The present invention relates to novel N-phenylimino heterocycles with herbicidal activity, processes for their preparation, compositions which comprise these compounds, and their use for controlling weeds, especially in growing crops or for inhibiting plant growth.

Iminothiazolines with a herbicidal action are described, for example, in EP-A-0 529 482, EP-A-0 446 802 and US-A-5 244 863.

Novel N-phenylimino heterocyclic compounds with herbicidal and growth-inhibiting properties have now been found.

The present invention thus relates to compounds of the formula I

in which

^R 3

-A- is a group — CH=C-N- (A.), I ³ (Aa) or

— CH=C-0-

F

I (A3) where the bonding of -A- to the nitrogen atom takes place via

— CH— C=N-NR—

the carbon atom;

R ₃ is CrC ₄ alkyl, it being possible for this radical to be substituted by halogen, cyano, d-

C ₄ alkoxy, benzyloxy, hydroxyl, C ₁ -C ₄ alkylthio, Cι-C ₄ alkylamino or di-d-C ₄ alkylamino, or is

C ₃ -C _β cycloalkyl, aryl or substituted aryl;

R ₅ and R ₆ are, independently of one another, hydrogen or CrC ₄ alkyl;

R _T is halogen, C ₁ -C ₄ alkyl, Cι-C ₄ haloalkyl, C C ₄ alkoxy, d-C haloalkoxy, CrC ₄ alkylthio, d-dhaloalkylthio, cyano or nitro;

R ₂ is hydrogen, halogen, Cι-C ₄ alkyl or Cι-C ₄ haloalkyl; or

R ₂ in position 2 of the phenyl ring and Ri together form a -OCF ₂ O- group;

R ₄ is Ci-Cβalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or C ₃ -C _β cycloalkyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, Cι-C ₃ alkyl, d-C ₃ alkoxy,

C C ₃ alkylthio, C ₃ -C _e cycloalkyl, C ₃ -C _e cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or

R ₄ is CrC ₇ alkylaminosulfonyl, di-d-CTalkylaminosulfonyl, Cι-C ₇ alkylsulfonyl or

C C ₇ alkylsul.inyl, it being possible for these alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl and alkylsulfinyl radicals to be substituted by halogen, C C ₃ alkoxy, d-daikylthio, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or

R ₄ is cyano, arylsulfonyl, sulfamoyl or a -C(X)R ₇ or -C(X)NHR group;

X is oxygen or sulfur;

R ₇ is Cι-C _β alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, d-C ₆ alkoxy, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

CrCβalkylthio, C ₂ -C ₆ alkenylthio, C ₃ -C _β alkynylthio or di-d-C ₆ alkylamino, it being possible for these alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio and dialkylamino radicals to be substituted by halogen, d-C ₃ alkyl, d-C ₃ alkoxy, d-C ₃ haloalkoxy, CrC ₆ alkylcarbonyl, Cι-C ₆ alkylcarbonyloxy, C C ₃ alkoxycarbonyl,

Cι-C ₃ alkylthio, C ₃ -C _e cycloalkyl, C ₃ -C ₆ cycloalkoxy, hydroxyl, cyano, aryl, aryloxy, benzyloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or

R ₇ is hydrogen, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, hetaryl, a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or a saturated heterocyclyloxy radical which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, and

R ₉ is hydrogen, CrC ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, d-C ₃ alkyl, d-C ₃ alkoxy, d-C ₃ alkylthio, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkoxy, hydroxyl, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or is C ₃ -C ₆ cycloalkyl or aryl, and agronomically suitable salts of compounds of the formula I.

These alkyl groups occurring in the definitions of substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl, hβxyl and heptyl radicals. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl are preferred.

Halogen means iodine and preferably fluorine, chlorine and bromine.

Alkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and one of the various isomeric pentoxy and hexyloxy radicals; preferably methoxy, ethoxy and propoxy.

Alkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino and the isomeric butylamino radicals.

Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylarnino, dibutylamino and diisopropylamino. Alkylamino radicals with a chain length of from 1 to 6 carbon atoms are preferred.

The cycioalkyl radicals preferably have 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The cycloalkyl radicals may, unless otherwise indicated, be substituted by halogen, Cι-C ₃ alkyl, d-C ₃ alkoxy or Cι-C ₃ alkylthio.

Aryl in the definition of the radicals R ₃ , FU, R and R ₉ is α- or β-naphthyl and, in particular, phenyl, it being possible for these aromatic rings to carry one or more, identical or different substituents, for example halogen, nitro, cyano, d-C alkoxy, d-C ₄ haloalkoxy, d-dalkylthio, d-dhaloalkylthio, Cι-C ₄ alkyl and d-C haloalkyl. Corresponding statements also apply to aryloxy and arylsulfonyl in the definition of R , R ₇ and R ₉ .

Heteroaryl in the definition of R ₇ means, in particular, five- or six-membered aromatic heterocyclic rings, for example 2-, 3- or 4-pyridyl, pyrimidyl, pyrazolyl, pyrazinyl, pyridazinyl, imidazolyl, triazolyl, pyrrolyl, furyl, thienyl, oxazolyl, thiazolyl or isoxazolyl; preferably 2- and 3-pyridyl, 2- and 3-furyl and 2-thienyl. These heterocycles can in turn be substituted; examples of substituents are d-C ₃ alkyl, halogen, d-C ₃ haloalkyl, cyano, nitro, hydroxyl, d- C ₃ alkoxy, Cι-C ₃ haloalkoxy, amino, Cι-C ₃ alkylamino, di-d-C ₃ alkylamino or carboxyl.

Saturated heterocyclic rings mean ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen or sulfur atom. Ring systems of these types preferably contain 3 to 6 ring atoms, for example oxiranyl, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, tetrahydropyranyl, dioxanyl, 1 ,3- dioxanyl, piperidinyl, morpholinyl, thiomorpholinyl or piperazinyl. In the case of nitrogen atom as hetero atom, the bonding to the ring system can take place both via the ring carbon atom and via the ring nitrogen atom.

These saturated heterocycles can in turn be substituted; examples of substituents are Cι-C ₃ alkyl.

Suitable as haloalkyl are alkyl groups substituted one or more times, in particular once to three times by halogen, where halogen means specifically iodine and, in particular, fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, fluorochloromethyl, 2-fluoroethyl, 2,2,2- trifluoroethyl, 1 ,1 ,2,2,2-pentafluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyi and 2-chloro-2- propyl.

Haloalkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 1 ,1 ,2,2,2-pentafiuoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Haloalkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms. Haloalkylthio is, for example, trifluoromethylthio or 2,2,2-trifluoroethylthio.

The alkenyl and alkynyl groups can be straight-chain or branched, and this also applies to the alkenyl and alkynyl moiety in alkenylthio, alkynylthio, alkenylamino and alkynylamino groups.

Alkenyl means, for example, vinyl, 1 -methylvinyl, allyl, methallyl or 2-butenyl. Alkenyl radicals with a chain length of from 2 to 6 carbon atoms are preferred. The alkenyl radicals are preferably linked via a saturated carbon atom to a hetero atom.

Examples of alkynyl which may be mentioned are propargyl, 2-butynyl, 2-methyl-3-butyn-2- yl, 3-butyn-2-yl and 4-pentynyl. Alkynyl radicals with a chain length of from 3 to 6 carbon atoms are preferred. The alkynyl radicals are preferably linked via a saturated carbon atom to a hetero atom.

Alkenylthio means, for example, allylthio, methallylthio, 3-butenylthio, 4-pentenylthio or 2-hexenylthio.

