DD282847A5 - MEDIUM WITH HERBICIDAL EFFECT - Google Patents

Abstract

According to the invention, the novel agents with herbicidal activity contain, as active ingredient, novel heterocyclic-substituted azoles and azines of the general formula in which R 1, X, Y and Z have the meanings given in the description, in admixture with carriers and / or auxiliaries. Formula (I) {strong herbicidal action; good compatibility with crops; high selectivity}

Description

Field of application of the invention

The invention relates to herbicidal agents having a content of novel heterocyclic substituted azoles and azines.

Characteristic of the known state of the art

Ee is already known that certain trlazolopyridazines and benzothiazolylazolidines have herbicidal properties (EP applications O 176 101 and O 230 874). In these known compounds, however, the herbicidal action is not sufficient in all cases or there are selectivity problems in important agricultural crops.

Object of the invention

The aim of the present invention is the provision of new agents which do not have these disadvantages and are superior in their bioluminescent properties to the previously known agents.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are suitable as active ingredient in herbicidal compositions having the desired properties ·

It has now been found that agents containing heterocyclic-substituted azoles and azines of the general formula I.

zn

in the

R. a Wasseretoffatoin, a Cj-Cg-alkyl group, a C ₃ Ce-alkenyl group, a Cj-Ce-Alklnylgruppe, a halogen-C ₃ -Cg-alkenyl group, a halogen-Cj-Cg-alkynyl group, a Cj-Cy Cycloalkyl group, a C ₃ -C ₇ -cycloalkyl-C 1 -C 4 -alkyl group, a halo-C ₁ -C ₆ -cycloalkyl group, a haloC-cycycloalkyl-C 1 -C ₄ -alkyl group, a C ₁ -C ₄ -Cg-alkoxy-Cj ^ -Cg-alkyl group, a C ₁ -C ₂ alkoxy-Cj ^ -Cg-alkoxy-Cj-Cg-alkyl group, a cyano-Cj ^ - C, -alkyl group, a carboxy-C ^ C ₁ -C ₅ -alkoxycarbonyl-C ₁ -C ₃ -alkyl group, a halogeno-C ₁ -C 6 -alkoxycarbonyl-C ₁ -C 4 -alkyl group, a C ₁ -C ₂ oxy-C ₁ -C ₄ -alkyl group; -cg alkoxy

-3-

carbonyl-C -C -alkyl group, a C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl group, a C 1 -C 6 alkylaminocarbonyl C 1 -C 4 alkyl group or a di -C _t -C ₅ alkylaminocarbonyl-C ₁ -C ₃ alkyl group.

Y is a hydrogen, fluorine or chlorine atom,. X is one of the groups ICR R) -W or (CR ₂ I = V, where V or W

are bound directly to the phenyl nucleus, η 0 odor I,

W one of the groups CR, R. or NO. or an oxygen or sulfur atom,

4 5 6

with the proviso that when '= Z and η = 1, W is not oxygen and, when 1-1 or Z, and η = 0, then W is not sulfur,

V is a group C-R or a nitrogen atom,

R, R, R and R, which are identical or different, are each a hydrogen or halogen atom or a C -C -alkyl or halogeno-C -C -alkylene group,

R. is a hydrogen atom, a methyl or halomethyl group b

Z is a heterocyclic radical of the formulas Z, to Z ₀

'3

or

L is a halogen atom, a C ₁ -C 6 -alkyl group, a haloGbn-C ₁ -C 4 -alkyl group, a cyano group or a C ₁ -C 4 -alkoxy group optionally substituted by up to 9 halogen atoms,

Q represents the group CH or a nitrogen atom, with the proviso that when Q = N and η - 1, W is not oxygen and if Q = CH or N and η = O, then W is not sulfur,

U is an oxygen or sulfur atom, U is an oxygen or sulfur atom, R ₇ , R ₀ and R _{n are} each a straight-chain, branched or cyclic,

( Q.

optionally substituted by halogen C -C ₇ alkyl, or R, and R _n together with the adjacent nitrogen and carbon

I o

atoms forms a heterocyclic 5- to 7-membered ring which is saturated or unsaturated, optionally containing further heteroatoms such as O, S or N and is optionally substituted by one to three methyl groups or one to six halogen atoms,

T is the group D-E, D is a group ^(CR ₁₆ ^R ₁₇ > _m · E is an oxygen or sulfur atom or one of the groups SO, SO NR ₄₀

C IO

or ^CR _iq ^R _{? n} . m O or 1, ρ 1 or 2,

"i 2 '" i3 "^ H'" i 5 "'iG ^R * ι ν ^r ia * ^R ig ^{untl R?} n ^e ^ ⁿ hydrogen atom, a hydroxy group, a C ^ -C ^ alkyl group, a Halugen- C ₁ -C 6 -alkyl group, C ₁ -C 6 -alkyloxy group, a C ₁ -C 3 -alkylthio group, a C ₁ -C -alkylcarboxylic group,

IJ ι J I ^

bonyloxy group or a C 1 -C 4 -alkyloxycarbonyl group, and R " ₇ denotes a hydrogen atom, a C 1 -C 6 -alkyl group, a halogeno-C 1 -C -alkyl-alkyl group

group, a C ₃ -C ₅ -alkenyl group or a C.Cg-alkynyl group, surprisingly excellent compatibility for crop plants

show at the same time interesting herbicidal activity.

The term halogen is fluorine, chlorine, bromine or iodine. The term haloalkyl states that one or more hydrogen atoms of the alkyl radical are replaced by halogen.

As an example of heterocyclic rings may be mentioned: pyrrole, oxazole, thiazole. Imidazole, pyridine, oxazine, thiazine, pyrimidine, pyrazine, triazine, oxadiazine and thiadiazine, and their Oi-, tetra- or optionally hexa hydroderivate.

The compounds of the general formula I to be used according to the invention can be prepared by reacting

A) if Z is a 3,4-dimethyl-3-pyrroline-2,5-dione-1-yl radical, an aniline of the general formula II

(ID ₁

in which R, X and Y have the meanings given under the general formula I, with 2,2'-dimethylmaleic anhydride,

B) if Z is a 4,5, b, 7-tetrahydro-2H-1,2,3-triazolo [3,4-a] pyridine-8-ium-3-olato-2-yl radical, a compound the general formula II

(II).

in which R X and Y are the formula given under the general formula I

-6-

diazotized with nitrous acid, reacted with piperidine-2-carboxylic acid and cyclized with the aid of dehydrating gowns,

C) if Z is a 3-c1ion-2-yl-2,3,5,6,7,8-hexahydro-1H-imidazo [1,5-a] pyridin-1 or _t 2, 3, 5, 6 , 7,8-hexahydro-1H-1,3, ^ -triazolot 1,2-a! Pyridazine-1,3-dione-2-yl radical, a compound of general formula II

(II)

in which R, X and Y have the meanings mentioned under the general formula I Be, with a compound of general formula V or VI

T-r

(V)

CK

U.

(VI) ₁

in which Q, U and U. those mentioned under the general formula I.

Have meanings and

represents a C 1 -C 4 -alkyl radical,

0) if Z is a 2,3,5,6,7,8-hexahydro-1H-imidazo [1,5-a] pyridine-1,3-dione-2-yl or a 2,3,5,6 , 7,8-hexahydro-IH-1,3,4-triazolo [1,2-a] pyridazine-1,3-dione-2-yl radical, a compound of general formula III

(III)

-7-

in which K, U, X and Y have the meanings given under general formula I, with a compound of general formula VII

(VII)

in which Q and U have the meanings stated under general formula I and R represents a C -C -alkyl radical,

E) if Z is a radical of the general formula

represents, in which R R R R and T have the meanings mentioned under "general formula I, a compound of general formula III a

N = C

(III a),

in which R ₁ X and Y have the meanings given under the general formula I, with a compound of general formula VIII

-β-

ZfZf ¹ /?

