AU2054699A

AU2054699A - Thiazole-, isothiazole- and thiadiazole-derivatives having microbicidal and plant immunizing activities

Info

Publication number: AU2054699A
Application number: AU20546/99A
Authority: AU
Inventors: Peter Ertl; Thomas Maetzke
Original assignee: Novartis AG
Current assignee: Novartis AG
Priority date: 1997-12-22
Filing date: 1998-12-18
Publication date: 1999-07-12
Also published as: BR9814394A; WO1999032464A1; GB9726989D0; HUP0100619A2; CA2309973A1; ZA9811706B; CN1282324A; PL341290A1; TR200001740T2; IL136589A0; JP2001526277A; EP1042306A1; HUP0100619A3; AR017438A1; GT199800193A

Description

WO 99/32464 PCT/EP98/08335 -1 Thiazole-, isothiazole- and thiadiazole-derivatives having microbicidal and plant immunizing activities. The invention relates to a method for protecting and immunizing plants against attack by phytopathogenic microorganisms by applying to the plants, to parts of the plants and/or to the locus of the plants a compound of formula I R1 R2 , S Z R3 wherein a) X is CR 4 and Y is N; or b) X is N and Y is CRs; or c) X and Y are N; and wherein Z is a Cl-group to which 1-3 halogen atoms or 1-3 unsubstituted or substituted hetero atoms selected from the group O, S and N are bonded;

R

1 and R 2 are independently H, OH, SH, CN, COOH, NO 2 , NH 2 , halogen, C 1

-C

6 alkyl, haloC 1

-C

6 alkyl, alkoxyC 1

-C

6 alkyl, aminoC,-C 6 alkyl, alkoxaminoCl-C 6 alkyl, Cl-C 6 alkoxy, halo

C

1

-C

6 alkoxy, Cl-C 6 alkanoyloxy, aroyloxy, Cl-C 6 alkoxycarbonyl, aryloxycarbonyl, benzyloxycarbonyl, Cl-C 6 alkylcarbonyl, arylcarbonyl, benzylcarbonyl, aminocarbonyl, Cl-C 6 alkylaminocarbonyl, Cl-C 6 dialkylaminocarbonyl,

C

1

.C

6 alkylthio, haloC 1

-C

6 alkylthio,

C

1

-C

6 alkylsulfinyl, haloC,-C 6 alkylsulfinyl, Cl-C 6 alkylsulfonyl, haloC 1

-C

6 alkylsulfonyl, arylsulfinyl, arylsulfonyl,

C

2

-C

6 alkenyl, haloC 2

-C

6 alkenyl, C 2

-C

6 alkinyl, carboxyCl-C6alkyl, alkoxycarbonylCl-C 6 alkyl, haloalkoxycarbonylCl-C6alkyl,

C

3

-C

6 cycloalkyl, alkanoylCl-C6alkyl, alkylcarbonyloxyC,-C6alkyl, phenylcarbonyloxyC-C6alkyl, C -C 6 alkylamino, Cs

C

6 dialkylamino,

C

2

-C

6 alkenylamino, Cl-C 6 alkanoylamino, Cl-C 6 alkoxycarbonylamino, benzylamino, benzoylamino, benzyloxyarbonylamino, phenyl, phenoxy, benzyl or phenethyl, wherein all the aromatic groups are unsubstituted or substituted from 1 to 5 substituents independently selected from halogen, hydroxy, C-C 4 alkyl, halo-C 1

-C

2 alkyl, Cl-C 2 alkoxy, halo-C 1

-C

2 alkoxy and nitro; or optionally substituted heterocyclyl; or tri(C 1

-C

6 alkyl)silyl or tri(C 1

-C

6 alkyl)silyloxy; WO 99/32464 PCT/EP98/08335 -2 with the proviso that R 1 and R 2 are not simultaneously a group selected from OH, SH, NO 2 ,

NH

2 , C 1

-C

6 alkylamino, C-C 6 dialkylamino and C 2 -Cealkenylamino; or R, and R 2 together are =0 or =S; or

R

1 and R 2 together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 8 membered isocyclic or heterocyclic ring; or

R

2 and Z together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 7 membered lactone, lactame, thiolactone or thiolactame, which ring may have 1 to 2 additional hetero atoms selected from the group O, S and N;

R

3 , R 4 and Rs are independently H, OH, SH, CN, NO 2 , NH 2 , halogen, C-C 6 alkyl, haloC,-C 6 alkyl, hydroxyC 1

-C

6 alkyl, alkoxyCl-C 6 alkyl, aminoC,-C 6 alkyl, alkoxaminoC 1

,-C

6 alkyl, C1-C 6 alkoxy, C0 1

-C

6 alkylthio, haloC 1

-C

6 alkylthio, C0 1

-C

6 alkylsulfinyl, haloC 1

-C

6 alkylsulfinyl, Cl-C 6 alkylsulfonyl, haloC 1

-C

6 alkylsulfonyl, halo-Cl-C 6 alkoxy, C2-C 6 alkenyl, haloC 2

-C

6 alkenyl, C2-C 6 alkinyl, carboxyC,-C 6 alkyl, Cl-C 6 alkanoyl, C 1

-C

6 alkoxycarbonyl, alkoxycarbonylCl-C 6 alkyl, haloalkoxycarbonylC 1

-C

6 alkyl, C 3

-C

6 cycloalkyl, alkanoylC 1

-C

6 alkyl, alkylcarbonyloxyC 1

-C

6 alkyl, phenylcarbonyloxyC,-C 6 alkyl, C-C 6 alkylamino, C1-C 6 dialkylamino, C 2

-C

6 alkenylamino, C 1

-C

6 alkanoylamino, C-C 6 alkoxycarbonylamino, benzylamino, benzoylamino, phenyl, phenoxy, benzyl or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, hydroxy, C 1

-C

4 alkyl, halo-C 1

-C

2 alkyl, C1-C 2 alkoxy, halo-Cl-C 2 alkoxy and nitro; or optionally substituted heterocyclyl. The invention relates also to new compounds of formula I, to the preparation of those compounds, to new intermediates and to agrochemical compositions comprising at least one of those compounds as active ingredient. Thiazole and thiadiazole derivatives having plant-fungicidal activities are known from EP-A-395,174, US 5,135,927, WO 96/17840, and WO 96/29871. EP-A-757,987 and WO 97/20465 discloses thiazole and thiadiazole derivatives exhibiting plant immunizing activities. These compounds have no or very weak direct activity against fungi and bacteria, but protect the plants from phytopathogenic microorganisms by activation and stimulation of the plant's own defence system (immunisation). That mode of action has also become known by the name "Systemic Activated Resistance" ("SAR"). Such compounds and methods are ecologically advantageous and are complementary to current methods in crop protection. It is therefore desirable to provide more compounds and WO 99/32464 PCT/EP98/08335 -3 methods for protecting plants by immunizing them against attack by phytopathogenic microorganisms. Surprisingly it has now been found that compounds of formula I can be used for protecting and immunizing plants against attack by microorganisms, such as phytopathogenic fungi, bacteria and viruses and for improving the qualities of the plants. The formula I embraces all stereoisomeric forms and mixtures thereof, such as enantiomeric and diastereomeric pure forms and mixtures thereof. The compounds of formula I and, where appropriate, their tautomers can be in the form of salts. Compounds of formula I that have at least one basic centre can form acid addition salts. Furthermore, compounds of formula I having at least one acid group can form salts with bases. Preference is given to agrochemically advantageous salts. Z is a C 1 -group which means that no additional carbon atoms are directly attached to this group. Examples for the group Z are trihalomethyl, dihalomethyl or halomethyl as chloromethyl; formyl or an acetal or thioacetal thereof; a carboxylic acid or derivatives thereof, as nitrile, esters, anhydrides, thioesters, amides, amidines, imidic-,hydrazonic- and hydroxamic-acids or derivatives thereof; or heterocyclyl, as 2-imidazolyl, 2-pyrimidinyl and 2 thiazolyl. Compounds of formula I wherein R 1 and R 2 are simultaneously a group selected from OH, SH, NO 2 , NH 2 , C 1

-C

6 alkylamino, Cl-C 6 dialkylamino and C 2

-C

6 alkenylamino are not stable in general and are thus not part of this invention. Unless defined otherwise, the general terms used hereinbefore and hereinafter have the meanings given below: Hydrocarbon radicals may be saturated or unsaturated, open-chained or cyclic, or mixed open-chained and cyclic, for example cyclopropylmethyl or benzyl. Alkyl groups are straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl. Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having not more than three multiple bonds, for example butadienyl, hexatrienyl or 2-penten-4-ynyl.

WO 99/32464 PCT/EP98/08335 -4 Alkenyl is straight-chained or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-l-yl. Preference is given to alkenyl radicals having a chain length of 2 to 4 carbon atoms. Alkynyl may be straight-chained or branched, for example propargyl, but-1 -yn-1 -yl or but-1 yn-3-yl. Propargyl is preferred. Cyclic unsaturated hydrocarbon radicals may be aromatic, for example phenyl and naphthyl, or non-aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partially aromatic, for example tetrahydronaphthyl and indanyl. Halogen, or halo, is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Haloalkyl may contain identical or different halogen atoms, for example fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloro methyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoro propyl. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec butoxy and tert-butoxy, preferably methoxy and ethoxy. Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2 tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy. Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkanoyl is either straight-chained or branched. Examples are formyl, acetyl, propionyl, butyryl, pivaloyl and octanoyl. A heterocyclyl radical is to be understood as being a 3 to 7-membered, aromatic or non aromatic ring having hetero atoms N, O and/or S. Furthermore, an unsubstituted or substitu ted benzo group may be fused onto such a heterocyclyl radical bonded to the rest of the molecule. Examples of heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the correspon ding partially or completely hydrogenated rings. Examples of heterocyclyl groups to which a benzo group is fused are quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl and indolinyl. Aryl is phenyl, naphthyl, phenanthryl or fluorenyl, in particular phenyl. The hydrocarbyl groups, as alkyl, alkenyl, alkynyl, and the haloalkyl, haloalkenyl, haloalkoxy and alkanoyl groups mentioned hereinabove and hereinbelow can be substituted by aryl, WO 99/32464 PCT/EP98/08335 -5 hetaryl, aryloxy, hetaryloxy, arylsulfenyl, arylsulfinyl, arylsulfonyl, heterarylsulfenyl, hetarylsulfinyl or heterarylsulfonyl, each of which is unsubstituted or additionally substituted. All the aryl, hetaryl and heterocyclyl groups mentioned hereinabove and hereinbelow can be mono- or polysubstituted, for example by halogen, C 1

-C

4 alkyl, C 2

-C

4 alkenyl, C 2

-C

4 alkynyl,

C

1

-C

4 alkoxy, C 1

-C

4 alkylthio, C 1

-C

4 haloalkyl, C 2

-C

4 haloalkenyl, C 2

-C

4 -haloalkynyl,

C

1

-C

4 haloalkoxy, halogen, cyano, cyano-Cl-C 2 alkyl, cyano-Cl-C 2 alkoxy, OH, NO 2 , SCN, thiocyanomethyl, Si(CH 3

)

3 , NH 2 , NH(Cl-C 4 alkyl), N(C 1

-C

4 alkyl) 2 , C 1

-C

4 alkoxymethyl,

C

1

-C

4 haloalkylcarbonyl, C 1

-C

4 haloalkyloxycarbonyl, Cl-C 4 alkylcarbonyl, C 1

-C

4 alkoxycarbonyl, aminocarbonyl, C 1

-C

4 alkylaminocarbonyl, bis(Cl-C 4 alkylamino)carbonyl, arylaminocarbonyl, arylaminothiocarbonyl, Cl-C 4 alkoximinomethyl, -CSNH 2 , -SH, C

C

4 alkylthiomethyl, C 2

-C

4 alkenyloxy, C 2

-C

4 alkynyloxy, C 2

-C

4 haloalkenyloxy, Cj

C

4 alkylsulfinylmethyl, C 1

-C

4 alkylsulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl, C 3

-C

6 cycloalkyl, C-C 4 haloalkylcarbonyloxy, C 1

-C

4 alkylcarbonyloxy,

C-C

4 alkoxycarbonyloxy, haloalkoxycarbonyloxy, aminocarbonyloxy, Cl-C 4 alkylaminocarbonyloxy, bis(Cl-C 4 alkylamino)carbonyloxy, arylaminocarbonyloxy, arylaminothiocarbonyloxy. Amongst the compounds and methods of their use the following groups are preferred: (1) Compounds of formula

R

1

R

2 R 4 Z I.A. N R The compounds of the formula R OMe Cl - CO-NH-CH 2

-CH

2

-

OMe N Cw T wherein WO 99/32464 PCT/EP98/08335 -6 a) R 1 is OCO-CH 3 and T is Br, b) R 1 is OH and T is Br, c) R 1 is OH and T is H, are known from WO 96/17840 as fungicides, but no indication is given therein to plant immunizing properties of these compounds ; these compounds are thus part of the invention only as far as the method for immunizing plants is concerned. (2) Compounds of formula R, R2 Nj R I R .B.

