DD283759A5 - AGENTS WITH HERBICIDER AND PLANT GROWTH REGULATORY EFFECT - Google Patents

Abstract

The invention relates to compositions with herbicidal and plant growth-regulating action containing novel substituted * or their imino derivatives of the general formula I and, if W is an oxygen atom, derived therefrom salts of general formula II in which M, W, Y1, Y2, Y3, Y4, Y5, Y6 and Z have the meanings given in the description, in admixture with carriers and / or auxiliaries. Formula * (II) {new means; herbicidal and plant growth regulating activity; Active substance substituted * and derivatives}

Description

Agent with herbicidal and plant growth regulating action

Field of application of the invention

The invention relates to novel substituted 2-thiadiazolylcarbonyl-cyclohexane-1,3-diones and their imino derivatives containing agents with herbicidal and Pflanzenwaohstumsregulierender Virkung.

Characteristic of the known state of the art

It is already known that certain Cyelohexandionearbonsäurederivate have a herbicidal action (EP applications O 157 963, O 186 118 and O 186 120). Often, however, the herbicidal activity of these known compounds is insufficient, or there are selectivity problems in important agricultural crops.

Object of the invention

The aim of the present invention is therefore to provide new agents which are superior in their biological properties to the hitherto known compounds.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are useful as active ingredient in herbicidal and plant growth regulating agents having the desired properties.

Li I Uu Ι: -ί

This object is achieved by means which as active ingredient new substituted 2-thiadiazolylcarbonyl-cyolohexan-1,3-diones and their imino derivatives of the general formula I.

included in the

Y is a hydrogen atom, a halogen atom, a cyano group, a O ^ -O ^ g alkyl, substituted by halogen or cyano, C ^ -C ^ g alkyl group, a Cg-C ^ ₂ alkenyl, substituted by halogen or cyano C 1-6 o-alkenyl, C 1- C 1-6 alkynyl, Cp-C 1-6 alkynyl substituted by halogen or cyano, C 1- C 6- cycloalkyl, 1- (C _1-1- C 1-4 alkoxyimino ) -C _/ | -C ^ - alkyl group, a 1- (C, -C ^ -Alkenyloxyimino) -C ^ -C ^ alkyl group, a 1- (C, -C ^ -Alkinyloxyimino) -C ^ -C ^ -alkyl radical or one of the groups - (CH ₂ ) _m C0 ₂ M, - (CHg ^ COgR or - (CH ₂ ²⁵

-3-

Y is a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₄₁₁ -alkyl group

1 IB

kylrest, a substituted by halogen or cyano C, -C, _o- alkyl,

1 18

a C -C -alkenyl radical, a C -C -alkenyl radical substituted by halogen or cyano, a C ₂ -C ₄ -alkynyl radical, a radical represented by halogen or

Cyano substituted C-C ^ .- alkynyl, a C, -C_ cycloalkyl or

1 2 3

one of the groups - (CH J CO, M, - (CH,) CO ₉ R or - (CH) CONR R or - 2mZ 2m2 2m

Y and Y together with the adjacent carbon atom form a C, -C.cyclo-

3 6 alkyl radical,

'

Y is a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₄₁₁ -alkyl group

1 ID

kylrest, substituted by halogen or cyano, C ₄ -C _4e alkyl radical,

1 18

a C -C -alkenyl radical, a C -C -alkenyl radical substituted by halogen or cyano, a C 1 -C -p-alkynyl radical, a radical represented by halogen or

Cyano substituted C -C ₁ , -Alkinylrest, a C, -C _c -cycloalkyl or

1 2 3

one of the groups - «CH ^ COgM, '^» _z ⁾ m ^C0 2 ^R or -ICH ^ CONR R,

Y is a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₁₀ -Al-

1 18

kylrest, a substituted by halogen or cyano C.-C ..- alkyl radical,

1 18

a C 1 -C 4 alkenyl radical, a C 1 -C 8 -alkynyl radical substituted by halogen / the cyano, a C 1 -C ₁₂ -alkynyl radical, a radical represented by halogen or

Cyano substituted C-C ^ -Alkihylrest, a C_-C_-cycloalkyl or

1 2 3

one of the groups - ^{CH ₂ ⁾ _m ^C0 2 ^H · ^(CH 2 ¹ m ^C0 2 ^{R or} - ^(CH ₂ ' _m ^{c0NR R or}

Y and Y together with the adjacent carbon atom represent a C -Cp -cyclo-

3 D

alkyl radical or a carbonyl group, 5

Y is a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₁₀ -Al-

1 18

kylrest, a substituted by halogen or cyano C -C, .- alkyl radical,

1 18

a C -C _-oalkenyl radical, one substituted by halogen or cyano

£. I C

C -C ₁₂ alkenyl radical, a C ₂ -C. Alkynyl radical, one by halogen or Cyano substituted C.-C _4O- alkynyl, a C.-C_-cycloalkyl or

1 2 3

one of the groups - (. CH) CO, M, - (CH ₀₎ CO, R or - (CH,) CONR R,

ZmZ zmz zm

Y is a hydrogen atom, a halogen atom, a cyano group, a CC ₁₀ -Al-

1 18

kylrest, a substituted by halogen or cyano C ₄ -C _4O- alkyl,

1 18

a C 1 -C 4 alkenyl radical, a C ₂ -C ₁₂ alkenyl radical substituted by halogen or cyano, a C ₁ -C -alkynyl radical, a radical represented by halogen or

Cyano substituted C.-C ^ alkynyl, a C_-C.-cycloalkyl or

1 2 3

one of the groups - (CH.) CO, M, - (CH,) CO, R or - (CH,) CONR R or

2m2 ZmZ Zm

-t

Y and Y together with the adjacent carbon atom have a C.-C.-cyclo

J 6

alkyl,

W is an oxygen atom or the group = N-R, Z is one of thiadiazolyl radicals

N or

Il

N N N

m 0,1,2,3 or 4,

M is a cation from the group lithium, sodium and potassium, one equivalent

from the group zinc, manganese, calcium, magnesium and barium or a

Ammonium ion of the general formula

R ⁵

R ^{1 is} a hydrogen atom, a C 1 -C 4 -alkyl radical, a C 1 -C 4 -alkyl radical which is monosubstituted or polysubstituted, identical or isubstituted by halogen, hydroxy or cyano, or mono- or polysubstituted by oxygen or sulfur, a C C ₂ -C ₁₂ -alkenyl radical, a mono- or polysubstituted by identical or different halogen, hydroxy or cyano or interrupted by oxygen or sulfur mono- or polysubstituted C -C-alkenyl radical, a C _? -C _1? -Alkinylrest, a mono- or polysubstituted by identical or different halogen, hydroxy or cyano or mono- or polysubstituted or interrupted by oxygen or sulfur C -C-alkynyl, a phenyl radical, a mono- or polysubstituted by identical or different halo nitro , Cyano or C -C, -alkyl-substituted phenyl radical, a phenyl-C -C -alkyl radical or a mono- or polysubstituted by identical or different halogen, nitro, cyano or