(VIII)

in which R ₁ R ₁ R, R and T have the meanings given under the general formula I, and reacted in the presence of an oxidizing agent to the thiadiazole ring,

F) if Z is a 4,5,6,7-tetrahydroindazol-2-yl radical and L is a C-C, -alkyl or halogeno-C -C -alkyl radical, sine compound of the general formula IV

NH-NH,

(IV),

in which R, X and Y have the Eerieutungen mentioned under the general formula I, with a compound of general formula IX

(IX)

in which R represents a C -C -alkyl radical or a halogeno-C -C -alkyl radical, brings to reaction,

G) if Z is a 4,5,6, T-tetrahydroindazol-Z-yl radical and L is a C 1 -C 4 -alkoxy group or a halogeno-C 1 -C -alkoxy radical, a compound of the general formula X.

-9-

LOAD * /?

(X) ₁

R ₁ X and Y have the angegubenen at (* he general Fcrmel I meanings, R but not · 'drrstellt Wasserstof with dialk ^»1 - sulfate or converts tosylate,

H) if Z is a 4,5,6,7-tetrahydroindazol-2-yl radical and L 1 is a halogen atom or a cyano group, a compound of general formula X.

in which R, X and Y have the meanings given under the general formula I, R, however, does not denote hydrogen, with phosphorus halides. Phosphorcxyhalogeniden, phosgene, thionyl chloride or oxalyl chloride in the corresponding compounds with L in the meaning of halogen and optionally subsequently reacted with sodium cyanide in the corresponding compounds with L in the meaning of cyano,

I) if Z is a 2H-1,2,4-triazolin-3-on-2-yl radical, a compound of general formula IV

-10-

NH-NH,

(IV),

in which R, X and Y have the meanings given in the general formula I, with a compound of the general formula XI

(XI)

wherein R and R _{n are} the meanings mentioned under the general formula I.

  8th

and R represents a C -C alkyl radical,

J) if Z represents a 3H-1,3, ^ -oxadiazole-Z-on-S-yl radical, a compound of general formula XII

(XII) ₁

in which R _{1 has} R, X and Y have the meanings given under the general formula I, reacting with phosgene or one of its reactive functional derivatives,

K) if Z is a 5,6,7,8-tetrahydroquinazoline Z, 4 (1H, 3H) -dione-3-yl radical or a 1,2,4,5,6,7-hexahydro-2,4 dioxo-3H-cyclopentapyrimidin-3-yl radical, a compound of general formula XXII

-11-

R ₂₈ OOC

(XXII)

in the R ₁ X, Y and ρ, which are specified under the general formula I.

Have meanings and R _{00 represents} a C -C -alkyl radical, under

about 1 *

cyclized basic conditions and optionally with a compound of general formula XXIII

^R 27 - ^B

(XXIII)

in which R has the meaning given under the general formula I but does not represent a hydrogen atom, and B represents a halogen atom or the p-toluenesulfonyloxy group, if appropriate using an acid-binding agent.

The reaction according to the ante Verfahrensvar A)? Is expediently carried out optionally at 20 ⁰ C to 200 ⁰ C in a suitable solvent, with 2,2'-dimethylmaleic anhydride is used in a molar ratio of 1 to 3 equivalents to 1 equivalent of amine of the formula II , The reaction time is 1 to 24 hours. It is convenient to carry out the reaction in the presence of an acid such as acetic acid, for example by working in acetic acid as a solvent. However, it is also possible to bring the two reactants using an inert solvent, such as dichloromethane or dimethyl sulfoxide, to react and to cyclize the intermediate resulting addition product with acid anhydrides, such as acetic anhydride.

The reaction according to process variant B) is generally carried out in three stages without intermediate purification of the products according to the following formula scheme:

-12-

(II)

(XIV) ₁

• sy

I ¹

O. s N

HO

(XV)

(I a)

The anilines of the general formula II in which R ₁ X and Y have the meanings given under the general formula I are

-13-

method in aqueous acidic suspension at a temperature of -20 ° to + 1O ⁰ C diazotized with sodium nitrite, wherein the reaction time is 0.5 to 3 hours.

The compounds of general formula XIV, in which G is a halogen atom, especially a chlorine atom, other inorganic radicals, such as hydrogen sulfate, or organic radicals such as acetate is, then at a temperature of -20 ° to + 20 ⁰ C with piperidine 2-carboxylic acid and acid-binding agents, such as trialkylamines implemented.

The compounds of general formula XV may be cyclized with acid anhydrides such as acetic anhydride using a base such as pyridine in an inert solvent such as ether to the compounds of formula Ia.

The reaction according to process variant C) is suitably carried out at a temperature above 20 ⁰ C, for example at 100 ⁰ C or at reflux temperature of the reaction mixture. If the reactant is an anhydride of the general formula V. For example, the reaction is conveniently carried out in the presence of an acid such as acetic acid, for example by working in acetic acid as a solvent. However, it is also possible to bring the two reaction partners into solution without or with the use of an inert solvent, such as, for example, dichloromethane or dimethyl sulfoxide, and to cyclise the intermediate product formed with acid anhydrides, for example acetic anhydride.

The reaction according to process variant d) is carried out in an inert solvent at temperatures between 20 ⁰ C and 150 ⁰ C ₁ preferably at the boiling point of the solvent. Suitable solvents are, for example, aliphatic and aromatic, optionally chlorinated hydrocarbons, such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and ethers, such as diethyl and di-n-butyl ether , Methyl tert-butyl ether, tetrahydrofuran, dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, furthermore nitriles such as acetonitrile and propionitrile, sulfoxides such as dimethyl sulfoxide, or sulfolane.

-K-

IU

The isocyanates or isothiocyanates of the general formula III used as starting material can be prepared from the anilines of the general formula II in which R, X and Y have the meanings given under the general formula I, according to methods known per se with phosgene or thiophosgene, or their readily produce reactive derivatives.

The reaction according to process variant E) is carried out in an inert solvent, such as ether, methylene chloride, chloroform or ethyl acetate, at a temperature of -50 ⁰ C to + 50 ⁰ C by reacting a compound of general formula IHa, in the R, X and Y have the meanings given under the general formula I, with a compound of the general formula VIII in which R, R ₁ R, R and T have the meanings given under the general formula I. The reaction time is 0.5 to 10 hours. The resulting compound of general formula XVI

(XVI)

is thermally unstable and is therefore preferably used without isolation in the next reaction.

The ring formation is carried out using an oxidizing agent in an organic solvent. As the organic solvent, an inert solvent such as methylene chloride, chloroform, N, N-dimethylformamide and ethyl acetate is suitable. Ring-forming condensation reaction may be carried out in the presence of effective acid acceptors, depending on the nature of the oxidizing agent. Suitable acid acceptors are organic bases, such as triethylamine, pyridine, dimethylaniline, inorganic bases, such as sodium hydroxide and sodium carbonate. As oxidizing agent

-15-

Bromine, chlorine, sodium hypochlorite and others are used. If at least one substituent R represents the hydroxy group, iodine is preferred as the oxidizing agent.

The reaction according to process variant F) is expediently carried out with catalysis in a suitable solvent. Oie reaction temperatures are between room temperature and 150 ⁰ C, preferably at the reflux temperature of the reaction mixture. Suitable solvents include, for example, dimethylsulfoxide, halohydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, as well as other solvents inert to the reactants such as diethyl ether, tetrahydrofuran or dimethylformamide ,

As catalysts, acids such as acetic acid or sulfuric acid, but also acidic ion exchangers can be used.

