WO1995018811A1

WO1995018811A1 - Phosphonic acid derivatives containing a triazole ring as herbicides

Info

Publication number: WO1995018811A1
Application number: PCT/IB1995/000004
Authority: WO
Inventors: Ichiro Mori; Yoko Kimura; Shinichiro Matsunaga; Toshihito Nakano; Anthony Cornelius O'sullivan
Original assignee: Japat Ltd.; Ciba-Geigy Japan Limited
Priority date: 1994-01-06
Filing date: 1995-01-03
Publication date: 1995-07-13
Also published as: EP0738271A1; IL112247A0; AU1249495A; MX9602657A; JPH09507243A; MD960284A; BR9506458A; CA2179822A1

Abstract

A triazole of formula (I) in which the meanings of the radicals are described in claim 1, have good pre- and post-emergence selective herbicidal and growth-regulating properties. They are suitable as active substances in weed killers and in compositions for inhibiting plant-growth.

Description

PHOSPHONIC ACID DERIVATIVES CONTAINING A TRIAZOLE RING AS HERBICIDES

The present invention relates to novel triazoles which have a herbicidal action and are plant-growth-inhibiting, to processes for their preparation, to compositions containing them as active substances, and to their use for controlling weeds, especially selectively in crops, or for inhibiting plant growth.

Triazole compounds which have a herbicidal action are generally known. For example, WO 93/15610 and US-A-5,248,655 describe herbicidally active triazole compounds.

It has been found that compounds of the formula (I) have a herbicidal and

plant-growth-inhibiting action. They are therefore suitable as active substances in weed killers and in compositions for inhibiting plant-growth.

The triazoles according to the invention are those of the formula I

in which

A is hydrogen, C₁-C₄-alkyl, C₂-C₄-alkenyl, triphenylmethyl, benzyl, a group , SO₂N(CH₃)₂, CH(C₁-C₄-alkoxy)₂ or

2-(trimethylsilyl)ethoxymethyl;

t is 4 or 5;

R₁ is hydrogen, C₁-C₆-alkyl, OR ₁₉ or NR₂₀R₂₁;

R₂ is hydrogen, C ₁-C₆-alkyl, OR₁₉ or NR₂₀R₂₁, or R₂ and R₂ together form an oxo group;

R₃ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or represents together with R₂ a chemical bond;

R₄ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkyl substituted by halogen, cyano, COOH,

C₁-C₄-alkoxycarbonyl, amino, di(C₁-C₄)-alkylamino, C₁-C₄-alkylamino, phenyl, benzyl or an alkali metal, alkaline earth metal, ammonium, mono-, bis- or

tris-C₁-C₆-alkylammonium, trialkylsulphonium, trialkylsulfoxonium, phosphonium or amidinium cation;

X is oxygen, S(O)_m, NR₅ or CR₆R₇;

Y is oxygen, S(O)_p, NR₅ or CR₈R₉;

Z is oxygen, S(O)_q, NR₅ or CR₁₀R₁₁;

m, p and q are each independently of the others 0, 1 or 2;

R₅ is hydrogen, C₁-C₆-alkyl which is unsubstituted or substituted by halogen,

C₁-C₄-alkoxy, COOH, C₁-C₄-alkoxycarbonyl, unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄ alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; or R₅ is C₃-C₆-alkenyl which is unsubstituted or substituted by C₁-C₄-alkoxycarbonyl, halogen, unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; C₃-C₆-alkynyl which is unsubstituted or substituted by unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfmyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; C₁-C₆-alkoxycarbonyl, unsubstituted phenyl or phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are each independently of the others hydrogen, C₁-C₆-alkyl which is unsubstituted or substituted by hydroxy, amino, C₁-C₄-alkoxy, C₁-C₄-alkylamino or phenyl, which itself is unsubstituted or substituted by C₁-C₄-alkyl, halogen,

C₁-C₄-haloalkyl, Q^-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; phenyl, benzyl which are unsubstituted or substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro,

C₁-C₄-alkylthio, C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; or R₆ and R₇ or R₈ and R₉ or R₁₀ and R ₁₁ together form an oxo group;

Q₁ is OR₁₂ or NR₁₃ R₁₄;

R₁₂ is hydrogen, a group or a group ;

R₁₃ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, hydroxy, C₁-C₆-alkylcarbonyl,

C₁-C₆-alkoxycarbonyl, benzoyl which is unsubstituted or substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C_1-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; a group , C₁-C₆-alkyl which is substituted by halogen, C₁-C₄-alkoxy,

C₁-C₄-alkoxycarbonyl, phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

R₁₄ is hydrogen or C₁-C₆-alkyl;

R₁₅ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl; or C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, halomethyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl; R₁₆ is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl; or C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfmyl or C₁-C₄-alkylsulfonyl; or is C₁-C₆-alkoxyalkyl, C₁-C₆-alkylcarbonyloxyalkyl, C₁-C₆-alkoxycarbonylalkyl or C₃-C₆-cycloalkyl;

R₁₇ is hydrogen or C₁-C₆-alkyl;

R₁₈ is hydrogen or C₁-C₆-alkyl;

R₁₉ is hydrogen, a group or a group ;

Q is oxygen or sulfur;

R₂₀ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, hydroxy, C₁-C₆-alkylcarbonyl,

C₁-C₆-alkoxycarbonyl, benzoyl which is unsubstituted or substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; R₂₁ is hydrogen or C₁-C₆-alkyl;

R₂₂ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkyl substituted by halogen, cyano, COOH,

C₁-C₄-alkoxycarbonyl, amino, di(C₁-C₄)-alkylamino, C₁-C₄-alkylamino, phenyl, benzyl or an alkali metal, alkaline earth metal, ammonium, mono-, bis- or tris-alkylammonium, trialkylsulphonium, trialkylsulfoxonium, phosphonium or amidinium cation;

R₂₃ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl; or C₁-C₆-alkyl, C₃-C₆-alkenyl,

C₃-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, halomethyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl;

R₂₄ is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl; or C₁-C₆-alkyl, C₂-C₆-alkenyl,

C₂-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl; or is C₁-C₆-alkoxyalkyl, C₁-C₆-alkylcarbonyloxyalkyl, C₁-C₆-alkoxycarbonylalkyl or

C₃-C₆-cycloalkyl;

R₂₅ is hydrogen or C₁-C₆-alkyl; and

R₂₆ is hydrogen or C₁-C₆-alkyl, with the proviso that a) at least two of the substituents X, Y and Z are carbon atoms, b) that R₁ or R₂ is OR₁₉ or NR₂₀R₂₁ if simultaneously X, Y and Z are carbon atoms and Q ₁ is OR₁₂ and c) that R₁ and R₂ are not simultaneously OR₁₉, NR₂₀R₂₁ or both of them.

