WO2010112826A2 - Herbicidal compounds - Google Patents

Abstract

The present invention relates to novel herbicidal compounds of Formula (I), or an agronomically acceptable salt of said compound wherein X₁, X₂, R¹, R², R³, m and Q are as defined herein. The invention further relates to processes and intermediates for the preparation of the novel herbicidal compounds, to compositions which comprise the herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL COMPOUNDS

The present invention relates to novel herbicidal [l,6]-naphthyridines and [l,7]-naphthyridines, to processes for their preparation, to compositions which comprise the herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.

According to the present invention there is provided a herbicidal compound of Formula (I).

or an agronomically acceptable salt of said compound,

wherein:-

X₁ is N(0)n and X₂ is CR⁴; or X₂ is N(O)n and Xj is CR⁵;

R¹ is selected from the group consisting of C]-C₃alkyl, C]-C₃haloalkyl, Ci-C₃alkoxy- C_1-C₃ alkyl, C₁-C₃ alkoxy-C₂-C₃alkoxy-Ci-C₃-alkyl, d-Qjalkoxy-Ci-s-haloalkyl, Q- C₃-alkoxy-Ci-C₃ -alkoxy-Ci -C₃ -haloalkyl, C₄-C₆ -oxasubstituted cycloalkoxy-Ci-C₃ ^■ alkyl, C₄-C₆-oxasubstituted cycloalkyl-Ci-C₃-alkoxy-C]-C₃ -alkyl, C₄-C₆- oxasubstituted cycloalkoxy-Ci-C₃ -haloalkyl, C₄-C₆-oxasubstituted cycloalkyl-C_!-C₃- alkoxy-Ci-C₃ -haloalkyl, (C₁-C₃ alkanesulfonyl-Ci-C₃ alkylamino)-Ci-C₃ alkyl and (C₁-C₃ alkanesulfonyl-C₃-C ₄ cycloalkylamino)-Ci-C₃ alkyl; R² is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃- C₆cycloalkyl, Ci-C_δhaloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂-C₆alkenyl, C₃-C₆alkynyl, Ci-C₆alkoxy, C_rC₆haloalkoxy, Ci-C₆alkylthio, Ci-C₆alkylsulfinyl, d- C₆alkylsulfonyl, Ci-C₆haloalkylthio, Ci-C_όalkylamino, C₂-C₆dialkylamino, C₂- C₆alkenylamino, Ci-Cβalkoxy C₂-C₄alkylamino, (Ci-C₆alkoxy C₂-C₄alkyl) Ci-

C₃alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, d-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino or a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, and/or optionally substituted by Ci-C₃-alkoxy or halogen (especially fluorine), C₁- C₆dialkylaminosulfonyl, C₂-C₆alkylaminosulfonyl, C]-C₆alkoxy-Ci-C₆alkyl, C_1-6 alkoxy-C_1-6 alkoxy-C_1-6-alkyl, C₂-C₆alkenyl-Ci-C₆alkoxy-d-C₃-alkyl, C₃-C₆alkynyl- Ci-C₆alkoxy-Ci-C₃alkyl, d-C₆alkoxycarbonyl, Ci-C₄alkylenyl-S(O)p-R' , C₁- C₄alkylenyl-CO₂-R', C₁-C₄alkylenyl-(CO)N-R'R', aryl and 5 or 6-membered heteroaryl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Ci-C₃alkyl, C]-C₃haloalkyl, C₁-C₃ alkoxy, Crdhaloalkoxy, halo, cyano and nitro;

R³ is hydrogen, chloro or methyl;

R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃- C₆cycloalkyl, d-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂-C₆alkenyl, C₃-C₆alkynyl, Ci-C₆alkoxy, C₄-C₇ cycloalkoxy, d-C₆haloalkoxy, Ci-C₆alkylthio, Ci- C₆alkylsulfinyl, d-C₆alkylsulfonyl, d-C_όhaloalkylthio, amino, d-C₆alkylamino, C₂- C₆dialkylamino, C₂-C₆alkenylamino, Ci-C₆alkoxy-C₂-C₆-alkylamino, (Ci-C₆alkoxy- C₂-C₄-alkyl)-Ci-C₆-alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, CrC₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino, dialkylamino in which the substituents join to form a 4-6 membered ring (e.g pyrrolidinyl, piperidinyl) optionally containing oxygen (e.g morpholinyl) and/or optionally substituted by C₁- C₃-alkoxy and/or halogen especially fluorine, C₂-C₆dialkylaminosulfonyl, Ci- C₆alkylaminosulfonyl, Ci-C₆alkoxy-Ci-C₆alkyl, Ci-C₆alkoxy-C₂-C₆alkoxy, C_r C₆alkoxy-C₂-C₆ alkoxy-Ci-C₆-alkyl, C₃-C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-Ci- C₆alkoxy, Ci-C₆alkoxycarbonyl, Ci-C₆alkylcarbonyl, Ci-C₄alkylenyl-S(O)p-R', Cr C₄alkylenyl-CO₂-R', C_rC₄alkylenyl-(CO)N-R'R\ aryl (e.g. phenyl), aryl d-C₃alkyl, phenylthio, phenylsulfinyl, phenylsulfonyl, aryloxy (e.g phenoxy) and 5 or 6- membered heteroaryl, heteroaryloxy or heteroaryl Ci-C₃ alkyl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Ci-C₃alkyl, d-C₃haloalkyl, C₁-C₃ alkoxy, Ci-C₃haloalkoxy, halo, cyano and nitro;

R⁵ is hydrogen, halogen or methyl;

m = 0 or 1 ;

n = 0 or 1;

provided that if m is 1 n is 0, and if n is 1 m is 0;

p - 0, lor 2;

R' is independently selected from the group consisting of hydrogen and Ci-Cβalkyl;

Q is selected from the group consisting of:-

and

wherein A' is selected from the group consisting of O, C(O), S, SO, SO₂ and (CR e^eτR> f\ )_q; q = O, 1 or 2; R\ R^b, R^c, R^d, R^e and R^f are each independently selected from the group consisting of Ci-C₄alkyl which may be mono-, di- or tri-substituted by substituents selected from the group consisting of Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Q-Cialkoxycarbonyl, Ci-C₄alkylthio, Ci-C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, C]- C₄alkylcarbonyl, phenyl and heteroaryl, it being possible for the phenyl and heteroaryl groups in turn to be mono-, di- or tri-substituted by substituents selected from the group consisting of Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Ci-C₄alkoxycarbonyl, d-C₄alkylsulfonyl and Ci-C₄haloalkyl, the substituents on the nitrogen in the heterocyclic ring being other than halogen; or

R^a, R , R^c, R^d, R^e and R^f are each independently selected from the group consisting of hydrogen, Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Ci- C₄alkoxycarbonyl, Ci-C₄alkylthio, Ci-C₄alkylsulfinyl, d-C₄alkylsulfonyl, Ci- C₄alkylcarbonyl, phenyl or heteroaryl, it being possible for the phenyl and heteroaryl groups in turn to be mono-, di- or tri-substituted by substituents selected from the group consisting of C]-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Ci-C₄alkoxycarbonyl, Ci-C₄alkylsulfonyl and d-C₄haloalkyl, the substituents on the nitrogen in the heterocyclic ring being other than halogen; or

R^a and R^b together form a 3- to 5-membered carbocyclic ring which may be substituted by Ci-C₄alkyl and may be interrupted by oxygen, sulfur, S(O), SO₂, OC(O), NR^g or by C(O); or

R^a and R^c together form a Ci-C₃alkylene chain which may be interrupted by oxygen, sulfur, SO, SO₂, OC(O), NR^h or by C(O); it being possible for that Ci-C₃alkylene chain in turn to be substituted by Ci-C₄alkyl;

R^ε and R^h are each independently of the other Ci-C₄alkyl, Ci-C₄haloalkyl, Q- C₄alkylsulfonyl, Ci-C₄alkylcarbonyl or Ci-C₄alkoxycarbonyl;

R¹ is Ci-C₄alkyl;

R^j is hydrogen, or Ci-C₄alkyl or CrQcycloalkyl such as methyl or cyclopropyl; R^k is selected from the group consisting of C|-C₆alkyl, optionally substituted with halogen and/or Ci-C₃alkoxy; and C₃-C₆ cycloalkyl optionally substituted with halogen and/or Ci-C₃alkoxy;

R⁶ is selected from the group consisting of cyclopropyl, CF₃ and i.-Pr;

R⁷ is selected from the group consisting of H, I, Br, SR⁸, S(O)R⁸, S(O)₂R⁸ and CO₂R⁸; and

R⁸is C_1-4 alkyl.

