3- (4-ethoxybenzyl) -2- are obtained. methylimino-Δ⁴-1,3,4-thiadiazdin with a melting point of 82 ° C.

Analogously to Example 1 and in accordance with the general description of the inventions The manufacturing method according to the invention can also be used, for example, in the following Compounds of formula (I) or the formulas listed in Table 1 above (Ia) or (Ib) can be produced.  

Table 1: Examples of the compounds of the formula (I)

For example, the compound listed in Table 1 as Example 35 may be like are produced as follows:

A mixture of 14.0 g (61 mmol) of 5- (3-chlorophenyl) -2-methylamino-1,3,4-thia diazole, 28.5 g (121 mmol) of 4-acetoxybenzyl bromide and 500 ml of dry dioxane is heated under reflux for 3 hours. After cooling with 500 ml Diluted hexane and filtered off. The filter cake is twice with 200 ml Washed diethyl ether and 2 hours in 100 ml of 10% methanolic Potassium hydroxide solution stirred. The solution is poured onto 300 ml of water and the product obtained in crystalline form isolated by filtration, with water washed and pressed onto clay.

19.7 g (96% of theory) of 5- (3-chlorophenyl) -3- (4-hydroxybenzyl) -2- are obtained. methylimino-Δ⁴-1,3,4-thiadiazoline with a melting point of 135 ° C.  

For example, the compound listed in Table 1 as Example 37 may be like are produced as follows:

A solution of 2.5 g (7.5 mmol) of 5- (3-chlorophenyl) -3- (4-hydroxybenzyl) -2- methylimino-Δ⁴-1,3,4-thiadiazoline and 1.0 g (7.9 mmol) of ethyldiisopropylamine in 100 ml of dry dichloromethane is stirred for 10 minutes at room temperature. After adding 0.62 g (7.9 mmol) of acetyl chloride, stirring is continued for 2 hours. The Solution is washed twice with 100 ml of water, dried and concentrated. The residue is stirred with petroleum ether. The product obtained in crystalline form isolated by filtration, washed with petroleum ether and dried.

2.0 g (73% of theory) of 5- (3-chlorophenyl) -3- (4-acetoxybenzyl) -2- are obtained. methylimino-Δ⁴-1,3,4-thiadiazoline with a melting point of 88 ° C.  

Application example

In the following application example, the following connection is used for comparison used:

2-methylimino-3-benzyl-5- (3-chlorophenyl) -Δ⁴-1,3,4-thiadiazoline (known from DE- A 27 17 742 / US-P 4020078).  

Example A Post emergence test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, indicates the given amount of emulsifier and dilute the concentrate with water to the desired concentration.

With the active ingredient preparation, test plants are sprayed, which have a height of 5- 15 cm so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 2000 l water / ha the desired amounts of active ingredient are applied. After three weeks, the degree of damage to the plants is rated in% Damage compared to the development of the untreated control.

It means:

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

In this test, for example, show the connections according to the manufacturing Examples 23 and 24 with an application rate of 250 g / ha and very good Compatibility with crops, such as. B. corn (10%), strong effect against weeds such as Abutilon (100%), Chenopodium (90-95%), Matricaria (70-90%) and Veronica (100%).

Claims (9)

