PYRROLECARBOXAMIDES AND PYRROLETHIOAMIDES AS FUNGICIDES The present invention relates to novel substituted pyrrolecarboxamides or pyrrofethioamides which have microbicidal activity, in particular fungicidal activity. The invention also relates to the preparation of these substances, 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 and horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

The pyrrolecarboxamides (thioamides) of the present invention have the general formula I wherein X is oxygen or sulfur ; R, is C1-C4alkyl unsubstituted or substituted, with the exception of CF3 ; C3-C6cycloalkyl unsubstituted or substituted ; or halogen ; R2 is hydrogen, C,-C4alkyl unsubstituted or substituted, C,-C4alkoxy unsubstituted or substituted, cyano or halogen ; R3 is C1-C4alkyl unsubstituted or substituted ; and A is orthosubstituted aryl ; orthosubstituted heteroaryl ; bicycloaryl unsubstituted or substituted ; or bicycloheteroaryl unsubstituted or substituted.

Surprisingly, it has now been found that the compounds of formula (I) exhibit improved biological properties which render them more suitable for the practical use in agriculture and horticulture.

Where asymmetrical carbon atoms are present in the compounds of formula 1, these compounds are in optically active form. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e. g. mixtures of diastereomers, racemates or mixture of racemates.

Within the present specification alkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, isobutyl and tert-butyl. Non-branched alkyl is preferred. Alkyl as part of other radicals such as alkoxy, haloalkyl, alkylcycloalkyl, alkylcycloalkoxy, etc. is understood in an analogous way. Halogen will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings. Halogen as part of other radicals such as haloalkyl, haloalkoxy, haloalkenyl, haloalkenyloxy, haloaryl or haloheteroaryl, etc. is understood in an analogous way. Haloaryl or haloheteroaryl designates mono-to five times halo-substituted aryl, whereby the halogens are independently chosen. Where more than two halogens are present, the halogens are preferably the same, e. g. trifluorophenyl, trichlorophenyl, tetrachlorophenyl or perchlorophenyl.

Haloalkyl is a monohalogenated to perhalogenated alkyl radical, such as, inter alia, fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2, 2, 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2, 2, 2- trichloroethyl, 3, 3, 3-trifluoropropyl.

Haloalkoxy is a monohalogenated to perhalogenated alkoxy radical, such as, inter alia, OCH2F, OCHF2, OCF3, OCHFCH3, OCH2CH2Br, OCF2CHFCI.

Substituted alkyl will be understood as for example haloalkyl, alkoxy-alkyl, haloalkoxy-alkyl.

Cycloalkyl is, depending on the ring size, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Substituted cycloalkyl will be understood for example as alkyl-cycloalkyl, haloalkyl-cycloalkyi, alkoxy-cycloalkyl, haloalkoxy-cycloalkyl, halo-cycloalkyl, alkoxyalkyl- cycloalkyl, haloalkoxyalkyl-cycloalkyl.

Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl or but-2-en1-yl. Preferred alkenyl radicals contain 3 to 4 carbon atoms in the chain.

Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl or but-1-yn-3yl.

Aryl is phenyl or naphthyl.

Heteroaryl will be understood as a 5-to 10membered ring that may contain up to 3 heteroatoms, such as nitrogen, oxygen or sulfur. The following list of examples is not exhaustive : furyl, thienyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrrolyl, dithiolyl, oxathiolyl, dioxazolyl, <BR> <BR> <BR> oxathiazolyl, oxathiolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl,<BR> <BR> <BR> <BR> <BR> <BR> benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyi, quinoxalinyl, quinazolinyl, cinnolinyl, naphthyridinyl, isobenzofuranyl, isoindolyl, benzothiadiazolyl, benzisoxazolyl, benzothienyl, purinyl, 5, 6-dihydro-1, 4, 2-dioxazinyl, and the like.

Bicycloaryl or bicycloheteroaryl will be understood as a 6-membered aryl or 6-membered heteroaryl ring, wherein it may contain up to 3 heteroatoms such as nitrogen, oxygen or sulfur, and which is fused to an additional ring. The fused ring may be aromatic, partially hydrogenated or completely saturated and may be a ring from 5 to 7 ring members, of which up to 3 members may be heteroatoms selected from he group nitrogen, oxygen and sulfur.

The following list of examples is not exhaustive : dihydroisobenzofuranyl, dihydroisoindolyl and the like.

Substituted aryl, substituted heteroaryl, substituted bicycloaryl or substituted bicycloheteroaryl will be understood as substituted by, inter alia, cycloalkyl, cycloalkenyl, cycloalkadienyl, phenyl, heteroaryl, cyano, nitro, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl.

Preferred embodiment of compounds of formula I are those wherein X is oxygen or sulfur ; or X is oxygen ; or X is sulfur ; or R, is C,-C4alkyl unsubstituted or substituted, with the exeption of CF3 ; C3-C6cycloalkyl unsubstituted or substitited ; or halogen ; or R, is C1-C4alkyl ; C,-C4haloalkyl ; C1-C4alkoxy-C1-C4alkyl ; C1-C4haloalkoxy-C1-C4-alkyl ; C3-C6cycloalkyl unsubstituted or substituted by C,-C4alkyl, C1-C4haloalkyl, C,-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxy-C1-C4alkyl or halogen ; or halogen ; or R, is C1-C3alkyl ; C1-C4haloalkyl ; C3-C6cycloalkyl unsubstituted or substituted by C1-C3alkyl, C1-C4haloalkyl or halogen ; or R, is C,-C2alkyl, C1-C3haloalkyl or cyclopropyl ; or R, is methyl, ethyl, CFH2 or CF2H ; or R2 is hydrogen, C1-C4alkyl C1-C4haloalkyl, C1-C4alkoxy, C1-C4aloalkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxy-C1-C4alkyl, cyano or halogen ; or R2 is hydrogen, C1-C4alkyl or C,-C4haloalkyl ; or R2 is hydrogen or C1-C3alkyl ; or R2 is hydrogen ; or R3 is C1-C4alkyl unsubstituted or substituted ; or R3 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl or C1-C4haloalkoxy-C1-C4alkyl; or R3 is C1-C4alkyl, C1-C3haloalkyl or C,-C3alkoxy-C,-C3alkyl ; or R3 is C1-C3alkyl or C1-C3alkoxy-C1-C3alkyl ; or R3 is methyl or CH2OCH3 ; or A is orthosubstituted aryl ; orthosubstituted heteroaryl ; bicycloaryl unsubstituted or substituted ; or bicycloheteroaryl unsubstituted or substituted ; or A is a group or A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20, A21, A22, A24, A25, A26, A27, A29, A31, A32 or A33 ; or A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27, A31 or A33 ; or A is A31 or A33 ; or R4 is C3-C7cycloalkyl, C4-C7cycloalkenyl, C5-C7cycloalkadienyl wherein the cycloalkyl group can be mono-to pentasubstituted by halogen, hydroxy, C1-C4alkyl, C,-C4alkoxy, C,-C4haloalkoxy, C2-C4alkenyl, C2-CSalkynyl, C,-C4haloalkyl ; phenyl unsubstituted or substituted by halogen, nitro, cyano, CHO, C,-C4alkyl, C,-C4alkoxy, C1-C4haloalkoxy, C2-C5alkenyl, C2-C5alkynyl, C1-C4haloalkyl, COOC1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-C1-C4alkoxy, C1-C4haloalkoxy-C1-C4alkyl, C1-C4haloalkyl-C1-C4alkoxy ; thienyl, furyl, <BR> <BR> <BR> <BR> pyrrolyl, pyrazolyl, oxazolyl, thiazolyi, isoxazolyl, isothiazolyl, thiadiazolyl, imidazolyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C5haloalkyl, C1-C6alkyl, C2-C5alkenyl, C2-C5alknyl, nitro, cyano, hydroxy, CHO, C,-C6alkoxy, COOC1-C6alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxy-C1-C4alkyl or C,-C6haloalkoxy ; or R4 is C5-C7cycloalkyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; C5-C7cycloalkenyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C,-C4alkoxy ; C5-C7cycloalkadienyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C1-C4alkyl, C1-C4alkoxy, C,-C4haloalkoxy, C2-C4alkenyl, C2-C4alkynyl or C1-C4haloalkyl ; phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy or C,-C4haloalkyl ; thienyl, furyl, oxazolyl, isoxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4haloalkyl, C,-C4alkyl, hydroxy, C,-C4alkoxy or C1-C4haloalkoxy ; or R4 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono-to disubstituted by chloro, bromo, C1-C2alkyl, C,-C2haloalkyl or C1-C2-haloalkoxy ; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C,-C4alkyl, C1-C4haloalkyl or C,-C4haloalkoxy ; or R4 is phenyl substituted by halogen ; C5-C7cycloalkyl ; or halothienyl ; or Rgjs hydrogen, cyano, nitro, halogen, C1-C4haloalkyl, C,-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxy-C1-C4alkyl, C1-C4alkoxy or C1-C4haloalkoxy ; or R5 is hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy ; or Rs is hydrogen, halogen, C,-C3alkyl, C1-C3haloalkyl, C,-C3alkoxy or C1-C3haloalkoxy ; or R6, R7, R8, Rg and Rio are identical or different and are each independently of the others hydrogen, halogen, C1-C4haloalkyl, C1-C4alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4haloalkoxy or C3-C7cycloalkyl ; or R6, R7, R8, Rg and Rio are identical or different and are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, C,-C4haloalkyl or C1-C4haloalkoxy ; or R6, R7, R8, Rg and Rio are identical or different and are each independently of the others hydrogen or Ci-Cgaikyi.

