FI92585B - Heterocyclic-substituted azoles and azines, methods for their preparation and their use as herbicides - Google Patents

Description

92585

The invention relates to novel heterocyclically substituted azoles and azines, to processes for their preparation and to their use as herbicidal agents.

It is already known that certain triazolopyr-10 -azines and benzothiazolylazolidines have herbicidal properties (EP-A-0 176 101 and 0 230 874). However, the herbicidal activity of these known compounds is not sufficient in all cases or their selectivity in important crops 15 is insufficient.

It is therefore an object of the invention to provide novel compounds which do not have these disadvantages and which have better biological properties than the known compounds.

It has now been found that it is heterocyclic substituted

azoles and azines of general formula I

fl

A "NV-Z ^ r

'25 | | (I) wherein R 1 is a hydrogen atom, a C 1-5 alkyl group, a C 3-5 alkenyl group, a C 3-5 alkynyl group, a halo-C 1-4 alkyl group, a halogen-C 3.

A 5-alkenyl group, a halogen-C3-5-alkynyl group or a cyano-C1.

3-alkyl group, Y is a hydrogen or fluorine atom, X is a group (CR2R3) nW or (CR2) = V, where V or 35 W, respectively, is directly attached to the phenyl ring, 92585 2 n is 0 or 1, W is a group CR, R5 or NR * or an oxygen or sulfur atom, with the proviso that when Z = Zt and n = 1, W is not oxygen, V is a group CR4 or a nitrogen atom, R2, R3, R1 and R5 are the same or different and each represents a hydrogen or halogen atom or a C 1-3 alkyl or halogen-C 1-6 alkyl group, R * is a hydrogen atom, Z is a heterocyclic residue having one of the formulas Z 1, Z 3 10 2 and Z 3 z 2 (z 2) (z3)

°> = ί / ^ Ί Ύ — N X

K

(Z5) (Z6)

When / X * 15 f 27. γγ \ N -1 I I (CH2),

X "X

^ (Z7) (Z8) 30 Q is a group CH with the proviso that when n = o, w is not sulfur, υ, is an oxygen or sulfur atom, 35 U2 is an oxygen atom, 92585 3

Rv and Rg together with adjacent nitrogen and carbon atoms form a heterocyclic 5-7 membered ring which may be saturated or unsaturated, T is a group DE, D is a group (CR16Rp) m, E is a sulfur atom or a group CR19R20, m is 0 , p is 2,

R 12, R 3, R 4, R 15, R 16, R 11, R 18, R 19 and R 20 are each a hydrogen atom 10 or a C 1-6 alkyl group and R 27 is a hydrogen atom or a C 1-5 alkyl group, are surprisingly very well tolerated by crops and have at the same time an interesting herbicidal effect.

The term halogen means fluorine, chlorine, bromine or iodine. Haloalkyl means that one or more of the hydrogen atoms of the alkyl group has been replaced by halogen.

Examples of heterocyclic rings are: pyrrole, oxazole, thiazole, imidazole, pyridine, oxazine, thiazine, pyrimidine, pyrazine, triazine, oxadiazine and thiaziazine and their ditetra or possibly hexahydro derivatives.

The compounds of general formula I according to the invention can be prepared as follows: A) when Z is 3,4-dimethyl-3-pyrroline-2,5-dione-1-

yyl group, aniline of general formula II

(%) wherein R 1, X and Y are as defined in the general formula I, is reacted with 2,2'-dimethylmalein-35 acid anhydride, 92585 4

B) when Z is a 4,5,6,7-tetrahydro-2H-1,2,3-triazolo [3,4-a] pyridin-8-ium-3-olat-2-yl group, a compound having the general formula is II

5x- (II) 10 wherein R 1, X and Y are as defined in general formula I, are diazotized with nitric acid, then reacted with piperidine-2-carboxylic acid and cyclized with a dehydrating agent, C) when Z is 2,3,5 , 6,7,8-hexahydro-1H-imidazo [1,5-a] pyridine-1,3-dion-2-yl or 2,3,5,6,7,8-hexa-

hydro-1H-1,3,4-triazolo [1,2-a] pyridazine-1,3-Dion-2-yl group, a compound of general formula II

N1 20 2 (II) x—

wherein R 1, X and Y are as defined in the general formula I, are reacted with a compound of the general formula V or VI

n ^ H2 _ T | R21 ° I - (V) (VI) 30 Ä »U2 ϋχ in which formulas Q, U, and U2 are as defined in connection with the general formula I and R21 is a C1-4 alkyl group, D) when Z is 2,3,5,6,7 , 8-hexahydro-1H-imidazo [35,5-a] pyridine-1,3-dion-2-yl or 2,3,5,6,7,8-hexa-92585 5

hydro-1H-1,3,4-triazolo [1,2-a] pyridazine-1,3-Dion-2-yl group, a compound of general formula III

* 1 5 N N = C = U χ x- (III)

wherein R 1, U 1, X and Y are as defined in general formula I, is reacted with a compound of general formula VII

B\

N KT

R22 ° \ c / ^ \ / (VII) «U2 wherein Q and U2 are as defined in the general formula I and R22 is a C1-4 alkyl group, E) when Z is of the general formula -, ·. ·> R? 5 A residue according to formula N-j 30, wherein R 12, R 13, R 14, R 15 and T are as defined in the context of the general formula I, a compound of the general formula purple fi 35 II li (Ula) 6 92585 wherein Rw X and Y represent the general formula I is reacted with a compound of the general formula Vili h = 1 (VIII) \ ϊη2 10 wherein R, 2, R [j, R | 4, Rij and T are as defined in the general formula I and cyclized in the presence of an oxidant to a thiadiazole ring ,

F) when Z is a 2H-1,2,4-triazolin-3-on-2-yl residue, a compound of general formula IV

15 fl 20

wherein R 1, X and Y are as defined in the general formula I, are reacted with a compound of the general formula XI

O

B

25 .c R? R24 °? ο ^ * 8 wherein R7 and R8 are as defined in the general formula I and R24 is a C1-4 alkyl group, G) when Z is 5,6,7,8-tetrahydroquinazoline-2,4-

(1H, 3H) -Dion-3-yl residue or 1,2,4,5,6,7-hexahydro-2,4-dioxo-3H-cyclopentapyrimidin-3-yl residue, a compound of general formula XXII

9 7 92585 f1 I? γγγ \ ^ »γ \ 5 Υ» L >> 1 Ο (CH2) ρ (XXII) γ r28ooc / '^ \ ^

wherein R 1, X and Υ and are as defined in general formula I and R 2g is a C 1-4 alkyl group, cyclized under temporal conditions and, if desired, reacted, optionally in the presence of an acid scavenger, with a compound of general formula XXIII

R27-B (XXIII) wherein R27 is as defined in the general formula I, but is not hydrogen, and B is a halogen atom or a p-toluenesulfonyloxy group.

The reaction according to process variant A) is expediently carried out at 20-200 ° C, optionally in the presence of a suitable solvent, using 2,2'-dimethylmaleic anhydride in a molar ratio of 1 to 3 equivalents per equivalent of amine of the formula II. The reaction time is 1 to 24 hours. The reaction is conveniently carried out in the presence of an acid, for example acetic acid, in which case, for example, acetic acid can be used as a solvent. However, it is also possible to react both reactants with each other in an inert solvent such as dichloromethane or di-methylsulfoxide and to cyclize the intermediate adduct with an acid anhydride such as acetic anhydride.