In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Alkyl is, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec -butyl, tert-butyl and the various isomeric pentyl or hexyl radicals.

Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy.

Alkenyl is to be understood as being straight-chain or branched alkenyl, for example vinyl, allyl, methallyl, 1-methyl vinyl, but-2-en-1-yl, 3-pentenyl, 2-hexenyl or 3-heptenyl. Alkenyl radicals having a chain length of 2 or 3 carbon atoms are preferred.

The alkynyl radicals occurring in the definitions of the substituents may be

straight-chained or branched, for example ethynyl, propargyl, 3-butynyl,

1-methylpropargyl, 2-pentynyl or 2-hexynyl. Ethynyl and propargyl are preferred.

Alkoxycarbonyl is, for example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.

If the compounds of the formula I contain an asymmetric carbon atom, this results in the fact that the compounds can occur in optically isomeric forms. If there is an aliphatic C=C double bond, geometric isomerism can also occur. The formula I therefore also embraces all stereoisomers which are possible and which are in the form of enantiomers, diastereomers or their mixtures.

The term organic ammonium cation is intended to include ammonium cations prepared from low molecular weight amines, that is to say those having a molecular weight below about 300. Examples of such amines include alkylamines, alkenylamines, and

alkanolamines containing not more than two amino groups, such as methylamine, ethylamine, n-propylamine, iso-propylamine, the four isomeric butylamines,

n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pen tadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-n-amylamine,

di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, N,N-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine,

2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylendiamine, diethanolamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine,

tri-sec.-butylamine, tri-n-amylamine, trimethylamine, triethylamine, tripropylamine; heterocychc amines as, for example, pyridine, chinoline, iso-chinoline, morpholine, piperidine, pyrrolidine, indoline, chinuclidine and azepine; primary arylamines as, for example, aniline, methoxyaniline, ethoxyaniline, o,m,p-toluidine, phenylendiamine, benzidine, naphthylamine and o,m,p-chloroaniline; in particular ethyl-, propyl-, diethyl- oder triethylamine, preferably iso-propylamine and diethanolamine.

Tetra-substituted ammonium cations are also included, for example

tetramethylammonium, tetrabutylammonium, benzyltrimethylammonium,

benzyltriethylammonium, tetra-ethylammonium and trimethylethylammonium cations.

Trialkylsulfonium cations include those, for example, in which each of the three alkyl groups, which are not necessary all the same, may contain from 1 to 6 carbon atoms. Trialkylsulfoxonium cations likewise include those in which each of the three alkyl groups, which may be the same or different, may contain from 1 to 6 carbon atoms.

Phosphonium cations include, for example, cations in which the phosphorus atom bears four substituents, each of which may be an alkyl group of one to ten carbon atoms or a phenyl group, for example, the tetramethylphosphonium, tetrabutylphosphonium, and tetraphenylphosphonium cations.

Amidinium cations include, for example, straight chain amidinium cations of formula R₂₇-C(NH₂)=NH₂ ⁺, wherein R₂₇ is an alkyl radical of, for example, from 1 to 10 carbon atoms, and cyclic amidinium cations such as 1,5-Diazabicyclo[5.4.0]undec-5-ene (DBU).

Alkali metal cations include lithium, sodium and potassium; and alkaline earth metal cations include magnesium, calcium, strontium and barium.

Preferred compounds of the formula I are those, in which A is hydrogen.

Compounds of the formula I which are of particular interest are those in which R₃ is hydrogen or C₁-C₆-alkyl.

Further preferred compounds of the formula I are those in which R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are hydrogen.

Preferred compounds of the formula I which must be emphasised are those in which Q₁ is hydroxy or amino. Further preferred compounds of the formula I are those in which R₁, R₂, R₃, R₄ and R₂₂ are hydrogen.

Furthermore, compounds of the formula I which are of particular interest are those in which X is CR₆R₇, Y is CR₈R₉ and Z is NR₅. Further preferred compounds from amongst those of the formula I are those in which Q₁ is hydroxy and A, R₄, R₆, R₇, R₈, R₉ and R₂₂ are hydrogen.

A preferred individual compound from the scope of formula I is

2-Oxa-3-hydroxy-3-(1,2,4-triazol-3-yl)-cyclohexane phosphonic acid.

Preferred compounds of the formula I which are of particular interest are those, in which the substituents Q₁ and are in trans-position.

A further subject of the present invention is a process for the preparation of compounds of the formula I which comprises a) for the preparation of a compound of the formula I, in which Q₁ is hydroxy, reacting a compound of the formula II ,

wherein A has the meanings given for formula I except for hydrogen, with a compound of the formula III

,

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I and A, R₄ and R₂₂ have the meanings given for formula I except for hydrogen, to a compound of the formula Ia

in which R_1; R₂, R₃, X, Y and Z have the meanings given for formula I and A, R₄ and R₂₂ have the meanings given for formula I except for hydrogen, and optionally cleaving protecting groups A and/or R₄ and R₂₂ and further converting them into a salt;

b) for the preparation of a compound of the formula Ib

in which R₁₂ is a group or a group and A, R₁, R₂, R₃, R₄, R₁₅,

R₁₆, R₂₂, X, Y and Z have the meanings given for formula I, reacting a compound of the formula IV

with a compound of the formula V: , VI: or VII:

(R₁₆CO)₂O (VII), wherein X₁ and X₂ are halogen and R₁₅ and R₁₆ have the meanings given for formula I, c) for the preparation of a compound of the formula I, in which Q₁ is NH₂, converting a compound of the formula Ia