Within the group of compounds of formula I those compounds are preferred wherein : R, is C,-C4alkyl ; C1-C4haloalkyl ; C1-C4alkoxy-C1-C4alkyl ; C,-C4haloalkoxy-C,-C4alkyl ; C3-C6cycloalkyl unsubstituted or substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxy-C1-C4alkyl or halogen ; or halogen ; R2 is hydrogen, C1-C4alkyi, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxyC1-C4alkyl, cyano or halogen ; R3 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl or C1-C4haloalkoxyC1-C4alkyl; A is a group and R4 is C3-C7cycloalkyl, C4-C7cycloalkenyl, C5-C7cycloalkadienyl wherein the cycloalkyl group can be mono-to pentasubstituted by halogen, hydroxy, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C4alkenyl, C2-C5alkynyl, C1-C4haloalkyl ; phenyl unsubstituted or substituted by halogen, nitro, cyano, CHO, C1-C4alkyl, C,-C4alkoxy, C,-C4haloalkoxy, C2-C5alkenyl, C2 C5alkynyl, C,-C4haloalkyl, COOC,-C4alkyl, C,-C4alkoxy-C,-C4alkyl, Ci-C4alkyl-C,-C4alkoxy, C1-C4haloalkoxy-C1-C4alkyl, C1-C4haloalkyl-C1-C4alkoxy ; thienyl, furyl, <BR> <BR> <BR> <BR> pyrrolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, thiadiazolyl, imidazolyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C6haloalkyl, C1-C6alkyl, C2-C5alkenyl, C2-C5alkynyl, nitro, cyano, hydroxy, CHO, C,-C6alkoxy, COOC,-C6alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4haloalkoxyC1-C4alkyl or C,-C6haloalkoxy ; R5 is hydrogen, cyano, nitro, halogen, C,-C4haloalkyl, C1-C4alkyl C1-C4alkoxy-C1-C4alkyl C1-C4haloalkoxy-C1-C4alkyl, C1-C4alkoxy or C1-C4haloalkoxy ; R6, R7, R8, Rg and Rio are identical or different and are each independently of the others hydrogen, halogen, C1-C4haloalkyo, C1-C4alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4haloalkoxy or C3-C7cycloalkyl (subgroup AA).

Within the group AA of compounds of formula I those compounds are preferred wherein X is oxygen (subgroup AB).

Another group of compounds of formula I within the group AA are those wherein X is sulfur (subgroup AC).

Within the subgroup AB are those compounds preferred wherein R, is C,-C3alkyl ; C1-C3haloalkyl ; C3-C6cycloalkyl unsubstituted or substituted by C1-C3alkyl C1-C3haloalkyl or halogen ; R2 is hydrogen, C1-C4alkyl or C1-C4haloalkyl ; R3 is C,-C4alkyl, C,-C3haloalkyl or C1-C3alkoxy-C1-C3-alkyl ; A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20, A21, A22, A24, A25, A26, A27, A29, A31, A32 or A33 ; R4 is C5-C7cycloalkyl, unsubstituted or mono-to trisubstituted by halogen ; hydroxy, C2-C4alkenyl, C2-C4aikynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; C5-C7cycloalkenyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; C5-C7cyclodialkenyl, unsubstituted or mono-to disubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; thienyl, furyl, isoxazolyl, oxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, which are unsubstituted or substituted by halogen, hydroxy, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy ; phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy ; R5 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy C1-C4haloalkyl or C1-C4haloalkoxy ; and R6, R7, R8, R9 and Rio are identical or different and are each independently of the others hydrogen, C1-C4alkyl, C1-C4akoxy, C1-C4haloalkyl or C,-C4haloalkoxy (subgroup AB1).

Within the subgroup AB1 are those compounds more preferred wherein A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27, A31 or A33 ; R, is C1-C2alkyl C1-C3haloalkyl or cyclopropyl ; R2 is hydrogen or C,-C3alkyl ; R3 is C1-C3alkyl or C1-C3alkoxy-C1-C3alkyl ; R4 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono-to disubstituted by chloro, bromo, C,-C2alkyl, C,-C2haloalkyl or C,-C2haloalkoxy ; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy ; R5 is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy or C,-C3haloalkoxy ; and R6, R7, R8, R9 and Rio are identical or different and are each independently of the others hydrogen or Ci-Csatkyt (subgroup AB2).

Preferred compounds whithin the subgroup AB2 are those compounds wherein R, is methyl, ethyl, CFH2 or CF2H ; R2 is hydrogen ; R3 is methyl or CH2OCH3 ; A is A31 or A33 ; and R4 is halophenyl, C5-C7cycloalkyl or halothienyl (subgroup AB3).

Within the subgroup AC are those compounds preferred wherein R, is C-C3alkyl ; C1-C3haloalkyl ; C3-C6cycloalkyl unsubstituted or substituted by C1-C3alkyl, C,-C3haloalkyl or halogen ; R2 is hydrogen, C1-C4alkyl or Ci-C4haloalkyl ; R3 is Ci-C4alkyl, C,-C3haloalkyl or Ci-C3alkoxy-C,-C3alkyl ; A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20, A21, A22, A24, A25, A26, A27, A29, A31, A32 or A33 ; R4 is C5-C7cycloalkyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; C5-C7cycloalkenyl, unsubstituted or mono-to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; C5-C7cyclodialkenyl, unsubstituted or mono-to disubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C,-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy or C1-C4alkoxy ; thienyl, furyl, isoxazolyl, oxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, which are unsubstituted or substituted by halogen, hydroxy, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy or C,-C4haloalkoxy ; phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy ; R5 is hydrogen, halogen, C,-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C,-C4haloalkoxy ; and R6, R7, Ra, R9 and Rio are identical or different and are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, C,-C4haloalkyl or Ci-C4haloalkoxy (subgroup AC1).

