WO2004035589A1

WO2004035589A1 - Heterocyclocarboxamide derivatives

Info

Publication number: WO2004035589A1
Application number: PCT/EP2003/011388
Authority: WO
Inventors: Josef Ehrenfreund; Hans Tobler; Harald Walter
Original assignee: Syngenta Participations Ag
Priority date: 2002-10-18
Filing date: 2003-10-14
Publication date: 2004-04-29
Also published as: US7598395B2; EA010264B1; NZ539376A; CA2498851C; HRP20050441A2; EA200500574A1; GEP20084500B; CA2498851A1; DE60331670D1; GEP20115347B; CR7727A; ECSP055675A; KR100872010B1; DK1556385T3; MXPA05003899A; PL221973B1; EG24050A; NO20052201L; FR18C1024I2; EA015708B1

Abstract

The invention relates to a fungicidally active compound of formula (I): where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R8, R9 and R10; X is a single or double bond; Y is O, S, N(R11) or (CR12R13)(CR14R15)m(CR16R17)n; m is 0 or 1; n is 0 or 1; and R1 to R17 each, independently, have a range of values; to the preparation of these compounds, to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

HETEROCYCLOCARBOXAMIDE DERIVATIVES

The present invention relates to novel tricyclic amine derivatives which have microbiocidal activity, in particular fiingicidal activity. The invention also relates to the preparation of these compounds, to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

The present invention provides a compound of formula (I):

where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R⁸, R⁹ and R¹⁰; X is a single or double bond; Y is O, S, N(R^π) or (CR¹²R¹³)(CR^I4R¹⁵)_m(CR¹⁶R¹⁷)_n; m is 0 or 1; n is 0 or 1; R¹ is hydrogen, C alkyl, C haloalkyl, C_M alkoxy, Cι-₄haloalkoxy, CH₂C≡CR¹⁸, CH₂CR^I9=CHR²⁰, CH=C=CH₂ or COR²¹; R² and R³ are each, independently, hydrogen, halogen, C alkyl, Cι- alkoxy or C_M haloalkoxy; R⁴, R⁵, R⁶ and R⁷ are each, independently, hydrogen, halogen, C_M alkyl, C_M haloalkyl, C_M alkoxy, C haloalkoxy, CM -ϋkylthio, CM haloalkylthio, hydroxymethyl, CM alkoxymethyl, C(O)CH₃ or C(O)OCH₃; R⁸, R⁹ and R¹⁰ are each, independently, hydrogen, halogen, cyano, nitro, CM alkyl, CM haloalkyl, CM alkoxy( - )alkylene or C haloalkoxy(CM)alkylene, provided that at least one of R⁸, R⁹ and R¹⁰ is not hydrogen; R¹¹ is hydrogen, C_M alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C_M alkyl, C haloalkyl and C alkoxy), formyl, C(O)C_M alkyl (optionally substituted by halogen or C alkoxy), C(=O)O-Cι-₆ alkyl (optionally substituted by halogen, C_M alkoxy or cyano) or CM alkoxy(Cι-₄)alkylene; R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently, hydrogen, halogen, hydroxy, Cι-₆ alkyl, C₂.₆ alkenyl [both optionally substituted by halogen, hydroxy, C_M alkoxy, =O, aryl or O-C(O)-C_M alkyl or a 3-7 membered carboxylic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered saturated ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen) or C_M alkoxy; or R¹² and R¹³ together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally with up to 2 heteroatoms each independently selected from O and N); or R¹² and R¹³ together form a Cι.₆ alkylidene (optionally substituted by up to three methyl groups) or a C₃.₆ cycloalkylidene group (optionally substituted by up to three methyl groups); R¹⁸, R¹⁹ and R²⁰ are each, independently, hydrogen, halogen, C_M alkyl, C_M haloalkyl or C alkoxy(Cι.₄)alkylene; and R²¹ is hydrogen, -₆ alkyl, Cj.₆ haloalkyl, CM alkoxy(Cι-4 )alkylene, CM alkyl-S-(CM)alkylene, C alkoxy or aryl.

Halogen is fluoro, chloro, bromo or iodo; preferably fluoro, chloro or bromo. Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, sec-butyl, wo-butyl, tert-butyl, neø-pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, l-methyl-3-ethyl-butyl or 1,3,3-trimethylbutyl. Likewise, each alkylene moiety is a straight or branched chain.

Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF₃, CF₂C1, CHF₂, CH₂F, CC1₃, CF₃CH₂, CHF₂CH₂, CH₂FCH₂, CH₃CHF or CH₃CF₂. Alkenyl and alkynyl moieties can be in the form of straight or branched chains.

Each alkenyl moiety, where appropriate, may be of either the (E)- or ©-configuration.

A 3-5 membered carbocyclic ring includes a spiro-three or five membered ring. Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.

