WO2013092460A1

WO2013092460A1 - Cyclic bisoxime microbicides

Info

Publication number: WO2013092460A1
Application number: PCT/EP2012/075712
Authority: WO
Inventors: Daniel Stierli; Kurt Nebel; Martin Pouliot; Laura Quaranta; Stephan Trah; Harald Walter; Werner Zambach
Original assignee: Syngenta Participations AG
Current assignee: Syngenta Participations AG
Priority date: 2011-12-20
Filing date: 2012-12-17
Publication date: 2013-06-27
Anticipated expiration: 2014-06-20

Abstract

The invention relates to compounds of formula (I) wherein A, X, Y¹, Y³, Y⁴, Y⁶, D¹, D², D³, G¹, G², G³ and p are as defined in the claims. The invention further provides intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

CYCLIC BISOXIME MICROBICIDES

The present invention relates to novel microbiocidally active, in particular fungicidally active, cyclic bisoxime derivatives. It further relates to intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic

microorganisms, preferably fungi.

Fungicidally active bisoximes are described in WO08074418.

Surprisingly, it has been found that novel cyclic bisoxime derivatives have microbiocidal activity.

The present invention accordingly relates to bisoxime derivatives of formula (I)

(I)

wherein

D¹ represents N or C-Y²;

D² represents N or C-Y⁵;

D³ represents N or C-Y⁷;

wherein at least one of D¹, D² or D³ is N;

wherein both D² and D³ cannot be N;

A represents hydrogen, halogen, CN, OH, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, d-C₈ alkylsulphonyl, NH₂, Ci-Cio alkyl, C₃-C₈ cycloalkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, (R¹⁰O)carbonyl(Ci- C4-alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C₃-C₆ cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;

or if D³ is C-Y⁷ then A and Y⁷ together may be -(G⁴)_q-G⁵-G⁶-;

X represents X-2, X-3, X-4 or X-5: #—∑—∑—# #— z— z— z— # #— z— z— z— z— #

X-2 X-3 X-4

_#__z12__zli__z12__z13__zli__#

X-5

Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ independently of one another represent CR^JR², C=CR³R⁴ or C=0;

Z⁴ and Z¹² independently of one another represent C=CR³R⁴, CR⁵R⁶, SiR⁷R⁸ or C=0;

each R¹ and R² independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl,

Ci-C₄ haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyi, C1-C4 alkylthio, C1-C4 alkylsulphinyl, C1-C4 alkylsulphonyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, d-C₄ alkoxy and C1-C4 haloalkoxy;

or R¹ and R² together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyi group;

each R³ and R⁴ independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyi;

each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, Ci- C₄ alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyi, phenyl or CN, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, d-C₄ alkoxy and C1-C4 haloalkoxy;

or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyi group;

wherein the groupings X-2, X-3, X-4 and X-5 may contain at most one ring which contains either only one of the radicals Z¹ to Z¹⁴ or two radicals Z¹ to Z¹⁴ or three radicals Z¹ to Z¹⁴ or four radicals Z¹ to Z¹⁴ as ring members; and wherein radicals Z¹, Z², Z³, Z⁵, Z⁶, Z⁹, Z¹⁰ and Z¹⁴ are not substituted by OH;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one another represent hydrogen, halogen, CN, N0₂, Ci-C₈ alkyl, Ci-C₄-alkoxy-Ci-C₄-alkyl, Ci-C₄-alkoxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂-C₈ alkynyl, phenyl, pyridyl, pyrimidinyl, COR⁹, OR¹⁰, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, C_rC₈ alkylsulphonyl, N(Rⁿ)₂, C0₂R¹⁰, 0(CO)R⁹, CON(Rⁿ)₂, NRⁿCOR⁹ or CR⁹N- OR¹⁰, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, pyrimidinyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci- C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and Ci-C₄ alkylsulphonyl;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from 0, S, N and N(Rⁿ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶, or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyi, d-C₄ alkoxy and C_rC₄ haloalkoxy;

each R⁹ independently of one another represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, C₂- C₈ alkenyl, C₂-C₈ alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

each R¹⁰ independently of one another represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, C₃-C₈ alkenyl, C₃-C₈ alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups

independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy and CrC₄-alkoxy-d-C₄-alkyl;

each R¹¹ independently of one another represents hydrogen, OH, d-C₈ alkyl, Ci-C₈ alkoxy, Ci-C₈-alkoxy-Ci-C₄-alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, COR⁹ or phenyl, wherein the alkyl, alkoxy, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, d-C₄ haloalkyi, C C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and d-C₄ alkylsulphonyl;

wherein when two radicals R¹¹ are attached to the same nitrogen atom, these radicals can be identical or different;

wherein when two radicals R¹¹ are attached to the same nitrogen atom, both of these radicals cannot be OH, d-C₄ alkoxy or Ci-C₄ haloalkoxy;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4, B-5, B-6, B-7 or B-8:

B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)-, 0, N(R¹⁴) or S;

G³ and G⁶ independently of one another represent -C(R¹²R¹³)-, 0, N(R¹⁴) or S;

or G¹ and G², or G² and G³, or G¹ and G¹, or G⁴ and G⁵, or G⁵ and G⁶, or G⁴ and G⁴ together represent -CR¹²=CR¹³-;

each R¹² and R¹³ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci- C₄ haloalkyl, Ci-C₄ alkoxy or Ci-C₄ haloalkoxy;

R¹⁴ represents hydrogen, OH, Ci-C₄ alkyl, Ci-C₄ alkoxy, C₃-C₆ cycloalkyl, Ci-C₈ alkylcarbonyl or Ci-C₈ haloalkylcarbonyl; and

p and q are each independently 0, 1 or 2;

or a salt or an N-oxide thereof.

Halogen, either as a lone substituent or in combination with another substituent (e.g.

haloalkyl) is generally fluorine, chlorine, bromine or iodine, and usually fluorine, chlorine or bromine.

Each alkyl moiety (including the alkyl moiety of alkoxy, alkylthio, etc.) is a straight or branched chain and, depending on the number of carbon atoms it contains, is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, /so-propyl, sec-butyl, /so-butyl, tert-butyl, neo-pentyl, n-heptyl or 1,3-dimethylbutyl, and usually methyl or ethyl.

The alkenyl and alkynyl groups can be mono- or di-unsaturated and are examples thereof are derived from the above mentioned alkyl groups.

Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl,

trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2- difluoroethyl, 2-fluoroethyl, 1,1 -difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1- difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2 -trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, /^'so-propoxy, n-butoxy, /so-butoxy, sec- butoxy and tert-butoxy, and usually methoxy or ethoxy.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, n-butylthio, iso- butylthio, sec-butylthio or tert- butylthio, and usually methylthio or ethylthio.

Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, /^'so-butylsulphonyl, sec-butylsulphonyl or tert-butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.

Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, n-butylsulphinyl, /so-butylsulphinyl, sec-butylsulphinyl or tert-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl

Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, /so-propoxymethyl or /so-propoxyethyl.

Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl.

Carbocycle includes cycloalkyl groups and aryl groups.

Heterocycloalkyl is a non-aromatic ring that may be saturated or partially unsaturated, preferably fully saturated, containing carbon atoms as ring members and at least one heteroatom selected from 0, S and N as ring members. Examples include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,4-dioxanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, oxazinanyl, morpholinyl, thiomorpholinyl, imidazolidinyl, pyrazolidinyl and piperazinyl, preferably morpholinyl, pyrrolidinyl, piperdinyl and piperazinyl, more preferably morpholinyl and pyrollidinyl.

Heteroaryl is, for example, a monovalent monocyclic or bicyclic aromatic hydrocarbon radical. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl. Examples of bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, benzimidazolyl, benzothiophenyl, and benzothiadiazolyl. Monocyclic heteroaryl groups are preferred, preferably pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, pyridyl and imidazolyl being most preferred.

The terms "heterocycle" and "heterocyclic ring" are used interchangeably and are defined to include heterocycloalkyl and heteroaryl groups. Any reference herein to a heterocycle or heterocyclic ring preferably refers to the specific examples given under the definition of heteroaryl and heterocycloalkyl above, and are preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl and imidazolyl.

Where a moiety is indicated as being (optionally) substituted, e.g. alkyl, this includes those moieties where they are part of a larger group, e.g. the alkyl in the alkylthio group. Where a moiety is indicated as being optionally substituted by one or more other groups, preferably there are one to five optional substituents, more preferably one to three optional substituents.

The following substituents definitions, including preferred definitions, may be combined in any combination:

D¹ represents N or C-Y²;

D² represents N or C-Y⁵;

D³ represents N or C-Y⁷;

wherein at least one of D¹, D² or D³ is N;

wherein both D² and D³ cannot be N.

In one group of compounds, D¹ represents C-Y², D² represents N and D³ represents C-Y⁷.

In one group of compounds, D¹ represents C-Y², D² represents C-Y⁵ and D³ represents N.

In one group of compounds, D¹ represents N, D² represents C-Y⁵ and D³ represents C-Y⁷.

In one group of compounds, D¹ represents N, D² represents N and D³ represents C-Y⁷.

In one group of compounds, D¹ represents N, D² represents C-Y⁵ and D³ represents N. A represents hydrogen, halogen, CN, OH, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, d-C₈ alkylsulphonyl, NH₂, Ci-Cio alkyl, C₃-C₈ cycloalkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, (R¹⁰O)carbonyl(Ci- C₄-alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyl, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy, C₃-C₆ cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;

or if D³ is C-Y⁷ then A and Y⁷ together may be -(G⁴)_q-G⁵-G⁶-. Preferably A represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, phenyl or pyridyl, wherein the alkyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, OH, C1-C4 alkoxy, C1-C4 haloalkoxy and C₃-C₆ cycloalkyi.

More preferably A represents hydrogen, C1-C4 alkyl, phenyl or pyridyl, wherein alkyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, OH, C1-C4 alkoxy and d-C₄ haloalkoxy, and wherein phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, OH, d-C₄ alkoxy, CrC₄ haloalkoxy and C₃-C₆ cycloalkyi.

Even more preferably A represents hydrogen, C1-C4 alkyl, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and

halomethoxy.

Yet more preferably, A represents C1-C4 alkyl.

In one preferred group of compounds A represents pyridyl, optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C4-alkyl, C1-C4- haloalkyl, d-C₄-alkoxy, d-C₄-haloalkoxy, C₃-C₆ cycloalkyi and a 5 or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms. The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.

In this preferred group of compounds A preferably represents pyridin-2-yl, optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, d- C₄ alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, C1-C4 haloalkoxy, C₃-C₆ cycloalkyi and a 5 or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms. The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.

In another group of compounds A represents hydrogen, C1-C4 alkyl, C₂-C₄ alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from d-C₄ alkyi, Ci-C₄ haloalkyi, halogen, CN, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy.

In another preferred group of compounds, A represents hydrogen, halogen, CN, OH, SH, Ci-Cs alkylthio, Ci-C₈ alkylsulphinyl, Ci-C₈ alkylsulphonyl, NH₂, C1-C10 alkyi, C₃-C₈ cycloalkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, (d-C₄ alkyloxycarbonyl) Ci-C₄ alkyi, (Ci-C₄ alkyl)0₂C, phenyl or pyridyl, wherein the alkyi, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyi, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, C₃-C₆ cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.

In another preferred group of compounds, A represents hydrogen, (Ci-C₄ alkyl)0₂C, C1-C10 alkyi, phenyl or pyridyl, wherein the alkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C₄ alkyi, Ci-C₄ haloalkyi, C₃-C₆ cycloalkyl and a 5- or 6-membered heterocycle containing one to three nitrogen atoms.

X represents X-2, X-3, X-4 or X-5:

#— z— z— # #— z— z— z— # #— z— z— z— z— #

X-2 X-3 X-4

_#__z12__zli__z12__z13__zlf__#

X-5

Preferably X represents X-3 or X-5. More preferably X represents X-3.

Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ independently of one another represent CR R², C=0 or C=CR³R⁴.

Preferably Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ independently of one another represent methylene, halomethylene, CH(CH₃) or C(CH₃)₂.

More preferably Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ represent methylene or halomethylene.

Most preferably Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ represent methylene.

Z⁴ and Z¹² independently of one another represent CR⁵R⁶, SiR⁷R⁸, C=0 or C=CR³R⁴.

Preferably Z⁴ and Z¹² independently of one another represent CR⁵R⁶, SiR⁷R⁸ or C=CR³R⁴. More preferably Z⁴ and Z¹² independently of one another represent CR⁵R⁶ or C=CR³R⁴. Most preferably Z⁴ and Z¹² independently of one another represent CR⁵R⁶. Each R¹ and R² independently of one another represent hydrogen, halogen, OH, Ci-C₄ alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyi, C1-C4 alkylthio, C1-C4 alkylsulphinyl, C1-C4 alkylsulphonyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, d-C₄ haloalkyi, C1-C4 alkoxy and d-C₄ haloalkoxy; or R¹ and R² together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyi group.

Each R³ and R⁴ independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyi.

Preferably each R³ and R⁴ independently of one another represent hydrogen, halogen, methyl or halomethyl.

Each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, Ci- C₄ alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyi, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyi group.

Preferably, each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, C1-C4 alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, phenyl or CN, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C₄ alkyl, C1-C4 haloalkyi, d-C₄ alkoxy and d-C₄ haloalkoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyi group.

More preferably, each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl, d-C₄ haloalkyi, phenyl or CN wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group optionally substituted by halogen.

More preferably still, each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, d-C₄ alkyl, C1-C4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group optionally substituted by halogen. Y¹, Y², Υ³, Υ⁴, Υ⁵, Y⁶and Υ⁷ independently of one another represent hydrogen, halogen, CN, N0₂, Ci-C₈ alkyl, Ci-C₄-alkoxy-Ci-C₄-alkyl, Ci-C₄-alkoxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂-C₈ alkynyl, phenyl, pyridyl, pyrimidinyl, COR⁹, OR¹⁰, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, d-C₈ alkylsulphonyl, N(Rⁿ)₂, C0₂R¹⁰, 0(CO)R⁹, CON(Rⁿ)₂, NRⁿCOR⁹ or CR⁹N- OR¹⁰, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, pyrimidinyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci- C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and Ci-C₄ alkylsulphonyl;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from 0, S, N and N(Rⁿ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyi, d-C₄ alkoxy and d-C₄ haloalkoxy.

Preferably, Y¹, Y², Y³, Y⁴, Y⁵, Y⁶ and Y⁷ independently of one represent hydrogen, halogen, OH, CN, Ci-C₈ alkyl, Ci-C₈ haloalkyi, Ci-C₈ alkoxy, Ci-C₈ haloalkoxy, Ci-C₈ alkylthio, C₃-C₈ cycloalkyi, phenyl, pyridyl, N(Rⁿ)₂, or NRⁿCOR⁹, wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and d-C₄ haloalkoxy;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from N and N(Rⁿ)₂ and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

wherein each R⁹ independently represents d-C₈ alkyl or Ci-C₈ haloalkyi;

wherein each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl, COR⁹ or phenyl, wherein the phenyl is optionally substituted by one or more group independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, d-C₄ haloalkyi, d-C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and d-C₄ alkylsulphonyl; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4, B-5;

wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.

More preferably, Y¹, Y², Y³, Y⁴, Y⁵, Y⁶ and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, d-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, C₃-C₆ cycloalkyl, Ci-C₄ alkylthio, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C₄ alkyl, Ci-C₄ haloalkyi, d- C₄ alkoxy and d-C₄ haloalkoxy;

wherein each R⁹ independently represents d-C₄ alkyl or Ci-C₄ haloalkyi;

wherein each R¹¹ independently of one another represents hydrogen, Ci-Cs alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, d-C₄ haloalkyi, d-C₄ alkoxy and d-C₄ haloalkoxy; wherein when two radicals R¹¹ are attached to the same nitrogen atom, these radicals can be identical or different;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4, B-5 wherein the cycle formed is optionally substituted by one or more independently selected from halogen, methyl and halomethyl.

Even more preferably, Y¹, Y², Y³, Y⁴, Y⁵, Y⁶ and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, d-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, C₃-C₆ cycloalkyl, d-C₄ alkylthio, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;

wherein each R⁹ independently represents d-C₄ alkyl or Ci-C₄ haloalkyi; wherein each R independently of one another represents hydrogen, Ci-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy.

Yet more preferably, Y¹, Y², Y³, Y⁴, Y⁵, Y⁶ and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, d-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, C₃-C₆ cycloalkyi, d-C₄ alkylthio, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;

wherein each R⁹ independently represents d-C₄ alkyl or Ci-C₄ haloalkyi;

wherein each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy.

Each R⁹ independently of one another represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, C₂- C₈ alkenyl, C₂-C₈ alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyi, Ci- C₄ alkoxy and Ci-C₄ haloalkoxy.

Preferably each R⁹ independently of one another represent Ci-Cs alkyl or d-C₈ haloalkyi.

More preferably each R⁹ independently of one another represent d-C₄ alkyl or Ci-C₄ haloalkyi.

Each R¹⁰ independently of one another represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, C₃-C₈ alkenyl, C₃-C₈ alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, Ci-C₄ haloalkyi, d-C₄alkoxy, Ci-C₄-haloalkoxy and Ci-C₄-alkoxy-Ci-C₄-alkyl.

Each R¹¹ independently of one another represents hydrogen, OH, Ci-C₈ alkyl, Ci-C₈ alkoxy, Ci-C₈-alkoxy-Ci-C₄-alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, COR⁹ or phenyl, wherein the alkyl, alkoxy, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, d-C₄ haloalkyi, d-C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and d-C₄ alkylsulphonyl;

wherein when two radicals R¹¹ are attached to the same nitrogen atom, these radicals can be identical or different; wherein when two radicals R are attached to the same nitrogen atom, both of these radicals cannot be OH, d-C₄ alkoxy or Ci-C₄ haloalkoxy;

B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy.