Within the subgroup AC1 are those compounds more preferred wherein A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27, A31 or A33 ; R, is C,-C2alkyl, C1-C3haloalkyl or cyclopropyl ; R2 is hydrogen or C1-C3alkyl ; R3 is C,-C3alkyl or Ci-C3alkoxy-C,-C3alkyl ; R4 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono-to disubstituted by chloro, bromo, C,-C2alkyl, C,-C2haloalkyl or C,-C2haloalkoxy ; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy ; R5 is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy or Ci-Cghafoafkoxy ; and R6, R7, R8, Rg and Rio are identical or different and are each independently of the others hydrogen or C,-C3alkyl (subgroup AC2).

The compounds according to formula I may be prepared according to the following reaction schemes.

A) Synthesis of the pyrrole carboxylic acids : Route 1 (Tosmic-route) : Scheme 1 1) Tosmic/base (NaH or others) -20* to reflux < > 11 11 Coo-c1-c-alkyl 2) R3X N X=leavin rou 3 OH/H20 R wCoOH 0°-reflux + cosolvens (MeOH/EtOH or R other alcohols) Route 2 ("acetoacetic acid"-route, see e. g. EP-326108 ; J. Am. Chem. Soc. 70, 497 (1948) or JP-07157466) Scheme 2 O O 1) HC (OR') 3 ; R'=Cl-C4alkyl 0 0 O O R,-') OC,-C4alkyl Ac2O or other solvents Rr/oC1-C4alkY z I 0°-reflux OR' (mixture of E/Z-isomers is possible) 1) H2NCHR2COOH R1 \ zCOOC-C4alkyl J 2) Ac2O R/N 2) Arc20 R2 I RT-reflux COCH3 Na2CO3 or NaHCO3/H2O COOC1-C¢alkyl (or other weak bases) C 0°-reflux R N H H Base/R3X R1 COOC-C4alkyl 0°-reflux (X=leaving group) 2 1 R3 OH-/H20 R1 \/COOH R'OH/0°-reflux I I (X) R2 R N R3- B) Synthesis of the amides/thioamides, Scheme 3 O s Ri Ri I I NH A l NH R, R2 Lawesson-Reagent R2 I ) z R3 or PSS R3 R3 in CHCI3 or CH2CI2 etc. 3 2) Dioxane or THF 2) base/H2NA or toluene 0°-reflux Base = NEt3, Hünig-base, Na2CO3, K2CO3 and others B1) Synthesis of the amides wherein A is phenyl, pyridine or pyrimidine Scheme 4 COCI HN G I I I NH G solvent, base R2 X R3 = halogen 3 "Pd-catalyst"-system O solvent, base Ri NH (Suzuki-coupling) R3 R4 Zu G = phenyl, pyridine, pyrimidine The"in situ"prepared pyrazole carboxylic acid chloride reacts with an ortho-halosubstituted phenylamine in the presence of a solvent like toluene, benzene, xylene, hexane, cyclohexane, THF, chloroform or methylenechloride and in the presence of a base like sodium carbonate, sodium hydrogencarbonate, potassium carbonate, Honig base, triethylamine or pyridine at a temperature between 0°C and reflux temperature. The obtained pyrazolecarboxamide reacts with a boronic acid of the formula R4-B (OH) 2 in the presence of a Pd-catalyst like Pd (P (phenyl) 3) 4, Pd (P (phenyl3)) 2CIz, PdC12dppb, Pd2 (dba) 3, Pd (OAc) 2, PdOAc2/(o-tolyl) 3P, Pd (OAc) 2/dppf, Pd (PhCN) wCl2/Ph3As, Pd (CH3CN) 2CI2, Pd2 (dba) 3/P (tert. butyl) 3, Pd (OAc) 2/P (tert. butyl) 2biphenyl, Pd (OAc) 2/TPPTS, Pd (OAc) 2/PCy3 Pd (OAc) 2/P (O-i-Pr) 3, Pd (OAc) 2/2-dimethylamino-2'-dicyclohexylphosphinobiphenyl, Pd (OAc) 2/2-dimethylamino-2'-ditert. butylphosphinobiphenyl, Pd (OAc) 2/ (o-biphenyl) P (cyclohexyl) 2 in a solvent like 1, 2-dimethoxyethane/water, DMF, DMA, THF/water, dioxane/water, benzene, toluene, xylene and others and a base like sodium carbonate, sodium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium phosphate, triethylamine, sodium hydroxide, sodium ethylat, sodium tert. butylate, silver oxide, barium carbonate, potassium fluoride or cesium fluoride at a temperature between 0°C and reflux temperature.

B2) Synthesis of pyrrolecarboxamides wherein R, is CF2H Scheme 5 o DAST CH benzene or hexane or CH2CI2 or CF H iVH-A CHCI3 or CICHZCHCI z ('NH-A y J 0°C-reflux K Rs C) Synthesis of the ortho-substituted amines A-NH2 : The compounds are either known from the literature or can be prepared by known methods.

Literature for the synthesis of amine-intermediates and/or amines Al-N H2 : A1-NH2 : Tetrahedron 1993, 49, 49-64 or EP-83975 or J. Org. Chem. 1995, 60, 292 ; A2-NH2 : EP-737682 ; A3-NH2 : J. Chem. Res. (S) 1978, 11, 428 or Chem. Scr. 1972, 2, 245 ; A17-NH2 : Org. Prep. Procedures int. 1989, 21, 141 ; A21-NH2 : J. Chem. Soc. Perkin I 1981, 5, 1591 ; A25-NH2 : Tetrahedron 1993, 49, 49-64 or Heterocycles 1999, 51, 721 ; A26-NH2 : Synthesis 1996, 10, 1015 or Synthesis 1994, 9, 931 ; ~ A27-NH2 : Liebigs Ann. Chemie 1977, 537-544 or J. Med. Chem. 1975, 18, 623 ; A31-NH2 : EP-315502 ; A32-NH2 : J. Pesticide Science 1993, 18, 245 ; A30-NH2 : J. Heterocyclic Chem. 1982, 19, 1285.

The invention relates also to the pyrrolecarboxylic acid of formula X, wherein R,, R2 and R3 have the meaning as defined for formula 1.

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.

The compounds f are, for example, effective against the phytopathogenic fungi of the following classes : Fungi imperfecti (e. g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e. g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e. g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e. g.

Phytophthora, Pythium, Plasmopara). 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, cucum- bers, 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 naturai 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, atomizing, 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 formula- tion technology, e. g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula I 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, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole ; pyrimidinyl carbinole such as ancymidol, fenarimol or nuarimol ; 2-amino- pyrimidine such as bupirimate, dimethirimol or ethirimol ; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph ; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim ; pyrroles such as fenpiclonil or fludioxonil ; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl ; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazofe or thiabendazole ; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin ; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide ; guanidine such as guazatine, dodine or iminoctadine ; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3- methoxyacrylate or 2- [a { [ (a-methyl-3-trifluoromethyl-benzyl) imino]-oxy}-o-tolyl]-glyoxylic acid- methylester-O-methyloxime (trifloxystrobin) ; dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram ; N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid ; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper ; nitrophenol derivatives such as dinocap or nitrothal-isopropyl ; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl ; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenyl-amino-3, 5- dihydroimidazol-4-one (RPA 407213), 3, 5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2- oxopropyl)-4-methylbenzamide (RH-7281), N-allyl-4, 5-dimethyl-2-trimethylsilylthiophene-3- carboxamide (MON 65500), 4-chloro-4-cyano-N, N-dimethyl-5-p-tolylimidazole-1-sulfon- amide (IKF-916), N- (1-cyano-1, 2-dimethylpropyl)-2- (2, 4-dichlorophenoxy)-propionamide (AC 382042), or iprovalicarb (SZX 722).

A preferred method of applying a compound of formula 1, 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 corre- sponding 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, e. g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.

The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

The formulation, i. e. the compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant, are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e. g. 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 1, 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 5 g to 2 kg of active ingredient (a. i.) per hectare (ha), preferably from 10 g to 1 kg a. i./ha, most preferably from 20 g to 600 g a. i./ha.