Halogen is, generally, fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl or halophenyl.

Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fiuoromethyl, difluoromethyl, trifiuoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difiuoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2- trichloroethyl, pentafluoroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl

Suitable alkyleneyl radicals include, for example CH₂, CHCH₃, C(CH₃)₂, CH₂CHCH₃, CH₂CH(C₂H₅).

Suitable haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and especially fluorine or chlorine, for example 2,2-difluoro-l-methylvinyl, 3-fluoropropenyl, 3- chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-l-yl. Preferred C₂-C₆alkenyl radicals substituted once, twice or three times by halogen are those having a chain length of from 2 to 5 carbon atoms. Suitable haloalkynyl radicals include, for example, alkynyl groups substituted one or more times by halogen, halogen being bromine or iodine and, especially, fluorine or chlorine, for example 3-fluoropropynyl, 5-chloropent-2-yn-l-yl, 5- bromopent-2-yn-l-yl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-l-yl. Preferred alkynyl groups substituted one or more times by halogen are those having a chain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.

Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl.

Haloalkoxy is, for example, fiuoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfmyl, ethylsulfmyl, propylsulfinyl, isopropylsulfϊnyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfinyl or tert- butylsulfmyl, preferably methylsulfmyl or ethylsulfmyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert- butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Cycloalkylamino or dicycloalkylamino is, for example cyclohexyl or dicyclopropylamino.

Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.

Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and may be substituted by one or more methyl groups; they are preferably unsubstituted, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Phenyl, including phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl, may be in mono- or poly-substituted form, in which case the substituents may, as desired, be in the ortho-, meta- and/or para-position(s).

Heterocyclyl, for example, includes morpholinyl, tetrahydrofuryl.

Heteroaryl, including heteroaryl as part of a substituent such as heteroaryloxy, means a five or six member heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur. It should be understood that the heteroaryl component may be optionally mono or poly substituted. The term heteroaryl thus includes, for example, furanyl, thiopheneyl, thiazole, oxazole, isoxazole, thiazole, pyrazole, isothiazole, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazole.

Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.

Similarly, where there are disubstituted alkenes, these may be present in E, or Z form or as mixtures of both in any proportion.

Compounds of Formula (I) wherein Q is Ql, Q5, Q6 or Q7 may be in equilibrium with alternative hydroxyl tautomeric forms. It should be appreciated that all tautomeric forms (single or mixtures thereof), racemic mixtures and isomers are included within the scope of the present invention.

The skilled person will also appreciate that if n or m is 1, with regard to Formulae 1, for these compounds to form the N-oxide then the nitrogen and oxygen will be charged accordingly (N⁺ O^").

In a preferred embodiment the herbicidal compound is of Formula Ia or Ib:

In a more preferred embodiment of the present invention Q is Ql, in particular wherein A¹ is CR^eR^f and wherein R^a, R^b, R^c, R^d, R^e and R^f are hydrogen, and wherein q = l.

In another preferred embodiment of the present invention Q is Ql, wherein A¹ is CR^eR^f and wherein, R^b, R^d, R^e and R^f are hydrogen, R^a and R^c together form an ethylene chain and wherein q = 1 In another preferred embodiment R¹ is (i) haloalkyl, in particularly fluoroalkyl, and most preferably difluoromethyl or trifluoromethyl, or (ii) Ci-C₃alkoxy-Ci-C₃- haloalkyl, in particular Ci-C₃alkoxy-Ci-C ₃-fluoroalkyl, most preferably methoxydifluoromethyl or 2-methoxy-l,l,-difluoroethyl.

In another preferred embodiment R² is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1-methylethyl, cyclopropyl, fluoromethyl, 1- fluoroethyl, 1,1-difluoroethyl, 1-fluoro- 1-methylethyl, ethoxy, methoxy, methoxymethyl, 1-methoxyethyl, 2-methoxyethoxy, 2-methoxyethoxymethyl, 2,2,2- trifluoroethoxy, (2-methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl.

In another preferred embodiment R³ is hydrogen.

In another preferred embodiment R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃-C₆cycloalkyl, Ci-C₆ haloalkyl, Ci-C₆ alkoxy, C₃- C₆ cycloalkoxy, Cj-C₆ alkoxy-C₂-C₆-alkoxy, Ci-C₆-alkoxy-Ci-C₆ alkyl, Ci-C₆- alkoxy-C₂-C₆-alkoxy-Cj-C₆ alkyl, Ci-C₆alkylamino, Ci-C₆dialkylamino, C₂- C₆alkenylamino, Ci-C₆alkoxy-C₂-C₃-alkylamino, (Ci-C₆alkoxy-C₂-C₃-alkyl) -C]-C₃- alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino and a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, or optionally substituted by Ci-C₃-alkoxy or halogen (especially fluorine), phenyl and heteroaryl_.

In an even more preferred embodiment R⁴ is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1-methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1-fluoro- 1-methylethyl, methoxy, ethoxy, methoxymethyl, 1-methoxyethyl, 2-methoxyethoxy, 2-methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2-methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl.

In another preferred embodiment R⁵ is hydrogen. The present invention also includes agronomically acceptable salts that the compounds of Formula I may form with amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers, emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium. The corresponding trimethylsulfonium salt may also be used.

The compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface- active agents (SFAs). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

For the avoidance of doubt, reference to compounds of Formula I below includes reference to compounds of either Formula (Ia) and (Ib).

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.

The compositions can be chosen from a number of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifϊable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).

Dustable powders (DP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre- formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

Emulsifϊable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N- methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C₈- C₁₀ fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.

Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 7O⁰C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water- soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I).

SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example ra-butane). A compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent thereof. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment. A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I))-

Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SFAs of the cationic type include quaternary ammonium compounds

(for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-wopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3 -sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

The composition of the present may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment the additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula I). I + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + ametryn, I + amicarbazone, I + amidosulfuron, I + aminopyralid, I + amitrole, I + anilofos, I + asulam, I + atrazine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I + bromoxynil, I + butachlor, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, I + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal- dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl,, I + 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedipham, I + dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofop-methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron-methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop-P, I + fenoxaprop-P-ethyl, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop-butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone-sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + fiumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + fluoroglycofen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate-ammonium, I + glyphosate, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I + indaziflam,I + iodomethane, I + iodosulfuron, I + iodosulfuron-methyl- sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor, I + methabenzthiazuron, I + methazole, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + molinate, I + monolinuron, I + naproanilide, I + napropamide, I + naptalam, I + neburon, I + nicosulfuron, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + phenmedipham, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyrafiufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxsulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + topramezone, I + tralkoxydim, I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, I + [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-dioxo- l,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), 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), and I + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3- pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one. The compounds of the present invention may also be combined with herbicidal compounds disclosed in WO06/024820 and/or WO07/096576. 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, Fourteenth Edition, British Crop Protection Council, 2006.

The compound of Formula I can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

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 safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31-8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, and N- isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4). Other possibilities include safener compounds disclosed in, for example, EP0365484. Particularly preferred are mixtures of a compound of Formula I with cyprosulfamide, isoxadifen-ethyl and/or cloquintocet-mexyl.

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, 14^th Edition (BCPC), 2006. 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).

The present invention still further provides a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention. 'Controlling' means killing, reducing or retarding growth or preventing or reducing germination. Generally the plants to be controlled are unwanted plants (weeds). 'Locus' means the area in which the plants are growing or will grow.

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 weed(s) 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.

The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.

Useful plants in which the composition according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf. Maize is particularly preferred.

Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.

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-, ACCase- 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®.

In a preferred embodiment the crop plant is rendered tolerant to HPPD- inhibitors via genetic engineering. Methods of rending crop plants tolerant to HPPD- inhibitors are known, for example from WO0246387. Thus in an even more preferred embodiment the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.

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 to include 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). Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.

The compositions can be used to control unwanted plants (collectively, 'weeds'). The weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. Weeds can also include plants which may be considered crop plants but which are growing outside a crop area ('escapes'), or which grow from seed left over from a previous planting of a different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain other herbicides.

Preparation of compounds of the present invention is outlined in the following schemes.

