WO2008074991A1 - Novel herbicides - Google Patents

Abstract

The present invention relates to novel compounds of formula (I): wherein R1, R2, R3, R4, m, R5, R6, n and Y are as defined in claim 1; or N-oxides, salts and optical isomers thereof. Furthermore, the present invention relates to processes for preparing compounds of formula (I), to intermediates used in the preparation of compounds of formula (I), to herbicidal compositions comprising compounds of formula (I) and to methods of using compounds of formula (I) to control plants or to inhibit plant growth.

Description

NOVEL HERBICIDES

The present invention relates to novel, herbicidal isoxazoline compounds, to processes for their preparation, to intermediates used in the preparation of these compounds, to compositions comprising these compounds, and to methods of using these compounds to control plants or to inhibit plant growth.

Isoxazoline compounds which display herbicidal action are described, for example, in WO 01/012613, WO 02/062770, WO 03/000686, WO 04/010165, JP 2005/035924, JP 2005/213168, WO 06/024820 and WO 07/003294. The preparation of these compounds is also described in WO 04/013106, WO 05/095352 and WO 07/003295. i

Novel isoxazoline compounds which display herbicidal and growth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula (I)

wherein

R¹ and R² are each independently of the other hydrogen, C₁-C_1OaIlCyI, Ci-Ciohaloalkyl,

C₃-C₈cycloalkyl or C₃-C₈cycloalkyl-Ci-C₃alkyl, or

R¹ and R² together with the carbon atom to which they are bonded form a C₃-C₇ring, R³ and R⁴ are each independently of the other hydrogen, C₁-C_1OaHCyI, Q-Qohaloalkyl,

C₃-C₈cycloalkyl, Ca-Cscycloalkyl-d-C^alkyl or C₁-C₆alkoxy-C₁-C₁oalkyl, or

R³ and R⁴ together with the carbon atom to which they are bonded form a C₃-C₇ring, or

R¹ with R³ or R⁴ and together with the carbon atoms to which they are bonded form a

C₅-C₈ring, or R² with R³ or R⁴ and together with the carbon atoms to which they are bonded form a

C₅-C₈ring;

R⁵ is halogen or Ci-C₆haloalkyl;

R⁶ is hydrogen, cyano, Ci-Cβalkyl, CrQalkoxycarbonyl, halogen or d-C₆haloalkyl; m is 0, 1 or 2; n is 1, 2 or 3; and

Y is one of the following groups

wherein

R⁷ is hydrogen, Q-Cioalkyl, C_ϊ-CjQalkylcarbonyl, Cj-Qohaloalkylcarbonyl, C₁- C₁₀alkoxycarbonyl, CrQohaloalkyl, C₂-Ci₀alkenyl, C₂-Ci_Oalkynyl, C₃-C₁₀cycloalkyl, C₃- Ciocycloalkyl-Cj-Cioalkyl, CrCioalkylcarbonyl-Ci-C_tQalkyl, CrC^alkylsulfonyl, C₁- C₁₀haloalkylsulfonyl or Ci-Qoalkoxy-Q-Cioalkyl;

R⁸ is hydrogen, Ci-C₁₀alkyl, Ci-Cioalkylcarbonyl, Ci-Qohaloalkylcarbonyl, C₁- Cioalkoxycarbonyl, CrC^haloalkyl, C₂-Ci₀alkenyl, C₂-C₁₀alkynyl, C₃-C_{1 O}cycloalkyl, C₃- Ciocycloalkyl-Ci-C_ϊoalkyl, halogen, thiol, hydroxy,, cyano, Crdoalkylsulfanyl, C₁- Cjohaloallcylsulfanyl, Q-CiQalkylsulfinyl, d-Ciohaloalkylsulflnyl, CrC^alkylsulfonyl, Ci-dohaloalkylsulfonyl, Ci-C₁₀alkoxy, Ci-C₁₀haloalkoxy, or NR⁹R¹⁰ wherein R⁹ and R¹⁰ are independently of each other hydrogen, Q-Cealkyl, Q-Cehaloalkyl, Q-Cβcycloalkyl, CrC_όalkylcarbonyl, CrColialoalkylcarbonyl, d-Cealkylsulfonyl, C_ϊ-C₆haloalkyl- sulfonyl, or R⁹ and R¹⁰ together form a C₃-C₈alkylene group which optionally contains one oxygen, sulfur, amino or an Ci-C₆alkylamino group; and to iV-oxides, salts and optical isomers of compounds of formula (I).

The compounds of the invention may contain one or more 'asymmetric carbon atoms, for example, in the -CR⁵R⁶- group or in the -CR³R⁴-group and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such. Further, when m is 1, the compounds of the invention are sulfoxides, which can exist in two enantiomeric forms, the adjacent carbon can also exist in two enantiomeric forms and the -CR³R⁴- group can also exist in two enantiomeric forms. Compounds of general formula (I) can therefore exist as racemates, diastereoisomers, or single enantiomers, and the invention includes all possible isomers or isomer mixtures in all proportions. It is to be expected that for any given compound, one isomer may be more herbicidal than another.

Alkyl groups, haloalkyl groups, hydroxyalkyl groups, alkoxy groups, haloalkoxy groups and alkylene groups can be straight or branched chain. Preferred alkyl groups, haloalkyl groups, hydroxyalkyl groups, alkoxy groups, haloalkoxy groups and alkylene groups each independently contain 1 to 4 carbons. Examples of alkyl groups are methyl, ethyl, n-and ώo-propyl and n-, sec-, iso- and tert-bvAy\, hexyl, nonyl and decyl. Examples of haloalkyl groups are difluoromethyl and 2,2,2-trifluoroethyl. Examples of hydroxy- alkyl groups are 1,2-dihydroxyethyl and 3-hydroxypropyl. Examples of alkoxy groups are methoxy, etlioxy, propoxy, butoxy, hexyloxy, nonyloxy and decyloxy. Examples of haloalkoxy groups are difluoromethoxy and 2,2,2-trifiuoroethoxy. Examples of alkylene groups are methylene, ethylene, «-and wo-propylene and n~, sec-, iso- and tert-butylene. Cycloalkyl groups can be in mono-, bi- or tri-cyclic form. Preferred cycloalkyl giOups independently contain 3 to 8 carbons. Examples of monocyclic cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Alkenyl and alkynyl groups and haloalkenyl groups and haloalkynyl groups can be straight or branched chain. Examples of alkenyl and alkynyl groups are allyl, but-2- enyl, 3-methylbut-2-enyl, ethynyl, propargyl and but-2-ynyl. Examples of haloalkenyl and haloalkynyl groups are trifluoroallyl and l-chloroprop-l-yn-3-yl.

Halogen means fluoro, chloro, bromo and iodo, preferably fluoro, chloro or bromo, more preferably fluoro or chloro.

The invention relates likewise to the salts which the compounds of formula (I) are able to form with amines, alkali metal and alkaline earth metal bases and quarternary ammonium bases.

Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium. The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Q-Qsalkylamines, Q-Qhydroxyalkylamines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n -propylamine, isopropylamine, the four butylamine isomers, R-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-rø-propylamine, diisopropylamine, di- n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, «-propanolamine, isopropanolamine, ΛζN-diethanolamine, N-ethylpropanolamine, N-butylethanolarnine, allylamine, n-butenyl-2-amine, rø-pentenyl- 2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, /z-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-ra~butylamme, triisobutylamine, tri-sec-butylamine, tri-«-amylamme, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as, for example, pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as, for example, anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quarternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R₃ R_bR₀R_d )]OH wherein R_a, R_b, R₀ and Ra are each independently of the others C₁-C₄OIlCyI. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example: killing, retardation, leaf bum, albinism, dwarfing and the like. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation.

Preferred values of R¹, R³, R⁴, R⁵, R⁶, m, n, Y, R⁷ and R⁸ are, in any combination, as set out below.

Preferably R¹ and R² are independently Ci-C₁₀alkyl or d-CiQhaloalkyl, more preferably Ci-C₆alkyl or d-C_δhaloalkyl, even more preferably d-Cβalkyl, yet even more preferably methyl or ethyl, most preferably methyl.

Li a preferred embodiment R¹ and R² are both methyl. hi a preferred embodiment R¹ is methyl and R² is ethyl.

Preferably R³ and R⁴ are independently hydrogen, d-C^alkyl or d-C₁₀haloalkyl, more preferably hydrogen, d-C₆alkyl or Ci-C₆haloalkyl, most preferably hydrogen.

Preferably R⁵ is halogen or trifluoromethyl, more preferably fluoro or chloro, most preferably fluoro.

Preferably R⁶ is hydrogen, methoxycarbonyl, d-C₆alkyl or halogen, more preferably hydrogen, fluoro or chloro, most preferably hydrogen or fluoro. In a preferred embodiment R⁵ is fluoro and R⁶ is hydrogen.

In a preferred embodiment R⁵ and R⁶ are both fluoro.

In a preferred embodiment R⁵ is chloro and R⁶ is hydrogen.

In a preferred embodiment R⁵ and R⁶ are both chloro.

In a preferred embodiment R⁵ is fluoro and R⁶ is chloro.

Preferably m is 1 or 2, more preferably 2.

Preferably n is 1.

Preferably Y is one of the following groups

Preferably R⁷ is hydrogen, Ci-C₁₀alkyl, Ci-C₁₀haloalkyl, C₃-docycloalkyl or C₃-

Ciocycloalkyl-Ci-Cioalkyl, more preferably hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl or cyclopropylmethyl, even more preferably methyl, ethyl or cyclopropyl, most preferably methyl or cyclopropyl.

Preferably R⁸ is hydrogen, Ci-C₁₀alkyl,

C₃-C₁₀cycloalkyl, C₃- Ciocycloalkyl-Ci-Cioalkyl, halogen, cyano, C₁-C₁QaIkOXy or Q-C^haloalkoxy, more preferably hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoro- methoxy or trifluoromethoxy, even more preferably hydrogen, methyl, ethyl, trifluoromethyl or chloro, most preferably hydrogen, methyl, ethyl or trifluoromethyl. A group of preferred compounds of formula (I) comprises those wherein Y is

1,2,4-triazolyl which is optionally substituted by one to two substituents independently selected from Ci-C₆alkyl, d-Cehaloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-Ci-C₆-alkyl, halogen, cyano, Ci-C₆alkoxy or Ci-C₆haloalkoxy, more preferably wherein Y is 1,2,4- triazolyl which is optionally substituted by one to two substituents independently selected from methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy, even more preferably wherein Y is 1,2,4-triazolyl which is optionally substituted by one to two substituents independently selected from methyl, ethyl, trifluoromethyl, cyclopropyl or chloro, most preferably wherein Y is 1,2,4-triazolyl which is optionally substituted by one to two substituents independently selected from methyl, ethyl, trifluoromethyl or cyclopropyl. A group of especially preferred compounds of formula (I) comprises those wherein Y is l,2,4-triazol-3-yl which is optionally substituted by one to two substituents independently selected from Q-dsalkyl, Ci-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cyclo- alkyl-Ci-C₆-alkyl, halogen, cyano, Ci-C₆alkoxy or Q-C_fjhaloalkoxy, more preferably methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difiuoromethoxy or trifluoromethoxy, even more preferably methyl, ethyl, trifluoromethyl, cyclopropyl or chloro, most preferably methyl, ethyl, trifluoromethyl or cyclopropyl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is

N-N R

A group of especially preferred compounds of formula (I) comprises those wherein Y is

A group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is l,5-dimethyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -methyl- 5 -trifluoromethyl- 1 ,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 5-chloro-l-methyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -ethyl- l,2,4-triazol-3-yl. A group of especially preferred compounds of formula (I) comprises those wherein Y is l-ethyl-5-methyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 4-methyl-l,2,4-triazol-3-yl. A group of especially preferred compounds of formula (I) comprises those wherein Y is 4,5-dimethyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 4-methyl-5-trifluoromethyl-l,2,4-triazol-3-yl. A group of especially preferred compounds of formula (I) comprises those wherein Y is 5-chloro-4-methyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 5-ethyl-4-methyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 4-cyclopropyl-5-ethyl-l,2,4-triazol-3-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is l,2,4-triazol-5-yl which is optionally substituted by one to two substituents independently selected from Q-Qalkyl, Ci-C₆haloalkyl, C₃-C_όcycloalkyl, C₃-C₆cyclo- alkyl-Q-Ce-alkyl, halogen, cyano, Q-Qalkoxy or Q-C_δhaloalkoxy, more preferably methyl, ethyl, monofiuoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclo- propylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoromethoxy or trifmoromethoxy, even more preferably methyl, ethyl, trifluoromethyl or chloro, yet even more preferably methyl, trifluoromethyl or chloro, most preferably methyl or trifluoromethyl. A group of especially preferred compounds of formula (I) comprises those wherein Y is

N-N V

A group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-l,2,4-triazol-5-yl. A group of especially preferred compounds of formula (I) comprises those wherein Y is l,3-dimethyl-l,2,4-triazol-5-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-3-trifluoromethyl-l,2,4-triazol-5-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 3-chloro- 1 -methyl- 1 ,2,4-triazol-5-yl.

A group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -ethyl- l,2,4-triazol-5-yl. A group of especially preferred compounds of formula (I) comprises those wherein Y is l-ethyl-3-methyl-l,2,4-triazol-5-yl.

The compounds of the invention may be made by a variety of methods, for example by the methods described in the Schemes below.

Methods of halogenation, alkylation and oxidation

1) The compounds of formula (I) wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined above, m is 1 or 2, and n is 1, can be prepared by processes known per se, by reacting e.g. a compound of formula (Ia)

wherein R¹, R², R³, R⁴ and Y are as defined above and m is 1 or 2, in a single step or stepwise in succession with a compound of formula R⁵-X and/or R⁶-X, wherein R⁵ and R⁶ are as defined above and X is a suitable leaving group e.g. halide, such as bromide or iodide, a carboxylate, such as acetate, an alkylsulfonate, such as methylsulfonate, an arylsulfonate, such as p-toluenesulfonate, a haloalkylsulfonate, such as trifluoromethyl- sulfonate, an imide, such as succinimide, a sulfonimide, such as bis(phenylsulfonyl)- imide, or an arylsulfmate, such as p-toluenesulfinate, in the presence of a base, e.g. an alkyl-lithium compound, such as methyl-lithium, n-butyl-lithium or tert-butyl-lithium, a lithium dialkylamide, such as lithium diisopropylamide, a metal hydride, preferably an alkali metal hydride, such as sodium hydride, or an alkali metal amide, such as sodium amide, a metal bis(tri(C₁-C₆alkyl)silyl)amide, such as lithium bis(trimethylsilyl)amide, a metal alkoxide, such as potassium tert-butoxide, or a phosphazene base, such as N^r-tert- butyl-JV,N,N',N',iV",N"-hexamethylphosphorimidic triamide ("Pi-t-Bu"), 1-tert-butyl- 2,2,4,4,4-pentakis(dimethylamino)-2-lambda⁵,41ambda⁵-catenadi(phosphazene) ("P₂-t- Bu"), l-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2-lambda⁵,41ambda⁵-catenadi- (phosphazene) ("P₂-Et") and 2-tert-butylimino-2-diethylamino-l,3-dimethyl-perhydro- 1,3,2-diazaphosphorine ("BEMP"), optionally in the presence of a diluent, preferably an inert solvent, e.g. a hydrocarbon, an ether, such as tetrahydrofuran, an amide, such as N,N-dimethylformamide, or a halogenated hydrocarbon, such as dichloromethane, or mixtures thereof and optionally in the presence of a complexing agent, such as hexamethylphosphoramide or tetramethylethylenediamine in a temperature range of from -120⁰C to 100⁰C, preferably from -8O⁰C to 5O⁰C. Such processes are known in the literature and are described, for example, in J. Med. Chem., 2003 (46) 3021-3032; J. Org. Chem., 2003 (68) 1443-1446; J. Org. Chem., 2002 (67) 5216-5225, J. Org. Chem., 2002 (67) 3065-3071, Heterocycles 2003 (59) 161-167 and WO06/024480.