The reaction according to process variant B) is usually carried out in three steps without purification of intermediates 35 according to the following reaction scheme:% δ 92585

yw

'-kA

N / 10 ", vSkV * '69 \ (XIV),

x kA

15 0

II

^ C / V

H0 'ύ' 20 V "y ^ vn = h / N '^ /

x kA

* 25 v ° · Α R | 1 β da) 30 VY \\ A / I n

X

- \ </ \ 35 92585 9

Aniline of general formula II, wherein R 1, X and Y are as defined in general formula I, is diazotized in the usual manner as an acidic aqueous suspension at -20 ° to + 10 ° C with sodium nitrite; the reaction time is 0.5 to 3 hours.

A compound of general formula XIV wherein G is a halogen atom, especially a chlorine atom, another inorganic group such as hydrogen sulfate, or an organic group such as acetate is then reacted at -20 ° to + 20 ° C with a piperidine-2-carboxylic acid. and an acid scavenger such as a trialkylamine.

A compound of general formula XV may be cyclized to a compound of formula Ia with an acid anhydride, for example acetic anhydride, in the presence of a base such as pyridine in an inert solvent, for example ether.

The reaction according to process variant C) is expediently carried out at a temperature above 20 ° C, for example at 100 ° C or at the reflux temperature of the reaction mixture. When the reactant is an anhydride of the general formula V, the reaction is conveniently carried out in the presence of an acid such as acetic acid, for example, using acetic acid as a solvent. However, it is also possible to carry out the reaction without a solvent or using an inert solvent such as dichloromethane or dimethyl sulfoxide, and to cyclize the intermediate adduct with an acid anhydride such as acetic anhydride.

The reaction according to process variant D) is carried out in an inert solvent at 20 to 150 ° C, preferably at the boiling point of the solvent. Suitable solvents include, for example, aliphatic and aromatic, optionally chlorinated hydrocarbons such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, 32585 tetrachloroethane, 1,2-dichloroethane, chlorobenzene, and ethers such as diethyl. -butyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, further nitriles such as acetonitrile and propionitrile, sulfoxides such as dimethyl sulfoxide or sulfolane.

The isocyanates or isothiocyanates of the general formula III used as starting materials can be easily prepared from anilines of the general formula II in which R 1, X and Y represent, as defined in the general formula I, aniline reacted with phosgene or thiophosgene or a reactive derivative thereof .

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 ° C to + 50 ° C by reacting a compound of general formula IIIa wherein R 1, X and Y represent the general formula I to react with a compound of general formula VIII, wherein R 1 2, R 1 3, Ru,

R, 5 and T are as defined in the context of general formula I. The reaction time is 0.5 to 10 hours. The obtained compound of general formula XVI

s'V <; R, i P * 12 - ^ nh (XVI) X XX \ is thermally unstable, so it is essentially subjected to the next reaction without isolation.

92585 11

The ring formation is performed by oxidation in an organic solvent. Suitable organic solvents are inert solvents, such as methylene chloride, chloroform, Ν, Ν-dimethylformamide and ethyl acetate. Depending on the nature of the oxidant, the condensation reaction leading to the formation of ring-5 can be carried out in the presence of an active acid-binding agent. Suitable acid-binding agents are organic bases, such as triethylamine, pyridine, dimethylaniline, inorganic bases, such as sodium hydroxide and sodium carbonate. As the oxidants, bromine, chlorine, sodium hypochlorite and the like are used. If at least one of the substituents R is a hydroxy group, iodine is preferably used as the oxidant.

The reaction according to process variant F) is conveniently carried out with the aid of a catalyst in a suitable solvent. The reaction temperature is from room temperature to 150 ° C, preferably the reflux temperature of the reaction mixture. Examples of suitable solvents include dimethyl sulfoxide, halohydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, dimethylformamide and liqueuryl ether, and other non-reactive solvents such as diethyl ether.

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

The reaction according to process variant G) is conveniently carried out in a suitable solvent and with the addition of a base such as alkali hydroxide and alcoholate, sodium hydride or triethylamine, optionally in a two-phase system with addition of a phase transfer catalyst at reflux at 5-150 ° C, preferably at 3 ° C. .

The starting materials of formula XXII are obtained according to the following reaction scheme: 92585 12 R, 1 yY \, itso I (III b) 5 x — k / \ ¥ γλ v. Fl i-CH2 'p, XXVI1 10' j.'oc'x /

R H H

- VlWkf "lV \ x — kA ...« «As / 20 Reaction between a compound of formula IIIb, wherein R 1, X and Y are as defined in the general formula I, and an enaminoester of formula XXVI, in which p is 1 or 2 and R 2g is a C 1 -C 4 alkyl group, conveniently carried out in an inert solvent such as dioxane.

The reaction temperature is between room temperature and 200 ° C, preferably the Boiling point of the solvent.

Usually the starting materials are used in stoichiometric ratios. In individual cases, however, it may be advantageous to use either in excess.

The compounds of the invention prepared by the above-mentioned methods can be isolated from the reaction mixture by conventional methods, for example, by distilling off the spent solvent under normal or reduced pressure or by extraction.

13 92585

Higher purity is usually obtained by column chromatography or fractional distillation.

The compounds of the invention are generally crystalline or viscous substances which are in part highly soluble in halogenated hydrocarbons, such as chloroform, sulfoxides, such as dimethyl sulfoxide, or esters, such as ethyl acetate.

The starting materials of the formulas III and IV are mainly new, but can be prepared by methods analogous to known methods.

The active compounds according to the invention have a good herbicidal effect on broadleaf weeds and grasses. The active compounds according to the invention can be used as selective herbicides in various crops, examples of which are oilseed rape, beets, soybeans, cotton, rice, barley, wheat and other cereals. In this case, the individual active ingredients are particularly suitable as selective herbicides for beet, cotton, soybean and cereal crops. The compounds can likewise be used for controlling weeds in permanent crops, for example forest, ornamental shrub, fruit tree, wine, citrus, walnut, banana, coffee, tea, rubber, oil palm, cocoa, berry bush and hop cultures and selective weed control in annual crops.

The active compounds according to the invention can be used, for example, against the following plant genera. Dicotyledonous weeds:

Mustard, Lepidium, Galium, Stellaria, Matricaria, Anthemis, 30 Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranth, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Soluus, Carduus, Sonch , Lamium, Veronica, Abutilon, Datura,

Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

35 «92585 14

Monocotyledonous weeds:

Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agro-Pyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ischaemum and Apera.

The amounts of use vary depending on the mode of use and whether it is pre-emergence or post-emergence use; application rate is 0.05-5 kg / ha.

The compounds of the invention may be used either alone or in admixture with each other. Possibly they can be used in mixtures with plant protection or pesticides, depending on the desired use. When a broader spectrum of action is desired, other herbicides may be added.