Preparation of compounds Formula (I)

where Q is selected from Ql and Q5 is carried out analogously to known processes (for example those described in WO97/46530, EP0353187 and US 6,498,125) and comprises reacting a compound of the following formula:

where the definitions R², R³, R⁴, R⁵, X₁, X₂, n and m are as for Formula (I) and LG is a suitable leaving group, for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group, such as 4-nitrophenoxy, in an inert organic solvent, such as dichloromethane or acetonitrile, in the presence of a base, such as triethylamine, with compounds

wherein

A¹ and R^a, R^b, R^c, R^d, R^e, R^f and R^! , R^j are as defined previously;

to give the following esters (3a) or (3b):

which may be rearranged using catalysts, such as 4-dimethylaminopyridine, or acetone cyanhydrin, or a metal cyanide salt, such as sodium cyanide, in the presence of a suitable base, such as triethylamine, to give compounds of Formula (I). It is advantageous to have a dehydrating agent, such as molecular sieves, present in the reaction medium to ensure any water initially present in the solvent or associated with the other components of the reaction mixture is prevented from causing any unwanted hydrolysis of intermediates. Scheme 1

e.g. e.g.

(3b)

Similar, analogous transformations can be used to produce isomeric [1,7] naphthyridines and [l,6]naphthyridines of Formula (I).

[l,7]Naphthyridine-3-carboxylic acid derivatives of Formulae 3a and 3b where X₂ is N(0)n and [l,6]naphthyridine-3-carboxylic acid derivatives of Formulae 3 a and 3b where X₂ is N(0)n may be prepared from carboxylic acids, for example by reaction with a suitable halogenating agent, such as oxalyl chloride, in a suitable inert solvent, such as dichloromethane, to generate the corresponding carboxylic acid chlorides. These derivatives may in turn be reacted with, for example, 4-nitrophenol and a suitable base, such as triethylamine, in an inert solvent, such as dichloromethane, to generate the corresponding 4-nitrophenyl esters.

By way of illustration as shown in Scheme 2, [l,7]naphthyridine-3-carboxylic acid esters of Formula 4a and [l,6]naphthyridine-3-carboxylic acid esters of Formula 4b may be obtained from 3-amino-4-formylpyridines and 4-amino-3-formylpyridines analogous to methods described in the literature [J. Org. Chem. 1990, 55, 4744-4750; Indian Journal of Chemistry, Section B;Organic Chemistry including Medicinal Chemistry (2006), 45B(4), 1051-1053; Indian Journal of Chemistry , Section B;Organic Chemistry including Medicinal Chemistry (2004), 43B(4), 897-900; J Org. Chem. (1993), 58(24), 6625-6628; J Chem. Soc.Org. (1966), (3), 315-321]. Scheme 2

The required β-ketoesters are either commercially available or may be prepared analogously to methods described in the literature.

The required 3-amino-4-formylpyridines and 4-amino-3-formylpyridines are either commercially available or may be prepared by methods described in the literature [for example Comptes Rendus des Seances de I'Academie des Sciences, Serie C: Sciences

Chimiques (1975), 280(6), 381-3,

J. Org. Chem. 1983, 48, 3401-3408 and J. Org. Chem. 1990, 55, 4744-4750] or by analogous methods.

By way of illustration as shown in Scheme 3, optionally substituted 4-aminopyridines may be N-acylated, for example with a suitable acylating reagent, such as acetyl chloride or pivaloyl chloride, and a suitable base, such as triethylamine, optionally with a suitable acylation catalyst such as 4-dimethylaminopyridine, in an inert solvent, such as dichloromethane, to give the corresponding iV-(pyridin-4-yl)amides. Analogous to methods described in the literature, these amides may in turn be reacted with a strong base, such as n.butyllithium or t.butyl lithium and then a formyl transfer agent, such as 7V,7V-dimethylformamide or N-formyl-N-methylaniline, to give the corresponding N-(3-forrnylpyridin-4-yl)amides. The required 4-amino-3- formylpyridines can be obtained by hydrolysis of these amides using, for example, aqueous hydrochloric acid heated under reflux for 1 to 24 hours. Similar processes can also be conducted to produce 3-amino-4-formylpyridines from 3-aminopyridines. Scheme 3

solvent e.g. CH₂CI₂

1. strong base 2. formyl transfer e α t BuLi reagent e.g. t.BuLi J e.g. Me₂NCHO

With regard to scheme 3, R'" is for example, Ci-C₆ alkyl.

Alternatively, as shown in Scheme 4, 3-aminopyridine-4-carboxylic esters may be reduced, using a suitable reducing agent, such as lithium aluminium hydride, in a suitable solvent, such as tetrahydrofuran, to 3-amino-4-hydroxymethylpyridyl esters and subsequently oxidised, using a suitable oxidising agent, such as manganese dioxide, in a suitable solvent , such as dichloromethane, to the required 3-amino-4- formylpyridines.

Scheme 4

CO₂R- reducing agent e.g. LiAIH4

NH, solvent e.g. THF

As shown in Scheme 5, [1,6] or [l,7]naphthyridine-3-carboxylic acid esters of Formula 5 may be conveniently hydrolysed to the corresponding carboxylic acids (6) using standard procedures, for example using aqueous sodium hydroxide and an inert co-solvent such as ethanol, or lithium hydroxide in aqueous tetrahydrofuran. Scheme 5

As shown in Scheme 6, [lJjnaphthyridine-S-carboxylic acid esters of Formula 5 may be conveniently converted to the corresponding N-oxides using a suitable oxidant, such as a peracid, for example per-trifluoroacetic acid generated from urea hydrogen peroxide complex and trifluoroacetic acid anhydride. The N-oxides generated may be further reacted with a suitable acid halide reagent, such as phosphoryl chloride, optionally with a suitable base, such as triethylamine, in a suitable solvent, such as dichloromethane or 1,2-dichloroethane, at 2O⁰C to 100⁰C to give the 8-halo derivatives. Similar reactions may also be also be conducted with analogous [l,6]-naphthyridine esters.

Scheme 6 peracid e.g.

acid halide base e.g. e.g. Et₃N

POCI₃ solvent e.g. CH₂CI₂

With regard to scheme 6, R¹ is, for example, Ci-C₄ alkyl.

As shown in Scheme 7, 8-halo-[l,7]naphthyridines may be further transformed into additional [l,7]naphthyridines useful for preparing compounds of Formula (I). For example, when R³ is hydrogen or methyl and R² is a chlorine atom, the chlorine may be displaced by an alkoxide reagent, such as sodium ethoxide, in a suitable solvent, such as tetrahydrofuran or ΛfN-dimethylformamide or an alcohol, such as ethanol, to generate the corresponding 8-alkoxy[l,7]naphthyridine. Similarly, 8- halo[l,7]naphthyridines may be reacted with an amine, such as morpholine, in a suitable solvent, such as tetrahydrofuran, to generate the corresponding 8- alkylamino[l,7]naphthyridine or 8-dialkylamino[l,7]naphthyridine. Additionally, 8- halo- [l,7]naphthyridines, such as 8-chloro[l,7]naphthyridines or 8-alkoxy- [l,7]naphthyridines, such as 8-methoxy[l,7]naphthyridines, may be converted to 7- hydroxy-[l,8]naphthyridines, for example by hydrolysis under acidic conditions, such as heating with aqueous hydrochloric acid. Such reactions may be conducted at temperatures from 2O⁰C to 15O⁰C, for example in a microwave oven.

Additionally, 8-hydroxy[l,7]naphthyridines may be transformed to the corresponding haloalkanesulfonate esters of [l,7]naphthyridines, such as 8- trifluoromethanesulfonyloxy[l,7]naphthyridines, with a suitable acylation agent, such as trifiuoromethane sulfonic anhydride, and a suitable base, such as triethylamine, in a suitable solvent , such as dichloromethane.

In another aspect, 8-halo [l,7]naphthyridines , such as 8-chloro[l,7]naphthyridines, or 8-haloalkanesulfonate esters of [l,7]naphthyridines, such as 8- trifluoromethanesulfonyloxy[l,7]naphthyridines, may be reacted with an alkyl or aryl or heteroaryl boronic acid reagent, such as methyl boronic acid or phenyl boronic acid or 3-thienylboronic acid, in the presence of a palladium catalyst, such as palladium acetate, and a suitable base such as potassium phosphate and a suitable palladium ligand, such as dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl) phosphane, to generate 8-methyl or 8-phenyl or 8-(thienyl-3-yl)[l,7]naphthyridine derivatives.

Scheme 7

Examples

Abbreviations as used in the following Examples are as follows: s= singlet, d=doublet, t= triplet, m= multiplet, bs = broad signal, bm = broad multiplet, dd = double doublet, dt = double triplet, td = triple doublet and dq - double quartet.