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I and A, R₄ and R₂₂ have the meanings given for formula I except for hydrogen, in the presence of NaN₃ and CF₃COOH to the corresponding azide and subsequently reducing the azide, d) for the preparation of a compound of formula I, in which Q₁ is NR₁₃R₁₄ and A, if bound to the 5-carbon atom of the triazole ring, is as defined for formula I or A, if bound to one of the 3 nitrogen atoms of the triazole ring, is hydrogen, reacting a compound of the formula la

,

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I and R₄ and R₂₂ have the meanings given for formula I except for hydrogen, with a compound of formula XVI

Q₀-Z₀ (XVI), wherein Z₀ is a leaving group, for example halogen, preferably chlorine, and Q₀ is for example S(O)Cl-, C(O)Cl-, PCI₄-, C(O)Cl-C(O)- or to form a

compound of formula XVII

,

wherein A, R ₁, R₂, R₃, R₄, R₂₂, X, Y, Z and Z₀ are as defined above, which is converted by reaction with a compound of formula XVIII

HNR₁₃R₁₄ (XVIII), wherein R₁₃ and R₁₄ are as defined under formula I, and optionally cleaving the groups R₄ and R₂₂, for example with trimethylsilyl bromide and a solvent, for example

dichlormethane, followed by treatment with an alcohol and propylene oxide, and further converting them into a salt, e) for the preparation of a compound of the formula I, in which Q₁ is NHR₁₃ and R₁₃ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, hydroxy, C₁-C₆-alkylcarbonyl,

C₁-C₆-alkoxycarbonyl, benzoyl which is unsubstituted or substituted by C_j^-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; a group

, C₁-C₆-alkyl which is substituted by halogen, C₁-C₄-alkoxy,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

or R₁₃ is a protecting group, for example arylthio, especially phenylthio or

4-chlorophenylthio, reacting a compound of the formula XI ,

wherein A has the meanings given for formula I except for hydrogen and M is Sodium, Magnesium, Lithium, Cerium or Copper, with a compound of the formula

in which R₁, R₂, R₃, R₁₃, X, Y and Z have the meanings given for formula I and R₄ and R₂₂ have the meanings given for formula I except for hydrogen in the presence of an inert solvent, or f) for the preparation of a compound of the formula I, in which A is hydrogen and Q₁ is NR₁₃R₁₄, wherein R₁₃ and R₁₄ have the meanings given for formula I except for hydrogen or R₁₃ and R₁₄ are protecting groups, for example arylthio, especially phenylthio or 4-chlorophenylthio, reacting a compound of the formula XIII

,

wherein R₃, R₄, R₂₂, X, Y and Z have the meanings given for formula I, in the presence of NaCN and HNR₁₃R₁₄ to a compound of the formula XIV

wherein R₃, R₄, R₂₂, X, Y and Z have the meanings given for formula I and R₁₃ and R₁₄ have the meanings given above and converting said compound in the presence of sodium methylate and formyl hydrazine to the compound of the formula I.

Process a) is carried out in a manner or analogously as given by A.R. Katritzky,

Tetrahedron 46 (1990), page 641 ff. The protecting group A as triphenylmethyl, benzyl, a group SO₂N(CH₃)₂, CH(C₁-C₄-alkoxy)₂ or

2-(trimethylsilyl)ethoxymethyl can be cleaved by:

A) hydrogenolysis, acidic hydrolysis or reductive conditions for the triphenylmethyl group,

B) hydrogenolysis with palladium on active charcoal or by reductive cleavage by sodium in liquid ammonia for the benzyl group,

C) cleavage with NaBH₄ for the group

D) cleavage with sodium hydroxide, sodium cyanide, tetra-n-butylammonium fluoride, H₂SO₄ or LiAlH₄ for the dimethylsulphamoyl group,

E) acid hydrolysis for the dialkoxymethyl group,

F) acid hydrolysis or cleavage with tetra-n-butylammonium fluoride for the

2-(trimethylsilyl)ethoxymethyl group.

Said reactions are carried out in a manner or analogously as given by US-A-5,248,655, D.K. Anderson, Heterocyclic Chemistry 23 (1986), pages 1257ff; A.R. Katritzky, Tetrahedron 46 (1990), page 641 ff.; A.J. Carpenter, Tetrahedron 1986, 42, 2351; P.J . Dudfield, Synlett. 1990, 277; S. Ohta, Chem. Pharm. Bull. 1993, 41, 1226 and W. Holzer, Heterocycles 1992, 34, 303.

Processes b), c), e) and f) are carried out in a manner or analogously as given in Chem. Rev. 1953, 52, pages 237 - 416 (b); D. Baldermann, Organic Synthesis 1981, 60, 104 (c); E. Ciganek, J. Org. Chem. 1992, 57, 4521; F.A. Davis, J. Org. Chem. 1977, 42, 398 and B. Lipschutz, Tetrahedron 1986, 27, 4241 (d) and S.L. Crooks, J. Med. Chem. 1986, 29, 1988 and T. Murakami, Heterocycles 1981, 15, 301 (e). In process variant b), the meaning chlorine is preferred for the substituents X₁ and X₂.

Process d) is carried out in a manner analogously as given in J. Org. Chem. 39, 940 (1974).

Compounds of formula II are well known and for instance are prepared by reacting a 1,2,4- triazole in an organic solvent, especially tetrahydrofurane or diethylether, in the presence of n-butyllithium at temperatures between -50 to -90°C. The preparation of compounds of the formula III is described, for example, in US-A-5,248,655.