C alkyl substituted phenyl-C.-C-alkyl radical, 2 R is a hydrogen atom, a C -C. _ö -Ax :: ylrest, a mono- or polysubstituted by identical or different halogen, hydroxy or cyano or interrupted by oxygen or sulfur one or more times

-5-

C ₁ -C, "- alkyl radical, a CC -.- alkenyl radical, a single or multiple,

I IO eic

identical or different, substituted by halogen, hydroxy or cyano or interrupted by oxygen or sulfur one or more times interrupted C -C ^ alkenyl radical, a C _? -C ..- alkynyl, a mono- or polysubstituted by identical or different halogen, hydroxy or cyano or interrupted by oxygen or sulfur mono- or polysubstituted Cp-C-alkynyl radical, a phenyl radical, a mono- or polysubstituted, identical or different by rialogen, nitro, cyano or C -C, -A3.kyl substituted phenyl radical, a phenyl-C -C -alkyl radical or a mono- or polysubstituted by identical or different halogen, nitro, cyano or CC-alkyl substituted phenyl-C.-C.-alkyl radical,

R is a hydrogen atom, a C -C _1fl -Aikylrest, mono- or mono- or polysubstituted, identically or differently by halogen, hydroxyl or cyano or substituted by oxygen or sulfur repeatedly interrupted C.-Cj-alkyl group, a C _o -C , _- alkenyl radical, a single or multiple,

110 eic

the same or different substituted by halogen, hydroxyl or cyano or by oxygen or sulfur mono- ocier repeatedly interrupted C -.- C alkenyl radical, a C.-C ₁₂ alkynyl a mono- or polysubstituted, identically or differently, by halogen, hydroxy or Cyano substituted or interrupted by oxygen or sulfur mono- or polysubstituted CC ₁ _ alkynyl. a phenyl radical, a mono- or polysubstituted by halogen, Ni *: ro, cyano or C.-C, alkyl substituted Phenvlrest, a phenyl-C -C-alkyl radical or a mono- or polysubstituted by identical or different, same or different by halogen, nitro, cyano or C_-

C 1-4 alkyl substituted phenyl-C 1 -C 4 alkyl radical or

and R together with the adjacent nitrogen atom is an I group, a fiperidino group or a pyrrolidino group,

R is a hydrogen atom, a halogen atom, a cyano group, a C.-C ₁₀ -Al-

1 oo

kylvest, a mono- or polysubstituted by identical or different halogen, cyano or one of the groups -υΤ <or -S (O) R-substituted CC-alkyl radical, a C ^ -C -.- alkenyl radical, a mono- or multiple, identical or different, by halogen, cyano or one of the groups -OR or -S (O) R substituted C -C ^ alkenyl, a C ₂ -C ₁₂ alkynyl, one or more times, identically or differently by halogen, cyano or a group -OR or -S (O) R substituted C ₂ -G ₁₂ -Al-

-6-

kinylrest, a phenyl radical, a mono- or polysubstituted by identical or different halogen, cyano, C ^ C ^ alkyl or one of the groups -OR ¹ or -S (U / R substituted phenyl radical, a phenyl-C -C-alkyl radical , a phenyl or C 1 -C 8 -alkyl radical which is monosubstituted or polysubstituted, identically or differently, by halogen, cyano, C 1 -C 4 -alkyl or one of the groups -OR or S (O) R, or one of the groups - (CH ₂ ) CO ₂ R ¹ , -COR ¹ ,

- (CH,) CO ₉ M ₁ - (CH ₀ ) CONR ² R ³ , -NHCONR ² R ³ . -NHCO.r ', -NHCOR ¹ . -NHSO.R ¹ .

i 3 1 1 1 1

- (CH) NR R ₁ -S (O) R, -OR, -CH = NNHR or -CH = MOR ¹ , Zm η

R is a hydrogen atom, a C.-C.-alkyl radical, a mono- or polysubstituted,

ι ο

identical or different with halogen, hydroxy, cyano or C.-C.-alkoxy

1 D

substituted C -C -alkyl radical, a phenyl radical, a mono- or poly-

1 O

phenyl which is identical or different and is substituted by halogen, hydroxyl, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,

bib 1

C-alkyl or one or more times, same or different

by halogen, hydroxyl, nitro, cyano, C -C -alkyl or C.C. -alkoxy sub-

Ib Ib

substituted phenyl-C -C -alkyl radical,

R is a hydrogen atom, a C.-C.-alkyl radical, a mono- or polysubstituted,

ι ο

identical or different by halogen, hydroxy, cyano or C -C alkoxy

1 6

substituted C -Co-alkyl radical, a phenyl radical, a mono- or poly-

1 o

phenyl which is identical or different and is substituted by halogen, hydroxyl, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,

b 1 b 1

C 1 -C 4 alkyl radical or a mono- or polysubstituted by identical or different halogen, hydroxyl, nitro, cyano, C 1 -C -alkyl or C 1 -C -alkoxy sub-

Ib Ib

substituted phenyl-C -C -alkyl radical,

7 R is a hydrogen atom, a C -C -alkyl radical, a mono- or polysubstituted,

1 0

identical or different by halogen, hydroxy, cyano or C -C alkoxy

1 b

substituted C -C -alkyl radical, a phenyl radical, a one- or more-1 ο

fold, the same or different, by halogen, hydroxy, nitro, cyano,

C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituted phenyl radical, a phenyl C 1 -bib 1

C-alkyl or one or more times, same or different

by halogen, hydroxy, nitro, cyano, C.-C.-alkyl or C.-C.-alkoxy sub-

Ib Ib

substituted phenyl-C ₂ -C ₂ -alkyl radical,

R is a hydrogen atom, a C -C _o -alkyl radical, a mono- or polysubstituted,

1 H

identical or different or by halogen, hydroxy, cyano or C -C -alkoxy-substituted C -C -alkyl radical, a phenyl radical, a mono- or poly-substituted

1 B

-7-

phenyl, C.sub.1 -C.sub.4 -alkyl, phenyl which is identical or different and is halogen, hydroxyl, nitro, cyano, C.sub.1 -C.sub.4 -alkyl or C.C.sub.-alkoxy, or a mono- or polysubstituted by halogen, Hydroxy, nitro, cyano, C -C -alkyl or C, -C _c -alkoxy sub-

Ib Ib

substituted phenyl-C ^ C-alkyl radical, and η 0, 1 or 2

mean, and which, if W is an oxygen atom, derived therefrom salts of the general formula II

OM

(II),

in the M, Y ¹ , Y ² , Y ³ . Y *. Y ⁵ , Y ⁶ and Z have the meanings given under the general formula I.