Example 1

Preparation of 2-(2-trifluoromethyl-[l,71-naphthyridine-3-carbonyl)-cvclohexane-l, 3- dione To a stirred solution of 2-trifluoromethyl-[l,7]-naphthyridine-3-carboxylic acid - (0.250 g) in dichloromethane (2ml) under an atmosphere of nitrogen was added oxalyl chloride (0.17 ml) and the reaction was stirred for 30 minutes. The solvents were evaporated under reduced pressure and the residue dissolved into dry acetonitrile (6 ml) and added dropwise to a stirred solution of cyclohexane-1,3- dione (0.127 g) and triethylamine (0.17 ml) in dry acetonitrile (3 ml) under an atmosphere of nitrogen at room temperature. The mixture was stirred for 2 hours then triethylamine (0.29 ml) and acetone cyanohydrin (0.047ml) were added and the reaction was stirred at ambient temperature for 18 hours. The reaction mixture was evaporated under reduced pressure to give a brown oil which was fractionated by chromatography (silica;

(toluene:dioxane;ethanol:triethylamine:water; ratio by volume 20:8:4:4:1) to yield the required product as a triethylamine salt. This salt was dissolved in ethyl acetate and the organic phase was acidified with dilute HCl. The organic phase was separated and the aqueous phase re-extracted with ethyl acetate. The extracts were combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure to yield the required product, 0.149g. ¹HNMR (CD₃OD) δ: 9.52(1Η, s); 8.69(1H, d); 8.35(1H, s); 7.93(1H, d); 2.63(4H, m); 2.00-2.14(2H, m).

In a similar process to Example 1, 2-difiuoromethyl-[l,7]-naphthyridine-3-carboxylic acid was reacted with cyclohexane-1,3 -dione to give 2-(2-difluoromethyl-[l,7]- naphthyridine-3-carbonyl)-cyclohexane-l,3-dione. ¹HNMR (CZ)₃Oi)) δ: 9.68(1Η, s); 8.75(1H, d); 8.45(1H, s); 8.19(1H, d); 6.97(1H, t); 2.67(4H, m); 2.01-2.15(2H, m).

In a similar process to Example 1, 2-methyl-[l,7]-naphthyridine-3-carboxylic acid was reacted with cyclohexane -1,3-dione to give 2-(2-methyl-[l,7]-naphthyridine-3- carbonyl)-cyclohexane-l,3-dione. ¹HNMR (CD₃OD) δ: 9.24(lΗ,s); 8.48(lH,d); 7.77- 7.93(2H, m); 2.70(3H, s); 2.39(4H, m); 1.93-2.01 (2H, m).

In a similar process to Example 1, 8-methyl-2-trifluoromethyl-[l,7]-naphthyridine-3- carboxylic acid was reacted with cyclohexane -1,3-dione to give 2-(8-methyl-2- trifluoromethyl-[ 1 Jj-naphthyridine-θ-carbonyty-cyclohexane- 1 ,3-dione, yellow gum. ¹HNMR (CDCl₃) δ: 2.03-2.12 (2H, m), 2.39-2.46 (2H, m), 2.81-2.89 (2H, m), 3.15

(3H, s), 7.54 (lH,d), 7.97 (IH, s), 8.60 (IH, d) and 16.80 (IH, s).

In a similar process to Example 1, 8-methoxy-2-trifluoromethyl-[l,7]-naphthyridine- 3-carboxylic acid was reacted with cyclohexane-1,3- dione to give 2-(8-methoxy-2- trifluoromethyl-[ 1 ,7]-naphthyridine-3-carbony)-cyclohexane- 1 ,3-dione, solid, ¹H NMR (CDCl₃) δ: 2.03-2.11 (2Η, m), 2.38-2.48 (2H, m), 2.79-2.89 (2H, m), 4.25 (3H, s), 7.23 (lH,d), 7.92 (IH, s) and 8.20 (IH, d).

In a similar process to Example 1, 8-ethoxy-2-trifluoromethyl-[l,7]-naphthyridine-3- carboxylic acid was reacted with cyclohexane-1,3- dione to give 2-(8-ethoxy-2- trifluoromethyl-[l,7]-naphthyridine-3-carbony)-cyclohexane-l,3-dione), solid, ¹H NMR (CDCl₃) δ: 1.58 (3Η,t), 2.03-2.11 (2H, m), 2.30-2.95 (4H,br m), 4.71 (2H, q), 7.21 (lH,d), 7.91 (IH, s) and 8.18 (IH, d).

In a similar process to Example 1, 8-methoxy-2-trifluoromethyl-[l,7]-naphthyridine- 3-carboxylic acid was reacted with 2,2,4,4,-tetramethylcyclohexane-l,3,5-trione to give 6-(8-methoxy-2-trifluoromethyl-[ 1 ,7]-naphthyridine-3-carbony)-(2,2,4,4- tetramethylcyclohexane-l,3,5-trione), ¹HNMR (CDCZj) δ: 1.31 (6Η, s), 1.61 (6H, s), 4.28 (3H, s), 7.28 (IH, d), 8.01 (IH, s) and 8.25 (IH, d).

In a similar process to Example 1, 8-methoxy-2-trifluoromethyl-[l,7]-naphthyridine- 3-carboxylic acid was reacted with bicyclo [3.2.1]octane-2,4-dione to give 3-(8- methoxy-2-trifluoromethyl-[l,7]-naphthyridine-3-carbony)-bicyclo[3.2.1]octane-2,4- dione, ¹HNMR (CDCl₃) δ: 1.70-2.32 (6Η, m), 2.88 (IH, br t), 3.19 (IH, br t), 4.25 (3H, s), 7.24 (IH, d), 7.95 (IH, s) and 8.21 (IH, d).

Similarly, 8-ethoxy-2-trifluoromethyl-[l,7]-naphthyridine-3-carboxylic acid was reacted with 2,2,4,4,-tetramethylcyclohexane- 1,3, 5-trione to give 6-(8-methoxy-2- trifluoromethyl-[l,7]-naphthyridine-3-carbony)-(2,2,4,4,-tetramethylcyclohexane- 1,3,5-trione), solid, ¹HNMR (CDCl₃) δ: 1.20-1.35 (6Η, br m), 1.49-1.68 (9H, br m), 4.72 (2H, q), 7.23 (IH, d), 7.99 (IH, s) and 8.21 (IH, d). Similarly, 8-ethoxy-2-trifluoromethyl-[l,7]-naphthyridine-3-carboxylic acid was reacted with bicyclo[3.2.1]octane-2,4-dione to give 3-(8-ethoxy-2-trifiuoromethyl- [l,7]-naphthyridine-3-carbony)-bicyclo[3.2.1]octane-2,4-dione, ¹HNMR (CDCl₃) δ: 1.55 (3Η, t), 1.70-1.80 (2H, m), 1.99-2.30 (4H, m), 2.87 (IH, br t), 3.19 (IH, br t), 4.71 (3H, q), 7.21 (IH, d), 7.92 (IH, s) and 8.18 (IH, d).

In a similar process to Example 1, 8-(2,2,2-trifluoroethoxy)-2-trifluoromethyl-[l,7]- naphthyridine-3-carboxylic acid was reacted with cyclohexane-1,3- dione to give 2- (8-(2,2,2-trifluoroethoxy-2-trifluoromethyl-[l,7]-naphthyridine-3-carbony)- cyclohexane-l,3-dione), solid, ¹HNMR (CDCl₃) δ: 2.03-2.12 (2Η, m), 2.42 (2H, t), 2.85 (2H, t), 5.10 (2H, q), 7.34 (lH,d), 7.95 (IH, s), 8.19 (IH, d) and 16.50 (IH, s).

In a similar process to Example 1, 8-(2-methoxyethoxy)-2-trifluoromethyl-[l,7]- naphthyridine-3-carboxylic acid was reacted with cyclohexane-1,3- dione to give 2- (8-(2-methoxyethoxy)-2-trifluoromethyl-[l,7]-naphthyridine-3-carbony)- cyclohexane-l,3-dione), solid, ¹HNMR (CDCl₃) δ: 2.03-2.11 (2Η, m), 2.41 (2H, t), 2.84 (2H, t), 3.51 (3H, s), 3.92-3.96 (2H, m), 4.77-4.91 (2H, m), 7.22 (IH, d), 7.91 (IH, s), 8.18 (IH, d) and 16.60 (IH, s).

In a similar process to Example 1, 8-phenyl-2-trifluoromethyl-[l,7]-naphthyridine-3- carboxylic acid was reacted with cyclohexane-1,3 -dione to give 2-(8-phenyl-2- trifluoromethyl-[l,7]-naphthyridine-3-carbony)-cyclohexane-l,3-dione), solid, ¹H NMR (CDCl₃) δ: 2.01-2.11 (2Η, m), 2.39-2.47 (2H, m), 2.80-2.89 (2H, m), 7.49-7.58 (3H, m), 7.66 (lH,d), 8.04 (IH, s), 8.21-8.29 (2H, m) and 8.84 (IH, d).