Alkynylthio means, for example, propargylthio, 1-methylpropargylthio, 3-butynylthio, 4-pentynylthio or 2-hexynylthio.

Alkenylamino is, for example, allylamino, methallylamino and 2-butenylamino.

Alkynylamino is, for example, propargylamino, 1 -methylpropargylamino and 4-pentynylamino.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfony, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and one of the isomeric pentyl-, hexyl- and heptylsulfonyl radicals; preferably methylsulfonyl and ethylsulfonyl.

Corresponding meanings can also be assigned to the substituents in composite definitions, for example alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, cycloalkoxy, cycloalkylamino, cycloalkylthio, (di-)alkylaminosulfonyl, alkylsulfinyl, alkenyloxy, alkynyloxy, benzyloxy and heterocyclyloxy.

The invention likewise embraces the salts which the compounds of the formula I are able to form with acids. Acids suitable for forming the acid addition salts are both organic and inorganic acids. Examples of such acids are, inter alia, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, various phosphorus acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid.

The compounds of the formula I contain an aliphatic C=N-R ₄ double bond, and thus geometric isomerism (syn/anti) may occur. Geometric isomerism (Z E) may likewise occur if an aliphatic C=C double bond is present. The present invention also embraces these isomers.

Preferred compounds of the formula I are those in which R, is halogen, d-C ₄ haloalkyl, cyano, nitro, d-C ₄ haloalkoxy or d-C ₄ haloalkylthio; and R ₇ has the same meaning as indicated under formula I with the exception of C ₇ and C ₈ alkyl.

Preferred compounds of the formula I are those in which Ri is trifluoromethyl or trifluoromethoxy.

Likewise preferred compounds of the formula I are those in which R is hydrogen.

Likewise among the preferred compounds of the formula I are those in which R ₃ is methyl, ethyl or cyclopropyl.

Further preferred compounds of the formula I are those in which R ₄ is a -C(X)R ₇ group; X is oxygen; and R ₇ is C C ₆ alkyl, d-C ₆ alkoxy or d-C _β alkylamino, it being possible for these radicals to be substituted by halogen, d-C ₃ alkyl, Cι-C ₃ alkoxy, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkoxy. Of these, particularly preferred compounds are those in which R ₇ is d-C ₆ alkyl, d-C ₆ haloalkyl or d-C ₆ -alkoxy.

Important compounds of the formula I are those in which -A- is a group

R ₃ has the meaning stated under formula I; and R _ε is hydrogen or methyl. Particularly important among these are those in which R ₅ is hydrogen.

Likewise important compounds of the formula I are those in which -A- is a group ft (As); R ₃ is methyl or ethyl; R ₂ is hydrogen or halogen; R ₆ is

— CH— C = N-NR—

hydrogen; Ri is trifluoromethyl or trifluoromethoxy; R ₄ is a -C(X)R ₇ group; X is oxygen; and R ₇ is Cι-C ₃ haloalkyl or d-C ₄ alkoxy.

Further important compounds are those in which -A- is a group

(A ₂ ); R ₃ is methyl or ethyl; Ri is trifluoromethyl or trifluoromethoxy; R ₂ is hydrogen; R ₄ is a -C(X)R ₇ group; X is oxygen; and R ₇ is d-C ₄ alkoxy.

A group of preferred compounds of the formula I is that in which -A- is a group

^R 3

| (A ₂ ); R ₃ is d-C ₄ alkyl, cyclopropyl, phenyl or benzyloxymethyl; Ri is

— CH=C-0- fiuorine, C or C ₂ alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio or cyano; R ₂ is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R ₂ in position 2 of the phenyl ring and R, together form a -OCF ₂ O- group; R ₄ is cyano, methyl, methyl • HI salt, propargyl, cyclopentyl, benzyl, methylsulfonyl, dimethylaminosulfonyl,

trifluoromethylsulfonyl, 2-chlorophenylsulfonyl or 2-chloro-2-propylsulfinyl; or R ₄ is a -C(X)R ₇ group; X is oxygen or sulfur; R ₇ is hydrogen, Cι-C ₃ alkyl, cyanomethyl, methoxymethyl, methoxyethyl, methylthiomethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, phenoxymethyl, d-C ₄ alkoxy, methoxyethoxy, vinyloxy, allyloxy, propargyloxy, d- C3alky.tl.i0, dimethylamino, difluoromethyl, trifluoromethyl, pentafluoroethyl, chloromethoxy, 2,2,2-trichloroethoxy, C ₃ -C ₆ cycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2,6- difluorophenyl, 2-furyl, phenoxy, benzyloxy, N-morpholino, N-piperidino or N-pyrrolidino; or R ₄ is a -C(X)NHR ₉ group; X is oxygen or sulfur; and R ₉ is d- or C ₂ alkyl, cyanomethyl or phenyl.

Another group of preferred compounds of the formula I is that in which -A- is a group ft (A3); R ₃ is Cι-C ₄ alkyl, hydroxymethyl, chloromethyl,

— CH— C=N-NR ₆ —

dimethylaminomethyl, cyclopropyl, phenyl or benzyloxymethyl; R ₆ is hydrogen or methyl; R _t is fluorine, Cι- or C ₂ alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoromethylthio; R ₂ is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R ₂ in position 2 of the phenyl ring and Ri together form a -OCF ₂ O- group; R ₄ is methyl, propargyl, cyclopentyl, benzyl, cyano, methylsulfonyl, isopropylsulfonyl, trifluoromethylsulfonyl, 2- chloro-2-propylsulfinyl, phenylsulfonyl or 2-chlorophenylsulfonyl; or R ₄ is a -C(X)R ₇ group; X is oxygen or sulfur; R ₇ is hydrogen, Cι-C ₄ alkyl, cyanomethyl, hydroxymethyl, methoxymethyl, methoxyethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, methylthiomethyl, benzyloxymethyl, phenoxymethyl, cyclopropyl, cyclopentyl, dimethylaminomethyl, d-C ₄ alkoxy, methoxyethoxy, vinyloxy, 1 -methylvinyloxy, allyloxy, propargyloxy, C C ₃ alkylthio, dimethylamino, cyanomethyl-methylamino, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, fluorochloro methyl, pentafluoroethyl, 2-chloroethoxy, 2,2,2-trichloroethoxy, C ₃ -C _β cycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2-furyl, phenyl, 2,6-difluorophenyl, 2,6- difluorobenzyl, phenoxy, benzyloxy, 3-oxetanyloxy, N-morpholino, N-piperidino or N- pyrrolidino; or R ₇ is a -C(X)NHR _β group; X is oxygen or sulfur; and R ₉ is hydrogen, C C ₃ alkyl, cyanomethyl, cyclopropyl, phenyl or 2-, 3- or 4-chlorophenyl.

Another group of preferred compounds of the formula I is that in which -A- is a group

^R ₃ I — CH=C-N— (A!); R ₃ is C or C ₂ alkyl, cyclopropyl or phenyl; R ₅ is hydrogen, methyl or

^R 5 cyclopropyl; R ₅ is hydrogen, methyl or cyclopropyl; Ri is cyano, trifluoromethyl, pentafluoroethyl, trifluoromethoxy or trifluoromethylthio; R ₂ is hydrogen; or R ₂ in position 2 of the phenyl ring and R together form a -OCF ₂ O- group; R ₄ is cyano or a -C(X)R ₇ group; X is oxygen; and R ₇ is methyl, difluoromethyl, trifluoromethyl, d-C ₃ alkoxy or pentafluoroethyl.