Preferably, each R¹¹ independently of one another represents hydrogen, d-C₈ alkyl, COR⁹ or phenyl, wherein the phenyl is optionally substituted by one or more group independently selected from halogen, CN, NH₂, N0₂, OH, d-C₄ alkyl, d-C₄ haloalkyi, C C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and d-C₄ alkylsulphonyl;

More preferably, each R¹¹ independently of one another represents hydrogen, d-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy; wherein when two radicals R¹¹ are attached to the same nitrogen atom, these radicals can be identical or different; wherein when two radicals R are attached to the same nitrogen atom, both of these radicals cannot be OH, d-C₄ alkoxy or Ci-C₄ haloalkoxy.

More preferably still, each R¹¹ independently of one another represents hydrogen, Ci-Cs alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, d-C₄ alkoxy and Ci-C₄ haloalkoxy.

G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)- , 0, N(R¹⁴) or S;

or G¹ and G², or G² and G³, or G¹ and G¹, or G⁴ and G⁵, or G⁵ and G⁶, or G⁴ and G⁴ together represent -CR¹²=CR¹³-. For the avoidance of doubt, when p is 2, G¹ and G¹ as well as G² and G³ may represent CR¹²=CR¹³ such that the ring contains two double bond moieties. Likewise, when q is 2, G⁴ and G⁴ as well as G⁵ and G⁶ may represent CR¹²=CR¹³.

Preferably G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)- ;

or G¹ and G², or G² and G³, or G¹ and G¹, or G⁴ and G⁵, or G⁵ and G⁶, or G⁴ and G⁴ together represent -CR¹²=CR¹³-.

More preferably, G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)-;

G³ and G⁶ independently of one another represent -C(R¹²R¹³)-, 0, N(R¹⁴) or S.

More preferably again, G¹, G², G³, G⁴, G⁵ and G⁶ independently of one another represent - C(R¹²R¹³)-.

Even more preferably G¹, G², G³, G⁴, G⁵ and G⁶ represent methylene.

Each R¹² and R¹³ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyi, d-C₄ alkoxy or Ci-C₄ haloalkoxy.

R¹⁴ represents hydrogen, OH, d-C₄ alkyl, Ci-C₄ alkoxy, d-C₆-cycloalkyl, Ci-Cs alkylcarbonyl or Ci-Q haloalkylcarbonyl.

p and q are each independently of one another 0, 1 or 2.

Preferably p and q are each independently of one another 1 or 2.

More preferably p and q are 1.

In one group of compounds, D¹ represents N or C-Y²;

D² represents N or C-Y⁵;

D³ represents N or C-Y⁷;

wherein at least one of D¹, D² or D³ is N;

wherein both D² and D³ cannot be N; A represents hydrogen, halogen, CN, OH, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, d-C₈ alkylsulphonyl, NH₂, Ci-Cio alkyl, C₃-C₈ cycloalkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, (R¹⁰O)carbonyl(Ci- C4-alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci- haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C₃-C₆ cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from 0, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;

or if D³ is C-Y⁷ then A and Y⁷ together may be -(G⁴)_q-G⁵-G⁶-.

X represents X-2, X-3, X-4 or X-5:

#—∑—∑—# #— z— z— z— # #— z— z— z— z— #

X-2 X-3 X-4

_#__z12__zU__z12__z13__zli__#

X-5

each R¹ and R² independently of one another represent hydrogen, halogen, OH, Ci-d alkyl,

C1-C4 haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, Ci-C₄ alkylthio, C1-C4 alkylsulphinyl, Ci-C₄ alkylsulphonyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, Ci-d alkoxy and C1-C4 haloalkoxy;

or R¹ and R² together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyl group or a C₃-C₆ halocycloalkyl group;

each R³ and R⁴ independently of one another represent hydrogen, halogen, d-C₄ alkyl or C1-C4 haloalkyl;

each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, Ci- C₄ alkyl, Ci-d haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-d alkyl, Ci- haloalkyl, Ci-d alkoxy and Ci-d haloalkoxy;

or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyl group or a C₃-C₆ halocycloalkyl group; wherein the groupings X-2, X-3, X-4 and X-5 may contain at most one ring which contains either only one of the radicals Z¹ to Z¹⁴ or two radicals Z¹ to Z¹⁴ or three radicals Z¹ to Z¹⁴ or four radicals Z¹ to Z¹⁴ as ring members; and wherein radicals Z¹, Z², Z³, Z⁵, Z⁶, Z⁹, Z¹⁰ and Z¹⁴ are not substituted by OH;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one another represent hydrogen, halogen, CN,

N0₂, Ci-C₈ alkyl, Ci-C₄-alkoxy-Ci-C₄-alkyl, Ci-C₄-alkoxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂-C₈ alkynyl, phenyl, pyridyl, pyrimidinyl, COR⁹, OR¹⁰, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, C_rC₈ alkylsulphonyl, N(Rⁿ)₂, C0₂R¹⁰, 0(CO)R⁹, CON(Rⁿ)₂, NRⁿCOR⁹ or CR⁹N- OR¹⁰, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, pyrimidinyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci- C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, d-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and Ci-C₄ alkylsulphonyl;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from 0, S, N and N(Rⁿ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C C₄ alkyl, C_rC₄ haloalkyi, C C₄ alkoxy and d-C₄ haloalkoxy;

independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄-haloalkyl, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy and d-C₄-alkoxy-Ci-C₄-alkyl;

each R¹¹ independently of one another represents hydrogen, OH, Ci-C₈ alkyl, Ci-C₈ alkoxy, Ci-C₈-alkoxy-Ci-C₄-alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, COR⁹ or phenyl, wherein the alkyl, alkoxy, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, C C₄ alkoxy, C C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and d-C₄ alkylsulphonyl;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4, B-5, B-6, B-7 or B-8;

wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)-;

each R¹² and R¹³ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci- C₄ haloalkyi, Ci-C₄ alkoxy or Ci-C₄ haloalkoxy;

R¹⁴ represents hydrogen, OH, d-C₄ alkyl, Ci-C₄ alkoxy, C₃-C₆ cycloalkyi, Ci-C₈ alkylcarbonyl or Ci-C₈ haloalkylcarbonyl; and

p and q are each independently 0, 1 or 2.

In another group of compounds, A represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, phenyl or pyridyl, wherein the alkyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, OH, d-C₄ alkoxy, Ci-C₄ haloalkoxy and C₃-C₆ cycloalkyi;

X represents X-3;

Z³ and Z⁵ independently of one another represent methylene or halomethylene;

Z⁴ represent C=CR³R⁴, CR⁵R⁶ or SiR⁷R⁸;

each R³ and R⁴ independently of one another represent hydrogen, halogen, methyl or halomethyl;

each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, Ci- C₄ alkyl, Ci-C₄ haloalkyi, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy;

or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one represent hydrogen, halogen, OH, CN, d-

C₈ alkyl, Ci-C₈ haloalkyi, Ci-C₈ alkoxy, d-C₈ haloalkoxy, Ci-C₈ alkylthio, C₃-C₈ cycloalkyl, phenyl, pyridyl, N(Rⁿ)₂, or NRⁿCOR⁹, wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from N and N(Rⁿ)₂ and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy;

each R⁹ independently represents Ci-C₈ alkyl or Ci-C₈ haloalkyi;

each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl, COR⁹ or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulphinyl and C1-C4 alkylsulphonyl;

wherein when two radicals R¹¹ are attached to the same nitrogen atom, both of these radicals cannot be OH, d-C₄ alkoxy or C1-C4 haloalkoxy;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-l, B-2, B-3, B-4, B-5;

wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl;

G¹, G², G³, G⁴ , G⁵ and G⁶ independently of one another represent -C(R¹²R¹³)-;

p and q are each independently 0, 1 or 2. In another group of compounds, A represents hydrogen, Ci-C₄ alkyl, phenyl or pyridyl, wherein alkyl is optionally substituted by one or more groups independently selected from halogen, OH, C1-C4 alkoxy and C1-C4 haloalkoxy, and wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, OH, d-C₄ alkoxy, Ci-C₄ haloalkoxy and C₃-C₆ cycloalkyi;

X represents X-3;

Z³ and Z⁵ represent methylene;

Z⁴ represents C=CR³R⁴ or CR⁵R⁶ ;

each R⁵ and R⁶ independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl, Ci-C₄ haloalkyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy, Ci-C₄ alkylthio, C₃-C₆ cycloalkyi, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

each R⁹ independently represents d-C₄ alkyl or Ci-C₄ haloalkyl;

each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyl, C C₄ alkoxy and C_rC₄ haloalkoxy;

and wherein when two radicals R¹¹ are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4, B-5 wherein the cycle formed is optionally substituted by one or more independently selected from halogen, methyl and halomethyl;

G¹, G², G³, G⁴, G⁵ and G⁶ represent methylene; p and q are each independently 0, 1 or 2.

In a further group of compounds, A represents hydrogen, d-C₄ alkyl, phenyl or pyridin-2-yl wherein phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;

X represents X-3;

Z³ and Z⁵ represent methylene;

Z⁴ represents C=CR³R⁴ or CR⁵R⁶ ;

each R⁵ and R⁶ independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl,

Ci-C₄ haloalkyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶ and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy, d-C₄ alkylthio, C₃-C₆ cycloalkyi, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;

each R⁹ independently represents d-C₄ alkyl or Ci-C₄ haloalkyl;

each R¹¹ independently of one another represents hydrogen, d-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

G¹, G², G³, G⁴, G⁵ and G⁶ represent methylene;

p and q are each independently 0, 1 or 2.

In one group of compounds, p is 1 and -G^G^G³- represent -CH₂-CH₂-CH₂-.

In another group of compounds, A and Y⁷ together represent -CH₂-CH₂-CH₂-.

Certain intermediates that can be used to prepare compounds of formula (I) are novel and as such also form part of the present invention.

Accordingly, in a further aspect the invention provides a compound of formula (II) FT -X

wherein R represents -ONH₂, halogen, -0-S0₂-R^2B or one of the groups LG, C-l, C-2A or C-2B:

(LG) (C-1 ) (C-2A) (C-2B)

R²⁸ represents C1-C4 alkyl, C1-C4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or two substituents independently selected from methyl, trihalomethyl, N0₂, CN, C1-C7 alkoxycarbonyl;

X" represents halogen;

R³⁷ represents either A as defined herein for compounds of formula (I) or the group R^'

R^37'

wherein X, G¹, G², G³, D¹, D², D³, Y¹, Y³, Y⁴, Y⁶ and p are as defined for the compound of formula (I);

or a salt or N-oxide thereof.

The preferred definitions of A, X, G¹, G², G³, D¹, D², D³, Y¹, Y³, Y⁴, Y⁶ and p defined in respect of compounds of formula (I) also apply to compounds of formula (II).

Preferably R²⁷ represents -ONH₂, -0-S0₂-R²⁸ or one of the groups LG, C-l or C-2.

Even more preferably R²⁷ represents -ONH₂, tosylate, mesylate, triflate or one of the groups LG, C-l or C-2.

In a further aspect the invention provides a compound of formula (III)

wherein X' represents one of the groupings X'-l, X'-2 or X'-3:

#— z— # #— z— z— # #—∑—∑—∑—#

X'-1 X'-2 X'-3

wherein Z³, Z⁶, Z⁷, Z¹⁰, Z¹¹ and Z¹² are as defined for a compound of formula (I);

R²⁹ and R³⁰ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyi, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkyoxy; and

G¹, G², G³, D¹, Y¹, Y³ and p are as defined for a compound of formula (I);

or a salt or N-oxide thereof.

Preferably, R²⁹and R³⁰ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyi, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and

halomethoxy.

In one group of compounds of formula (III) at least one of Y⁴, Y⁵ or Y⁶ represents pyrimidinyl, Ci-Cs haloalkylthio, Ci-Cs haloalkylsulphinyl or Ci-Cs haloalkylsulphonyl ,wherein the pyrimidinyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C C₄ alkyl, C C₄ haloalkyi, C C₄ alkoxy, d-C₄ haloalkoxy, d-C₄ alkylthio, Ci-C₄ alkylsulphinyl and Ci-C₄ alkylsulphonyl.

In another group of compounds of formula (III) G³ represents N(R¹⁴) wherein R¹⁴ represents

C₃-C₆ cycloalkyl.

The preferred definitions of Z⁵, Z⁶, Z⁹, Z¹³, Z¹⁴, D¹, G¹, G², G³, Y¹, Y³ and p defined in respect of compounds of formula (I) above also apply to compounds of formula (III).

Preferably X' represents X'-l.

In a further aspect the invention provides a compound of formula (VIII)

(VIII)

wherein G¹, G², G³, D¹, Y¹, Y³ and p are as defined for a compound of formula (I);

or a salt or N-oxide thereof.

The preferred definitions of G¹, G², G³, D¹, Y¹, Y³ and p defined in respect of compounds of formula (I) above also apply to compounds of formula (III).

In a further aspect the invention provides a compound of formula IVa

wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined for a compound of formula I, or a salt or N-oxide thereof. The preferred definitions of G¹, G², G³, p, D¹, Y¹ and Y³ are as defined in respect of compounds of formula (I) above also apply to compounds of formula (IVa).

In one preferred group of compounds of formula IVa, Y⁶ is Ci-C₆ alkyl, halogen, NH₂, CrC₆ haloalkyl, Ci-Cs haloalkoxy, or Ci-C₆ haloalkoxy;

Y⁷ and Y⁸ independently of one another represent hydrogen, halogen, CN, N0₂, CrC₈ alkyl, Ci-C₄-alkoxy-Ci-C₄-alkyl, Ci-C₄-alkoxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂- C₈ alkynyl, phenyl, pyridyl, COR¹³, OR²², SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, Ci-C₈ alkylsulphonyl, N(R²³)₂, C0₂R²², 0(CO)R¹³, CON(R²³)₂, NR²³COR¹³ or CR¹³N-OR²², wherein the alkyl, alkoxy, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and d-C₄ haloalkoxy;

G¹ and G² independently represent -C(R²⁴)(R²⁵)-;

G³ represents -C(R²⁴)(R²⁵)-, O, N(R²⁶) or S;

each R²⁴ and R²⁵ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci- C₄ haloalkyl, Ci-C₄ alkoxy, or d-C₄ haloalkyl;

R²⁶ is hydrogen, OH, d-C₄ alkyl or Ci-C₄ alkoxy; p is 0, 1 or 2. Preferably, p is 1 or 2.

In another group of preferred compounds of formula IVa, Y⁶ is hydrogen, methyl or halomethyl.

In another group of preferred compounds of formula IVa, Y⁶ is methyl or halomethyl.

In a further aspect the invention provides a compound of formula XVI.

wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined herein for a compound of formula I, and wherein R³⁸ is hydrogen, CO-CH₃, CO-CH₂CH₃, CO-CH₂CH₂CH₃, CO-CH(CH₃)₂, CO-CF₃, CO- CF₂CF₃, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, or a salt or N-oxide thereof.

In a further aspect the invention provides a process for the production of a compound of formula (I) comprising reacting a compound of formula (lib) with a compound of formula (X) as shown in scheme X

Scheme X

(lib) (I) wherein R represents halogen, -0-S0₂-R or group LG:

R represents Ci-C₄ alkyl, d-C₄ haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or two substituents independently selected from methyl, trihalomethyl, N0₂, CN, C1-C7 alkoxycarbonyl; and

X, G¹, G², G³, Y¹, Y³, Y⁴, Y⁶, D¹, D², D³, p and A are as defined for the compound of formula (I).

The preferred definitions of X, G¹, G², G³, Y¹, Y³, Y⁴, Y⁶, D¹, D², D³, p and A defined in respect of compounds of formula (I) above also apply to compound (lib) and (X).

The compounds of formula (I) may exist as different geometric or optical isomers or in different tautomeric forms. These may be separated and isolated by well-known (usually chromatographic) techniques, and all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms, such as deuterated compounds, are part of the present invention. In particular, the carbon-nitrogen double bonds of the compound of formula (I) allow the four cis/trans isomers shown below:

The present invention includes each of these isomers. The invention may provide a compound of formula (I) as just one of these isomers or as a mixture of one or more isomers in any ratio. Likewise, the invention also includes the corresponding isomers of the intermediates described herein, e.g. compounds (II), (III) and (VIII). In addition, where a reaction scheme depicts synthesis of one geometric isomer, the scheme also includes synthesis of the other geometric isomers where possible. For example Scheme X shown above encompasses the reactions:

The compounds in tables 1 to 7 illustrate compounds of formula (I).