2) The compounds of formula (I) wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined above, m is 1 or 2, and n is 1, can be prepared by processes known per se, by reacting e.g. a compound of formula (Ib)

wherein R¹, R², R³, R⁴, R⁶ and Y are as defined above and m is 1 or 2, with a compound of formula R⁵-X, wherein R⁵ is halogen and X is a suitable leaving group as defined in 1), in the presence of a base as defined in 1), optionally in the presence of a diluent as defined in 1), preferably an inert solvent, and optionally in the presence of a complexing agent as defined in 1) in a temperature range of from -12O⁰C to 100⁰C, preferably from -8O⁰C to 5O⁰C.

3) The compounds of formula (I) wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined above, m is 1 or 2, and n is 1, can be prepared by processes known per se, by reacting e.g. a compound of formula (Ic)

wherein R¹, R², R³, R⁴, R⁵ and Y are as defined above and m is 1 or 2, with a compound of formula R⁶-X, wherein R⁶ is cyano, Ci-C₆alkyl, Ci-C_δalkoxycarbonyl or halogen and X is a suitable leaving group as defined in 1), in the presence of a base as defined in 1), optionally in the presence of a diluent as defined in 1) and optionally in the presence of a complexing agent as defined in 1) in a temperature range of from -12O⁰C to 100⁰C, preferably from -8O⁰C to 5O⁰C.

4) The compounds of formula (I) wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined above, m is 1 or 2, and n is 1, can, furthermore, be prepared by processes known per se by starting from a compound of formula (Id)

wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined, above and reacting those compounds with a suitable organic or inorganic oxidising agent, e.g. a peroxy acid, such as 3-chloro- peroxybenzoic acid, peracetic acid or hydrogen peroxide, an alkoxyperoxide or a periodate, such as sodium periodate, optionally in the presence of a catalyst, such as ruthenium(III) chloride, optionally in the presence of a diluent, such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an alcohol, e.g. methanol, a polar solvent, e.g. ΛζAf-dimethylformamide, acetonitrile, water or acetic acid, or a mixture thereof. The reactions are usually carried out in a temperature range of from -8O⁰C to 15O⁰C, preferably from -2O⁰C to 12O⁰C. Such processes are known in the literature and are described e.g. in J. Org. Chem., 2003 (68) 3849-3859; J. Med. Chem., 2003 (46) 3021-3032; J. Org. Chem., 2003 (68) 500-511; Bioorg. Med. Chem., 1999 (9) 1837-1844. One equivalent of oxidizing agent is required to convert a sulfide to the corresponding sulfoxide. Two equivalents of oxidizing agent are required to convert a sulfide to the corresponding sulfone.

5) The compounds of formula (Ig) wherein R¹, R², R³, R⁴, R⁵ and Y are as defined above, can be prepared, for example, by starting from a compound of formula (Ie) wherein R¹, R², R³, R⁴ and Y are as defined above

(Ie) (If)

(ig) by reacting those compounds with a halogenating agent, e.g. bromine or an N-halo- succinimide, such as N-chlorosuccinimide or N-bromosuccinimide, to form compounds of formula (If) wherein R¹, R², R³, R⁴ and Y are as defined above, and X^c is halogen, optionally in the presence of a diluent, e.g. acetic acid or a halogenated hydrocarbon, such as carbon tetrachloride or dichloromethane, in a temperature range of from -8O⁰C to 12O⁰C, preferably from -2O⁰C to 6O⁰C. The compounds of formula (If) wherein R¹, R², R³, R⁴ and Y are as defined above and X^c is halogen can then be oxidised directly as described in 4), or optionally in a second step reacted with a compound of formula

M-R⁵

wherein R⁵ is fluoro and M-R⁵ is a suitable salt or an organometal compound in which M is e.g. Li, MgBr, Na, K, Ag or tetraalkylammonium, optionally in the presence of a Lewis acid, e.g. SnCl₄, optionally in the presence of a complexing agent, e.g. hexa- methylphosphoramide ("HMPA") or l,3-dimethyl-3,4,5,6-tetrahydro-2(lH)- pyrimidinone ("DMPU"), and optionally in the presence of a diluent, e.g. acetonitrile, dichloromethane, diethyl ether or tetrahydrofuran, in a temperature range of from -12O⁰C to 100⁰C, preferably from -8O⁰C to 8O⁰C. Such processes are known in the literature and are described, for example, in J. Org. Chem., 1998 (63) 3706-3716; J. Chem. Soc. Perkin Trans., 1995 (22) 2845-2848; Synthesis 1982 (2), 131-132; Liebigs Annalen, 1993, 49-54 and Synth. Commun., 1990 (20) 1943-1948.

6) The compounds of formula (Ii) wherein R¹, R², R³, R⁴, R⁵, R⁶ and Y are as defined above, can be prepared, for example, by starting from a compound of formula (Ie) wherein R¹, R², R³, R⁴ and Y are as defined above

(Ie) (Ih)

(IO

by reacting those compounds with a halogenating agent, e.g. bromine or an iV-halo- succinimide, such as TV-chlorosuccinimide or N-bromosuccinimide, to form compounds of formula (Ig) wherein R¹, R², R³, R⁴ and Y are as defined above and X^c is halogen, optionally in the presence of a diluent, e.g. acetic acid or a halogenated hydrocarbon, such as carbon tetrachloride or dichloromethane, in a temperature range of from -80⁰C to 12O⁰C, preferably from -2O⁰C to 6O⁰C. The compounds of formula (Ig) wherein R¹, R², R³, R⁴ and Y are as defined above and X^c is halogen can then be oxidised directly as described in 4) or optionally in a second or third step reacted with compounds of formula

M-R⁵ and / or M-R⁶,

wherein R⁵ and / or R⁶ are fluoro and M-R⁵ and / or M-R⁶ are a suitable salt or an organometal compound in which M is e.g. Li, MgBr, Na, K, Ag or tetraalkylammonium, optionally in the presence of a Lewis acid, e.g. SnCl₄, optionally in the presence of a complexing agent, e.g. hexamethylphosphoramide ("HMPA") or l,3-dimethyl-3 ,4,5,6- tetrahydro-2(lH)-pyrimidinone ("DMPU"), and optionally in the presence of a diluent, e.g. acetonitrile, dichloromethane, diethyl ether or tetrahydrofuran, in a temperature range of from -120⁰C to 100⁰C, preferably from -8O⁰C to 8O⁰C. Such processes are known in the literature and are described, for example, in J. Org. Chem., 1998 (63) 3706- 3716; J. Chem. Soc. Perkin Trans., 1995 (22) 2845-2848; Synthesis 1982 (2), 131-132; Liebigs Annalen, 1993, 49-54 and Synth. Commun., 1990 (20) 1943-1948. Methods for Coupling Reactions

7) The compounds of formula (Id) as defined in 4) can be prepared by reacting a compound of formula (II) wherein R⁵, R⁶ and Y are as defined above and X^A is a leaving group such as halide e.g. bromide or chloride, an alkylsulfonate, e.g. methylsulfonate, an arylsulfonate, e.g. p-toluenesulfonate, or a halo alkylsulfonate, e.g. trifluoromethyl- sulfonate, with thiourea, optionally in the presence of a diluent e.g. acetonitrile or an alcohol, e.g. ethanol, optionally in the presence of an alkali iodide, e.g. sodium iodide or potassium iodide, in a temperature range of from -3O⁰C to 100⁰C, preferably from 0⁰C to 80⁰C, to give an isothiourea intermediate of formula (IV), which is reacted with a compound of formula (V)

(III)

wherein R¹, R², R³ and R⁴ are as defined above, and X^B is a suitable leaving group such as halogen, e.g. chloro, an alkylsulfinyl group, an arylsulfmyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, e.g. methylsulfonyl, an arylsulfonyl group, e.g. p-toluene- sulfonyl, a haloalkylsulfonyl group, e.g. trifiuoromethylsulfonyl, or nitro, in the presence of a base, such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydro gencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of an alkali iodide, e.g. sodium iodide or sodium bromide, optionally in the presence of a diluent, such as an alcohol, e.g. ethanol, an ether, e.g. 1,4-dioxane or tetrahydrofuran, a polar solvent, e.g. water, acetonitrile or N,N- dimethylformamide, or a mixture of solvents, e.g. a mixture of 1,4-dioxane and water, in a temperature range of from 2O⁰C to 200⁰C, preferably from 5O⁰C to 15O⁰C, optionally in the presence of an inert gas e.g. nitrogen, and optionally under microwave irradiation. Such processes are known in the literature and are described, for example, in WO 04/0131106.

8) A further method of preparing intermediates of formula (IV), wherein R⁵, R⁶ and Y are as defined above, is to react a compound of formula (III), wherein R⁵, R and Y are as defined above, with thiourea in the presence of an acid, for example a mineral acid, such as hydrochloric acid or hydrobromic acid, or sulfuric acid, or an organic acid, such as trifluoroacetic acid, and optionally in the presence of a diluent, such as an ether, e.g. 1,4-dioxane or tetrahydrofuran, a polar solvent, e.g. water or ΛζiV-dimethyl- formamide, or a mixture of solvents, e.g. a mixture of 1,4-dioxane and water, in a temperature range of from 2O⁰C to 27O⁰C, preferably from 20⁰C to 15O⁰C, optionally under microwave irradiation. Such processes are known in the literature and are described, for example, in Buchwald and Neilsen, JACS, 110(10), 3171-3175 (1988); Frank and Smith, JACS, 68, 2103-2104 (1946); Vetter, Syn. Comm., 28, 3219-3233 (1998). The intermediate IV is then reacted with a compound of formula (V) as described in 7) to yield a compound of formula (Id) as described in 7).

9) A further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (VI) wherein R⁵, R⁶ and Y are as defined above

(Vl) (Id) with a compound of formula (V) as defined in 7), in the presence of a base, e.g. potassium carbonate, optionally in the presence of a diluent, e.g. an amide, such as N,N- dimethylformamide, or an alcohol, such as ethanol, in a temperature range of from O⁰C to 100⁰C, preferably from 20⁰C to 50⁰C, and optionally under an inert atmosphere, e.g. nitrogen. Such processes are known in the literature and are described, for example in WO 01/012613, WO 02/062770 and WO 04/010165. 10) Alternatively, the compounds of formula (Id) as defined in 4) can be prepared by reacting a compound of formula (V) as defined in 7) with thiourea, optionally in the presence of a diluent e.g. an alcohol, e.g. ethanol, in a temperature range of from -3O⁰C to 15O⁰C, preferably from 0⁰C to 80⁰C, to give an isothiourea intermediate of formula (VII),

(Id)

which is then reacted with a compound of formula (II) as defined in 7) in the presence of abase, such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydrogencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of a diluent, such as an alcohol, e.g. ethanol, a polar solvent, e.g. water or N,N-dimethylformamide, or a mixture of solvents, in a temperature range of from O⁰C to 200⁰C, preferably from O⁰C to 100⁰C. Such processes are known in the literature and are described, for example, in WO 05/095352.

H) A further method of preparing the compounds of formula (Id) as defined in 4) is to react an organometal reagent of formula (VIII) wherein R⁵, R⁶ and Y are as defined above and M^B is a group such as MgCl, MgBr, ZnBr or Li,

(Id) with a compound of formula (IX) wherein R¹, R², R³ and R⁴ are as defined above optionally in the presence of a diluent, e.g. an ether, such as diethyl ether or tetrahydro- furan, in a temperature range of from -5O⁰C to 100⁰C, preferably from -2O⁰C to 5O⁰C, and optionally under an inert atmosphere, e.g. nitrogen. The disulfide of formula (IX) can be formed in situ or prepared separately, e.g. by oxidation of the corresponding sulfide, which in turn is described in JP 2004/224714. Similar processes are known in the literature and are described, for example in J. Chem. Soc. Chem. Commun., 1991, 993- 994, J. Chem. Soc. Perkin Trans. 1992 (24) 3371-3375, J. Org. Chem., 1989 (54) 2452- 2453.

12) A further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (Ha) wherein R⁵, R⁶ and Y are as defined above, and X^D is functional group that may be cleaved as a radical, e.g. a halogen, such as bromo or chloro,

(Id) with a radical initiator or a precursor thereof and with a compound of formula (IX) as defined in 11), optionally in the presence of a base, e.g. a phosphate or hydrogen-

^% phosphate such as disodium hydrogenphosphate, a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydrogencarbonate, optionally in the presence of a diluent, e.g. a polar solvent, such as water or Λζ N-dimethylformamide, or mixtures thereof, in a temperature range of from -5O⁰C to 18O⁰C, preferably from -20⁰C to 50⁰C, and optionally under an inert atmosphere, e.g. nitrogen. As radical initiator or precursors can be used e.g. sodium dithionite or sodium hydroxymethanesulfinate.

13) A further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (II) as defined in 7),

(Id) with a compound of formula (IX) as defined in 11), in the presence of a reducing agent, e.g. a hydride, such as sodium borohydride, a metal, such as zinc, or a hydrosulfite, such as sodium hydrosulfite, optionally in the presence of a base, e.g. a hydroxide, such as sodium hydroxide, a phosphate or hydrogen phosphate, such as disodium hydrogen phosphate, or an amine, such as triethylamine, optionally in the presence of a diluent, e.g. water, an acid, such as acetic acid or hydrochloric acid, an alcohol such as methanol, an ether such as tetrahydrofuran or mixtures thereof, in a temperature range of from -5O⁰C to 18O⁰C, preferably from -2O⁰C to 5O⁰C, and optionally under an inert atmosphere, e.g. nitrogen.