The term "halogen" in this context includes fluorine, chlorine, bromine and iodine. The terms "alkyl", "alkenyl" and "alkynyl" are to be understood as meaning both straight-chain and branched hydrocarbon radicals.

The compounds of the general formula I to be used according to the invention can also be present as tautomers with the general formulas I 'and I' '

-8th-

in which W, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Z have the meanings given under the general formula I. These structures are also encompassed by the present invention, but for the sake of simplicity only the structure of general formula I will be given.

The compounds to be used according to the invention can be prepared by

A) if W is an oxygen atom, a compound of general formula III

(III),

in the Y ¹ , Y ² . Y ³ , Y *. Y ⁵ . Y ⁶ and Z have the meanings given under the general formula I, subjected to a catalytically promoted rearrangement reaction or

B) if W is the group = N-R, a compound of general formula IV

(IV),

in the Y ¹ , Y ² , Y ³ , Y *. Y ⁵ , Y ⁶ and Z have the meanings given under the general formula I, with amines of the general formula V

H ₂ N - R ² (V),

-9-

2 in which R has the mentioned under the general formula I Bedoutung condensed.

As catalysts for the rearrangement reaction A) to pyridine derivatives, such as 4- (N, N-dialkylamino) pyridines are suitable, preferably 4- (N ₁ N-Dimethylami.no) pyridine, N-alkylimidazoles such as N- Methylimidazole, metal cyanides such as cuprous cyanide, sodium cyanide, potassium cyanide and zinc cyanide, 2-hydroxyisobutyric acid nitrile, or Lewis acids such as zinc chloride or aluminum chloride.

The reaction is carried out with exclusion of moisture and preferably in the presence of an inert solvent. As bescr.üers have suitable for this aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, trichloromethane and dichloromethane, acetonitrile or organic bases such as triethylamine and pyridine proved.

The starting materials of general formula III are obtained by acylation of a ß-Dioxocyclohexanderivates the general formula VI

(VI),

in the Y, Y, Y ₁ Y, Y, Y have the meanings mentioned under the general formula I, with compounds of general formula VII

Il (VII),

X-C-Z

in which Z has the meaning given under general formula I and X represents a leaving group, such as halogen, preferably a chlorine or bromine atom.

-10-

This Ayclierungsreaktion is optionally carried out in the presence of an inert solvent and an acid-binding agent. Suitable acid-binding agents are various organic inorganic bases, but triethylamine and pyridine have proven to be particularly suitable.

The preparation process B) is advantageously carried out under dehydrating conditions and optionally in the presence of a suitable solvent or diluent. Chlorinated hydrocarbons, such as dichloromethane or chloroform, and alcohols, such as methanol, ethanol and 2-propanol, have proven particularly suitable for this purpose.

The dehydration may optionally be assisted by the usual methods, for example by adding a water-binding agent

such as molecular sieve (3A) or magnesium sulfate. The removal of the mass formed by distillation or azeotropic distillation may also be advantageous.

In the preparation methods A) and B) can - n? T? N the already mentioned - are also used in each case all such solvents or diluents, which are inert to the respective reactants. Examples of such solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, which may each be optionally chlorinated, for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, Ethers such as diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, alcohols such as Methanol, ethanol, isopropanol, butanol and ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, and sulfones such as sulfolane and bases such as pyridine ,

-11-

All reactions are preferably carried out under the pressure of the environment, although they could be carried out at elevated or reduced pressure. They can also be performed within a wide temperature range. In general, they are at a temperature between -20 C and the boiling point of the reaction mixture, preferably at ^{0 0} C to 15O ⁰ C performed.

The presence of an additional reaction catalyst may be advantageous. As such catalysts, potassium iodide and onium compounds such as quaternary ammonium, phosphonium, arsonium and sulfonium compounds are suitable. Also suitable are polyglycol ethers, especially cyclic ones, such as 18-crown-6, and tertiary amines, such as tributylamine. Preferred are quaternary ammonium compounds such as benzyltriethylammonium bromide and tetrabutylammonium bromide.

The compounds to be used according to the invention prepared by the abovementioned processes can be isolated from the reaction mixture by customary methods, for example by distilling off the solvent used under normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can be obtained as a rule by column chromatographic purification as well as by fractional distillation or crystallization.

The compounds to be used according to the invention generally represent almost colorless and odorless liquids or crystals which are conditionally soluble in water, aliphatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, readily 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, carbonitriles such as acetonitrile, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide, sulfoxides such as dimethylsulfoxide and, because of their usually acidic character in bases such as alkali metal hydroxide, alkali metal carbonate and alkali bicarbonate solutions, triethylamine or pyridine.

-12-

Oie in the preparation process A) required for the acylation compounds of the general formula VII are either known from the literature or can be prepared based on methods known from the literature. Relevant techniques are described, for example, in J. Am. Chem. Soc. 22 5359 (195 ¹ I) or Chem. Ber. JL9, 1610 (1966).

The agents of the invention show a good herbicidal action in broad-leaved weeds and grasses. Selective use of the agents of the invention is possible in various crops, for example, rapeseed, beet, soybean, cotton, rice, barley, wheat and other cereals. Individual agents are particularly suitable as selective herbicides in beets, cotton, soybeans and cereals. Similarly, weed control products may be used in permanent crops such as forest, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry and hops plants, and for selective weed control in annual crops.

The agents according to the invention can be used, for example, in the following plant genera:

Dicotyledonous weeds of the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solarium, Rorippa, Lamium, Veronica, Abutilon, Dacura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

Monocotyledonous weeds of the genera Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyrone, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ishamedum and Apera.

Depending on the type of application in the pre-emergence and post-emergence, the quantities vary from 0.03 to 5 kg / ha.

The agents according to the invention can also be used as defoliants, desiccants and as herbicide.

-13-

The compositions according to the invention can be used either alone, in admixture with one another or with other active ingredients. If necessary, other crop protection or pest control agents may be added according to the desired purpose. If a widening of the spectrum of action is intended, other herbicides can be added.