Table X represents Table 1 (when X is 1), Table 2 (when X is 2), Table 3 (when X is 3), Table 4 (when X is 4), Table 5 (when X is 5), Table 6 (when X is 6), Table 7 (when X is 7).

x.08 CH₃ H OCH₂CH₃ H -CH₂CH₂CH₂- x.09 CH₃ H CH(CH₃)₂ H -CH₂CH₂CH₂- x. lO CH₃ H cyclopropyl H -CH₂CH₂CH₂- x. ll CH₃ H SCH₃ H -CH₂CH₂CH₂-

X.12 CH₃ H Phenyl H -CH₂CH₂CH₂-

X.13 CH₃ H 2-CH₃-phenyl H -CH₂CH₂CH₂-

X.14 CH₃ H NH-CH₂CH₃ H -CH₂CH₂CH₂-

X.15 CH₃ H NH-(phenyl) H -CH₂CH₂CH₂-

X.16 CH₃ H NH-(3-CI-phenyl) H -CH₂CH₂CH₂-

X.17 CH₃ H CH₃ CH₃ -CH₂CH₂CH₂-

X.18 CH₃ H CH₂CH₃ CH₂CH₃ -CH₂CH₂CH₂-

X.19 CH₃ H OCH₃ OCH₃ -CH₂CH₂CH₂- x.20 CH₃ H OCH₂CH₃ OCH₂CH₃ -CH₂CH₂CH₂- x.21 CH₂CH₃ H H H -CH₂CH₂CH₂- x.22 CH₂CH₃ H CH₃ H -CH₂CH₂CH₂- x.23 CH₂CH₃ H CH₂CH₃ H -CH₂CH₂CH₂- x.24 CH₂CH₃ H OCH₃ H -CH₂CH₂CH₂- x.25 CH₂CH₃ H OCH₂CH₃ H -CH₂CH₂CH₂- x.26 CH₂CH₃ H CH(CH₃)₂ H -CH₂CH₂CH₂- x.27 CH₂CH₃ H cyclopropyl H -CH₂CH₂CH₂- x.28 CH₂CH₃ H SCH₃ H -CH₂CH₂CH₂- x.29 CH₂CH₃ H CH₃ CH₃ -CH₂CH₂CH₂- x.30 OCH₃ H H H -CH₂CH₂CH₂- x.31 OCH₃ H CH₃ H -CH₂CH₂CH₂- x.32 OCH₃ H CH₂CH₃ H -CH₂CH₂CH₂- x.33 OCH₃ H OCH₃ H -CH₂CH₂CH₂- x.34 OCH₃ H OCH₂CH₃ H -CH₂CH₂CH₂- x.35 OCH₃ H CH(CH₃)₂ H -CH₂CH₂CH₂- x.36 OCH₃ H cyclopropyl H -CH₂CH₂CH₂- x.37 OCH₃ H SCH₃ H -CH₂CH₂CH₂- x.38 OCH₃ H CH₃ CH₃ -CH₂CH₂CH₂- x.39 SCH₃ H H H -CH₂CH₂CH₂- x.40 SCH₃ H CH₃ H -CH₂CH₂CH₂- x.41 SCH₃ H CH₂CH₃ H -CH₂CH₂CH₂- x.42 SCH₃ H OCH₃ H -CH₂CH₂CH₂- x.43 SCH₃ H OCH₂CH₃ H -CH₂CH₂CH₂- x.44 SCH₃ H CH(CH₃)₂ H -CH₂CH₂CH₂- x.45 SCH₃ H cyclopropyl H -CH₂CH₂CH₂- x.46 SCH₃ H SCH₃ H -CH₂CH₂CH₂- x.47 SCH₃ H CH₃ CH₃ -CH₂CH₂CH₂- x.48 phenyl H CH₃ H -CH₂CH₂CH₂- x.49 phenyl H CH₂CH₃ H -CH₂CH₂CH₂- x.50 phenyl H OCH₃ H -CH₂CH₂CH₂- x.51 phenyl H CH₃ CH₃ -CH₂CH₂CH₂- x.52 phenyl H phenyl H -CH₂CH₂CH₂- x.53 2-CH₃-phenyl H CH₃ H -CH₂CH₂CH₂- x.54 2-CH₃-phenyl H CH₃ CH₃ -CH₂CH₂CH₂- x.55 2-CH₃-phenyl H 2-CH₃-phenyl H -CH₂CH₂CH₂- x.56 NH-CH₂CH₃ H CH₃ H -CH₂CH₂CH₂- x.57 NH-CH₂CH₃ H CH₃ CH₃ -CH₂CH₂CH₂- x.58 NH-CH₂CH₃ H NH-CH₂CH₃ H -CH₂CH₂CH₂- x.59 NH-(phenyl) H CH₃ H -CH₂CH₂CH₂- x.60 NH-(phenyl) H CH₃ CH₃ -CH₂CH₂CH₂- x.61 NH-(phenyl) H NH-(phenyl) H -CH₂CH₂CH₂- x.62 NH-(3-CI-phenyl) H CH₃ H -CH₂CH₂CH₂- x.63 NH-(3-CI-phenyl) H CH₃ CH₃ -CH₂CH₂CH₂- x.64 NH-(3-CI-phenyl) H NH-(3-CI-phenyl) H -CH₂CH₂CH₂- x.65 H H H H -CH₂-C(CH₃)₂-CH₂- x.66 H H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.67 H H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.68 CH₃ H H H -CH₂-C(CH₃)₂-CH₂- x.69 CH₃ H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.70 CH₃ H CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.71 CH₃ H OCH₃ H -CH₂-C(CH₃)₂-CH₂- x.72 CH₃ H OCH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.73 CH₃ H CH(CH₃)₂ H -CH₂-C(CH₃)₂-CH₂- x.74 CH₃ H cyclopropyl H -CH₂-C(CH₃)₂-CH₂- x.75 CH₃ H SCH₃ H -CH₂-C(CH₃)₂-CH₂- x.76 CH₃ H Phenyl H -CH₂-C(CH₃)₂-CH₂- x.77 CH₃ H 2-CH₃-phenyl H -CH₂-C(CH₃)₂-CH₂- x.78 CH₃ H NH-CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.79 CH₃ H NH-(phenyl) H -CH₂-C(CH₃)₂-CH₂- x.80 CH₃ H NH-(3-CI-phenyl) H -CH₂-C(CH₃)₂-CH₂- x.81 CH₃ H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.82 CH₃ H CH₂CH₃ CH₂CH₃ -CH₂-C(CH₃)₂-CH₂- x.83 CH₃ H OCH₃ OCH₃ -CH₂-C(CH₃)₂-CH₂- x.84 CH₃ H OCH₂CH₃ OCH₂CH₃ -CH₂-C(CH₃)₂-CH₂- x.85 CH₂CH₃ H H H -CH₂-C(CH₃)₂-CH₂- x.86 CH₂CH₃ H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.87 CH₂CH₃ H CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.88 CH₂CH₃ H OCH₃ H -CH₂-C(CH₃)₂-CH₂- x.89 CH₂CH₃ H OCH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.90 CH₂CH₃ H CH(CH₃)₂ H -CH₂-C(CH₃)₂-CH₂- x.91 CH₂CH₃ H cyclopropyl H -CH₂-C(CH₃)₂-CH₂- x.92 CH₂CH₃ H SCH₃ H -CH₂-C(CH₃)₂-CH₂- x.93 CH₂CH₃ H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.94 OCH₃ H H H -CH₂-C(CH₃)₂-CH₂- x.95 OCH₃ H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.96 OCH₃ H CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.97 OCH₃ H OCH₃ H -CH₂-C(CH₃)₂-CH₂- x.98 OCH₃ H OCH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.99 OCH₃ H CH(CH₃)₂ H -CH₂-C(CH₃)₂-CH₂-

X.100 OCH₃ H cyclopropyl H -CH₂-C(CH₃)₂-CH₂- x. lOl OCH₃ H SCH₃ H -CH₂-C(CH₃)₂-CH₂- x.102 OCH₃ H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂-

X.103 SCH₃ H H H -CH₂-C(CH₃)₂-CH₂- X.104 SCH₃ H CH₃ H -CH₂-C(CH₃)₂-CH₂-

X.105 SCH₃ H CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.106 SCH₃ H OCH₃ H -CH₂-C(CH₃)₂-CH₂-

X.107 SCH₃ H OCH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.108 SCH₃ H CH(CH₃)₂ H -CH₂-C(CH₃)₂-CH₂-

X.109 SCH₃ H cyclopropyl H -CH₂-C(CH₃)₂-CH₂- x. llO SCH₃ H SCH₃ H -CH₂-C(CH₃)₂-CH₂- x. lll SCH₃ H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.112 phenyl H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.113 phenyl H CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.114 phenyl H OCH₃ H -CH₂-C(CH₃)₂-CH₂- x.115 phenyl H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.116 phenyl H phenyl H -CH₂-C(CH₃)₂-CH₂- x.117 2-CH₃-phenyl H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.118 2-CH₃-phenyl H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.119 2-CH₃-phenyl H 2-CH₃-phenyl H -CH₂-C(CH₃)₂-CH₂- x.120 NH-CH₂CH₃ H CH₃ H -CH₂-C(CH₃)₂-CH₂- x.121 NH-CH₂CH₃ H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.122 NH-CH₂CH₃ H NH-CH₂CH₃ H -CH₂-C(CH₃)₂-CH₂- x.123 NH-(phenyl) H CH₃ H -CH₂-C(CH₃)₂-CH₂-

X.124 NH-(phenyl) H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂- x.125 NH-(phenyl) H NH-(phenyl) H -CH₂-C(CH₃)₂-CH₂-

X.126 NH-(3-CI-phenyl) H CH₃ H -CH₂-C(CH₃)₂-CH₂-

X.127 NH-(3-CI-phenyl) H CH₃ CH₃ -CH₂-C(CH₃)₂-CH₂-

X.128 NH-(3-CI-phenyl) H NH-(3-CI-phenyl) H -CH₂-C(CH₃)₂-CH₂- x.129 H H H H

X.130 H H CH₃ H -C Hp -^ -_^- C Hp -

X.131 H H CH₃ CH₃ -C Hp -^ -_^- C Hp -

X.132 CH₃ H H H -CHp-^__^--CHp- x.133 CH₃ H CH₃ H -C H2 -^^* C H2 ~ x.134 CH₃ H CH₂CH₃ H -C Hp -^ -_^- C Hp - x.135 CH₃ H OCH₃ H -CH -^_^--CH -

X.136 CH₃ H OCH₂CH₃ H -CHp-_^^^CHp- x.137 CH₃ H CH(CH₃)₂ H -C Hp -^ -_^- C Hp - X.138 CH₃ H cyclopropyl H -C H2 -^^* C H2 ~ x.139 CH₃ H SCH₃ H

X.140 CH₃ H Phenyl H -CHp-^__^--CHp-

X.141 CH₃ H 2-CH₃-phenyl H -CHp-_^^^CHp-

X.142 CH₃ H NH-CH₂CH₃ H -C Hp -^ -_^- C Hp -

X.143 CH₃ H NH-(phenyl) H -C Hp -^ -_^- C Hp -

X.144 CH₃ H NH-(3-CI-phenyl) H -CHp-_^^^CHp-

X.145 CH₃ H CH₃ CH₃ -C H2 -^^* C H2 ~

X.146 CH₃ H CH₂CH₃ CH₂CH₃ -C Hp -^ -_^- C Hp -

X.147 CH₃ H OCH₃ OCH₃ -CHp-^__^--CHp-

X.148 CH₃ H OCH₂CH₃ OCH₂CH₃ -CHp-_^^^CHp-

X.149 CH₂CH₃ H H H -C Hp -^ -_^- C Hp -

X.150 CH₂CH₃ H CH₃ H -C Hp -^ -_^- C Hp -

X.151 CH₂CH₃ H CH₂CH₃ H -CHp-_^^^CHp-

X.152 CH₂CH₃ H OCH₃ H -C H2 -^^* C H2 ~ x.153 CH₂CH₃ H OCH₂CH₃ H -C Hp -^ -_^- C Hp - x.154 CH₂CH₃ H CH(CH₃)₂ H -CHp-^__^--CHp- x.155 CH₂CH₃ H cyclopropyl H -CHp-_^^^CHp-

X.156 CH₂CH₃ H SCH₃ H -C Hp -^ -_^- C Hp -

X.176 phenyl H CH₃ H -C H2 -^^* C H2 ~

X.177 phenyl H CH₂CH₃ H

X.178 phenyl H OCH₃ H -CHp-^__^--CHp-

X.179 phenyl H CH₃ CH₃ -CHp-_^^^CHp- x.180 phenyl H phenyl H -C Hp -^ -_^- C Hp - x.181 2-CH₃-phenyl H CH₃ H -C Hp -^ -_^- C Hp -

X.182 2-CH₃-phenyl H CH₃ CH₃ -CHp-_^^^CHp-

X.183 2-CH₃-phenyl H 2-CH₃-phenyl H -C H2 -^^* C H2 ~

X.184 NH-CH₂CH₃ H CH₃ H -C Hp -^ -_^- C Hp -

X.185 NH-CH₂CH₃ H CH₃ CH₃ -CHp-^__^--CHp- x.186 NH-CH₂CH₃ H NH-CH₂CH₃ H -CHp-_^^^CHp-

X.187 NH-(phenyl) H CH₃ H -C Hp -^ -_^- C Hp - x.188 NH-(phenyl) H CH₃ CH₃ -C Hp -^ -_^- C Hp -

X.189 NH-(phenyl) H NH-(phenyl) H -CHp-_^^^CHp-

X.190 NH-(3-CI-phenyl) H CH₃ H -C H2 -^^* C H2 ~

X.191 NH-(3-CI-phenyl) H CH₃ CH₃ -C Hp -^ -_^- C Hp -

X.192 NH-(3-CI-phenyl) H NH-(3-CI-phenyl) H -CHp-^__^--CHp- Table 1: This table discloses com ounds 1.01 to 1.192 of the formula (I-I)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table. Table 2: This table discloses com ounds 1.01 to 1.192 of the formula (I-II)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table. Table 3: This table discloses com ounds 1.01 to 1.192 of the formula (I-III)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table. Table 4: This table discloses com ounds 1.01 to 1.192 of the formula (I-IV)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table. Table 5: This table discloses com ounds 1.01 to 1.192 of the formula (I-V)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table. Table 6: This table discloses compounds 1.01 to 1.192 of the formula (I-VI)

Wherein Y¹, Y³, Y⁴, Y⁶ and X have the specific meanings given in the table.

Table 7: This table discloses com ounds 1.01 to 1.192 of the formula (I-VII)

The compounds in Tables 1 to 7 include all isomers, tautomers and mixtures thereof, including the cis/trans isomers shown above.

The compounds of the invention may be made by a variety of methods, illustrated in schemes 1-8. The compounds depicted in the schemes also indicate any isomers and tautomers, in particular the geometric isomers arising from the oxime and oxime ether moieties.

Scheme 1

(I)

1) Compounds of formula (I) may be prepared by reacting a compound of formula (Ha), that is a compound of formula (II) wherein R is -ONH₂, with a compound of formula (VI), wherein A, D², D³, Y⁴ and Y⁶ are as defined herein for compounds of formula (I), and T¹ and T² are Ci-C₈ alkoxy, or T¹ and T² together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C₆-alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by d-C₆ alkyl, as seen in scheme 1.

A general description of condensation reactions is given below, and typical reaction conditions for this type of reaction may be found in Journal of Organic Chemistry, 52(22), 4978- 84; 1987; Chemical & Pharmaceutical Bulletin, 51(2), 138-151; 2003; Organic Letters, 10(2), 285-288; 2008; Journal of the American Chemical Society, 130(12), 4196-4201; 2008;

Chemistry & Biology, 9(1), 113-129; 2002; Organic Preparations and Procedures International, 32(2), 153-159; 2000; Scientia Pharmaceutica, 66(1), 9-21; 1998, Journal of Medicinal

Chemistry, 49(17), 5177-5186; 2006, Journal of Agricultural and Food Chemistry, 38(3), 839-44; 1990; Tetrahedron: Asymmetry, 8(2), 253-263; 1997; Journal of Medicinal Chemistry, 44(21), 3339-3342; 2001; Bioorganic & Medicinal Chemistry Letters, 12(3), 341-344; 2002; US

2007032470; WO 07/058504; Journal of Organic Chemistry, 73(5), 2007-2010; 2008; Bioorganic & Medicinal Chemistry Letters, 19(10), 2683-2687; 2009; and Bioorganic & Medicinal Chemistry Letters, 19(10), 2654-2660; 2009. 2) Hydroxylamine derivatives of formula (Ila) may be made by reacting compounds of formula (IV), wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined herein for compounds of formula (I), and T¹ and T² are Ci-Cs alkoxy, or T¹ and T² together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C₆- alkylidene-O) whereby the alkylidene fragment may optionally be mono- to tetra -substituted by Ci-C₆ alkyl, with a bishydroxylamine derivative of formula (V), wherein X is as defined herein for a compound of formula (I) and R³¹ and R³² are either hydrogen or suitable protecting groups such as tert-butyloxycarbonyl (BOC), allyloxycarbonyl, fluorenylmethyloxycarbonyl (FMOC), formyl, acetyl, propionyl, trifluoroacetyl, benzoyl, substituted benzoyl, STABASE, Si(0-Ci-C₈- alkyl)₃, bis-Si(0-Ci-C₈-alkyl)₃, bis-benzyl, substituted bis-benzyl, bis-allyl, substituted bis-allyl, bis Ci-Cs-alkoxy-alkyl, N-phenylmethylene, substituted N-phenylmethylene, trityl, benzhydryl, substituted benzhydryl, or R³¹ and R³² together with the nitrogen atom to which they are attached may form a phthalyl group (scheme 1). General conditions for this type of condensation reaction can be found below.

When R³¹ and R³² are hydrogen, in order to optimize the yield of compound (Ila) an excess of intermediate (V) over intermediate (IV) may preferably be used. If R³¹ or R³² is not hydrogen, the hydroxylamine derivative may be deprotected using techniques well known to the person skilled in the art. Examples can be found in Greene, T. W., Wuts, P. G. N., Protective Groups in Organic Synthesis, John Wiley & Sons, Inc, 2006.