Methods for the derivatisation of group Y

14) The compounds of formula (XIIa), (XIIb) and/or (XIIc) wherein R⁷ and R⁸ is as defined above and R¹² is hydrogen, Q-Cioalkyl, Ci-Cioalkoxycarbonyl, formyl, or the group Q can be prepared by reacting a compound of formula (XI)

(Q) wherein R⁸ is as defined above and R¹² is hydrogen, Cj-Cioalkyl, d-Qoalkoxycarbonyl, formyl, or the group Q, with a compound of formula R⁷-X^E wherein R⁷ is as defined above and X^E is a suitable leaving group e.g. halide, such as bromide or iodide, a carboxylate, such as acetate, an alkylsulfonate, such as methylsulfonate, an arylsulfonate, such as p-toluenesulfonate, a haloalkylsulfonate, such as trifluoromethylsulfonate, in the presence of a base, e.g. a carbonate, such as potassium carbonate, a hydroxide, such as potassium hydroxide, a metal hydride, such as sodium hydride, optionally in the presence of a diluent, e.g. an ether, such as tetrahydrofuran, an amide, such as iV,iV-dimethyl- formamide, an alcohol, such as methanol, acetonitrile or acetone or mixtures thereof and optionally in the presence of a phase transfer catalyst, such as trimethylammonium bromide, in a temperature range of from 120⁰C to 200⁰C, preferably from 2O⁰C to 8O⁰C. Depending on the reaction conditions, compounds of formula (XIIa), (XIIb) and (XIIc) are obtained exclusively or as mixtures in varying ratios. Such processes are known in the literature and are described, for example, in Journal of Organic Chemistry, 69(4), 1397-1400; 2004, Bioorganic & Medicinal Chemistry Letters, 2001, 11(24), 3165-3168 15) The compounds of formula (XIVa), wherein R⁷ is as defined above, R¹² is as defined in 14) and X^D is halogen can be prepared by reacting a compound of formula

(XIIIc) (XIVc) wherein R⁷ is as defined above, R¹² is as defined in 14) and X^F is hydroxy, thiol, nitro or amino. For X^F is hydroxy, the reaction can be carried out in the presence of a halogenating reagent such as phosphorus oxychloride or phosphorus pentachloride, optionally in the presence of an inert solvent such as an amide, e.g. N, iV-dimethyl- formamide, in a temperature range from 0°C to 25O⁰C, preferably from 20°C to 200⁰C. Similar processes are known in the literature and are described in, e.g. U.S. 4610717, DE 3631511. For X^F is thiol, the reaction can be carried out using chlorine, in the presence of a diluent such as a halogenated hydrocarbon, e.g. chloroform and in a temperature range from O⁰C to 150⁰C, preferably from 20⁰C to 80⁰C. Similar processes are known in the literature and are described in, e.g. Ind. J. Chem., 1975 (13) 851, Synthetic Commun. 2001 (31) 2447-2456. For X^F is nitro, the reaction can be carried out in the presence of a nucleophilic halogen source e.g. hydrochloric acid or hydrobromic acid, in the presence of a diluent such as water or an alcohol, e.g. ethanol. The reactions are usually carried out in a temperature range from -2O⁰C to 150⁰C, preferably from 0⁰C to 100⁰C. Similar processes are known in the literature and are described in, e.g. J. Med. Chem., 1996 (39) 3019-3029, Tetrahedron 1990 (46) 3211-3232. For X^F is amino, the starting material is usually reacted with a diazotisation reagent e.g. sodium nitrite/hydrochloric acid, in the presence of a nucleophilic halogen source, e.g. copper chloride, copper bromide or potassium iodide, optionally in the presence of a diluent such as water in a temperature range from -5O⁰C to 150⁰C, preferably from -10⁰C to 100⁰C to give a compound of formula (XIIIa). Similar processes are known in the literature and are described in, e.g. Xecheng Huaxue 2003 (11) 351-353, Xecheng Huaxue 2004 (12) 191-193. The compounds of formula (XIVb) can similarly be prepared from a compound (XIIIb) and the compounds of formula (XIVc) can similarly be prepared from a compound of formula (XIIIc).

16) The compounds of formula (XIIb) as defined in 14) can also be prepared by reacting a compound of formula (XIVb) as defined in 15)

(XIVb) (XIIb)

(XIVc) (^{χi lc}) with a compound of formula M^A-R⁸, wherein R⁸ is a halide e.g. iodide or fluoride, an alkyl, alkenyl, alkynyl or haloalkyl, such as methyl, allyl, propynyl or trifluoropropyl, cyanide, an alkoxy, such as methoxide, an alkylsulfanyl, such as thiomethoxide, and M^A is a suitable counterion such as sodium, potassium or ammonium. Alternatively, the reaction can be carried out using H-R⁸, wherein R⁸ is as defined above or NR⁹R¹⁰, such as morpholine, optionally in the presence of a base as defined in 1), optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. 1,2-dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound, e.g. toluene, an alcohol, e.g. methanol, an amide, e.g. ΛζN-dimethyl- formamide, water or a mixture thereof. The reactions are usually carried out in a temperature range from -5O⁰C to 200⁰C, preferably from 0⁰C to 150⁰C to give a compound of formula (XIIb). The compounds of formula (XIIc) can similarly be prepared from a compound of formula (XIVc). Similar processes are known in the literature and are described in, e.g. Synthesis, 2006 496, Synthesis 1998 (9) 1357-1361, Journal of Medicinal Chemistry, 33(4), 1230-41; 1990; Bulletin de Ia Societe Chimique de France, (7-8, Pt. 2), 1649-53; 1975; Synthetic Communications, 31(16), 2447-2456; 2001, U.S., 4762828, 09 Aug 1988, Journal of Medicinal Chemistry, 23(4), 402-5; 1980, Journal of Heterocyclic Chemistry, 15(3), 439-44; 1978.

17) The compounds of formula (XVIa), wherein R⁷ is as defined above and R¹² is as defined in 14) can be prepared by reacting a compound of formula (XVa)

(XVb) (XVIb)

(XVc) (XVIc) wherein R⁷ is as defined above, R¹² is as defined in 14) and X^G is -SH or amino. For X^G is thiol, this reaction can be carried out under photochemical conditions, or, alternatively, with an oxidising agent, e.g. nitric acid, or a peroxide e.g. hydrogen peroxide or peroxyacetic acid, optionally in the presence of a diluent, e.g. an alcohol, e.g. methanol, an acid, e.g. acetic acid, water or a halogenated hydrocarbon, e.g. 1,2-dichloroethane or carbon tetrachloride or mixtures thereof. The reactions are usually carried out in a temperature range from -5O⁰C to 200⁰C, preferably from 0⁰C to 150⁰C. Similar processes are known in the literature and are described in, e.g. Synthesis, (1), 156-160; 2006, Tetrahedron 2004 (60) 851-860, Bioorganic & Medicinal Chemistry, 13(2), 363- 386; 2004. For X^G is amino, the starting material is usually reacted with a diazotisation reagent e.g. sodium nitrite/hydrochloric acid, in the presence of water or an alcohol, e.g. methanol in a temperature range from -50⁰C to 150⁰C, preferably from -1O⁰C to 100⁰C to give compounds of formula (XIIIa). Similar processes are known in the literature and are described in, e.g. Tetrahedron, 2000 (56) 9495-9502. The compounds of formula (XVIb) can similarly be prepared from a compound (XVb) and the compounds of formula (XVIc) can similarly be prepared from a compound of formula (XVc). 18) The compounds of formula (XIIa) as defined in 14) can also be prepared by reacting a compound of formula (XVIa) as defined in 17)

(XVIa) (^χιla)

(XVIc) (XIIc) with a base , e.g. an alkyl-lithium compound, such as methyl-lithium, H-butyl-lithium or tert-butyl-lithium, a lithium dialkylamide, such as lithium diisopropylamide, a metal hydride, preferably an alkali metal hydride, such as sodium hydride, or a metal bis(tri(Ci- C₆alkyl)silyl)amide, such as lithium bis(trimethylsilyl)amide, followed by a compound of formula R⁸-X^E, wherein R⁸ is as defined above and X^E is as defined in 14), optionally in the presence of a metal chelator e.g. hexamethylphosphoryl triamide, 18-crown-6, optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. 1,2- dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound, e.g. toluene, an amide, e.g. ΛζiV-dimethylformamide, water or a mixture thereof. The reactions are usually carried out in a temperature range from -100⁰C to 150⁰C, preferably from -80°C to 100⁰C to give a compound of formula (XIIa). The compounds of formula (XIIb) can similarly be prepared from a compound (XVIb) and the compounds of formula (XIIc) can similarly be prepared from a compound of formula (XVIc). Similar processes are known in the literature and are described in, e.g. Heterocycles 1985 (23) 1645-9, Heterocycles 2003 (60) 351-363, Synthesis, 2006 (1) 156-160; U.S., 4481360, Chemische Berichte, 1983, 116(10), 3513-15, Journal of Heterocyclic Chemistry, 15(3), 439-44; 1978.

General methods for making heterocyclic intermediates 19) The compounds of formula (II) as defined in 7) can be prepared by reacting a compound of formula (III) as defined in 8)

(III) (II) with a halogenating agent, such as hydrogen chloride, hydrogen bromide, phosphorous tribromide, phosphorous trichloride or thionyl chloride, or with an alkyl-, aryl- or halo- alkylsulfonyl chloride, such as methanesulfonyl chloride, p-toluenesulfonyl chloride or trifluoromethylsulfonyl chloride, or with a combination of carbon tetrabromide and triphenyl phosphine, optionally in the presence of an inert solvent, e.g. a halogenated hydrocarbon, such as dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an ether, such as diethyl ether or tetrahydrofuran, or an acid, such as acetic acid, optionally in the presence of a base, e.g. an amine, such as triethyl amine, in a temperature range from -50°C to 100⁰C, preferably from O⁰C to 5O⁰C. Such processes are known in the literature and are described, for example, in J. Med. Chem.2005 (48) 3438-3442, J. Org. Chem., 2005 (70) 2274-2284, Org. and Biomolecular Chem., 2005 (3) 1013-1024, Bioorg. Med. Chem. 2004 (13) 363-384, Tetrahedron Asymmetry 2004 (15) 3719-3722.

20) Alternatively, the compounds of formula (Ha), wherein R⁵, R⁶ and Y are as defined above, and X^c is a leaving group such as halogen, e.g. bromo or chloro, can be prepared

(XVII) (Ha) by reacting a compound of formula (XVII) wherein R⁵, R⁶ and Y are as defined above, with a compound of formula R^{1 l}-X^c, wherein X^c is a leaving group such as halogen, e.g. bromo or chloro, and R is a functional group that may be cleaved to generate X as a radical, optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydro- furan, an aromatic compound, e.g. toluene, a polar solvent, e.g. acetonitrile,

N, JV-dimethylformamide or water, or a mixture thereof. The reactions are usually carried out in a temperature range from -50°C to 12O⁰C, preferably from -5°C to 100⁰C. The reactions maybe carried out optionally in the presence of light and or a radical initiator such as a peroxide, e.g. dibenzoylperoxide, or an azo compound, e.g. N,N'-azobis-

1 1 f •

(isobutyronitrile). Suitable compounds of formula R -X include compounds in which R¹¹ is a succinimido group, e.g. N-chlorosuccinimide and iV-bromosuccinimide. Similar processes are known in the literature and are described, e.g. Tetrahedron, 1988 (44) 461- 469; Journal of Organic Chemistry, 1981 (46) 679-686; J. Chem. Soα, Perkin Trans 1, 1985 (6), 1167-1170.

21) The compounds of formula (Ilia), wherein R⁶ is hydrogen or Ci-C₆alkyl and Y is as defined above, can be prepared

(XVIII) (Ilia) by reacting a compound of formula (XVIII) wherein R⁶ is hydrogen or Q-C_όalkyl and Y is as defined above with a reducing agent, e.g. a metal hydride, such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium boro- hydride, or diborane, optionally in the presence of an inert solvent, e.g. an ether, such as diethyl ether, 1,4-dioxane or tetrahydrofuran, an alcohol, such as methanol or ethanol, or an aromatic hydrocarbon, such as toluene. Such reactions are usually carried out in a temperature range from -50°C to 100°C, preferably from 0⁰C to 8O⁰C. Such processes are known in the literature and are described, for example, in Tetrahedron Asymmetry, 2004 (15) 363-386; J. Med. Chem., 2002 (45) 19-31; Justus Liebigs Annalen der Chemie, 1978 (8) 1241-49.

22) Alternatively, the compounds of formula (HIb), wherein Y is as defined above, can be prepared by reacting a compound of formula (XX),

(XX) (IMb) wherein Y is as defined above and R¹² is hydrogen or Ci-C₁₀alkyl, with a reducing agent, e.g. a metal hydride, such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium borohydride, or diborane, optionally in the presence of an inert solvent, e.g. an ether, such as diethyl ether, 1,4-dioxane or tetrahydrofuran, an alcohol, such as methanol or ethanol, or an aromatic hydrocarbon, such as toluene. Such reactions are usually carried out in a temperature range from -50°C to 100°C, preferably from O⁰C to 8O⁰C. Such processes are known in the literature and are described, for example, in Tetrahedron Asymmetry 2004 (15) 3719-3722, J. Med. Chem., 2004 (47) 2176-2179, Heterocyclic Communications 2002 (8) 385-390, J. Antibiotics, 1995 (48) 1320-1329.

23) Additionally, the compounds of formula (lie) wherein Y is as defined above and X^D is halogen, such as bromo or chloro, can be prepared from a compound of formula (XXI) wherein Y is as defined above

(XXi) (Hc) by reacting with a reagent of formula (XXII) wherein X^D is halogen, such as bromo or chloro, in the presence of a diluent such as a halogenated hydrocarbon such as dichloromethane, a hydrocarbon such as hexane, an alcohol such as ethanol, N₁N- dimethylformamide, tetrahydrofuran or a mixture thereof. The preparation of aromatic benzyl halides is described in Tetrahedron Letts. 2000 (41) 5161-5164. The preparation of the reagent XXI is described in J. Org. Chem. 1980 (45) 384-389.

24) The synthesis of 1,2,4-triazoles, 1 ,2,4-triazolines and derivatives thereof are well known within the literature, so for a general discussion of their synthesis see Temple, C, The Chemistry of Heterocyclic Compounds: 1,2,4-triazoles; VoI 37, Montgomery, J. A., ed., John Wiley and Sons, New York, 1981; Mustafa, Suni M.; Nair, Vipin A.; Chittoor, Joshua P.; Krishnapillai, Sreekumar. Synthesis of 1,2,4-triazoles and thiazoles from thiosemicarbazide and its derivatives. Mini-Reviews in Organic Chemistry (2004), 1(4), 375-385; Curtis, A. D. M. Product class 14: 1,2,4-triazoles. Science of Synthesis (2004), 13 603-639; Garratt, Peter J., 1 ,2,4-Triazoles. Comprehensive Heterocyclic Chemistry II (1996), 4 127-163, 905-1006;

Balasubramanian, Marudai; Keay, James G.; Scriven, Eric F. V.; Shobana, Navayath. Approaches to the synthesis of 1-substituted 1,2,4-triazoles. Heterocycles (1994), 37(3), 1951-75; Kadaba, Pankaja K. 1,2,4-Triazolines. Advances in Heterocyclic Chemistry (1989), 46, 169-281. The compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2- butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, ΛζiV-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzόate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma- butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy- propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, ra-hexane, n-octylamine, octa- decanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, Methylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981. Further adjuvants that can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers. The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters offish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters Of C₈-C₂₂ fatty acids, especially the methyl derivatives OfC₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.

The application and action of the oil additives can be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated Ci₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenof ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for .example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US-A- 4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent. The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight): Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % 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: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention.

Formulation Examples for herbicides of formula (T) (% = % by weight)

Fl. Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% castor oil polyglycol ether 4% - 4% 4%

(36 mol of ethylene oxide) octylphenol polyglycol ether - 4% - 2%

(7-8 mol of ethylene oxide)

NMP - - 10% 20% arom. hydrocarbon mixture 85% 78% 55% 16%

C₉-C₁₂

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

F2. Solutions a) t>) c) d) active ingredient 5% 10 % 50 % 90 % l-methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 % polyethylene glycol MW 400 20% 10 % -

NMP - - 30% 10% arom. hydrocarbon mixture 75 % 60 %

C₉-C₁₂

The solutions are suitable for use in the form of microdrops. F3. Wettable powders a) b) c) Φ active ingredient 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1% 2% -

(7-8 mol of ethylene oxide) highly dispersed silicic acid 1% 3% 5% 10% kaolin 88% 62% 35%

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

F4. Coated granules a) b) c) active ingredient 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%

(diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.

