AU765922B2

AU765922B2 - Substituted N-cyano amidines

Info

Publication number: AU765922B2
Application number: AU47553/00A
Authority: AU
Inventors: Mark Wilhelm Drewes; Dieter Feucht; Ernst-Rudolf F. Gesing; Achim Hense; Kristian Kather; Stefan Lehr; Rolf Pontzen; Hans-Jochem Riebel; Lothar Rohe; Katharina Voigt; Ingo Wetcholowsky
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1999-05-12
Filing date: 2000-05-04
Publication date: 2003-10-02
Anticipated expiration: 2020-05-04
Also published as: BR0010447A; DE19921886A1; PL351671A1; CA2373429A1; MXPA01011452A; WO2000069813A1; KR20020005008A; HK1044530A1; JP2002544255A; EP1178956A1; CN1350517A; AU4755300A

Description

WO 00/69813 PCT/EPOO/04013 -1- Substituted N-cyano-amidines The invention relates to novel substituted N-cyano-amidines, to a process for their preparation and to their use as herbicides.

It is already known that certain substituted N-cyano-guanidines have herbicidal properties (cf. DE-A-2505301, US-A-4661520, US-A-4684398, US-A-4689348, J.

Agric. Food Chem. 37 (1989), 809-814). However, various aspects of the properties of the substituted N-cyano-guanidines of the prior art do not meet the high requirements for modem crop treatment agents.

This invention now provides the novel substituted N-cyano-amidines of the general formula

R

2

R'TN'H

HC (I)

'CN

in which R' represents hydrogen or represents in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl and

R

2 represents in each case benzo-fused, pyrido-fused or thieno-fused cycloalk(en)yl, oxacycloalk(en)yl or thiacycloalk(en)yl, where all cyclic and heterocyclic groupings may be substituted.

The general formula includes the E and Z configuration isomers which are possible in each case.

In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.

Preferred substituents of the radicals listed in the formulae mentioned above and below are illustrated below.

R preferably represents hydrogen, represents optionally cyano-, halogen-,

C

1

-C

4 -alkoxy-, C 1

-C

4 -alkylthio-, C 1

-C

4 -alkylsulphinyl- or Ci-C 4 -alkylsulphonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen- or C 1

-C

4 alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-,

CI-C

4 -alkyl-, Cl-C 4 -halogenoalkyl-, C 1

-C

4 -alkoxy- or C 1

-C

4 -halogenoalkoxysubstituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl moiety.

R

2 preferably represents in each case benzo-fused, pyrido-fused or thieno-fused cycloalk(en)yl, oxacycloalk(en)yl or thiacycloalk(en)yl from the list below, O S N N 0 S N N v N. N- N -3where all cyclic and heterocyclic groupings may preferably be substituted by one of the groupings listed below: nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halogen, C 1

-C

4 -alkyl, C 1

-C

4 -halogenoalkyl, CI-C 4 -alkoxy, C 1

-C

4 -halogenoalkoxy, C 1

-C

4 -alkylthio, C 1

-C

4 -halogenoalkylthio, Cl-C 4 -alkylsulphinyl,

C

1

-C

4 -halogenoalkylsulphinyl, C 1

-C

4 -alkylsulphonyl, C 1

-C

4 -halogenoalkylsulphonyl, C 1

-C

4 -alkylamino, di-(C 1

-C

4 -alkyl)-amino, C 1

-C

4 -alkyl-carbonyl,

C

1

-C

4 -alkoxy-carbonyl, C 1

-C

4 -alkylamino-carbonyl, di-(C 1

-C

4 -alkyl)-aminocarbonyl, Cl-C 4 -alkyl-carbonyl-amino, Cl-C 4 -alkoxy-carbonyl-amino, C 1

-C

4 alkyl-amino-carbonyl-amino, C 1

-C

4 -alkyl-sulphonyl-amino.

R1 particularly preferably represents hydrogen, represents in each case optionally cyano-, fluorine, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or ipropyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or benzyl.