The hydrazines of the general formula IV ₁ used as starting material in which R, X and Y have the meanings given under the general formula I, are prepared by reacting compounds of the general formula II in acidic aqueous suspension at a temperature of -20 ⁰ C to + 10 ⁰ C with sodium nitrate and subsequent reaction with a reducing agent, such as stannous chloride, received.

The reaction according to process variants 6) and H) can optionally be carried out with or without solvent. The reaction temperatures are between room temperature and 180 ⁰ C, preferably at the reflux temperature of the reaction mixture. Suitable solvents include methylene chloride, chloroform, benzene, toluene, chlorobenzene, dichlorobenzene or xylene, as well as other solvents inert to the reactants.

The starting materials required for the processes G) and H) of the general formulas X, in which R, X and Y have the meanings given under the general formula I, but R is not hydrogen, are obtained according to the following equation, wherein in the general formula XVII R is a C -C, -alkyl group:

-16-

NH-NH

(IV)

(XVII)

(X)

The reaction is preferably carried out in a solvent in a temperature range from 80 ^° C. to 200 ^° C. within 0.5 to 20 hours. Suitable solvents include, for example, toluene, xylene and acetic acid.

Compounds of general formula X may exist in three tautomeric forms, but for the sake of simplicity only the above-mentioned form X will be used.

The reaction according to process variant I) is expediently carried out with catalysis in a suitable solvent. The reaction temperatures are between room temperature and 150 ⁰ C, preferably at reflux temperature of the reaction mixture. Suitable solvents include, for example, dimethylsulfoxide, halohydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, and others

-17-

towards the reactants inert solvent, such as diethyl ether, tetrahydrofuran or dimethylformamide.

As catalysts, acids such as acetic acid or sulfuric acid, but also acidic ion exchangers can be used.

The reaction according to process variant J) takes place without or using a suitable inert solvent. Suitable solvents include, for example, dimethylsulfoxide, halohydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, as well as other solvents inert to the reactants such as diethyl ether, tetrahydrofuran or dimethylformamide.

The starting compound of general formula XII is obtained, in which R ₁ X, Y and R have the meanings given under general formula I, by reacting a hydrazine of general formula IV in which R _{1 is} X and Y is the same as general formula I have the meanings mentioned, with an acid derivative of formula XVIII in which R _c is a C, -C, alkoxy or a halogen atom, is reacted according to the following equation:

NH-NK,

0 Il

(IV)

(XVIII)

/ NH-NH "

(XII)

-18-

ZfZ ft / y

The reaction according to process variant C) is suitably in an appropriate solvent under addition of a base such as an alkali metal hydroxide or alcoholate, sodium hydride or triethylamine, optionally in a Zwoiphasensystem with addition of a phase transfer catalyst and at temperatures between 0 ⁰ C and 150 ⁰ C. , preferably at the reflux temperature of the solvent.

The starting compounds of the formula XXII are obtained according to the following formula scheme:

N = C = O

R ₂₈ OOC

(III b)

'CH.) (XXVI) t ρ

R ₂₈ OOC

(XXII)

The reaction of compounds of the formula IIIb in which R, X and Y have the meanings given under the general formula I, with enamino esters of the formula XXVI ₁ in the ρ 1 or 2 and R is a C.-C, -alkyl group

Zo 1 *

is suitably carried out in an inert solvent such as dioxane. The reaction temperatures are between room temperature and 200 ^° C., preferably at the boiling point of the solvent.

Usually, the starting materials are used in a stoichiometric ratio. An excess of one eci? R andseren may be quite advantageous in individual cases.

ft

The compounds to be used according to the invention prepared by the above-mentioned processes can be isolated from the reaction mixture by customary methods, for example by distilling off the solvent used under normal or reduced pressure or by extraction.

An increased degree of purity can be obtained as a rule by column chromatography purification and by fractional distillation.

The compounds to be used according to the invention are generally crystalline or viscous substances, some of which are readily soluble in halogenated hydrocarbons, such as chloroform, sulfoxides, such as dimethyl sulfoxide, or esters, such as ethyl acetate.

The starting compounds of general formula III and IV are largely new, but can be prepared analogously to methods known per se.

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, the weed control agents can be used in permanent crops, for example forest, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and Hop plants, and used 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, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

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Monocotyledonous weeds of the genera Avena, Alopecurus. Echinochloe, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus,

Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ishamedum and Apera.

The application rates vary depending on the type of application in the pre-or Nachsuflauf in limits between 0.05 to 5 kg / ha.

The compositions according to the invention may be used either alone, in mixture 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, as herbicidally active compound, those active substances which are described in Weed Abstracts, Vol. 35, No.5, 1986, under the title "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstiacts" are suitable. are listed.

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, phospholipids, for example those from the group phosphatidyicholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acyl-phosphatidylethanolamines, phosphatidylinositol, phosphatidylserine, lysolecithin and phosphatidylglycerol can be used as the mixing partner.

Suitably, the marked agents or mixtures thereof in the form of preparations such as powders, scattering:? In. Granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally adhesion, wetting emulsifying and / or Oispergierhilfsmitteln applied.

-21-

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 supports 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 active substance (s) in the various preparations varies widely. For example, the compositions contain about 10 to 90% by weight of active ingredient, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surfactants.

The application of the agents can follow in the usual way, 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 carried out, for example, in the so-called tank mix process in practice.

-22-

For the preparation of the various preparations, for example, the following constituents are used:

A) Spray powder

20% by weight of active ingredient

35 weight percent bentonite

35 weight percent silica

8 weight percent calcium salt of lignin sulfonic acid

2 weight percent sodium salt of N-methyl-N-oleyl-taurine

B) paste

45% by weight of active ingredient

5 weight percent sodium aluminum silicate

15 weight percent cetyl polyglycol ether with 8 moles of ethylene oxide

2 percent by weight spindle oil

10 weight percent polyethylene glycol

23 weight percent water

C) Emulsion Concentrate

20% by weight of active ingredient

75 percent by weight isophorone

5% by weight of a mixture of the calcium salt of dodecylbenzenesulfonic acid and nonylphenyl polyoxyethylene

Cause example

The invention will be explained in more detail below with reference to some examples

-23-

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

Example 1.01 (method E)

6- (6 ₁ 6-0imethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] [1,2, k] thiadiazol-3-ylidenimino) -H- (2-propynyl) -2H-1 , 4-benzoxazine-3UH) -one

2.6 g of 2-amino-Λ-dimethylpyrroline hydrochloride were suspended in 0 0 ml of methylene dichloride. To this was then dropwise added dropwise with stirring at 0 ⁰ C, a solution of 0.75 o sodium hydroxide in 5 ml of water and stirred for 30 minutes, the reaction mixture was clear. Now a solution of 6-isothiocyanato-4- (2-propynyl) -2H-1, A-benzoxazin-3 ( ΊΗ) -one in 10C ml Met ^ -ylendichlorid was added dropwise so that 5 ⁰ C scored exceeded. The mixture was then stirred for 3 hours, the temperature rising to 20 ⁰ C. With cooling to -20 ⁰ C, a solution of 2.3 g of bromine in 10 ml of methylene chloride was then slowly added dropwise and stirred for 1 hour, the temperature rose to 10 ⁰ C. Thereafter, the solution was washed with 30 ml of water, 30 ml of 5 Ziger sodium hydroxide solution and with 30 ml of water in the order given. The methylsodichloride phase was dried over anhydrous magnesium sulfate, then filtered and concentrated. The residue was purified by chromatography on a silica gel column.

Yield: 1.5 g = 25 Ί. of theory mp: 65 ⁰ C

Preparation of the starting material for Example 1.01

6-isothiocyanato-4- (2-propynyl) -2H-1,4-benzoxazin-3UH) -one

4, U g 6-amino-4- (2-propynyl) -2H-1, A-benzoxazine-3HH) -one were dissolved in 100 ml of methylene chloride and at 5 ⁰ C with a suspension of 2.60 g

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Calcium carbonate in 20 ml of water. Subsequently, 2.9 g of thiophosgene were so zugetropt't that 5 ⁰ C inner temperature was not exceeded. After 10 hours at room temperature, the phases were separated. The organic phase was washed with 50 ml of water, dried over MgSO4 and the solvent removed in a water-jet vacuum.