For example, the active ingredients listed in Weed Abstracts can be used as herbicidally active mixture components. 35, No. 5, 1986, entitled "List of common names and abbreviations employed for currently used herbicides and plant growth Regulators 20 in Weed Abstracts".

For example, the effectiveness and rate of action can be improved with effect-enhancing additives such as organic solvents, wetting agents and oils. The use of these substances can potentially reduce the amount of active ingredient.

In addition, phospholipids can be used as mixture components, for example, belonging to the following groups: phosphatidylcholine, hydrogenated phosphatidylcholines, phosphatidylethanolamine, N-acyl-phosphatidylethanol-30 amines, phosphatidylinositol, fisphatidylserine, lysolecithin, lysolecithin.

Suitably, the active compounds according to the invention or mixtures thereof are used in the form of preparations, such as powders, sprays, granules, solutions, emulsions or suspensions, to which solid and / or liquid carriers or diluents have been added and, if appropriate, -, emulsifying and / or dispersing aids.

Suitable liquid carriers include, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, in addition to 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 flour.

Examples of surfactants which may be mentioned are calcium lignin sulphonate, polyethylene alkyl ethers, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates and substituted benzenesulphonic acids.

The proportion of active ingredient or ingredients in different preparations can vary within wide limits. The preparations contain, for example, from about 10 to 90% by weight of active ingredient, from about 9 to 10% by weight of liquid or solid carriers and possibly up to 20% by weight of surfactants.

The application of the preparations can be carried out in the usual manner, for example using water as a carrier, spraying the preparation broth at 100-1000 l / ha. The preparations can also be applied by the so-called Low-Volume and Ultra-Low-Volume methods and can also be used in the form of so-called microgranules.

30 These preparations can be prepared in a manner known per se, for example by grinding or mixing. If desired, the preparations of the individual components can also be mixed just before use, in which case the mixing is carried out, for example, by the so-called tank mixing method.

35 For example, the following ingredients are used in the preparation of various preparations: 16 92585 A) Spray powder 20% by weight of active ingredient 35% by weight of bentonite 35% by weight of silicic acid 5 8% by weight of calcium salt of lignin sulphonic acid 2% by weight of N-methyl-N-oleyl taurine sodium salt B) Paste 45% by weight of active ingredient 5% by weight of sodium aluminum silicate 10 15% by weight of cetyl polyglycol ether (8 mol of EtO) 2% by weight of spindle oil 10% by weight of polyethylene glycol 23% by weight of water C) Emulsion concentrate 15 20% by weight of active ingredient 75 % by weight of isophorone 5% by weight of a mixture of the calcium salt of dodecylbenzenesulfonic acid and nonylphenyl polyoxyethylene.

The following examples illustrate the preparation of the compounds of the invention:

Example 1.01 (Method E) 6- (6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo [2,1-c] yl, 2-47thiadiazol-3-ylidenimino) -4- (2-25 propynyl) -2H-1,4-benzoxazin-3 (4H) -one 2.6 g of 2-amino-4,4-dimethylpyrroline hydrochloride were suspended in 20 ml of methylene dichloride. A solution of sodium hydroxide (0.75 g) in 5 ml of water was then added dropwise to the suspension with stirring at 0 ° C, and the reaction mixture was stirred for 30 minutes, at which time it became clear. A solution of 6-isothiocyanato-4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one in 100 ml of methylene chloride was then added dropwise to the mixture without raising the temperature above 5 ° C. After stirring for 3 hours to 35 hours, the temperature rose to 20 ° C. The mixture was cooled to -20 ° C and a solution of bromine (2.3 g) in 10 ml of methylene chloride was slowly added dropwise, the mixture was stirred for 1 hour, at which time the temperature rose to 10 ° C. The solution was then washed with 30 ml of water, 30 ml of 5% NaOH solution and 30 ml of 5% NaOH solution and 30 ml of 5% NaOH solution and 30 ml of with water. The methylene dichloride phase was dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was purified by silica gel column chromatography.

Yield: 1.5 g = 25% of theory M.p .: 65 ° C.

Preparation of the starting material of Example 1.01 6-Isothiocyanato-4- (2-propynyl) -2H-1,4-benzoxazin-15-s-3 (4H) -one 4.0 g of 6-amino-4- (2-propynyl) -2H -1,4-Benzoxazin-3 (4H) -one was dissolved in 100 ml of methylene chloride, and a suspension of calcium carbonate (2.60 g) in 20 ml of water was added to the solution at 5 ° C. 2.9 g of thiophosgene were then added dropwise to the reaction mixture so that the temperature of the mixture did not rise above 5 ° C. After standing for 10 hours at room temperature, the phases were separated. The organic phase was washed with 50 ml of water, dried over MgSO 4 and the solvent was evaporated under reduced pressure.

2 * 5 Yield: 4.1 g = 84% of theory M.p .: 120-122 ° C.

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

Example Name Physical constant 20 No. Sp (° C) 1.02 6- (6,6-dimethyl-3,5,6,7-tetrahydro-133 pyrrolo [2,1-c] O-, 2,4] thiadistaol-3-ylidene -imirio) -4-methyl-2H-1,4-benzoxazin-3 (4H-one 35

Eg Name Physicist. constant (° C) 18,92585 1.03 6- (6,6-dimethyl-3,5,6,7-tetrahydro-62 pyrrolo [2,1-c] [1,2,4] thiadiazol-3-ylidenimino) -7-fluoro-4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one 1.04 4- (2,3-dibromo-2-propenyl) -6- (6, 6- 65 Dimethyl-3,5,6,7-tetrahydropyrrolo

Cz, 1 - [(1,2,4-thiadiazol-3-ylideneimino) -7-fluoro-2H-1,4-benzoxazin-3 (4H) -one 10 1.05 5- (6,6-dimethyl-5 , 6-dihydro-3H-thiaz-195 Solo [2,3-c] [1,2,4] triadiazol-3-ylideneimino) -6-fluoro-3- (2-propynyl) -2 (3H ) -benzothiazolone 1.06 5- (6,6-dimethyl-3,5,6,7-tetrahydro-190-pyrrolo [2,1-c] [1,2,47 "thiadiazol-3-11-ylidenoimino) -6 -fluoro-3- (2-propynyl) -2 (3H) -benzothiazolone 1.07 6- (6,6-dimethyl-5,6-dihydro-3H-124-126 thiazolo [1,3-q] E, 2.47 Thiadiazol-3-ylidenoimino) -4- (2-propenyl) -2H-1,4-benzoxazin-3 (4H) -one 20 1.08 6- (6,6-dimethyl-3,5,6 , 7-Tetrahydro-110-pyrrolo [2,1-c] (2,4,4-thiadiazol-3-ylidenoimino) -4- (2-propenyl) -2H-1,4-benzoxazin-3 (4H) -one 1.09 6- (6,6-Dimethyl-5,6-dihydro-3H-93 thiazolo [2,3-c] [1,2,4] thiadiazole-3-ylideneamino) -4- (2-propynyl) - 2H-1,4-benzoxazin-3 (4H) -one 1.10 6- (6,6-dimethyl-5,6-dihydro-3H-53 thiazolo [2,3-c] O- (2,4) thiadiazole) 3-ylideneamino) -4-propyl-2H-1,4-benzoxazin-3 (4H) -one 30 1.11 6- (6,6-dimethyl-3 , 5,6,7-tetrahydro-n-β: 1,6068-pyrrolo £ £ 1,1-c? Or 2,4-thiadiazol-3-ylidenoimino-4-propyl-2H-1,4-benzoxazin-3 (4H) -one 1.12 7- (6,6-dimethyl-3,5,6,7-tetrahydro-168 Pyrrolo [5,1-c] (1,2-thiadiazol-3-yl-3-dienoimino) -1- (2-propynyl) -2 (1H) -quinoxalinone

