KR20010041233A - Optically active substituted 2,4-diamino-1,3,5-triazines as herbicides - Google Patents

Abstract

The present invention relates to optically active novel substituted 2,4-diamino-1,3,5-triazines of the formula (I), to methods for their preparation and their use as novel intermediates and herbicides:

[Formula I]

In the above formula,

Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group and possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C _4- Alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -halogeno alkyl sulfinyl, C ₁ -C ₄ - alkylsulfonyl, C ₁ -C ₄ - halogenoalkyl alkylsulfonyl, C ₁ -C ₄ - alkylamino and C ₁ -C ₄ - is selected from the group consisting of alkoxycarbonyl ,

R ¹ represents alkyl having 1 to 4 carbon atoms,

R ² represents optionally hydroxyl-, cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted alkyl having 1 to 4 carbon atoms,

R ³ represents optionally cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted alkyl having 2 to 4 carbon atoms,

Herein, the substituents on the carbon atom bonded to R ¹ are arranged in R form.

Description

Optically active substituted 2,4-diamino-1,3,5-triazines as herbicides}

Substituted 2,4-diamino-triazines have already been described in the patents (see US 3 816 419, US 3 932 167, EP 273 328, EP 411 153 / WO 90/09378, WO 97/00254, WO 97/08156). Is well known in the art. However, these compounds have not gained any particular importance to date.

The present invention relates to optically active novel substituted 2,4-diamino-1,3,5-triazines, methods for their preparation and their use as novel intermediates and herbicides.

Accordingly, the present invention provides optically active novel substituted 2,4-diamino-1,3,5-triazines of the formula:

[Formula I]

In the above formula,

Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group and possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C _4- Alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -halogeno alkyl sulfinyl, C ₁ -C ₄ - alkylsulfonyl, C ₁ -C ₄ - halogenoalkyl alkylsulfonyl, C ₁ -C ₄ - alkylamino and C ₁ -C ₄ - is selected from the group consisting of alkoxycarbonyl ,

R ¹ represents alkyl having 1 to 4 carbon atoms,

R ² represents alkyl having 1 to 4 carbon atoms, optionally substituted with hydroxyl-, cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted,

R ³ represents alkyl having 2 to 4 carbon atoms, optionally cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted,

Herein, the substituents on the carbon atom bonded to R ¹ are arranged in R form.

The optically active novel substituted 2,4-diamino-1,3,5-triazines of formula (I) are represented by the following optically active substituted 2,4-diamino-1,3,5- Triazines are obtained by reacting an acylating agent of formula III in the presence of a reaction aid if appropriate and in the presence of a diluent if appropriate:

[Formula II]

[Formula III]

In the above formula,

Ar, R ¹ , R ² and R ³ are as defined above,

X represents halogen or group -O-CO-R ³ .

The optically active novel substituted 2,4-diamino-1,3,5-triazines of formula (I) have strong and selective herbicidal activity.

In the definition, hydrocarbon chains, such as alkyl, are each straight or branched and include combinations with heteroatoms such as alkoxy or alkylthio.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

The present invention preferably provides compounds of formula (I):

Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group, possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, halogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- Or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, Ethylsulfonyl, trifluoromethyl Sulfonyl, dimethylamino, diethylamino, methoxycarbonyl and a is selected from ethoxycarbonyl,

R ¹ represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl,

Each R ² is optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted meti, ethyl, n- or i-propyl, n-, i- or s- Butyl,

Each R ³ optionally represents cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl ,

Substituents at the carbon atom to which R ¹ is bonded are arranged in R form.

The invention particularly relates to compounds of the formula (I)

Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group, possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy , Trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoro Methylsulfonyl, dimethylamino, diethylamino, methoxycarbonyl and ethoxycarbonyl,

R ¹ represents methyl, ethyl, n- or i-propyl,

Each R ² optionally represents hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,

Each R ³ optionally represents cyano-, fluorine-, chlorine- or methoxy-substituted ethyl, n- or i-propyl,

Substituents at the carbon atom to which R ¹ is bonded are arranged in R form.

The general or preferred radical definitions mentioned above apply to both the final product of the formula (I) and correspondingly the starting materials or intermediates required for their preparation, respectively. These radical definitions may be combined with one another if necessary, ie they include combinations within the preferred ranges provided.