1. Substituted thiadiazolines of the general formula (I), in which
R¹ for hydrogen, cyano, nitro, halogen or for a radical optionally substituted by halogen from the series C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl or C₁-C₆-alkylsulfonyl stands,
R² is C₁-C₆ alkyl and
R³ for hydrogen or for a group optionally substituted by halo, cyano, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl or di- (C₁-C₄-alkyl) -amino-carbonyl radical of the series C₁-C₆ - alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl,
R³ further for an optionally substituted by halogen radical from the series C₁-C₆-alkyl-carbonyl, C₂-C₆-alkenyl carbonyl, C₁-C₆-alkoxy-carbonyl, C₁-C₆-alkylthio-carbonyl, di- (C₁-C₄ -alkyl) -amino-carbonyl or C₁-C₆-alkyl-sulfonyl,
R³ further represents C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl or C₅-C₆-cycloalkenyl, each optionally substituted by halogen or C₁-C₄-alkyl, or
R³ further for a radical optionally substituted by nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy, of the series phenyl, phenyl carbonyl, phenoxycarbonyl, phenylsulfonyl or phenyl -C₁-C₄-alkyl,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-benzyloxy-ben cyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-methoxy-benzyl) -5- (3-trifluoromethyl-phenyl) -D⁴-1 , 3,4-thiadiazoline, 2-methylimino-3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4th -methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiad-iazo lin are excluded. 2. Substituted thiadiazolines of the general formula (I) according to claim 1, characterized in that
R¹ for hydrogen, cyano, nitro, fluorine, chlorine, bromine or for C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfinyl or C₁- which are optionally substituted by fluorine and / or chlorine C₄-alkylsulfonyl is,
R² is C₁-C₄ alkyl and
R³ is hydrogen or a radical of the series C₁- which is optionally substituted by fluorine, chlorine, cyano, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-carbonyl or di- (C₁-C₃-alkyl) -amino-carbonyl C₅-alkyl, C₂-C₅-alkenyl or C₃-C₅-alkynyl,
R³ further for an optionally substituted by fluorine and / or chlorine radical from the series C₁-C₅-alkylcarbonyl, C₂-C₁-alkenyl-carbonyl, C₁-C₅-alkoxy-carbonyl, C₁-C₅-alkylthio carbonyl, di- ( C₁-C₃-alkyl) -amino-carbonyl or C₁-C₅-alkyl sulfonyl,
R³ furthermore represents a radical of the series C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₃-alkyl or C₅-C₆-cycloalkenyl, which is optionally substituted by fluorine, chlorine or C₁-C₃-alkyl, or
R³ furthermore represents a radical of the series phenyl, phenylcarbonyl, phenoxycarbonyl, phenylsulfonyl or phenyl-C₁- which is optionally substituted by nitro, cyano, fluorine, chlorine, bromine, C₁-C₃-alkyl, trifluoromethyl, C₁-C₃-alkoxy, difluoromethoxy or trifluoromethoxy C₃-alkyl is,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-benzyloxy-ben cyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-methoxy-benzyl) -5- (3-trifluoromethyl-phenyl) -D⁴-1 , 3,4-thiadiazoline, 2-methylimino-3- (3-methoxy-benzyl) -5- (4-fluoro-phenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4th -methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiad-ia zoline are excluded. 3. Substituted thiadiazolines of the general formula (Ia) characterized in that
R¹ stands for hydrogen, cyano, nitro, fluorine, chlorine, bromine or for methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine,
R² is methyl, ethyl, n- or i-propyl and
R³ for hydrogen or for methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl which is optionally substituted by fluorine, chlorine, cyano, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl or dimethylaminocarbonyl or butynyl,
R³ furthermore for acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, ethenylcarbonyl, propenylcarbonyl, butenylcarbonyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-, each optionally substituted by fluorine and / or chlorine. Butylsulfonyl or dimethylaminocarbonyl,
R³ further for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexyl methyl, cyclopentenyl or cyclohexenyl, each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or
R³ furthermore represents phenyl, phenylcarbonyl, in each case optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy, Phenoxycarbonyl or benzyl,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-benzyloxy-ben cyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-methoxybenzyl) -5- (3-trifluoromethyl-phenyl) -D⁴-1,3 , 4-thiadiazoline, 2-methylimino- 3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4-methoxy- benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadia-zoline are excluded by disclaimer. 4. Substituted thiadiazolines of the general formula (Ib) characterized in that
R¹ represents hydrogen, cyano, nitro, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine,
R² is methyl, ethyl, n- or i-propyl and
R³ for hydrogen or for methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl which is optionally substituted by fluorine, chlorine, cyano, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl or dimethylaminocarbonyl or butynyl,
R³ furthermore for acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, ethenylcarbonyl, propenylcarbonyl, butenylcarbonyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-, each optionally substituted by fluorine and / or chlorine. Butylsulfonyl or dimethylaminocarbonyl,
R³ further for each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentenyl or cyclohexenyl, or
R³ further for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy,
Ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl, phenylcarbonyl, phenoxycarbonyl or benzyl,
where the compounds 2-methylimino-3- (4-benzyloxy-benzyl) -5- (3-methyl-phenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-benzyloxy-ben cyl ) -5- (3-chlorophenyl) -D⁴-1,3,4-thiadiazoline, 2-methylimino-3- (4-methoxybenzyl) -5- (3-trifluoromethyl-phenyl) -D⁴-1,3 , 4-thiadiazoline, 2-methylimino- 3- (3-methoxy-benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadiazoline and 2-methylimino-3- (4-methoxy- benzyl) -5- (4-fluorophenyl) -D⁴-1,3,4-thiadia-zoline are excluded. 5. Process for the preparation of the substituted thiadiazolines of the general formula (I) in which R¹, R² and R³ have the meanings given in Claim 1,
characterized in that one

• (a) thiadiazoles of the general formula (II) in which
  R¹ and R² have the meanings given above,
  with substituted benzyl halides of the general formula (III) in which
  R³ has the meaning given above and
  X represents halogen,
  if appropriate in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary,
  or that one
• (b) thiadiazolines of the general formula (I) in which R¹ and R² have the meanings given above and R³ is hydrogen,
  with electrophilic compounds of the general formula (IV) X-R³ (IV) in which
  R³ and X have the meanings given above,
  if appropriate in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary.

6. Process for combating undesirable plants, characterized characterized in that substituted thiadiazolines of the general formula (I)  according to claims 1 to 5 on undesirable plants and / or their Living space. 7. Use of substituted thiadiazolines of the general formula (I) according to claims 1 to 5 for combating undesirable Plants. 8. A process for the preparation of herbicidal compositions, characterized in that that substituted thiadiazolines of the general formula (I) according to Claims 1 to 5 with extenders and / or surface-active Substances mixed. 9. Herbicidal agents, characterized by a content of at least one substituted thiadiazoline of the general formula (I) according to An sayings 1 to 5.