When used as seed drenching agent, convenient dosages are from 10 mg to 1 g 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.

Temperatures are given in degrees Celsius. The following abbreviations are used : m. p. = melting point ; b. p. = boiling point."NMR"means nuclear magnetic resonance spectrum. MS stands for mass spectrum."%"is percent by weight, unless corresponding concentrations are indicated in other units.

Example 1 : 1, 4-Dimethylpyrrole-3-carboxylic acid In a sulfonation flask 0. 87 g (20 mmol) NaH (55%) are dissolved in 10 ml of absolute THF.

Then a solution of 2. 8 g (20 mmol) 4-methylpyrrole-3-carboxylic acid methylester in 400 mi THF is added dropwise. After stirring of the mixture for 10 minutes at room temperature, 1. 2 ml (20 mmol) methyl iodide are added and stirring continued for 1 hour. After addition of 50 ml of a cold ca. 10% ammonium chloride solution the mixture is extracted twice with ethylacetate. After drying of the organic phase the solvent is removed in a water jet vacuum.

The obtained crude N-methylated ester is dissolved in 10 ml ethanol and 20 ml of a 2N sodium hydroxide solution. The resulted mixture is stirred at 80-85°C for 3 hours and then ethanol is removed in a water jet vacuum. After addition of 25 ml of water and extraction with ethylacetate the water phase is acidified with concentrated hydrochloric acid. After cooling the acid is separated by filtration. Yield after drying : 2. 1 g of 1, 4-dimethylpyrrole-3-carboxylic acid in form of a slightly brownish powder ; m. p. 166-168°C.

Example 2 : 1, 4-Dimethylpyrrole-3-carboxylic acid [ (4-fluorobiphenyl)-2-yl] amide A solution of 0. 49 g (3. 5 mmol) 1, 4-dimethylpyrrole-3-carboxylic acid and 0. 49 g (3. 8 mmol) oxalyl chloride in 20 ml of methylene chloride is stirred for 3 hours at room temperature in the presence of a catalytic amount of DMF. Then the acid chloride solution is slowly added to a solution of 0. 65 g (3. 5 mmol) 2- (4'-fluorophenyl) aniline, 0. 43 g (4. 2 mmol) triethylamine and 15 ml methylene chloride. The resulting mixture is then stirred for 16 hours at room temperature. After addition of ethylacetate, the organic phase is washed twice with water.

Drying of the organic phase (Na, SO,) and removal of the solvent in a water jet vacuum yielded the raw material. Purification by column chromatography over silica gel (eluant : ethylacetate/hexane 1 : 1) gave 0. 55 g 1, 4-dimethylpyrrole-3-carboxylic acid [ (4-fluorobiphenyl)-2-yl] amide in the form of slightly yellowish powder ; m. p. : 147-149°C.

The following compounds are prepared in a similar way, using analogous methods.