R2 particularly preferably represents one of the cyclic and heterocyclic groupings mentioned above, where the substituents may be selected from one of the groupings listed below: nitro, hydroxyl, amino, cyano, carbomoyl, thiocarbomoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s- or t-butyl, difluoromethyl, dichioromethyl, trifluoromethyl, trichioromethyl, chiorodifluoromethyl, fluorodichioromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chiorodifluoromethoxy, fluorodichioromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsuiphinyl, ethylsuiphinyl, trifluoromethylsuiphinyl, methylsuiphonyl, ethylsulphonyl, trifluoromethylsuiphonyl, methylamino, ethylamino, n- or ipropylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or ibutyroylamino, methoxycarbonyl amino, ethoxycarbonylamino n- or ipropoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsuiphonylamino, ethylsulphonylamino, n-or i-propylsulphonylamino.

R very particularly preferably represents hydrogen and represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsuiphonyl-, ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl.

R 2 very particularly preferably represents benzo-fused cycloalk(en)yl from the list below where all cyclic groupings may be substituted by one of the groupings listed below: [lacuna]

R

I most preferably represents hydrogen, methyl, ethyl of n- or i-propyl.

R

2 most preferably represents one of the groupings below:

NH

2 I

OH

CH

3 Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.

Particular preference according to the invention is given to the compounds of the formula which contain a combination of the meanings listed above as being particularly preferred.

Very particular preference according to the invention is given to the compounds of the formula which contain a combination of the meanings listed above as being very particularly preferred.

Most preference according to the invention is given to the compounds of the formula which contain a combination of the meanings listed above as being most preferred.

The abovementioned general or preferred radical definitions apply both to the end products of the formula and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.

-6- The novel substituted N-cyano-amidines of the general formula have interesting biological properties. In particular, they have strong herbicidal activities.

The novel substituted N-cyano-amidines of the general formula are obtained when N-cyano-imidates of the general formula (II)

R

N

in which R' is as defined above and R' represents alkyl are reacted with amino compunds of the general formula (II)

R

2 N (m) H H in which

R

2 is as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

Using, for example, ethyl N-cyano-propaneimidate and indan-2-yl-amine as starting materials, the course of the reaction in the process according to the invention can be illustrated by the formula scheme below: -7- C, H 2 'CN HC N HN'H H5C2 N H

N'CN

The formula (II) provides a general definition of the N-cyano-imidates to be used as starting materials in the process according to the invention for preparing compounds of the general formula In the general formula R' preferably has the meaning which has already been mentioned above, in connection with the description of the compounds of the general formula according to the invention, as being preferred, particularly preferred, very particularly preferred or most preferred for R' preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

The N-cyano-imidates of the general formula (II) are known and/or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 104 (1982), 235-239; loc. cit. 106 (1984), 2805-2811; J. Org. Chem. 28 (1963), 1816-1821; loc. cit. 46 (1981), 1457- 1465; Synthesis 1983, 402-404; Tetrahedron Lett. 21 (1980), 909-912).

The formula (III) provides a general definition of the amino compounds further to be used as starting materials in the process according to the invention for preparing compounds of the general formula In the general formula (Ill), R 2 preferably has that meaning which has already been mentioned above, in connection with the description of the compounds of the general formula according to the invention, as being preferred, particularly preferred, very particularly preferred or most preferred for R 2 The amino compounds of the general formula (UI) are known and/or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 88 (1966), 2233-2240; loc. cit. (1973), 4083-4084); J. Chem. Soc. C 1966, 717-722; Synthesis 1980, 695-697; Tetrahedron 24 (1968), 3681-3696; loc. cit. 50 (1994), 3627-3638).

The process according to the prevention for preparing compounds of the general formula is, if appropriate, carried out using a reaction auxiliary. Reaction auxiliaries suitable for the process according to the invention are, in general, the customary inorganic or organic bases or acidic acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, 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 or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, s- or t-butoxide or potassium methoxide, ethoxide, n- or ipropoxide, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, 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-, 3,4dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylaminopyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diazabicyclo[5,4,0]-undec-7-ene

(DBU).