Alkylidene moieties may be in the form of straight or branched chains. Alkylidene includes methyϋdene [CH₂=], ethylidene [CH₃C(H)=], n-propylidene, -propylidene [(CH₃)₂C=], n-butylidene, -butylidene, 2-butylidene, n-pentylidene, j^'-pentylidene, neø-pentylidene, 2-pentylidene, n-hexylidene, 2-hexylidene, 3-hexylidene, *-hexylidene and neo-hexylidene.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. Cycloalkylidene includes cyclopropylidene [c(C₃H₄)=], cyclobutylidene, cyclopentylidene and cyclohexylidene.

In one aspect of the invention, R¹¹ is hydrogen, C_M alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, C_M haloalkyl and CM alkoxy), formyl, C(O)C alkyl or C_M alkoxy(C_M)alkylene.

In another aspect of the invention, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently, hydrogen, C_M alkyl or C_M alkoxy. Het is preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrimidyl, pyridazinyl, 2,3-dihydro-[l,4]oxathiine-6-yl, oxazinyl, thiazinyl or triazinyl.

Het is more preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl or 2,3-dibydro-[l,4]oxathiine-yl.

Het is even more preferably pyrrolyl, pyrazolyl, thiazolyl or pyridinyl. Het is most preferably pyrrolyl or pyrazolyl.

Preferably X is a single bond.

In one aspect, Y is O, S, N(Rⁿ), CH₂, CH₂CH₂, CH₂CH₂CH₂, C(CH₃)₂, CH(CH₃), CH(C₂H₅), C(CH₃)(C₂H₅), CH(OCH₃) or C(OCH₃)₂; more preferably N(R"), O, S, CH₂, CH₂CH₂, CH₂CH₂CH₂, C(CH₃)₂, CH(CH₃) or CH(C₂H₅)^ even more preferably N(Rⁿ), O, S, CH₂ or CH₂CH₂; and still more preferably O, CH₂ or N(Rⁿ). Preferably Y is O, N(R^π) or (CR¹²R¹³)(CR¹⁴R¹⁵)_m(CR^l6R¹⁷)_π. More preferably Y is O or (CR^l2R¹³)(CR¹⁴R^,5)_m(CR^l6R¹⁷)_n. Even more preferably Y is (CR^l2R¹³)(CR¹⁴R¹⁵)_ra(CR¹⁶R¹⁷)_n. Still more preferably Y is (CR¹²R¹³). Preferably n is 0.

Preferably m is 0. Preferably R¹ is hydrogen, CH₂C≡CR¹⁸, CH=C=CH₂ or COR²¹. More preferably R¹ is hydrogen, CH₂C≡CH, CH=C=CH₂, C(O)H or C(O)CH₃. Yet more preferably R¹ is hydrogen, CH₂C≡CH, CH=C=CH₂ or C(O)CH₃. Even more preferably R¹ is hydrogen, CH₂C≡CH or CH=C=CH₂. Most preferably R¹ is hydrogen. Preferably R² is hydrogen, halogen or C_M alkyl.

More preferably R² is hydrogen or halogen. Most preferably R² is hydrogen. Preferably R³ is hydrogen or methyl. More preferably R³ is hydrogen. Preferably R⁴ is hydrogen, C_M alkyl, halogen, C haloalkyl, C_M alkoxy, C(O)CH₃ or C(O)OCH₃.

More preferably R⁴ is hydrogen, Cι.₂ alkyl, halogen, CF₃, methoxy, C(O)CH₃ or C(O)OCH₃.

Even more preferably R⁴ is hydrogen, methyl, chlorine, CF₃ or methoxy. Most preferably R⁴ is hydrogen or methyl.

Preferably R⁵ is hydrogen, C_M alkyl, halogen, C haloalkyl, CM alkoxy, C(O)CH₃ or C(O)OCH₃.

More preferably R⁵ is hydrogen, C₁-₂ alkyl, chlorine, CF₃, methoxy, C(O)CH₃ or C(O)OCH₃. Most preferably R⁵ is hydrogen or methyl.

Preferably R⁶ is hydrogen, C_M alkyl, C alkoxy or C(O)CH₃. More preferably R⁶ is hydrogen, methyl, methoxy or C(O)CH₃. Most preferably R⁶ is hydrogen or methyl. Preferably R⁷ is hydrogen, C_M alkyl, C_M alkoxy or C(O)CH₃. More preferably R⁷ is hydrogen, methyl, methoxy or C(O)CH₃.

Most preferably R⁷ is hydrogen or methyl.

Preferably R⁸ is hydrogen, halogen, C_M alkyl, C_Mhaloalkyl or methoxymethylene. More preferably R⁸ is hydrogen, chloro, fluoro, bromo, C1-2 alkyl, CF₃, CF₂C1, CHF₂, CH₂F or methoxymethylene. Even more preferably R⁸ is hydrogen, chloro, fluoro, Cι-₂ alkyl, CF₃, CF₂C1, CHF₂,

CH₂F or methoxymethylene.

Most preferably R⁸ is hydrogen, chloro, fluoro, methyl, CF₃, CHF₂or CH₂F. Preferably R⁹ is hydrogen, halogen, C alkyl or C haloalkyl or methoxymethylene.