Monoprotection of bis-hydroxylamines has been described in Tetrahedron (1997), 53(15),

5485-5492. It is to be understood that methods used to obtain mono-protected diamines can be used in an analogous way to obtain mono-protected bis-hydroxylamine derivatives. Typical conditions for this type of reaction can be found in Synthetic Communications (2007), 37(5), 737-742; Organic Preparations and Procedures International (2009), 41(4), 301-307;

Tetrahedron: Asymmetry (2003), 14(11), 1559-1563; Bulletin of the Korean Chemical Society (1994), 15(12), 1025-7; Synthesis (1990), (4), 366-8; and Synthesis (1984), (12), 1032-3.

Bishydroxylamine derivatives are known in the literature. A description of their preparation can be found in WO 08/074418; Inorganic Chemistry Communications (2009), 12(3), 234-236; WO 99/49314; Synthesis (1997), (1), 38-40; and Gazzetta Chimica Italiana (1954), 84 915-20. Scheme 2

(IV) (VII) (I)

3) Alternatively, as seen in scheme 2, compounds of formula (I) may be prepared by reacting a compound of formula (IV) and a compound of formula (VI) in the presence of a compound of formula (VII), wherein X is as defined herein for compounds of formula (I). Compounds of formula (IV) and (VI) are described under Scheme 1.

Typical reaction conditions for condensation reactions are seen below, and typical conditions for this particular condensation reaction are seen in the following references: Nature Chemical Biology, 5(6), 407-413; 2009; Acta Crystallographica, Section E: Structure Reports Online, E65(7), ol657; 2009; Acta Crystallographica, Section E: Structure Reports Online, E64(8), ol405, ol405/l-ol405/7; 2008; Acta Crystallographica, Section E: Structure Reports Online, E64(7), ol324, ol324/l-ol324/6; 2008; Acta Crystallographica, Section E: Structure Reports Online, E63(10), o4080, So4080/l-So4080/7; 2007; Synthetic Communications, 33(4), 543-546; 2003.

Scheme 3

4) Alternatively, compounds of formula (I) can be obtained by reacting a compound of formula (lib), that is a compound of formula (II) wherein R²⁷ is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, a phenylsulfonic acid ester, a nitro-phenylsulfonic acid ester, a nonafluorobutylsulfonic acid ester or LG with a compound of formula (X), wherein A, D², D³, Y⁴ and Y⁶ are as defined herein for compounds of formula (I) (scheme 3).

Typical reaction conditions for alkylation reactions such as this may be found below. These are further illustrated in Chinese Journal of Chemistry, 27(1), 33-42; 2009; WO 09/049846;

Journal of Antibiotics, 61(10), 603-614; 2008; Bioorganic & Medicinal Chemistry Letters, 18(24), 6471-6475; 2008; Journal of Medicinal Chemistry, 51(15), 4601-4608; 2008; WO 06/123145, Archiv der Pharmazie (Weinheim, Germany), 340(4), 202-208; 2007; Synthetic Communications, 37(7), 1155-1165; 2007; Russian Journal of Organic Chemistry, 42(5), 735-738; 2006;

Bioinorganic Chemistry and Applications, 1(3-4), 299-308; 2003; Synthetic Communications, 28(14), 2621-2633; 1998; Synthetic Communications, 19(18), 3129-38; 1989.

5) Compounds of formula (lib) may be obtained by reacting an oxime of formula (VIII) with a compound of formula (IX), wherein R²⁷ is as defined herein for compounds of formula (lib) and R³³ is a halogen, in particular chlorine, bromine or iodine, a sulfonic acid ester group, or the group LG (scheme 3). R²⁷and R³³ may be the same or different. Preferentially, R³³ is a better leaving group under the conditions of the reaction, such as tosylate or bromine when R is chlorine. Preferentially, an excess of the compound of formula (IX) relative to the oxime (VIII) would be used in the reaction, especially when R²⁷ and R³³ are the same.

Typical reaction conditions for alkylation reactions such as this can be found below, and are further illustrated in Journal of Agricultural and Food Chemistry (2008), 56(23), 11376-1139, Farmaco (2003), 58(9), 707-714; 1985; Journal of Heterocyclic Chemistry (1979), 16(7), 1459- 67; WO 08/074418; Journal of Medicinal Chemistry (2008), 51(20), 6421-6431; Synthetic Communications (2007), 37(7), 1155-1165; Bioorganic & Medicinal Chemistry (2007), 15(13), 4520-4527; Journal of Medicinal Chemistry (2006), 49(15), 4638-4649; and Synlett (2001), (Spec. Issue), 931-936.

Scheme 4

(IV)

6) Oximes of formula (VIII) may be obtained by a condensation reaction, whereby a compound of formula (IV), wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined herein for compounds of formula (I) and T¹ and T² are Ci-C₈ alkoxy, or T¹ and T² together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C₆- alkylidene-O) whereby the alkylidene fragment may optionally be mono- to tetra -substituted by Ci-C₆-alkyl, is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine. A more detailed description of condensation processes is given below.

Related references include the following: Journal of Heterocyclic Chemistry, 46(1), 116-118; 2009; Journal of Medicinal Chemistry, 20(5), 718-21; 1977; Journal of Organic Chemistry, 73(11), 4017-4026; 2008; EJEAFChe, Electronic Journal of Environmental, Agricultural and Food Chemistry, 5(5), 1515-1521; 2006; Advanced Synthesis & Catalysis, 346(13-15), 1798-1811; 2004.

Some compounds of formula (IV) are known and their preparation has been published or they are available commercially. A few typical examples are given in Table 8 together with the corresponding CAS numbers. Analogous protocols to those used to prepare the following compounds can be used to prepare other compounds of formula (IV).

Table 8

άχ ho

1196151-83-3 31170-78-2 41043-15-6

9568-10-7

14428-47-8 01622-35-9

N H₂

0 o 0

122910-29-6 844891-39-0

149194-86-5

N H₂

89967-17-9

O

857613-10-6

149194-90-1

1105664-58-1 1105662-77-8

Scheme 5

7) Alternatively, oximes of formula (VIII) can be obtained by a nitrosation reaction of compounds of formula (XI), wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined herein for compounds of formula (I), with base and an alkyl nitrite, as seen in scheme 5. Typical bases include lithium diisopropyl amide (LDA), lithium hexamethyldisilazane, n-butyl lithium, s-butyl lithium, tert-butyl lithium, sodium tert-butylate or potassium tert-butylate . Typical alkyl nitrites include isopentyl nitrite and tert-butyl nitrite. The compound of formula (XI), the alkyl nitrite or the base can be used in different stoichiometric amounts, with each reagent possibly being in excess with respect to the others. Preferentially, such reactions are carried out under nonaqueous conditions in an inert solvent such as hexane, heptanes, cyclohexane, toluene or ethers such as THF or tert-butyl methyl ether. The reaction may be performed at temperatures ranging from -80 to 250°C, preferably between -50 and 120°C.

Such reactions can lead to a mixture of the E- and the Z-oxime (ether) product, or the product may also be exclusively either the E- or the Z-oxime (ether).

A large number of these types of transformations are known in the art. Typical reaction conditions for this type of reaction may be found in Crawford, Jason B.; Chen, Gang; Gauthier, David; Wilson, Trevor; Carpenter, Bryon; Baird, Ian R.; McEachern, Ernie; Kaller, Alan; Harwig, Curtis; Atsma, Bern; Skerlj, Renato T.; Bridger, Gary 1, Organic Process Research &

Development (2008), 12(5), 823-830, McEachern, E. 1; Yang, W.; Chen, G.; Skerlj, R. T.;

Bridger, G. 1, Synthetic Communications (2003), 33(20), 3497-350; and Bark, Thomas;

Thummel, Randolph P., Inorganic Chemistry (2005), 44(24), 8733-8739.

Scheme 6

8) An alternative route to compounds of formula (I) is shown in Scheme 6. As in scheme 3, the compound of formula (I) is obtained by the reacting a compound of formula (lib) with a compound of formula (X) as an alkylation reaction. Typical conditions for this type of reaction are described below.

9) The compounds of (lib) can be formed by reacting a hydroxylamine derivative of formula (XIII), wherein R²⁷ halogen, with a compound of formula (IV), as seen in scheme 6.

Compounds of formula (IV) are described above.

Typical reaction conditions for this type of condensation reaction may be found below, and are further illustrated in Angewandte Chemie, International Edition (2006), 45(32), 5307-5311.

10) Compounds of formula (XIII) can be made by alkylating a hydroxylamine derivative of formula (XII), wherein R³⁴ and R³⁵, either independently of each other, or together with each other and the nitrogen atom to which they are attached, are protecting groups, such as tert- butoxy carbonyl, acetyl, benzyl, or phthalyl, with the alkylating agent (IX), wherein R is halogen and R³³ is halogen, in particular chloro, bromo or iodo, a sulfonic acid ester group, or LG (scheme 6). Typical conditions for such an alkylation reaction may be found below. The protecting groups or group can then be removed using techniques well known to a person skilled in the art, examples of which can be found in Greene, T. W., Wuts, P. G. N., Protective Groups in Organic Synthesis, John Wiley & Sons, Inc, 2006.

Scheme 7

(la)

11) Compounds of formula (la), that is compounds of formula I wherein X is X-3, X-4 or X-5 wherein Z³, Z⁶, Z⁷, Z¹⁰, Z¹¹ and Z¹² are as defined herein for compounds of formula (I)

(represented in scheme 7 as X'), i.e.:

6 7 10 11 1 ?

#—∑—# #—∑—∑—# #— z— z— z— #

X'-1 X'-2 X'-3

and Z⁴, Z⁸ and Z¹³ represent C(OH)R³⁰ and Z⁵, Z⁹ and Z¹⁴ represent CHR²⁹ wherein R²⁹ and R³⁰ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkyoxy, can be made by reacting compounds of formula (III) with compounds of formula (X) (scheme 7).

Typical conditions for an alkylation such as this are described below, and a further illustrated in Synthesis, (13), 2055-2064; 2008; Russian Journal of Organic Chemistry, 43(2), 181-183; 2007; Russian Journal of Organic Chemistry 43(3), 449-453; 2007; and Journal of Molecular Catalysis B: Enzymatic, 11(4-6), 255-263; 2001.

Compounds of formula (la) are especially useful as intermediates to a number of other compounds, wherein the hydroxy group formed by the opening of the epoxide is transformed into other functional groups, for example carbonyl, fluorine or chlorine. Such transformations can be effected using a number of conditions well known to the person skilled in the art.

12) Compounds of formula (III) can be obtained by the alkylation of oximes of formula (VIII) with epoxides of formula (XIV) wherein X', R²⁹ and R³⁰ are as defined above for compounds of formula (III) and R³⁶ is halogen. Such alkylation processes are described in more detail below.

Relevant references include the following: Synthetic Communications, 37(7), 1155-1165; 2007; Molecules, 10(7), 747-754; 2005; Molecules, 10(11), 1399-1408; 2005; European Journal of Medicinal Chemistry, 40(12), 1351-1358; 2005; Organic Preparations and Procedures International, 30(2), 195-202; 1998; WO 08/074418; and Journal fuer Praktische

Chemie/Chemiker-Zeitung (1993), 335(7), 623-7.

A large number of compounds of formula (XIV) are commercially available or their preparation is to be found in the literature. Commercially available compounds (XIV) include epichlorohydrin, 2(S)-epichlorohydrin, 2(R)-epichlorohydrin, 2-methyl-epichlorohydrin, epibromohydrin.

Scheme 8

13) Compounds of formula (I) may be formed from compounds of formula (lid), that is a compound of formula (II) wherein R²⁷ represents C-2B, as seen in scheme 8. This can be done by displacing the group X" with a suitable derivative of the group A or the fragment R³⁷ using one of several techniques well known to the person skilled in the art, including coupling reactions such as Suzuki (Suzuki-Miyaura) couplings and Stille couplings.

The Suzuki coupling comprises the reaction between an organoboron compound, such as the boronic acid derivative of A or R³⁷ or their esters and a halide of formula (lid) to give compounds of formula (I).

The reaction may be done in the presence of a palladium catalyst such as Pd(PPh₃)₄, Pd(OAc)₂, Pd(dppf)CI₂ and a base such as Na₂C0₃, Ba(OH)₂, K₃P0₄, Cs₂C0₃, K₂C0₃, KF, NaOH or alkali alcoholates, such as potassium tert-butoxide or sodium ethoxide. Typical catalyst loadings are in the range of 0.01 to 10 mol%. Preferred solvents for such cross coupling reactions include ethers such as THF or dimethoxyethane, acetonitrile, DMF, NMP, benzene or toluene or a mixture of such solvents. Such solvents can also be used together with water. The preferred temperature range for carrying out such reactions is between 0°C and 180°C. The Stille coupling comprises the use of an organotin compound, such as the tributylstannane derivative of A or R³⁷ and a halide of formula (lid) to give compounds of formula (I).

The reaction can be done in the presence of a palladium catalyst such as Pd(PPh₃)₄, Pd₂(dba)₃.CHCI₃ with or with an added ligand such as P(2-furyl)₃ or Pd(OAc)₂, Pd(dppf)CI₂,

Pd(MeCN)₂CI₂. Typical catalyst loadings are in the range of 0.01 to 10 mol%. Preferred solvents for such cross coupling reactions include ethers such as THF or dimethoxyethane, acetonitrile, DMF, NMP, benzene or toluene. Such solvents can also be used together with water. The preferred temperature range for carrying out such reactions is between 0°C and 180°C.

Typical reaction conditions for these types of reaction may be found in Bioorganic and

Medicinal Chemistry Letters 19(18), 5339-5345; 2009; Canadian Journal of Chemistry, 85(11), 913-922; 2007; Journal of Organic Chemistry, 72(13), 4892-4899; 2007; Tetrahedron Letters, 43(40), 7189-7191; 2002; Synlett, (10), 1557-1558; 2001; EP 792870; WO 95/20569.

14) Compounds of formula (lid) can be formed from compounds of formula (lie), that is a compound of formula (II) wherein R²⁷ represents C-l, by the action of a halogenating agent.

The reaction can be performed using an excess of either the halogenating agent, equimolar amounts of halogenating agent and the hydroxamic acid ester (XV), or with an excess of the hydroxamic acid ester (lie). Preferentially it is carried out with an excess of halogenating agent over the hydroxamic acid ester (lie).

Typical halogenating agents include CCI₄ or CBr₄ along with and a phosphine such as triphenyl phosphine or tributylphosphine. Other typical halogenating agents include Et₂NSF₃, (MeOCH₂CH₂)₂NSF₃ (Deoxo-Fluor), morpholinotrifluorosulfurane and SF₄, SOCI₂, COCI₂, PCI₅, PCI₃, PBr₃ or POCI₃, or a mixture of PCI₅ and POCI₃. Typical conditions include the use of a sub- stoichiometric, equimolar or excess amount of PCI₅ in POCI₃ relative to the compound of formula (lie), where POCI₃ itself may be present in an equimolar amount or alternatively, be used in a sub-stoichiometric amount or excess relative to the compound of formula (lie).

The halogenation of hydroxamic acid ester of formula (lie) can be done without a solvent in certain cases or, preferentially, in the presence of a solvent or mixture of solvents. Any organic solvent that is inert under the specific reaction conditions can be chosen. Preferred solvents include the following, without limiting the selection: aliphatic or aromatic hydrocarbons that may optionally be substituted by one or several halogen atoms such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, ethers such as diethylether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, 1,4- dioxane, dimethoxyethane, triethylene glycol dimethyl ether (methyltriglyme), or acetonitrile, propionitrile, benzonitrile or a substituted benzonitrile.

The use of catalysts to facilitate this type of reaction is established, comprising the use of catalysts such as dimethylformamide, diethylformamide and formylpiperidine. The

transformation can also be done without a reaction catalyst.

Depending on the properties of the starting materials the reaction temperature can be varied over a wide range. Typical reaction temperatures vary between - 100°C and 250°C. Preferentially, the temperature range is between 0°C and 100°C. On some occasions, the reaction may be carried out under reflux.

This transformation can also optionally be carried out under ultrasonication.

The use of organic bases in this type of reaction is well exemplified in the literature. The amount of base can be stoichiometric, sub- or super-stoichiometric. Typically an excess of base is used. Typical bases include the following without limiting the selction: Triethylamine, tripropylamine, tributylamine, di-isopropyl-ethylamine, Ν,Ν-dimethyl-cyclohexylamine, N-methyl- dicyclohexylamine, Ν,Ν-dimethyl-aniline, N,N-d iethyl-aniline, Ν,Ν-dimethyl-benzylamine, N,N- diethyl-benzylamine, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,6- dimethyl-pyridine, 2,4,6-trimethyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, N- ethyl-piperidine, N-methyl-morpholine, N-ethyl-morpholine, Ν,Ν'-dimethyl-piperazine. The transformation can also be done in the absence of bases

Typical reaction protocols for this type of reaction may be found in Bioorganic & Medicinal Chemistry Letters (2009), 19(18), 5339-5345; Journal of Medicinal Chemistry, 50(14), 3314- 3321; 2007; Journal of Organic Chemistry, 69(8), 2741-2749; 2004; WO 01/025206; Australian Journal of Chemistry, 52(8), 807-811; 1999; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 23B(8), 728-32; 1984 .

15) Compounds of formula (lie) can be formed by reacting compounds of formula (lib) with a hydroxamic acid derivative of formula (XV) wherein R³⁷ is as defined herein for compounds of formula (lid). This transformation is an alkylation of the hydroxamic acid derivative (XV) or its salt generated in situ by the action of a base. Typical conditions for alkylation reaction such as this are seen below, and are also described in the following references: WO 09/036020; Journal of the Chemical Society, Perkin Transactions 2, (10), 1728- 1739; 2002; Journal of Medicinal Chemistry, 42(1), 153-163; 1999; Journal of Medicinal Chemistry, 34(1), 57-65; 1991; Synthetic Communications, 19(3-4), 339-44; 1989; Journal of Organic Chemistry, 54(14), 3394-403; 1989; Tetrahedron, 43(11), 2577-92; 1987; Journal of Organic Chemistry, 51(26), 5047-50; 1986.