Preparation of intermediate acids

Preparation of 2-trifluoromethyl-f 1 ,71-naphthyridine-3-carboxylic acid

Stage 1

Preparation of ethyl 2-trifluoromethyl-[l JI-naphthyridine-3-carboxylate

A mixture of 3-aminopyridine-4-carboxaldehyde (0.4Og) in methanol (ImI) containing piperidine (0.32ml) and ethyl 4,4,4-trifluoroacetoacetate (0.47ml) was sealed in a tube and heated with stirring in a microwave oven to 13O⁰C for 10 minutes then cooled to ambient temperature. The solution was evaporated under reduced pressure and the residue washed with cold methanol to give the required product as a solid (0.723g) that was filtered from solution and sucked to dryness. ¹HNMR (CDCl₃) δ: 9.69(1Η, s); 8.83(1H, d); 8.67(1H, s); 7.81(1H, d); 4.50(2H, q); 1.45(3H, t).

The product from Stage 1 (0.475g) was dissolved in ethanol (5ml) with stirring at ambient temperature and a solution of lithium hydroxide (0.111 g) in water ( 1.OmI) was added dropwise. The mixture was stirred for 2 hours, evaporated under reduced pressure and the residue dissolved in aqueous sodium carbonate. The aqueous solution was washed with ethyl acetate and the aqueous fraction separated, acidified to pH 3 with aqueous 2M hydrochloric acid and extracted twice with ethyl acetate. The extracts were combined then dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the required product as a colourless solid, 0.378g. ¹H NMR {d₆-DMSO) δ: 9.62(1Η, s); 9.09(1H, s); 8.87(1H, d); 8.17(1H, d).

In a similar procedure, 3-aminopyridine-4-carboxaldehyde was reacted with ethyl acetoacetate to give ethyl 2-methyl-[l,7]-naphthyridine-3-carboxylate as a colourless solid. ¹HNMR (CDCl₃) δ: 9.39(1Η, s); 8.60(1H, s); 8.56(lH,d); 7.61(lH,d); 4.40(2H,q); 2.93(3H,s); 1.40(3H,t). This was hydrolysed with lithium hydroxide to give 2-methyl-[l,7]-naphthyridine-3-carboxylic acid as a colourless solid. ¹HNMR ((J₆-DMSO) δ: 9.37(1Η, s); 8.89(1H, s); 8.65(1H, d); 8.02(1H, d); 2.91(3H, s).

Preparation of 2-difluoromethyl-r 1 ,71-naphthyridine-3-carboxylic acid A mixture of 3-aminopyridine-4-carboxaldehyde (0.50g) in methanol (1.2ml) containing piperidine (0.40ml) and ethyl 4,4-difluoroacetoacetate (0.42ml) was sealed in a tube and heated with stirring in a microwave oven to 13O⁰C for 10 minutes then cooled to ambient temperature. The solution was evaporated under reduced pressure to afford a yellow oil that was dissolved in ethyl acetate and hexane added to give a yellow precipitate. The solid was filtered from solution and re-dissolved in ethyl acetate, extracted with aqueous IM hydrochloric acid and the aqueous phase separated, taken to pH3 with dilute aqueous sodium hydroxide and extracted twice with ethyl acetate. The extracts were combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure to give 2-difiuoromethyl-[l,7J-naphthyridine- 3-carboxylic acid as a pale yellow solid, 0.444g, ¹HNMR (d₆-DMS0) δ: 14.23(1Η, s); 9.59(1H, s); 9.15(1H, s); 8.81(1H, d); 8.17(1H, d); 7.66(1H, t).

Preparation of 8-methoxy-2-trifluoromethyl-[ 1 ,71naphthyridine-3-carboxylic acid

Stage 1 Preparation of ethyl 7-oxy-2-trifluoromethyl-[ 1 ,7^~|naphthyridine-3-carboxylate

To a stirred mixture of ethyl 2-trifluoromethyl-[l,7]naphthyridine-3-carboxylate (0.93g) in dry dichloromethane (20ml) cooled to O⁰C under an atmosphere of nitrogen was added urea hydrogen peroxide complex (0.48g). To this was added dropwise cautiously trifluoroacetic anhydride (0.66ml) and the mixture allowed to warm to ambient temperature and stirred for 48 hours. The reaction mixture was quenched with aqueous sodium thiosulfate and extracted with dichloromethane (three times). The extracts were combined, washed three times with water then aqueous IM hydrochloric acid followed by brine and dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by chromatography

(silica; hexane/ethyl acetate) to afford the required product as a colourless solid, 0.63g. ¹HNMR (CD₃OD) δ: 1.43 (1Η, t), 4.48 (1Η, s), 7.82 (1Η, d), 8.18 (1Η, d), 8.43 (1Η, s), 8.91 (1Η, s) and 9.14 (1Η, s).

Stage 2

Preparation of ethyl 8-chloro-2-trifluoromethyl-[l,71naphthyridine-3-carboxylate

To a stirred mixture of ethyl 7-oxy-2-trifluoromethyl-[l,7]naphthyridine-3- carboxylate (2.47g) in chloroform (40ml) at ambient temperature was added phosphorus oxychloride (9.2ml). The resulting solution was heated to reflux for 4 hours, cooled to ambient temperature then the chloroform solution was poured onto ice/water, and stirred vigorously whilst aqueous saturated sodium hydrogen carbonate was added. The phases were separated and the organic phase was washed with a further two portions of aqueous saturated sodium hydrogen carbonate then one portion of water. The organic phase was dried over magnesium sulphate and evaporated under reduced pressure to yield a yellow crystalline solid, which was purified by chromatography (silica; hexane: ethyl acetate, 2:1 by volume) to yield the desired product as an off-white solid, 1.3g. ¹HNMR (CD₃OD) δ: 1.47 (1Η, t), 4.51 (1Η, s), 7.75 (1Η, d), 8.57 (1Η, d) and 8.69 (1Η, s). Stage 3

To a stirred solution of ethyl 8-chloro-2-trifluoromethyl-[l,7]naphthyridine-3- carboxylate (0.48g) in dry methanol (5ml) and tetrahydrofuran (5ml) at ambient temperature was added a solution of sodium methoxide in methanol (5ml, 25% wt/vol). The mixture was stirred for 30 minutes then an aqueous 4M solution of sodium hydroxide (ImI) was added and the mixture stirred for a further 30 minutes then acidified with aqueous IM hydrochloric acid. The product was extracted with ethyl acetate (three times) and the extracts combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the required product as a colourless solid, 0.4Og. ¹HNMR (CD₃OD) δ: 4.19 (1Η, s), 7.49 (1Η, d), 8.22 (1Η, d) and 8.74 (1Η, s). hi a similar procedure, the following compounds were prepared from ethyl 8-chloro- 2-trifluoromethyl-[l,7]naphthyridine-3-carboxylate and the corresponding sodium or potassium alkoxylates:

8-Ethoxy-2-trifluoromethyl-[l,7]naphthyridine-3-carboxylic acid, colourless solid, ¹HNMR (CD₃OD) δ: 1.56 (3Η, t), 4.68 (3H, q), 7.49 (IH, d), 8.21 (IH, d) and 8.75 (IH, s).

8-(2,2,2 -Trifluoroethoxy)-2-trifluoromethyl-[l,7]naphthyridine-3-carboxylic acid, colourless solid, ¹HNMR (CD₃OD) δ: 5.15 (2Η, q), 7.60 (IH, d), 8.25 (lH,d), and 8.79 (IH, s).

8-(2-Methoxyethoxy)-2-trifluoromethyl-[l,7]naphthyridine-3-carboxylic acid, colourless solid, ¹HNMR (CD₃OD) δ: 3.49 (3Η, 3), 3.91 (2H,t), 4.73 (2H, t), 7.49 (IH, d), 8.21 (lH,s), and 8.72 (IH, d). Preparation of 8-chloro-24rifluoromethyl-ri Jinaphthyridine-3-carboxylic acid

To a stirred solution of ethyl 8-chloro-2-trifluoromethyl-[l,7]naphthyridine-3- carboxylate (0.113g) in ethanol (ImI) at ambient temperature was added a solution of lithium hydroxide (0.023g) in water (0.25ml) and the reaction mixture was stirred for 2 hours then evaporated under reduced pressure. The solid residue obtained was dissolved in aqueous sodium carbonate and washed with ethyl acetate. The aqueous phase was separated, acidified to pH 3-4 and extracted with ethyl acetate (twice). The organic extracts were combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the required product as a colourless solid, O.Oδlg. ¹HNMR (CD₃OD) δ: 8.02 (1Η, d) 8.55 (1Η, d), 8.97 (1Η, s). Molecular ion: (MH)⁺ 277.