Compounds of the formula III, in which R₂ is hydrogen, can also be prepared by

1) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I, with a compound of the formula IX

HOP(OR₄)OR₂₂ (IX)

in which R₄ and R₂₂ have the meanings given for formula I except for hydrogen, in an inert solvent, preferably dichloromethane, in the presence of

N,O-bis(trimethylsilyl)acetamide and trimethylsilyl trifluoromethanesulfonate at temperatures of from -78°C to 40°C, preferably -20°C to 20°C, or

2) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I, with a compound of the formula X

(CH₃)₂R₂₈SiOP(OR₄)OR₂₂ (X) in which R₄ and R₂₂ have the meanings given for formula I except for hydrogen and R₂₈ is methyl or tert.-butyl, in an inert solvent, preferably dichloromethane, in the presence of a compound of the formula XV

(CH₃)₂R₂₈SiOSO₂CF₃ (XV) in which R₂₈ is methyl or tert.-butyl, or

3) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I, preferably Z is NR₅ and R₅ is benzyl, with a compound of the formula XVI

P(OR₄)(OR₂₂)OR₂₂ (IX) in which R₄ and R₂₂ have the meanings given for formula I except for hydrogen, preferably R₄ and R₂₂ are i-propyl, in an inert solvent, preferably dichloromethane, in the presence of a base and of a silylating agent, preferably trimethylsilyl

trifluoromethanesulfonate or tert.-butyldimethylsilyltrifluoromethanesulfonate at temperatures of from -78°C to 40°C and cleavage of the resulting silyl ether with a cleaving agent, preferably tetrabutylammoniumfluoride in an inert solvent, preferably tetrahydrofurane, in the presence of a base. Process variants 1), 2) and 3) have been developed specifically for the preparation of the active ingredients of the formula I. The present invention therefore likewise relates to them. Compounds of the formula VIII are known and are described, for example, in Danishefsky, S.; Webb II, R.R.J. Org. Chem. 1984, 49, 1955, Guerry, P.; Neier, R.;

Synthesis, 1984, 485; Kozikowski, A.P.; Park, P.; J. Org. Chem., 1990, 55, 4688; Ziegler, F.E.; Bennet, G.B.; J. Am. Chem. Soc., 1973, 95, 7458; Chen, L.; Wang, E.; Lin, L.; Wu, S.; Heterocycles, 1984, 22, 2769; Terasawa, T.; Okada, T.; J. Org. Chem., 1977, 42, 1163; Batten, R.J.; Coyle, J.D.; Taylor, R.J.K.; Synthesis, 1980, 910.

The compounds of the formula I are employed in unaltered form, as obtainable by the synthesis, or preferably together with the auxiliaries conventionally used in formulation technology, and they are therefore processed in a known manner to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations, for example in polymeric substances. The application methods, such as spraying, atomising, dusting, scattering or pouring, as well as the type of compositions are selected to suit the intended aims and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or combinations comprising the active substance of the formula I and, if desired, one or more solid or liquid additives, are prepared in a known manner, for example by intimately mixing and/or grinding the active substances with extenders, for example with solvents, solid carriers and, if desired, surface-active compounds (surfactants).

The following are possible as solvents: aromatic hydrocarbons, in particular the fractions C₈ to C₁₂, such as mixtures of alkylbenzenes, for example xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols as well as their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils as well as their esters, such as rapeseed oil, castor oil or soybean oil; and if appropriate also silicone oils.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active substance of the formula I to be formulated. Surfactants are also to be understood as meaning mixtures of surfactants.

Anionic surfactants which are suitable can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C₁₀-C₂₂), such as the Na salts or K salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained, for example, from coconut oil or tallow oil. Mention must also be made of the fatty acid methyltaurinates.

However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or fatty alcohol sulfates are generally in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted 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 the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having 8 to 22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of

dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product.

Other suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of a p-nonylphenol/(4-14)-ethylene oxide adduct, or phospholipids.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of alkylphenols, which can 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 non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and

alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of non-ionic surfactants which may be mentioned are

nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and

octylphenoxypolyethoxyethanol.

Other suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts, which contain at least one alkyl radical having 8 to 22 C atoms as N-substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example

stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customary in formulation technology are described, inter alia, in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock,

New Jersey, 1988;

M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New

York, 1980-1981.

Dr. Helmut Stache, "Tensid-Taschenbuch [Surfactant Guide]", Carl Hanser Verlag,

Munich, Vienna, 1981;

As a rule, the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the active substance of the formula 1, 1 to 99 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.

While concentrated compositions are more preferred as commercial goods, the user generally uses dilute compositions. The compositions can also comprise further additives such as stabilisers, for example epoxidised or unepoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, as well as fertilisers or other active substances for achieving specific effects.

In particular, preferred formulations have the following composition: (% = per cent by weight)

Emulsifiable concentrates:

Active ingredient: 1 to 20 %, preferably 5 to 10 %

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

Liquid carrier: 15 to 94 %, preferably 70 to 85 %

Dusts:

Active ingredient: 0.1 to 10 %, 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: 5 to 95 %, preferably 15 to 90 %

Granules:

Active ingredient: 0.5 to 30 %, preferably 3 to 15 %

Solid carrier: 99.5 to 70 %, preferably 97 to 85 %

As a rule, the active substances of the formula I are sucessfully employed at application rates from 0.001 to 10 kg/ha, in particular 0.005 to 2 kg/ha. The dosage rate which is required for the desired action can be determined by tests. It depends on the nature of the action, the development stage of the crop plant and the weed, as well as on the application (location, time, method) and, due to these parameters, can vary within wide limits. Controlled release of active substance

The dissolved active substance is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and allowed to dry. If desired, a coating can be applied (coated granules), which permits slow release of the active substance over a certain period.

The following examples are intended to illustrate the invention in greater detail.

A. Preparation of compounds of formula I

Preparation of Compound No. 1.001

Method A:

To a solution of diethyl phosphite (9.1 ml, 70.6 mmol), N,O-bis(trimethylsilyl)acetamide (18.9 ml, 77.2 mmol) in 60 ml of dichloromethane was added trimethylsilyl

trifluoromethanesulfonate (1.45 ml, 6.4 mmol) at room temperature and stirred for 25 min. The resulting mixture was cooled to 0°C and 2,3-dihydro-4H-pyran-4-on 1 (6.3 g, 64.2 mmol) in 8 ml of dichloromethane was added and stirred for 1.5 h. The reaction was quenched with 30 ml of water and extracted several times with dichloromethane. The combined organic layers were dried over MgSO₄, concentrated, and purified by silica gel chromatography (hexane: acetone = 3:2) to give 4.0 g (26 % yield) of pure portion of the desired compound 2 (as a colorless oil).