For example, the herbicidally active mixture partners are those active ingredients which are described in Weed Abstracts, Vol. 12, 1987, entitled "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".

A promotion of the effective intensity and the rate of action can be achieved, for example, by means of action-enhancing additives, such as organic solvents, wetting agents and oils. Such additives may therefore allow a reduction in the dosage of active ingredient.

In addition, the agents according to the invention cause both qualitative and quantitative changes in plants as well as changes in the metabolism of the plants and are therefore to be classified in the class of plant growth regulators, which are distinguished by the following possible uses:

Inhibition of vegetative growth in woody and herbaceous plants, for example, on roadsides, railroad tracks and others, to prevent too abundant growth. Growth inhibition in cereals to prevent storage or buckling, in cotton to increase yield.

Influencing the branching of vegetative and generative organs in ornamental and crop plants to increase the flower bud or tobacco and tomato to inhibit side shoots.

- improving the quality of the fruit, for example increasing the sugar content of sugar cane, sugar beet or fruit and ensuring a more even ripeness of the harvest, leading to higher yields.

-H-

- Increasing the resistance to stress, for example, against climatic influences, such as cold and drought, but also against phytotoxic effects of chemicals.

Influence of latex flow in rubber plants.

- Training of parthenocarp fruits, male sterility and sex influence are also possible applications.

Control germination of seeds or budding buds. Defoliation or influence of the fruit case for harvest relief.

The means according to the invention are particularly suitable for inhibiting vegetative growth in different plant species. Such growth inhibition is hitherto caused in practice with substances which either do not act consistently or are thinner in their action than the compounds according to the invention.

These are, for example, substances for various cereals used to achieve straw shortening and to give the plant greater stability. In addition, such an effect can inhibit plants in growth whose growth is not desirable in certain locations, such as on roadsides, at railway tracks or at airfields. Even grasses in the lawn can be influenced, so that must be cut less frequently. Growth-inhibiting effects are also achieved with such substances in general in crop plants that branch too intensively due to the budding of resting buds, for example tobacco.

In cotton, growth inhibition can lead to a uniform maturation of the capsules and thus to higher yields.

In the case of fruit trees, the targeted influencing of vegetative growth leads to increased yields and economic advantages.

-15-

In ornamental plants is achieved by a reduction in growth often that more plants per footprint can be attracted n.

The compositions according to the invention have their effect both in pre- and post-emergence treatment. Depending on the application target, the application rates are from 0.001 to 5 kg / ha, and it is also possible to use higher charges.

The application time depends on the application target and the climatic conditions.

Appropriately, the marked agents oc'er their mixtures in the form of preparations such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally adhesive, wetting, emulsifying and / or dispersing agents applied.

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, furthermore mineral oil fractions and vegetable oils.

Suitable solid carriers are minerals, for example bentonite, silica gel, talc, kaolin, attapulgite, limestone, and vegetable products, for example flours.

Surfactants include, for example, calcium lignosulfonate, polyethylene alkylphenyl ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

The proportion of or of the active ingredient (s) in the various preparations can vary within wide limits. For example, the compositions contain about 1 to 90% by weight of active ingredient, about 99 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances.

- 16 -

The application of the agents can be carried out in the usual manner, for example with water as a carrier in Spritzbrühmengen about 100 to 1000 liters / ha. An application of the funds in the so-called low-volume and ultra-low-volume method is just as possible as their application in the form of so-called microgranules.

The preparation of these preparations can be carried out in a manner known per se, for example by milling or mixing processes. If desired, preparations of the individual components can also be mixed shortly before use, as is done in the example in the so-called tank mix process in practice.

embodiment

The invention is explained in more detail below with reference to some examples. For example, the following ingredients are used to prepare the various preparations. «

A) Spray powder

1.) 20 weight percent active ingredient 68 weight percent kaolin

10% by weight of calcium salt of lignin sulfonic acid 2% by weight of dialkylnaphthalenesulfonate

2.) 40 weight percent active ingredient

25% by weight colloidal silica 8% by weight calcium salt of lignin sulfonic acid 2% by weight sodium salt of N-methyl-N-ols;

taurins

- 16a B) Emulsions concentrate

20% by weight of active ingredient 75% by weight of isophorone

2% by weight ethoxylated castor oil

3% by weight of the calcium salt of dodecylphenyl

sulfonic acid

G) granules

1.66% by weight of active ingredient 98.34% by weight of attapulgite granules

-17-

The following examples illustrate the preparation of the compounds to be used according to the invention:

Example 1.01

2-U-Methyl-i, 2,3-thiadiazol-5-ylcarbonyl) cyclohexane-1,3-dione

To 10.00 g (89.2 mmol) of cyclohexane-1,3-dione dissolved in 175 ml of dichloromethane and 20 ml of triethylamine are added slowly at ice temperature 16.00 g (98, A mmol) of A-methyl-1,2, S-thiadiazole-δ-carboxylic acid chloride was added dropwise and then stirred for 3 hours at room temperature. Min poured on ice, separated and the organic phase washed with 1 N hydrochloric acid, saturated bicarbonate solution and Masser, dried (magnesium sulfate) and concentrated.

The thus obtained 3- (A-methyl-1,2,3-thiadiazol-5-ylcarbonyloxy) -2-cyclohexen-1-one is stirred in 120 ml of acetonitrile, 25 ml of triethylamine and 3 ml of acetone cyanohydrin for 24 hours at room temperature. The mixture is taken up in 100 ml of diethyl ether, washed with 100 ml N hydrochloric acid and Ί ζwein al extracted with 50 ml of 5 '/ potassium carbonate solution. After upper layers of this alkaline phase with 100 ml of diethyl ether is acidified with 4 N hydrochloric acid to pH 3, separated, washed with water, dried (magnesium sulfate) and rotated. Recrystallization from ethyl acetate provides the desired substance in the form of colorless needles.