The process according to the invention for preparing the compounds of the formula I comprises alkylating a compound of the formula II

in which Ri and R ₂ have the meanings stated under formula I, with a compound of the formula X

(X),

L CH-C-R ₃

in which R ₃ has the meanings stated under formula I, and L, is a leaving group, for example halogen, preferably chlorine, bromine or iodine, alkylsulfonyl or arylsulfonyl, preferably

CH ₃ SO ₂ O- or in the presence of a base and of a solvent to give a compound of the formula

cyclizing the latter in the presence of a base to give the compound of the formula IV

subsequently reacting the latter

1) to prepare compounds of the formula I in which R ₄ is d-C ₆ alkyl, C ₃ -C _e alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Cι-C ₇ alkylaminosulfonyl, di-C -C ₇ alkylaminosulfonyl, C C ₇ alkylsulfonyl or d-dalkylsulfinyl, it being possible for these radicals to be substituted as stated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa

L ₂ -R ₄ (XIa),

in which R has the stated meaning, L ₂ is a leaving group, for example halogen, preferably

chlorine, bromine or iodine, hydroxyl, R ₄ OSO ₂ O-, CH ₃ SO ₂ O- or _> or

2) to prepare compounds of the formula I in which R ₄ is a -C(X)R ₇ group; and R ₇ and X have the meanings stated under formula I, with a compound of the formula Xlb

X

II (Xlb),

R ₇ -C-L ₄

in which R ₇ and X have the stated meaning, and U is a leaving group, for example halogen, preferably fluorine, chlorine or bromine, imidazolide, triazolide, N-hydroxyphthalimide or R ₇ C(X)O-, or

3) to prepare compounds of the formula I in which R is a -C(X)NHR ₉ group; and R ₉ , with the exception of hydrogen, and X have the meaning stated under formula I, with a compound of the formula Xlc

R ₉ -N=C=X (Xlc),

in which R ₉ and X have the stated meaning, to give a compound of the formula la

in which R _{1 t} R ₂ , R ₃ and R ₄ have the stated meaning, and the latter subsequently either a) being converted with a compound of the formula XII

R ₆ -NH-NH ₂ (XII),

in which R ₆ has the meaning stated under formula I, into the compound of the formula Ic

or b) being rearranged with a compound of the formula XIII

R ₅ -NH ₂ (XIII),

in which R ₅ has the meaning stated under formula I, to give the compound of the formula V

and the latter subsequently being converted with elimination of water into the compound of the formula lb

Another process according to the invention for preparing compounds of the formula I in

^R 3 which -A- is a group „, . ' . , „,_ (A3) and R ₃ and R _e are defined as under

— Cπ^-C— N ^— NF.g — formula I, comprises c) cyclizing a compound of the formula

in which R _1t R ₂ and R ₃ have the meaning stated under formula I, with hydrazine to give the compound of the formula VI

obtaining, by ring expansion, the compound of the formula VII

and subsequently reacting the latter

1) to prepare compounds of the formula I in which R ₄ is d-C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Cι-C ₇ alkylaminosulfonyl, di-d-C ₇ alkylaminosulfonyl, Cι-C ₇ alkylsulfonyl or d-C ₇ alkylsulfinyl, it being possible for all of these radicals to be substituted as indicated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa

L ₂ -R ₄ (XIa),

in which R has the stated meaning, and L ₂ is a leaving group, for example halogen, preferably chlorine, bromine or iodine, hydroxyl, R OSO ₂ O-, CH ₃ SO ₂ O- or

2) to prepare compounds of the formula I in which R is a -C(X)R ₇ group; and R ₇ and X have the meaning stated under formula I, with a compound of the formula Xlb

(Xlb),

R ₇ -C-L ₄

in which R ₇ and X have the stated meaning, and is a leaving group, for example halogen, preferably fluorine, chlorine or bromine, or imidazolide, triazolide, N-hydroxyphthalimide or R ₇ C(X)O-, or

3) to prepare compounds of the formula I in which R ₄ is a -C(X)NHR ₉ group; and R ₉ , with the exception of hydrogen, and X have the meaning stated under formula I, with a compound of the formula Xlc

R ₉ -N=C=X (Xlc),

in which R ₉ and X have the stated meaning, to give the compound of the formula I, or d) reacting a compound of the formula IV

in which Ri, R ₂ and R ₃ have the meaning stated under formula I, with the compound of the formula XIV

in which L ₃ is a leaving group, for example halogen, preferably chlorine or bromine, and R _β

is — CHf-( ) or -C(CH ₃ ) ₃ to give a compound of the formula VIII

in which Ri, R ₂ , R ₃ and R ₈ have the stated meaning, and subsequently converting with the compound of the formula XII

R ₆ -NH-NH ₂ (XII),

in which R ₆ has the meaning stated under formula I, into the compound of the formula IX

reductively cleaving the latter in the presence of a catalyst to the compound of the formula VII

and subsequently converting with a compound of the formula XIa, Xlb or Xlc, as described above under c), into the compound of the formula I.

The processes according to the invention for preparing compounds of the formulae I and la, lb and Ic are explained in detail in the following reaction schemes 1 , 2 and 3.

Reaction scheme 1 :

or -C(X)NHR ₉ )

Reaction scheme 2: Route c):

VI

-C(X)NHR ₉ )

VII lc(R ₆ = H)

Route d):

R ₇ or -C(X)NHR _Θ )

Ic

The starting compounds of the formula II are known. They are prepared in analogy to known processes as described, for example, in DE-A-3 538 128.

The α-halo ketones of the formula X can be bought or can be prepared in analogy to known processes as described, for example, in Organic Synthesis, Vol. 55, page 24 (1973).

The α-alkyl- and α-arylsulfonyl ketones of the formula X (Li = alkylSO ₂ O- and arylSO ₂ O-) can be obtained, for example, in analogy to Chem. Ber. 119, 524 (1986) and Houben-Weyl, "Methoden der Organischen Chemie", Volume IX, page 388 et seq.

As shown in reaction scheme 1 , the α-cyanamido ketones of the formula III are expediently prepared by alkylation of the arylcyanamides of the formula II with α-halo ketones, α-alkylsulfonyl ketones or α-arylsulfonyl ketones of the formula X in the presence of a base in an organic solvent at temperatures of 0-200'C, preferably at 0-60°C. The alkylation is as a rule complete within 1-30 hours depending on the solvent used and the reaction temperature.

It is possible to use as base inorganic and organic bases , for example, hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium or calcium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine, N,N-diethylaniline and pyridine. It is moreover advantageous to add the base used in a ratio of amounts of 1 -100 equivalents based on the starting compound of the formula II. Suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitro compounds, for example nitroethane or nitrobenzene, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N- dimethylformamide or sulfur oxide compounds, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination.

Reactions of this type are generally known from the literature and described with diverse variations in respect of the leaving group Li, for example in in Houben-Weyl, "Methoden der Organischen Chemie", Volume XI/1 , pages 96 and 97.

Cyclization of the compound of the formula II to the 3H-oxazol-2-ylideneamines of the formula IV is expediently carried out in the presence of a base in a suitable organic solvent at temperatures of 0-100°C and is generally complete after a few minutes up to 10 hours. Suitable as base are inorganic and organic bases, for example hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, amidine bases, for example 1 ,8-diazabicyclo[5.4.0]uπdec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN), alkyl- or arylamines for example triethylamine or N,N-diethylaniline, and pyridine. Examples of suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N-dimethylformamide or sulfur oxides, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination.