Eg Name Physicist. constant, mp (° C) 19 92585 1.13 7- (6,6-dimethyl-5,6-dihydro-3H-174 thiazolo [2,2> -c] Q, 2,4,7-thiadiazol-3-ylidene- imino) -1- (2-propynyl) -2 (1H) -quinoxalinone 5,14 6- (6,6-dimethyl-3,5,6,7-tetrahydro-65-pyrrolo [2,2,12,2]] diadiazole 3-ylideneamino-4- (2-propynyl) -2H-1,4-benzothiazin-3 (4H) -one 1.15 6- (6,6-dimethyl-5,6-dihydro-3H-135-140 10 Thiazolo [2,3-c] 1,2,47 thiadiazol-3-ylidenoimino) -7-fluoro-4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one 1.16 6 - (6,6-Dimethyl-3,5,6,7-tetrahydro-161-pyrrolo [2,1-c] [1,2,1] thiadiazol-3-ylideneimino) -7-fluoro-4-propyl -2H-1,4-benzoxazin-3 (4H) -one 1.17 6- (6,6-dimethyl-5,6-dihydro-3H-156 thiazolo [2,3-c] 1,2,4} thiadiazole -3-ylideneamino) -7-fluoro-4-propyl-2H-1,4-benzoxazin-3 (4H) -one 20,18 4-cyanomethyl-6- (6,6-dimethyl-170-171 3, 5,6,7-Tetrahydropyrrolo [2,1-a] b, 2,47 thiadiazol-3-ylidenoimino) -2H-1,4-benzoxazin-3 (4H) -one 1.19 6- (6-methyl- 3,5,6,7-tetrahydro-171-172, pyrrolo ε 2,1-c7 ε 1,2,4 7-Thiadiazol-3-ylideneamino) -4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one 1.20 7-Fluoro-6- (6-methyl-3,5,6, 7- 161-162 Tetrahydropyrrolo [2,1-c] (1,2,47-thiadiazol-3-ylidenoimino) -4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one 1.21 5- (6,6-dimethyl-3,5,6,7-tetrahydro-113 pyrrolo [2,1-c], 2,4-thiadiazol-3-ylidenimino) -3-propyl-2 (3H ) -benzoxazolone 1.22 5- (6,6-Dimethyl-5,6-dihydro-3H-thiazol-113 Solo [2,3-c] 1,2,4,7-thiadiazol-3-yl-35-imino) - 3-propyl-2 (3H) -benzoxazole

Eg Name Physicist. constant, m.p. (° C) 20 92585 1.23 5- (6,6-dimethyl-3,5,6,7-tetra-124-127 hydropyrrolo [2,1-c] O, 2,4-thiadiazol-3-ylidene -imino) -6-fluoro-5-propyl-2 (3H) -benzoxazolone 1.24 5- (6,6-dimethyl-5,6-dihydro-3H-141-142 thiazolo [2,3-c] / l, 2, (and thiadiazol-3-ylidenoimino) -6-fluoro-3-propyl-2 (3H) -benzoxazolone 1.25 5- (6,6-dimethyl-3,5,6,7-tetrahydro-158 10 pyrrolo [2 1,1 - [(1,2,4] Thiadiazol-3-ylidenoimino) -3- (2-propynyl) -2 (3H) -benzoxazolone 1.26 5- (6,6-dimethyl-5,6-dihydro-3H - 137 thiazolo [2,3-c] O [2,4-thiadiazol-3-ylidenoimino) -3- (2-propynyl) -2- (3H) -benzoxazolone 1.27 5- (6,6-dimethyl-3,5 , 6,7-Tetrahydro-169-173 pyrrolo [2,1-c] O, 2,2-thiadiazol-3-ylideneamino) -6-fluoro-3- (2-propynyl) -2 (3H) -benzoxazolone 1.28 5- (6,6-Dimethyl-5,6-dihydro-3H-138-14220 thiazolo [5,3-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 [1,1-c] [1,2] thiadiazol-3-ylidene- ss o) -3-methyl-1-propyl-1,3-dihydro-2 (2H) -indolone 1.30 6- (6,6-dimethyl-5,6-dihydro-3H-thiazolo [2,3-c] E] 1,2,47 Thiadiazol-3-ylidenoimino) -3-methyl-1-propyl-1,3-dihydro-2 (2H) -indolone 30 1.31 7- (6,6-dimethyl-3,5 , 6,7-tetrahydropyrrolo [2,1-c] [1,2,4] thiadiazol-3-ylideneimino) -1- (2-propynyl) -3,4-dihydro-2 (1H) -quinoxalinone

Example 2.01 (Method A) 35 1-6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydro-; Benzoxazol-5-yl-3,4-dimethyl-3-pyrroline-2,5 (1H) -dione 92585 21 5-Amino-6-fluoro-3- (2-propynyl) -2 (3H) -benzoxat-Solone To a solution of (4 g) in glacial acetic acid (50 ml) was added 2.8 g of 2,3-dimethylmaleic anhydride. Stirred for 8 hours at 80 ° C. The cooled reaction mixture was poured into 500 ml of ice water, and the precipitated crystals were filtered off with suction and washed with ice water. The crystals were dried in vacuo at 50 ° C. Yield: 23, g = 38% of theory

M.p .: 165 ° C

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

Example Name Physical constant, O n ° m.p. (C) 2.02 1- [6-Fluoro-2-oxo-3- (2-propynyl) -229 2,3-dihydrobenzothiazol-5-yl] -3,4-dimethyl -3-pyrroline-2,5 (1H) -dione 2.03 1- [3-oxo-4- (2-propynyl) -3,4-dihydro-279-2H-1,4-bemptoazom-6-yl] -N- 3,4-Dimethyl-3-pyrroline-2,5 (1H) -dione 2Q 2.04 1- [2-oxo-2,3-dihydro-1H-benzimid-280-azol-5-yl] -3,4-dimethyl- 3-Pyrroline-2,5 (1H) -dione 2.05 1- {2-oxo-1- (2-propynyl) -1H-quinox-265-salin-7-yl] -3,4,4-dimethyl-3 -pyrroline-2,5 (1H) -dione 2.06 1- {2-oxo-1- (2-propynyl) -3,4-dihydro-1H-quinoxalin-7-yl] -3,4- dimethyl-3-pyrroline-2,5 (1H) -dione 2.07 1 H- [2-oxo-3- (2-propynyl) -2,3-di-189-hydroxybenzoxazol-5-yl] -3,4- dimethyl-3-pyrroline-2,5 (1H) -2,2. Dione 2.08 1- (2-Oxo-3-propyl-2,3-dihydro-110-benzoxdazol-5-yl) -3,4-dimethyl-3-pyrroline-2,5 (1H) -dione 2.09 1- (3-methyl-2-oxo-1-propyl-180-35 1,3-dihydro-2H-indol-6-yl) -3,4-dimethyl-3-pyrroline-2,5 (1H) -dione