Scheme 9

(IVa¹)

16) Ketones of formula (IVa⁷), that is a compound of formula (IVa) wherein D¹ is N, may be obtained by acidic hydrolysis methods, well known to the person skilled in the art from compounds of formula (XVIa), that is a compound of formula (XVI) wherein D¹ is N.

17) Enolethers of formula (XVIa) can be obtained by reacting enaminones of formula (XVIII) wherein G¹, G², G³ and p are as described herein for compounds of formula (I) and R³⁸ represents hydrogen, CO-CH₃, CO-CH₂CH₃, CO-CH₂CH₂CH₃, CO-CH(CH₃)₂, CO-CF₃, CO-CF₂CF₃, CH₃, CH₂CH₃, CH₂CH₂CH₃ or CH(CH₃)₂ with amidines or guanidines of formula (XVII) wherein Y¹ is as described herein for compounds of formula (I). Such condensation reactions can be performed using a number of conditions well known to the person skilled in the art. Such reactions are carried out in the presence of a base preferentially sodium or potassium alcoholate in ethanol or methanol. Specific reaction conditions may be found in Synthesis, 1012-1018, 1996; J. Heterocycl. Chem. 20, 649-653, 1983 or in WO2009010488. 18) Enaminones of formula (XVIII) can be obtained by reacting ketone of formula (XX) wherein G¹, G², G³ and p are as described herein for compounds of formula (I) and R³⁸ represents hydrogen, CO-CH₃, CO-CH₂CH₃, CO-CH₂CH₂CH₃, CO-CH(CH₃)₂, CO-CF₃, CO-CF₂CF₃, CH₃, CH₂CH₃, CH₂CH₂CH₃ or CH(CH₃)₂ with Ν,Ν-dimethylformamide dialkyl acetal of formula (XIX) wherein R³⁹ represents d-C₄ alkyl. Such condensation reactions are well known to the person skilled in the art. The reaction is carried out in an inert solvent or without solvent at temperatures ranging from 0°C to 250°C preferably between 50 and 160°C. Specific reaction conditions may be found in Synthesis, (97), 3397, 1964; Synthesis, (97), 3407, 1964; Journal of Med. Chem., Vol. 52, No. 16, 5152-5163; Tetrahedron Lett, (27), 2567, 1986; Tetrahedron Lett, (50), 2255-2264, 1994; Synthetic Commun., (28), 10, 1743-1753, 1998 or in Chem. Ber., (104), 2975, 1971.

19) Enol ethers of formula (XX) can be obtained by reacting ketones of formula (XXII) wherein G¹, G², G³ and p are as described herein for compounds of formula (I) with an alcohol of formula (XXI) wherein R³⁸ represents hydrogen, CO-CH₃, CO-CH₂CH₃, CO-CH₂CH₂CH₃, CO- CH(CH₃)₂, CO-CF₃, CO-CF₂CF₃, CH₃, CH₂CH₃, CH₂CH₂CH₃ or CH(CH₃)₂. Such reactions can be affected using a number of conditions well known to the person skilled in the art. Specific reaction conditions may be found in WO2004104007.

Typical conditions for condensation reactions:

This applies to procedures 1, 2, 3, 6 and 9.

Different stoichiometric set-ups may be used for these reactions, depending on the properties of reactants and product. An excess of the electrophile, the nudeophile, or equimolar amounts may be chosen. Preferentially equimolar amounts of electrophilic and nucleophilic compounds are used.

The reaction may be performed in the presence or absence of an inert organic or inorganic solvent, or in the presence of a mixture of such solvents. Preferentially, it is performed in the presence of one or more solvents. Preferred solvents include the following aliphatic or aromatic hydrocarbons, which may optionally be substituted by one or more halogen atoms, such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethane or carbon tetrachloride, ethers such as diethylether, diisopropyl ether, tert-butyl methyl ether,

tetrahydrofuran, 1,4-dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acids and ester such as acetic acid, ethyl acetate or methyl acetate, aprotic polar solvents such as acetonitrile, pripionitril, dimethyl formamide, dimethyl acetamide, N-methyl-pyrrolidone, dimethyl sulfoxide, sulfolane, DMPU, or pyridine and picolines. The selection of solvents includes water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert- butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.

The reaction may be performed between -20°C and 250°C, preferentially between 0°C and

100°C. In some cases the reaction mixture may be heated to reflux.

Where appropriate, compounds can be used in the form of the free compound, or, alternatively, they can be used in the form of a salt such as the acetate, trifluoroacetate, propionate, benzoate, oxalate, methylsolfonate, phenylsulfonate, p-tolylsulfonate,

trifluormethylsulfonate, fluoride, chloride, bromide, iodide, sulphate, hydrogensulphate or nitrate, including bis-salts if appropriate.

The reaction can be carried out in the absence of an acid using the free compounds.

Alternatively, the reaction may be performed in the presence of an acid in catalytic,

stoichiometric or excess amounts. Acids that could be used include acetic acid, propionic acid, oxalic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methansulfonic acid, para-toluenesulfonic acid, sulphuric acid, sodium hydrogensulphate and phosphoric acid. The reaction can optionally be carried out in a water-free solvent system in the presence of a drying agent, such as sodium or magnesium sulphate, potassium carbonate or molecular sieves.

If the two substituents at the carbon atom of the oxime or oxime ether function are different from each other, the condensation reaction can lead to a mixture of the E- and the Z- oxime (ether) product. The condensation product may also be exclusively either the E- or the Z- oxime (ether).

Condensations can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.

Typical conditions for alkylation reactions:

This applies to procedures 4, 5, 8, 10, 11, 12 and 15.

Different stoichiometric set-ups may be used for these reactions, depending on the properties of reactants and product. An excess of the electrophile, the nucleophile, or neither may be chosen. Usually, it is preferable that equimolar amounts of electrophilic and nucleophilic compounds are used.

The reaction may be performed in the absence or presence of a solvent or a mixture of solvents. Preferential solvents include the following aliphatic or aromatic hydrocarbons that may optionally be substituted by one or more halogen atoms such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethanev or carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, tert-butyl-methyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acids and ester such as acetic acid, ethyl acetate or methyl acetate, aprotic polar solvents such as acetonitrile, pripionitrile, dimethyl formamide, dimethyl acetamide, N-methyl-pyrrolidone, dimethyl sulfoxide, sulfolane, DMPU, or pyridine and picolines. The selction of solvents includes also water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.

The reaction may be performed in a biphasic system comprising an organic solvent that is not miscible with water, such as toluene, dichloromethane, dichloro-ethylene, and an aqueous solvent, such as water. Such a reaction would be performed in the presence of a phase-transfer catalyst, such as tetra-n-butylammonium bromide (TBAB), Tetradecyldimethylbenzylammonium chloride (TDMBAC), N-Benzyltrimethylammonium hydroxide, along with aqueous sodium or potassium hydroxide in stoichiometric amounts. The biphasic reaction may be performed with or without ultrasonication.

The reaction may be carried out at temperatures varying from -100°C and 250°C.

Preferentially, the temperature range is between 0°C and 100°C.

Optionally, an organic or inorganic base may be present such as alkali- and earth alkali acetates, amides, carbonates, hydrogencarbonates, hydrides, hydroxides or alcoholates such as sodium, potassium, caesium or calcium acetate, sodium, potassium, caesium or calcium carbonate, sodium, potassium, caesium or calcium hydrogencarbonate, sodium, potassium, caesium or calcium hydride, sodium, potassium, caesium or calcium amide, sodium, potassium, caesium or calcium hydroxide, sodium, potassium, caesium or calcium methanolate, sodium, potassium, caesium or calcium ethanolate, sodium, potassium, caesium or calcium n-, i-, s- or t- butanolate, triethylamine, tripropylamine, tributylamine, di-isopropyl-ethylamine, N,N-dimethyl- cyclohexylamine, N-methyl-dicyclohexylamine, N,N-dimethyl-aniline, Ν,Ν-diethyl-aniline, N,N- dimethyl-benzylamine, Ν,Ν-diethyl-benzylamine, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,6-dimethyl-pyridine, 2,4,6-trimethyl-pyridine, 4-dimethylamino-pyridine, N- methyl-piperidine, N-ethyl-piperidine, N-methyl-morpholine, N-ethyl-morpholine, N,N'-dimethyl- piperazine, l,4-Diazabicyclo[2.2.2]octane (DABCO), l,8-Diaza-7-bicyclo[5.4.0]undecene (DBU), l,5-Diazabicyclo[4.3.0]non-5-ene (DBN), l-tert-Butyl-2,2,2-tri(l-pyrrolidinyl)phosphazene (BTPP), l-tert-Butyl-2,2,2-tris(dimethylamino)phosphazene, sodium hexamethyldisilazane, potassium hexamethyldisilazane, lithium diisopropylamide, ethyl magnesium chloride, isopropylmagnesium chloride.

The alkylation can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.

The products of steps 1) to 19) may be required to be purified using, for example, chromatography, crystallisation or other purification techniques well known to the person skilled in the art.

The compounds of formula (I) to formula (XXII) and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisams, such as fungi, bacteria or viruses.

The invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof. The compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants. The compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. Furthermore the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.

The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium,

Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g.

Phytophthora, Pythium, Plasmopara). Within the scope of the invention, useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit

(oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is

Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names

RoundupReady® , Herculex I® and LibertyLink®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin- producing bacteria, especially those of the genus Bacillus.

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin);

Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btll corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so- called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds. The compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.

Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.

To this end compounds of formula (I) and inert carriers are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants (auxiliaries) can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier, can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

A preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as active ingredient and an inert carrier, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula (I) may also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation, i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i. /ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient rates of application are from lOmg to lg of active substance per kg of seeds. The rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.

The compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal. "Animal" can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human. "Treatment" means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection. "Prevention" means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.

According to the present invention there is provided the use of a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal. There is also provided the use of a compound of formula (I) as a pharmaceutical agent. There is also provided the use of a compound of formula (I) as an antimicrobial agent in the treatment of an animal. According to the present invention there is also provided a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal. This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.

Alternatively this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion. Alternatively this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection. Alternatively this

pharmaceutical composition can be in inhalable form, such as an aerosol spray.

The compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal. Examples of such microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terms, A. nidulans and A. niger, those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causing Coccidioidomycosis such as Coccidioides immitis; those causing Cryptococcosis such as Cryptococcus neoformans; those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus. Further examples are Fusarium Spp such as Fusarium oxysporum and Fusarium soiani and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans. Still further examples are Microsporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.

The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula I (herein after abbreviated by the term "TX" thus means a compound encompassed by the compounds of formula I, or preferably the term "TX" refers to a compound selected from the Tables 1-7 or Table 9) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide (insect, acarine, mollusc and nematode pesticide), fungicide, synergist, herbicide, safener or plant growth regulator where appropriate. The activity of the compositions according to the invention may thereby be broadened considerably and may have surprising advantages which can also be described, in a wider sense, as synergistic activity. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; provide a composition demonstrating better plant/crop tolerance by reducing phytotoxicity; provide a composition controlling insects in their different development stages; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the TX; or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate;

b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,

pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;

c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;

d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron;

e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin;

f) Pyrazoles, such as tebufenpyrad and fenpyroximate;

g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, or spinosad, spinetoram or azadirachtin;

h) Hormones or pheromones;

i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;

j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;

I) Neonicotinoid compounds such as imidacloprid, thiacloprid, acetamiprid, clothianidin, nitenpyram, dinotefuran or thiamethoxam;

m) Diacyl hydrazines, such as tebufenozide, chromafenozide or methoxyfenozide;

n) Diphenyl ethers, such as diofenolan or pyriproxifen;

o) Indoxacarb;

p) Chlorfenapyr;

q) Pymetrozine or pyrifluquinazon;

r) Spirotetramat, spirodiclofen or spiromesifen;

s) Flubendiamide, chloranthraliniprole, or cyanthraniliprole;

t) Cyenopyrafen or cyflumetofen; or

u) Sulfoxaflor.

In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).

The following mixtures of the compounds of formula I with active ingredients are preferred, wherein, preferably, the term "TX" refers to a compound covered by the compounds of formula I or preferably the term "TX" refers to a compound selected from the Tables 1 to 9 and the following List shows specific examples of mixtures comprising the component TX and the component (B):

an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

an acaricide selected from the group of substances consisting of l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-/V-methyl-/V-l-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439

(development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen

(alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX,

polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17

(development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau- fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302

(compound code) + TX,

an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

a bactericide selected from the group of substances consisting of l-hydroxy-lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,

a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp.

kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus

montrouzieri (alternative name) (178) + TX, Cydia pomoneiia GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia con vergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,

a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,

a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,

an insect pheromone selected from the group of substances consisting of (£)-dec-5-en-l-yl acetate with (£)-dec-5-en-l-ol (IUPAC name) (222) + TX, (£)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradeca-4, 10- dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-ll-enal (IUPAC name) (436) + TX, (Z)-hexadec-ll-en-l-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-en-ll-yn-l-yl acetate (IUPAC name) (438) + TX, (Z)-icos- 13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-l-al (IUPAC name) (782) + TX, (Z)- tetradec-9-en-l-ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-l-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-l-yl acetate (IUPAC name) (283) + TX, (9Z,11£> tetradeca-9,ll-dien-l-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-l-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-l-ene (IUPAC name) (545) + TX, 4- methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure

(alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-l-yl acetate (IUPAC name) (286) + TX, dodec-9-en-l-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-l-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-l-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-l-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure

(alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-ll-en- 1-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B₂ (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l,l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, l-bromo-2- chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l-(3,4-dichloro- phenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(l,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-l,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2- ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3-methyl- l-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex- 1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2- chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide

(IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, Gf-limonene (alternative name) [CCN] + TX, Gf-tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5- methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1142) + TX, EXD (1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion- ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O- (methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin- butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl

ethylphosphonothioate (IUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2H-chromen- 7-yl phosphorothioate (IUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2-propylpyrimidin-4- yl phosphorothioate (IUPAC name) (1075) + TX, Ο,Ο,Ο', O'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, pa rath ion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim- methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name)

[CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride

(IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX,

teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX,

tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta- cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX,

a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,

a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2- dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3- dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,

a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract

(alternative name) (720) + TX,

a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3- dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,

a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

an animal repellent selected from the group of substances consisting of anthraquinone (32)

+ TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name)

[CCN] and ribavirin (alternative name) [CCN] + TX,

a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,

and biologically active compounds selected from the group consisting of azaconazole (60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24- 3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX,

fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671- 89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX,

propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96- 3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol

[55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate

[41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc.

BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim- methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21- 7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427- 38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731-27-1] + TX, bordeaux mixture [8011-63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39- 1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos

[26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77 3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326- 34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol

[10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899- 03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80 7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid

[189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-l-methyl- lH-pyrazole-4-carboxylic acid (9-dichloromethylene-l,2,3,4-tetrahydro-l,4-methano-naphthalen 5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4- carboxylic acid [2-(2,4-dichlorophenyl)-2-methoxy-l-methyl-ethyl]-amide (disclosed in WO 2008/148570) + TX, l-[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3- thiazol-2-yl]piperidin-l-yl]-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone + TX, l-[4- [4-[5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5- methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone [1003318-67-9], both disclosed in WO 2010/123791, WO 2008/013925, WO 2008/013622 and WO 2011/051243 page 20) +TX, S)-[3- (4-Chloro-2-fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl-methanol + TX, 3 (4-Chloro-2-fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl-methanol + TX, 3 difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl-2- (2,4,6-trichlorophenyl)ethyl]-lH-Pyrazole-4-carboxamide + TX, 4-[(5S)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(th

yl)benzamide (WO2011/104089) + TX, 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5Λ)-5- (3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isox^^

yl)benzamide (WO2011/104089) + TX, 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-(trans-l-oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-

[(5/?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(tran

thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5S)-5-(3,5-dichlorophenyl)-5-

(trifluoromethyl)-4H-isoxazol-3-yl]-N-(l,l-dioxothietan-3-yl)-2-methyl-benzamide

(WO2011/104089) + TX, 4-[(5/?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-

(l,l-dioxothietan-3-yl)-2-methyl-benzamide (WO2011/104089) + TX, 4-[(5S)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-

(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, Penflufen [494793-67-8] + TX, 5- [(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-(l,2,4-triazol-l- yl)benzonitrile (WO2007/075459) + TX, 5-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitrile (WO2007/075459) +TX.

The components (B) are known. The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet under the internet address

http://www.alanwood.net/pesticides/ [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2012]; or preferably one of the further pesticides listed below. In the above different lists of active ingredients to be mixed with a TX, the compound of the formula I is preferably a compound selected from the Tables 1-7 or Table 9; more preferably Table 9;

and even more preferably a compound selected from P.01, P.02, P.03, P.04, P.05, P.06, P.08, P.09, P.10, P.ll, P.12, P.14, P.15, P.16, P.17 or P.18.

In the above-mentioned mixtures of compounds of formula I, in particular a compound selected from said Tables 1-7 or Table 9, with other insecticides, fungicides, herbicides, safeners, adjuvants and the like, the mixing ratios can vary over a large range and are, preferably 100: 1 to 1:6000, especially 50: 1 to 1:50, more especially 20: 1 to 1:20, even more especially 10: 1 to 1: 10. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

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

Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The mixtures comprising a TX selected from Tables 1-7 or Table 9 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Tables 1-7 or Table 9 and the active ingredients as described above is not essential for working the present invention.