The substituent R is introduced on the imino nitrogen atom of compounds of the formula IV expediently by standard methods via 1) alkylation or sulfonylation, 2) (thio)acylation (formylation), (thio)carboxylation or (thio)amidation, or 3) by reaction with iso(thio)cyanates using appropriate reagents of the formula XIa (for example alkyl halides, hydroxyalkanes, dialkyl sulfates or alkylsulfonyl chlorides), Xlb (for example chloroformic esters, carbonyl halides, anhydrides or carboxylic acids) or Xlc (for example iso(thio)cyanates) in an organic solvent in the presence or absence of a base.

For example, N-(thio)acrylations, N-(thio)carboxylations and N-(thio)amidations can be carried out in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 138 et seq., ibid. Volume VIII, page 154 et seq., Volume IX, page 833 et seq., Volume IX, page 885 et seq., Volume XI, pages 69-72 and Volume XI/2, page 3 et seq., and N-sulfonylations in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume IX, page 398 et seq. and page 609 et seq.

In the case of compounds of the formula Xlb as carboxylic acids, the acylation reaction is advantageously carried out in the presence of 1-10 equivalents of a carboxylic acid activating reagent, for example carbodiimide, for example N,N'-dicyclohexy!carbodiimide (DCC) or 1 ,1 '-carbonyldiimidazole (lm ₂ CO).

The alkylation, acylation, carboxylation, amidation and sulfonylation reactions with reagents XIa and Xlb are generally carried out in an organic solvent, in the presence or absence of a base, at temperatures of 0-100°C. The reactions are as a rule complete within 1/2-30 hours depending on the solvent used and base used.

Bases which can be used are both inorganic and organic bases, for example hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide, sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine or N,N-diethylaniline, and pyridine, 4-N,N-dimethylaminopyridine (DMAP) and DBU. The base is preferably used in a ratio of amounts of 1-100 equivalents relative to the compound of the formula IV employed.

Examples of suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N-dimethylformamide or sulfur oxide compounds, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination with one another.

The addition reactions with the reagent Xlc can expediently be carried out by allowing the compound of the formula IV and the iso(thio)cyanate of the formula Xlc to react together in an inert aprotic organic solvent such as an aliphatic or cyclic ether, for example diethyl ether, 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane, a chlorinated aliphatic hydrocarbon, for example methylene chloride, an aromatic compound, for example toluene or xylenes, an aliphatic ester, for example ethyl acetate, or a nitrile, for example acetonitrile,

in the presence of a catalyst, for example 4-N,N-dimethylaminopyridine or triethylamine, preferably at temperatures from 0°C to the reflux temperature of the reaction solution. The addition reaction is as a rule complete after a few minutes up to 15 hours. Addition reactions of this type are known and are described with diverse variations in respect of X and R ₉ , for example in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 154 et seq. and ibid., Volume IX, page 885 et seq.

The ring expansion reaction by route a) in reaction scheme 1 to give the 4,5-dihydro-2H- [1 ,2,4]triazin-3-ylideneamines of the formula Ic takes place starting from the 3H-oxazol-2- ylideneamines of the formula la, expediently with hydrazines of the formula XII in an organic solvent at temperatures of 0-150°C. The ring expansion reaction is as a rule complete after 1 -100 hours.

Examples of solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitrites, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamin, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.

The ring rearrangement reaction by route b) in reaction scheme 1 to give the imidazolidin-2- ylideneamines of the formula V takes place starting from 3H-oxazol-2-ylideneamine derivatives of the formula la expediently with ammonia (R ₅ = hydrogen) or primary amines of the formula XIII in an organic solvent at temperatures of 0-100°C. The ring rearrangement reaction is as a rule complete after 1-30 hours. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N- diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.

The subsequent dehydration of the compounds of the formula V takes place, for example, thermally in the presence of catalytic amounts of acid, for example p-toluenesulfonic acid, or in the presence or equimolar amounts of anhydrides, for example acetic anhydride or trifluoroacetic anhydride, or by reaction with alkyl- or arylsulfonyl halides, for example methylsulfonyl chloride, in the presence or absence of bases, for example triethylamine. The dehydration reaction advantageously takes place in an organic solvent at temperatures of 0-200°C and is as a rule complete after 1/2-30 hours. It is also possible where appropriate to employ the anhydride as solvent. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.

Reaction scheme 2 depicts two processes according to the invention for preparing

compounds of the formula I in which -A- is a group _ _u ft ' . , _κιn (A ₃ ).

— CH^C — N~NR —

The process by route c) starts from α-cyanamido ketones of the formula III which can expediently be cyclized with the aid of hydrazine hydrate in a solvent at temperatures of 0-100°C to the 3-amino-2-imino-4-imidazolidinol derivatives of the formula VI within 1/2-10 hours. Examples of solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine,

triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.

In route c), the compound of the formula Vi is subsequently subjected to a ring expansion which affords the 4,5-dihydro-2H-[1 ,2,4]triazin-3-ylidenamines of the formula VII. The ring expansion reaction expediently takes place thermally in an organic solvent. The reaction can take place in a time of 1/2-30 hours at temperatures of 0-200°C, depending on the solvent used. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine or amides, for example dimethyiformamide. These solvents can be used alone or in combination.

Conversion of the compounds of the formula VII into the 4,5-dihydro-2H-[1 ,2,4]triazin-3- ylideneamines of the formula Ic takes places in analogy to the description under reaction scheme 1 via 1) alkylation or sulfonylation, 2) (thio)acylation (formylation), (thio)carboxylation or (thio)amidation or 3) reaction with iso(thio)cyanates using the appropriate reagents of the formulae XIa, Xlb or Xlc depending on the required substituents R in the compounds of the formula Ic.

The process in route d) in reaction scheme 2 starts from compounds of the formula IV. The imino group is then expediently converted with chloroformic ester of the formula XIV in the presence of a base in an inert organic solvent into the corresponding 3H-oxazol-2- ylidenecarbamic esters of the formula VIII. The reaction is advantageously carried out at 0-200°C and is as a rule complete after 1 -100 hours.

Suitable bases are both inorganic and organic bases, for example carbonates and bicarbonates, for example sodium or potassium carbonate or sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium tert-butoxide, or tertiary bases, for example pyridine, triethylamine or

N,N-diethylaniline. The bases can advantageously be employed in a ratio of amounts of 1-100 equivalents based on the starting compound of the formula IV. Examples of suitable solvents are aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.

The ring expansion of the resulting compounds of the formula VIII with hydrazines of the formula XII in an organic solvent at temperatures of 0-150°C is carried out in analogy to the description under reaction scheme 1 , route a), and affords the 4,5-dihydro-2H-[1 ,2,4]triazin- 3-ylidenecarbamic esters of the formula IX.

The subsequent elimination of the carboxylate group in the compound of the formula IX is expediently carried out by reduction (hydrogenolysis) in analogy to known processes, for example with 5 % palladium on carbon as catalyst in an inert organic solvent at temperatures of 0-100°C. Elimination of the carboxylate group is as a rule complete after 1 -30 hours. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N- dimethylformamide. These solvents can be used alone or in combination.

Conversion of the compounds of the formula VII into the compounds of the formula Ic takes place in analogy to the description under route c).

Reaction scheme 3:

Id I (R ₄ = -C(X)NH ₂ )

As shown in reaction scheme 3, compounds of the formula I in which R ₄ is a -C(X)NHR ₉ group; X has the meaning stated under formula I; and R ₉ is hydrogen, are expediently prepared via aminolysis of the appropriate aryloxy carbamic ester derivatives of the formula Id, for example using ammonia dissolved in ethanol. This variant of the preparation is illustrated by Example H18.