An example of the compound of formula I according to the present invention is given in the following group.

Group 1

Where R ² has the meaning given for example:

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-hydroxy-ethyl, cyanomethyl, 1-cyano-ethyl, 2-cyano-ethyl, 1 -Cyano-1-methyl-ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromomethyl, chlorodifluoromethyl, fluorodichloromethyl , Bromodifluoromethyl, trichloromethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-chloro-1-fluoro-ethyl, 1- Fluoro-propyl, 2-fluoro-propyl, 3-fluoro-propyl, 1-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl , 1-fluoro-1-methyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-1-ethyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-2- Methyl-propyl, 1-chloro-2-methyl-propyl, 1-chloro-propyl, 2-chloro-propyl, 3-cle Loro-propyl, 1-chloro-1-methyl-ethyl, 2-chloro-1-methyl-ethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 1,1-dichloro- Ethyl, 2,2,2-trifluoro-ethyl, 1,2,2,2-tetrafluoro-ethyl, perfluoroethyl, 1,1-difluoro-propyl, 1,1-dichloro-propyl , Perfluoropropyl, 1-fluoro-butyl, 1-chloro-butyl, methoxymethyl, 1,1-dimethoxy-methyl, 1-methoxy-ethyl, 2-methoxy-ethyl, 1,1- Dimethoxy-ethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxy-ethyl, 2-methoxy-1-methyl-ethyl, 2-methoxy-1-ethyl-ethyl, 2-ethoxy-1 -Methyl-ethyl or 2-ethoxy-1-ethyl-ethyl.

Group 2

Here, R ² has the meaning given above in eg group 1.

Group 3

Here, R ² has the meaning given above in eg group 1.

Group 4

Here, R ² has the meaning given above in eg group 1.

Group 5

Here, R ² has the meaning given above in eg group 1.

Group 6

Here, R ² has the meaning given above in eg group 1.

Group 7

Here, R ² has the meaning given above in eg group 1.

Group 8

Here, R ² has the meaning given above in eg group 1.

Group 9

Here, R ² has the meaning given above in eg group 1.

Group 10

Here, R ² has the meaning given above in eg group 1.

Group 11

Here, R ² has the meaning given above in eg group 1.

Group 12

Here, R ² has the meaning given above in eg group 1.

Group 13

Here, R ² has the meaning given above in eg group 1.

Group 14

Here, R ² has the meaning given above in eg group 1.

Group 15

Here, R ² has the meaning given above in eg group 1.

Group 16

Here, R ² has the meaning given above in eg group 1.

Group 17

Here, R ² has the meaning given above in eg group 1.

Group 18

Here, R ² has the meaning given above in eg group 1.

Group 19

Here, R ² has the meaning given above in eg group 1.

Group 20

Here, R ² has the meaning given above in eg group 1.

Group 21

Here, R ² has the meaning given above in eg group 1.

Group 22

Here, R ² has the meaning given above in eg group 1.

Group 23

Here, R ² has the meaning given above in eg group 1.

Group 24

Here, R ² has the meaning given above in eg group 1.

Group 25

Here, R ² has the meaning given above in eg group 1.

Group 26

Here, R ² has the meaning given above in eg group 1.

Group 27

Here, R ² has the meaning given above in eg group 1.

Group 28

Here, R ² has the meaning given above in eg group 1.

Group 29

Here, R ² has the meaning given above in eg group 1.

Group 30

Here, R ² has the meaning given above in eg group 1.

Group 31

Here, R ² has the meaning given above in eg group 1.

Group 32

Here, R ² has the meaning given above in eg group 1.

Group 33

Here, R ² has the meaning given above in eg group 1.

Group 34

Here, R ² has the meaning given above in eg group 1.

Group 35

Here, R ² has the meaning given above in eg group 1.

Group 36

Here, R ² has the meaning given above in eg group 1.

Group 37

Here, R ² has the meaning given above in eg group 1.

Group 38

Here, R ² has the meaning given above in eg group 1.

Group 39

Here, R ² has the meaning given above in eg group 1.

Group 40

Here, R ² has the meaning given above in eg group 1.

Group 41

Here, R ² has the meaning given above in eg group 1.

Group 42

Here, R ² has the meaning given above in eg group 1.

Group 43

Here, R ² has the meaning given above in eg group 1.