R

/ R (3) Compounds of formula R R2 N I L.C. N R3 (4) Compounds of formula I, wherein Z is CN, CO-A, CS-A or CH(ORIo) 2 .; A is hydrogen, halogen, OR6, SRT, N(R 8

)R

9 , ON(R 11

)R

1 2 or N(R 13

)OR

1 4 ;

R

6 to R 14 are independently hydrogen, an unsubstituted or substituted, open-chained, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms, an unsubstituted or substituted, cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstituted or substituted benzyl or phenethyl, an unsubstituted or substituted acyl group containing up to 8 carbon atoms, an unsubstituted or substituted benzoyl group, or an unsubstituted or substituted heterocyclyl radical; or WO 99/32464 PCT/EP98/08335 -7

R

8 and R 9 , or R, 1 and R 1 2 , together with the nitrogen atom to which they are bonded, form a 5- or 6-membered, unsubstituted or substituted heterocycle having 1 to 3 hetero atoms selected from O, S and/or N; Rio are identical or different and are C 1

-C

6 alkyl that is unsubstituted or substituted by phenyl, CI-C 2 alkoxy, phenoxy or by benzyloxy; or two substituents ORo 10 , together with the carbon atom to which they are bonded, form a cyclic acetal group that is unsubstituted or substituted by C 1

-C

3 alkyl, phenyl, benzyl, hydroxy or by C 1

-C

3 hydroxyalkyl. (5) Compounds of formula I, wherein Z is CO-A or CS-A; A is OR 6 , SR 7 , N(R 8

)R

9 , ON(Rji)R 1 2 or N(R 13

)OR

14 ;

R

6 to R 14 are independently H, C 1 -Cealkyl, haloC 1

-C

6 alkyl, C 1

-C

4 alkoxycarbonyl,

C

1

-C

4 alkanoylCi-C 4 alkyl, C 3

-C

6 cycloalkyl, C 3

-C

6 cycloalkylmethyl, phenyl, benzyl, phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 5 substituents independently selected from halogen, C 1

-C

4 alkyl, halo-C 1

-C

2 alkyl, C 1

-C

2 alkoxy, halo

C

1

-C

2 alkoxy and C 1

-C

2 alkylenedioxy. (6) Compounds of formula I, wherein

R

3 is H, OH, CI-C 6 alkyl, C 3

-C

6 cycloalkyl, haloCj-C 6 alkyl, CI-C 6 alkoxy or haloC 1

-C

6 alkoxy. (7) Compounds of formula I, wherein Ri is H, OH, NH 2 , halogen, COOH, C 1

-C

4 alkyl, haloCj-C 4 alkyl, C 1

-C

4 alkoxy,

C

1

-C

4 alkanoyloxy, aroylyloxy, C 1

-C

4 alkoxycarbonyl, aryloxycarbonyl, benzyloxycarbonyl,

C

1

-C

4 alkylcarbonyl, arylcarbonyl, benzylcarbonyl, aminocarbonyl, Cl-C 4 alkylaminocarbonyl, Cl-C 4 dialkylaminocarbonyl, alkanoylCl-C 4 alkyl, alkylcarbonyloxyCl-C 4 alkyl, C 2

-C

4 alkenyl, haloC 2

-C

4 alkenyl, Cl-C 4 alkylamino, Cl-C 4 dialkylamino, C 1

-C

4 alkanoylamino,

C

1

-C

4 alkoxycarbonylamino, benzylamino, benzoylamino, phenyl, phenoxy, benzyl or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, hydroxy, C 1

-C

4 alkyl, halo-C 1

-C

2 alkyl,

C

1

-C

2 alkoxy, halo-C 1

-C

2 alkoxy and nitro;

R

2 is H, OH, C 1

-C

4 alkyl, C 1

-C

4 alkoxy or phenyl; or

R

1 and R 2 together are a group selected from WO 99/32464 PCT/EP98/08335 -8 R18 R 7 R 1 R 1 O N-R 19 'I / or

R

2 +Z together are a group selected from R 17 R 18 R 77 RRRH H O0R N O-O 17 R ,7 O 0 IOR 18 HOO O O O O wherein R 1 7 , R 1 8 and R 1 9 are independently H or C 1

-C

4 alkyl;

R

3 is H, halogen, Cl-C 6 alkyl, haloC,-C 6 alkyl, C3-C 6 -cycloalkyl, C 1

-C

4 alkoxycarbonyl, phenyl which is unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, C1-C 4 alkyl, halo-C-C 2 alkyl, C1-C 2 alkoxy, halo-C 1

-C

2 alkoxy, amino,

C

1

-C

4 alkylamino, C-C 4 dialkylamino, benzylamino, Cl-C 4 alkanoylamino, benzoylamino,

C

1

-C

4 alkoxycarbonylamino, formyl, or a 4-7-membered cyclic or Cl-C 4 alkyl open-chained acetal or thioacetal thereof;

R

4 is H, OH, halogen, amino, C 1

-C

6 alkyl, C 1

-C

4 alkylamino, C 1

-C

4 alkenylylamino,

C-C

4 dialkylamino, benzylamino, Cl-C 4 alkanoylamino, benzoylamino, Cl-C 4 alkoxycarbonylamino. (8) Amongst group (7) those, wherein

R

3 is H, OH, halogen, C-C 6 alkyl, haloC 1 -C6alkyl, C 3

-C

6 -cycloalkyl, C 1

-C

6 alkoxy, alkoxycarbonylCl-C 6 alkyl, phenyl, benzyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, Cl-C 4 alkyl, halo

C

1

-C

2 alkyl, C 1

-C

2 alkoxy and halo-Cl-C 2 alkoxy; or formyl, or a 4-7-membered cyclic or Cl-C 4 alkyl open-chained acetal or thioacetal thereof;

R

4 is H, OH, halogen, amino, C 1

-C

6 alkyl, C 1

-C

4 alkylamino, C 1

-C

4 alkenylylamino,

C

1

-C

4 dialkylamino, benzylamino, Cl-C 4 alkanoylamino, benzoylamino, or Cl-C 4 alkoxycarbonylamino.

WO 99/32464 PCT/EP98/08335 -9 (9) Amongst group (6) those, wherein Z is CO-A or CS-A; A is hydrogen, halogen, OR 6 , SR 7 , N(RE)R 9 , ON(Rjj)R 1 2 or N(R 13

)OR

14 ;

R

6 to R 9 and R 11 to R 14 are independently hydrogen, an unsubstituted or substituted, open chained, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms, an unsubstituted or substituted, cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstituted or substituted benzyl or phenethyl, an unsubstituted or substituted acyl group containing up to 8 carbon atoms, an unsubstituted or substituted benzoyl group, or an unsubstituted or substituted heterocyclyl radical; or Re and R 9 , or Ril and R 1 2 , together with the nitrogen atom to which they are bonded, form a 5- or 6-membered, unsubstituted or substituted heterocycle having 1 to 3 hetero atoms selected from O, S and/or N; Rio 0 are identical or different and are C 1

-C

6 alkyl that is unsubstituted or substituted by phenyl, C 1

-C

2 alkoxy, phenoxy or by benzyloxy; or two substituents ORio 0 , together with the carbon atom to which they are bonded, form a cyclic acetal group that is unsubstituted or substituted by Cl-C 3 alkyl, phenyl, benzyl, hydroxy or by C 1

-C

3 hydroxyalkyl. (10) Amongst group (9) those, wherein A is OR 6 , SR 7 , or N(Re)Rg; Re, R 7 , Re R 9 are independently H, C 1

-C

6 alkyl, haloCl-C 6 alkyl, Cl-C 4 alkoxycarbonyl, alkoxycarbonylCl-C 6 alkyl, C 1

-C

4 alkanoylC 1

-C

4 alkyl, C 3

-C

6 cycloalkyl, C 3

-C

6 cycloalkylmethyl, phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selectedfrom halogen, C 1

-C

4 alkyl, halo-C 1

-C

2 alkyl,

C

1

-C

2 alkoxy, halo-C 1

-C

2 alkoxy. (11) Amongst group (9) those, wherein Z is CO-A; A is OR 6 or N(R 8 )Rg; Ri is H, OH, halogen, C 1

-C

4 alkyl, haloC 1

-C

4 alkyl, C 1

-C

4 alkoxy, halo-C 1

-C

4 alkoxy, amino,

C

1

-C

4 alkylamino, C 1

-C

4 dialkylamino, benzylamino; phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 2 substituents independently selected from halogen, halo-Cl-C 2 alkyl, C 1

-C

2 alkoxy, halo-C 1

-C

2 alkoxy; WO 99/32464 PCT/EP98/08335 - 10

R

2 is H, OH, halogen, C 1

-C

4 alkyl, haloC-C 6 alkyl, or phenyl,

R

3 is H, OH, C 1

-C

6 alkyl, C 3

-C

6 cycloalkyl, haloC 1

-C

6 alkyl, C 1

-C

6 alkoxy or haloC 1

-C

6 alkoxy,

R

4 is H or CI,

R

6 , R 8 and R 9 are independently H, C 1

-C

6 alkyl, haloCj-C 6 alkyl, CI-C 6 alkoxy, haloCI-C 6 alkoxy, C,-C 4 alkoxycarbonyl, C 1

-C

4 alkanoylC 1

-C

4 alkyl, C 3

-C

6 cycloalkyl,

C

3

-C

6 cycloalkylmethyl, phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen,

C

1

-C

4 alkyl, halo-C 1

-C

2 alkyl, C 1

-C

2 alkoxy, halo-Cl-C 2 alkoxy. (12) Amongst group (11) those, wherein

R

1 is H, OH, halogen, C 1

-C

4 alkyl;

R

2 is H.