Yield: 4.1 g · - 84 I theory mp .: 120-122 ⁰ C

In an analogous manner, the following compounds were prepared by Method E:

Example no.

Surname

Physical constant

1.02 6- (6,6-Dimethy1-3,5,6,7-tetrahydropyrrolo [2,1-c] [1,2,4] thiadiazol-3-ylidenimino) -4-methyl-2H-1,4 benzoxazin-3 (4H) -one

Mp .: 133 C

1.03 6- (8,6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] [1,2,4] thiadiazol-3-ylidenimino) -7-fluoro-4- (2-yl) propynyl) -2 H -1,4-benzoxazin-3 (4H) -one

mp .:

62 ° C

1.04 4- (2,3-Dibromo-2-propenyl) -6- (6,6-dime-thy1-3,5,6,7-tetrahydropyrrolo [2,1-c] [1,2,4-thiadiazole-ylidenimino) -7-fluoro-2H-1,4-benzoxazin-3 (4H) -one

mp .:

65 ⁰ C

1.05 5- (6,6-dimethyl-5,6-dihydro-3H-thiazoleneC2,3-c] - mp: 195 C [1,2,4] thiadiazol-3-ylidenimino) -6-fluoro-3- (2-propynyl) -2 (3H) -benzthiazolon

1.06 5- {6,6-dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] - mp: 190 C [1,2,4] thiadiazol-3-ylidenimino) -6-fluoro 3- (2-propynyl) -2 (3H) -benzthiazolon

-25-

Example Physical No Name Constant

1:07 6- (6.6-dimethyl-5,6-dihydro-3H-thiazolo m.p .: 124-26 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -4- ( 2-propenyl) -2H-1,4-benzoxazin-3 (4H) -one

1.08 6- ( _6f 6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] - mp: 11O ⁰ C t1,2,4] thiadiazol-3-ylidenimino) -4- (2 propenyl) -2H-1,4-benzoxazin-3 (4H) -one

1.09 6- (6,6-Dimethyl-5,6-dihydro-3H-thiazolo-Fp .: 93 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -4- ( 2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one

10.1 6- (6,6-dimethyl-5,6-dihydro-3H-thiazolo m.p .: 53 ⁰ C L2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -4-propyl- 2H-1,4-benzoxazin-3 (4H) -one

1.11 6- (6,6-dimethyl-3,5,6,7-tetrahydropyrrolo ^{) -1} : 1,6068 [2.1-c] [1,2,4] thiadiazol-3-ylidenimino) -4-propyl 2H-1,4-benzoxazin-3 (4H) -one

1.12 7- (6,6-Diinethyl _3,5,6-1 7-tetrahydropyrrolo m.p .: 168 ⁰ C [2,1-c] [1,2,4] thiadiazol-3-ylidenimino) -1- ( 2-propynyl) -2 (1H) -quinoxalinone

1.13 7- (6,6-Dimethyl-5,6-dihydro-3H-thiazolo-Fp: 174 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -1- (2) propynyl) -2 (1H) -quinoxalinone

1.14 6- (6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo-Fp .: 65 ⁰ C [2,1-c] [1,2,4] thiadiai ->) .- 3-ylidenimino) -4 - (2-propynyl) -2H-1,4-benzothiazine-3 (4H) -one

-26-

Example Physical No. Name Constant

1.15 6- (6,6-Dimethyl-5,6-dihydro-3H-thiazolo-mp: 135-UO ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -7-fluoro -4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one

1.16 6- (6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] - Fp .: 161 C- [1,2,4] thiadiazol-3-ylidenimino) -7-fluoro -4-propyl-2H-1,4-benzoxazin-3 (4H) -one

1.17 6- (6,6-Dimethyl-5,6-dihydro-3H-thiazolo-Fp .: 156 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -7-fluoro-4-propyl -2H-1,4-benzoxazin-3 (4H) -one

1.18 4-cyanomethyl-6- (6 ₁ S-dimethyl-3.5,6,7-tetra- m.p .: 170-171 ⁰ C hydropyrrolo [2,1-c] [1,2,4] thiadiazol-3-ylidenimino ) -2H-1,4-benzoxazin-3- (4H) -one

19.1 6- (6-methyl - :, 5,6,7-tetrahydropyrrolo [2,1-c] - m.p .: 171-172 ⁰ C [1,2,4] thiadiazol-3-ylidenimino) -4- ( 2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one

1.20 7-Fluoro-6- (6-methyl-3,5,6,7-tetrahydropyrrolo-Fp .: 161-162 ⁰ C [2.1-c] [1,2,4] thiadiazol-3-ylidenimino) -4- ( 2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one

1.21 5- (6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2.1-c] - Fp .: 113 ⁰ C [1,2,4] thiadiazol-3-ylidenimino) -3-propyl-2 (3H) -benzoxazolone

1.22 5- (6,6-Dimethyl-5,6-dihydro-3H-thiazolo [2,3-c] - Fp .: 113 ° C [1,2,4] thiadiazol-3-ylidenimino) -3-propyl -2 (3H) -benzoxazolone

- ₂₇ - - z

Example Physical No name constant

23.1 5- (6,6-0imethyl-3,5,6,7-tetrahydropyrrolo [2 ₁ 1-c] - m.p .: 124-127 ⁰ C [i, 2, 4] thiadiazol-3-ylidenimino) -6 -fluoro-3-propyl-2 (3H) -benzoxazolone

24.1 5- {6,6-dimethyl-5,6-dihydro-3H-thiazolo m.p .: 141-142 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -6 -fluoro-3-propyl-2 (3H) -benzoxazolone

25.1 5- (6,6-dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] - m.p .: 158 ⁰ C [1,2,4] thiadiazol-3-ylidenimino) -3- ( 2-propynyl) -2 (3H) -benzoxazolone

1.26 5- (6,6-dimethyl-5,6-dihydro-3H-thiazolo-Fp .: 137 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -3- (2) propynyl) -2 (3H) -benzoxazolone

27.1 5- (6,6-0imethyl-3.5 ₁ 6 ₁ 7-tetrahydropyrrolo [2,1-c] - m.p .: 169-173 ⁰ C [1,2,4] thiadiazol-3-ylidenimino) -6-fluoro -3- (? -Propynyl) -2 (3H) -benzoxazolone

1.2Θ 5- (6,6-0imethyl-5,6-dihydro-3H-thiazolo m.p .: 138-142 ⁰ C [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) - 6-fluoro-3- (2-propynyl) -2 (3H) -benzoxazolone

1.29 6- (6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] - [1,2,4] thiadiazol-3-ylidenimino) -3-methyl-1-propyl-1 , 3-dihydro-2 (2H) -indolone

1.10 6- (6,6-Dimethyl-5,8-dihydro-3H-thiazolo [2,3-c] [1,2,4] thiadiazol-3-ylidenimino) -3-methyl-1-propyl-1 , 3-dihydro-2 (2H) -indolone

1.31 7- (6.6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2.1-c] - [1,2,4] thiadiazol-3-ylidenimino) -1- (2-propynyl) -3,4-dihydro -2 (1H) -quinoxalinone

-28-

A.

7 /

Example 2.01

(Method A)

1- [6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzoxazol-5-yl] -3, Ί -dimethyl-3-pyrroline-2,5 (1H) -dione

4 g of 5-amino-6-fluoro-3- (2-propynyl) -2 (3H) -benzoxazolone in 50 ml of glacial acetic acid are added and 2, g g of 2,3-dimethylmaleic anhydride are added. It is stirred for 8 hours at 8O ⁰ C. The cooled reaction mixture is poured into 500 ml of ice water and the precipitated crystals are filtered off and washed with ice water. It is dried in vacuo at 50.degree.