In most cases, the use of one of the reaction auxiliaries mentioned above can be dispensed with.

The process according to the invention for preparing compounds of the general formula is preferably carried out using a diluent. Suitable diluents are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, 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 methyl isobutyl ketone, nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N-dimethylacetamide, N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides such as dimethylsulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0°C and 150 0 C, preferably between 10 0 C and 120 0

C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure in general between 0.1 bar and 10 bar.

For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of in each case one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, if appropriate, and the reaction mixture is generally stirred at the required temperature for a plurality of hours. Work-up is carried out by customary methods (cf. the Preparation Examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides 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 genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Linderia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.

Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

Depending on the concentration, the active compounds according to the invention are suitable for total weed control, for example on industrial terrain and railway tracks and on paths and areas with or without tree growth. Equally, the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.

-11 The compounds of the formula according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on rough-ground parts of plants. To a certain extent, they are also suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.

If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are suitable are mainly: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.

Suitable solid carriers are for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are for example crushed and -12fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are for example lignosulphite waste liquors and methylcellulose.

Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.

Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulphuron, anilofos, asulam, atrazine, azafenidin, azimsulphuron, benazolin(-ethyl), benfuresate, bensulphuron(-methyl), bentazone, benzobicyclon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromo- 13 butide, bromofenoxim, bromoxynil, butachior, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chiomethoxyfen, chioramben, chioridazon, chlorimuron(-ethyl), chiomnitrofen, chiorsuiphuron, chiorotoluron, cinidon- (-ethyl), cinmethylin, cinosuiphuron, clefoxydim, clethodim, clodinafop(-propargyl), clomnazone, clomneprop, clopyralid, clopyrasulphuron(-methyl), cloransulam(-methyl), cumnyluron, cyanazine, cybutryne, cycloate, cyclosuiphamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmediphamn, diallate, dicamba, diclofop(-methyl), diclosulamn, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachior, dimethametryn, dimethenamid, dimexyflamn, dinitramine, diphenamnid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfiuralin, ethametsulphuron(-methyl), ethofumnesate, ethoxyfen, ethoxysuiphuron, etobenzanid, fenoxaprop(-P-ethyl), fentrazamide, flamprop(-i sopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasuiphuron, florasulam, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluomneturon, fluorochioidone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulphuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-methyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomnesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop- (-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamnethapyr, imazamnox, imazapic, imazapyr, imazaquin, imazethapyr, imazosuiphuron, iodosulphuron(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachiortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachior, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulphuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosuiphuron, norfiurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasuiphuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmediphamn, piperophos, pretilachior, primisulphuron(-methyl), prometryn, propachior, propanil, propaquizafop, propisochior, propyzamnide, prosulphocarb, prosuiphuron, pyraflufen(-ethyl), pyrazolate, pyrazosulphuron(-ethyl), pyrazoxyfen, pyribenzoxim, -14pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulphuron, sethoxydim, simazine, simetryn, sulcotrione, sulphentrazone, sulphometuron(-methyl), sulphosate, sulphosulphuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulphuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulphuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulphuron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.

The active compounds according to the invention can be applied both before and after the emergence of the plants. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

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

Preparation Examples: Example 1

H

3

C.

A mixture of 0.98 g (10 mmol) of methyl N-cyano-ethaneimidate, 1.42 g (10 mmol) of 1,2,3,4-tetrahydro-l-naphthylamine and 20 ml of water is stirred at room temperature (about 20 0 C) for 12 hours. The resulting crystalline product is then isolated by filtration with suction, washed with a little water and diethyl ether and dried on a disc made of clay.

This gives 1.3 g (62% of theory) of N'-cyano-N-(1,2,3,4-tetrahydro-l-naphthyl)ethaneimideamide of melting point 113 0

C.