R

3 is H, cyclopropyl or CF 3 ,

R

4 is Cl. (13) Amongst group (9) those, wherein

R

3 is H, halogen, C 1

-C

4 alkyl, haloC 1

-C

4 alkyl, C 3

-C

6 -cycloalkyl, C01-C4 alkoxycarbonyl, formyl, or a 4-7-membered cyclic or C 1

-C

4 alkyl open-chained acetal or thioacetal thereof. (14) Compounds of formula R

R

2 R 4 Z I.A N R Z is CO-A; A is hydrogen, OR 6 , SR 7 , N(Ra)Rg;

R

1 is H, OH, halogen or C 1

-C

4 alkyl,

R

2 is H;

R

3 is H, OH, C 1

-C

6 alkyl, C 3

-C

6 cycloalkyl, haloC-C 6 alkyl, C 1 -Cealkoxy, haloC 1

-C

6 alkoxy, formyl, or a 4-7-membered cyclic or C 1

-C

4 alkyl open-chained acetal or thioacetal thereof;

R

4 is Cl; Re, R 7 , Re and R 9 are independently H, Cs-C 6 alkyl, haloC 1

-C

6 alkyl, C 1

-C

6 alkoxy, haloC 1 -Cealkoxy, Cl-C4alkoxycarbonyl, Cl-C 4 alkanoylC-C 4 alkyl, C 3

-C

6 cycloalkyl, WO 99/32464 PCT/EP98/08335 -11 C 3

-C

C

1

-C

4 alkyl, halo-C 1

-C

2 alkyl, C 1

-C

2 alkoxy, halo-C 1

-C

2 alkoxy. (15) Amongst group (14) those, wherein A is OR 6 or SR 7 ; R, and R 2 are H;

R

3 is C-C 6 alkyl, C 3

-C

6 cycloalkyl, CF 3 or formyl;

R

4 is Cl;

R

6 and R 7 are independently H, Cl-C 6 alkyl, phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted with 1 to 2 substituents independently selected from halogen, CI-C 4 alkyl, halo-Cl-C 2 alkyl, C 1

-C

2 alkoxy and halo-C 1

-C

2 alkoxy. Also preferred are the compounds of the tables. The compounds of formula I may be prepared as outlined in the following reaction schemes. Abbreviations: position to which the rest of the molecule is attached Het: X 'Y'

R

3 Hal: halogen L: leaving group, preferably chlorine, bromine, mesylate or tosylate. R: a group which is inert under the reaction conditions WO 99/32464 PCT/EP98/08335 -12 Scheme 1 Het-COOR Het-CH 3 Het-H halogenation Lithiation Lithiation e.g. LiAIH 4 alometh lation r e.g.HC / 20 Het-CH 2 OH Het.CH2Li Het-Li halogenation L-CHH-COOR e.g.SOCl2 "Arndt-* tert" CO 2 OHC-COOR Het-CH 2 Hal carbonylation HetCHCOOR reduction Het-CH(OH)-COOR 2HlHet-CH2-COOR w Het-CH(OH)-COOR e.g. CO/cat: cobalt-carbonyl e.g. H 2 /cat Of particular importance is the reaction step S CH 2 C /S

CH

2 -COOH R3 R, 11.1 1.1 wherein X, Y and Ra are as defined for formula I, which comprises reaction of a compound of formula 11.1 with carbon monoxide under pressure of 2-20 bars, preferably 5-10 bars, in presence of a catalyst, for example cobalt carbonyl and optionally a phase transfer catalyst. Scheme 2 H H R1-L/base H R R2-L/base R 1 Het z Het z -e z WO 99/32464 PCT/EP98/08335 -13 Scheme 3 H H NXS H X RNH 2 H NHR Het z e.g.N-Bromo Het z Het z succinimide Scheme 4 R H OH H O R Het R Het O O O O 0 R H NHR HN- R HetOH R R H O Het O Het O 0 Scheme 5 1. Base O 2. RO- O'.R O 0 H 1. Base O'R Oxidation HetH Het Het 0 2. O O R2 O'RR O Nu HO H 1. Base O OR Nu- 'R Het Het Het 2. O O (nucleophil) O

O

WO 99/32464 PCT/EP98/08335 -14 The functional groups of the compounds of formula I can be converted by known methods. For example, carboxylic acid derivatives can be converted as follows: Scheme 6 R R A R 2

R

1

NH

3 R 2 1 Het CO-A Het COCI Het CONH 2 thionating agent reduction -H 2 0 e.g. Lawesson reagent e.g. H/cat e.g. SOC1 2

R

2 R1 R2 R R2 1 RRHet CN Het CS-A Het CHO I acetalisation with alcohol or glycol

R

2 RR 1 Het "CH(ORio)2 WO 99/32464 PCTIEP98/08335 -15 Of importance are the syntheses of schemes 7 and 8 Scheme 7 t-Bu-ONO CI COOR NH 2-CS-NH 2 S COOR CuCI 2

SH

2 N 0 R3 N R 3 S COOR S CH 2 COOR CI M Cl R N R 3 N R 3 ROH reduction 1. reduction, e.g. LiAIH4 e.g.H 2 /Pd/C 2. Halogenation; e.g.SOCI2 3. Carbonylation, e.g CO/Co2(CO)8 S COOR or S CH 2 COOR H R\ Cyanation/alcoholysis H N R N: R 3 R_______ N3 \4 S COOR S CH 2 COOR ROR\ RO R N R 3 N

R

3 WO 99/32464 PCT/EP98/08335 -16 Scheme 8 S COOR S COOR Soddation COOR Cl I halogenation ClI- oxidation Cl Se.g. bromination N Hal CH 3 with NBS e.g. MnO2 or CHO N-methyimorpholine N-oxide acetalisation S COOR reduction S CH 2 -OH 9 I O 0 N N e.g. :LiAIH4 N NE O O~~~ chlorination CH 2 C carboxylation S 2CH 2 COOH e.g. SOCl2 or N N e.g.CO/Co2(CO)8 N Ph3P/CCI4 0 E e.g.CO/Co2(CO)8 E m. Cl C-A hydrolysis C CO-A N 0 N CHO O-E E: optionally substituted C 2

-C

5 methylene Of particular importance is the reaction step S CH 2Cl S CH 2 -COOH R4~~<\R4 N R 3 N R 3 II.A.1 I.A.1 which comprises reaction of a compound of formula ll.A.1 with carbon monoxide under pressure of 2-20 bars, preferably 5-10 bars, in presence of a catalyst, for example cobalt carbonyl and optionally a phase transfer catalyst.

WO 99/32464 PCT/EP98/08335 -17 Particulartly preferred is this reaction with compounds wherein Ra is C 1

-C

6 alkyl, CF 3 or an acetal group, and R 4 is Cl. Suitable bases, leaving groups, solvents and catalysts are known to the skilled person. The thiazoles, isothiazoles and thiadiazoles can be synthesized by known methods or in analogy thereto according to the following references: 1.1 1,3-Thiazoles Ahluwalia V. K. et al, Heterocycles, 32, (1991), 907. Fukatsu H. et al, Heterocycles, 29, (1989) 1517. Byers J. R.et al, Org. Synthesis /II, (1943) 31. 1.2 1,2-Isothiazoles R. G. Micetich, Can J. Chem.; (1970), 48, 2006. Adams A., Slack, J. Chem. Soc. (1959) 3061. Buttimore D. et al, J. Chem. Soc. (1963) 2032. Wooldrige K.R.H. Adv. Het. Chem. (1972), 14, 1. 1.3 1,2,3-Thiadiazoles Hurd C. D., Mori E. J., J. Am. Chem. Soc., (1995), 5359. Ramsky S. I. et al., Acta Pharm. Suecica 10, (1973), 285. Scheitauer S., Mayer R. Chem. Ber. 100, (1967), 1413. R. Raap, Can. J. Chem. (1968), 46. 2255. The compounds of the invention can be used in the agricultural sector and related fields preventively and/or curatively. Besides their microbicidal properties, the compounds exhibit plant immunizing properties, i.e. plants can be protected by activation and stimulation of the plant's own defense system (immunization) which is known as "Systemic Activated Resistance" ("SAR"). Accordingly, with the compounds and methods of the invention, it is possible to control plant diseases on the one hand by strengthening the plant by activating its own defence system and on the other hand by additionally controlling the pathogens directly. The compounds offer a long lasting protection against a variety of pathogenes in different crops.

WO 99/32464 PCT/EP98/08335 -18 The compounds I can also be used as dressings in the treatment of seed (fruit, tubers, grains) and plant cuttings to provide protection against fungus infections as well as against phytopathogenic fungi which occur in the soil. The compounds I are effective, for example, against phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Moreover, they are effective against the classes of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e.g. Phyto phthora, Pythium, Plasmopara). Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and black berries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (marrows, cucumber, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor); and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals. The compounds I are generally 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, for example, fertilisers or micronutrient donors or other preparations that influence plant growth. 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 other application promoting adjuvants customarily employed in formulation technology. Suitable solvents, carriers and adjuvants are known to the skilled person.

WO 99/32464 PCT/EP98/08335 -19 A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the leaves (foliar application). The frequency and rate of application depend upon the risk of infestation by the correspon ding pathogen. The compounds I can, however, also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation or if the substances are introduced in solid form into the soil, e.g. in the form of granules (soil application). In paddy rice crops, such granules can be applied in metered amounts to the flooded rice field. In order to treat seed, the compounds I can, however, also be applied to the seeds (coating), either by impregnating the grains or tubers with a liquid formulation of the active ingredient, or by coating them with a solid formulation. Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 20 g to 600 g a.i./ha. When the compounds are used as seed dressings, dosages of from 10 mg to 1 g of active ingredient per kg of seed are advantageously employed. The agrochemical compositions generally comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects. The compounds of formula I can be mixed with other fungicides, producing in some cases unexpected synergistic effects. Especially preferred mixing partners are azoles, as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; WO 99/32464 PCT/EP98/08335 -20 pyrimidinyl carbinoles, as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, as bupirimate, dimethirimol, ethirimol; morpholines, as dodemorph, fenpropidin, fenpropimorph, spiroxamin, tridemorph; anilinopyrimidines, as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, as fenpiclonil, fludioxonil; phenylamides, as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, as guazatine, dodine, iminoctadine; strobilurines, as azoxystrobin, kresoxim-methyl, SSF-126 (metominostrobin or fenominostrobin; SSF-129 (a-methoximino-N-methyl-2-[(2,5-dimethylphenoxy)methyl] benzeneacetamide), trifloxystrobin (2-[a-{[(a-methyl-3-trifluormethyl-benzyl)imino]-oxy}-o tolyl] -glyoxylsaure-methylester-O-methyloxim); dithiocarbamates, as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiodicarboximides, as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; copper compounds, as bordeaux-mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, as dinocap, nitrothal-isopropyl; organo-P-derivatives, as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; other compounds, as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fentin, ferimzone,fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin.