(1) Contains ca. 30 % of trans-4-methoxy-3-buten-2-on.

¹HNMR (400 MHz, CDCl₃)δ 4.47-4.41 (m,1), 4.26-4.17 (m,4), 4.02-3.96 (m,1), 3.75 (dt,

1, J = 11.8, 3.0), 2.82-2.57 (m,3), 2.43-2.37 (m,l), 1.36 (t,6,J = 7.1).

Method B:

To a mixture of enon 1 (0.80 g, 8.15 mmol) and diethyl trimethylsilyl phosphite (1.89 g,

8.97 mmol) in 10 ml of dichloromethane was added trimethylsilyl

trifluoromethanesulfonate (18 μl, 0.08 mmol) at 0°C under nitrogen. After stirring for 1 h at 0°C, water (5 ml) was added and the mixture was stirred for 1 h at room temperature.

The organic layer was separated and the aqueous layer was extracted with

dichloromethane. The combined organic layers were dried over MgSO₄, concentrated and purified by silica gel chromatography (4 % ethanol in ethyl acetate) to give 600 mg (31 % yield) of the desired compound 2.

(1) Contains ca. 30 % of 4-methoxy-3-buten-2-on. Danishefsky, S.; Webb II, R.R.J. Org.

Chem. 1984, 49, 1955.

To a solution of 1-triphenylmethyl- 1,2,4-triazole (4.3 g, 13.8 mmol) in 100 ml of THF was added n-BuLi (1.63 M in hexane, 10.2 ml, 16.5 mmol) in 10 min at -78°C under nitrogen. The mixture was stirred for 1 h at -78°C, saturated ammonium chloride was added and the mixture was allowed to warm to room temperature. Most of organic solvent was removed under reduced pressure and the residue was extracted with ethyl acetate (3 × 50 ml). The combined organic layers were dried over MgSO₄, concentrated, and purified by silica gel chromatography (hexane: acetone = 3:2 to 2:3) to give 4A (2.5 g, 33 % yield) and 4B (1.5 g, 20 % yield).

4A

mp: 174-189°C

¹HNMR (400 MHz, CDCl₃)δ 7.89 (S,1), 7.35-7.12 (m,15), 4.16-4.08 (m,4), 3.78-3.69 (m,2), 3.44-3.38 (m, 1), 2.45 (dt,1,J = 13.1, 9.4), 2.26 (dt,1,J = 13.5, 5.0), 1.36-1.33 (m ,1), 1.32 (t,3,J = 7.1), 1.31 (t,3,J = 7.1), 1.00 (sJ), 0.85-0.81 (m,1).

4B

mp: 145-151°C

¹HNMR (400 MHz, CDCl₃)δ 7.86 (S,1), 7.30-7.08 (m,15), 4.43 (dt,1,J = 5.9, 12.7), 4.12 (quintet,2J = 7.4), 4.03 (quintet,2,J = 7.3), 3.86 (t,2,J = 5.4), 3.57 (S,1), 2.38-2.26 (m,1), 1.82-1.76 (m,1), 1.45-1.38 (m,1), 1.31 (t,3,J = 7.15), 1.30 (t,3,J = 7.17), 1.22-1.16 (m,1).

To a solution of 4A (1.8 g, 3.29 mmol) in 36 ml of dichloromethane was added trimethylsilyl bromide (2.2 ml, 16.4 mmol) and the mixture was stirred overnight at room temperature. After stirring with 20 ml of methanol for 2 h, propylene oxide (2 ml) and then ether was added until the precipitation was completed. The precipitates were collected on a glass filter, washed with ether, and dried in vacuo to give 800 mg (98 % yield) of 5A.

4B was deprotected in the same way as 4A to give quantitative yield of 5B.

5A

mp: 169-175°C (decomp.) ¹HNMR (400 MHz, D₂O) δ 8.92 (s,1), 4.04-3.98 (m,2), 3.90 (apparent t,1,J = 11.3), 2.31-2.13 (m,3), 1.92 (broad d,1, J=1.4).

5B

mp: 155-163°C

¹HNMR (400 MHz, D₂O) δ 9.02 (s,1), 4.09-4.05 (m,1), 3.61 (apparent t,1,J = 12.0), 3.50

(apparent t,1,J = 12.0), 2.66 (broad d, 1,J = 12.4), 2.45 (broad d,1,J = 14.0), 2.08-1.99

(m, 2).

Preparation of Compound No. 1.017 and 1.019:

Preparation of Compounds No. 1.010 and 1.002:

1.635 g (13,74 mmol) Thionylchlorid was added to a suspension of 1.062 g (3.50 mmol) of compound no. 6 in 1 ml toluene. The solution becomes homogeneous and was stirred for 10 minutes at room temperature. 20 ml diethylether was added under stirring. A sticky precipitate came out which was separated from the solvent by decantation and the residue was washed with ether and dried with the vacuum pump.

This product was dissolved in 5 ml dichloromethane and added slowly to a solution of ammonia in tetrahydrofurane with stirring at 0°C. A white precipitate came out which was separated by evaporation of the solvent and the residue was dissolved in 100 ml methanol, stirred with 3 g potassium carbonate, evaporated, dissolved in 20 ml toluene and again evaporated. Column chromatography on silica gel yields 218 mg of compound 7a, 156 mg of compound 7b, 61 mg of a mixture of compounds 7a and 7b, and as a by-product 582 mg of the olefin 8 1.

1H-NMR (400 MHz, CDCl₃) of compound 7a: 7.98 ppm (s, 1H), 4.12 ppm (m, 4H), 2.43 ppm (m, 1H), 2.06 ppm (m, 4H), 1.78 ppm (m, 2H), 1.48 ppm (m, 2H), 1.32 ppm (t, 6H).

Deprotection of the compound 7a was executed with trimethylsilyl bromide in

dichloromethane followed by treatment with methanol and propylene oxide as described above, to yield the desired product 1.010. 1H-NMR (400 MHz, CD₃OD): 8.62 ppm (s, 1H), 2.38 ppm (m, 1H), 2.12 ppm (m, 5H), 1.97 ppm (m, 1H), 1.73 ppm (m, 1H), 1.53 ppm (m, 1H).