Analogously to Example 1, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the general formula listed in Table 1 below.

1

NC

'CN

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

CH

3

CH

3 176

CH

3

C

2

H

17

C

3

H

7 -n

C

2

H

C

3

H

7 -n (amorphous) C3H7-n

CH

7 -n(amorphous 18 Ex. No. R Melting point 16 H H 3 C 223 17 H 149

HO

(1R,2S) 18 H 156

HO-*

(1S,2R) 19 H 136

CH

3 206 21 C 2

H

5 \150 22 C 3

H

7 -n 126 19

C

2

H

C

3

H

7 -n Br:o 20

CH

3 205

CH

3

CH

3

CH

3 -21 Use Examples: Example A Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amount of active compound desired is applied per unit area. The concentration of the spray liquor is chosen such that the particular amount of active compound desired is applied in 1000 litres of water per hectare.

After three weeks, the degree of damage to the plant is rated in% damage in comparison to the development of the untreated control.

The figures denote: 0% no effect (like untreated control) 100% total destruction In this test, for example, the compound of Preparation Example 1 shows strong activity against weeds.

-22- ExampDle B Post-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants of a height of 5 15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in% damage in comparison to the development of the untreated control.

P:\WPDOCS\CABSPECI\7646530.doc-04/08/03 -23- The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Claims

1. Subtituted N-cyano-amidines of the general formula R 2 R N I% H CN in which a 15 L represents optionally cyano-, halogen-, Ci-C 4 -alkoxy-, CI-C 4 alkylthio-, C 1 -C 4 -alkylsulphinyl- or C 1 -C4-alkylsulphonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen- or C 1 -C 4 -alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-, C1-C 4 -alkyl-, C 1 -C 4 -halogenoalkyl-, Ci-C 4 alkoxy- or C1-C4-halogenoalkoxy-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, and i r~ .i r R 2 represents one of the following groupings K- ca P:\WPflOCS\CABSPECI764653.dc-4/08IO3 25 which can be unsubstituted or substituted with one or more substituents selected from the following list: nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamnoyl, formyl- amino, halogen, CI-C 4 -alkyl, Cl-C 4 -halogenoalkyl, CI-C 4 -alkoxy, C 1 C 4 -halogenoallcoxy, Cl-C 4 -alkylthio, C 1 -C 4 -halogenoallcylthio, C 1 -C 4 alkylsulphinyl, C 1 -C 4 -halogenoalkylsulphinyl, C 1 -C 4 -alkylsuiphonyl, C 1 -C 4 -halogenoalkylsulphonyl, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)- amino, C 1 -C 4 -alkyl-carbonyl, C 1 -C 4 -alkoxy-carbonyl, C 1 -C 4 -alkyl- amnino-carbonyl, di-(C 1 -C 4 -alkyl)-amnino-carbonyl, C 1 -C 4 -alkyl-carb- onyl-amino, C 1 -C 4 -alkoxy-carbonyl-amino, C 1 -C 4 -alkyl-amino-carb- onyl-amino, C 1 -C 4 -alkyl-sulphonyl-amino.

2. Compounds according to Claim 1, characterized in that *R 1 represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsuiphinyl-, n- or i- propylsulphinyl-, methyl sulphonyl-, ethylsulphonyl-, n- or i- propylsuiphonyl-substituted. methyl, ethyl, n- or i-propyl, s- or t- butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, prop enyl, butenyl, ethinyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyl- :::Imethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-sub- stitutedphenyl or benzyl, and P:\WPDOCS\CAB\SPECI\764653.do-04/08/03 -26- R2 represents one of the cyclic groupings given in Claim 1, which can be unsubstituted or substituted with one or more substituents selected from the following list: nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamoyl, formyl- amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, tri- chioromethyl, chlorodifluoromethyl, fluorodichioromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chiorodi- fluoromethoxy, fluorodichioromethoxy, methylthio, ethylthio, n- or i- propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluo- romethylthio, fluorodichloromethylthio, methylsuiphinyl, ethyl- sulphinyl, trifluoromethylsuiphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethylsuiphonyl, methylamino, ethylamino, n- or i-propyl- 15 amino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-buty- royl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylamino- carbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, eth- oxycarbonylamino, n- or i-propoxycarbonylamino, methylamino- carbonylamino, ethylaminocarbonylamino, n- or i-propylamino- carbonylamino, methylsuiphonylamino, ethylsuiphonylamino, n- or i- propylsulphonylamino.