Table 1 : Compounds of the formula I, wherein A = A1 = Compd. R, R2 R3 R4 R5 X Phys. data No. [m. p.] 1. 1 CH3 H CH3 HOpo H O 1. 2 CH3 H CH3 c H O 1. 3 CH3 H CH3 8< H O Br 1. 4 CH3 H CH3 Br H 0 1. 5 CH3 H CH3 H 0 resin ; MS, JH-NMR 1. 6 CH3 H CH3, - H S 1. 7 CH3 H CH3 H 0 1. 8 CH3 H CH3 ocS H O 1. 9 CH3 H CH3 H 0 resin ; MS, 'H-NMR 1. 10 CH3 H CH3 oCHz H O CH 1. 11 CH3 H CH3 w CH H O 1. 12 CH3 CH3 CH3 (} c « H O 1. 13 CH3 H CH3 H 0 1. 14 CH3 H CH3 < H O 1. 15 CH3 H CH3 H 0 -b 1. 16 CH3 H CH3 F H O -b 1. 17 CH3 H CH3 c, H O 3 1. 18 CH3 H CH3 OCF, H O 1. 19 CH3 H CH3 H 0 if 1. 20 CH3 H CH3 F H O 1. 21 CH3 H CH3 'H 0 1. 22 CH3 H CH3 CF, H 0 -d 1. 23 CH3 H CH3 156-158 1. 24 CH3 H CH3 oc, H S 1. 25 CH3 H CH3 H 0 148-149 1. 26 CH3 H CH3 _ (3F H S resin 1. 27 CH3 H CH3 c F, H 0 1. 28 CH3 H CH3 oacF, H O 1. 29 CH3 H CH3 H 0 1. 30 CH3 H CH3 F H O F 1. 31 CH3 H CH3 gj H O s 1. 32 CH3 H CH3 % 3 H O s cl 1. 33 CH3 H CH3 H 0 b s 1. 34 CH3 H CH3 H O A a s 1. 35 CH3 H CH3 EX H O 1. 36 CH3 H CH3 rr- H 0 zou 1. 37 CH3 H CH3 o, N o'N 1. 38 CH3 H CH3 N H O o 1. 39 CH3 H CH3 /H 0 a NS CI 1. 40 CH3 H CH3 H O zon 1. 41 CH3 H CH3 ci H O /N 1. 42 CH3 H CH3 F H O N 1. 43 CH3 H CH3 cF, H O N 1. 44 CH3 H CH3 tOCF, H ° 0" 1. 45 CH3 H CH3 H 0 N 1. 46 CH3 H CH3 H O 118-120 N 1. 47 CH3 H CH3 F H O N 1. 48 CH3 H CH3 H 0 N 1. 49 CH3 H CH3 H 0 / N ci 1. 50 CH3 H CH3 H 0 N' N CF, 1. 51 CH3 H CH3 H 0 1 N 1. 52 CH3 H CH3 F H O N N 1. 53 CH3 H CH3 H 0 -N 1. 54 CH3 H CH3 H 0 N 1. 55 CH3 H CH3 cl H O N N 1. 56 CH3 H CH3 ß H O N N 1. 57 CH3 H CH3-- (\/ N 1. 58 CH3 H CH3 Nf N zon 1. 59 CH3 H CH3 H 0 N-N 1. 60 CH3 H CH3 H 0 N-N 1. 61 CFH2 H CH3 HO H O 1. 62 CFH2 H CH3 ci H 0 1. 63 CFH2 H CH3 B 5Q H O Y Er 1. 64 CFH2 H CH3 Br H 0 - 1. 65 CFH2 H CH3 H 0 1. 66 CFH2 H CH3 < H S 1. 67 CFH2 H CH3 H H O 1. 68 CFH2 H CH3 H 0 1. 69 CFH2 H CH3 < H O 1. 70 CFH2 H CH3 H 0 1. 71 CFH2 H CH3 H 0 1. 72 CFH2 CH3 CH3 H 0 1. 73 CFH2 H CH3 H 0 1. 74 CFH2 H CH3 o H O 1. 75 CFH2 H CH3 H 0 rv 1. 76 CFH2 H CH3 F H O r 1. 77 CFH2 H CH3 c H O 3 1. 78 CFH2 H CH3 °t H O ru 1. 79 CFH2 H CH3'H O -0 1. 80 CFH2 H CH3 H 0 -0 1. 81 CFH2 H CH3 H 0 i 1. 82 CFH2 H CH/° H 0 -0 1. 83 CFH2 H CH3 oc, H O 1. 84 CFH2 H CH3 tCI H S 1. 85 CFH2 H CH3 H 0 1. 86 CFH2 H CH3 eF H S 1. 87 CFH2 H CH3 i F, H O 1. 88 CFH2 H CH3 oOCF, H o 1. 89 CFH2 H CH3 nc, H O 1. 90 CFH2 H CH3 XF H O F 1. 91 CFH2 H CH3"Is H O S 1. 92 CFH2 H CH3 H 0 1. 93 CFH2 H CH3 H O I I s 1. 94 CFH2 H CH3 H O roi 1. 95 CFH2 H CH3, C3 H O 0 1. 96 CFH2 H CH3 JU, N -0- 1. 97 CFH2 H CH3 H 0 ! !- oL 1. 98 CFH2 H CH3 N H O 0 1. 99 CFH2 H CH3 Noacl "fi c. 1. 100 CFH2 H CH3 H O /N 1. 101 CFH2 H CH3 eCI H O zon 1. 102 CFH2 H CH3 ci S Zon 1. 103 CFH2 H CH3 F H O N 1. 104 CFH2 H CH3 =CF, H O N 1. 105 CFH2 H CH3 =OCF, H 0 N 1. 106 CFH2 H CH3 H 0 N 1. 107 CFH2 H CH3 H O N 1. 108 CFH2 H CH3 > H O N 1. 109 CFH2 H CH3 H 0 v N 1. 110 CFH2 H CH3 4 H O N N ci 1. 111 CFH2 H CH3 H 0 - y-N F 1. 112 CFH2 H CH3 O N N 1. 113 CFH2 H CH3 F H O ? N 1. 114 CFH2 H CH3 oCl H O N 1. 115 CFH2 H CH3 H 0 N 1. 116 CFH2 H CH3 ci H O N- N 1. 117 CFH2 H CH3 ß H O N N 1. 118 CFH2 H CH3 HN) H O NID 1. 119 CFH2 H CH3 Ni H O N 1. 120 CFH2 H CH3 ç H O N-N 1. 121 CFH2 H CH3 H 0 N-N 1. 122 CF2H H CH3 HO H O 1. 123 CF2H H CH3 cr>o H O J 1. 124 CF2H H CH3 s H O r 8 1. 125 CF2H H CH3 tr H O 1. 126 CF2H H CH3 < H O 1. 127 CF2H H CH3 H S 1. 128 CF2H H CH3 4-CH H o 1. 129 CF2H H CH3 H 0 1. 130 CF2H H CH3 H 0 1. 131 CF, H H CH3 {} CH, H O 1. 132 CF2H H CH3 H 0 1. 133 CF2H CH3 CH3 H 0 1. 134 CF2H H CH3 4 H O 1. 135 CF2H H CH3 o H O 1. 136 CF2H H CH3 H 0 i 1. 137 CF2H H CH3 H 0 i 1. 138 CF2H H CH3 CF3 H O -b 1. 139 CF2H H CH3 0CF3 H O i 1. 140 CF2H H CH3'H O - 1. 141 CF2H H CH3 F H O -0 1. 142 CF2H H CH3 SF H O -0 1, 143 CF2H H CH3 OCF H 0 -0 1. 144 CF2H H CH3 4-CI H O resin 1. 145 CF2H H CH3 3c, H S 1. 146 CF2H H CH3 H 0 1. 147 CF2H H CH3 oF H S 1. 148 CF2H H CH3 H 0 1. 149 CF2H H CH3 i , H O 1. 150 CF2H H CH3 c, H O 1. 151 CF2H H CH3 F H 0 F 1. 152 CF2H H CH3 g3 H O S 1. 153 CF2H H CH3 ci H 0 resin, MS s 1. 154 CF2H H CH3 H O I I s 1. 155 CF2H H CH3 H O I I 1. 156 CF2H H CH3, ç3 H O 0 1. 157 CF2H H CH3 n-) H 0 0-" 1. 158 CF2H H C H3 \C7 H 0 0 ion 1. 159 CF2H2 H CH3 N H 0 0 1. 160 CF2H H CH3 Ncl 11 1 1. 161 CF2H H CH3 H O 1. 162 C FAH H CH3 tCI H O N' 1. 163 C FAH H CH3 tN S -cl 1. 164 CF2H H CH3 F H O N 1. 165 C FAH H CH3 CF H O N 1. 166 CF2H H CH3 =OCF, H 0 N 1. 167 CF2H H CH3 H 0 N 1. 168 CF2H H CH3 H O N 1. 169 CF2H H CH3 H 0 N 1. 170 CF2H H CH3 H 0 N 1. 171 CF2H H CH3 H 0 N ci 1. 172 CF2H H CH3 H O N F, 1. 173 CF2H H CH3 H O ? N 1. 