Yield: 2.3 g = 38 l of theory mp.

165 ⁰ C

In an analogous manner, the following compounds were prepared according to method A:

Example, Nu,

Surname

Physical constant

2.02 1- [6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzothiazol-5-yl] -3, t -dimethyl-3-pyrroline-2,5 (1H) -dione

Mp .: 229 C

2.03 1- [3-0x0-4- (2-propynyl) -3 Λ-dihydro-2H-1,4-benzthiazin-6-yl] -3,3'-dimethyl-S-pyrroline-2,5 (1H) -dione

Mp .: 279 C

2.01, 1- [2-OXO-2,3-dihydro-1H-benzimidazol-5-yl] -3,4-dimethyl-3-pyrroline-2,5 (1H) -dione

Mp .: 280 C

2.05 1- [2-0xo-1- (2-propynyl) -1H-quinoxalin-7-yl] -3,4-dimethyl-3-pyrroline-2,5 (IH) -dione

Mp .: 265 C

2.06 1- [2-0xo-1- (2-propynyl) -3,4-dihydro-1H-quinoxalin-7-ylJ-3,4-dimethyl-3-pyrroline-2,5 (1H) -dione

-29-

Example Physical No. Name Constant

2.07 1- [2-Oxo-3- (2-propynyl) -2,3-dihydrobenzoxazole Fp: 189 ⁰ C 5-yl] -3,4-dimethyl-3-pyrroline-2,5 (IH) - dion

2.08 1- (2-0xo-3-propyl-2,3-dihydiobenzoxazol-5-yD-mp: 11O ⁰ C 3,4-dimethyl-3-pyrroline-2,51IH) -dione

2.09 1- (3-methyl-2-oxo-1-propyl-1,3-dihydro-2H-in-Fp, 18O ⁰ C dol-6-yl) -3,4-dimethy] -3-pyrroline 2,5 (1H) -dione

2.10 1- [3-methyl-2-oxo-1- (1-methylethyl) -1,3-dihy-Fp .: 142-1U ⁰ C-dro-2H-indol-6-yl] -3,4-dimethyl -3-pyrroline-2,5 (1H) -dione

-30-

Example 3.01

(Method 0)

2- [7-fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -perhydroimidazoC1,5-a] pyridine-1,3- dion

Dissolve 6.4 g of 7-fluoro-4- (2-propynyl) -1,4-benzoxazine-3 (4H) -one-6-yl isocyanate in 50 ml of tetrahydrofuran and add 4.1 ml of piperidine-2-one. added carboxylic acid ethyl ester. It is refluxed for 10 hours. After cooling, the solvent is removed in vacuo and the residue is separated on a silica gel column with ethyl acetate / hexane.

Yield: 4.8 g = 52.7 of theory mp.

202-204 C

In analogous titre, the following compounds were prepared by Method D:

Example no.

Surname

Physical constant

3.02 2- [3-0XO-4- (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -perhydroimidazo [1,5-a] -pyridine - ', 3 dion

Mp .: 180-185 C

3.03 2- [3-Oxo-4- (2-propenyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -perhydroimidazoC1,5-a] -pyridine-1,3-dione

Mp .: 157-158 C

3.04 2-Π-fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -3-thioxoporhydroimidazot1,5-a] pyridine-1 on

Mp .: 151 C

3.05 2-t6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzoxazol-5-yl] -3-thioxoperhydroimidazo [1,5-a] pyridin-1-one

Fp .: 189-195 C

-31-

Beispj. α. No.

Surname

Physical constant

3.06 2- (7-Fluoro-3-oxo-4-propyl-3,4-dihydro-2H-1,1'-i-benzoxazin-6-yl) -perhydroimidazo [1,5-a] -pyridine-t, 3 -dione

3.07 2- (2-Oxo-i-U-propyno-U-quinoxyquinol-yl)

perhydroimidazoC1,5-a] pyridine-I ₁ 3-dione

Mp: 199-200 C

3.08 2-t2-Oxo-1- (2-propynyl) -3 _l 4-dihydro-1H-quinoxalin-7-yl] -perhydroimidazo [1,5-a] pyridine-1,3-dione

3. 09 2- [2-0XO-3-1 2-propynyl] -2,3-dihydoxo-benzoxazol-5-yl] -perhydroimidazo [1,5-a] pyridine-1,3-dione

Mp .: 179 C

3.10 2- (6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzoxazol-5-yl] -perhydroimidazo [1,5-a] pyridine-1,3-dione

3.11 2- (3-Heethyl-2-oxo-1-pro; ·, yl-1,3-dihydro-2H-indol-6-yl) -perhydroimidazo-1,5-a] pyridine-1,3-dione

3.12 2- (3-methyl-2-oxo-1-propyl-1,3-dihydro-2H-indol-6-yl) -perhydro-IH-1, 2, A-triazolo [1,2-alpyridazine 1,3-dione

3.13 2- [6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzoxazol-5-yl] -perhydro-1H-1,2,4-triazolo [1,2-a] pyridazine-1,3-dione

3.H 2-C2-OXO-1-propyl-1H-quinoxalin-7-yl] -perhydro-1H-1,2,4-triazolo [1,2-a] pyridazine-1,3-dione

-32-

Example 4.01 (Method K)

3- (3-oxo-4-propyl-3, t-dihydro-Zl.-i, 4-benzo * azin-6-yl) -5,6,7,8-tetrahydroquinazoline-2,4 (1H, 3H) - dion

2.0 g of sodium metal are dissolved in 100 ml of ethanol, 4.4 g of 2-13- (3-oxo-4-propyl-3,4-dihydro - (2H) -1,4-benzoxazin-6-yl) - ureido] -1-cyclohexencarbonsaureethylester, dissolved in 50 ml of ethanol, was added and the reaction mixture 1 hour for boiling erztzt. After completion of the reaction, the solution is concentrated and the residue taken up in 300 ml of water. The precipitate is filtered off and the filtrate is acidified with hydrochloric acid. The precipitated product is filtered off with suction, washed with water and recrystallized from ethyl acetate / diisopropyl ether.

Yield: 3.56 g = 56 Z of theory mp:> 250 ° C

Example 4.02 (method K)

-dione 1-methyl-3- (4-propyl-3,4-dihydro-2H-1,4-benzoxazin-6-yl) -5,6,7,8-tetrahydroquinazoline-2,4 (IH, 3H)

2.0 g of 3- (4-propyl-1,4-benzoxazin-3 (4H) -one-6-yl) -5,6,7,8-tetrahydroquinazoline-2,4 (IH, 3H) -dj. one are dissolved in 20 ml of dimethylformamide, 0.17 g 8O '/ sodium hydride suspension was added and stirred for 1 hour at 6O ⁰ C. Allow to cool to room temperature and add 0.77 g of iodomethane. It is heated to 60 C for 2 hours. After cooling, the precipitated crystals are filtered off and recrystallized from diisopropyl ether / ethyl acetate.

Yield: 1.3 g = 65 Z of theory mp: 218 ° C

-33-

Example 5.01 (Procedure I)

2- [6-fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzthiazol-5-yl] -2,3,5,6,7,8-hexahydro-1,2,4- triazolo [4,3-a] pyridin-3-one

3.6 g of S-hydrazino-δ-fluoro-S- (2-prcpinyl) -benzothiazolone are dissolved in 40 ml of xylene, 2.8 g of 1-ethoxycarborvyl-2-piperidone and 1 g of phosphorus pentoxide are added and the mixture is stirred for 2 hours Reflux cooked. After cooling, the reaction mixture is added to 100 ml of Masser and the organic phase separated. The organic phase is washed with 40 ml of potassium bicarbonate solution, dried over magnesium sulfate and concentrated. The residue is chromatographed on silica gel with ethyl acetate / hexane mixtures as eluent.