Compounds of the formulae XIa, Xlb and Xlc can either be bought or be prepared in analogy to known processes as described, for example, in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 120 et seq. and page 463 et seq., and ibid., Volume IX, page 867 et seq.

Compounds of the formulae XII and XIII can be bought.

Compounds of the formula XIV are known or can be prepared in analogy to known processes as described, for example, in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 101 et seq.

The final products of the formula I can be isolated in a conventional way by concentration and/or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are not very soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography or flash column chromatography with a suitable eluent.

The preferences applying to the intermediates of the formulae II, III, IV, V, VI and VII are the same as for the compounds of the formula I.

Where no specific synthesis for isolating pure isomers is carried out, the product may result as a mixture of two or more isomers. The isomers can be fractionated by methods known per se.

Applications which are suitable for the use according to the invention of the compounds of the formula I or compositions containing them are all those customary in agriculture, for example preemergence application, postemergence application and seed dressing, and various methods and techniques, for example controlled release of active ingredient. For this purpose, the active ingredient in solution is adsorbed onto granular mineral carriers or polymerized granules (urea/formaldehyde) and dried. It is possible where appropriate additionally to apply a coating (coated granules) which permits dosed release of the active ingredient over a defined period.

The compounds of the formula I can be employed in unchanged form, i.e. as they result in the synthesis, but are preferably processed in a conventional way with the auxiliaries employed in formulation technology, for example to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powder, soluble powders, dusts, granules or microcapsules. The application methods such as spraying, atomizing, dusting, wetting, scattering or pouring are, just like the type of compositions, chosen appropriate for the intended aims and the given conditions.

The formulations, i.e. the compositions comprising the active ingredient of the formula I or at least one active ingredient of the formula I and, as a rule, one or more soiid or liquid formulation auxiliaries, are produced in a known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. It is furthermore possible additionally to use surface-active compounds (surfactants) for producing the formulations.

Suitable solvents may be: aromatic hydrocarbons, preferably C ₈ to d ₂ fractions, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or

dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethylformamide, and vegetable oils which may be epoxidized, such as epoxidized coconut oil or soya oil; or water.

The solid carriers used as a rule, for example for dusts and dispersible powders, are natural rock powders such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly disperse silica or highly disperse absorbent polymers to improve the physical properties of the formulation. Suitable particulate, adsorptive granule carriers are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and nonsorptive carrier materials are, for example, calcite or sand. It is also possible to use a large number of pregranulated materials of an inorganic or organic nature such as, in particular, dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of the active ingredient of the formula I to be formulated, nonionic, cationic and/or anionic surfactants and surfactant mixtures with good emulsifiying, dispersing and wetting properties.

Suitable anionic surfactants may be both so-called water-soluble salts and water-soluble synthetic surface-active compounds.

Soaps which may be mentioned are the alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids ( o-da), for example the Na or K salts of oleic acid or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. Mention should also be made of the fatty acid methyltaurine salts.

However, so-called synthetic surfactants will be used more often, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfona.es.

The fatty alcohol sulfonates or sulfates are, as a rule, in the form of alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts and have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the Na or Ca salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These also include the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and one fatty acid residue having 8-22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolamine salts of dodecyl benzenesulfonic acid, of dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.

Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids.

Suitable nonionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaiiphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide onto polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The said compounds normally contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Also suitable are fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, in particular, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and have as further

substituents lower, uπhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants which are customary in formulation technology and can also be used in the compositions according to the invention are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations comprise as a rule 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of herbicide, 1 to 99.9 % by weight, in particular 5 to 99.8 % by weight, of a solid or liquid formulation aid and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.

Whereas more concentrated compositions are preferred as commercial products, the final user as a rule employs dilute compositions.

The compositions may also comprise other additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.

Preferred formulations have, in particular, the following compositions: (% = per cent by weight)

Emulsifiable concentrates:

Active ingredient: 1 to 90 %, preferably 5 to 50 %

Surface-active agent: 5 to 30 %, preferably 10 to 20 %

Solvent: 15 to 94 % , preferably 70 to 85 %

Dusts:

Active ingredient: 0.1 to 50 %, preferably 0.1 to 1 %

Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates: Active ingredient: 5 to 75 %, preferably 10 to 50 % Water: 94 to 24 %, preferably 88 to 30 % Surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders: Active ingredient: 0.5 to 90 %, preferably 1 to 80 % Surface-active agent: 0.5 to 20 %, preferably 1 to 15 % Solid carrier material: 5 to 95 %, preferably 15 to 90 %

Granules: Active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % Solid carrier: 99.5 bis 70 %, vorzugsweise 97 bis 85 %

The active ingredients of the formula I are, as a rule, successfully employed on the plant or its habitat with application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dose necessary for the required effect can be found by tests. It depends on the mode of action, the stage of development of the crop plant and of the weed, and on the application (site, time, method) and may vary within wide ranges determined by these parameters.

The compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties which mean that they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, vegetables, plantations, for example fruit and citrus plantations, oilseed rape, maize, sorghum, rice and fodder crops, and for nonselective weed control.

Crops are also to be understood to mean those which have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods. The weeds to be controlled may be both mono- and dicotyledonous weeds, for

example stellaria, nasturtium, agrostis, digitaria, avena, setaria, sinapis, lolium, solanum, phaseoius, echinochloa, scirpus, monochoria, sagittaria, bromus, alopecurus, sorghum halepense, rottboellia, cyperus, abutilon, sida, xanthium, amaranthus, chenopodium, ipomoea, chrysanthemum, galium, viola and veronica.

The following examples illustrate the invention further without restricting it.

Preparation examples;

Example H1 : (2-QxobutvD (3-trifluoromethylphenyl)cvanamide

37.8 g of potassium carbonate are introduced into a solution of 52 g (0.275 mol) of 3-trifluoromethylphenylcyanamide in 300 ml of N.N-dimethylformamide (DMF) at 10°C. After 10 minutes, 41 .4 g (0.275 mol) of 1 -bromo-2-butanone are added dropwise at 10-15 ^C C. After the reaction mixture has been stirred at 25°C for 2 hours, it is poured into ice-water and stirred thoroughly, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 67.6 g (96 % of theory). Melting point 81-83 °C.

Analysis: Cι ₂ HnF ₃ N ₂ O (256.23)

Calculated [%] : C: 56.25 H: 4.33 N: 10.93 F: 22.24

Found [%] : C: 55.8 H: 4.2 N: 11.1 F: 22.8

Example H2: (2-Oxobutyl) (3-trifluorophenylmethyl)cvanamide

6.9 g of potassium carbonate are introduced into a solution of 9.3 g (0.05 mol) of 3-trifluoromethylphenylcyanamide in 75 ml of DMF at 5°C. After 10 minutes, 8.3 g (0.05 mol) of 2-oxobutyl methanesulfonate are introduced in portions at 10-15 ^C C. After the reaction mixture has been stirred at 25°C for 2.5 hours, it is poured into ice-water and thoroughly stirred, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 10.3 g (80 % of theory). Melting point 78-82 °C.