Example Name Physical constant no. Mp (° C) 22 92585 2.10 1- [3-methyl-2-oxo-1- (1-methyl-142-144 ethyl) -1,3-dihydro-2H-indol-6-yl] -3,4-dimethyl-3-pyrroline-5,5 (1H) -dione

Example 3.01 (Method D) 2- (7-Fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl) perhydroimidazo [1,5-a] pyridine -1,3-dione 6.4 g of 7-fluoro-4- (2-propynyl) -1,4-benzoxazin-3 (4H) -on-6-yl isocyanate were dissolved in 50 ml of tetrahydrofuran and dissolved in 4.1 ml of piperidine-2-carboxylic acid ethyl ester were added, the mixture was refluxed for 10 hours, after which the solvent was evaporated in vacuo and the residue was separated on a silica gel column with ethyl acetate-hexane.

Yield: 4.8 g = 52% of theory.

Mp: 202-204 ° C.

20

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

Example Name Physical constant No. mp (° C) * 25 3.02 2- [3-oxo-4- (2-propynyl) -3,4-180-185 dihydro-2H-1,4-benzoxazin-6-yl] perhydroimidazole 1,5-α-pyridine-1,3-dione 3.03 2- [3-oxo-4- (2-propenyl) -3,4-157-158 dihydro-2H-1,4-benzoxazin-6-yl] perhydroimidazo [. 1,5-N-pyridine-1,3-dione 3.04 2 -, / 7-fluoro-3-oxo-4- (2-propynyl) -3,4-dihydro-2H-1,4 Benzooxazin-6-yl-3-thioxoper-hydroimidazo [1,5-a] pyridin-1-one 92585 23

Example Name Physical constant No. m.p. (C) 3.05 2- [6-Fluoro-2-oxo-3- (2-propynyl) -189-195 2,3-dihydrobenzoxazol-5-yl] -3-thioxoperhydroimidazo [1,5-a] pyridine- 5 1-one 3.06 2- (7-Fluoro-3-oxo-4-propyl-3,4-dihydro-2H-1,4-benzoxazin-6-yl) perhydroimidazo [1,5-a] pyridine-1,3- dione 10 3.07 2- [2-oxo-1- (2-propynyl) -1H-199-200 quinoxalin-7-yl] perhydroimidazo [1,5-a] pyridine-1,3-dione 3.08 2- [2- oxo-1- (2-propynyl) -3,4-dihydro-1H-quinoxalin-7-yl-7-perhydroimidazo [1,5-a] pyridine-1,3-dione

ID

3.09 2- [2-oxo-3- (2-propynyl) -2,3-179 dihydrobenzoxazol-5-yl] perhydroimidazo [1,5-a] pyridine-1,3-dione 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-methyl- 2-Oxo-1-propyl-1,3-dihydro-2H-indol-6-yl) -perhydroimidiazo [1,5-a] pyridine: 1,3-dione

Example 4.01 (Method G) 3- (3-Oxo-4-propyl-3,4-dihydro-2H-1,4-benzooxazin-6-yl) -5,6,7,8-tetrahydroquinazoline-30 2 , 4- (1H, 3H) -dione 92585 24 2.0 g of sodium were dissolved in 100 ethanol, to the solution was added 2- [3- (3-oxo-4-propyl-3,4-dihydro- (2H) -1.4 A solution of benzoxazin-6-yl-ureid-7-1-cyclohexenecarboxylic acid ethyl ester (4.4 g) in ethanol 5 (50 ml), and the reaction mixture was heated at reflux for 1 hour. After completion of the reaction, the solution was evaporated and 300 ml of water were added to the residue. The precipitate was filtered and the filtrate was acidified with hydrochloric acid. The precipitated product was filtered off with suction, washed with water and crystallized from ethyl acetate-10-diisopropyl ether.

Yield: 3.56 g = 56% of theory. M.p .:> 250 ° C

Example 4.02 (Method G) 1-Methyl-3- (4-propyl-3,4-dihydro-2H-1,4-benzoxazin-6-yl) -5,6,7,8-tetrahydroquinazoline-2 , 4 (1H, 3H) -dione 2.0 g 3- (4-propyl-1,4-benzoxazin-3 (4H) -on-6-yl) -5,6,7,8-tetrahydroquinazoline-2,4 ( 1H, 3H) -dione was dissolved in 20 ml of dimethylformamide, 0.17 g of an 80% sodium hydride suspension was added to the solution, and the mixture was stirred at 60 ° C for 1 hour. The mixture was allowed to cool to room temperature and 0.77 g of iodomethane was added. The mixture was heated at 60 ° C for 2 hours. As the mixture cools. the separated crystals were suction filtered and recrystallized from diisopropyl ether-ethyl acetate.

Yield: 1.3 g = 65% of theory. Mp: 218 ° C.

Example 5.01 (Method F) 2- / 6-Fluoro-2-oxo-3- (2-propynyl) -2,3-dihydro-benzothiazol-5-yl] -2,3,5,6,7,8- hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one 3.6 g of 5-hydrazino-6-fluoro-3- (2-propynyl) benzothiazolone were dissolved in 40 ml of xylene, added to the solution. 2.8 g of 1-ethoxycarbonyl-2-piperidone and 1 g of phosphorus pentoxide and the mixture were heated under reflux for 2 hours. The cooled reaction mixture was poured into 100 ml of water and the organic phase was separated. The organic phase was washed with potassium hydrogen carbonate solution (40 ml), dried over magnesium sulphate and evaporated. The residue Kro-5 was chromatographed on a silica gel column using ethyl acetate-hexane mixtures as eluent.

Yield: 380 mg = 6.7% of theory. M.p .: 153-160 ° C. Preparation of the starting material of Example 5.01 5-Hydrazino-6-fluoro-3- (2-propynyl) benzo-10-tazolone 4 g of 5-amino-6-fluoro-3- (2-propynyl) -2 (3H) -benzothiazolone were dissolved 50 ml of concentrated hydrochloric acid and the solution were stirred at room temperature for 30 minutes. The solution was cooled to -5 ° to + 5 ° C and 1.3 g of sodium nitrite in 5.6 ml of water was added dropwise. After stirring for 30 minutes, the mixture was cooled to -30 ° C. A solution of stannous chloride (6.8 g) in 15 ml of concentrated hydrochloric acid was then slowly added dropwise to the mixture. The mixture was stirred for 2 hours keeping the temperature at -10 to 0 ° C. The solid was filtered off and the filtrate was neutralized and extracted with ethyl acetate (3 x 50 mL). The extract was dried over magnesium sulfate and the solvent was evaporated in vacuo.

Yield: 2.6 g = 61% of theory.