Compound no. 1.002 can be obtained analogously, starting from the corresponding compound 6b .

Η-NMR (400 MHz, CD₃OD) of compound no. 1.002: 8.46 ppm (s, 1H), 4.08 ppm (dxd, 1H), 3.81 ppm (t, 2H), 2.48 ppm (m, 2H), 2.28 ppm (d, 1H), 1.94 ppm (d, 1H).

B. Preparation of a compound of the formula IIIa:

To a solution of diethylphosphite (4.2 ml, 32.5 mmol) in 50 ml of dichloromethane was added N,O-bistrimethylsilylacetamide (8.0 ml, 32.6 mmol) and trimethylsilyl triflate (0,28 ml, 1.45 mmol) at room temperature and stirred for 30 min. After the mixture was cooled to 0°C, 3-ethoxy-2-cyclohexen-1-one (4.10 g 29.2 mmol) in 7 ml of dichloromethane was added and stirred at 0°C for 20 min and then at room temperature for 15 min. To the resulting solution was added 50 ml of IN hydrochloric acid and stirred at room

temperature for 20 min. The mixture was extracted with dichloromethane, and the organic phase was dried over MgSO₄ and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 1:3 to ethyl acetate) to give compound IIIa (6.55 g, 90% yield, containing ca. 10% of diethylphosphite) as a colorless oil.

¹HNMR (400 MHz, CDCl₃) δ 6.57 (dt, 1,J = 21.1, 1.8), 4.20-4.10 (m, 4), 2.55-2.45 (m, 4), 2.13-2.06 (m, 2), 1.36 (t, 6, J = 7.1).

C. Preparation of a compound of the formula IIIb:

Preparation of 2

To a mixture of triisopropyl phosphite (2.91 ml, 11.8 mmol) and 1-benzyl-1,6- dihydro-3(2H)-pyridinone 1 (2.02 g, 10.7 mmol) in 24 ml of dichloromethane was added tert-butyldimethylsilyl trifluoromethanesulfonate (2.71 ml, 11.8 mmol) in 7 min at -78°C. After stirring for 1 h at -78°C, 20 ml of saturated NaHCO₃ was added. The mixture was extracted with 200 ml of ether. The organic layer was washed with 2 × 15 ml of brine, dried over MgSO₄, and concentrated to give 6.74 g of a crude product. Purification by silica gel chromatography (dichloromethane:ether = 4:1) gave 2.75 g (55% yield) of 2 as a colorless oil.

¹HNMR (400 MHz, CDCl₃) δ 7.35-7.25 (m, 5), 4.91 (d, 1, J = 9,0). 4,70-4,63 (m, 2), 3.60 (m, 2), 2.97-2.80 (m, 4), 2.48 (dt, 1, J = 7.8, 11.1), 1.34-1.24 (m, 12), 0.89 (s, 9), 0.14 (s, 6). Preparation of 3

To a solution of 2 (2.75 g, 5.88 mmol) in 15 ml of THF was added tetrabtuylammonium fluoride (7,06 mmol, 1.0 M in THF) in 7 min at 0°C. After stirring for 10 min, 3 ml of water and 15 ml of saturated NaHCO₃ was added. The mixture was extracted 150 ml of ether. The organic layer was dried over MgSO₄ and concentrated to give 3.1 g of a crude product. The crude product was purified by silica gel chromatography (dichloromethane:ether:ethyl acetate = 3:1:1) to give 950 mg (46% yield) of 3 as an orange oil.

¹HNMR (400 MHz, CDCl₃) δ 7.34-7.26 (m, 5), 4.72-4.65 (m, 2), 3.63 (d, 1, J = 13.0), 3.58 (d, 1, J = 13.0), 3.23 (d, 1, J = 15.0), 3.14 (bt, 1, J = 6.2), 2.82 (d, 1, J = 15.0), 2.62-2.43 (m, 4) 1.31-1.25 (m, 12).

Formulation examples for active ingredients of the formula I

(% = per cent by weight)

1. Wettable powder a) b) c)

Active ingredient according to

Tables 1-2 20 % 50 % 0.5 %

Sodium lignin sulfonate 5 % 5 % 5

Sodium lauryl sulfate 3 % - - %

Sodium diisobutylnaphthalenesulfonate - 6 % 6 % Octylphenol polyethylene glycol

ether (7-8 mol of ethylene oxide) - 2 % 2

Highly disperse silicic acid 5 % 27 % 27 %

Kaolin 67 % - % -

Sodium chloride - - 59.5 %

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

2. Emulsion concentrates a) b)

active ingredient according to

Tables 1-2 10 % 1 %

Calcium dodecylbenzenesulfonate 3 % 3 %

Octylphenol polyethylene glycol

ether (4-5 mol of ethylene oxide) 3 % 3 %

Castor oil polyethylene glycol

ether (36 mol of ethylene oxide) 4 % 4

Cyclohexanone 30 10 %

Xylene mixture 50 % 79 %

Emulsions of any desired concentation can be prepared from such concentrates by dilution with water. 3. Dusts a) b)

Active ingredient according to

Tables 1-2 0.1 % 1 %

Talc 99.9 % - Kaolin - 99 %

Ready-to-use dusts are obtained by intimate mixing of the carriers

with the active ingredient.

4. Extruded granules a) b)

Active ingredient according to

Tables 1-2 10 % 1 %

Sodium ligninsulfonate 2 % 2 %

Carboxymethylcellulose 1 % 1 %

Kaolin 87 % 96 %

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

5. Coated granules

Active ingredient according to

Tables 1-2 3 %

Polyethylene glycol (molecular

weight 200) 3 %

Kaolin 94 %

The finely ground active ingredient is applied uniformly to the kaolin, which has been moistene with polyethylene glycol, in a mixer. Dust-free coated granules are obtained in this manner.