F5. Coated granules a) b) c) active ingredient 0.1 % 5% 15% polyethylene glycol MW 200 1.0% 2% 3% highly dispersed silicic acid 0.9 % 1% 2% inorganic carrier 98.0 % 92% 80%

(diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. F6. Extruder granules a) b) c) d) active ingredient 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 97.0 % 93% 90% ^■ 79 %

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

F7. Dusts a) b) c) active ingredient 0.1% h% 5% talcum 39.9% 49% 35% kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2 % (15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %

37 % aqueous formaldehyde 0.2% 0.2% 0.2% 0.2% solution _t silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87% 79% 62% 38%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

- The invention also relates to a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I). The invention also relates to a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) .

The invention also relates to a method of selectively controlling grasses and weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I).

Crops of useful plants in which the composition according to the invention can be used include cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet and sugar cane, especially cereals and maize.

Crops can also include trees, such as palm trees, coconut trees or other nuts, and vines such as grapes.

The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Nasturtium, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). Areas under cultivation include land on which the crop plants are already growing and land intended for cultivation with those crop plants.

The compounds of formula (I) according to the invention can also be used in combination with one or more further herbicides. In particular, the following mixtures of the compound of formula (I) are important: Mixtures of a compound of formula (I) with S-metolachlor (549) or a compound of formula (I) with metolachlor (548).

Mixtures of a compound of formula (I) with a triazine (e.g. compound of formula (I) + ametryn (20), compound of formula (I) + atrazine (37), compound of formula (I) + cyanazine (183), compound of foπnula (I) + dimethametryn (259), compound of formula (I) + metribuzin (554), compound of formula (I) + prometon (665), compound of formula (I) + prometryn (666), compound of formula (I) + propazine (672), compound of formula (I) + simazine (730), compound of formula (I) + simetryn (732), compound of formula (I) + terbumeton (774), compound of formula (I) + terbuthylazine (775), compound of formula (I) + terbutryn (776), compound of formula (I) + trietazine (831)). Particularly preferred are mixtures of a compound of formula (I) with atrazine, metribuzin, prometryn or with terbuthylazine.

Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. compound of formula (I) + isoxaflutole (479), compound of formula (I) + mesotrione (515), compound of formula (I) + sulcotrione (747), compound of formula (I) + tembotrione (CAS RN 335104-84-2), compound of formula (I) + topramezone (CAS RN 210631-68-8), compound of formula (I) + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoro- methyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS RN 352010-68-5), compound of formula (I) + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3- ρyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one) (CAS RN 894355-80-7).

Mixtures of a compound of formula (I) with an HPPD inhibitor and a triazine. Mixtures of a compound of formula (I) with glyphosate (419). Mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor

(e.g. compound of formula (I) + glyphosate + isoxaflutole, compound of formula (T) + glyphosate + mesotrione, compound of formula (I) + glyphosate + sulcotrione, compound of formula (T) + glyphosate + tembotrione, compound of formula (I) + glyphosate + topramezone, compound of formula (I) + glyphosate + 4-hydroxy-3-[[2-[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3- en-2-one, compound of formula (I) + glyphosate + 4-hydroxy-3-[[2-(3-methoxypropyl)- 6-(difluoromethyl)-3 -pyridinyl] carbonyl] -bicyclo[3.2.1 ] oct-3 -en-2-one) .

Mixtures of a compound of formula (I) with glufosinate-ammonium (418). Mixtures of a compound of formula (T) with glufosinate-ammonium and an HPPD inhibitor (e.g. compound of formula (I) + glufosinate-ammonium + isoxaflutole, compound of formula (I) + glufosinate-ammonium + mesotrione, compound of formula (I) + glufosinate-ammonium + sulcotrione, compound of formula (I) + glufosinate- ammonium + tembotrione, compound of formula (I) + glufosinate-ammonium + topramezone, compound of formula (I) + glufosinate-ammonium + 4-hydroxy-3-[[2~[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3- en-2-one, compound of formula (I) + glufosinate-ammonium + 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one).

Mixtures of a compound of formula (I) with a triazolinone (e.g. compound of formula (I) + amicarbazone (21)). Mixtures of a compound of formula (I) with an ALS inhibitor (e.g. compound of formula (I) + chlorsulfuron (147), compound of formula (I) + cinosulfuron (154), compound of formula (I) + cloransulam-methyl (164), compound of formula (I) + ethametsulfuron-methyl (306), compound of formula (I) + flazasulfuron (356), compound of formula (I) + foramsulfuron (402), compound of formula (I) + flumetsulam (374), compound of formula (I) + imazamethabenz-methyl (450), compound of formula (I) + imazamox (451), compound of formula (I) + imazapic (452), compound of formula (I) + imazapyr (453), compound of formula (I) + imazethapyr (455), compound of formula (T) + iodosulfuron-methyl-sodium (466), compound of formula (I) + metsulfuron-methyl (555), compound of formula (I) + nicosulfuron (577), compound of formula (T) + oxasulfuron (603), compound of formula (T) + primisulfuron-methyl (657), compound of formula (I) + prosulfuron (684), compound of formula (I) + pyrithiobac- sodium (709), compound of formula (T) + rimsulfuron (721), compound of formula (I) + sulfosulfuron (752), compound of formula (T) + thifensulfuron-methyl (thiameturon- methyl) (795), compound of formula (I) + triasulfuron (817), compound of formula (I) + tribenuron-methyl (822), compound of formula (I) + trifloxysulfuron-sodium (833), compound of formula (I) + thiencarbazone (BAY636)). Particularly preferred are mixtures of a compound of formula (I) with flazasulfuron, foramsulfuron, flumetsulam, imazapyr, imazethapyr, iodosulfuron-methyl-sodium, nicosulfuron, rimsulfuron, trifloxysulfuron-sodium or with 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-lH-l,2,4- triazol-l-ylcarbonylsulfamoylJ-S-methylthiophene-S-carboxylic acid (BAY636).

Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (I) + fomesafen (401), compound of formula (I) + flumioxazin (376), compound of formula (I) + sulfentrazone (749), compound of formula (T) + [3-[2-chloro-4-fluoro-5- (1 -methyl-6-trifluoromethyl-2,4-dioxo- 1 ,2,3 ,4-tetrahydropyrimidin-3 -yl)phenoxy] -2- pyridyloxy] acetic acid ethyl ester) (CAS RN 353292-31-6). Particularly preferred are mixtures of a compound of formula (I) with flumioxazin, sulfentrazone or [3-[2-chloro-4- fiuoro-5-(l -methyl-6-trifluoromethyl-2,4-dioxo- 1 ,2,3,4-tetrahydropyrimidin-3- yl)phenoxy]-2-pyridyloxy] acetic acid ethyl ester. Mixtures of a compound of formula (I) with paraquat dichloride (614).

Mixtures of a compound of formula (I) with pendimethalin (621) or a compound of formula (T) with trifluralin (836). Particularly preferred are mixtures of a compound of formula (I) with pendimethalin.

Mixtures of a compound of formula (I) with metamitron (521). Mixtures of a compound of formula (I) with clomazone (159).

Mixtures of a compound of formula (I) with metazachlor (524). Mixtures of a compound of formula (I) with clodinafop-propargyl (156) or a compound of formula (I) with pinoxaden (CAS RN 243973-20-8).

The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 13^th Edition (BCPC), 2003. The reference to glufosinate-ammonium also applies to glufosinate, the reference to cloransulam-methyl also applies to cloransulam, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc. The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1: 100 to 1000:1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner).

Additionally, one or more of the following herbicides can be used in combination with a compound of formula (I) according to the invention or in combination with a mixture as described above: compound of formula (I) + acetochlor (5), compound of formula (I) + acifluorfen-sodium (7), compound of formula (I) + aclonifen (8), compound of formula (I) + acrolein (10), compound of formula (I) + alachlόr (14), compound of formula (I) + alloxydim (18), compound of formula (I) + allyl alcohol (CAS RN 107-18-6), compound of formula (I) + amidosulfuron (22), compound of formula (I) + aminopyralid (CAS RN 150114-71-9), compound of formula (I) 4- amitrole (aminotriazole) (25), compound of formula (I) + ammonium sulfamate (26), compound of formula (I) + anilofos (31), compound of formula (I) + asulam (36), compound of formula (I) + atraton (CAS RN 1610-17-9), compound of formula (I) + aviglycine (39), compound of formula (I) + azafenidin (CAS RN 68049-83-2), compound of formula (I) + azimsulfuron (43), compound of formula (I) + BAS 800H (CAS RN 372137-35-4), compound of formula (I) + BCPC (CAS RN 2164-13-8), compound of formula (I) + beflubutamid (55), compound of formula (I) + benazolin (57), compound of formula (I) + bencarbazone (CAS RN 173980-17-1), compound of formula (I) + benfluralin (59), compound of formula (I) + benfuresate (61), compound of formula (I) + bensulfuron- methyl (64), compound of formula (I) + bensulide (65), compound of formula (I) + bentazone (67), compound of formula (I) + benzfendizone (CAS RN 158755-95-4), compound of formula (I) + benzobicyclon (69), compound of formula (I) + benzofenap (70), compound of formula (I) + bifenox (75), compound of formula (I) + bilanafos (bialaphos) (77), compound of formula (I) + bispyribac-sodium (82), compound of formula (T) + borax (86), compound of formula (I) + bromacil (90), compound of formula (T) + bromobutide (93), compound of formula (T) + bromofenoxim (CAS RN 13181-17- 4), compound of formula (I) + bromoxynil (95), compound of formula (I) + butachlor (100), compound of formula (I) + butafenacil (101), compound of formula (T) + butamifos (102), compound of formula (I) + butralin (105), compound of formula (I) + butroxydim (106), compound of formula (I) + butylate (108), compound of formula (I) + cacodylic acid (CAS RN 75-60-5), compound of formula (I) + calcium chlorate (CAS RN 10137-74-3), compound of formula (I) + cafenstrole (110), compound of formula (T) + carbetamide (117), compound of formula (I) + carfentrazone-ethyl (121), compound of formula (I) + CDEA (CAS RN 2315-36-8), compound of formula (I) + CEPC (CAS RN 587-56-4), compound of formula (I) + chlorbromuron (CAS RN 13360-45-7), compound of formula (I) + chlorflurenol-methyl (133), compound of formula (I) + chloridazon (134), compound of formula (I) + chlorimuron-ethyl (135), compound of formula (I) + chloroacetic acid (138), compound of formula (I) + chlorotoluron (143), compound of formula (I) + chlorpropham (144), compound of formula (I) + chlorthal-dimethyl (148), compound of formula (I) + cinidon-ethyl (152), compound of formula (I) + cinrnethylin (153), compound of formula (I) + cisanilide (CAS RN 34484-77-0), compound of formula (I) + clefoxydim (CAS RN 211496-02-5), compound of formula (I) + clethodim (155), compound of formula (I) + clomeprop (160), compound of formula (I) + clopyralid (162), compound of formula (I) + CMA (CAS RN 5902-95-4), compound of formula (I) + 4-CPB (CAS RN 3547-07-7), compound of formula (T) + CPMF, compound of formula (I) + 4-CPP (CAS RN 3307-39-9), compound of formula (I) + CPPC (CAS RN 2150-32-5), compound of formula (T) + cresol (CAS RN 1319-77-3), compound of formula (I) + cumyluron (180), compound of formula (I) + cyanamide (182), compound of formula (I) + cyclanilide (186), compound of formula (I) + cycloate (187), compound of formula (I) + cyclosulfamuron (189), compound of formula (I) + cycloxydim (190), compound of formula (I) + cyhalofop-butyl (195), compound of formula (I) + 2,4-D (211), compound of formula (I) + 3,4-DA (CAS RN 588-22-7), compound of formula (I) + daimuron (213), compound of formula (T) + dalapon (214), compound of formula (I) + dazomet (216), compound of formula (I) + 2,4-DB (217), compound of formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB (CAS RN 94- 83-7), compound of formula (T) + desmedipham (225), compound of formula (I) + desmetryn (CAS RN 1014-69-3), compound of formula (T) + dicamba (228), compound of formula (I) + dichlobenil (229), compound of formula (I) + ortho-dichlorobenzene (CAS RN 95-50-1), compound of formula (T) + para-dichlorobenzene (CAS RN 106-46- 7), compound of formula (I) + dichlorprop (234), compound of formula (I) + dichlorprop-P (235), compound of formula (I) + diclo fop-methyl (238), compound of formula (I) + diclosulam (241), compound of formula (I) + difenzoquat metilsulfate (248), compound of formula (I) + difiufenican (251), compound of formula (I) + diflufenzopyr (252), compound of formula (I) + dimefuron (256), compound of formula (I) + dimepiperate (257), compound of formula (I) + dimethachlor (258), compound of formula (I) + dimethenamid (260), compound of formula (I) + dimethenamid-P, compound of formula (I) + dimethipin (261), compound of formula (I) + dimethylarsinic acid (264), compound of formula (T) + dinitramine (268), compound of formula (I) + dinoterb (272), compound of formula (I) + diphenamid (274), compound of formula (I) + dipropetryn (CAS RN 41^*47-51 -7), compound of formula (I) + diquat dibromide (276), compound of formula (I) + dithiopyr (280), compound of formula (I) + diuron (281), compound of formula (I) + DNOC (282), compound of formula (I) + 3,4-DP (CAS RN 3307-41-3), compound of formula (I) + DSMA (CAS RN 144-21-8), compound of formula (I) + EBEP, compound of formula (I) + endothal (295), compound of formula (T) + EPTC (299), compound of formula (I) + esprocarb (303), compound of formula (I) + ethalfluralin (305), compound of formula (I) + ethephon (307), compound of formula (I) + ethofumesate (311), compound of formula (I) + ethoxyfen (CAS RN 188634-90-4), compound of formula (I) + ethoxyfen-ethyl (CAS RN 131086-42-5), compound of formula (I) + ethoxysulfuron (314), compound of formula (I) + etobenzanid (318), compound of formula (I) + fenoxaprop-P-ethyl (339), compound of formula (T) + fentrazamide (348), compound of formula (I) + ferrous sulfate (353), compound of formula (I) + fiamprop, compound of formula (I) + flamprop-M (355), compound of formula (I) + fiorasulam (359), compound of formula (I) + fluazifop-butyl (361), compound of formula (I) 4- fluazifop-P-butyl (362), compound of formula (I) + fluazolate (isopropazol) (CAS RN 174514-07-9), compound of formula (I) + flucarbazone-sodium (364), compound of formula (I) + flucetosulfuron (CAS RN 412928-75-7), compound of formula (I) + fluchloralin (365), compound of formula (I) + flufenacet (BAY FOE 5043) (369), compound of formula (I) + flufenpyr-ethyl (371), compound of formula (I) + flumetralin (373), compound of formula (T) + flumiclorac-pentyl (375), compound of formula (I) + flumipropyn (flumipropin) (CAS RN 84478-52-4), compound of formula (I) + fluometuron (378), compound of formula (I) + fluoroglycofen-ethyl (380), compound of formula (I) + flupoxam (CAS RN 119126-15-7), compound of formula (I) + flupropacil (CAS RN 120890-70-2), compound of formula (I) + flupropanate (383), compound of formula (I) + flupyrsulfuron-methyl-sodium (384), compound of formula (I) + fiurenol (387), compound of formula (I) + fluridone (388), compound of formula (I) + flurochloridone (389), compound of formula (I) + fluroxypyr (390), compound of formula (I) + fiurtamone (392), compound of formula (I) + fluthiacet-niethyl (395), compound of formula (I) + fosamine (406), compound of formula (I) + halosulfuron- methyl (426), compound of formula (I) + haloxyfop (427), compound of formula (I) + haloxyfop-P (428), compound of formula (I) + HC-252 (429), compound of formula (I) + hexazinone (440), compound of formula (I) + imazaquin (454), compound of formula (T) + imazosulfuron (456), compound of formula (I) + indanofan' (462), compound of formula (I) + iodomethane (CAS RN 74-88-4), compound of formula (I) + ioxynil (467), compound of formula (I) + isoproturon (475), compound of formula (T) + isouron (476), compound of formula (I) + isoxaben (All), compound of formula (T) + isoxachlortole (CAS RN 141112-06-3), compound of formula (I) + isoxapyrifop (CAS RN 87757-18- 4), compound of formula (I) + karbutilate (482), compound of formula (I) + lactofen (486), compound of formula (I) + lenacil (487), compound of formula (T) + linuron (489), compound of formula (I) + MAA (CAS RN 124-58-3), compound of formula (I) +