Example H3: (2-Oxopropyl) (3-trifluoromethylphenyl)cvanamide

69 g of potassium carbonate are introduced into a solution of 93 g (0.5 mol) of 3-trifluoromethylphenyl cyanamide in 625 ml of DMF at 5°C. After a few minutes, 42 ml (0.5 mol) of chloroacetone are added dropwise at 10-15°C, and the mixture is stirred at 25°C for 2 hours. The reaction mixture is then poured into 3 I of ice-water and thoroughly stirred, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 99.2 g (82 % of theory). Melting point 93-95 °C.

Analysis: CnH ₉ F ₃ N ₂ O (242.20)

Calculated [%] : C: 54.55 H: 3.75 N: 11.57 F: 23.53

Found [%] : C: 54.3 H: 3.6 N: 11.6 F: 23.9

The compounds listed in following Table 1 can be prepared in analogy to the Preparation Examples H1 to H3.

Table 1 : Compounds of the formula HI

Example H4: 5-Cvclopropyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-yliden amine

10 drops of 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are added dropwise to a solution of 5.36 g (0.02 mol) of (2-cyclopropyl-2-oxoethyl) (3-trifluoromethylphenyi)cyanamide in 50 ml of tetrahydrofuran at 25°C. After half an hour, the mixture is evaporated, the oily residue is taken up in diethyl ether, and the ethereal solution is washed thoroughly with water, dried and evaporated. The required product is obtained as an oil in a yield of 5.1 g (95 % of theory).

Analysis: Cι ₃ HnF ₃ N ₂ O (268)

Calculated [%] : C: 58.20 H: 4.10 N: 10.44 F: 21.26

Found f%l : C: 58.2 H: 4.2 N: 10.2 F: 21.2

Example Hδ: 5-Ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine

1 ml of DBU is added dropwise to a solution of 60.3 g (0.235 mol) of (2-oxo-butyl) (3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) in 250 ml of tetrahydrofuran at 25°C. After 1 hour, the mixture is evaporated, the oily residue is taken up in diethyl ether, and the ethereal solution is washed thoroughly with water, dried and evaporated. The required product is obtained as an oil in a yield of 61.7 g (95 % of theory). Addition of a little diethyl ether at low temperature is followed by crystallization of the compound. Melting point 50-52°C.

Analysis: C ₁₂ HnF ₃ N ₂ O (256.23)

Calculated [%] : C: 56.25 H: 4.33 N: 10.93 F: 22.24

Found [%] : C: 56.3 H: 4.3 N: 11.0 F: 22.3

The compounds listed in following Table 2 can be prepared in analogy to Preparation Examples H4 and H5.

Table 2: Compounds of the formula IV

Example H6: 3-Amino-4-ethyl-2-imino-1 -(3-trifluoromethylphenyl)-4-imidazolidinol

12.8 ml (0.263 mol) of hydrazine hydrate are added dropwise to a solution of 67.5 g (0.263 mol) of (2-oxobutyl) (3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) in 675 ml of acetonitrile while cooling with an ice/salt mixture at 0-5°C. The resulting suspension is stirred while cooling in ice-water for 1 hour, and then the precipitated solid is filtered off, washed with acetonitrile and diethyl ether and dried under high vacuum. Yield of required product 66 g (87 % of theory). Melting point > 135°C (decomposition)

Analysis: C ₁₂ Hι ₅ F ₃ N ₄ O (288.27)

Calculated [%] : C: 50.00 H: 5.24 N: 19.44 F: 19.77

Found [%] : C: 50.1 H: 5.2 N: 19.5 F: 19.8

The compounds listed in following Table 3 can be prepared in analogy to Preparation Example H6.

Table 3: Compounds of the formula VI

Example H7: 6-Methyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.41t riazin-3- ylidenamine

36.3 g (0.93 mol) of benzyl [6-methyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H- [1 ,2,4]triazin-3-ylidene]carbamate is hydrogenated using 5 g of 5% palladium on carbon as catalyst in 720 ml of tetrahydrofuran at 25°C under atmospheric pressure. After the hydrogenation has ceased, the reaction solution is filtered off from the catalyst and evaporated to half the volume, and the resulting solution is treated with active carbon. It is again filtered and evaporated completely. The resulting residue is stirred with cold diethyl ether, filtered off and dried under high vacuum. The required product is obtained in a yield of 22.4 g (94% of theory) with melting point 145-148°C.

Analysis: CnHnF ₃ N ₄ (256.23)

Calculated [%] : C: 51.56 H: 4.33 N: 21.87 F: 22.24

Found [%]: C: 51.4 H: 4.3 N: 21.8 F: 22.2

Example H8: 6-Ethyl-4-(3-trifluoromethylphenyl)-4.5-dihydro-2H-f1.2.41tr iazin-3-ylidenamine

71.3 g (0.248 mol) of 3-amino-4-ethyl-2-imino-1-(3-trifluoromethylphenyl)-4-imidaz oiidinol (Example H6) are suspended in 500 ml of ethanol and heated to the reflux temperature and kept there for half an hour. The clear solution is then evaporated, and 500 ml of diethyl

ether are added to the oily residue while cooling. The precipitated crystalline product is filtered off, washed with hexane and dried under high vacuum. The required product is obtained in a yield of 52 g (78% of theory) with melting point 124-126°C.

Analysis: Cι ₂ Hι ₃ F ₃ N ₄ (270.26)

Calculated [%] : C: 53.33 H: 4.85 N: 20.73 F: 21.09

Found [%] : C: 53.2 H: 4.9 N: 20.5 R 21.1

The compounds listed in following Table 4 can be prepared in analogy to Preparation Examples H7 and H8.

Table 4: Compounds of the formula VII

Example H9: Ethyl f5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelca rbamate

10.5 g (0.1 mol) of ethyl chloroformate are added dropwise to a solution of 0.1 mol of 5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine (crude product; see Example H5) in 200 ml of acetonitrile at 5°C. Subsequently, 16.7 ml (0.12 mol) of triethylamine are added dropwise at 5-15°C, and the mixture is stirred for 3/4 hour. The reaction mixture is evaporated, stirred with ice-water and filtered. The crystalline product is dried under high vacuum. Yield of required product 25.8 g (82% of theory). Melting point 96-98°C.

Analysis: Cι ₄ Hι ₃ F ₃ N ₂ 0 ₃ (314.26)

Calculated [%] : C: 53.51 H. 4.17 N: 8.91 F: 18.14 found [%] : C: 53.4 H: 4.2 N: 9.0 F: 18.2

Example H10: 1 -|5-Ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidene]-3 -methylurea

A solution of 3.84 g (0.015 mol) of 5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidenamine (Example H5), 1.25 ml (0.0165 mol) of methyl isocyanate and 3 drops of triethylamine in 25 ml of acetonitrile is stirred at 25°C for 6 hours. After evaporation of the solution, the reaction mixture is stirred with 25 ml of cold diethyl ether and filtered. Yield of required product 2.8 g (60% of theory). Melting point 102-103°C.

Analysis: d ₄ Hι ₄ F ₃ N ₃ 0 ₂ (313.28)

Calculated [%] : C: 53.68 H: 4.50 N: 13.41 F: 18.19

Found [%]: C: 53.5 H: 4.5 N: 13.5 F: 18.3

Example H11 : Benzyl r5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelca rbamate

36.3 g (0.15 mol) of 5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine (see Example H5) are introduced into 280 ml of pyridine, and 19.5 g (0.18 mol) of benzyl chloroformate are added dropwise at 10-15°C. After the reaction mixture has been stirred at 25°C for 1.5 hours it is poured into ice-water and extracted with ethyl acetate. The combined organic phases are washed with water and brine, dried and evaporated. The crude oily product crystallizes on stirring with a mixture of 100 ml of diethyl ether and 150 ml of hexane and is filtered off. The required product is obtained in a yield of 45.4 g (80.5% of theory) with melting point 68-70°C.