WO 99/32464 PCT/EP98/08335 -21 Examples A. Preparation Examples Abbreviations: Me = methyl; Et = ethyl; Pr = n-propyl; i-Pr = isopropyl; Bu = n-butyl; i-Bu = isobutyl; sec-Bu = sec-butyl; t-butyl = tert-butyl, Ph = phenyl; Ac = acetyl, THF = tetrahydrofuran; TPP = triphenylphosphine; Val = valine; m.p. = melting point 1. Compound No.1.1 (E) 0 O S S OH SOC2 S C NaAIH, 2

(OCH

2

CH

2

CH)

2 C OH CIi 0 -. CI-\ C N F N F N F FF FF C F A B

SOCI

2 0 CI-.\ OH CO 2 / Co 2

(CO)

8 CI-<\ / CI N F N F FF FF E D A mixture of thiazole A (synthesized according to EP 0279239) (25.5 g, 0.11 Mol) and thionyl chloride (26.2 g, 0.22 Mol) in 25ml of toluene, is held at reflux for 1.5 hours. After, evaporation of the toluene under reduced pressure, 24 g of the acid chloride B (b.p 90-920, 45mbar) is distilled through a Vigreux column. To the acid chloride B (97.5 g, 0.39 Mol) in 11 dry tetrahydrofuran at -700C under nitrogen atmosphere, NaAIH 2

(OCH

2

CH

2 0CH 3

)

2 (commercial solution 3.5M in toluene, 0.429Mol), diluted in 300ml of toluene, is added dropwise. After 45min of stirring at -700C, the cooling bath is removed and the reaction is quenched with 370 ml of 3.5N HCI is added. The organic phase extracted with ethyl acetate, dried over sodium sulfate, concentrated under reduced pressure and flash-chromatographed to afford 67.5g of the alcohol C as an oil. A mixture of alcohol C (60 g, 0.276 Mol) and thionyl chloride (98.5 g, 0828 Mol) in 400 ml of dichloromethane containing 0.1 ml of dimethyl formamide is stirred at reflux for 8 hours: Another portion of thionyl chloride (16.4 g, 0.138 Mol) is then added and the reaction WO 99/32464 PCT/EP98/08335 -22 heated for additional 16 hours. After the reaction is cooled down to room temperature, the solvent is removed under reduced pressure (600C, 200 mbar) and the resulting crude yellow oil is distilled through a 5 cm Vigreux column (92-950C, 20 mbar) to give 53.5 g of compound D as an colorless oil. A mixture of compound D (125 g, 1.059 Mol), benzyltriethylammonium chloride (4.8 g, 0.042 Mol), cobalt carbonyl (7.2 g, 0.042 Mol), sodium carbonate (101 g, 2.4 Mol), 1.5 I of water and 1.361 of dichloromethane is stirred under carbon monoxide pressure (10 bars) for 24 hours at room temperature. The biphasic mixture is then filtered over celite, extracted two times with dichloromethane. The water phase is acidified with105 ml of concentrated HCI and extracted with ethyl acetate. The organic layer is then washed with brine, dried over sodium sulfate, treated with active charcoal at 600C, filtered over celite and concentrated in vacuo to give 114 g of the acid E which is used without further purification. 2. Compound No 2.5 (J) (by Arndt-Eistert-reaction) 0 O S OH 1. (COC) 2 S C-N 2 TMS PhCHc20H S. \ / H2C1 COOCH Ph 2. Me 3 SiCH 2

N

2 N 180*C N G G H J To compound G (2.0 g, 10.44 mmol) dissolved in 20 ml of dichloromethane at 00C, is added oxalyl chloride (0.9 ml, 10.5 mmol). After the development of carbon dioxide stopped, 0.1 ml of dimethylformamide is added and the yellow suspension is stirred at room temperature for 3 hours. The resulting yellow solution is then concentrated under reduced pressure, dissolved in a mixture of 10 ml tetrahydrofuran and 10 ml acetonitrile, cooled down to 00C, and successively treated with triethylamine (1.8 ml), trimethylsilyldiazomethane (commercial 2N solution in hexane) (6.05 ml, 13.05 mmol). After 12 hours of stirring at 00C, the solvents are evaporated under reduced pressure, and the intermediate diazoketone G is rearanged in a mixture of 13 ml of benzylalcohol and 13 ml of trimethylpyridine at 1800C for 8 min. The dark mixture is cooled down to room tempature, diluted with ethyl acetate, washed 3 times with citric acid (10% aqueous solution). The ethyl acetate layer is dried over magnesium sulfate, filtered, evaporated under reduced pressure, and flash-chromatographed to give the compound J as an oil.

WO 99/32464 PCT/EP98/08335 - 23 3. Compound No.1.2 CS COOCH 3 C F 3 2-Chloro-4-trifluoromethyl-5-acetic acid (10 g, 40.71 mmol) in 100 ml of methanol is heat refluxed in presence of concentrated sulfuric acid (4 g, 40.71 mol) for 12hours. After cooling at room temperature, the methanol is distilled off under reduced pressure, the residue is dissolved in ethyl acetate, and successively washed with a saturated solution of sodium bicarbonate (3 times) and brine. After drying over magnesium sulfate, the ethyl acetate layer is filtered, evaporated under reduced pressure and flash-chromatographed on silica gel to give 10.36g of the the title compound as a pale red oil. 4. Compound No.1.21 S CO-NH-CH(COOMe)-CH(CH 3

)

2 Cl \ I CIC

CF

3 The acid chloride of comp. 1.2 (78.5 g, 0.2973 Mol) and L-Valine methyl ester hydrochloride are suspended in 600 ml of toluene, and heated at 1100C for 25 minutes. The resulting clear solution is cooled down to room temperature, extracted successively with water, a saturated solution of sodium bicarbonate, brine. The organic layer is then dried over sodium sulfate and the solvent removed under reduced pressure to give a crude oil which is chromatographed on silica-gel to afford 102g of the title compound (mp:51-53 0 C). 5. Compound No.1.76 Br I

COOCH

3 N"

CF

3 A mixture of compound 1.2 (9 g, 34.7 mmol) and N-Bromosuccinimide (15.49 g, 87 mmol) in 200 ml of carbon tetrachloride, irradiated with a 150W quartz lamp is heated at reflux temperature. After 1.5 hours of stirring, the mixture is cooled down to room temperature and WO 99/32464 PCT/EP98/08335 - 24 filtered over celite. After removal of the solvent under reduced pressure, the filtrate is suspended in hexane at 60 0 C and the solid filtered over celite. The hexane evaporated under reduced pressure to give a red oil, which after distillation (1500C, 0.13mbars) gives 10g of the title compound as a pale red oil. 6. Compound No. 1.97

NH-CH

2 -Ph S

COOCH

3 CI N

CF

3 A mixture of compound 1.76 (1 g, 2.9 mmol) and (0.63 g, 5.9 mmol) of benzylamin is stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture is removed under reduced pressure, and chromatographed on silica to give 0.8 g of the title compound as an oil. 7. Compound No.1.82

CH

3 S COOCH N

CF

3 Compound 1.2 (1 g, 3.8 mmol) is added to a suspension of sodium hydride (55% in mineral oil) (0.17g, 4,2mmol) in tetrahydrofuran at -500C, and the resulting red solution stirred for 1 hour at -350C. After this period, methyl iodide (0.7 g, 5 mmol) is rapidly added. After 2 hours of stirring, the reaction is quenched with a saturated aqueous ammonium chloride solution, and extracted with ethyl acetate. The organic layer is dried over magnesium sulfate, evaporated under reduced pressure and chromatographed on silica to give 0.72 g of the title compound as a pale yellow oil.

WO 99/32464 PCT/EP98/08335 -25 8. Compound No.1.92

COOCH

3 S

COOCH

3 ND

CF

3 Compound 1.2 (1 g, 3.8 mmol) is added to a suspension of sodium hydride (55% in mineral oil) (0.17 g, 4,2 mmol) in dry tetrahydrofuran at -50 0 C, and the resulting red solution stirred for 1 hr at -35oC. Methyl chloroformiate ( 6 mmol) is then added, and after 2hours of stirring, the reaction is quenched with a saturated aqueous ammonium chloride solution, and heated up to room temperature. After extraction with ethyl acetate, the organic layer is dried over magnesium sulfate, filtered and evaporated under reduced pressure. The reaction mixture is purified on silica to afford 0.79g of the title compound as a white solid. 9. Compound No. 1.99

H

3 C

CH

3 S COOCH N:

CF

3 To a suspension of sodium hydride (55% in mineral oil)(0.61 g, 25.4 mmol) at -500C, is added compound 1.2 (3 g, 11.55 mmol). After 2.5 hours of stirring at -300C, the red mixture is cooled down to -780C, treated with methyliodide (4.92 g, 34,65 mmol), and slowly heated up to -20C over a period of 1.5hrs. After hydrolysis with a saturated aqueous ammonium chloride solution, the reaction mixture is extracted with ethyl acetate, dried over magnesium sulfate, and after evaporation of the solvent under reduced pressure, the resulting crude material is purified by flash-chromatography to give 2.06g of the title compound as an oil.

WO 99/32464 PCT/EP98/08335 -26 10. Compound No.1.100 OH S COOEt CHK\ I

N

CF 3 To a tetrahydrofuran solution kept at -780C of lithium diisopropylamide, prepared at 00C from diisopropylamine (0.83 ml, 5.9 mmol) and n-butyl lithium (3.33 ml, 5.3 mmol), 2-chloro 4-trifluoromethyl-thiazole is slowly added (1 g, 5.33 mmol). After 2 hours of stirring, the green solution is transferred, via a canula to a flask containing a solution of ethylglyoxylate (50% toluene commercial solution) (15ml, 10.6mmol) in tetrahydrofuran kept at -780C. After 5 minutes, the mixture is treated with a saturated aqueous ammonium chloride solution, extracted with ethyl acetate and concentrated in vacuo. The resulting crude residue is then purified by chromatography on silica-gel to give 0.28 g of the title compound as an oil. 11. Compound No.1.106 HO CH 3 S COOEt N

CF

3 2-chloro-4-trifluoromethyl-thiazole (0.5 g, 2,66 mmol) dissolved in tetrahydrofurane is treated at -780C with lithium hexamethyldisilyamide (commercial solution, 1 M in tetrahydrofuran, 2,67ml), stirred for 1.5 hours, followed by the addition of ethylpyruvate (0.305 ml, 2.9 mmol). After the reaction is completed, it is quenched with a saturated aqueous ammonium chloride solution, extracted with ethyl acetate. The organic layer is dried over magnesium sulfate, concentrated under reduced pressure and chromatographed on silica-gel to afford 0.730 g of the title compound as a yellow oil.

WO 99/32464 PCT/EP98/08335 -27 12. Compound No. 1.113 0 S COOEt CHK\ I N

CF

3 2-Chloro-4-trifluoromethyl-thiazole (2 g, 10.66 mmol) dissolved in tetrahydrofuran is treated at -780C with lithium hexamethyldisilyamide (commercial solution, 1 M in tetrahydrofuran, 2,67 ml), stirred for 1.5 hours, followed by the addition of ethylbromopyruvate (1.79 ml, 12.79 mmol). After the reaction is completed, it is quenched with a saturated aqueous ammonium chloride solution and heated up to room temperature. The reaction mixture is then extracted with ethyl acetate, the organic layer dried over magnesium sulfate, the solvent removed under reduced pressure, and the crude material chromatographed on silica-gel to afford 0.254g of 2.08g of the title compound as oils. 13. Compounds Nos. 2.18 (Q), 2.19 (R), 2.25 (S) (Scheme 13) (a) A mixture of compound K (179 g, 0.871 Mol) NBS (159.8 g, 0.871 Mol) and Azoisobutyronitrile (AIBN) (14.6 g, 87 mmol) in 600 ml of CC14 is heated at reflux for 16 hrs. After cooling, the crude mixture is filtered, concentrated under reduced pressure and flash chromatographed to afford 190 g of compound L contaminated with the starting material K. (b) To a solution of compound L (189.4 g, 0.666 Mol) in 1.5 I of acetonitrile, is added 0.3 I of 4A molecular sieves followed by N-methylmorpholine-N-oxide (139.2 g, 0.99 Mol). After 2.5 hrs. of stirring at room temperature, the mixture is filtered on silicagel, concentrated in vacuo and purified by flash-chromatography to give 92 g of aldehyde M. (c) A solution of aldehyde L (91.25 g, 0.415 Mol), ethylene glycol (29 ml, 0.5 Mol) and p-toluenesulfonic acid (9.12 g, 41 mmol) is heated for 16 hrs. at reflux in 300 ml of benzene while water is destilled off. After cooling, the crude mixture is extracted with water and ether, the organic phase is then dried over MgSO 4 , concentrated under reduced pressure and purified by flash-chromatography to give 65 g of the dioxolane N.