Yield: 380 mg = 6.7 7. of theory mp: 154-16O ⁰ C

Preparation of the dispensing material for Example 5.01

S-hydrazino-ö-fluoro-S-ί2-propynyl) -benzthiazolon

Dissolve 4 g of 5-mino-6-fluoro-3- (2-propynyl) -2 (3H) -benzothiazolone in 50 ml of concentrated hydrochloric acid and stir for 30 minutes at room temperature. It is cooled down to -5 to +5 C and dropwise add a solution of 1.3 g NatriuiTinitrit in 5.6 ml of water. It is stirred for 30 minutes and then cooled to -30 <*. Now, a solution of 6.8 g of tin! 11) chloride in 15 ml of concentrated hydrochloric acid is slowly added dropwise. It will ? Hours, with u. *. ·· * temperature kept between -10 and 0 C. Filter !: the festival. ¹ .off, neutralized and extrahiart three times with 50 ml Essigsäureethy. \ E ct-r. It is dried over magnesium sulfate and the _t ; -sur: O agent is stripped off in vacuo.

Yield: 2, ö g = 61 '/ 3er theory

IfI

In an analogous manner, the following compounds are prepared according to method I:

Example no.

Surname

Physical constant

5.02 2- [2-0xo-3- (2-propynyl) -2,: i-dihydrobenzoxazol-5-yl] -2,3,5,6,7,8-hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one

Mp .: 190 C

5.03 2- [7-Fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -2,3,5,6 _I 7,8 hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one

Mp .: 194-196 C

5.04 2- [6-Fluoro-2-oxo-1- (2-propynyl) -3,4-dihydro-1H-quinoxalin-7-yl] -2,3,5,6,7,8-hexahydro-1 , 2,4-triazolo [4,3-a] pyridin-3-one

5.05 2- [6-Fluoro-2-oxo-1- (2-propynyl) -1H-quinoxalin-7-yl] -2,3,5,6,7,8-hexahydro-1,2,4-triazolo - [4,3-a] pyriCiin-3-one

Mp .: 210-211 C

5.06 2- [6-fluoro-2-oxo-3 _; 4-dihydro-1H-quinoxaline-7 -p.: 190-192 C yl] -2,3,5,6,7,8-hexahyrtro-1,2,4-triazolo [4,3-a] pyridine -3-one

-35-

Example 6.01 (Method B)

2- [7-fluoro-S-OXO - * - (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -4,5,6,7-tetrahydro-2H- 1,2,3-triazolo [3,4-a] pyridin-8-ium-3-olate

5.0 g of e-amino-fluoro-A- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one are suspended in a mixture of 12.2 ml of concentrated hydrochloric acid and 52 ml of water and cooled to -10 to -5 C A solution of 1.74 g of sodium nitrite in 6 ml of Masser is added dropwise so that the temperature of the reaction mixture does not exceed -5 ° C. After completion of the addition for 1 hour at -5 ⁰ C is stirred and destroying excess nitrous acid with urea until the test with starch iodide paper is negative. The resulting solution is warmed to ⁰ ° C. and added dropwise to an ice-cooled solution of 2.9 g of pipecolic acid and 10.5 ml of triethylamine in 30 ml of water. After completion of the addition, stirring is continued for 1 hour at 0 C and the reaction mixture extracted several times with methylene chloride. The combined organic phases are dried over magnesium sulfate and the solvent is evaporated. The residue is taken up in 60 ml of ether and admixed with 5.2 ml of acetic anhydride and 2.6 ml of pyridine. It is allowed to stir overnight at room temperature and then poured onto 150 ml of ice water. It is extracted with ethyl acetate, dried with magnesium sulfate and the solvent evaporated. The residue is chromatographed on silica gel with the eluent ethyl acetate / methanol = 95: 5.

Yield: 1.0 g = 13 Ί. of theory mp .: 202-203 ° C

In an analogous manner, the following compounds were prepared by Method B:

-36-

Example Kr.

Surname

Physical constant

6.02 2- [6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydro-Fp .: 203 C benzoxazol-5-yl] - *, 5, 6, 7-tetrahydro ^ -1 , 2,3-triazolo [3,4-a] pyridin-8-iuif.-3-olate

6.03 2- [6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydro-Fp .: 210C-benzothiazol-5-yl] - ;, 5,6,7-tetrahydro-2H- 1,2,3-triazolo [3, * - a] pyridin-8-ium-3-olate

-37-

Example 7.01 (Method J)

3- (3-Ethyl-2-oxo-1-propyl-1,3-dihydro-2H-indol-6-yl) -5- (1,1-dimethylethyl) -1,3'-oxadiazole-2 ( 3H) -one

Dissolve 2.6 g of 3-methyl-6- [N '- (2,2-dimethyl-propanoyl) -hydrazino] -1-propyl-1H-indole-2 (3H) -one in 15 ml of a 20% solution Solution of phosgene in toluene and then boiled for 4 hours at reflux. It is stirred overnight at room temperature, then 20 ml of methanol are added carefully and the solvents are distilled off in vacuo. The residue is chromatographed on silica gel with the eluent hexane / ethyl acetate-7: 3.

Yield: 1.7 g = 61 t of theory n * °: 1.5366

Preparation of the starting material for Example 7.01

3-methyl-6- [N '- (2,2-dimethylpropanoyl) hydrazino] -1-propyl-1H-indole-2 (3H) -one

5.9 g of 6-hydrazino-3-methyl-1-propyl-1H-indole-2 (3H) -one are dissolved in a mixture of 50 ml of toluene and 20 ml of acetonitrile and 2.5 g of triethylamine are added. Now 3.1 ml of pivaloyl chloride are added dropwise, with a warming to about 40 C occurs. The mixture is stirred for 1.5 hours, extracted by shaking with 100 ml of water and Kaliumhydrogencarbonatlosung, dried over magnesium sulfate and the solvent removed. The residue is chromatographed on silica gel with the eluent hexane / ethyl acetate.

Yield: 2.7 g = 33 7. theory

In an analogous manner, the following compounds were prepared by Method J:

- ³⁸ -

zn

Example Physical No. Name Konst a nte

7.02 3- [2-Oxo-3 - (? - propynyl) -2,3-dihydrobenzoxazole m.p .: 127-130 ° C 5-yl] -5- (1,1-dimethylethyl) -1,3,4 oxadiazol-2 (3H) -one

7.03 3- [7-Fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-Fp .: U3-144 ° C 1,4-benzoxazin-6-yl] -5- ( 1,1-dimethylethyl) -1,3,4-oxadiazol-2 (3H) -one

7.04 3- [6-Fluoro-2-oxo-1- (2-propynyl) -3,4-dihydro-1H-Fp .: 66-69 ⁰ C quinoxalin-7-yl] -5- (1,1- dimethylethyl) -1,3,4-oxadiazol-2 (3H) -one

7.05 3- [6-Fluoro-2-oxo-1- (2-propynyl) -1H-quinoxaline M.p .: 152-153 ⁰ C 7-yl] -5- (1,1-dimethylethyl) -1,3 , 4-oxadiazol-2 (3H) -one

7.06 3- [7-Fluoro-3-oxo-3,4-dihydro-2H-1,4-benzoxazine m.p .: 171-172 ⁰ C 6-yl] -5- (I ₁ 1-dimethylethyl) -1 , 3,4-oxadiazol-2 (3H) -one

7.07 3- [6-Fluoro-2-oxo-3,4-dihydro-1H-quinoxaline-7-mp: 248 ° C yl] -5- (1,1-dimethylethyl) -1,3,4-oxadiazo ] -2 (3H) -one

-39-

Example 8.01 (method Ί)

3-chloro-2- [2-oxo-3- (2-propynyl) -2,3-dihydro-benzoxazol-5-yl] -4,5,6,7-tetrahydro-2H-indazole

Is added to k, 5 g of 2- [2-0xo-3- (2-prcoinyl) -2,3-dihydro-benzoxazol-5-yl] · 1, 3, Ί, 5, 6, 7-hexahydro-2H-indazole 3-on with 20 ml of oxalyl chloride and refluxed for > hours. After cooling, the reaction mixture is poured into 100 ml of ice-water and extracted with methylene chloride. The combined organic phases are shaken with saturated sodium bicarbonate solution and with water and dried over magnesium sulfate. The solvents are removed in vacuo. The residue is chromatographed on silica gel with hexane / ethyl acetate mixtures as eluent.