Group 44

Here, R ² has the meaning given above in eg group 1.

Group 45

Here, R ² has the meaning given above in eg group 1.

Group 46

Here, R ² has the meaning given above in eg group 1.

Group 47

Here, R ² has the meaning given above in eg group 1.

Group 48

Here, R ² has the meaning given above in eg group 1.

Group 49

Here, R ² has the meaning given above in eg group 1.

Group 50

Here, R ² has the meaning given above in eg group 1.

Group 51

Here, R ² has the meaning given above in eg group 1.

Group 52

Here, R ² has the meaning given above in eg group 1.

Group 53

Here, R ² has the meaning given above in eg group 1.

Group 54

Here, R ² has the meaning given above in eg group 1.

Group 55

Here, R ² has the meaning given above in eg group 1.

Group 56

Here, R ² has the meaning given above in eg group 1.

Group 57

Here, R ² has the meaning given above in eg group 1.

Group 58

Here, R ² has the meaning given above in eg group 1.

Group 59

Here, R ² has the meaning given above in eg group 1.

Group 60

Here, R ² has the meaning given above in eg group 1.

Group 61

Here, R ² has the meaning given above in eg group 1.

Group 62

Here, R ² has the meaning given above in eg group 1.

Group 63

Here, R ² has the meaning given above in eg group 1.

Group 64

Here, R ² has the meaning given above in eg group 1.

Group 65

Here, R ² has the meaning given above in eg group 1.

Group 66

Here, R ² has the meaning given above in eg group 1.

Group 67

Here, R ² has the meaning given above in eg group 1.

Group 68

Here, R ² has the meaning given above in eg group 1.

Group 69

Here, R ² has the meaning given above in eg group 1.

Group 70

Here, R ² has the meaning given above in eg group 1.

Group 71

Here, R ² has the meaning given above in eg group 1.

Group 72

Here, R ² has the meaning given above in eg group 1.

Group 73

Here, R ² has the meaning given above in eg group 1.

Group 74

Here, R ² has the meaning given above in eg group 1.

Group 75

Here, R ² has the meaning given above in eg group 1.

Group 76

Here, R ² has the meaning given above in eg group 1.

Group 77

Here, R ² has the meaning given above in eg group 1.

Group 78

Here, R ² has the meaning given above in eg group 1.

Group 79

Here, R ² has the meaning given above in eg group 1.

Group 80

Here, R ² has the meaning given above in eg group 1.

For example, (R) -2-amino-4- (1-methyl-3-phenyl-propylamino) -6- (1-fluoroethyl) -1,3,5-triazine and propy as starting materials Using O'Neill Chloride, the reaction pathway and process according to the invention can be illustrated by the following scheme:

Formula II provides a general definition of optically active substituted 2,4-diamino-1,3,5-triazines to be used as starting materials in the process according to the invention for preparing compounds of formula I. In formula (II), Ar, R ¹ and R ² are already mentioned above as preferred or particularly preferred for Ar, R ¹ and R ² , preferably in particular or in connection with the description of the compounds of formula (I) according to the invention. Has a meaning.

No starting material of formula (II) has ever been disclosed in the literature; As new materials, they form part of the subject matter of the original patent application (see DE 19641693 / LeA 31975; DE 19641964 / LeA 31994).

Optically active substituted 2,4-diamino-1,3,5-triazines of formula (II)

(a) an optically active substituted biguanide of formula (IV) and / or an acid adduct of a compound of formula (IV), such as the corresponding hydrochloride, if appropriate in the presence of a reaction aid, for example sodium methoxide And, if appropriate, by reaction with an alkoxycarbonyl compound of formula V in the presence of a diluent, for example methanol, at a temperature of 0 ° C. to 100 ° C. (see DE 19641693 / LeA 31975; DE 19641694 / LeA 31994; see also WO 97/08156; Preparation):

[Formula IV]

[Formula V]

R ² -CO-OR

In the above formula,

Ar, R ¹ , and R ² are as defined above,

R represents alkyl.

The optically active substituted biguanides of formula IV required as precursors have not been disclosed in the literature so far; As novel materials, they form part of the subject of previous patent applications (see DE 19641693 / LeA 31975; DE 19641694 / LeA 31994).