Analysis: d Hi ₅ F ₃ N ₂ 0 ₃ (376.33)

Calculated [%] : C: 60.64 H: 4.02 N: 7.44 F: 15.14

Found [%] : C: 60.6 H: 4.0 N: 7.5 F: 15.2

Example H12: sec-Butyl [5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelcar bamate

7.68 g (0.03 mol) of (2-oxobutyl)(3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) are introduced into 60 ml of pyridine at 25°C, and 0.3 ml of DBU is added. The reaction is slightly exothermic. After cooling to 5°C, 4.3 g (0.0315 mol) of sec-butyl chloroformate are added dropwise at 5-10°C, and the reaction mixture is stirred at 25°C for 1 hour. Evaporation is followed by addition of ice-water to the residue and extraction with ethyl acetate. The organic phases are washed with water, dried and evaporated, and the resulting oil is chromatographed on silica gel with ethyl acetate/hexane 2/3 as eluent. Yield of required product 9.3 g (87% of theory) as oil which crystallizes on standing. Melting point 40-44°C.

Analysis: Cι ₇ Hι ₉ F ₃ N ₂ 0 ₃ (356.34)

Calculated [%] : C: 57.30 H: 5.37 N: 7.86 F: 15.99

Found [%] : C: 57.7 H: 5.4 N: 8.0 F: 16.1

The compounds listed in following Table 5 can be prepared in analogy to Preparation Examples H9 to H12.

Table 5: Compounds of the formula la

Examole H13: Ethyl f6-methyl-4-(3-trifluoromethylphenyll-4.5-dihvdro-2H-f1.2.4l triazin-3- ylidenelcarbamate

25.8 g (0.0822 mol) of ethyl [5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidene]- carbamate (Example H9) are suspended in 150 ml of ethanol at 5°C, and 4.8 ml (0.0986 mol) of hydrazine hydrate are added dropwise. The reaction mixture is left to stir overnight and is then evaporated, ice-water is added, and the mixture is extracted with methylene chloride. The combined organic phases are washed with water, dried and evaporated, and the resulting oily product is chromatographed on silica gel with ethyl acetate/hexane 1/1 as eluant. The oil resulting after evaporation crystallizes by stirring with a little diethyl ether/hexane mixture. Yield of required product 22 g (81% of theory). Melting point 89-90°C.

Analysis: Cι ₄ Hι ₅ F ₃ N ₄ 0 ₂ (328.29)

Calculated [%] : C: 51.22 H: 4.61 N: 17.07 F: 17.36

Found [%] : C: 51.4 H: 4.6 N: 16.9 F: 17.4

Example H14: 1 -r6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.4. triazin-3-ylidenel- 3-ethylurea

A mixture of 1.31 g (0.004 mol) of 1-[5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidene]-3-ethylurea (see Example H10) and 0.25 ml of hydrazine hydrate in 15 ml of ethanol is boiled under reflux for 7 hours. The crude product after evaporation of the reaction mixture is chromatographed on silica gel with ethyl acetate/hexane 2/1 as eluent. The resulting oil crystallizes from a diethyl ether/hexane mixture. The required product is obtained in a yield of 0.95 g (70% of theory) with melting point 126-127°C.

Analysis: C ₁₅ Hι ₈ F ₃ N ₅ 0 (341.34)

Calculated [%] : C: 52.78 H: 5.32 N: 20.52 F: 16.70

Found [%] : C: 52.7 H: 5.2 N: 20.5 F: 16.9

Example H15: N-f6-Methyl-4-.3-trifluoromethylphenyl .5-dihvdro-2H-f1.2.41triazin-3- ylidene]-2.2.2-trifluoracetamide

39 ml of trifluoroacetic anhydride are added dropwise to a suspension of 34.3 g (0.134 mol) of 6-methyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3-ylideneamine (Example H7) in 350 ml of methylene chloride at 10-20°C. Then 75 ml of triethylamine are added dropwise at 10-20 ^C C, and the mixture is then stirred at 25°C for 1 hour. The reaction mixture is subsequently stirred vigorously with ice-water for 10 minutes, the organic phase is separated off, and the aqueous phase is washed with methylene chloride. The methylene chloride phase is dried and evaporated. The resulting oil is chromatographed on silica gel with ethyl acetate/hexane 2/3 as eluant. After evaporation of the collected fractions, the required product crystallizes from a diethyl ether/hexane mixture (1/10). The product is filtered off and dried under high vacuum. Yield 38.2 g (81% of theory). Melting point. 118- 119°C.

Analysis: d ₃ H ₁₀ F _e N ₄ 0 (352.24)

Calculated [%] : C: 44.33 H: 2.86 N: 15.91 F: 32.36

Found [%] : C: 44.5 H: 2.9 N: 15.9 F: 32.4

Example H16: N-f6-Ethyl-4-(3-trifluoromethylPhenyl)-4.5-dihvdro-2H-f1.2.4 1triazin-3-ylidene1- 2-fluoroacetamide

0.78 g (0.01 mol) of fluoroacetic acid is dissolved in 30 ml of tetrahydrofuran at 25°C, and 1.62 g (0.01 mol) of carbonyldiimidazole are added in portions. After stirring for 1 hour, 2.7 g (0.01 mol) of 6-ethyl-4-(3-trrfluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3- ylideneamine (Example H8) are added to this clear solution, which is then stirred for a further 1 hour. The reaction mixture is then evaporated, ice-water is added, and the mixture is acidified with 2N hydrochloric acid and extracted with ethyl acetate. The combined organic phases are washed with water and brine, dried and evaporated. The resulting oil crystallizes from an ether/hexane mixture. The required product is obtained in a yield of 2.7 g (82% of theory) with melting point 90-91 °C.

Analysis: Cι ₄ Hι ₄ F ₄ N ₄ 0 (330.29)

Calculated [%] : C: 50.91 H: 4.27 N: 16.96 F: 23.01

Found [%] : C: 51.3 H: 4.4 N: 16.9 23.1

Example H17: 2-Methoxy-N-f6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihvdro -2H- f1.2.4|triazin-3-ylidene]acetamide

0.61 ml (0.005 mol) of 4-N,N-dimethylaminopyridine (DMAP) is introduced into 6 ml of methylene chloride at 0-5°C, and 0.45 ml (0.005 mol) of methoxyacetyl chloride is added dropwise. This clear solution is added dropwise to a prepared solution of 1.35 g (0.005 mol) of 6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3-ylideneamine (Example H8) in 14 ml of methylene chloride at 5°C. The reaction solution is then stirred overnight, washed with water, dried and evaporated. The resulting oil is chromatographed on silica gel with ethyl acetate as eluent. After evaporation of the collected fractions, the required product crystallizes from diethyl ether/hexane. Yield 0.8 g (47% of theory). Melting point 105-106°C.

Analysis: d ₅ Hi ₇ F ₃ N ₄ 0 ₂ (342.32)

Calculated [%] : C: 52.63 H: 5.01 N: 16.37 F: 16.65

Found [%] : C: 52.5 H: 5.0 N: 16.2 F: 16.8

Example H18: 1 -■6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-ri ,2.41triazin-3- ylidenelurea

A suspension of 7 g (0.018 mol) of phenyl [6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihydro- 2H-[1 ,2,4]triazin-3-ylidene]carbamate (see Example H13) in 20 ml of a saturated ammonia/ethanol solution is stirred at 25°C overnight. This results in crystal transformation and suspension of the required product. The latter is filtered off and washed with alcohol, and the product is dried. Yield 4.8 g (85% of theory). Melting point 179-180°C.