More preferably R⁹ is hydrogen, chloro, fluoro, bromo, Cι-₂ alkyl, CF₃, CF₂C1, CHF₂, CH₂F or methoxymethylene. Even more preferably R⁹ is hydrogen, chloro, fluoro, Cι-₂ alkyl, CF₃, CF₂C1, CHF₂,

CH₂F or methoxymethylene.

Most preferably R⁹ is hydrogen, chloro, fluoro, methyl, CF₃, CHF₂ or CH₂F. Preferably R¹⁰ is hydrogen, halogen, C_M alkyl, C_M aloalkyl or methoxymethylene. More preferably R¹⁰ is hydrogen, chloro, fluoro, bromo, Cj.₂ alkyl, CF₃, CF₂C1, CHF₂, CH₂F or methoxymethylene.

Even more preferably R¹⁰ is hydrogen, chloro, fluoro, Cι.₂ alkyl, CF₃, CF₂C1, CHF₂, CH₂F or methoxymethylene.

Most preferably R¹⁰ is hydrogen, chloro, fluoro, methyl, CF , CHF₂ or CH₂F. In one aspect of the invention R¹¹ is hydrogen, C_M alkyl, benzyl, formyl, C(O)CH₃ or C(O)OC(CH₃)₃; more preferably hydrogen or Cι-₂ alkyl.

Preferably R¹¹ is C alkyl, formyl, C(O)CH₃ or C(O)OC_w alkyl (optionaUy substituted by halogen, CN or C alkoxy). More preferably R¹¹ is C(O)OCι-₄ alkyl.

In one aspect of the invention R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently, hydrogen, d.₂ alkyl or methoxy.

Preferably R¹² and R¹³ are each, independently, hydrogen, halogen, .₅ alkyl, -3 alkoxy, CH₂OH, CH(O), -e cycloalkyl, CH₂O-C(=O)CH₃, CH₂-C₃.₆ cycloalkyl or benzyl; or R¹² and R¹³ together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring; or R¹² and R¹³ together form C₁-₅ alkylidene or C₃.₆ cycloalkylidene.

More preferably R¹² and R¹³ are, independently, H, CH₃, C₂H₅, n-C₃H_7). /-C₃H₇, «-C H₉, Λ^,ec-C₄H₉, /-C₄H₉, CH(C₂H₅)₂, CH₂-cyclopropyl or cyclopentyl; or R¹² and R¹³ together with the carbon atom to which they are attached form a 3-membered or 5-membered carbocyclic ring. Preferably R¹⁴ is H or CH₃.

Preferably R¹⁵ is H or CH₃. Preferably R¹⁶ is H or CH₃. Preferably R¹⁷ is H or CH₃.

Preferably R¹⁸ is hydrogen, chloro, bromo, methyl or methoxy.

More preferably R¹⁸ is hydrogen, chloro or methyl.

Most preferably R¹⁸ is hydrogen. Preferably R¹⁹ is hydrogen, chloro, bromo, methyl or methoxy.

More preferably R¹⁹ is hydrogen, chloro or methyl.

Most preferably R¹⁹ is hydrogen.

Preferably R²⁰ is hydrogen, chloro, bromo, methyl or methoxy.

More preferably R²⁰ is hydrogen, chloro or methyl. Most preferably R²⁰ is hydrogen.

Preferably R²¹ is hydrogen, methyl, OC(CH₃)₃ or CH₃OCH₂.

Compounds of formula (C):

where Y, R⁴, R⁵, R⁶ and R⁷ are as defined above for a compound of formula (I) are useful as intermediates in the preparation of compounds of formula (I). Some Compounds of formula (C) are novel but some are already known.

Therefore, in another aspect, the present invention provides a compound of formula (C) where Y is O or S; and R⁴, R⁵, R⁶ and R⁷ are each C(O)OCH₃; or Y is N(R' ') or (CR¹²R¹³)(CR^l4R¹⁵)_m(CR^l0R^,7)_n; R⁴, R⁵, R⁶, R⁷, R¹⁴, R¹⁵, R¹⁶, R¹⁷, m and n are each as defined above for a compound of formula (I); R¹¹ is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C_M alkyl, C_M haloalkyl and C_M alkoxy); and R¹² and R¹³ together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N). Compounds of formula (D):

where Y, R⁴, R⁵, R⁶ and R⁷ are as defined above for a compound of formula (I) are also useful as intermediates in the preparation of compounds of formula (I). Some Compounds of formula (D) are novel but some are already known. Therefore, in another aspect, the present invention provides a compound of formula (D) where Y is O or S; and R⁴, R⁵, R⁶ and R⁷ are each C(O)OCH₃; or Y is N(R") or (CR¹²R¹³)(CR¹⁴R¹⁵)_m(CR¹⁶R¹⁷)_n; R⁴, R⁵, R⁶, R⁷, R¹⁴, R¹⁵, R¹⁶, R¹⁷, m and n are each as defined above for a compound of formula (I); R^u is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C alkyl, C_M haloalkyl and C_M alkoxy) ; and R¹² and R¹³ together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).