Preparation of ethyl 8-methyl-2-trifluoromethyl-[ 1 ,71naphthyridine-3-carboxylate A mixture of ethyl 8-chloro-2-trifluoromethyl-[l,7]naphthyridine-3-carboxylate

(0.15g), methyl boronic acid (0.060g), potassium phosphate (0.157g), dicyclohexyl- (2',6'-dimethoxybiphenyl-2-yl) phosphane (0.030g) in toluene (2ml) were stirred under an atmosphere of nitrogen and heated to reflux for 4 hours. The mixture was cooled to ambient temperature, diluted with ethyl acetate (200ml) and washed with water (100ml) then separated. The aqueous fraction was re-extracted with ethyl acetate (2x 100ml) and the extracts combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue obtained was purified by chromatography (silica; hexane/ ethyl acetate) to afford the required product as a yellow gum (0.088g). ¹HNMR (CDCl₃) δ: 1.46 (3H, t), 3.13 (3H, s), 4.50 (2H, q), 7.62 (IH, d), 8.60 (IH, s), and 8.67 (IH, d).

In a similar procedure, ethyl 8-chloro-2-trifluoromethyl-[l,7]naphthyridine-3- carboxylate was reacted with phenyl boronic acid to give ethyl 8-phenyl-2- trifluoromethyl-[l,7]naphthyridine-3-carboxylate as a yellow gum, ¹HNMR (CDCl₃) δ: 1.47 (3Η, t), 4.51 (2H, q), 7.49-7.58 (3H, m), 7.74 (IH, d), 8.25-8.29 (2H, m) 8.69 (IH, s) and 8.90 (IH, d). Example 3

Preparation of 2-methyl-4-(2-trifluoromethyl-|^" 1 ,6]-naphthyridine-3-carbony)- 2,4- dihvdropyrazol-3-one. In a similar procedure to Example 1 , 2-trifluoromethyl-[l ,6]-naphthyridine-3- carboxylic acid was reacted with 2-methyl-2,4-dihydropyrazol-3-one to give 2- methyl-4-(2-trifluoromethyl-[l,6]-naphthyridine-3-carbony)- 2,4-dihydropyrazol-3- one as a colourless solid. ¹HNMR (d₆-DMS0) δ: 9.63(1Η, s); 8.98(1H, s); 8.97(1H, d); 8.16(1H, d); 7.64(1H, s); 3.52(3H, s); Molecular ion: (M-H) 321.

In a similar procedure to Example 1, 2-trifluoromethyl-[l,6]-naphthyridine-3- carboxylic acid was reacted with cyclohexane-l,3-dione to give 2-(2-trifluoromethyl- [l,6]-naphthyridine-3-carbony)-cyclohexane-l,3-dione, yellow solid. ¹H NMR (CDCl₃) δ: 16.6O(1H, s); 9.38(1H, s); 8.9O(1H, d); 8.20(1H, s); 8.10(1H, d); 2.86 (2H, t); 2.43(2H, t); 2.09(2H, quintet).

The present invention further provides a method of making a compound of Formula (I) wherein Q = Ql which comprises reacting together a compound of Formula (F)

wherein the various substituents are as defined previously, and wherein R⁹ is halogen or aryloxy with a compound of Formula (II)

wherein the various substituents are as defined previously, in the presence of an inert organic solvent and a base. The method may further comprise a subsequent rearrangement step known to the skilled person using, for example, a suitable catalyst, for example acetone cyanhydrin.

Preferably R⁹ is selected from the group consisting of fluorine, chlorine, bromine, and 4-nitrophenoxy. In an especially preferred embodiment R⁹ is chlorine.

The present invention still further provides a compound of Formula (III)

wherein

X₁ and X₂ are as defined in Formula (I) above;

R¹ is haloalkyl, in particularly fluoroalkyl, and most preferably difluoromethyl or trifluoromethyl; or alkoxyhaloalkyl, in particular alkoxyfluoroalkyl especially methoxydifluoromethyl or 2-methoxy-l,l-difluoroethyl.

R is selected from the group consiting of hydrogen, halogen, Ci-C₆alkyl, C₃-

C₆cycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂-C₆alkenyl, C₃-C₆alkynyl, Ci-C₆alkoxy, Ci-C₆haloalkoxy, Ci-C₆alkylthio, Ci-C₆alkylsulfmyl, C_r C₆alkylsulfonyl, C]-C₆haloalkylthio, Ci-C₆alkylamino, C₂-C₆dialkylamino, C₂- C₆alkenylamino, C]-C₆alkoxy-C₂-C₄alkylamino, (Ci-C₆alkoxy-C₂-C₄alkyl)-Ci- C₃alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, d-C₃alkoxy-C₃- C₆ cycloalkylamino, C₃-C₆ alkynylamino or a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, or optionally substituted by Ci-C₃-alkoxy or halogen (especially fluorine), Ci- C₆dialkylaminosulfonyl, C₂-C₆alkylaminosulfonyl, Ci-C₆alkoxy-Ci-C₆alkyl, Ci_-6 alkoxy-C_)-6 alkoxy-Ci_-6-alkyl, C₂-C₆alkenyl-Ci-C₆alkoxy-Ci-C₃-alkyl, C₃-C₆alkynyl- Ci-C₆alkoxy-Ci-C₃alkyl, Ci-C₆alkoxycarbonyl, C_rC₄alkylenyl-S(O)p-R' , C_r C₄alkylenyl-CO₂-R', Ci-C₄alkylenyl-(CO)N-R'R', aryl, 5 or 6-membered heteroaryl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Cj-C₃alkyl, Ci-C₃haloalkyl, Ci-C₃ alkoxy, Cj-C₃haloalkoxy, halo cyano and nitro;

R³ is hydrogen, halogen or methyl, preferably hydrogen;

R is selected from the group consisting of hydrogen, halogen, C_!-C₆alkyl, C₃- C₆cycloalkyl, d-Qhaloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂-C₆alkenyl, C₃-C₆alkynyl, Cι-C₆alkoxy, C_4-C₇ cycloalkoxy, Ci-C₆haloalkoxy, Ci-C₆alkylthio, C₁- C₆alkylsulfinyl, Ci-C₆alkylsulfonyl, C]-C₆haloalkylthio, amino, Ci-C₆alkylamino, C₂- C₆dialkylamino, C₂-C₆alkenylamino, C]-C₆alkoxy-Ci-C₆-alkylamino, (Ci-C₆alkoxy- C₂-C₄-alkyl) -Ci-C₆-alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino, dialkylamino in which the substituents join to form a 4-6 membered ring (e.g pyrrolidinyl, piperidinyl) optionally containing oxygen (e.g morpholinyl) and/or optionally substituted by C₁- C₃-alkoxy and/or halogen especially fluorine, C₂-C₆dialkylaminosulfonyl, Cp C₆alkylaminosulfonyl, Ci-C₆alkoxy-Ci-C₆alkyl, Ci-C₆alkoxy-C₂-C₆alkoxy, C₁- C₆alkoxy-C₂-C₆ alkoxy-Ci-C₆-alkyl, C₃-C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-Ci- C₆alkoxy, Ci-C₆alkoxycarbonyl, Ci-C₆alkylcarbonyl, Ci-C₄alkylenyl-S(O)p-R' , C₁- C₄alkylenyl-CO₂-R', C₁-C₄alkylenyl-(CO)N-R'R', aryl (e.g. phenyl), phenylthio, phenylsulfinyl, phenylsulfonyl, aryloxy (e.g phenoxy) and 5 or 6-membered heteroaryl or heteroaryloxy, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Ci-C₃alkyl, Ci-C₃haloalkyl, C₁-C₃ alkoxy, Ci-C₃haloalkoxy, halo, cyano and nitro;

R⁵ is hydrogen, halogen or methyl; n and m are as defined above; and

R¹⁰ is selected from the group consisting of halogen, d-C₆-alkoxy, aryloxy, OH, O^" M^τ wherein M^τ is an alkali metal cation (preferably sodium) or an ammonium cation; with the exception of 2-trifluoromethyl-[ 1 ,6]-naphthyridine-3-carboxylic acid.