Yield: 15.30 g = 72 '/. of theory mp .: A8- * 9 ° C

-18-

Analogously, the following compounds according to the invention were prepared: Example Name of the connection Physical constant

1.02 5,5-Dimethyl-2- (4-methyl-1,2,3-Fp .: 68-7O ⁰ C thiadiazol-S-ylcarbonyU-cyclohexane-1,3-dione

1.03 3,5-Dioxo-4-U-methyl-1,2, '3-Fp .: 58-6O ⁰ C thiadiazol- ⁶ -ylcarbonylj-cyclohexanecarboxylic acid ethyl ester

1.04 5-Methyl-2- (4-methyl-1,2,3-Fp.: 59-6O ⁰ C thiadiazol- ⁶ -ylcarbonyl-cyclohexane-1,3-dione

1.05 ·. , 4-Dimethyl-2 - (* - methyl-1,2,3-Fp .: 57 ° C thiadiazol- ⁶ -ylcarbonyU-cyclohexane-1,3-dione

1.06 2- (1,2,3-Thiadiazol-5-ylcarbonyD-Fp .: H5-U7 ° C cyclohexane-1,3-dione

1.07 5,5-dimethyl-2- (1,2,3-thiadiazole-Fp.: 109 ⁰ C S-ylcarbonyU-cyclohexane-i, 3-dione

1.08 4,4-Dimethyl-2- (1,2,3-thiadiazole-Fp .: 82 ⁰ C 5-ylcarbonyl) -cyclohexane-1,3-dione

1.09 3,5-Dioxo-4- (1,2,3-thiadiazol-5-Fp .: 9O ⁰ C ylcarbonyU-cyclohexanecarboxylic acid ethyl ester

20

1.10 5-Isopropyl-2-U-methyl-1,2,3-thiamine _Q : 1.5812

diazo.l-5-ylcarbonyl) cyclohexane-1,3-dione

-19-

example Name of the connection Physical constant

3, 5-dioxo-1-methyl-4- (4-methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexanecarboxylic acid ethyl ester: 1.5615

.12

2- (1, a.G-thiadiazol-A-ylcarbonyl) cyclohexane-1,3-dione

Mp: 93-95 ⁰ C

.13

1.U

2- (4-Methoxycarbonyl-1,2,3-thiadiazol-6-ylcarbonyD-cyclohexane-1,3-dione

2- (4-ethyl-1,2,3-thiadiazol-5-ylcarbonyl) cyclohexane-1,3-dione

Mp: 78-8O ⁰ C η !: ⁰ : 1.5887

1. 15

2- (4-methoxymethyl-1,2,3-thiadiazol-S-ylcarbonyU-cyclohexane-1,3-dione

: 1.5944

1.16

4,4,6,6-tetramethyl-2- (4-methyl-1,2,3-thiadiazol-5-ylcarbonyl) cyclohexane-1,3,5-trione

Mp .: 70-71 ⁰ C

.17

2- (4-ethyl-1,2,3-thiadiazol-5-ylcarbonyl) -4,4,6,6-tetramethylcyclohexane-1,3,5-trione

Mp: 37 ⁰ C

1.18

4,4,6,6-Tetramethyl-2- (4-methoxymethyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3,5-trione nJ ⁰ : 1.5668

, 19

4-11-Ethoxyiminoethyl) -2-

(4-methyl-1,2,3-thiadiazol-5-yl

carbonyU-cyclohexane-1,3-dione

Πρ °: 1.5848

-20-

Example 2.01

3,5rDioxo-4 - (* - methyl-1,2,3-thiadiazol-5-ylcarbonyl) cyclohexanecarboxylic acid

4.50 g (H, 5 mmol) of 3,5-dioxo-4-U-methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexanecarboxylic acid ethyl ester are heated in 30 ml 5 Ziger sodium hydroxide solution for 30 minutes on the Masserbad, then covered with ether and adjusted to pH 3 with hydrochloric acid. Separation and evaporation of the aqueous phase gives, after recrystallization from methanol, the product in the form of colorless crystals.

Yield: 3.20 g = 78 Ί of theory Fp .: 185 ⁰ C (dec.)

Example 2.02

3, S-dioxo-4- (1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexanecarboxylic acid sodium salt

To 2.50 g (8.4 mmol) of 3,5-dioxo -; (1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexanecarboxylic acid ethyl ester (Examples 1.09) in 30 ml of ethanol is the equivalent amount of ethanolic sodium hydroxide in Eistemperator Added dropwise solution and then stirred for 2 hours at room temperature. Removal of the solvent in vacuo gives the desired substance.

Yield: 2.7 g = 100 % of theory mp: 111 ^° C.

-21-

Analogously, the following compounds of the invention were prepared: example Name of the connection Physical constant

2- (4-Methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3-dione sodium salt M.p .: 267 ^° C

2- (4-methyl-1,2,3-thiadiazol-5-ylcarbonyll-cyclohexane-1,3-dione triethylene! Ammonium salt m.p .: 57 ⁰ C

2- (4-Methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3-dione magnesium salt M.p .:> 27O ⁰ C

2-U-methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3-dione calcium salt M.p .:> 27O ⁰ C

4,4,6,6-Tetramethyl-2- (4-methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3,5-trione magnesium salt M.p .:> 27O ⁰ C

4,4,6,6-tetramethyl-2-U-methyl-1,2,3-thiadiazol-5-ylcarbonyl) -cyclohexane-1,3,5-trione calcium salt M.p .:> 27O ⁰ C

-22-

Example 3.01

2- [1- (4-methyl-1,2,3-thiadiazol-5-yl) -1- (phenylimino) methyl] cyclohexane-1,3-dione

3.00 g (12.6 mmol) of 2-U-methyl-1,2-S-thiadiazol-6-ylcarbonyD-cyclohexane-1,3-dione and 1.5 ml of aniline are added in 30 ml of absolute ethanol for 12 hours Room temperature stirred. The solid obtained after Abdesti'llieren the solvent is washed with hexane and recrystallized from ethanol.

Yield: 2.90 g = 73.5 '/. of theory mp .: 117 ^° C.

8 3 7 59

-23-

Analogously, the following compounds according to the invention were prepared: Example Name of the connection Physical constant

3.02 2-U- (o-Butylimino) -1- (4-methyl-1,2,3-thiadiazol-5-yl) -methyl] -cyclohexane-1,3-dione

Mp.

55-58 ⁰ C

3.03 5,5-dimethyl-2- [1-U-methyl-1,2,3-thiadiazol-5-yl) -1- (phenylimino) -methyl] -cyclohexane-1,3-dione m.p.

136 ⁰ C

3.04 2- [1 - ("- 8utylimino) -1- (4-methyl-1,2,3-thiadiazol-5-yl) -methyl] -S, S-dimethylcyclohexane-1,3-dione M.P.

82-83 ⁰ C

3.05 3,5-Dioxo-4- [1- (4-methyl-1,2,3-

thiadiazol-5-yl) -1- (phenylimino) -

methyll-cyclohexane carboxylic acid

ethyl ester

Mp.