3. Compounds according to Claim 1 or 2, characterized in that R represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, methylsuiphinyl-, ethylsuiphinyl-, methylsuiphonyl-, ethylsuiphonyl- substituted methyl, ethyl, n- or i-propyl, and P:\WPDOCS\CAB\SPECI\7646530.doc-04/08/03 -27- represents one of the following groupings I0-

4. Compounds according to any of Claims 1 to 3, characterized in that represents methyl, ethyl or n- or i-propyl. r r r r

5. Process for preparing compounds according to any of Claims 1 to 4, charac- terized in that compounds of the general formula (II) R' NCN in which R 1 is as defined in any of Claims 1 to 4 and R' represents Ci-C 4 -alkyl, are reacted with compounds of the general formula (II) P:\WPDOCS\CAB\SPECX7646530.doc-04/0803 -28- R 2 N (III) HN 'H in which R 2 is as defined in any of Claims 1 to 3, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

6. Herbicidal compositions, characterized in that they comprise at least one compound according to any of Claims 1 to 4 and customary extenders.

7. Use of at least one compound of the formula (I) 2. N 'CN 15 in which R represents hydrogen, represents optionally cyano-, halogen-, C 1 -C 4 alkoxy-, C 1 -C 4 -alkylthio-, Cl-C 4 -alkylsulphinyl- or Ci-C 4 -alkyl- sulphonyl-substituted alkyl having 1 to 6 carbon atoms, represents in 20 each case optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen- or C 1 -C 4 -alkyl-substituted cycloalkyl or cycloalkyl- alkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, or represents in each case optionally nitro-, cyano-, halogen-, CI-C 4 -alkyl-, Ci-C 4 halogenoalkyl-, CI-C 4 -alkoxy- or Cl-C 4 -halogenoalkoxy-substituted P:\WPDOCS\CAB\SPECI\7646530.do-4/8/03 29 aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, and R2 represents one of the following groupings C K K 0o K a a. a C*, C which can be unsubstituted or substituted with one or more of the sub stituents of the following list: nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamnoyl, formylamino, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, CI -C 4 -alkoxy, C 1 -C 4 -halogeno- alkoxy, C 1 -C 4 -alkylthio, Cl-C 4 -halogenoalkylthio, C 1 -C 4 -alkylsulphinyl, C 1 -C 4 -halogenoalkylsulphinyl, Cl-C 4 alkylsulphonyl, C 1 -C 4 -halogeno- alkylsuiphonyl, C 1 -C 4 -alkylamino, di-(CI -C 4 -alkyl)-amino, CI -C 4 -alkyl- carbonyl, C 1 -C 4 -alkoxy-carbonyl, Ci -C 4 -alkylamino-carbonyl, di- (C 1 -C 4 -alkyl)-amino-carbonyl, C 1 -C 4 -alkyl-carbonyl-amino, C 1 -C 4 -alkoxy- PA\WPDOCS\CAB\SPEC\764653.d-(O4/O8/3 carbonyl-amino, Ci -C 4 -alkyl-amnino-carbonyl-amino, C 1 -C 4 -alkyl-sulphonyl- amino, for controlling undesirable plants.

8. Substituted N-cyano-amidines of the general formula according to claim 1, compositions containing same and uses thereof substantially as herein described with references to the Examples. DATED this 4t day of August 2003. BAYER AKTIENGESELLSCHAFTr By Its Patent Attorneys DAVIES COLLISON CAVE