In a preferred embodiment of the compound of Formula (III) R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃-C₆cycloalkyl, Ci-C₆ haloalkyl, Ci-C₆ alkoxy, C₃-C₆ cycloalkoxy, C₁-C₆ alkoxy-C₂-C₆-alkoxy, Ci-C₆- alkoxy-Ci-C₆ alkyl, Ci-C₆-alkoxy-C₂-C₆-alkoxy-Ci-C₆ alkyl, Ci-C₆alkylamino, Ci- C₆dialkylamino, C₂-C₆alkenylamino, Ci-C₆alkoxy-C₂-C₃-alkylamino, (Ci-C₆alkoxy- C₂-C₃-alkyl) -Ci-C₃-alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino and a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, or optionally substituted by Ci-C₃-alkoxy or halogen (especially fluorine) phenyl and heteroaryl

In an even more preferred embodiment of the compound of Formula (III) R is selected from the group consisting of hydrogen, methyl, ethyl, 1-methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1-fiuoro- 1-methylethyl, methyoxy, ethoxy, methoxymethyl, 1-methoxyethyl, 2-methoxyethoxy, 2- methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2-methoxyethyl)amino, (2- methoxyethyl)methylamino, phenyl and chloro.

The present invention further provides the use of a compound of Formula as a herbicide.

The following Tables provide Examples of herbicidal compounds of the present invention.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Biological Examples

Seeds of a variety of test species were sown in standard soil in pots (Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI) and Amaranthus retoflexus (AM ARE)). After cultivation for one day (pre-emergence) or 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). Compounds were applied at 1000 g/ha. 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 for pre and post- emergence, the test was evaluated (100 = total damage to plant; 0 = no damage to plant).

Claims

Claims

1. A herbicidal compound of Formula (I).

or an agronomically acceptable salt of said compound,

wherein :-

X, is N(O)n and X₂ is CR⁴; or X₂ is N(O)n and X₁ is CR⁵;

R¹ is selected from the group consisting of d-C₃alkyl, Ci-C₃haloalkyl, C]- C₃alkoxy-Ci.C₃ alkyl, CpC₃ alkoxy-C₂-C₃alkoxy-C_rC₃-alkyl, d-C₃alkoxy- Ci_-3-haloalkyl, Ci- C₃-alkoxy-Ci-C₃ -alkoxy-C_rC₃ -haloalkyl; C₄-C₆- oxasubstituted cycloalkoxy-Ci-C₃ -alkyl, C₄-C₆-oxasubstituted cycloalkyl-Ci- C₃-alkoxy-Ci-C₃ -alkyl, C₄-C_ό-oxasubstituted cycloalkoxy-Ci-C₃ -haloalkyl, C₄-C₆-oxasubstituted cycloalkyl-Ci-C₃-alkoxy-Ci-C₃ -haloalkyl, (Ci-C₃ alkanesulfonyl-Ci-C₃ alkylamino)-Ci-C₃ alkyl and (Ci-C₃ alkanesulfonyl-C₃-C 4 cycloalkylamino)-Ci-C₃ alkyl;

R is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃- C₆cycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl-C₂- C₆alkenyl, C₃-C₆alkynyl, C)-C₆alkoxy, Ci-C₆haloalkoxy, Ci-C₆alkylthio, Ci- C₆alkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylthio, Ci-C₆alkylamino, C₂- C₆dialkylamino, C₂-C₆alkenylamino, Ci-C₆alkoxy-C₂-C₄alkylamino, (C]- C₆alkoxyC₂-C₄alkyl)-Ci-C₃alkylamino,C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci -C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino or a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen and/or optionally substituted by Ci-C₃-alkoxy or halogen, Ci-Cedialkylaminosulfonyl, C₂- C₆alkylaminosulfonyl, Ci-C₆alkoxy-Ci-C₆alkyl, Ci_-6 alkoxy-Ci_-6 alkoxy-Ci_-6- alkyl, C₂-C₆alkenyl-Ci-C₆alkoxy-Ci-C₃-alkyl, C₃-C₆alkynyl-Ci-C₆alkoxy-C]- C₃alkyl, Ci-C₆alkoxycarbonyl, Ci-C₄alkylenyl-S(O)p-R' , Ci-C₄alkylenyl- CO₂-R', C_rC₄alkylenyl-(CO)N-R'R', aryl and 5 or 6-membered heteroaryl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Q-Qalkyl, C₁-C₃haloalkyl, Ci-C₃ alkoxy, Ci-C₃haloalkoxy, halo cyano and nitro;

R is selected from the group consisting of hydrogen, chloro and methyl;

R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃- C₆cycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl-C₂-

C₆alkenyl, C₃-C₆alkynyl, Ci-C₆alkoxy, C_4-C₇ cycloalkoxy, Ci-C₆haloalkoxy, Ci-C₆alkylthio, Ci-C₆alkylsulfmyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylthio, amino, Ci-C₆alkylamino, C₂-C₆dialkylamino, C₂-C_όalkenylamino, Ci- C₆alkoxy-C₂-C₆-alkylamino, (Ci-C₆alkoxy-C₂-C₄-alkyl)-Ci-C₆-alkylamino,C₃- C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino, dialkylamino in which the substituents join to form a 4-6 membered ring optionally containing oxygen and/or optionally substituted by Ci-C₃-alkoxy and/or halogen, C₂- C₆dialkylaminosulfonyl, Ci-C_όalkylaminosulfonyl, Ci-C₆alkoxy-C]-C₆alkyl, Ci-C₆alkoxy-C₂-C₆alkoxy, C_rC₆alkoxy-C₂-C₆ alkoxy-Ci-C₆-alkyl, C₃-

C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-Ci-C₆alkoxy, C]-C₆alkoxycarbonyl, Ci- C₆alkylcarbonyl, Ci-C₄alkylenyl-S(O)p-R', Ci-C₄alkylenyl-CO₂-R', Ci- C₄alkylenyl-(CO)N-R'R', aryl, aryl C_rC₃ alkyl, phenylthio, phenylsulfinyl, phenylsulfonyl, aryloxy and 5 or 6-membered heteroaryl, heteroaryloxy or heteroaryl C]-C₃ alkyl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Ci-C₃alkyl, C]-C₃haloalkyl, C]-C₃ alkoxy, Ci-C₃haloalkoxy, halo, cyano and nitro; R⁵ is selected from the group consisting of hydrogen, halogen and methyl;

m = 0 or 1 ;

n = 0 or 1;

provided that if m is 1 then n is 0, and if n is 1 m is 0;

p = 0, lor 2;

R' is independently selected from the group consisting of hydrogen and C₁- Qalkyl;

Q is selected from the group consisting of:-

and

wherein

A¹ is selected from the group consisting of O, C(O), S, SO, SO₂

q = 0, 1 or 2;

R^a, R^b, R^c, R^d, R^e and R^f are each independently selected from the group consisting of C₁-C₄alkyl which may be mono-, di- or tri-substituted by substituents selected from the group consisting of Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Ci-C₄alkoxycarbonyl, Ci-C4alkylthio, Cr C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylcarbonyl, phenyl and heteroaryl, it being possible for the phenyl and heteroaryl groups in turn to be mono-, di- or tri-substituted by substituents selected from the group consisting of Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, Ci-C₄alkoxycarbonyl, Ci-C₄alkylsulfonyl and Ci-C₄haloalkyl, the substituents on the nitrogen in the heterocyclic ring being other than halogen; or

R^a, R^b, R^c, R^d, R^e and R^f are each independently selected from the group consisting of hydrogen, Ci-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, CpC₄alkoxycarbonyl, C₁-C₄alkylthio, Ci-C₄alkylsulfinyl, d-C₄alkylsulfonyl, C]-C₄alkylcarbonyl, phenyl or heteroaryl, it being possible for the phenyl and heteroaryl groups in turn to be mono-, di- or tri-substituted by substituents selected from the group consisting of C]-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl, CrQalkoxycarbonyl, Ci-C₄alkylsulfonyl and Ci-C₄haloalkyl, the substituents on the nitrogen in the heterocyclic ring being other than halogen; or

R^a and R^b together form a 3- to 5-membered carbocyclic ring which may be substituted by CrC₄alkyl and may be interrupted by oxygen, sulfur, S(O), SO₂, OC(O), NR^g or by C(O); or

R^a and R^c together form a C]-C₃alkylene chain which may be interrupted by oxygen, sulfur, SO, SO₂, OC(O), NR^h or by C(O); it being possible for that CrC₃alkylene chain in turn to be substituted by C]-C₄alkyl;

R^g and R^h are each independently of the other Ci-C₄alkyl, Ci-C₄haloalkyl, Q- C₄alkylsulfonyl, Ci-C₄alkylcarbonyl or Ci-C₄alkoxycarbonyl;

R' is C,-C₄alkyl;

R^J is hydrogen, or Ci-C₄alkyl or C₃-C₄cycloalkyl such as methyl or cyclopropyl; R is selected from the group consisting of C|-C₆alkyl, optionally substituted with halogen and/or Ci-C₃alkoxy; and C₃-C₆ cycloalkyl optionally substituted with halogen and/or Ci-C₃alkoxy.