WO 99/32464 PCT/EP98/08335 -28 Scheme 13 C S COOEt OEt C1S- C O O Et (a) Br (b)\N CHO K L M S COOEt S CH 2 OH CI\ C I N 0 S CH 2 CI CI S COOH (c) (f) 0 N O PS S COOMe ,SCOOMe CI\ N (g) No (h) CHO R S R (d) To a suspension of LiAIH 4 (1.78 g, 45.4 mmol) in 220 ml of dry THF at 0°C, is added dropwise compound N (10 g, 37.9 mmol) dissolved in 100 ml of THF. After 5 min of stirring the reaction is completed. The mixture is successively treated with 1.78 ml of water, 1.78 ml of NaOH (15% aqueous solution) and 5.34 ml of water. The suspension is then filtered over celite, extracted 3 times with ethylacetate and water. The combined organic phases are concentrated under reduced pressure and chromatographed on silica to afford 31 g of the alcohol O.

WO 99/32464 PCT/EP98/08335 - 29 (e) To a solution of compound O (9.85 g, 44.46 mmol) in 180 ml of CCI 4 is added triphenlyphosphine (11.8 g, 44.46 mmol). The mixture is stirred at 850C for 24 hrs. After cooling, the crude solution is concentrated under reduced pressure and purified by chromatography on silica to afford 6.4 g of compound P. (f) A mixture of compound P (7.43 g, 30.9 mmol), benzyltriethylammonium chloride (283 mg, 1.24 mmol), cobalt carbonyl (423 mg, 1.24 mmol), sodium carbonate (5.83 g, 69.4 mmol), 68 ml of water and 62 ml of dichloromethane is stirred under carbon monoxide pressure (10 bars) for 24 hours at room temperature. The biphasic mixture is then filtered over celite, extracted two times with dichloromethane. The water phase is acidified to pH 2 with concentrated HCI and extracted with ethyl acetate. The organic layer is then washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give 3.2 g of the acid Q which is used without further purification. (g) A solution of the acid Q in THF is carefully treated at room temperature with an ether solution diazomethane. The reaction is monitored by tic. After completion of the reaction, the crude mixture is concentrated under reduced pressure and chromatographed to 2 g of the methylester R. (h) Compound R (1.61 g, 6.47 mmol) is stirred for 40 min in 19 ml of THF, 19 ml of water and 9 ml of trifluoroacetic acid. After evaporation of the solvent, the crude mixture is diluted with ether and washed with NaHCO 3 (sat. aqueous solution). The ether phase is concentrated under reduced pressure to afford the aldehyde S which is an oil. The aldehyde group may be converted by known methods into many different other groups.

WO 99/32464 PCT/EP98/08335 -30 Table 1.A

R

1 R2 Tablel S CO-A

CF

3 No. R, R2 A Phys. data m.p OC 1.1. H H OH 122-1230C 1.2. H H OMe oil 1.3. H H C2Et oil 1.4. H H Ot-Bu oil 1.5. H H OCH 2

CH=CH

2 oil 1.6. H H OCH 2 oil 1.7. H H OCH 2 Ph oil 1.8. H H oO oil OCH - / OMe 1.9. H H OMe solid

OCH

2 OMe 1.10. H H OMe oil OCHe 2 OMe OMe 1.11. H H Mo OMe oil

OCH

2 7OMe 1.12. H H oil OcH 2

O

WO 99/32464 PCT/EP98/08335 -31 No. R 1 R2 A Phys. data m.p °C 1.13. H H MeO solid

OCH

2 --- OMe 1.14. H H oil

OCH

2 / OCF 3 1.15. H H / solid

OCH

2

NO

2 1.16. H H oil OCH i / OCH 2 Ph 1.17. H H oil

OCH

2 \ 1.18. H H 90-91

OCH

2 N 1.19. H H cl oil

OCH

2 i / CI N 1.20. H H OCH 2 COMe oil 1.21. H H co 2 Me 51-53 NHe 1.22. H H NMe 2 1.23. H H NHMe 1.24. H H NHEt 1.25. H H NHn-Bu 1.26. H H NHt-Bu 1.27. H H cl 127-8

NHCH

2 -- "/ Cl 1.28. H H 142-3

NHCH

2 -Ci WO 99/32464 PCT/EP98/08335 - 32 No. R, R 2 A Phys. data m.p oC 1.29. H H CI 122-3

NHCH

2 -- / CI 1.30. H H ci solid

NHCH

2 -- b 1.31. H H F 105-6

NHCH

2 --- F 1.32. H H F 51-2

NHCH

2 / F 1.33. H H F solid

NHCH

2 -- / 1.34. H H F 85-6 NHCH 2 F 1.35. H H F solid NHCH1 2 F 1.36. H H F 115-6

NHCH

2 - / 1.37. H H 110-20

NHCH

2 F 1.38. H H F 123-4

NHCH

2 -- Br WO 99/32464 PCT/EP98/08335 - 33 No. R 1 R2 A Phys. data m.p oC 1.39. H H CF 3 98

NHCH

2

,-

1.40. H H NH CF 3 97-101

NHCH

2 -- / 1.41. H H 102-4

NHCH

2 CF3 1.42. H H CF 3 106-7 NHCH2-- ~C

CF

3 1.43. H H - M99-101

NHCH

2 Me 1.44. H H 120

NHCH

2 Me 1.45. H H N solid

NHCH

2

NO

2 1.46. H H NHCH 2 Ph 110-1 1.47. H H 126-30

NHCH

2 OMe 1.48. H H MeO 115

NHCH

2 --- b 1.49. H H NHH2OMe 107-8

NHCH

2 -- / 1.50. H H Me 132-3

NHCH

2 - OMe WO 99/32464 PCT/EP98/08335 - 34 No. R 1 R2 A Phys. data m.p oC 1.51. H H MeO 159-60 NHCH i OMe MeO 1.52. H H OMe 140-2

NHCH

2 i / OMe 1.53. H H 0 130-1 NHCHi O 1.54. H H Br 188-9 NH -O Br 1.55. H H Br solid NH ~ Br Br 1.56. H Br 51 NH

OCF

3 Br 1.57. H H ONHCOOCH 2 Ph oil 1.58. H H ONHCH(CH 3

)

2 oil 1.59. H H ONHC(CH 3

)

3 oil 1.60. H H ON=C(CH 3 )OEt oil 1.61. H H ONHCOOC(CH 3

)

3 oil 1.62. H H ONHCOOEt oil 1.63. H H ONHSO 2 Ph 114-20 1.64. H H NHOC(Ph) 3 177 1.65. H H NHOCH 2 Ph 78-85 1.66. H H NHOMe 117-8 1.67. H H NHOCH 2

CH=CH

2 73-4 WO 99/32464 PCT/EP98/08335 - 35 No. R 1 R2 A Phys. data m.p OC 1.68. H H NHOC(CH 3

)

3 solid 1.69. H H NHOPh 1.70. H H F F solid

NHOCH

2 F F F 1.71. H H SMe oil 1.72. H H SEt 1.73. H H SPh 1.74. H H SCH 2 Ph 1.75. Br H OH oil 1.76. Br H OMe oil 1.77. F H OH 1.78. F H OMe oil 1.79. CI H OMe 1.80. CI H OH 1.81. Me H OH oil 1.82. Me H OMe oil 1.83. Et H OMe oil 1.84. Et H OH oil 1.85. Pr H OH 1.86. Pr H OMe 1.87. nBu H OH 1.88. nBu H OMe 1.89. CH 2

CH=CH

2 H OH oil 1.90. CH 2 Ph H OH 127-80C 1.91. CH 2 Ph H OMe oil 1.92. COOMe H OMe oil 1.93. CH 2 COOH H OH 130-1 OC 1.94. NH 2 H OH 166-70C 1.95. NH 2 .HCI H OMe 176-7°C 1.96. NEt 2 H OMe 56-80C WO 99/32464 PCT/EP98/08335 - 36 No. R 1

R

2 A Phys. data m.p OC 1.97. NHCH 2 Ph H OMe oil 1.98. Me Me OH 137-80C 1.99. Me Me OMe oil 1.100. OH H OEt oil 1.101. OH H OH 1.102. OAc H OEt oil R, R2 A 1.103. ci H OEt oil OCO

-

1.104. OMe H OEt oil 1.105. OSi-t-BuMe 2 H OEt oil 1.106. OH Me OEt oil 1.107. OH

CF

3 OMe oil 1.108. OH Ph OEt 77-90C 1.109. OH CH 2 Br OEt oil 1.110. s CF 3 OH OEt oil N CH, 1.111. s CF 3 H OMe 151-2oC CI H N COOMe

CH

2 1.112. R1+R 2 =0 H OEt oil 1.113. R1+R2 / H OEt oil 1.114. f-.N OH OEt oil Nk--N-CH 2 WO 99/32464 PCT/EP98/08335 -37 Table 1.B Compounds of the formula R

R

2 /S CO-A N\I

CF

3 CI wherein the R 1 , R 2 and A have the meanings of the corresponding compounds of Table 1.A. Table 1.C Compounds of the formula

R

1 R 2 /S CO-A N\I N:

CF

3 wherein R 1 , R 2 and A have the meanings of the corresponding compounds of Table 1.A. Phys. data of compound(s) of Table 1.C: No. R 1 R2 A Phys. data m.p. °C 1.C.1 H H OH oil WO 99/32464 PCT/EP98/08335 - 38 Table 2.A

R

1 R 2 S CO-A Cl---\I C' N

R

3 No R, R2 R3 A Phys.data m.p.oC 2.1. H H H OCH 2 Ph oil 2.2. H H H OH 2.3. H H Me OCH 2 Ph oil 2.4. H H Me OH 2.5. H H Et OCH 2 Ph oil 2.6. H H Et OMe oil 2.7. H H Et OH 191-3 2.8. H H n-Pr OMe oil 2.9. H H 2-Pr OMe oil 2.10. H H 2-Pr OH 2.11. H H cyclo-Pr OMe oil 2.12. H H t-Bu OMe oil 2.13. H H t-Bu OH 2.14. H H Ph OMe oil 2.15. H H CH 2 Ph OMe oil 2.16. H H 2-thiophenyl OMe oil 2.17. H H COOMe OMe oil 2.18. H H o- OH oil 0 2.19. H H 0- OMe oil 0 WO 99/32464 PCT/EP98/08335 - 39 No R, R2 R 3 A Phys.data m.p.