6. Suspension concentrate a) b)

active ingredient according to

Tables 1-2 5 % 40 %

Ethylene glycol 10 % 10 %

Nonylphenol polyethylene glycol

ether (15 mol of ethylene oxide) 1 % 6 %

Sodium ligninsulfonate 5 % 10 % Carboxymethylcellulose 1 % 1 %

37% aqueous formaldehyde solution 0.2 % 0.2 %

Silicone oil in the foim of a

75% aqueous emulsion 0.8 % 0.8 %

Water 77 % 32 %

The finely ground active ingredient is intimately mixed with the additives. A suspension concentrate is thus obtained, from which suspensions of any desired concentration can be prepared by dilution with water.

7. Salt solution

Active ingredient according to

Tables 1-2 5 %

Isopropylamine 1 %

Octylphenol polyethylene glycol

ether (78 mol of ethylene oxide) 3 %

water 91 %

The compounds of the formula I are employed in unchanged form or, preferably, as compositions together with the auxiliaries customary in formulation technology, and are therefore processed in a known manner for example to emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules in, for example, polymeric substances. The methods of use, such as spraying, misting, dusting, scattering or pouring, like the nature of the compositions, are chosen according to the desired effets and the given circumstances.

Biological Examples

Example B1 : Post-emergence herbicidal action (contact herbicide)

Monocotyledonous and dicotyledonous test species are raised in plastic pots containing standard soil. At the 4-6 leaf-stage, the plants are sprayed with an aqueous suspension of the test-compounds at rates of 2 kg ai/ha (5001 water/ha) and transferred to the greenhouse for further cultivation under optimal conditions. The evaluation takes place after 18 days, whereby the rating scale of 1-9 is employed (1 = 100 % to 9 = no herbicidal effect). Ratings of 1 to 4 (especially 1 to 3) indicate good to excellent herbicidal effect. In this test, the compounds according to tables 1 and 2 show good herbicidal activity. An example for the herbicidal activity of compound 1.001 is given in Table B1: Table B1: post-emergence herbicidal action:

Compound: Avena Setaria Sinapis Stellaria

1.001 2 2 1 2

Claims

What is claimed is:

1. A triazole of the formula I

in which

2-(trimethylsilyl)ethoxymethyl;

t is 4 or 5;

R₁ is hydrogen, C₁-C₆-alkyl, OR₁₉ or NR₂₀R₂₁;

R₂ is hydrogen, C₁-C₆-alkyl, OR₁₉ or NR₂₀R₂₁, or R₁ and R₂ together form an oxo group;

R₃ is hydrogen, C₁-C₆- alkyl, C₁-C₆-alkoxy or represents together with R₂ a chemical bond;

X is oxygen, S(O)_m, NR₅ or CR₆R₇;

Y is oxygen, S(O)_p, NR₅ or CR₈R₉;

Z is oxygen, S(O)_q, NR₅ or CR₁₀R₁₁;

m, p and q are each independently of the others 0, 1 or 2;

C₁-C₄-alkoxy, COOH, C₁-C₄-alkoxycarbonyl, unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; or R₅ is C₃-C₆-alkenyl which is unsubstituted or substituted by C₁-C₄-alkoxycarbonyl, halogen, unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C_ι-C₄-alkoxycarbonyl; C₃-C₆-alkynyl which is unsubstituted or substituted by unsubstituted phenyl or by phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; C₁-C₆-alkoxycarbonyl, unsubstituted phenyl or phenyl which itself is substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

R₆, R₇, R_g, R₉, R₁₀ and R₁₁ are each independently of the others hydrogen, C₁-C₆-alkyl which is unsubstituted or substituted by hydroxy, amino, C₁-C₄-alkoxy, C₁-C₄-alkylamino or phenyl, which itself is unsubstituted or substituted by C₁-C₄-alkyl, halogen,

C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; phenyl, benzyl which are unsubstituted or substituted by C₁-C₄ alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro,

C₁-C₄-alkylthio, C₁-C₄-alkylsulfιnyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; or R₆ and R₇ or R₈ and R₉ or R₁₀ and R₁₁ together form an oxo group;

Q₁ is OR ₁₂or NR ₁₃R ₁₄;

R₁₂ is hydrogen, a group or a group ;

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl; a group , C₁-C₆-alkyl which is substituted by halogen, C₁-C₄-alkoxy,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

R₁₄ is hydrogen or C₁-C₆-alkyl;

R₁₅ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl; or C₁-C₆-alkyl, C₃-C₆-alkenyl,

C₃-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, halomethyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl; R₁₆ is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl; or C₁-C₆-alkyl, C₂-C₆-alkenyl,

C₃-C₆-cycloalkyl;

R₁₇ is hydrogen or C₁-C₆-alkyl;

R₁₈ is hydrogen or C₁-C₆-alkyl;

R₁₉ is hydrogen, a group or a group

Q is oxygen or sulfur;

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

R₂₁ is hydrogen or Q-Q-alkyl;

R_22, is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkyl substituted by halogen, cyano, COOH,

R^ is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl; or C₁-C₆-alkyl, C₃-C₆-alkenyl,

C₂-C₆-alkynyl substituted by halogen or C₁-C₄-alkoxy; or phenyl, benzyl; or phenyl, benzyl substituted by C₁-C₄-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl; or is

C₁-C₆-alkoxyalkyl, C₁-C₆-alkylcarbonyloxyalkyl, C₁-C₆-alkoxycarbonylalkyl or

C₃-C₆-cycloalkyl;

R₂₅ is hydrogen or C₁-C₆-alkyl; and

R₂₆ is hydrogen or C₁-C₆-alkyl, with the proviso that a) at least two of the substituents X,

Y and Z are carbon atoms, b) that R₁ or R₂ is OR₁₉ or NR₂₀R₂₁ if simultaneously X, Y and

Z are carbon atoms and Q₁ is OR₁₂ and c) that R₁ and R₂ are not simultaneously OR₁₉,

NR₂₀R₂₁ or both of them.

2. A compound according to claim 1, in which R₃ is hydrogen or C₁-C₆-alkyl.

3. A compound according to claim 1, in which A is hydrogen.

4. A compound of the formula I according to claim 1, in which R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are hydrogen.