R⁶ is selected from the group consisting of cyclopropyl, CF₃ and i.-Pr,

R⁷ is selected from the group consisting of H, I, Br, SR⁸, S(O)R⁸, S(O)₂R⁸ and CO₂R⁸; and

R⁸ is Ci_-4 alkyl.

2. A herbicidal compound according to claim 1 having Formula (Ia) or (Ib):

3. A herbicidal compound according to claim 1 or claim 2, wherein Q is Ql .

4. A herbicidal compound according to claim 3, wherein A¹ is CR^eR^f and wherein R^a, R^b, R^c, R^d, R^e and R^f are hydrogen and wherein q = 1.

5. A herbicidal compound of any one of the previous claims, wherein R¹ is fluoroalkyl or C_1-3alkoxy-Ci_-3-haloalkyl.

6. A herbicidal compound according to claim 5, wherein R¹ is trifluoromethyl.

7. A herbicidal compound according to any one of the previous claims, wherein R² is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1- methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1- fluoro-1-methylethyl, ethoxy, methoxy, methoxymethyl, 1-methoxyethyl, 2- methoxyethoxy, 2-methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2- methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl.

8. A herbicidal compound according to any one of the previous claims, wherein R⁵ is hydrogen.

9. A herbicidal compound according to any one of the previous claims, wherein R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃- C₆cycloalkyl, Ci-C₆ haloalkyl, Ci-C₆ alkoxy, C₃-C₆ cycloalkoxy, CpC₆ alkoxy-C₂-C₆-alkoxy, Ci-C₆-alkoxy-Ci-C₆ alkyl, Ci-C_ό-alkoxy-C₂-C₆-alkoxy- Ci-C₆ alkyl, Ci-C₆alkylamino, Ci-C₆dialkylamino, C₂-C₆alkenylamino, C₁- C₆alkoxy-C₂-C₃-alkylamino, (Ci-C₆alkoxy-C₂-C₃-alkyl) -Ci-C₃- alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy- C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino and a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, or optionally substituted by Ci-C₃-alkoxy or halogen.

10. A herbicidal compound according to claim 9, wherein R⁴ is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1 -methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1-fluoro-l- methylethyl, methoxy, ethoxy, methoxymethyl, 1-methoxyethyl, 2- methoxyethoxy, 2-methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2- methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl.

11. An agronomically acceptable salt of the herbicidal compound according any one of the previous claims, wherein the salt is selected from the group consisting OfNa⁺, Mg²⁺ and Ca²⁺.

12. A herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.

13. A herbicidal composition according to claim 12, further comprising at least one additional pesticide.

14. A herbicidal composition according to claim 13, wherein the additional pesticide is a herbicide or herbicide safener.

15. A method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to any one of claims 12 to 14.

16. A method of making a compound of Formula (F) wherein Q = Ql which comprises reacting together a compound of Formula (F)

wherein the various substituents are as defined in claim 1, and wherein R⁹ is halogen or aryloxy with a compound of Formula (II)

wherein the various substituents are as defined in claim 1 , in the presence of an inert organic solvent and a base.

17. A compound of Formula (III)

wherein

X) and X₂ are as defined in Formula (I) above;

R¹ is haloalkyl;

R² is selected from the group consiting of hydrogen, halogen, d-C₆alkyl, C₃- Cecycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂-

C₆alkenyl, C₃-C₆alkynyl, C_rC₆alkoxy, C_rC₆haloalkoxy, Ci-C₆alkylthio, C₁- C₆alkylsulfinyl, Ci-C₆alkylsulfonyl, d-C₆haloalkylthio, Ci-C₆alkylamino, C₂- C₆dialkylamino, C₂-C₆alkenylamino, Ci-C₆alkoxy-C₂-C₄alkylamino, (Q- C₆alkoxy C₂-C₄alkyl)-Ci-C₃alkylamino,C₃-C₆cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino or a dialkylamino group in which the substituents join to form a 4-6 membered ring, optionally containing oxygen, or optionally substituted by Ci-C₃-alkoxy or halogen, especially fluorine. Ci-C₆dialkylaminosulfonyl, C₂-C₆alkylaminosulfonyl, Ci-C₆alkoxy-Ci-C₆alkyl, Ci_-6 alkoxy-Ci_-6 alkoxy- Ci-₆-alkyl, C₂-C₆alkenyl-C₁-C₆alkoxy-Ci-C₃-alkyl, C₃-C₆alkynyl-Ci-C₆alkoxy-

Ci-C₃alkyl, C_rC₆alkoxycarbonyl, Ci-C₄alkylenyl-S(O)p-R' , d-C₄alkylenyl- CO₂-R', Ci-C₄alkylenyl-(CO)N-R'R', aryl, 5 or 6-membered heteroaryl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of d-Qalkyl, Ci-C₃haloalkyl, C]-C₃ alkoxy, Ci-C₃haloalkoxy, halo cyano and nitro;

R³ is selected from the group consisting of hydrogen, chloro and methyl; R⁴ is selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, C₃-C₆cycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl- C₂- C₆alkenyl, C₃-C₆alkynyl, Ci-C₆alkoxy, C_4-C₇ cycloalkoxy, Ci-C₆haloalkoxy, Ci-C₆alkylthio, Ci-C₆alkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylthio, amino, Ci-C_δalkylamino, C₂-C₆dialkylamino, C₂-C₆alkenylamino, Ci- C₆alkoxy-C₂-C₆-alkylamino, (C₁-C₆alkoxy-C₂-C₄-alkyl)-Ci-C₆-alkylamino,C₃- C₆ cycloalkylamino, C₃-C₆ cyclohaloalkylamino, Ci-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆ alkynylamino, dialkylamino in which the substituents join to form a 4-6 membered ring optionally containing oxygen and/or optionally substituted by Ci-C₃-alkoxy and/or halogen, C₂- C₆dialkylaminosulfonyl, Ci-C₆alkylaminosulfonyl, Ci-C₆alkoxy-C]-C₆alkyl, Ci-C₆alkoxy-C₂-C₆alkoxy, Ci-C₆alkoxy-C₂-C₆ alkoxy-C₁-C₆-alkyl, C₃- C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-Ci-C₆alkoxy, d-C₆alkoxycarbonyl, Ci- C₆alkylcarbonyl, Ci-C₄alkylenyl-S(O)p-R' , d-C₄alkylenyl-CO₂-R', Q-

C₄alkylenyl-(CO)N-R'R', aryl, aryl-C_rC₃alkyl, phenylthio, phenylsulfmyl, phenylsulfonyl, aryloxy and 5 or 6-membered heteroaryl, heteroaryloxy or heteroaryl-Ci-C₃alkyl, the heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein the aryl or heteroaryl component may be optionally substituted by a substituent selected from the group consisting of Ci-C₃alkyl, Ci-C₃haloalkyl, Ci-C₃ alkoxy, Ci-C₃haloalkoxy, halo, cyano and nitro;

R⁵ is selectyed from the group consisiting of hydrogen, halogen and methyl;

n and m are as defined above; and

R¹⁰ is selected from the group consisting of halogen, Ci-C₆-alkoxy, aryloxy, OH, 0^"M⁺ wherein M⁺ is an alkali metal cation (preferably sodium) or an ammonium cation; with the exception of 2-trifluoromethyl-[l,6]-naphthyridine-3-carboxylic acid.

18. A compound according to claim 17, wherein R⁴ is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1-methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1-fluoro-l-methylethyl, methoxy, ethoxy, methoxymethyl, 1-methoxyethyl, 2-methoxyethoxy, 2- methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2-methoxyethyl)amino, (2- methoxyethyl)methylamino and phenyl.

19. A compound according to claim 17 or claim 18, wherein the compound is of Formula (III) and wherein: X, is N; X₂ is CR⁴; m is 0;

R¹ is CF₃;

R² is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1- methylethyl, cyclopropyl, fluoromethyl, l-fluoroethyl, 1,1-difluoroethyl, 1- fluoro-1-methylethyl, ethoxy, methoxy, methoxymethyl, methoxyethyl, methoxyethoxy, methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2- methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl;

R³ = hydrogen; and

R⁴ is selected from the group consisting of hydrogen, chloro, methyl, ethyl, 1- methylethyl, cyclopropyl, fluoromethyl, 1-fluoro ethyl, 1,1-difluoroethyl, 1- fluoro-1-methylethyl, methyoxy, ethoxy, methoxymethyl, 1-methoxyethyl, 2- methoxyethoxy, 2-methoxyethoxymethyl, 2,2,2-trifluoroethoxy, (2- methoxyethyl)amino, (2-methoxyethyl)methylamino and phenyl.