0 C 2.20. H H OH 00D 2.21. H H sOH 2.22. H H s- OH

S

2.23. H H s- OH S 2.24. H H o OMe 2.25. H H CHO OMe oil 2.26. H H CH 2 0H OMe solid 2.27. H H CH 2 CI OMe oil 2.28. H H CH 2 Br OMe 2.29. H H CH 2 F OMe 2.30. H H CH 2 NHCOO- OMe t-Bu 2.31. H H CH 2 NEt 2 OMe 2.32. H H CH 2

NH

2 OMe 2.33. H H CH 2 NHOH OMe 2.34. H H CH=CH 2 OMe 2.35. H H CH=CHCOOMe OMe 2.36. H H CH=CHMe OMe 2.37. H H CH=CBr 2 OMe 2.38. H H CHOHMe OMe 2.39. H H CHOHEt OMe 2.40. H H CHOHCIMe OMe 2.41. H H CHOHFMe OMe 2.42. H H CHOHBrMe OMe WO 99/32464 PCT/EP98/08335 -40 No R, R2 Ra A Phys.data m.p.°C 2.43. H H CH=CF 2 OMe 2.44. H H COEt OMe 2.45. H H CHOHMe OMe 2.46. H H CHCIMe OMe 2.47. H H CHFMe OMe 2.48. H H CHBrMe OMe 2.49. H H 4-Cl-Ph OMe 2.50. H H 3-MeO-Ph OMe 2.51. H H 2,4-Me 2 -Ph OMe 2.52. H H --- = H OMe 2.53. Br H COHMe 2

OCH

2 Ph 2.54. Br H COHEt 2 OH 2.55. F H Et OCH 2 Ph 2.56. CI H Et OH 2.57. CI H n-Pr OCH 2 Ph 2.58. Me H 2-Pr OMe 2.59. Et H cyclo-Pr OH 2.60. Et H t-Bu OMe 2.61. Pr H t-Bu OMe 2.62. Pr H Ph OH 2.63. nBu H CH 2 Ph OMe 2.64. nBu H 2-thiophen OMe 2.65. CH 2

CH=CH

2 H COOMe OH 2.66. CH 2 Ph H o- OMe 0 2.67. CH 2 Ph H 0- OMe 0 2.68. COOMe H 0 OMe 11, 0 WO 99/32464 PCT/EP98/08335 -41 No R, R 2

R

3 A Phys.data m.p.

0 C 2.69. CH 2 COOH H s OMe 2.70. NH 2 H s- OMe s 2.71. NH 2 .HCI H s OCH 2 Ph S 2.72. NEt 2 H OH 2.73. NHCH 2 Ph H CHO OCH 2 Ph 2.74. Me H CH 2 OH OH 2.75. Me H CH 2 CI OCH 2 Ph 2.76. OH H CH 2 Br OMe 2.77. OH H CH 2 F OH 2.78. OAc H CHCI 2 OMe 2.79. ci H H OMe

OCO

2.80. OMe H Me OH 2.81. OSi-t-BuMe 2 H Me OMe 2.82. OH H Et OMe 2.83. OH H Et OH 2.84. OH H Et OMe 2.85. OH H n-Pr OMe 2.86. s CF3 CF 3 2-Pr OMe 2.87. s cF3 Ph 2-Pr OMe N COOMe 2.88. Ri+R 2 =0 CH 2 Br cyclo-Pr OMe WO 99/32464 PCT/EP98/08335 -42 No R 1

R

2 Ra A Phys.data m.p.oC 2.89. R oR2 /0OH t-Bu OMe 2.90. H H cyclo-Pr OCH 2 Ph oil Table 2.B Compounds of the formula

R

1 R 2 /S CO-A N \I Rz CI wherein R 1 , R 2 , R 3 and A have the meanings of the corresponding compounds of Table 2.A. Table 2.C Compounds of the formula

R

1

R

2 /S CO-A N\\ N R 3 wherein R 1 , R 2 , R 3 and A have the meanings of the corresponding compounds of Table 2.A. Phys. data of compounds of Table 2.C: No. R, R2 Ra A Phys.data m.p.°C 2.C.3 H H Me OCH 2 Ph oil 2.C.5 H H Et OCH 2 Ph oil 2.C.7 H H Et OH oil 2.C.20 H H o OH solid 2.C.90 H H cyclo-Pr OCH 2 Ph oil WO 99/32464 PCT/EP98/08335 -43 Table 3.A R 1 R 2 _ S R Cl Nj

R

3 No. R, R 2 + Z Ra Phys. data m.p.OC 3.1. H CF 3 159-61OC Me H HO o o 3.2. R+R2+Z Me H H CF 3 oil 0 0 3.3. H eMe CF 3 solid 0 Me .I I o 0 3.4. H Me Me CF 3 solid o 0 3.5. H Me Me CF 3 y NH o 3.6. H Me Me CF 3 o 0 0 WO 99/32464 PCT/EP98/08335 -44 No. R, R 2 + Z

R

3 Phys. data m.p.OC 3.7. H e Me CF 3 H O Me S NH 0 3.8. H Me me

CF

3 N ee 0O 0 3.19. H Me Me CF 3 e H H HO--- O 3.12. H N Me .HM y NH 0 3.10. H Me Me CF 3 o 0 3.14. H Me H Et o O 0 0 3.12. H H H Me R1+R2+Z Me M0 3.13. H Me MeEt OH M 0IMe 0 3.14. H Me Me Et 0 WO 99/32464 PCT/EP98/08335 - 45 No. R, R 2 + Z

R

3 Phys. data m.p.

0 C 3.15. H Me Me Et oX I -ryNH o 3.16. H Me Me n-Pr o y0 3.17. H Me Me 2-Pr OMe / NH 0 3.18. H Me me 2-Pr H H N Me /' O 0 3.19. H Me Me cyclo-Pr HH NI Me S NH 0 3.20. H Me Me t-Bu S NH 0 WO 99/32464 PCTIEP98/08335 -46 Table 3.B Compounds of the formula

R

2 S/ Sz tR3 CI cl wherein R 1 , R 2 , R 3 and Z have the meanings of the corresponding compounds of Table 3.A. Table 3.C Compounds of the formula R R2 /:: z N\ I N a R3 wherein R1, R2, R3 and Z have the meanings of the corresponding compounds of Table 3.A.

WO 99/32464 PCT/EP98/08335 -47 Table 4.A R

R

2 S z

R

4 Z N) S

R

3 No. R 1

R

2

R

3 R4 Z Phys.data m.p.°C 4.1. H H CF 3 Ph COOMe oil 4.2. H H Me CF 3 COOH 4.3. H H CF 3 H COOH 4.4. H H CF 3 H COOMe oil 4.5. H H Me H COOEt solid 4.6. R,+R 2 =0 Me H COOEt solid 4.7. Ri+R 2 =O Me NHCOOEt COOEt solid 4.8. R,+R 2 =0 Me NHn-Bu COOEt solid 4.9. R,+R 2 =0 Me NHt-Bu COOEt solid 4.10. H H Me NHMe COOEt solid 4.11. H H Me NHCH 2

CH=CH

2 COOH solid 4.12. H H Et NH-t-Bu COOEt solid 4.13. H H Ph p-PhSO 2

NH

2 COOEt solid 4.14. H H p-CIPh NHPh COOEt solid 4.15. H H OH OH COOH solid 4.16. R,+R 2 =0 Me NH-COOEt COSMe 4.17. R 1

+R

2 =0 Me NH-n-Bu COSMe 4.18. R,+R 2 =0 Me NH-t-Bu COSMe 4.19. H H CF 3

CF

3 COSMe 4.20. H H CF 3 OMe COOMe 4.21. H H CF 3 OEt COOMe 4.22. H H CF 3 O-n-Pr COOMe 4.23. H H CF 3 SMe COOMe 4.24. H H CF 3 SEt COOMe WO 99/32464 PCT/EP98/08335 -48 No. R 1

R

2

R

3 R4 Z Phys.data m.p.OC 4.25. H H CF 3 SPh COOMe 4.26. H H CF 3 NMe 2 COOMe 4.27. H H CF 3 NEt 2 COOMe 4.28. H H CF 3

NH

2 COOMe 4.29. H H CF 3 SH COOMe 4.30. H H CF 3

NH

2 CSOMe 4.31. H H Me Cl Nsolid N-N 4.32. H H CF 3 Ph CSOMe 4.33. H H Me CF 3 CSOH 4.34. H H CF 3 H CSOH 4.35. H H CF 3 H CSOMe 4.36. H H Me H CSOEt 4.37. R 1

+R

2 =S Me H COOEt 4.38. R 1

+R

2 =S Me NHCOOEt COOEt 4.39. R 1

+R

2 =S Me NH-n-Bu CSOEt 4.40. R 1

+R

2 =S Me NH-t-Bu CSOEt 4.41. H H Me NHMe CSOEt 4.42. H H Me NHCH 2

CH=CH

2 CSOH 4.43. H H Et NHt-Bu CSOEt 4.44. H H Ph p-PhSO 2

NH

2 CSOEt 4.45. H H p-CIPh NHPh CSOEt 4.46. H H OH OH CSOH 4.47. R 1

+R

2 =0 Me NH-COOEt CSSMe 4.48. R 1

+R

2 =0 Me NHn-Bu CSSMe 4.49. R,+R 2 =S Me NHt-Bu CSSMe 4.50. H H Et CF 3 COSMe 4.51. H H Et OMe COOMe 4.52. H H n-Pr OEt COOMe 4.53. H H i-Pr n-Pr COOMe 4.54. H H OH SMe COOMe WO 99/32464 PCT/EP98/08335 -49 No. R 1

R

2 Ra F Z Phys.data m.p.oC 4.55. H H OH SEt COOMe 4.56. H H CF 3 SPh CONHMe 4.57. H H CF 3 NMe 2 CONHMe 4.58. H H CF 3 NEt 2 CONHMe 4.59. H H CF 3

NH

2 CSNHMe 4.60. H H CF 3 SH CSNHMe 4.61. H H CF 3 CSNHMe Table 4.B Compounds of the formula

R

1 R 2 S z N

R

3 R4 wherein R 1 , R 2 , R 3 , R 4 and Z have the meanings of the corresponding compounds of Table 4.A. Table 4.C Compounds of the formula

R

1

R

2 S z N N: RN 3 wherein R 1 , R 2 , R 3 and Z have the meanings of the corresponding compounds of Table 4.A. Formulation Examples for similar purposes of pesticidal use are descibed for example in WO 97/33890.

WO 99/32464 PCT/EP98/08335 -50 Biological Examples Example B.1: Immunization of Cucumis sativus L. against Colletotrichum laqenarium a) After a cultivation period of 2 weeks, cucumber plants are sprayed with a spray mixture prepared from a wettable powder formulation of the test compound (concentration: 200 ppm). After 72 hours, the plants are infected with a spore suspension (1.0 x 10 s spores/ml) of the fungus and incubated for 30 hours at high humidity and a temperature of 230C. Incubation is then continued at normal humidity and 220C to 230C. Evaluation of protective action is made 7 to 8 days after infection and is based on fungus infestation. b) After a cultivation period of 2 weeks, cucumber plants are treated by soil application with a spray mixture prepared from a wettable powder formulation of the test compound (concentration: 20 ppm, based on the volume of the soil). After 72 hours, the plants are infected with a spore suspension (1.5 x 105 spores/ml) of the fungus and incubated for 30 hours at high humidity and a temperature of 230C. Incubation is then continued at normal humidity and 220C. Evaluation of protective action is made 7 to 8 days after infection and is based on fungus infestation. Compounds of the Tables exhibit good activity in tests (a) and (b) and reduce fungus infestation to 0 to 20 %. On the other hand, Colletotrichum infestation is 90 % on untreated and infected control plants. c) Comparison test: Direct action against Colletotrichum lagenarium The formulated active ingredient is mixed in various concentrations (100, 10, 1, 0.1 ppm) with autoclaved and cooled nutrient medium containing 10 000 spores per ml and is poured into microtitre plates. Incubation is then carried out at 220C in the dark. After 2 to 3 days, fungus growth is measured by spectrophotometry. With compounds of the Tables, no inhibition of fungus growth is observed; on the other hand, when the fungicide "Benomyl" (commercial product) is used as comparison substance at 0.2 ppm, 50 % inhibition (ECso) of fungus growth occurs.