The following non-limiting Examples illustrate the above-described invention in greater detail without limiting it. Those skilled in the art will promptly recognize appropriate variations from the procedures both as to reactants and as to reaction conditions and techniques. All references mentioned herein are incorporated by reference in their entirety.

Preparatory examples:

Pre aration of compound P.2

A 15 mL flask was charged with a solution of 2-methyl-6,7-dihydro-5H-quinolin-8-one 0-(3- aminooxy-propyl)-E-oxime (64 mg; 0.23 mmol) in methanol (10 mL). Under stirring l-(4,6- diethoxy-pyrimidin-2-yl)-ethanone (49 mg; 0.23 mmol) was added. The resulting solution was stirred at room temperature for 17 hours. TLC analysis of an aliquot of the reaction mixture showed that all of the starting materials was consumed. After evaporation of the solvent in vacuo, the title compound was recovered as a yellowish gum (106 mg, 98%). No further purification was required.

TLC: Plates: Merck DC-Plates, silica gel F₂5₄, saturated atmosphere in developing tank, UV detection, eluent: cyclohexane/ ethylacetate 1: 1 (v:v); R_f of title compound = 0.59, R_f oxime starting material = 0.11.

LC-MS (Method ZMD): R_t = 1.72 min. MS: (M⁺+l)=470

^JH NMR (200 MHz, CDCI₃) 6_(ppm): 7.34 (d, 1H), 7.04 (d, 1H), 5.94 (s, 1H), 4.34-4.46 (q, 4H), 4.26 (s, 2H), 4.22 (s, 2H), 2.87 (t, 2H), 2.71 (m, 2H), 2.59 (s, 3H), 2.30 (s, 3H), 1.84 (m, 2H), 1.37-1.42 (t, 6H), 1.10 (s, 6H).

Preparation of 2-Methyl-6,7-dihydro-5H-quinolin-8-one-Q-(3-aminooxy-2,2-dimethyl-propyl>

E-oxime

A solution of hydroxylamine-0-[3-(aminooxy)-2,2-dimethylpropyl] hydrochloride (1:2) (21.7 g) in absolute ethanol (300 mL) was charged to a 500 mL reaction flask which had previously been placed under an atmosphere of argon. Under stirring, p-toluenesulphonic acid (1.2 g) was added, followed by the dropwise addition of 2-methyl-6,7-dihydro-5H-quinolin-8-one (6.77 g) dissolved in absolute ethanol (30 ml_). The resulting yellow solution was stirred at room temperature for 1.5 hours. Following the course of the reaction by TLC indicated that no starting materials were left at this point in time. The ethanol was removed in vacuo. Aqueous sodium bicarbonate solution (150 mL) was then added. Extraction was carried out using ethyl acetate (2x100 mL). The combined organic layers were dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a beige oil (10.9 g). This raw material was purified by chromatography on silica gel (eluent: heptane/ ethyl acetate 2: 1 (v:v) with 1 vol-% of triethylamine). This was followed by RP-HPLC chromatography (Separation Laboratory: Method 10-40). The title compound (6.00 g) was obtained in the form of a light yellow gum.

LC-MS (Method ZMD): UV Detection: 220 nm; R_t = 0.83 min.

TLC: Plates: Merck DC-Plates, silica gel F₂5₄, saturated atmosphere in developing tank, UV detection, eluent: heptane/ ethyl acetate 1:2 (v:v); Rf of title compound = 0.11.

Pre aration of compound P.11

A solution of hydroxylamine-0-[3-(aminooxy)-2,2-dimethylpropyl] hydrochloride (1:2) (100 mg; 0.48 mmol) in ethanol (18 mL) was charged to a 25 mL reaction flask. Under stirring 2- methyl-6,7-dihydro-5H-quinazolin-8-one (157 mg; 0.97 mmol) and and potassium carbonate (73 mg; 0.53 mmol) were added. The resulting suspension was stirred at room temperature for 15 hours, poured onto water (100 mL) and extracted with ethyl acetate (3x80 mL). The combined organic layers were dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a beige oil. This raw material was purified by chromatography (combiflash RF, 0-70% ethylacetate in cyclohexane) to give the title compound (116 mg, 57% yield) as brown crystals (decomposition from 180°C). LC-MS (Method ZCQ): R_t = 1.64 min. MS: ([M+l]⁺)=423.

Pre aration of compound P.15

A 10 mL flask was charged with a solution of 2-methyl-6,7-dihydro-5H-quinolin-8-one 0-(3- aminooxy-propyl)-E-oxime (101 mg; 0.36 mmol) in methanol (8 mL). Under stirring 2(3-Chloro- phenylamino)-6,7-dihydro-5H-quinazolin-8-one (100 mg; 0.36 mmol) was added. The resulting solution was stirred at room temperature for 18 hours. After evaporation of the solvent in vacuo, the crude was purified via chromatography (combiflash RF, 0-60% ethylacetate in cyclohexane) to give 2-(3-chlorophenylamino)-6,7-dihydro-5-quinazolin-8-one 0-(2,2-dimethyl-3-(2-methyl- 6,7-dihydro-5H-quinolin-(8E)-ylideneaminooxy)-propyl)-oxime (compound P.15) (0.17g, 87% yield) as a yellow solid decomposition from 79°C. LC-MS (Method ZCQ) R_t = 1.73 min., MS: (M⁺+l) = 533.

Preparation of 2(3-Chloro-phenylamino)-6,7-dihydro-5H-quinazolin-8-one

In a 25 mL single-necked round -bottomed flask equipped with a condenser, (3-chloro- phenyl)-(8-ethoxy-5,6-dihydro-quinazolin-2-yl)-amine (0.39 g; 1.31 mmol) was dissolved in a mixture of acetic acid (7.0 mL) and water (0.70 mL). Stirring was continued under heating to reflux for 1 hour. TLC indicated that starting materials were consumed. The mixture was cooled to room temperature, then water and saturated NaHC0₃ were added. Extraction was carried out using dichloromethane (3x20 mL). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give an oil. The crude was purified via chromatography (combiflash RF, 0-80% ethylacetate in cyclohexane) to give 2(3-Chloro-phenylamino)-6,7-dihydro-5H-quinazolin-8-one (0.21g, 58% of theory) as a white solid MP. 220-222°C. LC-MS (Method ZCQ) R_t = 1.68 min. , MS: (M⁺+l) = 274. ^JH-NMR (CDCI₃, 400 MHz): 2.23 (m, 2H); 2.84 (m, 2H); 2.94 (m, 2H); 7.05 (m, 1H); 7.24 (m, 1H); 7.22 (m, 2H); 7.83 (d, 1H); 8.68 (s, 1H). TLC: Plates: Merck DC-Plates, silica gel F₂₅₄, saturated atmosphere in developing tank, UV detection, eluent: heptane/ ethyl acetate 1: 1 (v:v); R_f of title compound = 0.56.

Preparation of (3-chloro- henyl>(8-ethoxy-5,6-dihydro-quinazolin-2-yn-amine

In a 25mL single-necked round-bottomed flask equipped with a condenser, a mixture of 6- [l-dimethylamino-meth-(E)-ylidene]-2-ethoxy-cyclohex-2-enone (WO 2004/104007) (2.60 g; 13.32 mmol), N-(3-chloro-phenyl)guanidine carbonate (4.01 g; 17.31 mmol) and potassium carbonate (2.02 g; 14.65 mmol) in absolute ethanol (50 mL) was stirred at reflux temperature over night for 17 hours. The reaction mixture was evaporated to dryness, taken up in water (80 mL), extracted with dichloromethane (3x 50 mL). Combined organic layers were dried over sodium sulphate, filtered and the solvent was removed in vacuo . The crude was purified via chromatography (combiflash RF, 0-80% ethylacetate in cyclohexane) to give (3-chloro-phenyl)- (8-ethoxy-5,6-dihydro-quinazolin-2-yl)-amine (0.39g, 10% of theory) as a white solid melting MP. 113-116°C. LC-MS (Method ZCQ) R_t = 1.97 min., MS: (M⁺+l) = 302.

The following examples illustrate the preparation of useful intermediates:

2-Methyl-6,7-Dihydro-5H-quinolin-8-one-(E>oxime

H

A 250 mL single-necked round-bottomed flask equipped with a condenser was charged with a solution of 2-methyl-6,7-dihydro-5H-quinolin-8-one (7.00 g) (CA Registry Number: 849643-01- 2) in absolute ethanol (70 mL). Under stirring, hydroxylamine-hydrochloride (4.50 g) was added, followed by portionwise addition of a solution of NaOH (8.70 g) in water (14.00 mL). Stirring was continued under heating to reflux for 6.0 hours. Following the course of the reaction by TLC indicated that starting materials were consumed by this time. The suspension was cooled to room temperature. Under stirring and cooling with an ice-water cooling bath, water (10 mL) was added and the pH was adjusted to 6 by the addition of 6 M aqueous HCI. Extraction was carried out using ethyl acetate (2x100 mL). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a yellow solid (7.65 g).

Analytical data for the title compound:

LC-MS (Method ZMD) UV Detection: 220 nm; R_t = 0.20 , MS: (M⁺+l) = 177, (M⁺ +23) = 179; melting point = 177-181°C.

TLC: Plates: Merck DC-Plates, silica gel F₂5₄, saturated atmosphere in developing tank, UV detection, eluent: ethyl acetate/triethylamine 10: 1 (v:v); R_f of title compound = 0.26, R_f of the ketone starting material = 0.46.

The preparation of the following starting materials is described in the literature

CA Registry Number: 849643-01-2

U.S. Pat. Appl. Publ. (2005), 75 pp., Cont.-in-part of U.S. Ser. No. 437,807. CODEN:

USXXCO US 2005075366 Al 20050407

^■2 HCI CA Registry Number: 1034433-68-5

PCT Int. Appl. (2008), 187 pp. CODEN: PIXXD2 WO 2008074418 A2 20080626

E CA Registry Number: 23089-39-6

CA Registry Number: 18103-88-3

Talanta (1969), 16(3), 448-52; DE 2447258 (19760408); Journal of Heterocyclic Chemistry (1968), 5(2), 161-4.

Preparation of 4-chloro-2-methyl-6,7-dihydro-8(5H)-quinolinone

Step A) 4-Hydroxy-2-methylquinoline (10.0 g) (CA Registry Number: 607-67-0) was charged to a reactor containing absolute ethanol (90.0 mL) under a nitrogen atmosphere. Under stirring, a suspension of Raney nickel (2.0 g) in absolute ethanol (10.0 mL) was added to the reaction mixture. The nitrogen atmosphere was then replaced by hydrogen. The reaction mixture was stirred at 75°C for 22 hours under a 100 bar hydrogen atmosphere, at which time analysis of the reaction mixture by TLC indicated that starting material was consumed. The catalyst was filtered off and the solvent was removed in vacuo to give a white solid (8.35 g). The compound was used as such for the next step.

LC-MS (ZMD): UV Detection: 220 nm; R_t = 0.40 min. MS: (M⁺+l) 164; melting point = 237-

240°C. TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: dichloromethane / methanol 9: 1 (v:v); R_f of title compound = 0.22, R_f of quinoline starting material = 0.34.

Step B) A 50 mL single-necked round-bottom flask equipped with a condenser was charged with a solution of 2-methyl-5,6,7,8-tetrahydro-quinolin-4-ol (4.00 g) in phosphorus oxide chloride (18.3 mL) under an argon atmosphere. The resulting colourless solution was stirred at 100°C for 3.5 hours, after which time TLC indicated that no starting material was remaining. The solvent was removed in vacuo and hot water (40-50°C) was added carefully and slowly to the residue to hydrolyse the remaining phosphorus oxide chloride. Under cooling with an ice- water cooling bath, the pH was adjusted to 12 by the addition of 4 M aqueous NaOH. The resulting solution was extracted using chloroform (2x50 mL). The combined organic layers were washed with brine (25 mL) and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a light yellow oil (4.21 g). The compound was used as such for the next step.

LC-MS (ZMD): UV Detection: 220 nm; R_t = 0.87 min. MS: (M⁺+ l) = 182.

TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptane / ethyl acetate 1 :4 (v:v); Rf of title compound = 0.40, Rf of quinolinol starting material = 0.

Step C) A 25 mL single-necked round-bottom flask equipped with a condenser was charged with a solution of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline (560 mg) in acetic anhydride (0.49 mL). Under stirring, benzaldehyde (0.34 mL) was added and the resulting yellow solution was stirred under heating to reflux for 3.5 hours. Following the course of the reaction by TLC indicated that starting material was consumed by this time. The resulting brown solution was cooled to room temperature. Crushed ice was added and the pH was adjusted to 10 using a small amount of 2 M aqueous NaOH. Extraction was carried out using ethyl acetate (2x20 mL). The combined organic phases were dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a brown gum (750 mg). The crude material was purified by chromatography on silica gel (eluent: heptane / ethyl acetate 98:2 (v:v)). This gave the title compound (263 mg) as a yellow oil.

LC-MS (Method ZMD) UV Detection: 220 nm; R_t = 2.23 , MS: (M⁺+ l) = 270.

TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptanes / ethyl acetate 9: 1 (v:v); R_f of title compound = 0.44, R_f of the chloroquinoline starting material = 0.09. Step D) A 25 mL single-necked round-bottom flask was charged with a solution of 8- benzylidene-4-chloro-2-methyl-5,6,7,8-tetrahydro-quinoline (263 mg) in dichloromethane (2.0 mL) / methanol (3.8 mL). Under stirring and cooling to -78°C with a dry ice-acetone cooling bath, ozone was passed through the reaction mixture for 3 minutes until a light blue color was observed. Then dimethyl sulfide (2.0 mL) was added at -78°C. Then, the reaction mixture was allowed to reach room temperature and was stirred for 4 hours. Solvents were removed in vacuo, then the resulting orange gum was taken up in diethyl ether and 1 M aqueous HCI (5 mL) was added. Extraction of the acidic by-products was carried out using diethyl ether (2x20 mL). Crushed ice was added to the aqueous layer and the pH was adjusted to 10 by the addition of 2 M aqueous NaOH. The resulting solution was extracted using chloroform (2x20 mL). The combined organic layers were dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a yellow solid (96 mg).

Analytical data for the title compound:

LC-MS (Method ZMD) UV Detection: 220 nm; R_t = 1.28 , MS: (M⁺+l) = 196.

TLC: Plates: Merck DC-Plates, silica gel F₂5₄, saturated atmosphere in developing tank, UV detection, eluent: heptanes / ethyl acetate 4: 1 (v:v); R_f of title compound = 0.04, R_f of the benzylidene starting material = 0.59.

Preparation of 2,4-dimethyl-6,7-dihydro-8(5H)-quinolinone

Step A) A 5 mL microwave tube was charged with a solution of 4-chloro-2-methyl-5,6,7,8- tetrahydroquinoline (500 mg) in 1,2-dichloroethane (2.50 mL). Under stirring, trimethylboroxine (380 mg), potassium carbonate (647 mg) and dichloro[l,l'-bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (101 mg) were added and the resulting red suspension was degassed under argon for 5 minutes. The reaction mixture was subjected to microwave irradiation at 120°C for 0.5 hour. After addition of new portions of trimethylboroxine (2x380 mg) and catalyst (101 mg), the reaction mixture was again subjected to microwave irradiation at 120°C for 2x0.5 hour. Following the course of the reaction by TLC indicated that starting material was consumed by this time. The resulting brown material was purified by

chromatography on silica gel (eluent: heptane / ethyl acetate 4: 1 (v:v)). This gave the tittle compound (345 mg) as a light brown oil. LC-MS (Method ZMD) UV Detection: 220 nm; R_t = 0.75 , MS: (M⁺+ l) = 162.

TLC: Plates: Merck DC-Plates, silica gel F₂₅₄, saturated atmosphere in developing tank, UV detection, eluent: heptane / ethyl acetate 1:2 (v:v); Rf of title compound = 0.28, Rf of the chloroquinoline starting material = 0.40.

Step B) 2,4-Dimethyl-5,6,7,8-tetrahydro-quinoline (150 mg) was charged to a 10 mL single- necked round-bottom flask containing chloroform (1.50 mL). Under stirring and cooling with an ice-water cooling bath, 3-chloroperbenzoic acid (344 mg) was added portion wise. The resulting orange solution was stirred at room temperature for 5 hours, at which time analysis of the reaction mixture by TLC indicated that starting material was consumed. Under cooling with an ice-water cooling bath, the pH was adjusted to pH 12 by the addition of 4 M aqueous NaOH (2.0 mL). The resulting solution was extracted using chloroform (3x10 mL). The combined organic layers were washed with brine (10 mL) and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a light orange gum (180 mg). This intermediate was used as such for the following step.

LC-MS (ZMD): UV Detection: 220 nm; R_t = 1.26 min. MS: (M⁺+ l) 178.

TLC: Plates: Merck DC-Plates, silica gel F₂5₄, saturated atmosphere in developing tank, UV detection, eluent: heptane / ethyl acetate 1:2 (v:v); Rf of title compound = 0, Rf of quinoline starting material = 0.28.