9O ⁰ C

3.06 ethyl 3,5-dioxo-4- [1-phenylimino-1- (1,2,3-thiadiazol-5-yl) -methyl] -cyclohexanecarboxylate M.p .: 115-117 ° C

3:07 2- [1- (2-Hydroxyethylimino) -1- (4-methyl-1,2,3-thiadiazol-5-yl) -methyl] -cyclohexane-1,3-dione mp .: 124 ⁰ C.

83759

-24-

The following examples illustrate the possible uses of the agents according to the invention:

Example A

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 0.3 kg / ha. The means were sprayed for this purpose as emulsions with 500 liters of water / ha evenly over the plants. Here, two weeks after the treatment, the Arfindungs.gemäße means high crop selectivity in wheat and corn with excellent activity against the weeds. The comparison agent did not show the same high effectiveness.

In the following table mean:

0 = not damaged 4 = totally annihilated

TRZAX = Triticium aestivum

ZEAMX = Zea mays

ABUTH = Abutilon theophrasti

MATCH = Matricaria chamomilla

Compound to be used according to the invention

Z A SEBEX = Sesbania exaltata e B SOLSS = Solanum sp. i A U VERPE = Veronica persica la M T SETVI = Setaria viridis T X H M s SVS R A E OEE Z T B LRT A C E SPV X H X BE

Example 1.01

untreated

Comparative agent compound (from EP application 0 137 963)

1 4

-25-

Example B

In the greenhouse, the agents listed in the table were applied with the application rates also mentioned. For this purpose, the agents were added as emulsion concentrates to vessels containing 1500 ml of water. As test plant species, Oryza sativa (ORYSA), Cyperus spp. (CYPSS), Sagittaria spp. (SAGSS), Scirpus juncoides (SCPJU) and Eleocharis kuroguwai (ELOKU) at the 2 to 5 leaf stage. Three weeks after the application, the damage to the plants was scored, according to the following scheme:

0 = no damage

1 = weak damage

2 = mean damage J = severe damage

4 = totally annihilated - = not checked

water application 0 C S S e DDm R Y A C L According to the invention 30 Y P G P 0 to be used 30 S S S <_. K links 10 A S S G U Example 1.01 10 0 4 4 4 4 Example 1.06 10 0 4 - - - Example 1.15 10 0 3 - 3 - Example 2.04 0 3 - - - Example 3.01 0 4 - 3 - Example 3.07 0 4 - 4 -

As the table shows, the agents according to the invention are highly active against important rice weeds and at the same time selective for water rice.

-26-

Example C

In the greenhouse, the compound to be used according to the invention listed in the table was applied at the rate of application likewise mentioned

 For this purpose, the agent was scattered as granules on the soil surface. The test plants used were Oryza sativa (ORYSA), Cyperus difformis (CYPDI), Scirpus juncoides (SCPJU), Eleocharis acicularis (F.LOAC), Monochoria vaginalis (MOOVA) and Eleocharis riurogqwai (ELOKU) at the 1 to 2-leaf stage , Three weeks after the application, the damage to the plants was scored, according to the following scheme:

0 = no damage

1 = weak damage

2 = mean damage

3 = severe damage

4 = totally annihilated

OCSEME R Y CL 0 L

; According to the invention YPPOOO to use kg of active ingredient / ha SDJAVK

Connection AIUCAU

Example 1.01 1.1 1 A 4 * 3 4

Verqleichsmittel Pyrazolates 2.0 14 2 3 2 0

As the table shows, the agent according to the invention is highly effective in attracting important rice weeds and, at the same time, selectively as water rice.

-27-

Beispiol D

In the greenhouse, the listed plant species were treated before emergence with the listed agents in an application rate of 1.0 kg active ingredient / na. The compositions were sprayed for this purpose as emulsions with 500 liters of water / ha evenly over the plants. Here, three weeks after the treatment, the compositions according to the invention show a high crop selectivity in wheat and maize with excellent action against the weeds. The comparison agent did not show the same high selectivity.

In the following table mean:

0 = no damage

1 = 1 - 24 7. Injury

2 = 25 - 74 7. Injury

3 = 75 - 89 7. Injury

4 = 90 - 100 7. Injury

TRZAX = Triticum aestivum ZEAMX = Zea mays BEAVX = Beta vulgaris altissima BRSSS = Brassica sp. HELAN = Helianthus annuus SETVI = Setaria viridis PANSS = Panicum maximum CYPES = Cyperus esculentus ABUTH = Abutilon theophrasti GALAP = Galium aparine MATCH = Matricaria chamomilla POLSS = Polygonum sp.

-28-

T Z B B H S P C A G M P R e e R e e A Y B A A 0 According to the invention ISL A A S L T N P U L T L to be used A M V S A V S e T A C S connection X X X S N I S S H P H § Example 1.16 1 0 A A 3 A A A » 3 A 3 untreated 0 0 0 t 0 0 0 0 0 0 0 0 0 Comparative agent norflurazon 3 3 A A 3 A 3 A 3 A 1

Example E

In the greenhouse, the listed plant species were treated before emergence with the listed agents in an application rate of 3.0 kg / ha. The compositions were sprayed for this purpose as emulsions with 500 liters of water / ha evenly over the plants. Here, three weeks after the treatment, the compositions according to the invention show an excellent action against the weeds.

In the following table mean:

0 = no damage

1 = 1 - 2AZ damage

2 = 25 - 7AZ damage

3 = 75 - 89 Z Damage A = 90 - 100 Z Damage

AVEFA = Avena fatua SETVI = Setaria viridis ABUTH = Abutilon theophrasti GALAP = Galium aparine MATCH = Matricaria chamomilla

-29-

He inventively used compounds

A S A G M V e B A A e T U L T F V T A C A I H P H 3 4 4 3 4 3 4 ¹ 4 4 4 O 4 2 3 3 O 1 O 4 2 O 2 4 3 3 O 3 4 4 4 2 2 4 4 4 O O 3 3 4 2 4 4 1 2 O 4 4 4 4 3 4 4 3 4 3 4 4 4 4 O 3 1 4 2 O 2 O 2 3 O 4 4 4

Example 1.04 Example 1.05 Example 1.06 Example 1.07 Example 1.14 Example 1.15 Example 1.17 Example 1.19 Example 2.03 Example 2.04 Example 3.01 Example 3.02 Example 3.03 Example 3.04 Example 3.07

Example F

In the greenhouse, the listed plant species were treated prior to emergence with don listed funds at a rate of 3.0 kg / ha. For this purpose, the agents were sprayed uniformly over the plants as emulsions containing 500 liters of groundwater / ha. Here, two weeks after the treatment, the compositions according to the invention show an excellent action against the weeds.