Optically active substituted biguanides of formula IV are optically active substituted alkylamino compounds of formula VI and / or acid adducts of compounds of formula VI, such as, for example, hydrochloride, if appropriate, reaction aids, eg Obtained by reaction with cyanoguanidine of the formula (VII), for example in the presence of hydrogen chloride and, where appropriate, in the presence of a diluent, for example n-decane or 1,2-dichloro-benzene (see EP 492 615, Preparation):

[Formula VI]

[Formula VII]

In the above formula,

Ar and R ¹ are as defined above.

Optically active substituted alkylamino compounds of the formula VI required as precursors for this purpose are known and / or known per se (see DE 3 462 919; DE 4 000 610; DE 4 332 738, EP 320 898; EP 443 606; Tetrahedron; Asymmetry 5 (1994), 817-820; Tetrahedron Lett. 29 (1988), 223-224; loc. Cit. 36 (1995), 3917-3920).

Formula III provides a general definition of acylating agents which will be further used as starting materials in the process according to the invention for preparing compounds of formula I. In formula (III), R ³ preferably has the meanings already mentioned above as preferred or especially preferred for R ³ in relation to the description of the compounds of formula (I) according to the invention; X preferably represents fluorine, chlorine, bromine, acetyloxy, propionyloxy, n- or i-butyroyloxy, in particular chlorine, acetyloxy or propionyloxy.

Starting materials of formula III are organic chemicals known for synthesis.

If appropriate, the process according to the invention for preparing compounds of formula I is carried out using reaction reaction aids. Suitable reaction aids are generally customary inorganic or organic bases or acid acceptors. They are preferably alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, Sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride, or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide Roxoxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i- Propoxide, n-, i-, s- or t-butoxide; Basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine , N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3 , 4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2.2.2 ] -Octane (DABCO), 1.5-diazabicyclo [4.3.0] -non-5-ene (DBN), or 1,8-diazabicyclo [5.4.0] -undec-7-ene (DBU) Include.

Suitable diluents for carrying out the process according to the invention are especially inert organic solvents. These are in particular aliphatic, cycloaliphatic or aromatic, optionally halogenated hydrocarbons such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; Ketones such as acetone, butanone or ethyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene Alcohols such as glycol monoethyl ether, water or pure water and mixtures thereof.

When carrying out the process according to the invention, the reaction temperature can vary relatively broadly. In general, this process is carried out at temperatures of 0 ° C to 200 ° C, preferably 10 ° C to 150 ° C.

The process according to the invention is generally carried out under atmospheric pressure. However, the process according to the invention can be carried out under elevated or reduced pressures-generally from 0.1 bar to 10 bar.

To carry out the process according to the invention, the starting materials are generally used in approximately equal molar amounts. However, either of the components may be used in a relatively excess amount. In general, the reaction is carried out in a suitable solvent, if appropriate, in the presence of the reaction aid, and the reaction mixture is stirred at the desired temperature, usually for several hours. Work-up is performed by a conventional method (reference preparation example).

The active compounds according to the invention can be used as defoliants, desiccants, stem-killers and in particular weed-killers. In the broadest sense, weeds should be understood as all plants that grow in undesirable positions. Whether the material according to the invention acts as a comprehensive or selective herbicide depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledonous weeds of the following genus: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Ke Nopodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala ), Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledonous crops of the following genus: Gossypium, Glycine, Beta, Doucus, Phaseolus, Pisum, Solanum, Linum ), Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis ) And Cucurbita.

Monocot weeds in the following genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festusca, Festuca, Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sino Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Iscamum ), Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocot crops of the following genus: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum Panicum), Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is not limited at all in the above, but also extends to other plants in the same way.

The compounds of the invention are suitable for the total control of weeds, depending on concentration, for example on industrial areas and railway lines, and on walkways and plazas with or without trees. Similarly, the compounds of the present invention include, for example, plantation, ornamental water, orchard, vineyard, citrus field, nut orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, palm plantation, cocoa plantation, soft fruit plantation and hop field, grass And to control weeds in perennial crops growing on racetrack grass and pasture, and to selectively control weeds in annual crops.

The active compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops by both pre- and post-germination methods.

The active compounds are usually used as solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and microcapsules in polymeric materials. It can be converted into the formulation of.