In an analogous manner, the following compounds are prepared by method F:

Example Name Physical constant no. M.p. (° C) 5.02 2- {2-oxo-3- (2-propynyl) -2,3-1,190-dihydrobenzoxazol-5-yl] -2,3,5,6,7,8- Hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one 5.03 2- [7-fluoro-3-oxo-4- (2-propynyl) -1,194-196 3,4-dihydro-2H- 1,4-benzoxazin-6-yl] -2,3,5,6,7,8-hexahydro-1,2,4-35 triazolo [4,3-a] pyridin-3-one ^ 2585 26

Example Name Physical Constant No. mp (C) 5.04 2- [6-Fluoro-2-oxo-1- (2-propynyl) -3,4-dihydro-1H-quinoxalin-7-yl] -2,3,5,6,7,7 , 8-hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one 5.05 2- (5-fluoro-2-oxo-1- (2-propynyl) -210-211 1H-quinoxalin-7-yl] -2,3,5,6,7,8-hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one 5.06 2- (6-f) fluoro-2-oxo-3,4-dihydro-190-192 1H-quinoxalin-7-yl] -2,3,5,6,7,8-hexahydro-1,2,4-triazolo [4,3-a] pyridin-3-one

Example 6.01 15 (Method B) 2- [7-Fluoro-3-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 6-amino-7-fluoro-4- (2-propynyl) -2H-1,4- Benzoxazin-3 (4H) -one was suspended in a mixture of concentrated hydrochloric acid (12.2 ml) and water (52 ml) and the suspension was cooled to -10 ° to -5 ° C. Sodium nitrite (1, 4 ml) was added dropwise. 74 g) a solution in water (6 ml) so that the temperature of the reaction mixture does not rise above -5 ° C.

At the end of the addition, the mixture was stirred for 1 hour at -5 ° C and the excess nitric acid was decomposed with urea until a negative test result was obtained with iodine starch paper.

The solution thus obtained was warmed to 0 ° C and added dropwise to an ice-cooled solution of pipecolic acid (2.9 g) and tri-ethylamine (10.5 ml) in water (38 ml). After the addition was complete, the mixture was stirred for an additional hour at 0 ° C, then the reaction mixture was extracted several times with methylene chloride. The combined organic extracts were dried over magnesium sulfate and the solvent was evaporated. The residue 35 was dissolved in 60 ml of ether and 4,92585 27 5.2 ml of acetic anhydride and 2.6 ml of pyridine were added to the solution.

The mixture was stirred at room temperature overnight, then the mixture was poured into 150 ml of ice water. The mixture was extracted with ethyl. with acetate, the extract was dried over magnesium sulfate and the solvent was evaporated. The residue was chromatographed on silica gel using 95: 5 ethyl acetate-methanol as eluent.

Yield: 1.0 g = 13% of theory. Mp: 202-203 ° C.

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

Example Name Physical constant neo mp (° C) 6.02 2- [6-fluoro-2-oxo-3- (2-propynyl) -2,3-dihydrobenzoxazol-5-yl] -4,5,6, 7-Tetrahydro-2H-1,2,3-triazolo [3,4-a] pyridin-8-ium-3-olate 6.03 2- [6-fluoro-2-oxo-3- (2-propynyl-210)] - 2,3-Dihydrobenzothiazol-5-yl E 7-4,5,6,7-tetrahydro-2H-1,2,3-triazolo [3,4-a] pyridin-8-ium-3-olate.

The following examples illustrate the use of the following compounds:

Example A

, In the greenhouse, the following '25 plant species were treated with the compounds shown after germination at an application rate of 0.1 kg active ingredient / ha. The compounds were then sprayed evenly on the plants in the form of an emulsion or suspension at 500 liters of water / ha. After 3 weeks of treatment, the compounds of the invention were found to have good crop selectivity and to have a very effective effect on the weeds.

92585 28

In the following table: 0 = not damaged 4 = completely destroyed TRZAX = Triticum aestivum 5 BRSSS = Brassica sp.

SOLSS = Solanum sp.

HELAN = Helianthus annuus ABUTH = Abutilon theophrasti MATCH = Matricaria chamomilla 10 VIOSS = Viola sp.

IPSS = Ipomoea purpurea VERPE = Veronica persica GALAP = Galium aparine

15 TBSHAHVIVG

According to the rroeb of the invention

compound z s L L u T o o R L

ASSATCSSPA

_X S S N H H S_S_E_L ·.

E.g.

20 1.01 0444444444 1. 02 0344444444 1. 03 0444444444 1. 04 0444422444 1.05 1143444443 1. 06 0143443432 1. 08 02-343244-

Λ D

1. 09 03-4444443 1.10 11-3443443 1.11 03-344-443 1.12 0 34-44-442 1.15 134-444433 1.16 144-433332 30 1. 17 024-433322 1.18 133-432341 1. 19 134-433342 1.20 144-443444 1. 23 0 3 4 - 4 3 2 3 3 3 1. 27 024-433431 1.28 014-433422 Unprocessed 0000000000 92585 29

Example B

The indicated amounts of the compounds listed in the table were applied in the greenhouse. In this case, the active ingredients were mixed in containers with 1500 ml of water. The experimental plant was Echinochloa crus-Galli (ECHCG) in 2-5 leaf stage.

After 3 weeks of treatment, the compounds of the invention were shown to have a strong effect on Echinochloa crusgalli seedlings.

Meaning in the table: 10 0 = no damage 1 = slightly damaged 2 = moderately damaged 3 = severely damaged 4 = completely destroyed

Addition of ECHCG in water according to the invention

compound example ppm 1.01 3 3 1.02 3 4 Untreated 0

Example C

In the greenhouse, the presented plant species were treated with the indicated compounds after germination at an application rate of 0.01 kg active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha for the plants. Three weeks after spraying, the crops were found to be selectively well tolerated by treatment with the compounds of the invention and to have an effective effect of the compounds of the invention on weeds. The reference substance did not prove to be as effective.

n J In the following table denote: 0 = not damaged 4 = completely destroyed TRZAX = Triticum aestivum ZEAMX = Zea mays 35 VIOSS = Viola sp.

92585 30 VERPE = Veronica persica SOLSS = Solanum sp.

SEBEX = Sesbania exaltata IPOSS = Ipomoea purpurea 5 ABUTH = Abutilon theophrasti

T Z V V S S I A

R E I E 0 E P B

The invention,

according to Z L B 0 U

compound AMSPSEST

10 Example_ xxsesxsh 1.01 003344 * 4 2 01 00344244 2'02 10334--4 15 3 '° 1 - 1 2 4 4 4 4 4 3.02 0 0-3--34 6.01 20344444 Unprocessed 00000000 20 Reference substance

Oxadiazone 00000112 Example D

In the greenhouse, the 25 plant species shown were treated with the compounds shown before germination at an application rate of 0.1 kg active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha evenly on the plants. Three weeks after spraying, the compounds according to the invention showed good crop selectivity for sugar beet, wheat and maize and a very strong effect on weeds. The selectivity of the control compound was not as good.