Yield: 3.9 g = 82 Ί. of the theory Mp .: H3-H6 ° C

Preparation of the starting material for Example 8.01

2- [2-0x0-3- (2-propynyl) -2,3-di> iydrobenzoxazol-5-yl] -1,3,4,5,6,7-hexahydro-2H-indazol-3-one

A solution of 5.8 g of 5-hydrazino-3- (2-propynyl) -2 (3H) -benzoxazolone in 24 ml of glacial acetic acid with 4.9 g of ethyl 2-cyclohexanonecarboxylate, refluxed for 1 hour and then distilled Excess glacial acetic acid in a vacuum. The residue is recrystallized from isopropyl ether.

Yield: 5.8 = 65 '/ of theory mp: 177-180 ° C

In an analogous manner, the following compounds were prepared by Method H:

Example Physical No Name Constant

8.02 3-Chloro-2- [7-fluoro-3-oxo-4- (2-propynyl) -3, -; m.p .: 15O ⁰ C dihydro-2H-1,4-benzoxazin-6-yl] -4 , 5,6,7-tetrahydro-2H-indazole

8:03 3-chloro-2- [6-fluoro-3-oxo-1- (2-propynyl) -3,4 m.p .: 195 ⁰ C dihydro-1H-quinoxalin-7-yl] - *, 5.6 , 7-tetrahydro-2H-indazole

-U-

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 means in an application rate of 0.1 kg / ha. The agents were sprayed uniformly over the plants for this purpose as emulsions or suspensions containing 500 liters of water / ha. Here, three weeks after the treatment, the compositions of the invention showed a high crop selectivity with excellent activity against the weeds.

In the following table mean: 0 = not damaged 4 = totally annihilated

TRZAX = Triticum aestivum BRSSS = Brassica sp. SOLSS = Solanum sp. HELAN = Helianthus annuus ABUTH = Abutilon theophrasti MATCH = Matricaria chamomilla VIOSS = Viola sp. IPOSS = Ipomoea purpurea VERPE = Veronica persica GALAP = Galium aparine

T B S H A M V I V 6 R R O e B A I P e A According to the invention Z S L L U T 0 0 R L to be used A S S A T C S S P A links X S S N H H on S e P Example 1.01 0 4 4 4 4 4 4 4 4 4 Example 1.02 0 3 4 4 4 4 4 4 4 4 Example 1.03 0 4 4 4 4 4 4 4 4 ή Example 1.04 0 4 4 4 4 2 2 4 4 4 Example 1.05 1 1 4 3 4 4 4 4 4 3 Example 1.06 0 1 4 3 4 4 3 4 3 2 Example 1.08 0 2 - 3 4 3 2 4 4 - Example 1.09 0 3 - 4 4 4 4 4 4 3 Example 1.10 1 1 - 3 4 4 3 4 4 3 Example 1.11 0 3 - 3 4 4 - 4 4 3 Example 1.12 0 3 4 - 4 4 - 4 4 2 Example 1.15 1 3 4 - 4 4 4 4 3 3 Example 1.16 1 4 4 - 4 3 3 3 3 2 Example 1.17 0 2 4 - 4 3 3 3 2 2 Example 1.18 1 3 3 - 4 3 2 3 4 1 Example 1.19 1 3 4 - 4 3 3 3 4 2 Example 1.20 1 4 4 - 4 4 3 4 4 4 Example 1.23 0 3 4 - 4 3 2 3 3 3 Example 1.27 0 2 4 - 4 3 3 4 3 1 Example 1.28 0 1 4 - 4 3 3 4 2 2 untreated 0 0 0 0 0 0 0 0 0 0

- ^ -. zn

Example B

In the greenhouse, the agents listed in the table were applied with the application rate also mentioned. For this purpose, the funds were placed in vessels containing 1500 ml of Walser. The test plant species used was cchinochloa crusgaili (ECHCG) at the 2- to 5-leaf stage. Three weeks after the treatment showed that the compositions of the invention are highly effective against Echinochloa crus-galli.

In the table mean:

0 = no damage

1 = weak damage

2 = mean damage

3 = severe damage

4 = totally annihilated

E C

According to the invention H Wasserapplikatiü.- to use

Compounds ppm G_

Example 1.01 3 3

Example 1.02 3 4

Untreated 0

TO

Example C

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an amount of O ₁ OI kg / ha. The compositions were sprayed for this purpose as emulsions or suspensions with 500 liters of water / ha gleici-moderately on the plants , Here, three weeks after the treatment, the compositions of the invention showed a high crop selectivity with excellent activity against the weeds. The comparison means did not show the high effectiveness.

In the following table mean:

0 = not damaged 4 = totally damaged

TRZAX = Triticum aestivum ZEAMX = Zea mays VIOSS = Viola sp. VERPE = Veronica persica SOLSS = Solanum sp. SEBFX = Sesbania exaltata IPOSS = Ipomoea purpurea ABUTH = Abutilon theophrasti

-4 ¹ J-

T 7 V V S S I A R e I e 0 e P B According to the invention Z A 0 R L B 0 U to be used A M S P S e S T links X X OO e S X S H For example "1:01 0 0 3 3 4 4 /, 4 Example 2.01 0 0 3 4 4 2 4 4 Example 2.02 1 0 3 3 4 - - 4 Example 3.01 - 1 ? 4 4 4 4 4 Example 3.02 0 0 - 3 - - 3 4 Example 6.01 2 0 3 4 4 4 4 4 untreated 0 0 0 0 0 0 0 0 Verqleichsmittel oxadiazon 0 0 0 0 0 1 1 2

-46-

Example D

In the greenhouse, the listed plant species were treated before emergence with the listed agents in an application rate of 0.1 kg / ha. The agents were sprayed uniformly over the plants for this purpose as emulsions or suspensions containing 500 liters of water / ha. Here, three weeks after treatment, the compositions of the invention showed a high crop selectivity in sugar beet, wheat and corn with excellent activity against the Unkr. it. The Verglejchsmittel 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. Damage

4 = 90 - 100 7. Injury

BEAVX = Beta vulgaris altissima

TRZAX = Triticum aestivum

ZEAMX = Zea mays

GALAP = Ga.lium aparine

MATCH = Matricaria chamomilla

-W-

ZfZf tff

Compounds to be used according to the invention

8th T Z G M UJ R e A A A rsi A L T V A M A C X X X P H O 4 _ O O 4

Step Example]. 3.04 Example 4.01

Untreated 0 0 0 0

Verqleichsmittel

oxadiazon

-48-

Example E

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 0.1 kg / ha. The agents were sprayed uniformly over the plants for this purpose as emulsions or suspensions containing 500 liters of water / ha. Here, two weeks after the treatment, the compositions according to the invention showed a high crop selectivity in maize with excellent action against the weed. 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. Damage 3 = 75- 89 Z Damage 4 = 90 - 100 7. Injury

ZEAMX = Zea mays

ABUTH = Abutilon theophrasti

MATCH = Matricaria chamomilla

POLSS - Polygonum sp.