WO 99/32464 PCT/EP98/08335 -51 Example B.2: Action against Phytophthora infestans on tomato plants a) After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture prepared from a wettable powder formulation of the test compound (0.02 % active ingre dient). After 72 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 5 days at 90-100 % relative humidity and 200C. Compounds of the Tables exhibit good activityin the tests and reduce fungus infestation to 0 to 20 %. On the other hand, Phytophthora infestation is 60 % on untreated and infected control plants. Example B.3: Action against Pyricularia oryzae on rice plants 2-week-old rice plants are watered with a spray mixture prepared from a wettable powder formulation of the test compound (0.006 % active ingredient, based on the volume of the soil). The pots are then filled with water until the lowermost parts of the stems of the rice plants are standing in water. After 96 hours, the treated rice plants are infected with a conidia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 5 days at 95-100 % relative humidity and approximately 240C. In comparison with untreated control plants (100 % infestation), fungus infestation on rice plants treated with a spray mixture comprising a compound of the Tables as active ingre dient is only approximately 50 %. Example B.4: Action against Cercospora nicotina on tobacco plants a) Foliar application Tobacco plants (8 weeks old) are sprayed with a formulated solution of the test compound (concentration: 0.02 % active ingredient). Four days after treatment, the plants are inocu lated with a sporangia suspension of Cercospora nicotina (150 000 spores/ml), kept for 5 days in the dark at 250C and high humidity and then incubated further under a normal day/night sequence. Evaluation of the symptoms in the tests is based on the leaf surface infested with fungus. Infestation is approximately 60 % on the control plants; on plants treated with compounds of the Tables, infestation is 0 to 30 %.

WO 99/32464 PCT/EP98/08335 - 52 Example B.5: Action against Erysiphe graminis on wheat Protective action: 18-day-old wheat plants are sprayed with a formulated solution of the test compound (0.02 % active ingredient). Immediately after the treatment the plants are incuba ted under cylinders. 24 hours later, the plants are covered. After a further 3 days, the treated plants are cut off above the primary leaf. The primary leaves are arranged horizon tally and are inoculated in a dusting bell with Erysiphe graminis spores (spore density: 0.2 mg/m 2 ). The test is carried out in a climatic chamber with 12 hours of light (18 KLux), at 20 0 C and 12 hours of darkness, at 180C. Infestation is evaluated 9 and 13 days after inoculation. Compounds of the Tables exhibit good activity in the tests and reduce fungus infestation to 0 to 20 %. On the other hand, Erysiphe infestation is 70 % on untreated and infected control plants.

Claims

1. A process for protecting and immunizing plants against attack by phytopathogenic microorganisms which comprises applying a compound of formula I as active ingredient to the plants, to parts of the plants and/or to the locus of the plants R 1 R 2 , S Z R3 wherein a) X is CR 4 and Y is N; or b) X is N and Y is CR 5 ; or c) X and Y are N; and wherein Z is a C 1 -group to which 1-3 halogen atoms or 1-3 unsubstituted or substituted hetero atoms selected from the group O, S and N are bonded; R 1 and R 2 are independently H, OH, SH, CN, COOH, NO 2 , NH 2 , halogen, Cl-C 6 alkyl, haloC 1 -C 6 alkyl, alkoxyC,-C 6 alkyl, aminoC-C 6 alkyl, alkoxaminoC,-C 6 alkyl, C 1 -C 6 alkoxy, halo Cs-C 6 alkoxy, Cl-C 6 alkanoyloxy, aroyloxy, C 1 -C 6 alkoxycarbonyl, aryloxycarbonyl, benzyloxy carbonyl, C 1 -C 6 alkylcarbonyl, arylcarbonyl, benzylcarbonyl, aminocarbonyl, Cl-C 6 alkylamino carbonyl, Cl-C 6 dialkylaminocarbonyl, C 1 .C 6 alkylthio, haloC,-C 6 alkylthio, Cl-C 6 alkylsulfinyl, haloC 1 -C 6 alkylsulfinyl, CI-C 6 alkylsulfonyl, haloC 1 -C6alkylsulfonyl, arylsulfinyl, arylsulfonyl, C 2 -C 6 alkenyl, haloC 2 -C 6 alkenyl, C 2 -C 6 alkinyl, carboxyC 1 -C 6 alkyl, alkoxycarbonylCl-C 6 alkyl, haloalkoxycarbonylCl-C 6 alkyl, C 3 -C 6 cycloalkyl, alkanoylCl-C 6 alkyl, alkylcarbonyloxy C 1 -C 6 alkyl, phenylcarbonyloxyC-C 6 alkyl, C 1 -C 6 alkylamino, C 1 -C 6 dialkylamino, C 2 -C 6 alkenylamino, Cl-C 6 alkanoylamino, Cl-C 6 alkoxycarbonylamino, benzylamino, benzoylamino, benzyloxyarbonylamino, phenyl, phenoxy, benzyl or phenethyl, wherein all the aromatic groups are unsubstituted or substituted from 1 to 5 substituents independently selected from halogen, hydroxy, Cl-C 4 alkyl, halo-C 1 -C 2 alkyl, C 1 -C 2 alkoxy, halo-CI-C 2 alkoxy and nitro; or optionally substituted heterocyclyl; or tri(Cj-C 6 alkyl)silyl or tri(C 1 -C 6 alkyl)silyloxy; with the proviso that R, and R 2 are not simultaneously a group selected from OH, SH, NO 2 , NH 2 , Cl-C 6 alkylamino, C 1 -C6dialkylamino and C 2 -C 6 alkenylamino; or WO 99/32464 PCT/EP98/08335 -54 R 1 and R 2 together are =0 or =S; or R 1 and R 2 together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 8 membered isocyclic or heterocyclic ring; or R 2 and Z together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 7 membered lactone, lactame, thiolactone or thiolactame, which ring may have 1 to 2 additional hetero atoms selected from the group O, S and N; R 3 , R 4 and R 5 are independently H, OH, SH, CN, NO 2 , NH 2 , halogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, hydroxyC 1 -C 6 alkyl, alkoxyC-C 6 alkyl, aminoC,-C 6 alkyl, alkoxaminoC 1 -C 6 alkyl, Cl-C 6 alkoxy, C-C 6 alkylthio, haloC 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, haloC,-C 6 alkylsulfinyl, C1-C 6 alkylsulfonyl, haloC 1 -C 6 alkylsulfonyl, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, haloC 2 -C 6 alkenyl, C 2 -C 6 alkinyl, carboxyC 1 -C 6 alkyl, Cl-C 6 alkanoyl, C 1 -C 6 alkoxycarbonyl, alkoxycarbonyl C,-C 6 alkyl, haloalkoxycarbonylCl-C 6 alkyl, C 3 -C 6 cycloalkyl, alkanoylC 1 -C 6 alkyl, alkylcarbonyloxyC,-C 6 alkyl, phenylcarbonyloxyCj-C 6 alkyl, Cl-C 6 alkylamino, C 1 -C 6 dialkylamino, C 2 -C 6 alkenylamino, Cl-C 6 alkanoylamino, C 1 -C 6 alkoxycarbonylamino, benzylamino, benzoylamino, phenyl, phenoxy, benzyl or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, hydroxy, C 1 -C 4 alkyl, halo-C-C 2 alkyl, C-C 2 alkoxy, halo-Cl-C 2 alkoxy and nitro; or optionally substituted heterocyclyl.

2. A compound of formula I R 1 R 2 ,/S z Y R3 wherein a) X is CR 4 and Y is N; or b) X is N and Y is CRs; or c) X and Y are N; and wherein Z is a C 1 -group to which 1-3 halogen atoms or 1-3 unsubstituted or substituted hetero atoms selected from the group O, S and N are bonded; R 1 and R 2 are independently H, OH, SH, CN, COOH, NO 2 , NH 2 , halogen, Cl-C 6 alkyl, haloC 1 -C 6 alkyl, alkoxyC,-C 6 alkyl, aminoC 1 -C 6 alkyl, alkoxaminoC,-C 6 alkyl, C 1 -C 6 alkoxy, halo- WO 99/32464 PCT/EP98/08335 -55 C 1 -C 6 alkoxy, C 1 -C 6 alkanoyloxy, aroyloxy, Cl-C 6 alkoxycarbonyl, aryloxycarbonyl, benzyloxycarbonyl, Cl-C 6 alkylcarbonyl, arylcarbonyl, benzylcarbonyl, aminocarbonyl, Cl-C 6 alkylaminocarbonyl, C 1 -C 6 dialkylaminocarbonyl, Cl.C 6 alkylthio, haloC,-C 6 alkylthio, Cl-C 6 alkylsulfinyl, haloC 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, haloC 1 -C 6 alkylsulfonyl, arylsulfinyl, arylsulfonyl, C 2 -C 6 alkenyl, haloC 2 -C 6 alkenyl, C 2 -C 6 alkinyl, carboxyC 1 -C 6 alkyl, alkoxycarbonylC 1 -C 6 alkyl, haloalkoxycarbonylCl-C 6 alkyl, C 3 -C 6 cycloalkyl, alkanoylC 1 -C 6 alkyl, alkylcarbonyloxyC 1 -C 6 alkyl, phenylcarbonyloxyC,-C 6 alkyl, C 1 -C 6 alkylamino, Cl-Cedialkylamino, C 2 -C 6 alkenylamino, C 1 -C 6 alkanoylamino, C-C 6 alkoxycarbonylamino, benzylamino, benzoylamino, benzyloxyarbonylamino, phenyl, phenoxy, benzyl or phenethyl, wherein all the aromatic groups are unsubstituted or substituted from 1 to 5 substituents independently selected from halogen, hydroxy, C 1 -C 4 alkyl, halo-C 1 -C 2 alkyl, C1-C 2 alkoxy, halo-C 1 -C 2 alkoxy and nitro; or optionally substituted heterocyclyl; or tri(Cl-C 6 alkyl)silyl or tri(C 1 -C 6 alkyl)silyloxy; with the proviso that R 1 and R 2 are not simultaneously a group selected from OH, SH, NO 2 , NH 2 , C 1 -C 6 alkylamino, Cl-C6dialkylamino and C 2 -C6alkenylamino; or R, and R 2 together are =0 or =S; or R 1 and R 2 together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 8 membered isocyclic or heterocyclic ring; or R 2 and Z together with the carbon atom to which they are bonded are an unsubstituted or substituted 3 to 7 membered lactone, lactame, thiolactone or thiolactame, which ring may have 1 to 2 additional hetero atoms selected from the group O, S and N; R 3 , R 4 and R5 are independently H, OH, SH, CN, NO 2 , NH 2 , halogen, Cl-C 6 alkyl, haloC 1 -C 6 alkyl, hydroxyC,-C 6 alkyl, alkoxyC 1 -C 6 alkyl, aminoC,-C 6 alkyl, alkoxaminoC-C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, haloCl-C 6 alkylthio, Cl-C 6 alkylsulfinyl, haloC 1 -C 6 alkylsulfinyl, Cl-C 6 alkylsulfonyl, haloCl-C 6 alkylsulfonyl, halo-C-C 6 alkoxy, C 2 -C 6 alkenyl, haloC 2 -C 6 alkenyl, C 2 -C 6 alkinyl, carboxyC,-C 6 alkyl, C l -C 6 alkanoyl, C 1 -C 6 alkoxycarbonyl, alkoxycarbonylC 1 -C 6 alkyl, haloalkoxycarbonylCl-Cealkyl, C 3 -C 6 cycloalkyl, alkanoylCl-C 6 alkyl, alkylcarbonyloxyC,-C 6 alkyl, phenylcarbonyloxyC,-C 6 alkyl, C 1 -C 6 alkylamino, C1-C 6 dialkylamino, C 2 -C 6 alkenylamino, C 1 -C 6 alkanoylamino, C 1 -C 6 alkoxycarbonylamino, benzylamino, benzoylamino, phenyl, phenoxy, benzyl or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, hydroxy, C 1 -C 4 alkyl, halo-C 1 -C 2 alkyl, Cl-C 2 alkoxy, halo-C l -C 2 alkoxy and nitro; or optionally substituted heterocyclyl; WO 99/32464 PCT/EP98/08335 - 56 with the exception of the compounds of the formula R OMe S CO-NH-CH 2 -CH 2 / OMe N Cl T wherein a) R 1 is OCO-CH 3 and T is Br, b) R 1 is OH and T is Br, c) R 1 is OH and T is H.