MAMA (CAS RN 2321-53-1), compound of formula (T) + MCPA (499), compound of formula (I) + MCPA-thioethyl (500), compound of formula (I) + MCPB (501), compound of formula (T) + mecoprop (503), compound of formula (I) + mecoprop-P (504), compound of formula (I) + mefenacet (505), compound of formula (I) + mefluidide (507), compound of formula (I) + mesosulfuron-methyl (514), compound of formula (I) + metam (519), compound of formula (I) + metamifop (mefluoxafop) (520), compound of formula (I) + methabenzthiazuron (526), compound of formula (T) + methazole (CAS RN 20354-26-1), compound of formula (I) + methylarsonic acid (536), compound of formula (I) + methyldymron (539), compound of formula (I) + methyl isothiocyanate (543), compound of formula (I) + metobenzuron (547), compound of formula (I) + metobromuron (CAS RN 3060-89-7), compound of formula (T) + metosulam (552), compound of formula (I) + metoxuron (553), compound of formula (I) + MK-616 (559), compound of formula (I) + molinate (560), compound of formula (I) + monolinuron (562), compound of formula (I) + MSMA (CAS RN 2163-80-6), compound of formula (T) + naproanilide (571), compound of formula (T) + napropamide (572), compound of formula (I) + naptalam (573), compound of formula (I) + neburon (574), compound of formula (I) + nipyraclofen (CAS RN 99662-11-0), compound of formula (I) + n-methyl-glyphosate, compound of formula (I) + nonanoic acid (583), compound of formula (I) + norfiurazon (584), compound of formula (T) + oleic acid (fatty acids) (593), compound of formula (I) + orbencarb (595), compound of formula (I) + orthosulfamuron (CAS RN 213464-77-8), compound of formula (I) 4- oryzalin (597), compound of formula (T) + oxadiargyl (599), compound of formula (I) + oxadiazon (600), compound of formula (I) + oxaziclomefone (604), compound of formula (I) + oxyfluorfen (610), compound of formula (I) + pebulate (617), compound of formula (I) + penoxsulam (622), compound of formula (I) + pentachlorophenol (623), compound of formula (I) + pentanochlor (624), compound of formula (I) + pentoxazone (625), compound of formula (I) + pethoxamid (627), compound of formula (I) + petrolium oils (628), compound of formula (I) + phenmedipham (629), compound of formula (I) + picloram (645), compound of formula (I) + picolinafen (646), compound of formula (I) + piperophos (650), compound of formula (I) + potassium arsenite (CAS RN 10124-50-2), compound of formula (I) + potassium azide (CAS RN 20762-80-1), compound of formula (I) + pretilachlor (656), compound of formula (I) + prodiamine (661), compound of formula (I) + profluazol (CAS RN 190314-43-3), compound of formula (I) + profoxydim (663), compound of formula (I) + prohexadione calcium (664), compound of formula (I) + propachlor (667), compound of formula (I) + propanil (669), compound of formula (I) + propaquizafop (670), compound of formula (I) + propham (674), compound of formula (I) + propisochlor (667), compound of formula (I) + propoxycarbazone-sodium (procarbazone-sodium) (679), compound of formula (I) + propyzamide (681), compound of formula (I) + prosulfocarb (683), compound of formula (I) + pyraclonil (pyrazogyl) (CAS RN 158353-15-2), compound of formula (I) + pyraflufen-ethyl (691), compound of formula (I) + pyrasulfotole (CAS RN 365400-11-9), compound of formula (I) + pyrazolynate (692), compound of formula (I) + pyrazosulfuron-ethyl (694), compound of formula (I) + pyrazoxyfen (695), compound of formula (I) + pyribenzoxim (697), compound of formula (I) + pyributicarb (698), compound of formula (I) + pyridafol

(CAS RN 40020-01-7), compound of formula (I) + pyridate (702), compound of formula (I) + pyriftalid (704), compound of formula (I) + pyriminobac-methyl (707), compound of formula (I) + pyrimisulfan (CAS RN 221205-90-9), compound of formula (I) + pyroxasulfone (CAS RN 447399-55-5), compound of formula (I) + pyroxsulam (triflosulam) (CAS RN 422556-08-9), compound of formula (I) + quinclorac (712), compound of formula (I) + quinmerac (713), compound of formula (I) + quinoclamine (714), compound of formula (I) + quizalofop (717), compound of formula (I) + quizalofop-P (718), compound of formula (I) + sequestrene, compound of formula (I) + sethoxydim (726), compound of formula (I) + siduron (727), compound of formula (I) + SMA (CAS RN 3926-62-3), compound of formula (I) + sodium arsenite (CAS RN 7784- 46-5), compound of formula (I) + sodium azide (CAS RN 26628-22-8), compound of formula (I) + sodium chlorate (734), compound of formula (I) + sulfometuron-methyl (751), compound of formula (I) + sulfosate (CAS RN 81591-81-3), compound of formula (I) + sulfuric acid (755), compound of formula (I) + tar oils (758), compound of formula (I) + 2,3,6-TB A (759), compound of formula (I) + TCA-sodium (760), compound of formula (I) + tebutam (CAS RN 35256-85-0), compound of formula (I) + tebuthiuron (765), compound of formula (I) + tepraloxydim (771), compound of formula (I) + terbacil (772), compound of formula (I) + tefuryltrione (CAS RN 473278-76-1), compound of formula (I) + thenylchlor (789), compound of formula (I) + thidiazimin (CAS RN 123249-43-4), compound of formula (I) + thiazafluron (CAS RN 25366-23-8), compound of formula (I) + thiazopyr (793), compound of formula (I) + thiobencarb (797), compound of formula (I) + tiocarbazil (807), compound of formula (I) + tralkoxydim (811), compound of formula (I) + tri-allate (816), compound of formula (I) + triaziflam (819), compound of formula (I) + tricamba (CAS RN 2307-49-5), compound of formula (I) + triclopyr (827), compound of formula (I) + triflusulfuron-methyl (837), compound of formula (I) + trihydroxytriazine (CAS RN 108-80-5), compound of formula (I) + trinexapac-ethyl (CAS RN 95266-40-3) and compound of formula (I) + tritosulfuron (843). The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 13^th Edition (BCPC), 2003. The reference to acifluorfen-sodium also applies to acifluorfen, and the reference to bensulfuron-methyl also applies to bensulfuron, etc.

The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000: 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner).

The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (I) according to the invention with one or more further herbicides can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds. The safeners can be AD 67 (MON 4660) (11), benoxacor (63), cloquintocet-mexyl (163), cyometrinil (CAS RN 78370-21-5) and the corresponding (Z) isomer, cyprosulfamide (CAS RN 221667-31-8), dichlormid (231), fenchlorazole-ethyl (331), fenclorim (332), flurazole (386), fluxofenim (399), furilazole (413) and the corresponding R isomer, isoxadifen- ethyl (478), mefenpyr-diethyl (506), oxabetrinil (598), naphthalic anhydride (CAS RN 81-84-5), N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4), 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]- benzamide (CAS RN 129531-12-0), I,l,3-trioxo-l,3-dihydro-llambda⁶-benzo[d]- isothiazole-2-carboxylic acid 4-chloro-benzyl ester (CAS RN 863554-50-1), 2-[[[[(4- chlorophenyl)methoxy]carbonyl] amino] sulfonyl] -benzoic acid (CAS RN 808197-84-4), l,l,3-trioxo-l,3-dihydro-llambda⁶-benzo[d]isothiazole-2-carboxylic acid 2-chloro- benzyl ester (CAS RN 927419-03-2) and 4-tert-butyl-benzoic acid (CAS RN 98-73-7). Particularly preferred are mixtures of a compound of formula (I) with benoxacor. The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 13^th Edition (BCPC), 2003. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phos- phonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole- ethyl also applies to fenchlorazole, etc.

Preferably the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the safener). It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post- emergence. It is also possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre- emergence or might be applied to the crop post-emergence.

Preferred mixtures of a compound of formula (I) with further herbicides and safeners include:

Mixtures of a compound of formula (I) with S-metolachlor and a safener.

Mixtures of a compound of formula (I) with a triazine and a safener.

Mixtures of a compound of formula (I) with glyphosate and a safener.

Mixtures of a compound of formula (I) with glufosinate and a safener. Mixtures of a compound of formula (I) with isoxaflutole and a safener.

Mixtures of a compound of formula (I) with isoxaflutole and a triazine and a safener.

Mixtures of a compound of formula (I) with isoxaflutole and glyphosate and a safener.

Mixtures of a compound of formula (I) with isoxaflutole and glufosinate and a safener.

Mixtures of a compound of formula (I) with mesotrione and a safener.

Mixtures of a compound of formula (I) with mesotrione and a triazine and a safener.

Mixtures of a compound of formula (I) with mesotrione and glyphosate and a safener.

Mixtures of a compound of formula (I) with mesotrione and glufosinate and a safener. Mixtures of a compound of formula (I) with sulcotrione and a safener.

Mixtures of a compound of formula (I) with sulcotrione and a triazine and a safener.

Mixtures of a compound of formula (I) with sulcotrione and glyphosate and a safener. Mixtures of a compound of formula (I) with sulcotrione and glufosinate and a safener.

Mixtures of a compound of formula (I) with tembotrione and a safener.

Mixtures of a compound of formula (I) with tembotrione and a triazine and a safener. Mixtures of a compound of formula (I) with tembotrione and glyphosate and a safener.

Mixtures of a compound of formula (I) with tembotrione and glufosinate and a safener.

Mixtures of a compound of formula (T) with topramezone and a safener. Mixtures of a compound of formula (I) with topramezone and a triazine and a safener.

Mixtures of a compound of formula (I) with topramezone and glyphosate and a safener. Mixtures of a compound of formula (I) with topramezone and glufosinate and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-[(2-methoxy- ethoxy)methyl]-6-(trifiuoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-[(2-methoxy- ethoxy)methyl]-6-(trifluoromethyl)-3-pyridmyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one and a triazine and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-[(2-methoxy- ethoxy)methyl] -6-(trifluoromethyl)-3 -pyiϊdinyl] carbonyl] -bicyclo [3.2.1 ] oct-3 -en-2-one and glyphosate and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-[(2-methoxy- ethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one and glufosinate and a safener. Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-(3-methoxypropyl)-

6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one) and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-(3-methoxypropyl)- 6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one) and a triazine and a safener. Mixtures of a compound of formula (T) with 4-hydroxy-3 - [ [2-(3 -methoxypropyl)-

6-(difluoromethyl)-3 -pyridinyl] carbonyl] -bicyclo [3.2.1 ] oct-3 -en-2-one) and glypho sate and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-(3-methoxypropyl)- 6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2. l]oct-3-en-2-one) and glufosinate and a safener.

The following Examples further illustrate, but do not limit, the invention.

Preparation Examples: 1) Methods for making triazole derivatives

The synthesis of 5-chloromethyl-l-methyl-lH-[l,2,4]triazole was described in EP 421210.

The synthesis of 5-chloromethyl-l,3-dimethyl-lH-[l,2,4]triazole was described in DE 3118258. 5-Chloromethyl-l-ethyl-3-methyl-lH-[l,2,4]triazole was prepared from N- (ethylamino)acetamidine and chloroacetyl chloride according to the processes described in DB 3118258. ¹H-NMR (400 MHz, CDCl₃): 1.50 (3H, t), 2.37 (3H, s), 4.17 (3H, q), 4.63 (2H, s) ppm. The synthesis of 5-chloromethyl-l-ethyl-lH-[l,2,4]triazole was described in

WO 99/65904.

The synthesis of 5-chloromethyl-2,4-dihydro-[l,2,4]triazol-3-one was described in Tetrahedron Letters, 2000, 41(44), 8661-4.

The synthesis of 3-chloromethyl-l-methyl-lH-[l,2,4]triazole was described in EP 421210.

The synthesis of 3-chloromethyl-4-methyl-4/i-[l,2,4]triazole was described in EP 421210.

The synthesis of 3-chloromethyl-4,5-dimethyl-4H-[l,2,4]triazole was described in Synthesis, 2006, 156-160. 5-Ethyl-4-methyl-4H-[l,2,4]triazole-3-thiol was oxidised as described in

Synthesis, 2006, 156-160 to give 5-ethyl-4-methyl-4/f-[l,2,4]triazole. ¹H-NMR (400 MHz, CDCl₃): 1.4 (t, 3H), 2.78 (q, 2H), 3.62 (s, 3H), 8.05 (s, IH) ppm.

5-Ethyl-4-methyl-4H-[l,2,4]triazole was treated with formaldehyde followed by thionyl chloride as described in Synthesis, 2006, 156-160 to give 3-chloromethyl-5-ethyl- 4-methyl-4H-[l,2,4]triazole hydrochloride salt. ¹H-NMR (400 MHz, D₂O): 1.37 (t, 3H), 2.99 (q, 2H), 3.78 (s, 3H), 4.89 (s, 2H) ppm.

4-Cyclopropyl-5-ethyl-4H-[l,2,4]triazole-3-thiol was oxidised as described in Synthesis, 2006, 156-160 to give 4-cycloproρyl-5-ethyl-4H-[l,2,4]triazole. ¹H-NMR (400 MHz, CDCl₃): 0.97 (m, 2H), 1.13 (m, 2H), 1.44 (t, 3H), 2.88 (q, 2H), 3.13 (m, IH), 8.02 (s, IH) ppm.