These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

When water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent. Liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example mineral oil fractions, mineral oils and vegetable oils. Alcohols such as aliphatic hydrocarbons, butanol or glycol and ethers and esters thereof, as well as strong polar solvents such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethylformamide and dimethyl sulfoxide, are suitable Do.

Solid carriers are suitable, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and silicates. . Solid carriers for granulation include, for example, crushed and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husks, corncobs and tobacco stems. Granules of material are suitable. Emulsifiers and / or foam-forming agents include, for example, nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, aryls Sulfonates and proteolytic products are suitable. Suitable dispersants are, for example, lignin-sulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose, gum arabic, natural and synthetic polymers in the form of powders, granules or emulsions, such as polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids Can be used for As other additives, mineral oil and vegetable oil may be used.

Inorganic nutrients such as iron oxide, titanium oxide and prussian blue, and dyes such as alizarin dyes, azo dyes and organic dyes such as metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Can be used.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% of the active compound.

In controlling weeds, the active compounds according to the invention, either by themselves or in the form of preparations, can be used as mixtures with known herbicides, as a finished preparation or as a possible tank mixture.

Possible components for the mixture include known herbicides such as acetochlor, acifluorfen (-sodium), acloniphene, alachlor, alkoxydim (-sodium), amethrin, amidochlor, amidosulfuron, Anilophos, Asulam, Atrazine, Azaphenidine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazone, Benzophene, Benzoylprop (-ethyl), Bialaphos, Biff Knox, Bispyribac (-sodium), Bromobutide, Bromophenoxime, Bromocinyl, Butaclor, Butoxydimdim, Butyrate, Carpenstrol, Carloxidim, Carvetamide, Carpentrazone (-ethyl ), Chlomethoxyphene, Chlorambene, Chloridazone, Chlorimuron (-ethyl), Chlornitrophene, Chlorsulphron, Chlortoluron, Cinmethyllin, Cinosulfuron, Cletodim, Clodinafof (- Propargyl), clomazone, clomeprop, clopyralide, clopyrasulfuron (-methyl), chlorane Ram (-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cyanoxydim, sihalofop (-butyl), 2,4-D, 2,4-DB, 2,4- DP, desmedipharm, diallate, dicamba, diclofo (-butyl), diclosulam, dietatyl (-ethyl), dipfencuart, diflufenican, diflufenzopyr, dimefuron, dimepipe Latex, dimethaclor, dimethamethrin, dimethenamid, dimexlam, dinitramine, diphenamide, diquat, dithiopyr, diuron, dimron, epoprodan, EPTC, esprocarb, ethal Fluralin, etamethsulfuron (-methyl), etofumesate, ethoxyphene, ethoxysulfuron, etobenzanide, phenoxaprop (-ethyl), flamprop (-isopropyl), flamprop ( -Isopropyl-L), flamprop (-methyl), plazasulfuron, fluazifop (-butyl), flumetsulam, pullumiclolac (-pentyl), flumioxazine, flumipropine, flu Metsullam, Flu Meturon, fluorochloridone, fluoroglycopene (-ethyl), flupoxam, flupropacyl, flupyrsulfuron (-methyl, -sodium), flurenol (-butyl), flulidone, fluoroxypyr (-Mephthyl), fluprimidol, flutarmone, fluthiacet (-methyl), flutiamide, pomesafen, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafene , Halooxyphosph (-ethoxyethyl), halooxyphosph (p-methyl), hexazinone, imazamethabenz (-methyl), imazamethafil, imazamox, imazaphyr, imazaquin, imazeta Pyr, imazasulfuron, isocinyl, isoprophalin, isoproturon, isourone, isoxaben, isoxaplutol, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet , Metamitrone, metazachlor, metabenzthiazuron, methopenzuron, methopromurolone, (alpha-) metolachlor, methosullam, methoxuron, metribuzin, Tsulfuron (-methyl), molinate, monolinuron, naproanilide, naproproamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzaline, oxadiargyl, oxadione, ox Private furon, oxaziclomethone, oxyfluorophene, paraquat, pellagonate, pendimethalin, pentoxazone, phenmedipham, piperophosph, pretilachlor, primisulfuron (-methyl), promethrin, Propachlor, propanyl, propaquizapop, propisolchlor, propizamide, propsulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazolate, pyrazosulfuron (-ethyl), pyra Yoxifen, pyribenzoxime, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac (-sodium), quinclolac, quinmerak, quinoclammine, quizolopop (-P- Ethyl), quizolopop (-P-tefuryl), rimsulfuron, cetoxydim, simazine, cymetrin, sulcotrione, sulfentrazone, sulfomethuron (-meth Til), sulfosate, sulfosulfuron, tebutam, tebutiuurone, tebutylrazine, terbutrin, tenylchlor, thiafluamide, thiazopyr, thiadiazimine, thifensulfuron (-methyl), thioben Carb, thiocarbazyl, tralcoxidim, trialate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trituralurine and triflusulfuron.

Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil structure improvers are also possible.

The active compounds can be used on their own, in the form of preparations or by further dilution, in the form of use, for example in the form of ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The active compounds are used in conventional manner, for example by spraying, spraying, atomizing or scattering.

The active compounds according to the invention can be applied before or after germination of plants. They can be incorporated into the soil before seeding.

The amount of active compound used may vary within a substantial range. This is essentially dependent on the nature of the desired effect. Generally used amounts are from 1 g to 10 kg, preferably from 5 g to 5 kg of active compound per hectare of soil surface.

The formulations and uses of the active compounds according to the invention can be seen from the examples below.

<Production example>

Example 1

3.4 g (11 mmol) of (R) -2-amino-4- (1-methyl-3-phenyl-propylamino) -6- (1-fluoro-1-methyl-ethyl) -1,3,5 A mixture of triazine and 10 g (77 mmol) propionic anhydride is stirred at 120 ° C. for 2 hours. After cooling to room temperature (approx. 20 ° C.), the mixture is diluted with 200 ml of water and stirred at room temperature for 15 hours. The aqueous phase is decanted and the residue is taken up in methylene chloride, washed with water, dried over sodium sulphate and filtered. In the filtrate, the solvent is carefully distilled off under a water pump vacuum.

This resulted in 3.0 g (75% of theory) of (R) -2-propionylamino-4- (1-methyl-3-phenyl-propylamino) -6- (1-fluoro-1- as an amorphous residue. Methyl-ethyl) -1,3,5-triazine. [a] ²⁰ _D = -5.0 °.

Similarly to Preparation Example 1 and according to the general description of the preparation process according to the invention, for example, the compounds of formula (I) set forth in Table 1 can be prepared.

[Formula I]

TABLE 1

Examples for Compounds of Formula (I)

Starting material of formula II:

<Example II-1>

A mixture of 18 g (66 mmol) of (R) -1- (1-methyl-3-phenyl-propyl) -biguanide hydrochloride, 3.6 g (66 mmol) of sodium methoxide and 50 ml of methanol was cooled to room temperature. Stir at (approximately 20 ° C.) for 30 min and then mix with 8.2 g (61 mmol) of ethyl 2-fluoro-isobutyrate. The reaction mixture is then stirred for 18 hours at room temperature, diluted about three times in its initial volume with methylene chloride, washed with water, dried over sodium sulfate and filtered. In the filtrate, the solvent is carefully distilled off under a water pump vacuum.

This resulted in 6.5 g (34% of theory) of (R) -2-amino-4- (1-methyl-3-phenyl-propyl-amino) -6- (1-fluoro-1-methyl) as an amorphous residue. -Ethyl) -1,3,5-triazine.

Starting material of formula IV:

<Example IV-1>

A mixture of 17.9 g (96 mmol) of (R) -1-methyl-3-phenyl-propylamine hydrochloride and 8.1 g (96 mmol) of cyanoguanidine is heated at 160 ° C. (internal temperature) for 3 hours. The resulting melt is then diluted with approximately 100 ml of 1,2-dichloro-benzene at the temperatures mentioned above, cooled to room temperature and diluted with approximately the same amount of diethyl ether. The obtained crystal product is separated by suction filtration.

This gives 18.0 g (70% of theory) of (R) -1- (1-methyl-3-phenyl-propyl) -biguanide hydrochloride.

Example usage:

<Example A>

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

One part by weight of the active compound is mixed with a specified amount of solvent, a specified amount of emulsifier is added, and the concentrate is then diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

The seeds of the test plant are sown in ordinary soil. After about 24 hours, water is added to the soil with the preparation of the active compound. It is useful to keep the amount of water per unit area constant. The concentration of active compound in the formulation is not critical, only the rate of application of the active compound per unit area.