5. A compound of the formula I according to claim 1, in which Q₁ is hydroxy or amino.

6. A compound of the formula I according to claim 1, in which R₁ is hydrogen.

7. A compound of the formula I according to claim 1, in which R₂ is hydrogen.

8. A compound of the formula I according to claim 1, in which R₃ is hydrogen.

9. A compound of the formula I according to claim 1, in which R₄ and R₂₂ are hydrogen.

10. A compound of the formula I according to claim 1, in which X is CR₆R₇, Y is CR₈R₉ and Z is NR₅.

11. A compound according to claim 10, in which Q₁ is hydroxy and A, R₄, R₆, R₇, R₈, R₉ and R₂₂ are hydrogen.

12. A compound of the formula I according to claim 1, in which Q₁ is hydroxy or amino.

13. 2-Oxa-3-hydroxy-3-(1,2,4-triazol-3-yl)-cyclohexane phosphonic acid according to claim 1.

14. A compound of the formula I according to claim 1, wherein the substituents Q₁ and are in trans-position.

15. A process for the preparation of compounds of formula I according to claim 1, which comprises a) for the preparation of a compound of the formula I, in which Q₁ is hydroxy, reacting a compound of the formula II ,

wherein A has the meanings given for formula I in claim 1 except for hydrogen, with a compound of the formula III

,

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I in claim 1 and A, R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, to a compound of the formula Ia

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I in claim 1 and A, R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, and optionally cleaving protecting groups A and/or R₄ and R₂₂ and further convening them into a salt;

b) for the preparation of a compound of the formula lb

in which R₁₂ is a group or a group and A, R₁, R₂, R₃, R₄, R₁₅,

R₁₆, R₂₂, X, Y and Z have the meanings given for formula I in claim 1, reacting a compound of the formula IV

with a compound of the formula V: , VI: or VII:

(R₁₆CO)₂O (VII), wherein X₁ and X₂ are halogen and R₁₅ and R₁₆ have the meanings given for formula I in claim 1, c) for the preparation of a compound of the formula I, in which Q₁ is NH₂, convening a compound of the formula Ia

in which R₁, R₂, R₃, X, Y and Z have the meanings given for formula I in claim 1 and A, R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, in the presence of NaN₃ and CF₃COOH to the corresponding azide and subsequently reducing the acide, e) for the preparation of a compound of the formula I, in which Q₁ is NHR₁₃ and R₁₃ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, hydroxy, C₁-C₆-alkylcarbonyl,

, C₁-C₆-alkyl which is substituted by halogen, C₁-C₄-alkoxy,

C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkoxycarbonyl;

4-chlorophenylthio, reacting a compound of the formula XI ,

in which R₁, R₂, R₃, R₁₃, X, Y and Z have the meanings given for formula I and R₄ and R₂₂ have the meanings given for formula I except for hydrogen in the presence of an inert solvent, or

f) for the preparation of a compound of the formula I, in which A is hydrogen and Q₁ is NR₁₃R₁₄, wherein R₁₃ and R₁₄ have the meanings given for formula I except for hydrogen or R₁₃ and R₁₄ are protecting groups, for example arylthio, especially phenylthio or 4-chlorophenylthio, reacting a compound of the formula XIII

,

wherein R₃, R₄, R₂₂, X, Y and Z have the meanings given for formula I and R₁₃ and R₁₄ have the meanings given above and convening said compound in the presence of sodium methylate and formyl hydrazine to the compound of the formula I.

16. A process for the preparation of compounds of formula I according to claim 1, in which Q₁ is NR₁₃R₁₄ and A, if bound to the 5-carbon atom of the triazole ring, is as defined in claim 1 or A, if bound to one of the 3 nitrogen atoms of the triazole ring, is hydrogen, reacting a compound of the formula la

,

in which R₁, R₂, R₃, X, Y and Z have the meanings given in claim 1 and R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, with a compound of formula XVI

Q₀-Z₀ (XVI), wherein Z₀ is a leaving group, especially halogen, and Q₀ S(O)Cl-, C(O)Cl-, PCl₄-,

C(O)Cl-C(O)- or , to form a compound of formula XVII

,

wherein A, R₁, R₂, R₃, R₄, R₂₂, X, Y, Z and Z₀ are as defined above, which is convened by reaction with a compound of formula XVIII

HNR₁₃R₁₄ (XVIII), wherein R₁₃ and R₁₄ are as defined in claim 1, and optionally cleaving the groups R₄ and R₂₂ and further convening them into a salt.

17. A process for the preparation of compounds of the formula III

,

in which R₁, R₃, X, Y and Z have the meanings given for formula I in claim 1, R₂ is hydrogen and R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, which comprises

1) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I in claim 1, with a compound of the formula IX

HOP(OR₄)OR₂₂ (IX) in which R₄ and R₂₂ have the meanings given for formula I except for hydrogen, in an inert solvent, in the presence of N,O-bis(trimethylsilyl)acetamide and trimethylsilyl trifluoromethanesulfonate at temperatures of from -78°C to 40°C, or

2) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I in claim 1, with a compound of the formula X

(CH₃)₂R₂₈SiOP(OR₄)OR₂₂ (X) in which R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen and R₂₈ is methyl or tert. -butyl, in an inert solvent, preferably dichloromethane, in the presence of a compound of the formula XV

3) reacting a compound of the formula VIII

in which R₁, R₃, X, Y and Z have the meanings given for formula I in claim 1, with a compound of the formula XVI

P(OR₄)(OR₂₂)OR₂₂ (XVI) in which R₄ and R₂₂ have the meanings given for formula I in claim 1 except for hydrogen, in an inert solvent in the presence of a base and of a silylating agent at temperatures of from -78°C to 40°C and cleavage of the resulting silyl ether with a cleaving agent in an inert solvent, in the presence of a base.

18. A herbicidal and plant-growth-inhibiting composition, which comprises one or more triazoles of the formula I according to claim 1.

19. A composition according to claim 18, which comprises between 0.1 % and 95 % of active substance of the formula I according to claims 1.

20. A method of controlling undesired plant growth, which comprises applying an effective amount of an active substance of the formula I according to claim 1, or a composition comprising this active substance to the plants or their environment.

21. A method according to claim 20, in which an amount of active substance of between 0.001 and 10 kg is applied per hectare.

22. The use of a compound according to claim 1 or of a composition comprising this active substance for controlling undesired plant growth.