The compounds of formula (I), (C) and (D) may exist as different geometric or optical isomers or in different tautomeric forms. This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

The compounds in Tables 1 to 29 below illustrate compounds of the invention. Table 1 provides 94 compounds of formula (C) wherein Y, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 1.

Table 1

Table 2 provides 111 compounds of formula (D) wherein Y, R⁴, R⁵, R⁶ and R⁷ are defined in Table 2.

Table 2

Table Z represents Table 3 [when Z is 3], Table 4 [when Z is 4], Table 5 [when Z is 5], Table 6 [when Z is 6] , Table 7 [when Z is 7], Table 8 [when Z is 8], Table 9 [when Z is 9], Table 10 [when Z is 10], Table 11 [when Z is 11], Table 12 [when Z is 12] , Table 13 [when Z is 13], Table 14 [when Z is 14], Table 15 [when Z is 15], Table 16 [when Z is 16], Table 17 [when Z is 17], Table 18 [when Z is 18], Table 19 [when Z is 19], Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24], Table 25 [when Z is 25], Table 26 [when Z is 26], Table 27 [when Z is 27], Table 28 [when Z is 28] and represents Table 29 [when Z s 29]. X is either a single bond (-) or a double bond (=).

Table Z

Table 3 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 3. Table 4 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 4. Table 5 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 5. Table 6 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 6. Table 7 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 7. Table 8 provides 235 compounds of formula (I) where Het is

H₃

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 8. Table 9 provides 235 compounds of formula (I) where Het is

H₃C

tf N

I

CH, R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 9. Table 10 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 10. Table 11 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 11. Table 12 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 12. Table 13 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 13. Table 14 provides 235 compounds of formula (I) where Het is

CF,

^■to N ^'

I

CH,

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 14. Table 15 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 15. Table 16 provides 235 compounds of formula (I) where Het is

CFH,

to^*

N

I

CH,

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 16. Table 17 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 17. Table 18 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 18. Table 19 provides 235 compounds of formula (I) where Het is

H₃

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 19. Table 20 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 20. Table 21 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 21. Table 22 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 22. Table 23 provides 235 compounds of formula (I) where Het is

H-C

CH₃

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 23. Table 24 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 24. Table 25 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 25. Table 26 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R^l, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 26. Table 27 provides 235 compounds of formula (I) where Het is

R² and R , 3³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 27. Table 28 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 28. Table 29 provides 235 compounds of formula (I) where Het is

R² and R³ are both hydrogen; and X, Y, R¹, R⁴, R⁵, R⁶ and R⁷ are as defined in Table 29.

Throughout this description, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; MS stands for mass spectrum; and "%" is percent by weight, unless corresponding concentrations are indicated in other units; "syn" refers to a syn configuration of the relevant substituent with respect to the armellated benzene ring; and "anti" refers to an anti configuration of the relevant substituent with respect to the armellated benzene ring.

The following abbreviations are used throughout this description: m.p. = melting point b.p.= boiling point. s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet ppm = parts per million

Table 30 shows selected melting point and selected NMR data, all with CDC1₃ as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, [CDC1₃ / d₆-DMSO]), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 29.

Table 30

The compounds according to formula (I) may be prepared according to the following reaction schemes. Preparation of a compound of formula (I)

A compound of formula (I) [where R¹ is hydrogen; and Het, R², R³, R⁴, R⁵, R⁶, R⁷, X and Y are as defined above for a compound of formula (I)] may be synthesized by reacting a compound of (II) [where Het is as defined above for a compound of formula (I) and R' is C,.₅ alkyl] with an aniline of formula (III) [where R², R³, R⁴, R⁵, R⁶, R⁷, X and Y are as defined above for a compound of formula (I)] in the presence of NaN(TMS)₂ at -10°C to ambient temperature, preferably in dry THF, as described by J. Wang et al. Synlett, 2001, 1485. Scheme 2

Alternatively, a compound of formula (I) [where R¹ is hydrogen; and Het, R², R³, R⁴, R⁵, R⁶, R⁷, X and Y are as defined above for a compound of formula (I)] may be prepared by reacting a compound of formula (II') [where Het is as defined above for a compound of formula (I)] with an aniline of formula (III) [where R², R³, R⁴, R⁵, R⁶, R⁷, X and Y are as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-C1] and two equivalents of a base [such as triethylamine] or by reacting a compound of formula (II") [where Het is as defined above for a compound of formula (I); and Q is Cl, F or Br] which is obtained from a compound of formula (IF) by treatment with a halogenating agent such as thionyl chloride, oxalyl chloride, phosgene, SF₄, DAST, Deoxofluor or thionlylbromide, with an aniline of formula (III) [where R², R³, R⁴, R⁵, R⁶, R⁷, X and Y are as defined above for a compound of formula (I)] in the presence of one equivalent of base [such as NEt₃, NaHCO₃, KHCO₃, Na₂CO₃ or K₂CO₃] in a solvent [such as dichloromethane, ethyl acetate or DMF] preferably at -10 to 30°C.