SOLSS = Solanum ssp.

VERPE = Veronica persica

-49-

Z A M P S V e B A O O e According to the invention A U T L L R to ν. rwendende M T C S S P links X H H S S e

Example 3.04 0 - 3 3 A 3

Example 3.05 0 4-434

Untreated 0 0 0 0 0 0

Verqleichsmittel

Oxadiazone 10 4 3 4 4

-50-

To ftf}

Example F

In the greenhouse, the listed plant species were treated before emergence with the listed agents in an application rate of 1.0 kg / ha. For this purpose, the compositions were sprayed uniformly over the plants as emulsions or suspensions containing 500 liters of water / ha. Here, one week after the treatment, the agents according to the invention showed an excellent activity against the weeds.

In the following table mean:

0 = no damage

1 = 1 - 24 7 Damage

2 = 25 - 7; 7. Damage

3 = 75- 89 7. Damage

4 = 90 - 100 7 damage

ALOMY = Alopecurus myosuroides AVEFA = Avena fatua SETVI = Setaria viridis CYPES = Cyperus esculentus ABUTH = Abutilon theophrasti

IPOSS- Ipomoea purpurea

MATCH = Matricaria chamomilla

-51-

AASCAIM LVEYBPA

According to the invention OETPUOT

MFVETSC compounds YAISHSH to use

example 6th 01 4 4 4 4 4 4 4 example 6th 02 4 4 4 3 4 4 4 example 6th 03 4 4 4 4 4 4 4

Untreated 0 0 0 0 0 0

-52-

Example G

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 0.1 kg / ha. The agents were sprayed uniformly over the plants for this purpose as emulsions or suspensions containing 500 liters of water / ha. Here, one week after the treatment, the agents according to the invention showed a high crop selectivity in wheat with excellent activity against the weed.

In the following table mean:

0 = no damage

1 = 1 - 24 7. Injury

2 = 25 - 74 Z Damage 3 = 75- 69 Z Damage 4 = 90 - 100 Z Damage

TRZAX = Triticum aestivum

ABUTH = Abutilon theophrasti

GALAP = Galium aparine

IPOSS - Ipomoea purpurea

MATCH = Matricaria chamomilla

-53-

TAGIM RBAPA

According to the invention ZULOT to be used ATASC

XHPSH connections

Example .6.01 14 3 4 4

Example 6.02 14 3 3 3

Untreated 0 0 0 0 0

ZJl JW

ul

Example M

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 agents were sprayed uniformly over the plants for this purpose as emulsions or suspensions containing 500 liters of water / ha. Here, two weeks after the treatment, the agents according to the invention showed a high crop selectivity in wheat and maize with excellent activity against the weed.

In the following table mean:

0 = no damage

1 = 1 - 2W damage

2 = 25- ΤΙ '/. damage

3 = 75 - 89 7. Injury; = 90 - 100 '/ damage

TRZAX = Triticum aestivum

ZEAMX = Zea mays

ABUTH = Abutilon theophrasti

IPOSS - Ipomoea purpurea

MATCH = Matricaria chamomilla

SOLSS = Solanum sp.

VIOSS = Viola sp.

-55-

T Z A I M S V S e B P A O I According to the invention ISL A U 0 T L 0 to be used A M T S C S S Verbindunqen X X H S H S S Example 1.13 0 0 3 3 3 4 2 Example 1.14 0 0 4 4 2 4 1 Example 1.21 0 0 4 3 3 4 2 Example 1.22 0 0 4 3 3 4 3 Example 1.24 0 0 4 4 3 4 3 Example 1.25 0 0 4 ' 3 4 3 Example 1.26 0 0 3 3 3 4 3 Example 2.05 2 1 4 4 3 4 1

Untreated 0 0 0 0

Claims (1)

claims in the R is a hydrogen atom, a C -C -alkyl group, a C -C -alkenyl group, a C -C -alkynyl group, a halogeno-C 1 -C 4 -alkyl group, a halogeno-C 1 -C 4 -alkenyl group, a halogeno-C 1 -C 5 -alkyl group C ₁ -C ₄ -alkynyl group, a C ₁ -C ₇ -cycloalkyl group, a C -C -cycloalkyl-C -C -alkyl group, a halogeno-C ₁ -C -cycloalkyl group, a halogeno-C ₁ -C ₇ -cycloalkyl- C 1 -C 6 -alkyl group, a C 2 -C 4 alkoxy-C 1 -C 4 alkyl group, a C 1 -C 6 alkoxyC-C 1 -C 4 alkoxy-C 1 -C 4 alkyl group, a cyano-C 1 -C 4 alkyl group, a carboxy C 1 -C 6 -alkoxycarbonyl-C 1 -C 4 -alkyl group, a haloC-C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl group, a CC.-alkoxy-C 2 -C 4 -alkoxycarbonyl I-C 2 -C 8 -alkyl alkyl group, a CC-alkoxycarbonyl-C -C -alkoxycarbonyl- Ij 1 ü Ic C 1 -C 6 -alkyl group, a C 1 -C 6 -alkylaminocarbonyl-C 1 -C 4 -alkyl group or a C 1 -C 8 -alkylaminocarbonyl-C 1 -C 4 -alkyl group, 13 years Y is a hydrogen, fluorine or chlorine atom, X is one of the groups (CR R) -W or (CR J = V ₁ where V or W bound directly to the phenyl nucleus,
η 0 or 1, W is one of the groups CR ₁ R ,. or NR "or an oxygen or sulfur atom, 4 5 6 with the proviso that when Z = Z and η = 1, W is not oxygen and, when Z = Z or Z and η = 0, W is not sulfur, V is a group CR or a nitrogen atom, R ₁ R, R and R, the same or different, each represents a water-octane or L ·JH D Halogen atom or a C -C -alkyl or halogeno-C 1 -C -alkyl group, R _{c is} a hydrogen atom, a methyl or halomethyl group, Z is a heterocyclic radical of the formulas Z to Z _n -57- CH. Z " N 8 L / / ^N \ '/ R N 9 or L is a halogen atom, a C -C -alkyl group, a halogeno-C -C -alkyl group, a cyano group or a C -C alkoxy group optionally substituted by up to 9 halogen atoms, Q represents the group CH or a nitrogen atom, with the proviso that, when Q = N and η = 1, M is not oxygen and, when Q = CH or N and η = 0, W is not sulfur, U is an oxygen or sulfur atom, U is an oxygen or sulfur atom, -58- R_, R and R are each a straight-chain, branched or cyclic, f 8 9 optionally substituted with halogen C -C alkyl, or R- and R- together with the adjacent nitrogen and carbon ι ο atoms forms a heterocyclic 5- to 7-membered ring which is saturated or unsaturated, optionally contains further heteroatoms such as O ₁ 5 or N and is optionally substituted by one to three methyl groups or one to six halogen atoms, T is the group DE, a group (CR ₁ -R ,,),
lb running time E is an oxygen or sulfur atom or one of the groups SO, S0 ", NR. C (O or CR ₁₉ R ₂₀ ,
m is 0 or 1,
ρ 1 or 2, ^R 12 " ^R 13" ^R H ' ^R 15 " ^R 16" ^R 17' ^R 18 ' ^R 19 ^{and R} 20 is ^{a hydrogen atom} · ^a hydroxy group, a C -C alkyl group, a halogeno-C -C alkyl group, C - C 1-4 alkyloxy, C 1-4 alkylthio, C 1-6 alkylcarbonyloxy or C 1-6 alkyloxycarbonyl, and R is a hydrogen atom, a C -C -alkyl group, a halogeno-C -C -alkyl group, a C -C -alkenyl group or a C -C -alkynyl group means, in mixture with carriers and / or excipients.