174 CF2H H CH3 F H O N 1. 175 CF2H H CH3 H 0 N 1. 176 CF2H H CH3 H 0 N 1. 177 CF2H H CH3 G H O N N 1. 178 CF2H H CH3 H 0 N 1. 179 CF2H H CH3 N H N 1. 180 CF2H H CH3 =g H O N 1. 181 CF2H H CH3 < H O N-N 1. 182CF, HHCHgH0 N-N 1. 183 CF2CF3 H CH3 H 0 113-114 1. 184 CF2CF3 H CH3 < H S 1. 185 CFzCF3 H CH3/r'1_.. H H O 1. 186CFCFgHCHg-<Q-c. , H0 1. 187 CF2CF3 H CH3 H 0 120-121 1. 188 CF2CF3 H CH3 H 0 1. 189 CF2CF3 H CH3 H 0 1. 190 CF2CF3 H CH3 oc, H O 148-150 1. 191 CF2CF3 H CH3 oc, H S 1. 192 CF2CF3 H GH3 oF H O 134-136 1. 193 CF2CF3 H CH3 oF H S 1. 194 CF2CF3 H CH3 oCF ; H O 1. 195 CF2CF3 H CH3 toCF, H o 1. 196 CF2CF3 H CH3 ec, H O 1. 197 CF2CF3 H CH3 F H 0 F 1. 198 p H CH3 HO H O zu 1. 199 A H CH3 c H O 1. 200 p H CH3 ar. H O 8r 1. 201 p H CH3 < H O 1. 202 A H CH3 < H O 1. 203 A H CH3 H S 1. 204 A H CH3 _> H O 1. 205 A H CH3 H 0 1. 206 A H CH3 < H O resin ; MS, 'H-NMR 1. 207 A H CH3 H 0 1. 208 L H CH3 > H O 1. 209 A CH3 CH3 H 0 1. 210 p H CH3 < H O 1. 211 A H CH3 H 0 1. 212 p H CH3 H 0 ru 1. 213 A H CH3-b H O ru 1. 214 A H CH3 t H O ru 1. 215 A H CH3 3 H O r 1. 216 p H CH3 H O r 1. 217 A H CH3 F H O i 1. 218 A H CH3 : Fz H O i 1. 219 A H CH3 ocF, H ° - 1. 220 A H CH3 oc, H O 1. 221 A H CH3 ocl H S 1. 222 p H CH3 oF H O 1. 223 p H CH3 wF H S 1. 224 IL H CH3 H 0 1. 225 p H CH3 H 0 1. 226 A H CH3 H 0 1. 227 p H CH3 X F H O Zu 1. 228 A H CH3 % 3 H O s 1. 229 IL H CH3 5Cs H O s Cl 1. 230 A H CH3 H O I I s 1. 231 A H CH3 c) v H O 1. 232 A H C H3 H 0 0 1. 233 A H CH3 i H O 0 1. 234 A H CH3 F7jN H 0 o. N 1. 235 A H CH3 r- nu 0 0 1. 236 A H CH3, N, H O S Cl 1. 237 A H CH3 H O 1. 238 A H CH3 ci H O N 1. 239 p H CH3 ci H s N' 1. 240 A H CH3 N : H 0 1. 241 A H CH3 H 0 N 1. 242 A H CH3 OCF3H 0 N 1. 243 A H CH3 H 0 _N 1. 244 A H CH3 H O 105-107 N 1. 245 p H CH3 CF, H O N 1. 246 A H CH3 H 0 N 1. 247 A H CH3 H 0 N CI 1. 248 IL H CH3 H 0 -F N y-N 6F, 1. 249 A H CH3, H O zon N 1. 250 A H CH3 F H O N N 1. 251 A H CH3 +, H O Zon 1. 252 H CH3 \D H 0 1. 253 A H CH3 ci H O , i N 1. 254 A H CH3 H 0 W N 1. 255 A H CH3 N H 0 N 1. 256 A H CH3 H 0 --cl N 1. 257 A H CH3 ç H O N-N 1. 258 A H CH3 ¢ H O N-N 1. 259 CH3 H CH3 Ac, H S N 1. 260 CH2CH3 H CH3 H 0 152-153 1. 261 CH2CH3 H CH3 H 0 120-121 1. 262 CH2CH3 H CH3 {) H O 1. 263 CH2CH3 H CH3 eCH H O 1. 264 CH2CH3 H CH3 H 0 1. 265 CH2CH3 H CH2CH3 H 0 97-98 1. 266 CH2CH3 H CH2CH3 H 0 95-96 1. 267 CH2CH3 H CH2CH3 H 0 1. 268 (CH3) 2CH H CH3 H 0 102-103 1. 269 (CH3) 2CH H CH3 oF H O 99-100 1. 270 (CH3) 2CH H CH3 CH, H 0 1. 271 (CH3) 2CH H CH2CH3 H 0 116-117 1. 272 (CH3) 2CH H CH2CH3 H 0 93-94 Table 2 : Compounds of the formula I, where A = A2 = Compd. R, R2 R3 R4 Rs X Phys. data No. No. [M. P.] 2. 1 CH3 H CH3 HOpO H O 2. 2 CH3 H CH3 c5o H O 2. 3 CH3 H CH3 er H O J Br 2. 4 CH3 H CH3 tr H O --C 2. 5 CH3 H CH3 H 2. 6 CH3 H CH3 H S 2. 7 CH3 H CH3 oH H O 2. 8 CH3 H CH3 {} m H o 2. 9 CH3 H CH3 H 0 2. 10 CH3 H CH3 WO-CH, H O 2. 11 CH3 H CH3 H 0 2. 12 CH3 CH3 CH3 {) s H O 2. 13 CH3 H CH3 H 0 2. 14 CH3 H CH3 o H O 2. 15 CH3 H CH3 H 0 i 2. 16 CH3 H CH3 43 H O -0 2. 17 CH3 H CH3 CF, H O -0 2. 18 CH3 H CH3 3 H O i 2. 19 CH3 H CH3'H O w 2. 20 CH3 H CH3 F H O -0 2. 21 CH3 H CH3 H 0 -0 2. 22 CH3 H CH3 OCF, H O w 2. 23 CH3 H CH3 H 0 resin, MS 2. 24 CH3 H CH3 oc, H S 2. 25 CH3 H CH3 H 0 2. 26 CH3 H CH3 oF H S 2. 27 CH3 H CH3 H 0 2. 28 CH3 H CH3 H 0 2. 29 CH3 H CH3-tc, H O 2. 30 CH3 H CH3 H 0 F : 2. 31 CH3 H CH3 H 0 s 2. 32 CH3 H CH3 03 H O sa 2. 33 CH3 H CH3 H O I I S 2. 34 CH3 H CH3 H O Jan s 2. 35 CH3 H CH3 I I _ H O 2. 36 CH3 H CH3 JCN H O 0 2. 37 CH3 H CH3 \, N zu 2. 38 CH3 H CH3 CJN H O 0 2. 39 CH3 H CH3 Ncl =. 2. 40 CH3 H CH3 H O zon 2. 41 CH3 H CH/° H 0 N 2. 42 CH3 H CH3, =c, H S N 2. 43 CH3 H CH3 =CF, H O t/N 2. 44 CH3 H CH3 F, H O 2. 45 CH3 H CH3 O N N 2. 46 CH3 H CH3 H O N 2. 47 CH3 H Cl3 ; H O N 2. 48 CH3 H CH3 H 0 v N 2. 49 CH3 H CH3 ç H O / N ci 2. 50 CH3 H CH3 H 0 n N FI 2. 51 CH3 H CH3 H 0 ? N 2. 52 CH3 H CH3 F H O N 2. 53 CH3 H CH3 H 0 N 2. 54 CH3 H CH3 H 0 N 2. 55 CH3 H CH3 c, H O xi N 2. 56 CH3 H CH3 ß H O - 2. 57 CH3 H CH3 \ H O NID 2. 58 CH3 H CH3 Nf H O N 2. 59 CH3 H CH3 < H O N-N 2. 60 CH3 H CH3 H 0 N-N 2. 61 CFH2 H CH3 HO H O 2. 62 CFH2 H CH3 c5o H O J 2. 63 CFH2 H CH3 er H O zu Br 2. 64 CFH2 H CH3 Bc H 0 2. 65 CFH2 H CH3 H 0 2. 66 CFH2 H CH3 H S 2. 67 CFH2 H CH3 oCH, H 0 2. 68 CFH2 H CH3 H 0 2. 69 CFH2 H CH3 H 0 Z. J 2. 70 CFH2 H CH3 H 0 2. 71 CFH2 H CH3 +,, H O 2. 72 CFH2 CH3 CH3 H 0 2. 73 CFH2 H CH3 < H O 2. 74 CFH2 H CH3 0 2. 75 CFH2 H CH3 H 0 if 2. 76 CFH2 H CHO H O i 2. 77 CFH2 H CH3 °F, H O ru 2. 78 CFH2 H CH3 °°'H 0 w 2. 79 CFH2 H CH3'H O - 2. 