Furthermore a compound of formula (I) [where R^l is hydrogen; and Het, R² to R⁷, X and Y are as defined for a compound of formula (I)] is reacted with a species Z-R¹ [where R¹ is as defined for formula (I), except that it is not hydrogen; and Z is preferably Cl, Br or I; or Z is such that Z-R¹ is an anhydride, that is, when R¹ is COR*, Z is

OCOR*] in the presence of a base [for example NaH, NEt₃, NaHCO₃ or K₂CO₃] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane /water mixture], at -10 to 30°C. Starting Materials Heterocyclic acids and esters [that is, compounds of formula (II') or (II)] are generally known from the literature or may be synthesized according to known methods. Ortbo-substituted aminobenzonorbonenes (including homologues) of formula (C) or (D) (scheme 4) may be accomplished through Diels-Alder addition of an in situ generated benzyne [for example starting from a 6-nitroanthranilic acid of formula (A), as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable precursers (see H. Pellissier et al. Tetrahedron, 59, 701 (2003)] to a 5-7 membered cyclic 1 ,4-diene to give a nitro-benzonorbornadiene of formula (B) according to or by analogy to L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), D. Gravel et al. Can. J. Chem. 69, 1193 (1991), J.R. Malpass et al. Tetrahedron , 48, 861 (1992), D.E. Lewis et al. Synthetic Communications, 23, 993 (1993), R.N. Warrener et al. Molecules, 6, 353

(2001), R.N. Warrener et al. Molecules, 6, 194 (2001) or I. Fleming et al. J. Chem. Soc, Perkin Trans.1, 2645 (1998). Suitable aprotic solvents for this step include ethyl acetate, dichloromethane, acetone, THF and dimethoxyethane. Reaction temperatures range from room temperature to 100°C, preferably 40-80°C. Subsequent selective reduction of the nitro-group in a compound of formula (B) to give an amino-benzonorbornadiene of formula (C) requires mild conditions [for example, either metallic zinc in the presence of ammonium chloride, or aluminium amalgam]. Both methods work in protic solvents such as ethanol, water or mixtures thereof. Alternatively a compound of formula (C) may also be obtained from a compound of formula (B) by catalytic hydrogen reduction with a modified 5% Pt/C catalyst at elevated pressure (~10bar) and elevated temperature (~100°C) in toluene- water. Catalytic reduction under standard conditions (for example 5% Pd C or 5% Ra Ni or 5% Rh/C) in a solvent [such as methanol, ethanol, THF or ethyl acetate] reduces both the nitro-group and the double bond to furnish a benzonorbornene of formula (D). Preferred reaction conditions are ambient temperature and normal pressure.

Scheme 4

Some of the compounds of formulae (B), (C) and (D) are described in the literature

[see, for example, L. A Paquette et al., J. Amer. Chem Soc. 99, 3134 (1977); D. Gravel et al., Canad. J. Chem. 69, 1193 (1991); T. Nishiyama et al., Rikagaku-hen, 28, 37 (2000); H. Plieninger et al., Chem. Ber. 109, 2121 (1976); and A. J. Kirby et al, J. Chem. Soc, Perkin Trans. 2, 1997, 1081]. Novel starting materials of formulae (C) or (D) may be synthesized by analogy to scheme 4 or according to the literature cited above.

Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses. The compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds 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 cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests 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 according to present 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, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Hekninthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Nenturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).

Within the scope of present invention, target crops 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 compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they 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 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 WO97/33890. The compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area 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.

The compounds of formula (I) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibencon- azole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, fiiralaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metomi- nostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

A preferred method of applying a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, 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 can 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, for example 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 [that is, a composition containing 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.

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 dosages are from lOmg to lg of active substance per kg of seeds. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The following non-limiting Examples illustrate the above-described invention in more detail.

EXAMPLE 1 This Example illustrates the preparation of Compound No. 2.01.

A solution of l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (5.49g; 25.27mmol) (see T. Nishiyama et al., Rikagaku-hen, 28, 37-43 (2000)) in THF (55ml) was hydrogenated in the presence of RaNi (l.lg) at ambient temparature. Hydrogen uptake was 2.231itres (97%) after lδhours. After filtering off the catalyst the filtrate was evaporated and taken up into ether, washed with an aqueous NaHCO₃-solution and dried (NaSO ) to give 4.60g of crude product as an oil. Trituration with hexane and a trace of ether furnished a total of 4.51g (94%) of reddish crystalline product.

EXAMPLE 2 This Example illustrates the preparation of Compound No. 1.01. To l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (4.22g; 19.43mmol)

(see Example 1) in ethanol (60ml) was added a solution of ammoniumchloride (2.08g) in water (5.2ml) at 47°C. Under vigorous stirring, zinc powder (9.10g; 0.14mol) was added in portions over a period of 5minutes. The suspension was heated to reflux for 5'/2hours followed by filtration through Hyflo™ to give a clear yellow filtrate. After evaporation the crude product amounted 4.57g of a viscous oil. Column chro matography on silica gel in ethyl acetate-hexane (1:4) gave 1.24g (34%) of the desired product as brownish crystals.