3. A compound according to claim 2 of formula L.A R R2 R 4Z I.A. N N R3

4. A compound according to claim 2 of formula L.B R R2 N S I.B. R5 R3 R 5 WO 99/32464 PCTIEP98/08335 -57 5. A compound according to claim 2 of formula .LC R R2 N I R 3 I.C. N R 3

6. A compound according to claim 2 wherein Z is CN, CO-A, CS-A or CH(ORo 0 ) 2 .; A is hydrogen, halogen, OR 6 , SRT, N(RB)Rg, ON(R 11 )R 1 2 or N(R 13 )OR 1 4 ; R 6 to R 1 4 are independently hydrogen, an unsubstituted or substituted, open-chained, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms, an unsubstituted or substituted, cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstituted or substituted benzyl or phenethyl, an unsubstituted or substituted acyl group containing up to 8 carbon atoms, an unsubstituted or substituted benzoyl group, or an unsubstituted or substituted heterocyclyl radical; or Ra and R 9 , or Rii and R 1 2 , together with the nitrogen atom to which they are bonded, form a 5- or 6-membered, unsubstituted or substituted heterocycle having 1 to 3 hetero atoms selected from O, S and/or N; Rio are identical or different and are Cl-C 6 alkyl that is unsubstituted or substituted by phenyl, Cl-C 2 alkoxy, phenoxy or by benzyloxy; or two substituents ORio, together with the carbon atom to which they are bonded, form a cyclic acetal group that is unsubstituted or substituted by Cl-C 3 alkyl, phenyl, benzyl, hydroxy or by Cl-C 3 hydroxyalkyl.

7. A compound according to claim 2 wherein Ri is H, OH, NH 2 , halogen, COOH, C-C 4 alkyl, haloCi-C 4 alkyl, C-C 4 alkoxy, Cj C 4 alkanoyloxy, aroylyloxy, Cl-C 4 alkoxycarbonyl, aryloxycarbonyl, benzyloxycarbonyl, C-C 4 alkylcarbonyl, arylcarbonyl, benzylcarbonyl, aminocarbonyl, C 1 -C 4 alkylaminocarbonyl, C-C 4 dialkylaminocarbonyl, alkanoylC 1 -C 4 alkyl, alkylcarbonyloxyC,-C 4 alkyl, C 2 -C 4 alkenyl, haloC 2 -C 4 alkenyl, C-C 4 alkylamino, C-C 4 dialkylamino, C 1 -C 4 alkanoylamino, Cj C 4 alkoxycarbonylamino, benzylamino, benzoylamino, phenyl, phenoxy, benzyl or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents WO 99/32464 PCT/EP98/08335 -58 independently selected from halogen, hydroxy, Cl-C 4 alkyl, halo-C 1 -C 2 alkyl, C 1 -C 2 alkoxy, halo-C,-C 2 alkoxy and nitro; R 2 is H, OH, C,-C 4 alkyl, C 1 -C 4 alkoxy or phenyl; or R 1 and R 2 together are a group selected from R ,8 , R ,8 R ,7 O N - R 9 'le or R 2 +Z together are a group selected from R 17 R 18 R 17 R R R H H O 1< R 1-N O O 0 17 0"- O SOR 1 HO O O OO 0 0 0 0 wherein R 1 7 , R 18 and R 19 are independently H or C 1 -C 4 alkyl; R 3 is H, halogen, C,-C 6 alkyl, haloCl-C 6 alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 alkoxycarbonyl, phenyl which is unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, C,-C 4 alkyl, halo-C,-C 2 alkyl, C 1 -C 2 alkoxy, halo-C-C 2 alkoxy, amino, C 1 -C 4 alkylamino, C 1 -C 4 dialkylamino, benzylamino, C 1 -C 4 alkanoylamino, benzoylamino, Cl-C 4 alkoxycarbonylamino, formyl, or a 4-7-membered cyclic or C 1 -C 4 alkyl open-chained acetal or thioacetal thereof; R 4 is H, OH, halogen, amino, C,-C 6 alkyl, C,-C 4 alkylamino, C-C 4 alkenylylamino, Cl-C 4 dialkylamino, benzylamino, C 1 -C 4 alkanoylamino, benzoylamino, C 1 -C 4 alkoxycarbonylamino.

8. A compound according to claim 3 of formula L.A WO 99/32464 PCT/EP98/08335 - 59 R 1 R2 R 4 Z I.A N R R3 wherein Z is CO-A; A is hydrogen, OR 6 , SR 7 , N(Ra)Rg; R 1 is H, OH, halogen or C 1 -C 4 alkyl, R 2 is H; R 3 is H, OH, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, haloCI-C 6 alkyl, C 1 -C 6 alkoxy or haloC 1 -C 6 alkoxy, formyl, or a 4-7-membered cyclic or C 1 -C 4 alkyl open-chained acetal or thioacetal thereof; R 4 is Cl; R 6 , R 7 , R 8 and R 9 are independently H, C 1 -C 6 alkyl, haloC,-C 6 alkyl, Cl-C 6 alkoxy, haloC,-C 6 alkoxy, Cl-C 4 alkoxycarbonyl, Cl-C 4 alkanoylCs-C 4 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkylmethyl, phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, C 1 -C 4 alkyl, halo-C 1 -C 2 alkyl, C 1 -C 2 alkoxy, halo-Cl-C 2 alkoxy.

9. A process for the preparation of a compound of formula 1.1 S- CH2Cl ,s CH 2 -COOH R 3 R3

11.1 1.1 wherein X, Y and R 3 are as defined for formula I, which comprises reaction of a compound of formula 11.1 with carbon monoxide under pressure of 2-20 bars in presence of a catalyst. 10. A composition for protecting and immunizing plants against attack by microorganisms, comprising a compound of formula I of claim 1 together with a suitable carrier. WO 99/32464 60 PCT/EP98/08335 AMENDED CLAIMS [received by the International Bureau on 09 June 1999 (09.06.99); original claims 2 and 10 amended; remaining claims unchanged (4 pages)] A) with the exception of the compounds of the formula Ri Me S CO-NH-CH 2 -CH 2 j Me C1 < N Cl T wherein a) R 1 is OCO-CH 3 and T is Br, b) R 1 is OH and T is Br, c) R 1 is OH and T is H; and B) with the exception of thiadiazole derivatives having the formula A-B R' N wherein R' is methyl or phenyl, H 3C A is OH 2 , CHCI, CHCH 3 , C(0H 3 ) 2 , CH-C 6 H 5 , , and B is CHO, CN, COOH, COOCH 3 , COOC 2 H 5 , COOC 3 H 7 (iso), COOC 8 H 17 (n), COOCH 2 CH=CH 2 , CONH 2 , CONHCH 3 , CONHC 3 H7(iso), CON(CH 3 ) 2 , pyrrolidinoyl, morpholinoyl, 4-methoxicarbonyl-piperazinoyl, 4-oxo-piperidinoyl, CH(SCH 3 )(SOCH 3 ), CONH-C6H 4 -OCH 3 (4) or CON(CH 3 )C 6 H 5 ; WO 99/32464 61 PCT/EP98/08335 and C) with the exception of thiazolyl derivatives having the formula R22 R 2 3 G 2 A N CH 3 CH 2 -CH 2 -O-CO C 3 ,H (iso) R 20 S O N R 2 1 wherein R 20 is hydrogen, CH 3 , C 2 H 5 , R 21 is hydrogen, CH 3 , C 2 H 5 , R 22 is hydrogen, C1-C 3 alkyl, n-C 4 H 9 , CI or Br, R 2 3 is hydrogen, CH 3 , C 2 Hs, or R 2 2 and R 23 together with the ring to which they are attached form a condensed six membered carbocyclic aromatic ring which may be monochlorinated, and G represents CH or N; and D) with the exception of 7-(1,2,3-thiadiazolyl-5-acetamido)-3-(5-methyl-1,3,4-thiadiazol-2 ylthiomethyl)-3-cephem-4-carboxylic acid. 3. A compound according to claim 2 of formula L.A R 1 R2 S R. L.A. N R 3 WO 99/32464 62 PCT/EP98/08335 4. A compound according to claim 2 of formula I.B. R 1 R2 N R3 R 5 WO 99/32464 63 PCT/EP98/08335 63 R 1 R 2 R 4 Z I.A NR3 wherein Z is CO-A; A is hydrogen, OR 6 , SR 7 , N(R 8 )R 9 ; R 1 is H, OH, halogen or C 1 -C 4 alkyl, R 2 is H; R 3 is H, OH, C 1 -C 6 alkyl, C3-C 6 cycloalkyl, haloC 1 -C 6 alkyl, Cl-C 6 alkoxy or haloC 1 -C 6 alkoxy, formyl, or a 4-7-membered cyclic or C 1 -C 4 alkyl open-chained acetal or thioacetal thereof; R 4 is Cl; R 6 , R 7 , R 8 and R 9 are independently H, C 1 -C 6 alkyl, haloC 1 -C 6 alkyl, C 1 -C 6 alkoxy, haloC 1 -C 6 alkoxy, C1-C4alkoxycarbonyl, C1-C 4 alkanoylC 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C3-C6cycloalkylmethyl, phenyl, benzyl, or phenethyl, the phenyl rings of which are unsubstituted or substituted from 1 to 3 substituents independently selected from halogen, C 1 -C 4 alkyl, halo-C 1 -C 2 alkyl, C1-C 2 alkoxy, halo-Cl-C 2 alkoxy. 9. A process for the preparation of a compound of formula 1.1 S CH 2 CI CH 2 -COOH y R 3 R 3 11.1 1.1 wherein X, Y and R 3 are as defined for formula I, which comprises reaction of a compound of formula 11.1 with carbon monoxide under pressure of 2-20 bars in presence of a catalyst. 10. A composition for protecting and immunizing plants against attack by microorganisms, comprising a compound of formula I of claim 2together with a suitable carrier. WO 99/32464 PCT/EP98/08335 64 STATEMENT UNDER ARTICLE 19 The amendments effected in claim 2 will restore the novelty by way of disclaimer. They take the following references of the International Search Report into account: - WO 98 14437 A (NIHON NOHYAKU Co., Ltd.) Examples 307 to 321, 325, 327 to 331, 335, 336, 347, 383, 384 and 385 (identical to 422); [disclaimer B] - DE 19 53 861 A (Fujisawa Pharmaceutical Co. Ltd.) Example 16, which is identical to DE 22 62 262, example 65; [disclaimer D] - DE 22 62 262 A (Fujisawa Pharmaceutical Co. Ltd.) Example 65, which is identical to DE 19 53 861 A, example 16; [disclaimer D] - EP 0 213 079 A (Ciba-Geigy AG) Compounds Nos. 1.01 to 1.22, 1.50 to 1.54, 3.01 to 3.22, 3.58 and 3.59. [disclaimer C]