80 CFH2 H CH3 F H O - 2. 81 CFH2 H CH3 H 0 if 2. 82 CFH2 H CH3 OCF, H 0 i 2. 83 CFH2 H CH3 H 0 2. 84 CFH2 H CH3 oc, H S 2. 85 CFH2 H CH3 H 0 2. 86 CFH2 H CH3 oF H S 2. 87 CFH2 H CH3 oCp H O 2. 88 CFH2 H CH3 H 0 2. 89 CFH2 H CH3 cl H 0 2. 90 CFH2 H CH3 XF H O P 2. 91 CFH2 H CH3 H 0 s 2. 92 CFH2 H CH3 I I H O S a 2. 93 CFH2 H CH3 H O I I S 2. 94 CFH2 H CH3 H O I I ci s 2. 95 CFH2 H CH3 H 0 0 2. 96 CFH2 H CH3 Xo, N 0 2. 97 CFH2 H CH3 o, N o'N 2. 98 CFH2 H CH3,) H O 0) 2. 99 CFH2 H CH3 Ncl c, 2. 100 CFH2 H CH3 N H O ZON 2. 101 CFH2 H CH3 0 -' 2. 102 CFH2 H CH3 ci H S N 2. 103 CFH2 H CH3 H 0 N 2. 104 CFH2 H CH3 CF, H O -le, N 2. 105 CFH2 H CHg/° H 0 N 2. 106 CFH2 H CH3 H 0 m _ gN 2. 107 CFH2 H CH3 H O it _ gN 2. 108 CFH2 H CH3, H O N 2. 109 CFH2 H CH3 H 0 N 2. 110 CFH2 H CH3 H O N ci 2. 111 CFH2 H CH3 H O CL, CF 2. 112 CFH2 H CH3 H O zon N 2. 113 CFH2 H CH3 F H O N N 2. 114 CFH2 H CH3 H 0 2. 115 CFH2 H CH3 H 0 N 2. 116 CFH2 H CH3 H H O N N 2. 117 CFH2 H CH3 F= H O . D 2. 118 CFH2 H CH3 N H 0 N 2. 119 CFH2 H CH3 Nf H O N 9 N 2. 120 CFH2 H CH3 ç H O N-N 2. 121 CFH2 H CH3 ç H O N-N 2. 122 CF2H H CH3 Ho H 0 2. 123 CF2H H CH3 c H 0 zu 2. 124 CF2H H CH3 s\/H O Sr 8r 2. 125 CF2H H CH3 Sr H 0 2. 126 CF2H H CH3 < H O 2. 127 CF2H H CH3 < H S 2. 128 CF2H H CH3 H 0 2. 129 CF2H H CH3 > H O 2. 130 CF2H H CH3 H 0 2. 131 CF2H H CH3 H 0 2. 132 CF2H H CH3 H 0 2. 133 CF2H CH3 CH3 H 0 2. 134 CF2H H CH3 < H O 2. 135 CF2H H CH3 H 0 2. 136 CF2H H CH3 H 0 F 2. 137 CF2H H CHO H O 2. 138 CF2H H CH3 t H O if 2. 139 CF2H H CH3 3 H O -0 2. 140 CF2H H CH3 H 0 r 2. 141 CF2H H CH3 F H O if 2. 142 CF2H H CH3 H 0 ru 2. 143 CF2H H CH3 OCF, H ° r 2. 144 CF2H H CH3 H 0 2. 145 CF2H H CH3 t--c, H S 2. 146 CF2H H CH3 H O 2. 147 CF2H H CH3-F H S 2. 148 CF2H H CH3 t--CF, H O 2. 149 CF2H H CH3 ocCF, H o 2. 150 CF2H H CH3 Xc, H O 2. 151 CF2H H CH3 H 0 F 2. 152 CF2H2 H CH3 H 0 s 2. 153 CF2H H CH3 03 H O s 2. 154 CF2H H CH3 H O I I s 2. 155 CF2H H CH3 ~3~ H O cl s ci bu 2. 156 CF2H H CH3, H O a 2. 157 CF2H H CH3 j-] N 0 0 2. 158 CF2H H CH3 eo, N 0ion 2. 159 CF2H2 H CH3 N H O 0 2. 160 CF2H H CH3 INIi H O NS Cl 2. 161 CF2H H CH3 H O zon 2. 162 CF2H H CH3 eC'H O N 2. 163 CF2H H CH3 ci H S N 2. 164 CF2H H CH3 F H O N 2. 165 CF2H H CH3 eCF H O /==\ 2. 166 CF2H H CH3 =OCF, H 0 N' 2. 167 CF2H H CH3 H 0 N 2. 168 CF2H H CH3 H O N 2. 169 CF2H H CH3 CF, H O /N 2. 170 CF2H H CH3 H 0 N 2. 171 CF2H H CH3 H O ci cl 2. 172 CF2H H CH3 H 0 N F, 2. 173 CF2H H CH3 H 0 N 2. 174 CF2H H CH3 F H O N 2. 175 CF2H H CH3 H 0 2. 176 CF2H H CH3 < H O H 0 2. 177 CF2H H CH3 ci H O __ ( N 2. 178 CF2H H CH3 ß H O N 2. 179 CF2H H CH3 HN) H O NID 2. 180 CF2H H CH3 N5'H 0 N N 2. 181 CF2H H CH3 < H O N-N 2. 182 CF2H H CH3 ç H O N-N 2. 183 CF2CF3 H CH3 < H O 2. 184 CF, CF, H CH3 < H S 2. 185 CF2CF3 H CH3 H 0 2. 186 CF2CF3 H CH3 > H O 2. 187 CF2C F. 3 H C H3 H 0 2. 188 CF2CF3 H C {) CH, 2. 189 CF2CF3 H CH3 {} 6hCHz H O 2. 190 CF2CF3 H CH3 oc, H O 145-146 2. 191 CF2CF3 H C H3 H s 2. 192 CF2CF3 H CH3 oF H O 136-137 2. 193 CF2CF3 H CH3 t3F H S 2. 194 CF2CF3 H CH-- 0 2. 195 CF2CF3 H CH3 H 0 2. 196 CF2CF3 H CH3 Xc, H O 2. 197 CF2CF3 H CH3 F H O F 2. 198 p H CH3 HOpO H O 2. 199 p H CH3 c. y H 0 J 2. 200 p H CH3 3< H O Br 2. 201 p H CH3 [3r H 0 2. 202 p H CH3 H O 2. 203 A H CH3 H S 2. 204 p H CH3 3CH H o 2. 205 p H CH3 H O 2. 206 A H CH3 {> H O 2. 207 p H CH, 0 H 0 2. 208 A H CH3 o*, H O 2. 209 A CH3 CH3 H 0 2. 210 A H CH3 H 0 2. 211 A H CH3 H 0 21. 212 A H CH3 H 0 i 2. 213 A H CH3 H 0 CF 2. 214 p H CH3 F, H O i 2. 215 IL H CH3 °°' H 0 if 2. 216 A H CH3'H O -) 2. 217 A H CH3 F H O i 2. 218 p H CH3 H 0 2. 219 p H CH3 ocF, H 0 i 2. 220 p H CH3 tct H O 2. 221 p H CH3 bc, H S 2. 222 IL H CH3 t3F H O 2. 223 p H CH3 oF H S 2. 224 p H CH3 t--CF, H 0 2. 225 p H CH3 H 0 2. 226 A H CH3 Xc, H O CI 2. 227 p H CH3 F H O p 2. 228 A H CH3 C H O s 2. 229 A H CH3 C3 H O s 2. 230 p H CH3 H O s s 2. 231 p H CH3 H O I I c s 2. 232 H CH3, H O 0 2. 233 p H CH3 J oH, N ° 0 2. 234 p H CH3 uo, N o'N 2. 235 H CH3 CN H O 0 2. 236 A H CH,,/H 0 NS CI 2. 237 H CH3 CN H O -j' 2. 238 p H CH3 cl H 0 N 2. 239 p H CH3 'H S N 2. 240 A H CH3 F H 0 N 2. 241 p H CH3 CF, H O N 2. 242 p H CH3 =OCF, H ° _N 2. 243 p H CH3 H 0 N 2. 244 A H CH3 H O - N 2. 245 p H CH3 ; H O N 2. 246 A H CH3 H 0 -N 2. 247 A H CH3 H 0 -N N cl 2. 248 p H CH3 H 0 f, CF. FI 2. 249 A H CH3 H 0 N) N 2. 250 A H CH3 F H O i-? 2. 251 A H CH3 +, H O Zon 2. 252 A H CH3 H O N 2. 253 A H CH3 ci H O N zd N 2. 254 p H CH3 F H O N 2. 255 A H CH3 N H 0 N 2. 256 A H CH3 Ni H O N 2. 257 p H CH3 ç H O N-N 2. 258 A H CH3 ç H O N-N N-N 2. 