EXAMPLE 3 This Example illustrates the preparation of Compound No. 2.16. A solution of 5-nitrobenzonorbornadiene (L.A. Paquette et al., J. Amer. Chem. Soc. 99, 3734 (1977)) (2.52g; 13.46mmol) in methanol (100ml) was hydrogenated in the presence of 5% Pd/C (0.5g) at ambient temperature. H₂-uptake was 1.141itres (95%) after 11 minutes. The solution was filtered from the catalyst and evaporated to give pure product (1.86g; 87% ) as a yellow oil, which solidified on standing at room temperature (m.p. 63-64°C).

EXAMPLE 4 This Example illustrates the preparation of Compound No. 3.023.

A solution of l-methyl-4-trifluoromethyl-lH-pyrrole-3-carboxylic acid (1.02g; 5.3 mmol) and a catalytic amount of DMF (3drops) in dichloromethane (20ml) was reacted under initial ice cooling with oxalyl chloride (0.805g; 1.2eq.) for 2hours. Within 15minutes, the reaction mixture was then added dropwise to a solution of 1,8-dimethyl- 1 l-oxa-tricyclo[6.2.1.0*2,7*]undeca-2,4,6-trien-3-ylamine (Compound No. 2.01 ; see preparation above) (l.Og; 5.284mmol) and triethylamine (1.07g; 10.57mmol) in 20ml dichloromethane under cooling (3-7°C) with subsequent stirring at ambient temperature for 3' hours. The reaction mixture was then poured on to ice water and extracted with dichloromethane to give 2.26g of crude product. Purification on silica gel in ethyl acetate-hexane (1: 1) followed by trituration with ether-hexane furnished a solid ( 1.14g; 59%) as a mixture of isomers.

EXAMPLE 5

This Example illustrates the preparation of Compound No.3.024. A suspension of NaH (0.107g; 60% oil dispersion, ~2.7mmol) in DMF (5ml) was reacted with a solution of 1 -methyl-4-trifluoromethyl- 1 H-pyrrole-3-carboxylic acid( 1 ,8- dimethyl-1 l-oxa-tricyclo[6.2.1.0*2,7*]undeca-2,4,6-trien-3-yl)-amide (Compound No. 3.023; see preparation above) (0.65g; 1.784mmol) in 5ml DMF at 10-15°C for 30minutes. 3-Bromo-l-propyne (0.276g; 2.32mmol) was added and the mixture was further reacted overnight at ambient temperature. After aqueous work up with ice water and ethyl acetate and purification on silica gel 0.36g (50%) of the desired product as a mixture of isomers were obtained.

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I) Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in WO97/33890. BIOLOGICAL EXAMPLES: FUNGICIDAL ACTIONS

Example B-l: Action against Puccinia recondita / wheat (Brownrust on wheat)

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (lxl0⁵uredospores/ml) on the test plants. After an incubation period of 2 days at 20°C and 95%r.h. the plants are kept in a greenhouse for 8days at 20°C and 60%r.h. The disease incidence is assessed 10 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of Compounds 3.048, 14.048, 29.048, 15.048, 20.048, 3.028, 22.048, 21.048, 15.023, 15.027, 15.028, 3.035, 14.035, 15.035, 15.052, 14.210, 15.210, 14.202 and 15.202. Example B-2: Action against Podosphaera leucotricha / apple (Powdery mildew on apple)

5 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.

Compounds 3.048, 14,048, 15.048, 22.048, 14.210, 15.210, 14.202, 15.202 and 15.023 each exhibit strong efficacy (<20% infestation). Example B-3: Action against Nenturia inaequalis / apple (^"Scab on apple)

4 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4xl0⁵conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%r.h. the plants are placed for 4 days at 21°C and 60%r.h. in a greenhouse. After another 4 day incubation period at 21°C and 95%r.h. the disease incidence is assessed. Compounds 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each exhibit strong efficacy (<20% infestation). Example B-4: Action against Erysiphe graminis / barley (Powdery mildew on barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20°C / 18°C (day/night) and 60%r.h. in a greenhouse the disease incidence is assessed.

Compounds 3.023, 14.023, 3.048, 14.048, 15.048, 3.027, 3.028, 15.023, 14.210, 15.210, 14.202, 15.202 and 15.027 each exhibit strong efficacy (<20% infestation). Example B-5: Action against Botrytis cinerea / grape (Botrytis on grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (lxl0⁶conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%r.h. in a greenhouse the disease incidence is assessed.

Compounds 14.048, 15.048, 3.028, 14.210, 15.210, 14.202, 15.202 and 15.027 each show good activity in this test (<50% disease incidence). Example B-6: Action against Botrytis cinerea / tomato (Botrytis on tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (lxl0⁵conidia/ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.