4-Cyclopropyl-5-ethyl-4H-[l,2,4]triazole was treated with formaldehyde followed by thionyl chloride as described in Synthesis, 2006, 156-160 to give 3- chloromethyl-4-cyclopropyl-5-ethyl-4H-[l,2,4]triazole hydrochloride salt. ¹H-NMR (400 MHz, CDCl₃): 1.06 (m, 2H), 1.23 (m, 2H), 1.42 (t, 3H), 2.87 (q, 2H), 3.12 (m, IH), 4.79 (s, 2H) ppm. Example 1.1: Preparation of l,5-dimethyl-3-trifluoromethyl-lH-[l,2,4]triazole and 3,4- dimethyl-5-trifluoroinethyl-4H-ri,2,41triazole

A B Sodium hydride (60% in mineral oil) (1.64 g, 40.7 mmol) was added in portions to a solution of 5-methyl-3-trifluoromethyl-lH-[l,2,4]triazole (5.62 g, 37 mmol) in dry tetrahydrofuran (150 ml) at 0°C under a nitrogen atmosphere. The reaction mixture was heated to reflux for 3 hours and then allowed to cool to ambient temperature. Iodomethane (5.29 g, 37 mmol) was added at ambient temperature. The reaction mixture was heated to reflux for 10 hours and then allowed to cool to ambient temperature. The reaction mixture was concentrated and the residue partitioned between water and ethyl acetate. The phases were separated and the aqueous phase was saturated with sodium chloride and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: methanol / ethyl acetate) to give 1,5- dimethyl-3-trifluoromethyl-lH-[l,2,4]triazole as an oil (2.87 g, 47% yield) and 3,4- dimethyl-5-trifluoromethyl-4H-[l,2,4]triazole as a solid (488 mg, 8% yield). Isomer A ¹H-NMR (400 MHz, CDCl₃): 2.52 (s, 3H), 3.89 (s, 3H) ppm. Isomer B ¹H-NMR (400 MHz, CDCl₃): 2.53 (s, 3H), 3.70 (s, 3H) ppm.

Example 1.2: Preparation of 5-bromomethyl-l-methyl-3-trifluoromethyl-lH^'-[l,2,4]- triazole

l,5-Dimethyl-3-trifluoromethyl-lH-[l,2,4]triazole (Example 1.1) (420 mg, 2.54 mmol) was dissolved in carbon tetrachloride (5 ml). N-Bromosuccinimide ("NBS") (573 mg, 3.2 mmol) and azobisisobutyronitrile ("AIBN") (64 mg, 0.4 mmol) were added and the reaction mixture illuminated with a halogen lamp under a nitrogen atmosphere. The heat of the lamp soon caused the reaction mixture reflux. After 2 hours the reaction mixture was allowed to cool to ambient temperature and filtered through silica gel. The silica gel was washed with dichloromethane. The combined filtrates were concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give 5-bromomethyl-l-methyl-3-trifluoromethyl-l/i-[l,2,4]triazole as an oil (233 mg, 38% yield) which solidified on standing. ¹H-NMR (400 MHz, CDCl₃): 4.00 (s, 3H), 4.52 (s, 2H) ppm.

3,4~Dimethyl-5-trifluoromethyl-4H-[l,2,4]triazole was brominated as described in Example 1.2 to give 3-bromomethyl-4-methyl-5-trifluoromethyl-4H-[l,2,4]triazole. ¹H-NMR (400 MHz, CDCl₃): 3.81 (s, 3H), 4.50 (s, 2H) ppm.

Example 1.3: Preparation of l,3-dimethyl-5-trifluoromethyl-lH~ri,2,41triazole

JV-Methyl-acetamidine (preparation according to DE 3118258) (158 mg, 1.28 mmol) was dissolved in trifiuoroacetic acid (1 ml, 12.8 mmol) under a nitrogen atmosphere. The reaction mixture was heated to reflux for 3 hours and then stored at ambient temperature for 16 hours. The reaction mixture was cooled to 0⁰C and diluted with water before addition of aqueous sodium hydroxide (5N). The mixture was extracted with dichloromethane. The combined organic extracts were concentrated carefully as the product is volatile to give l,3-dimethyl-5-trifluoromethyl-lH-[l,2,4]- triazole as a liquid (115 mg, 54% yield). ¹H-NMR (400 MHz, CDCl₃): 2.41 (s, 3H), 3.98 (s, 3H) ppm.

l,3-Dimethyl-5-trifluoromethyl-l/f-[l,2,4]triazole was brominated as described in Example 1.2 to give 3-bromomethyl-l-methyl-5-trifluoromethyl-lH-[l,2,4]triazole. ¹H-NMR (400 MHz, CDCl₃): 4.04 (s, 3H), 4.47 (s, 2H) ppm. Example 1.4: Preparation of (acetyl-methyl-hvdrazono)-amino-acetic acid ethyl ester

(Methyl-hydrazono)-amino-acetic acid ethyl ester (preparation according to WO 99/37668) (1.545 g, 10.65 mmol) was dissolved in tetrahydrofuran (25 ml) under a nitrogen atmosphere. Triethylamine (1.78 ml, 12.78 mmol) was added to the mixture at ambient temperature. The solution was cooled to 0⁰C and acetic anhydride (1.1 ml, 11.72 mol) was added drop wise. The reaction mixture was allowed to warm to ambient temperature, stirred at ambient temperature for 1 hour and then stored at ambient temperature for 16 hours. The reaction mixture was concentrated and the residue partitioned between ethyl acetate and water. The phases were separated and the organic layer was washed with brine, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: 0-20% methanol / dichloromethane) to give (acetyl-methyl-hydrazono)-amino-acetic acid ethyl ester as an off-white solid (466 mg, 25% yield). ¹H-NMR (400 MHz, CDCl₃): 1.42 (t, 3H), 2.04 (s, 3H), 3.12 (s, 3H), 4.45 (q, 2H), 5.78 (bs, 2H) ppm.

Example 1.5: Preparation of l,5-dimethyl-lH-[^'l,2,4^'1triazole-3-carboxyric acid ethyl ester

(Acetyl-methyl-hydrazono)-amino-acetic acid ethyl ester (Example 1.4) (500 mg,

2.67 mmol) was suspended in xylene (40 ml) and heated to reflux (160°C) under a nitrogen atmosphere for 16 hours. The reaction mixture was allowed to cool to ambient temperature and concentrated. The residue was purified by column chromatography on silica gel (eluent: methanol / dichloromethane) to give l,5-dimethyl-l.H-[l,2,4]triazole-3- carboxylic acid ethyl ester as an off-white solid (316 mg, 70% yield). ¹H-NMR (400 MHz, CDCl₃): 1.42 (t, 3H), 2.52 (s, 3H), 3.9 (s, 3H), 4.47 (q, 2H) ppm. Example 1.6: Preparation of (1.5-dimethyl-lH-[l,2,4]triazol-3-yl)-niethanol

l,5-Dimethyl-lH-[l,2,4]triazole-3-carboxylic acid ethyl ester (Example 1.5) (316 mg, 1.87 mmol) was dissolved in tetrahydrofuran (15 ml) and the solution cooled to 0⁰C. Lithium aluminium hydride (IM in TΗF) (1.87 ml, 1.87 mmol) was added dropwise at 0°C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 45 minutes. The reaction mixture was cooled to 0⁰C, diluted with ethyl acetate and quenched by addition of water. The mixture was filtered through Celite® and the Celite® washed well with ethyl acetate. The combined filtrates were concentrated to give (l,5-dimethyl-lH-[l,2,4]triazol-3-yl)-methanol as an orange oil (190 mg, 80% yield). ¹H-NMR (400 MHz, d₄-MeOH): 2.47 (s, 3H), 3.81 (s, 3H), 4.57 (s, 2H) ppm.

Example 1.7: Preparation of 3-chloromethyl-l,5-dimethyl-lH-ri,2,41triazole hydrochloride salt

(l,5-Dimethyl-lH-[l,2,4]triazol-3-yl)-methanol (230 mg, 1.86 mmol) was suspended in dry dichloromethane (10 ml) under nitrogen and cooled to 0⁰C before the addition of thionyl chloride (270 μl, 3.72 mmol). The reaction mixture was then stirred at ambient temperature for 3 hours. The reaction mixture was concentrated to give 3-chloro- methyl-l,5-dimethyl-lH-[l,2,4]-triazole hydrochloride salt as a semi-solid (280 mg, 82% yield). ¹H-NMR (400 MHz, d₄-Me0H): 2.76 (s, 3H), 4.00 (s, 3H) 4.89 (s, 2H) ppm. Example 1.8: Preparation of 5-chloro-3-(5,5-dimethyl-4,5-dihvdro-isoxazol-3-yl- sulfanylmethylV IH-[1.2,41triazole

A solution of 5-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-2,4- dihydro-[l,2,4]triazol-3-one (Example 2.2) (456 mg, 2.0 mmol) in phenylphosphonic dichloride (3.92 g, 20 mmol) was heated to 130°C under a nitrogen atmosphere for 90 minutes. The mixture was allowed to cool to ambient temperature and added drop-wise to a slurry of sodium hydrogen carbonate (10 g) in water (10 ml) at 0°C. The mixture was extracted with ethyl acetate (3x 50 ml), the combined organic extracts dried over magnesium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give 5-chloro-3-(5,5- dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-lH-[l,2,4]triazole as a white solid (230 mg, 47% yield). ¹H-NMR (400 MHz, CDCl₃): 1.44 (s, 6H), 2.85 (s, 2H), 4.27 (s, 2H), 11.63 (bs, IH) ppm.

Example 1.9: Preparation of S-chloro-S-fS^-dimethyl^^-dihydro-isoxazol-S-yl- sulfanylmethviyi -methyl- lH-[L2,41triazole, 3-chloro-5-(5,5-dimethyl-4,5-dihydro- isoxazol-S-ylsulfanyhnethyD-l-methyl-lH-fl^^itriazole and S-chloro-S-fS^-dimethyl- 4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-4-methyl-4H-[l,2,4]triazole

A solution of potassium fert-butoxide (1.0 M in THF) (8.41 ml, 8.41 mmol) was added dropwise, during 10 minutes to a solution of 5-chloro~3-(5,5-dimethyl-4,5- dihydro-isoxazol-3-ylsulfanylmethyl)-lH-[l,2,4]triazole (Example 1.8) (2.073 g, 8.41 mmol) in tetrahydrofuran (42 ml) under a nitrogen atmosphere at 0°C. After 30 minutes the mixture was cooled to -78°C and iodomethane (1 ml, excess) added. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for one hour. The reaction mixture was filtered through silica gel and the silica gel washed with ethyl acetate. The combined filtrates were concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / dichloro- methane) to give 5-chloro-3-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l- methyl-lH-[l,2,4]triazole as a colourless oil (268 mg, 12% yield), 3-chloro-5-(5,5- dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-methyl-lH-[l,2,4]triazole as a colourless oil (100 mg, 5% yield) and 3-chloro-5-(5,5-dimethyl-4,5-dihydro-isoxazol~3- ylsulfanylmethyl)-4-methyl-4H^"-[l,2,4]triazole as a white solid (127 mg, 6% yield). Isomer A ¹H-NMR (400 MHz, CDCl₃): 1.42 (s, 6H), 2.85 (s, 2H), 3.83 (s, 3H), 4.27 (s, 2H) ppm. Isomer B ¹H-NMR (400 MHz, CDCl₃): 1.41 (s, 6H), 2.81 (s, 2H), 3.91 (s, 3H), 4.28 (s, 2H) ppm. Isomer C ¹H-NMR (400 MHz, CDCl₃): 1.42 (s, 6H), 2.84 (s, 2H), 3.66 (s, 3H), 4.39 (s, 2H) ppm.

Example 1.10: Preparation of l-ethyl-lH-[l,2,,4^~|triazole~3-carboxyric acid methyl ester and 1 -ethyl- IH-[1, 2,4]triazole-5-carboxylic acid methyl ester

To a suspension of IH-[1, 2,4]-triazole-3-carboxylic acid methyl ester (25 g, commercially available) in dry ΛζN-dimethylformamide (200 ml) at O⁰C under an atmosphere of nitrogen was added in portions sodium hydride (60% by weight dispersion in mineral oil) (8.66 g). On complete addition, the mixture was stirred for 1 hour at ambient temperature then re-cooled to O⁰C and ethyl iodide (15.5 ml) was added. The reaction mixture was stirred for 1 hour, stored for 18 hours then treated with aqueous ammonium chloride (IM) and concentrated to give a yellow oil. The oil was dissolved in chloroform (300 ml), washed with water (100 ml), dried over magnesium sulfate and concentrated. The oil that remained was washed with hexane and then triturated with diethyl ether to give a mixture of l-ethyl-lH-[l,2,4]triazole-3-carboxylic acid methyl ester and 1 -ethyl- IH-[1, 2,4]triazole-5-carboxylic acid methyl ester which was used without further purification.

Example 1.11: Preparation of ri-ethyl-lH-[l,2,41triazol-3-ylVmethanol and (1-ethyl-lH- [1 ,2,41triazol-5-yl)-methanol

LiAIH,

A mixture of l-ethyl-lH-[l,2,4]triazole-3-carboxylic acid methyl ester and 1- ethyl-lH-[l,2,4]triazole-5-carboxylic acid methyl ester (Example 1.10) (42 g) was suspended in dry tetrahydrofuran (200 ml) with stirring under an atmosphere of nitrogen at O⁰C. Pellets of lithium aluminium hydride (7 g) were added over a period of 1 hour at 0⁰C. The cooling bath was removed allowing the temperature of the reaction mixture to rise gradually until it began to reflux. The mixture was re-cooled to O⁰C, treated with ethyl acetate followed by a small amount of water then filtered through a bed of Celite®. The bed was washed with a mixture of methanol / ethyl acetate (1:1) and the filtrate concentrated to give a mixture of (l-ethyl-lH-[l,2,4]triazol-3-yl)-methanol and (1-ethyl- IH-[1, 2,4]triazol-5-yl)-methanol (26 g, 70% purity) which was used further purification.

The mixture was chlorinated as described in Example 1.7 to give 5-chloromethyl- 1 -ethyl- IH-[1, 2,4]triazole and 3-chloromethyl-l-ethyl-lH-[l,2,4]triazole. 5-Chloro- methyl-l-ethyl-lH-[l,2,4]triazole ¹H-NMR (400 MHz, d₄-Me0H): 1.57 (3H, t), 4.31 (2H, q), 4.88 (2H, s) 8.07 (IH, s) ppm. 3-Chloromethyl-l-ethyl-lH-[l,2,4]triazole ¹H- NMR (400 MHz, d₄-Me0H): 1.57 (3H, t), 4.31 (2H₅ q), 4.70 (2H, s) 9.0_.0 (IH, s) ppm. Example 1.12: Preparation of 3-ffe^butyl-dimemyl-silanyloxymethyl)- 1 -ethyl- IH- π.2.41triazole

The mixture of (1 -ethyl- IH-[1, 2,4]triazol-3-yl)-methanol and (1-ethyl-lH- [l,2,4]triazol-5-yl)-methanol (Example 1.11) (26.3 g) was dissolved in dry N,N- dimethylformamide (200 ml) containing tert-butyl-chloro-dimethyl-silane (30.0 g) with stirring and the mixture treated in portions with imidazole (13.6 g). The mixture was stirred for 4 hours and the residue dissolved in chloroform then washed with aqueous sodium hydrogen carbonate (saturated). The solvent was evaporated under reduced pressure and the residue purified by column chromatography on silica gel (eluent: hexane / ethyl acetate) to provide 3-(tert-butyl-dimethyl-silanyloxymethyl)-l-ethyl-lH-[l,2,4]- triazole as an oil (8 g). ¹H-NMR (400 MHz, CDCl₃): 0.11 (6H, s), 0.91 (9H, s), 1.50 (3H, t), 4.17 (2H, q), 4.75 (2H, s), 7.98 (IH, s) ppm.