Step C) A 25 mL single-necked round-bottom flask equipped with a condenser was charged with a solution of 2,4-dimethyl-5,6,7,8-tetrahydro-quinoline-l-oxide (334 mg) in

dichloromethane (2.00 mL) under an argon atmosphere. Under stirring and cooling with an ice- water cooling bath, trifluoroacetic anhydride (2.66 mL) was added dropwise and the resulting orange solution was stirred under heating to reflux for 22 hours. Following the course of the reaction by TLC indicated that starting material was consumed by this time. The resulting brown solution was cooled to room temperature. Crushed ice was added and the pH was adjusted to 12 using 2 M aqueous NaOH (5 mL). Extraction was carried out using dichloromethane (3x10 mL). The combined organic phases were dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a dark brown gum (226 mg). Th is intermediate was used without further purification in the next step.

LC-MS (Method ZMD) UV Detection: 220 nm; R_t = 0.25 , MS: (M⁺+ l) = 178, (M⁺ -18) =

160. TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptanes / ethyl acetate 1:4 (v:v); R_f of title compound = 0.08, R_f of the quinoline-oxide starting material = 0.

Step D) A 25 mL single-necked round-bottom flask equipped with a condenser was charged with a solution of 2,4-dimethyl-5,6,7,8-tetrahydro-quinolin-8-ol (226 mg) in chloroform (2.00 mL). Under stirring, manganese(IV) oxide (443 mg) was added and the resulting black suspension was stirred under heating to reflux for 18 hours, after which time TLC indicated that no starting material was remaining. The resulting black material was purified by chromatography on silica gel (eluent: heptane / ethyl acetate gradient from 1:1 to 1:2 (v:v)). This gave the tittle compound (78 mg) as an orange gum.

Analytical data for the title compound:

LC-MS (ZMD): UV Detection: 220 nm; R_t = 0.34 min. MS: (M⁺+l) = 176.

TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptane / ethyl acetate 1:4 (v:v); R_f of title compound = 0.11, R_f of quinolinol starting material = 0.08.

Preparation of 9-methyl-2,3-dihydro-lH-acridin-4-one

Step A) 9-Methyl-l,2,3,4-tetrahydroacridine: In a round-bottom flask, cyclohexanone (6.1 mL, 58 mmol) was heated at 90°C, and 2-aminoacetophenone hydrochloride (10 g; 58 mmol) was added by small fractions. The bottom flask was then equipped with a condenser, and the crude heterogeneous mixture was further heated overnight at 110°C. After cooling to room temperature, the red-orange solid was dissolved in ethanol/HCI (12 N) [95/5 v/v]. The solution was then neutralized with an aqueous NaOH solution. Ethanol was evaporated, and the product extracted with diethyl ether (2 x 100 mL). The combined organic layers were washed with water (2 x 100 mL), dried over magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The desired product was finally obtained as a brown-yellow solid (10.2 g, 89%). *H NMR (200.131 MHz; CDCI₃) 6_(ppm): 7.94 (dd, ³J = 8.3 Hz and ⁴J = 1.1 Hz, 1H), 7.87 (dd, ³J = 8.3 Hz and ⁴J = 1.3 Hz, 1H), 7.55 (ddd, ³J = 8.3 Hz, ³J = 8.3 Hz and ⁴J = 1.3 Hz, 1H), 7.38 (ddd, ³J = 8.3 Hz, ³J = 8.3 Hz and ⁴J = 1.1 Hz, 1H), 3.07 (t br, ³J = 6.7 Hz, 2H), 2.79 (t br, ³J = 6.1 Hz, 2H), 2.43 (s, 3H), 1.86 (m, 2 x 2H). ¹³C NMR (50.332 MHz, CDCI₃) 6_(ppm): 157.8, 145.5, 140.6, 128.0, 126.4, 128.6, 127.6, 124.8, 122.9, 34.2, 26.5, 22.8, 22.4, 12.9. HRMS (EI) m/z: calcd for [M]⁺ (found): 197.1204 (197.1198). Anal. Calcd for C₁₄H₁₅N (found): C 85.24 (85.25); H 7.66 (7.72); N 7.10 (6.78).

Step B) N xide-9-methyl-l,2,3,4-tetrahydroacridine: A dichloromethane solution (300 mL) of 3-chloroperbenzoic acid (26 g, 105 mmol) was slowly added to a dichloromethane solution (100 mL) of 9-methyl-l,2,3,4-tetrahydroacridine (10.2 g, 52 mmol) at 0°C. The mixture was stirred for 4 h at room temperature and quenched with an aqueous NaOH solution. The organic layers were further washed with water (5 x 100 mL) and dried over MgS0₄, and the solvent was removed under reduced pressure giving desired product as a brownish solid. (10.83 g, 98%). H NMR (200.131 MHz, CDCI₃) 6_(ppm): 8.77 (dd, ³ J = 8.5 Hz and J = 1.2 Hz, 1H), 7.97 (dd, ³ J = 8.5 Hz and ⁴J = 0.9 Hz, 1H), 7.70-7.50 (m, 2x lH), 3.19 (t, ³J = 6.1 Hz, 2H), 2.85 (t, ³J = 6.2 Hz, 2H), 2.51 (s, 3H), 1.88 (m, 2 x 2H). ¹³C NMR (50.332 MHz, CDCI₃) 6_(ppm): 146.7, 139.1, 131.6, 129.9, 127.7, 129.0, 127.3, 123.9, 119.6, 27.1, 26.6, 22.0, 21.4, 13.4. HRMS (EI) calcd for [M]⁺ (found): 213.1154 (213.1159).

Step C) 9-Methyl-l,2,3,4-tetrahydroacridin-4-ol: In a two-neck round-bottom flask equipped with a reflux condenser, /V-oxide-9-methyl-l,2,3,4-tetrahydroacridine (11.2 g, 52 mmol) was dissolved in dichloromethane (250 mL). Trifluoroacetic anhydride (17 mL, 120 mmol) was slowly added at room temperature (the reaction is exothermic). The solution was stirred for 5 h, and the solvent was evaporated. The crude solid was dissolved in methanol (50 mL) and saponified by an aqueous K₂C0₃ solution (2 M, 150 mL); a brown solid precipitated. The methanol was removed under reduced pressure, and the product was extracted with dichloromethane (2 x 150 mL). The combined organic layers were washed with brine (2 x 50 mL), dried over magnesium sulfate, and evaporated to dryness. The desired product was recovered as a brown solid (9.4 g, 84%). ^JH NMR (200.131 MHz, CDCI₃) 6_(ppm): 7.96 (d, ³ J = 8.3 Hz, 1H), 7.91 (d, ³ J = 8.4 Hz, 1H), 7.58 (dd, ³ J = 8.3 Hz and ³ J = 8.1 Hz, 1H), 7.45 (dd, ³ J = 8.1 Hz and ³ J = 8.4 Hz, 1H), 4.95 (s br, 1H), 4.76 (dd, ³ J = 10.3 Hz and ³ J = 10.0 Hz, 1H), 2.89 (m, 2H), 2.54 (s, 3H), 2.40-1.92 (2xm, 2x lH), 1.82 (m, 2H). ¹³C NMR (50.332 MHz, CDCI₃) 6_(ppm): 159.2, 145.3, 142.0, 127.7, 127.3, 129.2, 128.5, 126.0, 123.5, 70.2, 30.3, 26.7, 19.6, 13.8. HRMS (EI) calcd for [M]⁺ (found): 213.1153 (213.1154).

Step D) 9-methyl-2,3-dihydro-lH-acridin-4-one: To a dichloromethane solution (300 mL) of

9-Methyl-l,2,3,4-tetrahydroacridin-4-ol (9.4 g, 44 mmol) was added Mn0₂ (23 g, 264 mmol) at room temperature, and the heterogeneous solution was allowed to stir for 2 days. After filtration over Celite, the solvent was evaporated. The crude dark solid was purified by column chromatography (neutral alumina, dichloromethane as eluant). After evaporation of the solvent, the title compound was recovered as a brownish solid (5.41 g, 58%). H NMR (200.131 MHz, CDCI₃) 6_(ppm): 8.31 (dd, ³J = 8.1 Hz and ⁴J = 0.8 Hz, 1H), 7.94 (dd, ³J = 8.0 Hz and ⁴J = 1.4 Hz, 1H), 7.67-7.51 (m, 2H), 3.08 (t, ³ J = 6.1 Hz, 2H), 2.82 (t, ³J = 6.4 Hz, 2H), 2.60 (s, 3H), 2.22 (m, 2H). ¹³C NMR (50.332 MHz, CDCI₃) 6_(ppm): 198.2, 148.4, 146.9, 143.6, 134.1, 129.4, 132.4, 129.6, 128.9, 123.8, 40.2, 27.2, 22.4, 14.5. HRMS (EI) m/z calcd for [M]⁺ (found): 211.0997 (211.0989). Anal. Calcd for C₁₄H₁₃NO (found): C 79.59 (79.72); H 6.20 (6.28); N 6.63 (6.10).

Preparation of 2-Methyl-6,7-dihydro-5H-quinazolin-8-one

Step A) 8-Ethoxy-2-methyl-5,6-dihydro-quinazoline: In a 25ml_ single-necked round- bottomed flask equipped with a condenser, a mixture of 6-[l-dimethylamino-meth-(E)-ylidene]- 2-ethoxy-cyclohex-2-enone (WO 2004/104007) (2.80 g; 14.3 mmol), acetamidine hydrochloride (1.70 g; 17.9 mmol) and potassium carbonate (2.73 g; 19.7 mmol) in absolute ethanol (50 mL) was stirred at reflux temperature over night for 16 hours. The reaction mixture was cooled to room temperature, poured onto water (400 mL) and extracted with dichloromethane (3x100 mL). The crude reaction mixture is purified via chromatography (combiflash RF, 70-100% ethylacetate in cydohexane) to give 8-Ethoxy-2-methyl-5,6-dihydro-quinazoline (1.47 g, 54% of theory) as brown oil. LC-MS (Method ZCQ) R_t = 1.21 min. , MS: (M⁺+l) = 191. ^JH-NMR (CDCI₃, 400 MHz): 1.49 (t, 3H); 2.41 (m, 2H); 2.74 (t, 2H); 2.75 (s, 3H); 3.99 (q, 2H); 5.46 (t,lH); 8.47 (s, 1H).

Step B) 2-Methyl-6,7-dihydro-5H-quinazolin-8-one: In a 25mL single-necked round- bottomed flask equipped with a condenser 8-Ethoxy-2-methyl-5,6-dihydro-quinazoline (1.30 g; 6.80 mmol) was dissolved in a mixture of acetic acid (31 mL) and water (3.1 mL). Stirring was continued under heating to reflux over night for 20 hours. TLC indicated that starting materials were consumed by this time. The mixture was cooled to room temperature, water and saturated NaHC03 was added. Extraction was carried out using dichloromethane (3x100 mL). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo. The crude is purified via chromatography (combiflash RF, 0-10% methanol in dichloromethane) to give 2-Methyl-6,7-dihydro-5H-quinazolin-8-one (764 mg; 69% of theory)as a brown oil. LC-MS (Method ZCQ) R_t = 0.91 min. , MS: (M⁺+l) = 163. ^-NMR (CDCI₃, 400 MHz): 2.24 (m, 2H); 2.83 (m, 2H); 2.84 (s, 3H); 3.01 (m, 2H); 8.85 (s, 1H).

Preparation of 2-Phenyl-6,7-dihydro-5H-quinazolin-8-one

Step A) 8-Ethoxy-2-phenyl-5,6-dihydro-quinazoline: In a 25mL single-necked round- bottomed flask equipped with a condenser, a mixture of 6-[l-dimethylamino-meth-(E)-ylidene]- 2-ethoxy-cyclohex-2-enone (WO 2004/104007) (0.51 g; 2.6mmol) and Benzamidine (0.38 g; 3.2mmol) in absolute ethanol (9 mL) is stirred at reflux temperature over night for 17 hours. The reaction mixture is evaporated to dryness, taken up in dichloromethane and purified via chromatography (combiflash RF, 0-40% ethylacetate in cyclohexane) to give 8-ethoxy-2-phenyl- 5,6-dihydro-quinazoline (0.50g, 63% of theory) as a white solid melting MP. 101-103°C. LC-MS (Method ZCQ) R_t = 1.84 min. , MS: (M⁺+l) = 253. ^JH-NMR (CDCI₃, 400 MHz): 1.48 (t, 3H); 2.45 (m, 2H); 2.81 (t, 2H); 4.02 (q, 2H); 5.52 (t,lH); 7.47 (m, 3H); 8.46 (m, 2H); 8.51 (s, 1H).

Step B) 2-Phenyl-6,7-dihydro-5H-quinazolin-8-one: In a 25ml_ single-necked round- bottomed flask equipped with a condenser, 8-ethoxy-2-phenyl-5,6-dihydro-quinazoline (0.45 g; 1.18 mmol) was dissolved in a mixture of acetic acid (9.5 mL) and water (0.95 mL). Stirring was continued under heating to reflux for 15 minutes. TLC indicated that starting materials were consumed by this time. The mixture was cooled to room temperature, water and saturated NaHC03 was added. Extraction was carried out using dichloromethane (3x20 mL). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give 2-Phenyl-6,7-dihydro-5H-quinazolin-8-one (380 mg; 95% of theory)as a beige solid MP. 154-156°C. LC-MS (Method ZCQ) R_t = 1.49 min. , MS: (M⁺+l) = 225. l-NMR (CDCI₃, 400 MHz): 2.25 (m, 2H); 2.86 (m, 2H); 3.03 (m, 2H); 7.51 (m, 3H); 8.52 (m, 2H); 8.94 (s, 1H). Table 9: Physical data of compounds of formula (I):

Structure RT (mins) Molecular mp

(method) ion C°C)

P.l 1.40 442.49 resin

(UPLCl) ([M+l]⁺)

P.2 1.61 470 resin

(UPLCl) ([M+l]⁺)

1.17 470.49

(ZMD) ([M+1D

P.3 1.50 504.46 resin

(UPLCl) ([M+l]⁺)

P.4 . O^ /\ ,o_s 1.39 408 resin

(ZCQ) ([M+l]⁺)

P.5 1.24 382 oil

N' ^^^^ ^XN

(ZCQ) ([M+l]⁺)

LC-method used

Method A

Autopurification System from Waters: 2767 sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module.

Column: Phenomenex Synergi C18 Reversed Phase, 4 m particle size, 80 A, 75 x 30.00 mm, 100 mg of product dissolve in DMF injected

DAD Wavelength (nm): 220 and 254

Solvent Gradient:

A = water (Fluka Analytical)

B= Acetonitrile for praep. HPLC (Fluka Analytical)

Time A% B% Flow (mL/min)

0.00 90.0 10.0 50.00

0.01 90.0 10.0 50.00

6.00 60.0 40.0 50.00

7.90 60.0 40.0 50.00

8.00 0.0 100.0 50.00

8.90 0.0 100.0 50.00

9.00 90.0 10.0 50.00

9.50 90.0 10.0 50.00

9.55 90.0 10.0 50.00

Method ZMD

ZMD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

Instrument Parameter:

Ionisation method: Electrospray

Polarity: positive ions

Capillary (kV) 3.80, Cone (V), Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) OFF, Desolvation Gas Flow (L/Hr) 600

Mass range: 100 to 900 Da

HP 1100 HPLC from Agilent: solvent degasser, binary pump, heated column compartment and diode-array detector.

Column: Phenomenex Gemini C18, 3 mm particle size, 110 A 30 x 3 mm,

Temp: 60°C

DAD Wavelength range (nm): 200 to 500

Solvent Gradient:

A = water + 0.05 % HCOOH

B= Acetonitril/Methanol (4: 1, v:v) + 0.04 % HCOOH

Time A% B% Flow (mL/min)

0.00 95.0 5.0 1.700 2.00 0.0 100.0 1.700

2.80 0.0 100.0 1.700

2.90 95.0 5.0 1.700

3.00 95.0 5.0 1.700

Method ZCQ

ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

Instrument Parameter:

Ionisation method: Electrospray

Polarity: positive ions

Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400 Mass range: 100 to 900 Da

HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ) / binary pump (ZDQ), heated column compartment and diode-array detector.

Column: Phenomenex Gemini C18, 3 mm particle size, 110 A, 30 x 3 mm,

Temp: 60°C

DAD Wavelength range (nm): 200 to 500

Solvent Gradient:

A = water + 0.05 % HCOOH

B= Acetonitril/Methanol (4: 1, v:v) + 0.04 % HCOOH

Time A% B% Flow (mL/min)

0.00 95.0 5.0 1.700

2.00 0.0 100.0 1.700

2.80 0.0 100.0 1.700

2.90 95.0 5.0 1.700

3.00 95.0 5.0 1.700

Method UPLC1

ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

Ionisation method: Electrospray

Polarity: positive ions Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700 Mass range: 100 to 800 Da

DAD Wavelength range (nm): 210 to 400

Method Waters ACQUITY UPLC with the following HPLC gradient conditions

(Solvent A: Water/Methanol 9: 1,0.1% formic acid and Solvent B: Acetonitrile,0.1% formic acid)

Time (minutes) A (%) B (%) Flow rate (mL/min)

0 100 0 0.75

2.5 0 100 0.75

2.8 0 100 0.75

3.0 100 0 0.75

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.

OA_3min_30V

ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer):

Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV): 3.00; Cone (V): 30.00; Extractor (V): 2.00; Source Temperature (°C): 100; Desolvation Temperature (°C): 250; Cone Gas Flow (L/Hr): 50; Desolvation Gas Flow (L/Hr): 400; Mass range: 100 to 900 Da

HP 1100 HPLC from Agilent:

Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: Phenomenex Gemini C18, 3 - m, 30 x 3 mm; Temp: 60°C; DAD Wavelength range (nm): 210 to 500;

Solvent Gradient:

A = water + 5% MeOH + 0.05 % HCOOH

B= Acetonitrile + 0.05 % HCOOH

Time A% B% Flow (mL/min)

0.00 100 0 1.700

2.00 0 100 1.700

2.80 0 100 1.700

2.90 100 0 1.700 00 100 0 1.700

OA_Standard

ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

Instrument Parameter:

Ionization method: Electrospray

Polarity: positive and negative ions

Capillary: 3.00 kV

Cone: 30 V

Extractor: 2.00 V

Source Temperature: 150°C,

Desolvation Temperature: 350C

Cone Gas Flow: 50 L/Hr

Desolvation Gas Flow: 400 L/Hr

Mass range: 100 to 900 Da

Acquity UPLC from Waters:

Binary pump, heated column compartment and diode-array detector.