Compounds 3.048, 3.052, 14.052, 15.048, 14.210, 15.210, 14.202, 15.202 and 15.023 each exhibit good efficacy (<50% disease incidence).

Example B-7: Action against Septoria nodorum / wheat (Septoria leaf spot on wheat . 1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5xl0⁵conidia/ml) on the test plants. After an incubation period of 1 day at 20°C and 95%r.h. the plants are kept for 10 days at 20°C and 60%r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation. Compounds 3.002, 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each show good activity in this test (<50% disease incidence). Example B-8: Action against Helminthosporium teres / barley (Net blotch on barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3xl0⁴conidia/ ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a greenhouse the disease incidence is assessed.

Compounds 3.023, 14.023, 3.048, 14.048, 15.048, 3.027, 15.023, 15.027, 14.210, 15.210, 14.202, 15.202 and 15.028 each show good activity in this test (<20% disease incidence). Example B-9: Action against Alternaria solani / tomato (Early blight on tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2xl0⁵conidia/ml) on the test plants. After an incubation period of 3days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.

Compounds 3.023, 14.023, 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each show good activity in this test (<20% disease incidence). Example B-10: Action against Uncinula necator / grape (Powdery mildew on grapes) 5week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7days at 26°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.

Compounds 14.048, 15.048, 14.028 and 15.023 each show good activity in this test (<20% disease incidence). Example B-l 1: Systemic Action against Erysiphe graminis / barley (Powdery mildew on barley) (Pouch test)

The formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application barley seeds (cv.Express) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing barley plants were inoculated by shaking powdery mildew infected plants above the test plants.

After an incubation period of 6days the disease incidence was assessed. The efficacy of each test compound is used as an indicator for systemic activity. Compounds 14.024, 3.002, 3.048, 29.048, 3.027, 22.048, 21.048, 15.023, 15.027,

15.028 and 15.035 each show good activity in this test (<50% disease incidence).

Example B-l 2: Action against Fusarium culmorum / wheat (Fusarium head blight on wheat) (Pouch test)

A conidia suspension of F. culmorum (7xl0⁵conidia/ml) is mixed with the formulated test compound (0.002% active ingredient). The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper. The prepared pouches are then incubated for 1 ldays at ca.10-18° C and 100%r.h. with a daily light period of

14hours. The evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.

Compounds 14.024, 15.048, 20.048, 14.027, 24.048 and 3.035 each show good activity in this test (<50% disease incidence).

Example B-13: Action Gaeumannomyces graminis / wheat (Take- all on wheat) (pouch test) A defined amount of mycelium of G. graminis is mixed with water. The formulated test compound (0.002% active ingredient) is added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.

The prepared pouches are then incubated for 14days at 18°C/16°C (day/night) and 80%r.h. with a daily light period of 14hours. The evaluation is made by assessing the degree of root browning. Compounds 15.048, 20.048, 21.048, 15.028 and 15.052 each show good activity in this test (<50% disease incidence).

Example B-14: Action against Puccinia recondita / wheat (Brownrust on wheat) (Pouch test) Formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Arina) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (lxl0⁵uredospores/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h . The disease incidence was assessed lOdays after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.

Compounds 14.024, 3.002, 14.002, 15.048, 20.048, 3.027, 22.048, 15.023, 15.027, 15.028, 3.035, 14.035 and 15.035 each show good activity in this test (<50% disease incidence).

Example B-15: Action against Rhizoctonia solani / rice (Sheath blight on rice) (Pouch test)

A defined amount of mycelium of R. solani is mixed with water. The formulated test compound (0.002% active ingredient) is added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application rice seeds (cv.Koshihikari) are sown into the upper fault of the filter paper. The prepared pouches are then incubated for lOdays at 23°C/21°C (day/night) and 100%r.h. with a daily light period of 14hours. The evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.

Compounds 3.048, 14.048, 29.048, 3.052, 29.052, 14.052, 15.048, 20.048, 3.027, 14.028, 22.048, 21.048, 4.048, 15.023, 3.035, 14.035 and 15.035 each show good activity in this test (<50% disease incidence). Example B-16: Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) .Pouch test)

The formulated test compound (0.002% active ingredient) was applied into a pouch which was previously equipped with a filter paper. After the application, wheat seeds (cv. Arina) were sown into the upper fault of the filter paper. The prepared pouches were then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (5xl0⁵conidia/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h. The disease incidence was assessed 8days after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.

Compounds 3.048, 29.048, 15.048, 14.027, 15.023 and 15.027 each show good activity in this test (<50% disease incidence). Example B-l 7: Action against Septoria tritici / wheat (Septoria leaf spot on wheat)

2 week old wheat plants cv. Riband are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, wheat plants are inoculated by spraying a spore suspension (10xl0⁵conidia/ml) on the test plants. After an incubation period of 1 day at 23°C and 95% r.h., the plants are kept for 16 days at 23°C and 60% r.h. in a greenhouse. The disease incidence is assessed 18 days after inoculation.