Example 1.13: Preparation of 3-(fer^butyl-dimethyl-silanyloxymethyl)-l-ethyl-5-methyl- lH-n.2.41triazole

To a solution of 3 -(tert-butyl-dimethyl-silanyloxymethyl)-l -ethyl- IH-[1, 2,4]- triazole (Example 1.12) (0.43 g) in dry tetrahydrofuran (10 ml) at -50°C under an atmosphere of nitrogen was added dropwise n-butyl lithium (2.5M in hexanes) (0.71ml). The reaction mixture was kept below -30°C during the addition then stirred at -40°C for 15 minutes then treated with methyl iodide (0.11 ml) and allowed to warm to ambient temperature over 1 hour. The reaction was stirred for a further 30 minutes then quenched with aqueous ammonium chloride (IM). The mixture was concentrated and the residue partitioned between ethyl acetate and water. The organic fraction was separated and the aqueous phase treated with sodium chloride and re-extracted with ethyl acetate. The combined organic extracts were washed with brine, dried and concentrated to give a brown oil. The oil was purified by column chromatography on silica gel (eluent: hexane / ethyl acetate) to give 3-(tert-butyl-dimethyl-silanyloxymethyl)-l-ethyl-5-methyl-lH- [l,2,4]triazole as an oil (0.26 g). ¹H-NMR (400 MHz, CDCl₃): 0.1 (6H, s), 0.9 (9H, s), 1.41 (3H, t), 2.42 (3H, s), 4.06 (2H, q), 4.68 (2H₃ s) ppm.

Example 1.14: Preparation of (l-ethyl-5-methyl-lH~ri,2,41triazol-3-ylVmethanol

To a solution of 3-(tert-butyl-dimethyl-silanyloxymethyl)-l-ethyl-5-methyl-liϊ- [l,2,4]triazole (Example 1.13) (0.26g) in ethanol (5ml) was added aqueous sodium hydroxide (5M) (0.33 ml). The reaction mixture was heated to 45°C for 5 hours under a nitrogen atmosphere and then stored for 18 hours. The mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: dichloromethane / methanol) to give (l-ethyl-5-methyl-lH-[l,2,4]triazol-3-yl)-methanol as a clear oil (121 mg). ¹H-NMR (400 MHz, CDCl₃): 1.43 (3H, t), 2.43 (3H, s), 4.07 (2H, q), 4.68 (2H, s) ppm.

(l-Ethyl-5-methyl-lH-[l,2,4]triazol-3-yl)-methanol was chlorinated as described in Example 1.7 to give 3-chloromethyl-l-ethyl-5-methyl~lH-[l,2,4]triazole. ¹H-NMR (400 MHz, d₄-Me0H): 1.56 (3H, t), 2.83 (3H, s), 4.23 (2H, q), 4.75 (2H, s) ppm. 2) Methods for couplings and oxidations

Example 2.1: Preparation of 5-(5.,5-dimethyl-4,5-dihvdro-isoxazol-3-ylsulfanylmethyl)-

1 -methyl-3 -trifluoromethyl- \H-\ 1.2,41triazole

F 3

5-Bromomethyl-l-methyl-3-trifluorometliyl-lH-[l,2,4]triazole (Example 1.2)

(230 mg, 0.94 mmol) was dissolved in ethanol (5 ml) and thiourea (80 mg, 1.03 mmol) was added at ambient temperature. The reaction mixture was heated to reflux for 1 hour. The mixture was allowed to cool to ambient temperature before 3-methanesulfonyl-5,5- dimethyl-4,5-dihydro-isoxazole (200 mg, 1.13 mmol) and potassium carbonate (156 mg, 1.13 mmol) were added. The reaction mixture was heated to reflux for 3 hours. The reaction mixture was allowed to cool to ambient temperature and then concentrated. The residue was partitioned between dichloromethane and water. The phases were separated and the organic phase concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give 5-(5,5-dimethyl-4,5-dihydro- isoxazol-3-ylsulfanylmethyl)-l -methyl-3-trifluoromethyl- lH-[ 1 ,2,4]triazole as a clear mobile oil (210 mg, 76% yield). ¹H-NMR (400 MHz, CDCl₃): 1.41 (s, 6H), 2.82 (s, 2H), 4.02 (s, 3H), 4.35 (s, 2H) ppm.

The following compound was made using the same method described above: 3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-methyl-5-trifluoro- methyl-lH-[l,2,4]triazole from 3-bromomethyl-l-methyl-5-trifluoromethyl-l/i-[l,2,4]- triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-4-methyl-5-trifluoro- methyl-4/f-[ 1 ,2,4]triazole from 3-brornomethyl-4-methyl-5 -trifluoromethyl-4H- [ 1 ,2,4]triazole as starting material. Example 2.2: Preparation of 3-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)- 4,5-dimethyl-4H-|^"l ,2,41triazole

1. NEt₃

3-Chloromethyl-4,5-dimethyl-4H-[l,2,4]triazole hydrochloride salt (preparation 5 according to Synthesis, 2006, 156-160) (653 mg, 3.3 mmol) was dissolved in ethanol (20 ml) and triethylamine (0.5 ml, 3.57 mmol) added at ambient temperature. Thiourea (271 ' mg, 3.57 mmol) was added at ambient temperature and the reaction mixture was heated to reflux for 1 hour. The reaction mixture was allowed to cool to ambient temperature before the addition of 3-methanesulfonyl-5,5-dimethyl-4,5-dihydro-isoxazole (695 mg, 10 3.9 mmol) and potassium carbonate (591 mg, 4.28 mmol). The reaction mixture was heated to reflux for 6 hours and then stored at ambient temperature for 16 hours. The reaction mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: methanol / dichloromethane) to give 3-(5,5-dimethyl-4,5-dihydro- isoxazol-3-ylsulfanylmethyl)-4,5-dimethyl-4H-[l,2,4]triazole as an oil (535 mg, 60% 15 yield). ¹H-NMR (400 MHz, CDCl₃): 1.41 (s, 6H), 2.43 (s, 3H), 2.87 (s, 2H) 3.59 (s, 3H), 4.38 (s, 2H) ppm.

The following compounds were made using the same method described above: 5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-methyl-lH-[l,2,4]- 20 triazole from 5-chloromethyl-l-methyl-lH-[l,2,4]triazole as starting material.

5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l,3-dimethyl-lJJ- [l,2,4]triazole from 5-chloromethyl- 1,3 -dimethyl- IH-[1, 2,4]triazole as starting material. 5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-ethyl-3-methyl-lH- [l,2,4]triazole was prepared from 5-chloromethyl-l-ethyl-3-methyl-lH-[l,2,4]triazole as 25 starting material.

5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-ethyl-lH-[l,2,4]- triazole was prepared from 5-chloromethyl-l-ethyl-lH-[l,2,4]triazole as starting material. 5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-2,4-dihydro-[l,2,4]- triazol-3-one from 5-chloromethyl-2,4-dihydro-[l,2,4]triazol-3-one as starting material.

3-(5,5-Dimethyl-4,5 -dihydro-isoxazol-3 -ylsulfanylmethyl)- 1 -methyl- lH-[ 1 ,2,4] - triazole from 3-chloromethyΗ -methyl- lH-[l,2,4]triazole as starting material. 3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)- 1 ,5-dimethyl- IH-

[l,2,4]triazole from 3-chloromethyl-l,5-dimethyl-lH-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4₃5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-ethyl-5-methyl-lH- [l,2,4]triazole from 3-chloromethyl-l-ethyl-5-methyl-lH-[l,2,4]triazole as starting material. 3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-ethyl-lH-[l,2,4]- triazole from 3-chloromethyl-l-ethyl~lH-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-4-methyl-4H-[l,2,4]- triazole from 3-chloromethyl-4-methyl-4H-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-5-ethyl-4-methyl-4H- [l,2,4]triazole from 3-chloromethyl-5-ethyl-4-methyl-4H-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-4-cyclopropyl-5- ethyl-4H-[l,2,4]triazole from 3-chloromethyl-4-cyclopropyl-5-ethyl-4H-[l,2,4]triazole as starting material.

Example 2.3: Preparation of 5-(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfinylmethvD-l- methyl-3-trifluoromethyl-lH-ri.2,41triazole

M^CPBA

5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l-methyl-3-trifluoro- methyl- IH- [l,2,4]triazole (Example 2.1) (173 mg, 0.58 mmol) was dissolved in dichloro- methane (5 ml) and cooled to 0⁰C. 3-Chloroperoxybenzoic acid ("MCPBA") (145 mg, 0.58 mmol) was added in one portion at 0°C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 1 hour and then stored at ambient temperature for 16 hours. The reaction mixture was diluted with more dichloromethane and aqueous sodium hydrogen carbonate (saturated) and the biphasic mixture stirred vigorously for 15 minutes. The phases were separated and the organic phase was concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give 5-(5,5-dimethyl-4,5-dihydro-isoxazole-3- sulfmylmethyl)-l-methyl-3-trifluoromethyl-lH^"-[l,2,4]triazole as a colourless oil (139 mg, 77% yield). ¹H-NMR (CDCl₃, 400 MHz): 1.49 (s, 3H), 1.51 (s, 3H), 2.87-3.07 (dd, 2H), 4.04 (s, 3H), 4.4-4.64 (dd, 2H) ppm.

The following compounds were made using the same method described above:

5-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-l-methyl-lH- [ 1 ,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)- 1 -methyl- IH-[1, 2,4]triazole.

5-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-l,3-dimethyl-lH- [l,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-l,3- dimethyl-lH-[l,2,4]triazole.

3-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-l-methyl-lH- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-l-methyl- IH-[1, 2,4]triazole.

3-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-5-chloro-l-methyl-lH- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-5-chloro- 1 -methyl-lH-[ 1 ,2,4]triazole. 3-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfmylmethyl)- 1 ,5-dimethyl- IH-

[l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-l,5- dimethyl- lH-[ 1 ,2,4]triazole.

3-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-l-methyl-5-trifluoro- methyl-lH-[l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanyl- methyl)-l-methyl-5-trifluoromethyl-lH-[l,2,4]triazole.

3-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-4,5-dimethyl-4H- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-4,5- dimethyl-4H- [ 1 ,2,4]triazole. Example 2.4: Preparation of 5-(5,5-dimethyl-4.5-dihvdro-isoxazole-3-sulfonylmethyl)-l- methyl-3-trifluoromethyl-lH-ri,2,41triazole

MCPBA

5-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfinylmetliyl)-l-methyl-3-trifluoro- methyl-lH-[l,2,4]triazole (Example 2.3) (86 mg, 0.27 mmol) was dissolved in dichloro- methane (5 ml) and cooled to 0°C. 3-Chloroperoxybenzoic acid ("MCPBA") (leq) was added in one portion at 0°C. The reaction mixture was stirred at ambient temperature for 1 hour then stored at ambient temperature for 16 hours. The reaction mixture was diluted with dichloromethane and aqueous sodium hydrogen carbonate (saturated) and the biphasic mixture stirred vigorously for 15 minutes. The phases were separated and the organic phase was concentrated to give 5-(5,5-dimethyl-4,5-dihydro-isoxazole-3- sulfonylmethyl)-l-methyl-3-trifluoromethyl-lH-[l,2,4]triazole as a clear oil (103 mg, 100% yield) which solidified on standing. ¹H-NMR (CDCl₃, 400 MHz): 1.5 (s, 6H), 3.0 (s, 2H), 4.09 (s, 3H), 4.8 (s, 2H) ppm.

The following compounds were made using the same method described above using two equivalents of MCPBA:

5-(5 , 5 -Dimethyl-4, 5 -dihydroisoxazol-3 -ylsulfonylmethyl)- 1 -methyl- IH- [l,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-methyl- IH-[1 ,2,4]triazole as starting material.

5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-l,3-dimethyl-lH- [l,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l,3- dimethyl-lH-[l,2,4]triazole as starting material.

5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-l-methyl-3-trifluoro- methyl-lH-[l,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanyl- methyl)-l-methyl-3-trifluoromethyl-lH-[l,2,4]triazole as starting material.

5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-3-chloro-l-methyl-lH- [ 1 ,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-3-chloro- 1 -methyl- IH- [l,2,4]triazole as starting material. 5 -(5 , 5 -Dimethyl-4, 5 -dihydroisoxazol-3 -ylsulfonylmethyl)- 1 -ethyl-3 -methyl- IH- [l,2,4]triazole from 5-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-ethyl-3- methyl-lH-[l,2,4]triazole as starting material.

5-[(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl]-l-ethyl-lH^'-[l,2,4]- triazole from 5-[(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl]-l-ethyl-lH- [l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)~ 1 -methyl- IH- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-methyl- IH-[1, 2,4]triazole as starting material. 3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-l-methyl-5-trifluoro- methyl-lH-[l ,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3- ylsulfanylmethyl)-l-methyl-5-trifluoromethyl-lH-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-5-chloro- 1 -methyl- IH- [ 1 ,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmemyl)-5-chloro- 1 -methyl- IH-[1, 2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)- 1 ,5-dimethyl- IH- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l_J5- dimethyl-lH-[l,2,4]triazole as starting material.

3-[(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonybnethyl]-l-ethyl-5-methyl-lH- [l,2,4]triazole from 3-[(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl]-l-ethyl-5- methyl-lH-[l,2,4]triazole as starting material.

3-[(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl]-l-ethyl-lH-[l,2,4]- triazole from 3-[(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl]-l-ethyl-lH- [l,2,4]triazole as starting material. 3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-4-methyl-4H-

[l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-4-methyl- 4H-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-4,5-dimethyl-4H- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-4,5- dimethyl-4H-[ 1 ,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-5-ethyl-4-methyl-4H- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-5-ethyl-4- methyl-4H-[l,2,4]triazole as starting material. 3 -(5 , 5-Dimethyl~4, 5 -dihydroisoxazol-3 -ylsulfonylmethyl)-4-cyclopropyl-5 - ethyl- 4H-[l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-4- cyclopropyl-5-ethyl-4/f-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-4-methyl-5-trifluoro- methyl-4H-[l,2,4]triazole from 3-(5,5-dimetliyl-4,5-dihydroisoxazol-3-ylsulfanyl- methyl)-4-methyl-5-trifluoromethyl-4H-[l,2,4]triazole as starting material.

3-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfonylmethyl)-5-chloro-4-methyl-4H- [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-5-chloro- 4-methyl-4H-[l,2,4]triazole as starting material.

3) Methods for halogenations

Example 3.1: Preparation of 5-r(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfonyl)-fluoro- methyll-l-methyl-3-trifluoromethyl-lH-ri,2,41triazole (Compound No. 1.08 of Table 1) and 5-[r5.5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-difluoro-methyl]-l-methyl-3- trifluoromethyl-lH-ri,2,41triazole (Compound No. 1.07 of Table 1)

5-(5,5-Dimethyl-4,5-dihydro-isoxazole-3-sulfonyl-methyl)-l-methyl-3-trifluoro- methyl-l/i-[l,2,4]triazole (Example 2.4) (294 mg, 0.9 mmol) and iV-fluoro-benzene- sulfonimide ("NFSI") (568 mg, 1.8 mmol) were dissolved in dichloromethane (10 ml) and cooled to O⁰C under a nitrogen atmosphere. l-Ethyl-2,2,4,4,4-pentakis-(dimethyl- amino)-2-lambda⁵'⁴lambda⁵-catenadi-(phosphazene) ("P₂-Et") (678 mg, 1.8 mmol) was added dropwise at O⁰C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 20 minutes. The reaction mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give a clear oil. The oil was triturated with isopropyl alcohol to give Compound No. 1.07 of Table 1 as awhite solid (135 mg, 60% yield). Fractions containing Compound No. 1.08 of Table 1 were purified further by column chromatography on silica gel (eluent: dichloromethane / hexane) to give Compound No. 1.08 of Table 1 as a gum (36 mg, 11% yield).