In the following table: 92585 31 0 = no damage 1 = 1-24% damage 2 = 25-74% damage 3 = 75-89% damage 5 4 = 90-100% damage BEAVX = Beta vulgaris altissima TRZAX = Triticum aestivum ZEAMX = Zea mays GALAP = Galium aparine 10 MATCH = Matricaria chamomilla

B T Z G M of the invention

according to E r e A A

compound A Z A L T

V A M A C

15 X -E_S-E- &

Example 3.04 0 _ _ - 4

Example 4.01 - 0 0 A - 20 Unprocessed 0 0 0 0 0

Reference substance _c Oxadiazon 1 1 1 0 4

£. D

Example E

In the greenhouse, the indicated plant species were treated with the indicated compounds after germination at application rates of 0.1 to 0.1 kg of active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha evenly on the plants. After 3 weeks of treatment, the compounds according to the invention were shown to have good crop selectivity for maize and a very potent effect on weeds. The selectivity of the reference substance was not as good.

92585 32

In the following table they mean: 0 = no damage 1 = 1 - 24% damage 2 = 25-74% damage 5 3 = 75-89% damage 4 = 90 - 100% damage ZEAMX = Sea mays ABUTH = Abutilon theophrasti MATCH = Matricaria chamomilla 10 POLSS = Polygonum sp.

SOLSS = Solanum ssp.

VERPE = Veronica persica

Z A M P S V

Invention E B A 0 0 E

according to A U T L L R

compound M T C S S P

X H H S S E

20 Example 3.04 0-3343

Example 3.05 04-434 Unprocessed 000000 25

Reference substance

Oxadiazon 104344

^ 0 Example F

In the greenhouse, the presented plant species were treated with the indicated compounds before application at application rates of 1.0 kg active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha evenly on the plants. One week after treatment, it was found that 92585 33 of the compounds according to the invention had a very strong effect on weeds.

In the following table: 0 = no damage 5 1 = 1 - 24% damage 2 = 25 - 74% damage 3 = 75-89% damage 4 = 90 - 100% damage ALOMY = Alopecurus myosuroides 10 AVEFA = Avena fatua SETVI = Setaria viridis CYPES = Cyperus esculentus ABUTH = Abutilon theophrasti IPOSS = Ipomoea purpurea 15 MATCH = Matricaria chamomilla

A A S C A I M

L V E Y B P A of the invention

according to 0 E T P U 0 T

20 compound M F V E T S C

Y A I S H_S_Il

Example 6.01 4 4 4 4 4 4 4

Example 6.02 4 4 4 3 444 25 Example 6.03 4444444 Unprocessed 0 0 o 0 0 0 0

Example G

In the greenhouse, the indicated plant species were treated with the indicated compounds after germination at application rates of 0.1 kg active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha evenly on the plants. One week after treatment, it was found that the compounds according to the invention had good crop selectivity for wheat while having a strong effect on weeds.

In the following table they mean: 0 = no damage 5 1 = 1 - 24% damage 2 = 25 - 74% damage 3 = 75-89% damage 4 = 90 = 100% damage TRZAX = Triticum aestivum 10 ABUTH = Abutilon theophrasti GALAP = Galium aparine IPOSS = Ipomoea purpurea MATCH = Matricaria chamomilla 15 TAGI h

R B A P A of the invention

according to Z U L 0 T

compound A T A S C

X H P S H

20

Example 6.01 1 4 3 4 i

Example 6.02 14333 Unprocessed 00000 25

Example H

In the greenhouse, the indicated plant species were treated with the indicated compounds after germination at application rates of 0.3 kg of active ingredient / ha. The compounds were then sprayed as emulsions or suspensions in 500 liters of water / ha evenly on the plants. After 2 weeks of treatment, the compounds of the invention proved to have good crop selectivity for wheat and maize while having a strong effect on weeds.

35 In the following table they mean: * 92585 35 0 = no damage 1 = 1 - 24% damage 2 = 25 - 74% damage 3 = 75 - 89% damage 5 4 = 90 - 100% damage TRZAX = Triticum aestivum ZEAMX = Zea mays ABUTH = Abutilon theophrasti IPOSS = Ipomoea purpurea 10 MATCH = Matricaria chamomilla SOLSS = Solanum sp.

VIOSS = Viola sp.

T Z A I M S V

15 R E B P A 0 I OF THE INVENTION

according to Z A U 0 T L 0

compound A M T S C S S

_X_X_H S H_S_S.

Example 20 1.13 0033342 1.14 0 0 4 4 2 4 1 1 .21 0 0 4 3 3 4 2 1.22 0 0 4 3 3 4 3 1.24 0044343 25 1.25 0044343 1. 26 0 0 3 3 3 4 3 2.05 2144341 Unprocessed 0000000 30 92585 36

Example I

In the greenhouse, the plant species listed below were treated with the compounds shown after germination at an application rate of 0.03 kg active ingredient / ha. Compounds 5 were then sprayed evenly on the plants in the form of an emulsion at 500 liters of water / ha. After 2 weeks of treatment, the compound of the invention was shown to be very effective on weeds. The reference compound known from EP application 176 101 did not have 10 equally effective effects on weeds.

In the following table, mean: 0 = no damage 1 = 1-24% damage 2 = 25-74% damage 15 3 = 75-89% damage 4 = 90-100% damage ZEAMX = Zea mays AGRRE = Elymus repens BROTE = Bromus tectorum 20 PANSS = Panicum sp.

92585 37

Z A B P

E G R A

ARON OF THE INVENTION

according to M R T S

5 compound X E E S

XXXys 10 dVc = CH J3 3 2 3

Example 3.01 15 Unprocessed 000 0 XXXv, i.— Λ— O 3 2 2 2

20 0X

EP 0 176 101 (comp. 7, p. 7) (Reference compound) 25

Example J

In the greenhouse, the plant species listed below were treated with the compounds shown after germination at an application rate of 0.03 kg active ingredient / ha. Compounds 30 were then sprayed evenly on the plants in the form of an emulsion at 500 liters of water / ha. After 2 weeks of treatment, the compound of the invention showed good crop selectivity for soybean (GLXMA) and that the effect of the compound on weeds was very effective. The reference compound known from EP-A-230 874 did not have such a selective and effective effect.

92585 38

In the following table they mean: 0 = no damage 1 = 1-24% damage 2 = 25-74% damage 5 3 = 75-89% damage 4 = 90-100% damage GLXMA = Glycine max SETVI = Setaria viridis SORHA = Sorghum halepense 10 IPOSS = Ipomoea purpurea

G S S I

L E O P

X T R O of the invention

15 according to M V H s

compound A I A S

r * YY.

20 III 0 3 3 3 ch_-c = cx I I 2

Example 3.01 25, Untreated 000 0 3 0 SÄC_J ^ 2 2 2 1 EP 0 230 874 (p.12, comp. 16) 35 (Reference compound) 92585 39

Example K

In the greenhouse, the presented plant species were treated with the indicated compounds before germination at an application rate of 0.01 kg active ingredient / ha. The compounds were then sprayed as emul-5 pigs in 500 liters of water / ha evenly on the plants. Three weeks after spraying, a strong effect of the compound of the invention on weeds was observed. The effect of the reference compound known from EP-A-230 874 was not as good.

10 In the following table mean: 0 = no damage 1 = 1-24% damage 2 = 25-74% damage 3 = 75-89% damage 15 4 = 90-100% damage ALOMY = Alopecurus myosurides AVEFA = Avena fatua ^ 2585 40

A A

L V

0 E of the invention

5 according to M F

compound Y A

ί'Ύ'ν ”λΑΑ ^ Λΐ,, cV-chch / 15 Example 3.01 Unprocessed 0 0” -pCC <. .