Compounds 14.202 or 14.210 each show good activity in this test (<20% disease incidence).

Claims

A compound of formula (I):

where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R⁸, R⁹ and R¹⁰; X is a single or double bond; Y is O, S, N(Rⁿ) or (CR¹²R^,3)(CR¹⁴R¹⁵)_m(CR¹⁶R¹⁷)_n; m is 0 or 1; n is 0 or 1; R¹ is hydrogen, 01-43 !, Cι-4 haloalkyl, C alkoxy, C_M haloalkoxy, CH₂C≡CR¹⁸, CH₂CR^I9=CHR²⁰, CH=C=CH₂ or COR²¹; R² and R³ are each, independently, hydrogen, halogen, C1-4 alkyl, C alkoxy or d -₄ haloalkoxy; R⁴, R⁵, R⁶ and R⁷ are each, independently, hydrogen, halogen, C_M alkyl, C_Mhaloalkyl, C alkoxy, C_M haloalkoxy, C_Malkylthio, C haloalkylthio, hydroxymethyl, C,-₄ alkoxymethyl, C(O)CH₃ or C(O)OCH₃; R⁸, R⁹ and R¹⁰ are each, independently, hydrogen, halogen, cyano, nitro, C_M alkyl, C haloalkyl, Cι- alkoxy(Cι-₄)alkylene or C_M haloalkoxy(CM)alkylene, provided that at least one of R⁸, R⁹ and R¹⁰ is not hydrogen; R¹¹ is hydrogen, C_M alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C_M alkyl, CMhaloalkyl and C alkoxy), formyl, C(0)C_M alkyl (optionally substituted by halogen or C alkoxy), C(=O)O-Cι-₆ alkyl (optionally substituted by halogen, C alkoxy or cyano) or C alkoxy(C )alkylene; R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently, hydrogen, halogen, hydroxy, C].₆ alkyl, C₂.₆ alkenyl [both optionally substituted by halogen, hydroxy, C alkoxy, =O, aryl or O-C(O-CM alkyl or a 3-7 membered carboxylic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered saturated ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen) or d-₄ alkoxy; or R¹² and R¹³ together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally with up to 2 heteroatoms each independently selected from

O and N); or R¹² and R¹³ together form a Cι.₆ alkylidene (optionally substituted by up to three methyl groups) or a C₃.₆ cycloalkylidene group (optionally substituted by up to three methyl groups); R¹⁸, R¹⁹ and R²⁰ are each, independently, hydrogen, halogen, C_M alkyl, C_M haloalkyl or C_M alkoxy(C )alkylene; and R²¹ is hydrogen, Cι-₆ alkyl, Cι_s haloalkyl,

CM alkoxy(Cι-4 )alkylene, CM alkyl-S-(CM_. alky_εne, CM alkoxy or aryl.

2. A compound of formula (I) as claimed in claim 1 where Het is pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrimidyl, pyridazinyl, 2,3-dihydro-[l,4]oxathϋne-6-yl, oxazinyl, thiazinyl or triazinyl.

3. A compound of formula (I) as claimed in claim 1 or 2 where Y is O, N(R' ') or (CR^l2R^,3)(CR¹⁴R¹⁵)_m(CR^l0R^,7)„.

4. A compound of formula (I) as claimed in claim 1, 2 or 3 where R¹ is hydrogen, CH₂C≡CR¹⁸, CH=C=CH₂ or COR²¹.

A compound of formula (I) as claimed in claim 1, 2, 3 or 4 where R² is hydrogen, halogen or CM alkyl.

A compound of formula (I) as claimed in claim 1, 2, 3, 4 or 5 where R³ is hydrogen or methyl.

7. A compound of formula (C):

where Y is O or S; and R⁴, R⁵, R⁶ and R⁷ are each C(O)OCH₃; or Y isN(R") or (CR¹²R¹³)(CR¹⁴R¹⁵)_m(CR¹⁶R^l7)_n; R⁴, R⁵, R⁶, R⁷, R¹⁴, R¹⁵, R¹⁶, R¹⁷, m and n are each as defined in claim 1 ; R¹ ' is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C_M alkyl, C haloalkyl and C_M alkoxy); and R¹² and R¹³ together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).

8. A compound of formula (D):

where Y is O or S; and R⁴, R⁵, R⁶ and R⁷ are each C(O)OCH₃; or Y isN(R^π) or (CR^I2R^l3)(CR¹⁴R¹⁵)_m(CR^I6R¹⁷)_n; R⁴, R⁵, R⁶, R⁷, R¹⁴, R¹⁵, R¹⁶, R¹⁷, m and n are each as defined in claim 1 ; Rⁿ is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, CM haloalkyl and C_M alkoxy); and R¹² and R¹³ together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).

9. A composition for controlling microorganisms and preventing attack and infestation of plants therewith, wherein the active ingredient is a compound of formula (I) as claimed in claim 1 together with a suitable carrier.

10. A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula (I) as claimed in claim 1 to plants, to parts thereof or the locus thereof.