Solvent degasser, binary pump, heated column compartment and diode-array detector.

Column: Waters UPLC HSS T3 , 1.8 - m, 30 x 2.1 mm,

Temp: 60 °C

DAD Wavelength range (nm): 210 to 500

Solvent Gradient:

A = H20 + 5% MeOH + 0.05 % HCOOH

B= Acetonitril + 0.05 % HCOOH

Time A% B% Flow (mL/min)

0.00 90 10 0.85

2.70 0 100.0 0.85

3.00 0 100.0 0.85

Biological examples:

Puccinia recondite f. sp. tri^'ti^'ci I wheat / leaf disc preventative (Brown rust):

Wheat leaf segments cultivated variety (cv) Kanzler were placed on agar in 24-well plates and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application). The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici: P.01, P.02, P.04, P.05, P.06, P.08, P.09. P.20, P.23, P.27, P.28, P.29, P.30.

Puccinia recondita f. sp. tritici I wheat / leaf disc curative (^"Brown rust):

Wheat leaf segments cv Kanzler were placed on agar in 24-well plates. The leaf segments were inoculated with a spore suspension of the fungus. The plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied at an application rate of 200ppm 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application). The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici: P.01, P.02, P.04, P.05, P.06, P.08, P.09, P.11. P.20, P.23, P.27, P.28, P.29.

Phaeosphaeria nodorum (Seotoria nodorum) / wheat / leaf disc preventative (Glume blotch):

Wheat leaf segments cv Kanzler were placed on agar in a 24-well plate and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20°C and 75% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum: P.01, P.02, P.04, P.05, P.06, P.08, P.09, P.ll, P.14, P.16, P.17, P.18P.19, P.20, P.21, P.22, P.23, P.27, P.28, P.29, P.30.

Pyrenophora teres / barley / leaf disc preventative (Net blotch):

Barley leaf segments cv Hasso are placed on agar in a 24-well plate and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf segments are inoculated with a spore suspension of the fungus two days after application of the test solution. The inoculated leaf segments are incubated at 20°C and 65% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). The following compounds gave at least 80% control of Pyrenophora teres: P.01, P.02, P.04, P.05, P.06, P.08, P.09, P.ll, P.14, P.20, P.21, P.22, P.23, P.27, P.28, P.29, P.30.

Alternaria solani I tomato / leaf disc (early blight):

Tomato leaf disks cv Baby are placed on agar in 24-well plates (24-well format) and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23°C/21°C (day/night) and 80% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Alternaria solani: P.08,P.29.

Pythium ultimum I liquid culture (seedling damping off):

Mycelia fragments and oospores of a newly grown liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96 well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal mycelia/spore mixture was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 2-3 days after application. The following compounds gave at least 80% control of Pythium ultimum: P.08,P.27, P.28.

Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Botryotinia fuckeliana: P.01, P.02, P.03, P.04, P.05, P.06, P.07, P.09, P.10, P. ll, P.12, P.14, P.15. P.18, P.19, P.20, P.21, P.22, P.23, P.27, P.28, P.29, P.30, P.31.

Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose) :

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application. The following compounds gave at least 80% control of Glomerella lagenarium: P.01, P.02, P.03, P.04, P.06, P.08, P.09, P.ll, P.14, P.15. P.22, P.23, P.27, P.28, P.29, P.30.

Mycosphaerella arachidis CCercospora arachidicola) I liquid culture (early leaf spot):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates are incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella arachidis: P.01, P.02, P.03, P.04, P.05, P.06, P.08, P.09, P.10, P. ll, P.12, P.14, P.15. P.18, P.20, P.21, P.22, P.23, P.27, P.28, P.29, P.31.

Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola: P.01, P.02, P.03, P.04, P.06, P.08, P.09, P.10, P.ll, P.12, P.14, P.15. P.18, P.19, P.20, P.21, P.22, P.23, P.27, P.28, P.29, P.30, P.31.

Gaeumannomyces graminis I liquid culture (Take-all of cereals):

Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96- well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores is added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Gaeumannomyces graminis: P.01, P.02, P.03, P.08, P.09, P. ll, P.14, P.15., P.20, P.21, P.22, P.23, P.27, P.31.

Thanatephorus cucumeris (Rhizoctonia solani) I liquid culture (foot rot, dampinq-off): Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of the test compounds into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Thanatephorus cucumeris: P.01, P.02, P.04, P.06, P.08, P.09, P.14, P.15.

Monographella nivalis (Microdochium nivale) I liquid culture (foot rot cereals^'):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Monographella nivalis: P.01, P.02, P.04, P.06, P.08, P.09. P.21, P.22, P.23,.28, P.29.

Blumeria graminisf. so. tritici (Erysiphe graminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat):

Wheat leaf segments cv. Kanzler were placed on agar in a 24-well plate and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20°C and 60% relative humidity under a light regime of 24 h darkness followed by 12h/12h (dark/light) in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application). The following compounds gave at least 80% control of Blumeria graminis: P.01, P.02, P.04, P.05, P.06, P.08, P.09, P. ll. P.20, P.22, P.23, P.27, P.28, P.29, P.30, P.31.

Sclerotinia sclerotiorum / liquid culture (cottony rot)

Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate at an application rate of 200ppm (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80% control of ^:_Sclerotinia sclerotiorum: P.04, P.06, P.09, P.15. P.23, P.27.

Magnaporthe grisea (Pyricularia oryzae) I rice / leaf disc preventative (Rice Blast)

Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22°C and 80% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). The following compounds gave at least 80% control of_Magnaporthe grisea: P.04, P.05, P.06, P.08, P.09, P.ll, P.17. P.19, P.20, P.22, P.23, P.27, P.30.

Claims

Claims:

1. A compound of formula (I)

wherein

D¹ represents N or C-Y²;

D² represents N or C-Y⁵;

D³ represents N or C-Y⁷;

wherein at least one of D¹, D² or D³ is N;

wherein both D² and D³ cannot be N;

A represents hydrogen, halogen, CN, OH, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, Ci-C₈ alkylsulphonyl, NH₂, Ci-Cio alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂-C₈ alkynyl, (R¹⁰O)carbonyl(Ci- C₄-alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, d-C₄ haloalkyl, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy, C₃-C₆ cycloalkyi and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;

or if D³ is C-Y⁷ then A and Y⁷ together may be -(G⁴)_q-G⁵-G⁶-;

X represents X-2, X-3, X-4 or X-5:

#—∑—∑—# #— z— z— z— # #— z— z— z— z— #

X-2 X-3 X-4

_#__z12__zU__z12__z13__zli__#

X-5

Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹³ and Z¹⁴ independently of one another represent CR R², C=CR³R⁴ or C=0;

Z⁴ and Z¹² independently of one another represent C=CR³R⁴, CR⁵R⁶, SiR⁷R⁸ or C=0; each R¹ and R² independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyl, C1-C4 alkylthio, C1-C4 alkylsulphinyl, C1-C4 alkylsulphonyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, d-C₄ alkoxy and C1-C4 haloalkoxy;

or R¹ and R² together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyl group;

each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, Ci-

C₄ alkyl, C1-C4 haloalkyi, C₃-C₆ cycloalkyi, C₃-C₆ halocycloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, d-C₄ alkoxy and C1-C4 haloalkoxy;

or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyi group or a C₃-C₆ halocycloalkyl group;

N0₂, Ci-C₈ alkyl, Ci-C₄-alkoxy-Ci-C₄-alkyl, Ci-C₄-alkoxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, C₃-C₈ cycloalkyi, C₂-C₈ alkenyl, C₂-C₈ alkynyl, phenyl, pyridyl, pyrimidinyl, COR⁹, OR¹⁰, SH, Ci-C₈ alkylthio, Ci-C₈ alkylsulphinyl, C_rC₈ alkylsulphonyl, N(Rⁿ)₂, C0₂R¹⁰, 0(CO)R⁹, CON(Rⁿ)₂, NRⁿCOR⁹ or CR⁹N- OR¹⁰, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, pyrimidinyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci- C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy, Ci-C₄ haloalkoxy, Ci-C₄ alkylthio, Ci-C₄ alkylsulphinyl and C1-C4 alkylsulphonyl;

or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(Rⁿ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;

each R⁹ independently of one another represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, C₂- C₈ alkenyl, C₂-C₈ alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;

independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, d-C₄-haloalkyl, C1-C4 alkoxy, Ci-C₄ haloalkoxy and Ci-C₄-alkoxy-Ci-C₄-alkyl;

each R¹¹ independently of one another represents hydrogen, OH, d-C₈ alkyl, Ci-C₈ alkoxy, Ci-C₈-alkoxy-Ci-C₄-alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, COR⁹ or phenyl, wherein the alkyl, alkoxy, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulphinyl and C1-C4 alkylsulphonyl;

B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; G¹, G², G⁴ and G⁵ independently of one another represent -C(R¹²R¹³)-, 0, N(R¹⁴) or S;

G³ and G⁶ independently of one another represent -C(R¹²R¹³)-, O, N(R¹⁴) or S;

each R¹² and R¹³ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-

C₄ haloalkyi, Ci-C₄ alkoxy or Ci-C₄ haloalkoxy;

R¹⁴ represents hydrogen, OH, d-C₄ alkyl, Ci-C₄ alkoxy, C₃-C₆ cycloalkyi, Ci-C₈ alkylcarbonyl or Ci-Cs haloalkylcarbonyl; and

p and q are each independently 0, 1 or 2;

or a salt or an N-oxide thereof.

2. A compound according to claim 1, wherein

A represents hydrogen, Ci-C₈ alkyl, C₃-C₈ cycloalkyi, phenyl or pyridyl, wherein the alkyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, OH, Ci-C₄ alkoxy, d-C₄ haloalkoxy and C₃-C₆ cycloalkyi;

X represents X-3;

Z³ and Z⁵ independently of one another represent methylene or halomethylene;

Z⁴ represent C=CR³R⁴, CR⁵R⁶ or SiR⁷R⁸;

each R⁵, R⁶, R⁷ and R⁸ independently of one another represent hydrogen, halogen, OH, d- C₄ alkyl, Ci-C₄ haloalkyi, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy;

or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C3-C6 cycloalkyi group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one represent hydrogen, halogen, OH, CN, d- C₈ alkyl, Ci-Cs haloalkyi, Ci-Cs alkoxy, Ci-Cs haloalkoxy, Ci-Cs alkylthio, C₃-C₈ cycloalkyi, phenyl, pyridyl, N(Rⁿ)₂, or NRⁿCOR⁹, wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy; or independently Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from N and N(Rⁿ)₂ and wherein the ring formed by Y¹ and Y², Y² and Y³, Y⁴ and Y⁵, Y⁵ and Y⁶ or Y⁶ and Y⁷ is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, Ci-C₄ alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and Ci-C₄ haloalkoxy;

each R⁹ independently represents d-C₈ alkyl or Ci-C₈ haloalkyl;

each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl, COR⁹ or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C C₄ alkyl, C C₄ haloalkyl, d-C₄ alkoxy, d-C₄ haloalkoxy, d-C₄ alkylthio, Ci-C₄ alkylsulphinyl and Ci-C₄ alkylsulphonyl;

G¹, G², G³, G⁴, G⁵ and G⁶ independently of one another represent -C(R¹²R¹³)-;

p and q are each independently 0, 1 or 2. 3. A compound according to claim 1, wherein

A represents hydrogen, Ci-C₄ alkyl, phenyl or pyridyl, wherein alkyl is optionally substituted by one or more groups independently selected from halogen, OH, d-C₄ alkoxy and Ci-C₄ haloalkoxy, and wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyl, OH, Ci-C₄ alkoxy, d-C₄ haloalkoxy and C₃-C₆ cycloalkyl;

X represents X-3;

Z³ and Z⁵ represent methylene;

Z⁴ represents C=CR³R⁴ or CR⁵R⁶ ; each R³ and R⁴ independently of one another represent hydrogen, halogen, methyl or halomethyl;

each R⁵ and R⁶ independently of one another represent hydrogen, halogen, OH, C1-C4 alkyl, C1-C4 haloalkyi, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyl group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, C1-C4 haloalkoxy, C₃-C₆ cycloalkyl, d-C₄ alkylthio, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy;

each R⁹ independently represents d-C₄ alkyl or C1-C4 haloalkyi;

each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, NH₂, N0₂, OH, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy;

G¹, G², G³, G⁴, G⁵ and G⁶ represent methylene;

p and q are each independently 0, 1 or 2.

4. A compound according to claim 1, wherein

A represents hydrogen, C1-C4 alkyl, phenyl or pyridin-2-yl wherein phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;

X represents X-3;

Z³ and Z⁵ represent methylene; Z⁴ represents C=CR³R⁴ or CR⁵R⁶ ;

each R⁵ and R⁶ independently of one another represent hydrogen, halogen, OH, d-C₄ alkyl, C1-C4 haloalkyl, phenyl or CN, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy or halomethoxy; or R⁵ and R⁶ together with the carbon atom to which they are attached may form a C₃-C₆ cycloalkyl group or a C₃-C₆ halocycloalkyl group;

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶and Y⁷ independently of one another represent hydrogen, CN, OH, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C₃-C₆ cycloalkyl, d-C₄ alkylthio, N(Rⁿ)₂, NRⁿCOR⁹ or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;

each R⁹ independently represents d-C₄ alkyl or C1-C4 haloalkyl;

each R¹¹ independently of one another represents hydrogen, Ci-C₈ alkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and G-C₄ haloalkoxy;

G¹, G², G³, G⁴, G⁵ and G⁶ represent methylene;

p and q are each independently 0, 1 or 2.

5. A compound according to any one of the preceding claims, wherein G¹, G² and G³ represent methylene.

6. A compound according to any one of the preceding claims, wherein p is 1.

7. A compound according to any one of claims 1-6 wherein A and Y⁷ together represent -

8. A compound according to any one of claims 1-6 wherein A represents C1-C4 alkyl.

9. A compound according to any one of claims 1-8 wherein p is 1 and -G^G^G³- represents -CH₂-CH₂-CH₂-. A compound of formula (II)

R — X

wherein R represents -ONH₂, halogen, -0-S0₂-R or one of the groups LG, C-l, C-2A or C-2B:

(LG) (C-1 ) (C-2A) (C-2B)

R²⁸ represents Ci-C₄ alkyl, d-C₄ haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or two substituents independently selected from methyl, trihalomethyl, N0₂, CN, C1-C7 alkoxycarbonyl;

X" represents halogen;

R³⁷ represents either A as defined herein for compounds of formula (I) in any one of claims 1 to 9 or the group R³⁷

wherein X, G¹, G², G³, D¹, D², D³, Y¹, Y³, Y⁴, Y⁶ and p are as defined for the compound of formula (I) in any one of claims 1 to 9;

or a salt or N-oxide thereof, or;

a compound of formula (III)

wherein X' represents one of the groupings X'-l, X'-2 or X'-3

wherein Z³, Z⁶, Z⁷, Z¹⁰, Z¹¹ and Z¹² are as defined for a compound of formula (I) in any one of claims 1 to 9;

R²⁹ and R³⁰ independently of one another represent hydrogen, halogen, Ci-C₄ alkyl, Ci-C₄ haloalkyi, phenyl or CN, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C₄ alkyl, Ci-C₄ haloalkyi, d-C₄ alkoxy and Ci-C₄ haloalkyoxy; and

G¹, G², G³, D¹, Y¹, Y³ and p are as defined for a compound of formula (I) in any one of claims 1 to 9; or a salt or N-oxide thereof;

or a compound of formula (VIII)

(VIM)

wherein G¹, G², G³, D¹, Y¹, Y³ and p are as defined for a compound of formula (I) in any one of claims 1 to 9;

or a salt or N-oxide thereof, or;

a compound of formula IVa

wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined for a compound of formula I in any one of claims 1 to 9;

or a salt or N-oxide thereof, or;

a compound of formula XVI

wherein G¹, G², G³, p, D¹, Y¹ and Y³ are as defined herein for a compound of formula I in any one of claims 1 to 9;

R³⁸ is hydrogen, CO-CH₃, CO-CH₂CH₃, CO-CH₂CH₂CH₃, CO-CH(CH₃)₂, CO-CF₃, CO-CF₂CF₃, CH₃, CH₂CH₃, CH₂CH₂CH₃ or CH(CH₃)₂; or a salt or N-oxide thereof.

11. A process for the production of a compound of formula (I) as defined in any one of claims 1 to 9 comprising reacting a compound of formula (lib) with a compound of formula (X) as shown in scheme X

Scheme X

(lib) (I) wherein R represents halogen, -0-S0₂-R or group LG:

R represents Ci-C₄-alkyl, Ci-C₄-haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or two substituents independently selected from methyl, trihalomethyl, N0₂, CN, C1-C7 alkoxycarbonyl; and

X, G¹, G², G³, Y¹, Y³, Y⁴, Y⁶, D¹, D², D³, p and A are as defined for the compound of formula

(I) in any one of claims 1 to 9.

12. A fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 9, optionally comprising an additional active ingredient.

13. A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 9.