The following compounds were made using the same method described above:

Compound No. 1.02, 1.04, 1.05, 1.12, 1.13 and 1.14 of Table 1, Compound No. 2.02, 2.03, 2.06, 2.08, 2.11 and 2.12 of Table 2, and Compound No. 3.01, 3.03, 3.04, 3.05, 3.06, 3.07 and 3.08 of Table 3.

Example 3.2: Preparation of 5-[chloro-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)~ methyl14-metfayl-3-trifluorometfavl-l/f-flJ2.41triazole (Compound No. 1.11 of Table 1) ^' and 5-|^"dichloro-(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfonyl)-methyl]-l-methyl-3- trifluoromethvl-lH-π.2.41triazole f Compound No. 1.10 of Table 1)

5-(5,5 -Dimethyl-4, 5 -dihydro-isoxazole-3 -sulfonylmethyl)- 1 -methyl-3 -trifluoro- methyl-lH-[l,2,4]triazole (Example 2.4) (423 mg, 1.3 mmol) was dissolved in tetra- hydrofuran (10 ml) and cooled to 0⁰C under a nitrogen atmosphere. 2-^r^-Butylimino-2- diethylamino-l,3-dimethyl-ρerhydro-l,3,2-diazaρhosρhorine ("BEMP") (0.375 ml, 1.3 mmol) was added dropwise at 0°C. After 10 minutes hexachloroethane (320 mg, 1.3 mmol) was added in one portion at O⁰C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 30 minutes. The reaction mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give Compound No. 1.10 of Table 1 as a solid (18 mg, 4% yield) and Compound No. 1.11 of Table 1 as a clear oil (162 mg, 35% yield).

The following compound was made using the same method described above: Compound No. 1.06 of Table 1.

Example 3.3: Preparation of 5-[chloro-(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfonyl)- fluoro-methyli-l-methyl-S-trifluoromethyl-lH-fl^^itriazole (Compound No. 1.09 of Table 1)

Compound No. 1.11 of Table 1 (Example 3.2) (134 mg, 0.39 mmol) was dissolved in tetrahydrofuran (10 ml) and cooled to 0⁰C under a nitrogen atmosphere. 1- tert-Butyl-2,2,4,4,4-pentakis(dimethylamino)-2-lambda⁵,41ambda⁵-catenadi- (phosphazene) ("P₂-t-Bu") (2M in THF) (0.194 ml, 0.39 mmol) was added dropwise at O⁰C. After 10 minutes N-fluorobenzenesulfonimide ("NFSI") (123 mg, 0.39 mmol) was added in one portion at 0⁰C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 30 minutes. The reaction mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give a residue which was further purified by column chromatography on silica get (eluent: dichloromethane / hexane) to give Compound No. 1.09 of Table 1 as a clear oil (42 mg, 28% yield).

Example 3.4: Preparation of 3-r(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfϊnyl)-difluoro- methyll-4,5-dimethyl-4H-[1.2,41triazole (Compound No. 3.02 of Table 3)

3-(5,5-Dimetliyl-4,5-dihydro-isoxazole-3-sulfinylmethyl)-4,5-dimethyl-4H- [l,2,4]triazole (Example 2.3) (80 mg, 0.31 mmol) and iV-fluorobenzenesulfonimide ("NFSI") (197 mg, 0.62 mmol) were dissolved in tetrahydrofuran (10 ml) and cooled to -78°C under a nitrogen atmosphere. Lithium hexamethyldisilazide ("LiΗMDS") (IM in TΗF) (0.625 ml, 0.62 mmol) was added dropwise at -78°C and the reaction mixture allowed to slowly warm to O⁰C over a period of 5 hours. The reaction mixture was quenched by addition of aqueous ammonium chloride (saturated) at 0⁰C and the mixture extracted with ethyl acetate. The aqueous layer was saturated with sodium chloride and extracted with ethyl acetate. The combined organic extracts were concentrated and the residue partitioned between dichloromethane and water. The organic extract was concentrated and purified by column chromatography on silica gel (eluent: methanol / dichloromethane) to give Compound No. 3.02 of Table 3 as an oil (56 mg, 60% yield) which solidified on standing. M.p. 95-98°C.

The following compounds were made using the same method described above: Compound No. 1.01 and 1.03 of Table 1, and Compound No. 2.01, 2.04, 2.05, 2.07, 2.09 and 2.10 of Table 2.

Table 1 : Compounds of formula (I.I)

Key:

Me = methyl; Et = ethyl; s = singlet; d = doublet; t = triplet; q = quartet; dd = double doublet.

Table Ia: Compounds of formula (LIa)

Key: Me = methyl; Et = ethyl. Table 2: Compounds of formula (1.2)

Key: Me = methyl; Et = ethyl; s = singlet; d = doublet; t = triplet; q = quartet; dd = double doublet. Table 2a: Compounds of formula (I.2a)

Key: Me = methyl; Et = ethyl.

Table 3: Compounds of formula (1.3)

Key;

Me = methyl; Et = ethyl; ⁰Pr = cyclopropyl; s = singlet; d = doublet; t = triplet; q ^: quartet; m - multiplet.

Table 3a: Compounds of formula (I.3a)

Key: Me = methyl; Et = ethyl; ⁰Pr = cyclopropyl.

Biological Examples Example Bl: Herbicidal action Monocotyledonous and dicotyledonous test plants were sown in sterilised standard soil in seed trays each having 96 cells. After one day (pre-emergence) or after 8 to 9 days cultivation (post-emergence) under controlled conditions in a climatic chamber (cultivation at 23/17⁰C, day/night; 13 hours light; 50-60% humidity; after application at 24/19⁰C, day/night), the plants were treated with an aqueous spray solution of 1000 mg/1 of the active ingredient used (incl. 10% DMSO as solvent). The plants were grown on in the climatic chamber until the test was evaluated (10 = total damage to plant, 0 = no damage to plant) after 9 or 13 days.

Table Bl : Application pre-emergence

Comp. No. g/ha DIGSA AGRTE POATR AMARE SE

1.01 1000 10 10 0 10 10

1.02 1000 10 10 10 10 9

1.03 1000 10 10 10 10 9

1.04 1000 10 10 10 10 9

1.05 1000 10 10 10 10 9

1.06 1000 9 0 0 0 6

1.07 1000 10 10 10 10 9

1.08 1000 9 10 10 9 3

1.09 1000 10 10 10 8 9

1.10 1000 9 0 5 0 0

1.11 1000 8 0 5 0 0

1.12 1000 9 10 10 10 9

2.01 1000 9 10 8 6 9

2.02 1000 10 10 0 10 9

2.03 1000 10 10 10 10 10

2.04 1000 9 10 10 10 9

2.05 1000 9 10 10 9 9

2.06 1000 10 10 10 10 9

2.07 1000 9 10 0 5 7

2.08 1000 10 10 10 10 9

2.09 1000 9 10 9 10 9

2.10 1000 9 10 9 9 9

3.01 1000 9 10 10 10 9

3.02 1000 8 9 0 0 7

3.03 1000 9 10 10 10 9

3.04 1000 9 10 9 6 8

3.05 1000 10 10 10 10 9

3.06 1000 10 10 10 10 9

3.07 1000 9 10 10 10 8

3.08 1000 9 10 10 10 9 DIGSA = Digitaria sanguinalis; AGRTE = Agrostis tenius; POATR = Poa trivialis; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi.

Example B2: Herbicidal action Seeds of a variety of test species were sown in standard soil in pots. After 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16⁰C, day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16⁰C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test was evaluated (10 = total damage to plant; 0 = no damage to plant).

Table B2: Application pre-emergence

Comp. No. g/ha SOLNI AMARE SETFA ALOMY ECHCG

1.14 1000 8 10 10 9 10

2.11 1000 8 10 9 9 9

2.12 1000 1 1 7 5 6 SOLNI = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crusgalli.

Example B3 : Herbicidal action

Seeds of a variety of test species were sown in sterilised compost in small pots. After cultivation for seven days (post-emergence) in controlled conditions in the glasshouse (at 24/16⁰C, day/night; 14 hours light; 65% humidity) the plants were sprayed with 1 mg of the active ingredient, formulated in 2.5ml acetone / water (50:50) solution, which is equivalent to 1000 g/ha. Once the foliage was dry, the pots were kept in the glasshouse (at 24/16⁰C, day/night; 14 hours light; 65% humidity), and were watered twice daily. After 13 days the test was evaluated (10 = total damage to plant, 0 = no damage to plant). Table B3: Application pre-emergence

Comp. No. g/ha AMARE DIGSA ALOMY CHEAL

1.13 1000 10 10 9 10

AMARE = Amaranthus retroflexus; DIGSA = Digitaria sanguinalis; ALOMY =

Alopecums myosuroides; CHEAL = Chenopodium album.

Claims

CLAIMS:

1. A compound of formula (I)

wherein

R¹ and R² are each independently of the other hydrogen, d-Cioalkyl, Ci-Ciohaloalkyl, C₃-C₈cycloalkyl or C₃-C₈cycloalkyl-Ci-C₃alkyl, or

R¹ and R² together with the carbon atom to which they are bonded form a C₃-C₇ring,

R³ and R⁴ are each independently of the other hydrogen, Ci-Cioalkyl, Ci-Ciohaloalkyl,

C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-CrCioalkyl or Ci-C₆alkoxy-C₁-C₁₀alkyl, or

R³ and R⁴ together with the carbon atom to which they are bonded form a C₃-C₇ring, or R¹ with R³ or R⁴ and together with the carbon atoms to which they are bonded form a

C₅-C₈ring, or

R² with R³ or R⁴ and together with the carbon atoms to which they are bonded form a

C₅-C₈rmg;

R⁵ is halogen or Ci-C₆haloalkyl; R⁶ is hydrogen, cyano, Ci-C₆alkyl, d-C_όalkoxycarbonyl, halogen or Ci-Cβhaloalkyl; m is 0, 1 or 2; n is 1, 2 or 3; and

Y is one of the following groups

wherein

R⁷ is hydrogen,

C₁- Cioalkoxycarbonyl, Ci-Ciohaloalkyl, C₂-C₁oalkenyl, C₂-Cioalkynyl, C₃-Ciocycloalkyl, C₃- Ciocycloalkyl-Ci-Ci₀alkyl, Ci-C₁₀alkylcarbonyl-Cj-C₁₀alkyl, Ci-Ci₀alkylsulfonyl, C₁- Ciohaloalkylsulfonyl or CrQoalkoxy-CrQoalkyl; R⁸ is hydrogen, Ci-C_loalkyl, Cj-CiQalkylcarbonyl,

C₁-

Qoalkoxycarbonyl, Crdohaloalkyl, C₂-C₁oalkenyl, C₂-Cioalkynyl, C₃-C₁OCyClOaIlCyI, C₃- C^cycloalkyl-d-doalkyl, halogen, thiol, hydroxy, cyano, Ci-Ci_Oalkylsulfanyl, Ci- Ciohaloalkylsulfanyl, CrCioalkylsulfinyl, Cj-Ciohaloalkylsulfinyl, Ci-C₁₀alkylsulfonyl, Ci-Ciohaloalkylsulfonyl, Ci-C_]0alkoxy, Q-Qohaloalkoxy, or NR⁹R¹⁰ wherein R⁹ and R¹⁰ are independently of each other hydrogen, C]-C₆alkyl, Ci-C₆haloalkyl, Q-CόCycloalkyl, Q-Coalkylcarbonyl, Ci-Cehaloalkylcarbonyl, Q-Cealkylsulfonyl, Q-Cehaloalkyl- sulfonyl, or R⁹ and R¹⁰ together form a C₃-C₈alkylene group which optionally contains one oxygen, sulfur, amino or an d-Cealkylamino group; and to iV-oxides, salts and optical isomers of compounds of formula (I).

2. A compound according to claim 1 in which R¹ and R² are independently C₁- C^alkyl or Q-Qohaloalkyl.

3. A compound according to claim 1 or claim 2 in which R¹ and R² are both methyl.

4. A compound according to any one of claims 1 to 3 in which R³ and R⁴ are both hydrogen.

5. A compound according to any one of claims 1 to 4 in which R⁵ is halogen or trifluoromethyl.

6. A compound according to any one of claims 1 to 5 in which R⁵ is fiuoro or chloro.

7. A compound according to any one of claims 1 to 6 in which R is hydrogen, methoxycarbonyl, d-C₆alkyl or halogen.

8. A compound according to any one of claims 1 to 7 in which R⁶ is hydrogen, fiuoro or chloro.

9. A compound according to any one of claims 1 to 8 in which m is 1 or 2.

10. A compound according to any one of claims 1 to 9 in which n is 1.

11. A compound according to any one of claims 1 to 10 in which Y is one of the following groups

12. A compound according to any one of claims 1 to 11 in which R⁷ is hydrogen, C₁- Ci_Oalkyl, Q-Ciohaloalkyl, C₃-C₁₀cycloalkyl or CrCiocycloalkyl-CrQoalkyl.

13. A compound according to any one of claims 1 to 12 in which R⁷ is hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl or cyclopropylmethyl.

14. A compound according to any one of claims 1 to 13 in which R⁸ is hydrogen, C₁- C₁₀alkyl, Q-Qohaloalkyl, C₃-C₁ ocycloalkyl,

halogen, cyano, Ci-C₁₀alkoxy or C₁-C₁₀ImIOaIkOXy.

15. A compound according to any one of claims 1 to 14 in which R⁸ is hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy.

16. A process in which a compound of formula (Id) is formed

by reacting a compound of formula (VIII) wherein R⁵, R⁶ and Y are as defined in claim 1 and M^B is selected from the group comprising MgCl, MgBr, ZnBr and Li,

with a compound of formula (IX),

wherein R¹, R², R³ and R⁴ are as defined in claim 1, optionally in the presence of a diluent.

17. A process in which a compound of formula (Id) is formed

by reacting a compound of formula (Ha) wherein R⁵, R⁶ and Y are as defined in claim 1 and X^D is functional group that may be cleaved as a radical,

with a compound of formula (IX),

wherein R¹, R², R³ and R⁴ are as defined in claim 1 with a radical initiator or a precursor thereof, optionally in the presence of a base and optionally in the presence of a diluent.

18. A process in which a compound of formula (Id) is formed

by reacting a compound of formula (II) wherein R⁵, R⁶ and Y are as defined in claim 1, and X^A is a leaving group selected from the group comprising halogen, an alkylsulfonate, an arylsulfonate, and a haloalkylsulfonate,

with a compound of formula (IX)

wherein R¹, R², R³ and R⁴ are as defined in claim 1 in the presence of a reducing agent, optionally in the presence of a base and optionally in the presence of a diluent.

19. A method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 15.

20. A herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 15 in addition to formulation adjuvants.

21. A herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 15, optionally one or more further herbicides, and optionally one or more safeners.