-30-

In the following table mean:

0 = no damage

1 = 1 - 24 Z damage

2 = 25 - 74 1. Injury

3 = 75 - 89 '/ damage

4 = 90 - 100 Ί. damage

AVEFA = Avena fatua SETVI = Setaria viridis ABUTH = Abutilon theophrasti GALAP = Galium aparine MATCH = Matricaria chamomilla

Compounds to be used according to the invention

A S A G M V e B A A e T U L T F V T A C A I H P H 3 3 4 3 2 2 2 4 3 4 4 3 3 4 4 3 2 0 3 0 0 3 4 1 3 1 4 2 2 2 0 3 4 3 4 1 2 4 3 3 3 4 4 3 4 2 4 4 4 4 0 1 0 3 0 2 0 4 3 4

Example 1.04 Example 1.05 Example 1.06 Example 1.08 Example 1.14 Example 1.15 Example 2.03 Example 2.04 Example 3.01 Example 3.02 Example 3.04 Example 3.07

Claims (1)

claim in the
Y a hydrogen atom, a halogen atom, a cyano group, a C -C.Oι 18 Alkyl radical, a substituted by halogen or cyano C.-C, _o- alkyl 1 oo a C -C -alkenyl radical, a C -C -alkenyl radical substituted by halogen or cyano, a C 1 -C 4 -alkynyl radical, a C 1 -C 4 -alkynyl radical substituted by halogen or cyano, a C, -C_-cycloalkyl c Λ C jb a 1- (C ₃ -C 6 -alkenyloxyimino) C -C ₄ -alkyl radical, a 1-C 1 -C ₄ -alkoxyimino-C 1 -C ₄ -alkyl radical, a C 1 -C ₄ -alkynyloxyiminoJ-CC, alkyl or one of the groups - (CH.) CO_M, - (CH ₀ ) CO.R or 2m2 2m2 R _{1 2m} Y is a hydrogen atom, a halogen atom, a cyano group, a C, -C ₄ .- 1 oo Alkyl radical, a substituted by halogen or cyano C -C ^ .- alkyl 1 1 D radical, a C -C -C -alkenyl radical, a C 1 -C 4 -alkanyl radical substituted by halogen or cyano, a C 1 -C -alkynyl radical, one by halogen or cyano-substituted C -C alkynyl -.-, _c a C.-C cycloalkyl 1 ? 3 or one of the groups - (CH ₀ J CO ₀ M, - (CH-J CO.R or - (CH ₀ ) CONR R or 2m2 2m2 2m Y and Y together with the adjacent carbon atom form a C, -C.cyclo- 3 ο alkyl, Y is a hydrogen atom, a halogen atom, a cyano group, a C.-C, o Ib Alkyl radical, a C, -C. _E -alkyl radical substituted by halogen or cyano 1 10 radical, a t.-C -.- alkenyl radical, a C -C -p alkenyl radical substituted by halogen or cyano, a C 1 -C -alkynyl radical, one by halogen -32- or cyano substituted C ₀ -C, _o- alkynyl, a C, -C_-cycloalkyl 1 2 3 or one of the groups "ICHg ^ COgM, - (CH ^ COgR or - (CH) CONR R, Y is a hydrogen atom, a halogen atom, a cyano group, a CC _1n - 1 IO Alkyl radical, a substituted by halogen or cyano C.-C. "- Alkyl 1 18 radical, a Cg-C-.alkenyl radical, a C ₂ -C ₁₂ -alkenyl radical substituted by halogen or cyano, a C ₃ -C -alkynyl radical, a C ₁ -C -alkynyl radical substituted by halogen or cyano, a C , -C.-cycloalkyl 1 2 3 or one of the groups - (CH) CO ₉ M. - (CH.) CO, R or - (CH.) CONR R or ί m 2 »2 m 2 2m Y and Y taken together with the adjacent carbon atom form a C -C -cyclo- JD alkyl radical or a carbonyl group, Y is a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₁₀ - 1 16 Alkyl radical, a substituted by halogen or cyano C -C -.- alkyl 1 16 radical, a C.sub.-C.sub.-alkenyl radical, a C.sub.1-C.sub.8-alkenyl radical substituted by halogen or cyano, or C_-C. _? Alkynyl, a C ₁ -C ₁ "alkynyl radical substituted by halogen or cyano, a C.C.C. cycloalkyl radical 1 2 3 or one of the groups -i ^CH ₂ ⁾ _m ^c0 ₂ ^M · " ^(CH 2 ⁾ m ^CO 2 ^{R or} " ^(CH ₂ ⁾ _m ^{C0NR R} ' Y is a hydrogen atom, a halogen atom, a cyano group, a CC ₁₀ - 1 18 Alkyl radical, a substituted by halogen or cyano CC _iO alkyl 1 16 radical, a C -C -alkenyl radical, a C -C -alkenyl radical substituted by halogen or cyano, a C - C ₁₂ -alkynyl radical, one by halogen or cyano substituted C 1 -C 4 alkynyl, C 1 -C 3 cycloalkyl 1 2 3 or one of the groups - < ^CH ₂ ) _m CO ₂ M, - < ^c H ₂ ) _m CO ₂ R or - (CH ^ CONR R or Y and Y together with the adjacent carbon atom have a C.-C.-cyclo J 0 alkyl, W is an oxygen atom or the group = N-R, Z is one of thiadiazolyl radicals or -33- m 0,1,2,3 or A, H is a cation from the group lithium, sodium and potassium, one equivalent from the group zinc, manganese, calcium, magnesium and barium or a Ammonium ion of the general formula R ⁶ - Ν ^β - R ⁸ ,
R ⁷ R "in hydrogen atom, a C -C ^ .- alkyl radical, a single or multiple, 1 10 identical or different halogen, hydroxy or cyano-substituted or interrupted by oxygen or sulfur mono- or polysubstituted C -Cg-alkyl radical, a C "-C. _2- alkenyl radical, a C 1 -C 4 -alkenyl radical which is monosubstituted or polysubstituted, identically or differently by halogen, hydroxyl or cyano, or monosubstituted or polysubstituted by oxygen or sulfur, a C.sub.1 -C.sub.-alkyryl radical, a or multiply, identically or differently by halogen, hydroxy or cyano-substituted or by oxygen or sulfur mono- or polysubstituted CC-alkynyl radical. a phenyl radical, a mono- or polysubstituted by identical or different halogen, nitro, cyano or C -C, -alkyl, phenyl, a phenyl-C -C-alkyl radical or a mono- or polysubstituted by identical or different halogen, nitro , Cyano or C 1 -C 4 alkyl-substituted phenyl-C 1 -C -alkyl radical, 2