- 25 EP 0 230 874 (p.12, conc. 16) (Reference compound)

Example L

In the greenhouse, the 30 plant species shown were treated with the compounds shown before germination at an application rate of 0.01 kg active ingredient / ha. The compounds were then sprayed as emulsions in 500 liters of water / ha evenly on the plants. Three weeks after spraying, the compound of the invention showed good crop selectivity for wheat (TRZAX) and a very strong effect on weeds. The selectivity of the reference compound known from EP-A-255 601 was not as good.

9256S

41

In the following table they mean: 0 = no damage 1 = 1-24% damage 2 = 25-74% damage 5 3 = 75-89% damage 4 = 90-100% damage TRZAX = Triticum aestivum GALAP = Galium aparine IPOSS = Ipomoea purpurea 10 SEBEX = Sesbania exaltata

T G I S

RAPE 15 OF THE INVENTION Z L 0 B

according to A A S E

compound X P S X

2 0 o \\ / - ~ ° ^ 14 3 3/0 25

Example 2.02 Unprocessed 0000 r0YY \ o.

O N - 0 0 11

: ^ oM

EP 0 255 601 (Example 34) (Reference compound) 35

Claims (5)

1. Heterocyclic substituted azoles and azines of the general formula I (fi) L____, (i), Y is R, is a hydrogen atom, C1-6 alkyl group, C3.5 alkenyl group, C3. 5-alkynyl group, halo-C1-4 alkyl group, halo-C3-5 alkenyl group, halo-C3.5 alkynyl group or cyano-C1-3 alkyl group, Y is a hydrogen or fluorine atom, X Mr group (CR2R3) nW or (CR2) = V, wherein V or the corresponding W has directly attached to the phenyl ring, n Mr 0 or 1, 20. Mr group CR 2 or NR * or an oxygen or sulfur atom, provided that, W Mr not oxygen, where Z = and n = 1, V Mr group CR 4 or a hydrogen atom, r 2, R 3, R, and R 5 Mr is the same or different and each represents a vMte or halogen atom or a C 1-3 alkyl or halogen C 1 -C 3 alkyl group, R 1 Mr a vteatome, Z Mr a heterocyclic residue with any of the formulas Z, Z3 and Z5 - Zg 30 ° <& _ ^ CHj ^ _n ^ R7 0 (Zx) (Z3) 92585 “IN-N> TT, I 1 / yv u 2 (Z5) (Z6> VY \ jd V> · N 2 Xs O 2 (Z 7) (Z 8) Q is the group CH, provided that, W is not sulfur, where n = 0, U, is an oxygen or sulfur atom, U 2 is an oxygen atom, r7 and Rg form together with the adjacent nitrogen and carbon atoms a heterocyclic 5-7 membered ring which may be saturated or unsaturated, T is the group DE, D is the group (CRI6R17) m, E is a sulfur atom or the group CR19R20, m is 0, 25 p is 2, Ri 2 / Ri 3 f rm, R 15 / R 16 / R n, Ri alkyl group and R27 is a hydrogen atom or C1-5 alkyl group. Process for the preparation of substituted azoles and azines of general formula I according to claim 1, characterized in that A) where Z is a 3,4-dimethyl-3-pyrroline-2,5-dione-1- yl group, an aniline of the general formula II 925b5 pi V "NV V5> / NH2 IT (II) is reacted X is where R 1, X and Y represent what is defined in connection with general formula I, with 2,2'-dimethylmaleic anhydride, B) da Z is a 4,5,6,7-tetrahydro-2H -1,2,3-triazolo [3,4-a] pyridin-8-ium-3-olate-2-yl group, a compound of the general formula II is diazotized in 15% by weight (II) 2. wherein Rt, X and Y represent what is defined in connection with general formula I, with nitric acid, then reacted with piperidine-2-carboxylic acid and cyclized by a dehydrating agent, C) where Z is a 2,3,5,6,7,8-hexahydro-1H-imidazo [1,5- a] pyridin-1,3-dione-2-yl- or 2,3,5,6,7,8- hexahydro-1H-1,3,4 "triazolo [1,2-a] pyridazine-1,3-dione-2-yl group, a compound of general formula II is reacted with XI (II) 92585 where R X and Y denote that defined in connection with the general formula I, with a compound of the all-internal formula V or VI, II (II) II (II) II (II) II U1 in which formulas Q, U, and U2 represent what is defined in connection with general formulas I and R21 is a CM-alkyl group, D) dii Z is a 2,3,5,6,7,8- hexahydro-1H-imidazo [1,5-15 a] pyridin-1,3-dione-2-yl- or 2,3,5,6,7,8-hexahydro-1H-1,3,4-triazolo [ 1,2-a] pyridazine-1,3-dione-2-yl group, a compound of general formula III is reacted N = c = ui x - (iii) where R 1, U 1, X and Y denote that defined in connection with the general formula I, with a compound of the general formula VII H. "22%, (VII> U2 92585 where Q and U2 denote what is defined in connection with general formula I and R22 is a C1-4 alkyl group, E) where Z is a residue of general formula N - Where R12, R, 3, R, 4, R, 5 and T denote that defined in connection with general formula I, a compound of the general formula is reacted purple / N = S 20 'χ_ (IIIa) where R [, X and Y denote that defined in connection with the general formula I with a compound of the general formula Vili * 12 N = 1 (VIII) tj2 where R12, R13, R14, R1S and T denote that defined in connection with the general formula I and are cyclized in the presence of an oxidizing agent to a thiadiazole ring, 92565 F) where Z is a 2H-1,2,4-triazolin-3-one-2-yl residue, a compound of the general formula IV R 1 is reacted with N denotes the soin defined in connection with the general formula I, with a compound of the general formula XI 0 15 / R7 R24 ° I (XI) 0 Rg 20 where R7 and R8 denote that defined in connection with the general formula I and R 24 is a C 1-4 alkyl group, G) where Z is a 5,6,7,8-tetrahydroquinazoline-2,4- (1H, 3H) -dione-3-yl residue or 1,2,4,5,6,7 -hexahydro-2,4-dio-xo-3H-cyclopentapyrimidin-3-yl residue, a compound of the general formula XXII is cyclized to five N / c / N 30 y 11 Jl ö I (CH2) p (XXII) Y R28oocy where R 1, X and Y and p denote that defined in connection with the general formula I and R28 is a CM-alkyl-Jb group, under alkaline conditions and, if desired, 92585 is reacted, optionally in the presence of an acid-binding agent, with a compound of the general formula XXIII R27-B (XXIII) wherein R27 represents what is defined in the context of general formula I, wherein it is not hydrogen at all, and B is a halogen atom or p-toluenesulfonyloxy group. 3. An agent with herbicidal activity, characterized in that it contains ethinostone a compound according to claim 1. Use of an agent according to claim 3 for the control of monocotyledons and dicotylendones of herbaceous plants in the main agricultural crops. 15 Process for the preparation of agents with herbicidal activity, characterized in that compounds of the general formula I according to claim 1 are mixed with the carrier and / or auxiliaries.