Analysis: Cι ₃ Hι ₄ F ₃ N ₅ 0 (342.32)

Calculated [%] : C: 49.84 H: 4.50 N: 22.35 F: 18.19

Found [%1 : C: 49.5 H: 4.6 N: 22.3 F: 18.3

The compounds listed in following Table 6 can be prepared in analogy to Preparation Examples H13 to H 18.

Table 6: Compounds of the formula Ic

Example H19: Isopropyl f4-Ethyl-4-hvdroxy-1-(3-trifluoromethylphenyl)-2- imidazolidinylidenej-carbamate

2.7 g (0.008 mol) of isopropyl [5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidene]carbamate (see Example H12) are introduced into 20 ml of a saturated ammonia/ethanol solution diluted with 5 ml of ethanol at 25°C. After stirring for 2 hours, the clear solution is evaporated, and the resulting residue is thoroughly stirred with cold diethyl ether, filtered off and dried. The required product is obtained in a yield of 2.3 g (75% of theory) with melting point 132-134°C.

Analysis: Cι ₆ H _2O F ₃ N ₃ 0 ₃ (359.75)

Calculated [%] : C: 53.48 H: 5.60 N: 11.70 F: 15.86

Found [%] : C: 52.9 H: 5.5 N: 11.7 F: 16.0

The compounds listed in following Table 7 can be prepared in analogy to Preparation Example H19.

-84-

Table 7: Compounds of the formula V

85-

Example H20: Isopropyl [4-ethyl-1-(3-trifluoromethylphenyl)-1.3-dihydro-2-imidazoly lidenel- carbamate

1.25 g (0.00336 mol) of isopropyl [4-ethyl-4-hydroxy-1-(3-trifluoromethylphenyl)-2- imidazolidinylidene]carbamate (Example H19) are introduced into 15 ml of trifluoroacetic anhydride at 25°C. After stirring for half an hour, the clear solution is concentrated, and the resulting residue is taken up in ethyl acetate. The ethyl acetate solution is washed with • dilute sodium bicarbonate solution and then with water and brine. Evaporation results in a solid residue which is stirred with diethyl ether/hexane 2/3 and then filtered off. The required product is obtained in a yield of 1.05 g (88% of theory) with melting point 116-118°C.

Analysis: Cι ₆ Hι ₈ F ₃ N ₃ 0 ₂ (359.75)

Calculated [%] : C: 56.30 H: 5.31 N: 12.31 F: 16.69

Found [%) : C: 56.2 H: 5.3 N: 12.3 F: 16.7

The compounds listed in following Table 8 can also be prepared in an analogous manner.

87-

Table 8: Compounds of the formula lb

88

Examples of formulations of active ingredients of the formula I (% = per cent bv weight)

F1. Emulsion concentrates a) b) c) d)

Active ingredient in Tables 5, 6 and 8 5% 10% 25% 50%

Ca dodecylbenzenesulfonate 6 % 8 % 6 % 8 %

Castor oil polyglycol ether 4 % - 4 % 4 %

(36 mol EO)

Octylphenol polyglycol ether - 4 % - 2 %

(7-8 mol EO)

Cyclohexanone - - 10% 20%

Arom. Cg-Cι ₂ 85% 78% 55% 16% hydrocarbon mixture

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d)

Active ingredient in Tables 5, 6 and 8 5% 10% 50% 90%

1 -Methoxy-3-(3-methoxy- propoxy)propane - 20% 20%

Polyethylene glycol MW 400 20% 10%

N-Methyl-2-pyrrolidone - - 30% 10%

Arom. C ₉ -Cι ₂ 75 % 60 % hydrocarbon mixture

The solutions are suitable for use in the form of very fine drops.

F3. Wettable powders a) b) c) d)

Active ingredient in Tables 5, 6 and 8 5% 25% 50% 80%

Na ligninsulfonate 4 % - 3 %

Na lauryl sulfate 2% 3% - 4%

Nadiisobutylnaphthalenesulfonate - 6% 5% 6%

Octylphenol polyglycol ether - 1 % 2 %

(7-8 mol EO)

Highly disperse silica 1 % 3% 5% 10%

Kaolin 88% 62% 35%

The active ingredient is thoroughly mixed with the additives and thoroughly ground in a suitable mill. The resulting wettable powders can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c)

Active ingredient in Tables 5, 6 and 8 0.1 %

Highly disperse silica 0.9 %

Inorg. carrier material 99.0 %

(00.1 - 1 mm) for example CaCO ₃ or SiO ₂

The active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is thoroughly evaporated off in vacuo.

F5. Coated granules a) b) c)

Active ingredient in Tables 5, 6 and 8 0.1 % 5% 15%

Polyethylene glycol MW 200 1.0 %

High disperse silica 0.9 %

Inorg. carrier material 98.0 %

(0 0.1 - 1 mm) for example CaCO ₃ or SiO ₂

The finely ground active ingredient is applied uniformly to the carrier material which is moistened with polyethylene glycol in a mixer. This results in dust-free coated granules.

F6. Pellets a) b) c) d)

Active ingredient in Tables 5, 6

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.

Dusts ready for application are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill.

F8. Suspension concentrates a) b) c) d)

Active ingredient in Tables 5, 6 and 8 3 % 10 % 25 % 50 %

Ethylene glycol 5 % 5 % 5 % 5 %

0.2

0.8

The finely ground active ingredient is intimately mixed with the additives. This results in a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Biological examples

Example B1 : Herbicidal action before emergence of the plants (preemergence action.

Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on as aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or as emulsion (prepared from a 25% emulsion concentrate (Example F1 , c)) corresponding to a dose of 2 kg AS/ha (5001 water/ha). The test plants are then grown in a glasshouse under optimal conditions. After the test has lasted 3 weeks, the experiment is evaluated using a nine-point scoring scale (1 = complete damage, 9 = no action). Rating scores from 1 to 4 (in particular 1 to 3) mean that the herbicidal action is good to very good.

Table B1 : Preemeroence action:

Test plant: Setaria Sinapis Stellaria n r dient No.

6.73 1 2

6.84 2 2

6.87 2

6.88 2

6.89

6.93

6.166

6.206

6.208

6.250

7.16

8.3 3 3

8.11 2 1

8.17 1 2

The same results are obtained when the compounds of the formula I are formulated as in Examples F2 and F4 to F8.

Example B2: Postemergence herbicidal action

Monocotyledonous and dicotyledonous test plants are grown in plastic pots containing standard soil in a glasshouse and sprayed at the 4- to 6-leaf stage with an aqueous suspension of the test substances of the formula I prepared from a 25% wettable powder (Example F3, b)) or with an emulsion of the test substances of the formula I prepared from a 25% emulsion concentrate (Example F1 , c)), corresponding to a dose of 2 kg AS/ha (500 I water/ha). The test plants are then grown further in a glasshouse under optimal conditions. After the test has lasted about 18 days, the experiment is evaluated using a nine-point scoring scale (1 = complete damage, 9 = no action). Rating scores from 1 to 4 (in particular 1 to 3) mean that the herbicidal action is good to very good. The compounds of the formula I show a strong herbicidal action in this experiment.

Table B2: Postemer ence action:

inapis

The same results are obtained when the compounds of the formula I are formulated as in Examples F2 and F4 to F8.