R is a hydrogen atom, a C 1 -C 6 -alkyl radical, a mono- or polysubstituted 1 IO identical or different, by halogen, hydroxy or cyano-substituted or interrupted by oxygen or sulfur mono- or polysubstituted C -C -alkyl radical, a C, -C _1? -Alkenylrest, a mono- or polysubstituted by identical or different halogen, hydroxy or cyano or interrupted by oxygen or sulfur mono- or polysubstituted C -C -alkenyl, a C_-C ₁₂ alkynyl, one or more times , C.sub.1 -C. -alkynyl radical which is monosubstituted or disubstituted by halogen, hydroxyl or cyano or mono- or polysubstituted by oxygen or sulfur, a phenyl radical, mono- or polysubstituted, identically or differently, by halogen, nitro, cyano or C. -C, alkyl substituents -34- Phenyl-C -Cg-alkyl radical or a mono- or polysubstituted by identical or different halogen, nitro, cyano or C.-C-alkyl-substituted phenyl-C.-C "alkyl radical, R is a hydrogen atom, a C -C, _e alkyl group, a mono- or polysubstituted, 1 18 C ₁ -C -alkyl radical which is monosubstituted or disubstituted by halogen, hydroxyl or cyano or mono- or polysubstituted by oxygen or sulfur, or a C.sub.2 -C.sub.p-alkenyl radical, one or more times, identically or differently, by halogen, hydroxyl or cyano substituted C ₂ -C ₁₂ alkenyl radical, mono- or polysubstituted by oxygen or sulfur, a C 1 -C 4 -alkynyl radical, monosubstituted or polysubstituted by identical or different substituents by halogen, hydroxy or cyano, or by oxygen or sulfur mono- or polysubstituted C -C -alkynyl radical, a phenyl radical, a mono- or polysubstituted by identical or different halogen, nitro, cyano or C -C, -alkyl, phenyl, a phenyl-C -C -alkyl radical or one or more times, identically or differently, by halogen, nitro, cyano or C 1 -C 4 alkyl-substituted phenyl-C 1 -C 4 -alkyl radical or 3
and R together with the adjacent nitrogen atom is a group, a piperidino group or a pyrrolidino group, R is a hydrogen atom, a halogen atom, a cyano group, a CC _1n - 1 16 Alkyl radical, a mono- or polysubstituted by identical or different halogen, cyano or one of the groups -OR or -S (O) R substituted CC alkyl, a C ₀ -C "- alkenyl radical, one or more times, the same or C 1 -C 3 -alkenyl radical which is substituted by halogen, cyano or one of the groups -OR or -S (O) R, a C 1 -C 4 -alkynyl radical, one or more times, identically or differently, by halogen, cyano or one of the groups -OR or -S (O) R substituted C -C ₁₂ alkynyl, a phenyl radical, one or more times, identically or differently, by halogen, cyano, C 1 -C 4 -alkyl, or one of the groups -OR or -S (O) R substituted phenyl radical, a phenyl-C -C-alkyl radical, a mono- or polysubstituted by identical or different halogen, cyano, CC, alkyl or one of the groups -OR or -S (O) R substituted Phenyl-C - -35- C-alkyl radical or one of the groups - (CH ₂ ) CO ₀ R, -COR, - (CH ₀ ) CO ₀ M, - 23 23 11 1 £ 3 (CH.) CONrV. -NHCONrV, -NHCO.R ^1, -NHCOR ^1, -NHSO ₀ R ^1, - (CH ₀₎ NR R ₁ 11 ι ι ^{2 2 m} -S (O) R ₁ -OR, -CH = NNHR or -CH = NOR, ⁿ R is a hydrogen atom, a C -C _o -alkyl radical, a mono- or polysubstituted, 1 o identical or different by halogen, hydroxy, cyano or C, -C _e alkoxy I D substituted C -Cg-alkyl radical, a phenyl radical, a phenyl radical which is monosubstituted or polysubstituted, identically or differently by halogen, hydroxyl, nitro, cyano, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy, a phenylCj-C ₂ - alkyl radical or a mono- or polysubstituted by identical or different halogen, hydroxyl, nitro, cyano, C.sub.1-C.-alkyl or C.sub.-C.sub.alkoxy sub- Ib Ib stituiertem C ₀ R is a hydrogen atom, a C -C -alkyl radical, a mono- or polysubstituted, ι υ identical or different by halogen, hydroxy, cyano or C, -C _e alkoxy 1 b substituted C -C alkyl radical, a phenyl radical, a mono- or polysubstituted by identical or different halogen, hydroxy, nitro, cyano, C, -C alkyl or C, -C alkoxy-substituted phenyl radical, a phenyl-C, -C alkyl or one or more times, same or different by halogen, hydroxyl, nitro, cyano, C -C -alkyl or C -C -alkoxy sub- Ib Ib substituted phenyl-C -C -alkyl radical, R is a hydrogen atom, a C -C -alkyl radical, a mono- or polysubstituted, ι ο identical or different by halogen, hydroxy, cyano or C -C alkoxy 1 D substituted C -C -alkyl radical, a phenyl radical, a mono- or poly- 1 O phenyl which is identical or different and is substituted by halogen, hydroxyl, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, a phenylC, 0 10 I C 1 -C 4 alkyl radical or a mono- or polysubstituted by identical or different halogen, hydroxyl, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C -alkoxy sub- Ib Ib substituted phenyl-C -C -alkyl radical, R is a hydrogen atom, a C -C -alkyl radical, a mono- or polysubstituted, 1 o identical or different through halogen, hydroxy, cyano or C.-C.-alkoxy substituted C -C -alkyl radical, a phenyl radical, a mono- or more-1 ö phenyl, C 1 -C 4 -alkyl, phenyl which is identical or different and is substituted by halogen, hydroxyl, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; UlO I C is alkyl or a mono- or polysubstituted by identical or different halogen, hydroxyl, nitro, cyano, C ^ Cg-alkyl or Cj-Cg-alkoxy-substituted phenyl-C -Cp-alkyl radical, and -36- n O ₁ I or 2 mean, and which, if W is an oxygen atom, derived therefrom salts of the general formula II II) in the M, Y ¹ , Y ² , Y ³ , Y *. Y ⁵ . Y ⁶ and Z have the meanings given under the general formula I, in admixture with carriers and / or excipients.