After 3 weeks, the degree of damage to the plants is graded in percent of damage compared to the occurrence of untreated controls.

The definition of a number is as follows:

0% = no effect (same as untreated control)

100% = total kill

In this test, for example, the compound of Preparation Example 1 exhibits strong activity against weeds and is well tolerated by crop plants such as sunflowers.

TABLE A-1

Germination Test / Greenhouse

TABLE A-2

Germination Test / Greenhouse

<Example B>

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation of the active compound is prepared by mixing 1 part by weight of the active compound with the specified amount of solvent, adding the specified amount of emulsifier and then diluting the concentrate with water to the desired concentration.

Formulations of active compounds are sprayed so that a specific amount of the desired active compound is applied per unit area to test plants 5-15 cm tall. The concentration of the spray liquid is selected so that a specific amount of the desired active compound is applied at 1000 l / ha of water.

After three weeks, the degree of damage to the plants is graded in% damage compared to the occurrence of untreated controls.

The definition of a number is as follows:

0% = no effect (same as untreated control)

100% = total kill

In this test, for example, the compound of Preparation Example 1 exhibits strong activity against weeds.

TABLE B

After germination test / greenhouse

Claims (9)

Optically active substituted 2,4-diamino-1,3,5-triazines of [Formula I] In the above formula, Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group, possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -Alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -halo halogeno-alkyl sulfinyl, C ₁ -C ₄ - alkylsulfonyl, C ₁ -C ₄ - halogenoalkyl alkylsulfonyl, C ₁ -C ₄ - alkylamino and C ₁ -C ₄ - selected from the group consisting of alkoxycarbonyl , R ¹ represents alkyl having 1 to 4 carbon atoms, R ² represents alkyl having 1 to 4 carbon atoms, optionally substituted with hydroxyl-, cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted, R ³ represents alkyl having 2 to 4 carbon atoms, optionally cyano-, halogen- or C ₁ -C ₄ -alkoxy-substituted, Wherein the substituent on the carbon atom to which R ¹ is bonded is arranged in R form. The method of claim 1, Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group, possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, halogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- Or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, Ethylsulfonyl, trifluoromethyl Sulfonyl, is selected from dimethylamino, diethylamino, methoxycarbonyl and ethoxycarbonyl group consisting of a, R ¹ represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, Each R ² is optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s- Butyl, Each R ³ optionally represents cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Wherein the substituents at the carbon atom to which R ¹ is bonded are arranged in R form. The method of claim 1, Ar represents optionally substituted aryl, wherein aryl is carbocyclic or heterocyclic, monocyclic in the group consisting of phenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, benzofuryl, thienyl and benzothienyl Or a bicyclic, aromatic group, possible substituents are cyano, nitro, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy , Trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoro Is selected from the group consisting of methylsulfonyl, dimethylamino, diethylamino, methoxycarbonyl and ethoxycarbonyl, R ¹ represents methyl, ethyl, n- or i-propyl, Each R ² optionally represents hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, Each R ³ optionally represents cyano-, fluorine-, chlorine- or methoxy-substituted ethyl, n- or i-propyl, Wherein the substituents at the carbon atom to which R ¹ is bonded are arranged in R form. A compound according to claim 1, wherein (R) -2-propionylamino-4- (1-methyl-3-phenyl-propylamino) -6- (1-fluoro-1-methyl-ethyl)- Compounds that are 1,3,5-triazines: [Formula 1] And then reacting the optically active substituted 2,4-diamino-1,3,5-triazine of Formula II with the acylating agent of Formula III in the presence of a reaction aid if appropriate and in the presence of a diluent if appropriate To prepare a compound of formula (I) according to claim 1 [Formula II] [Formula III] In the above formula, Ar, R ¹ , R ² and R ³ are as defined in claim 1, X represents halogen or group -O-CO-R ³ . Herbicide composition characterized in that it contains at least one compound of formula (I) according to claim 1. Use of a compound of formula I according to claim 1 for controlling unwanted plants. A method of controlling weeds, characterized in that the compound of formula (I) according to claim 1 is acted on a weed or its habitat. A process for preparing a herbicide composition, characterized in that the compound of formula (I) according to claim 1 is mixed with an extender and / or a surfactant.