259 CH3 H CH3/F H O N 2. 260 CH2CH3 H CH3 H 0 2. 261 CH2CH3 H CH3 H 0 Table 3 : Compounds of the formula I, wherein A = A17 = Compd. R, R2 R3 R4 Rs X Phys. data No. No. [M. P.] 3. 1 CH3 H CH3 H 0 3. 2CHHCHg/-\HS 3. 3 CH3 H CH3 H 0 3. 4 CH3 H CH3 H 0 3. 5 CH3 H CH3 H 0 3. 6 CH3 H CH3 ~ 3. 7 CH3 H CH3 H 0 3. 8 CH3 H CH3'H O 3. 9 CH3 H CH3 F H O 3. 10 CH3 H CH3 < H O 3. 11 CH3 H CH3 oc, H S 3. 12 CH3 H CH3 H O F 3. 13 CH3 H CH3 H S 3. 14 CH3 H CH3 oCF, H 0 3. 15 CH3 H CH3 eOCFz H O 3. 16 CH3 H CH3-ci H 0 3. 17 CH3 H CH3 H 0 s 3. 18 CH3 H CH3 H O I I ci s 3. 19 CH3 H CH3'luo H O 0 3. 20 CH3 H CH3 r-) H 0 N ; 3. 21 CH3 H CH3 H O '0'' 3. 22 CH3 H CH3 N H 0 0 3. 23 CH3 H CH3 IN§| (H O S Cl 3. 24 CH3 H CH3 H O N 3. 25 CH3 H CH3 tC'H O Icy 3. 26 CH3 H CH3 Wc, H S N 3. 27 CH3 H CH3 CFs H O N 3. 28 CH3 H CH3 H 0 N 3. 29 CH3 H CH3 H O N 3. 30 CH3 H CH3 H 0 \ N 3. 31 CH3 H CH3 H 0 N N ci 3. 32 CH3 H CH3 H 0 XbN -N 3. 33 CH3 H CH3 F H O -0 N 3. 34 CH3 H CH3 H 0 -N 3. 35 CH3 H CH3 H 0 N 3. 36 CH3 H CH3 cl H O N 3. 37 CH3 H CH3 \_ H O N 3. 38 CH3 H CH3 =ga H O N H 0 3. 39 CH3 H CH3 n H O N-N 3. 40 CH3 H CH3 H 0 N-N 3. 41 H CH3 < H O 3. 42 A H CH3 < H S 3. 43 A H CH3 H 0 3. 44 A H CH3 3CH H O 3. 45 A H CH3 H 0 3. 46 A H CH3 F H O -0 3. 47 A H CH3'H O -d 3. 48 A H CH3 F H O -xJ 3. 49 A H CH3 o H O 3. 5û A H CH3 oc, H S 3. 51 H CH3 q3 H O 3. 52/H CH3 oF H S 3. 53 A H CH3 oCFl H O 3. 54 A H CH3 oOCF ; H O 3. 55 A H CH3 9 H O 3. 56 A H CH3 H O "'\/' 3. 57 H CH3 ci H 0 N 3. 58 H CH3 'H S N 3. 59 A H CH3 CF H O 0' 3. 60 A H CH3 H 0 N 3. 61 A H CH3 H O N 3. 62 A H CH3 H 0 \ N 3. 63 A H CH3 H 0 / N ci 3. 64 A H CH3 H 0 -N N 3. 65 H CH3 F H O N 3. 66 A H CH3 <, H O 3. 67 A H CH3 \NOI H O N 3. 68/H CH3 4 H O N 3. 69 A H CH3 H 0 N 3. 70 CF2H H CH3 < H O 3. 71 CF2H H CH3 H S 3. 72 CF2H H CH3 H 0 3. 73 CFzH H CH3 SO--CH H O 3. 74 CF2H H CH3 H 0 3. 75 CF2H H CH3 F H O 3. 76 CFZH H CH3'H O 3. 77 CF2H H CH3 F H O - 3. 78 CF2H H CH3 < H O 3. 79 CF2H H CH3 oc, H S 3. 80 CF2H H CH3 3F H O F 3. 81 CF2H H CH3 eF H S F 3. 82 CF2H H CH3 oCFz H O 3. 83 CF2H H CH3 oOCF H O -O- 3. 84 CF2H H CH3 < H O 3. 85 CF2H H CH3 H O N 3. 86 CF2H H CH3 ec H O Cy 3. 87 CF2H H CH3 ci S Icy 3. 88 CF2H H CH3 WCF, H O zon 3. 89 CF2H H CH3 H 0 _% _ gN 3. 90 CF2H H CH3 H O N N 3. 91 CF2H H CH3 H 0 N 3. 92 CF2H H CH3/=> H 0 O N Cl 3. 93 CFZH H CH3 H O ? N 3. 94 CF2H H CH3 F H O N 3. 95 CF2H H CH3 \ N H O N 3. 96 CF2H H CH3 H O N ~ 3. 97 CF2H H CH3 cl H O N 3. 98 CF2H H CH3 >, H O Table 4 : Compounds of the formula I, wherein A = A21 = Compd. R, R2 R3 R4 X Phys. data No. No. cm P.] 4. 1 CH3 H CH3 0 4. 2 CH3 H CH3 < S 4. 3 CH3 H CH3 0 4. 4 CH3 H CH3 0 4. 5 CH3 H CH3 0 4. 6 CH3 H CH3 t-O -b 4. 7 CH3 H CH3 43 if 4. 8 CH3 H CH3 3'O 4. 9 CH3 H CH3 0 if 4. 10 CH3 H CH3 oc, O 4. 11 CH3 H CH3 oc, S 4. 12 CH3 H CH3 0 resin 4. 13 CH3 H CH3 oF S 4. 14 CH3 H CH3 bCF, o 4. 15 CH3 H CH3 0 4. 16 CH3 H CH3 cri 0 4. 17 CH3 H CH3 t3uct ° s 4. 18 CH3 H CH3 0 ci ci s 4. 19 CH3 H CH3 0 0 4. 20 CH3 H CH3 fi-) 0 0 N 4. 21 CH3 H CH3 eo, N fuzz 4. 22 CH3 H CH3 N 0 0 4. 23 CH3 H CH3 t4 0 zizi sa 4. 24 CH3 H CHs/=\ 0 '"\ 4. 25 CH3 H CH3 =c, O N 4. 26 CH3 H CH3 cl s N 4. 27 CH3 H CH3 tCF, o zon 4. 28 CH3 H CH3 0 N 4. 29 CH3 H CH3 aN -'0' 4. 30 CH3 H CH3 0 N 4. 31 CH3 H CH3 0 N CI 4. 32 CH3 H CH3 0 N 4. 33 CH3 H CH3 F O ? N 4. 34 CH3 H CH3 0 -N N 4. 35 CH3 H CH3 0 N 4. 36 CH3 H CH3 ci 0 zu N 4. 37 CH3 H CH3 > O N 4. 38 CH3 H CHO N Zon 4. 39 CH3 H CH3 ç O N-N 4. 40 CH3 H CH3 ocl o N-N 4. 41 A H CH3 0 4. 42 A H CH3, S 4. 43 H CH3 4 O 4. 44 IL H CH3-0-H, 0 4. 45 A H CH3 X O 4. 46 A H CH3 4 O 4. 47 A H CH3 3'O - 4. 48 A H CH3 XF o 4. 49 A H CH3 0 4. 50 A H CH3 oc, S 4. 51 A H CH3 oF ° 4. 52 A H CH3 oF S 4. 53 A H CH3 0 4. 54 A H CH3 oCCF, o 4. 55, H CH3 c O cl 4. 56 A H CH3 0 "\/' 4. 57 A H CH3 v=4c O icy 4. 58 H CH3 =c, S N 4. 59 A H CH3 CF3 O ZON 4. 60 A H CH3 tN D' 4. 61 A H CH3 0 N 4. 62 A H CH3 0 -N N 4. 63 A H CH3 0 n cl 4. 64 A H CH3 0 N 4. 65 A H CH3 F O N N 4. 66 A H CH3 0 4. 67 A H CH3 \NOI 0 N 4. 68 A H CH3 4 O N N 4. 69, H CH3 0 N)) 4. 70 CF2H H CH3 0 4. 71 CF2H H CH3 < S 4. 72 CF2H H CH3 0 4. 73 CF2H H CH/-\ 0 4. 74 CF2H H CH3 0 4. 75 CF2H H CH3 X -b 4. 76 CF2H H CH3'O 4. 77 CF2H H CH3 0 4. 78 CF2H H CH3 q3c, ° 4. 79 CF2H H CH3 oc, S 4. 80 CF2H H CH3 0 ° 4. 81 CF2H H CH3 S 4. 82 CFzH H CH3 zCF, o 4. 83 CF2H H CH3 0 4. 84 CF2H H CH3 c O 0 4. 85 CF2H H CH3 0 -tV 4. 86 CF2H H CH3 N'ci 0 C/' 4. 87 CF2H H CH3 tN C" 4. 88 CF2H H CH3 =CF, O N 4. 89 CF2H H CH3 0 N N 4. 90 CF2H H CH3 = N 4. 91 CF2H H CH3 0 N 4. 92 CF2H H CH3 0 -N cl 4. 93 CF2H H CH3 0 1 -bN 4. 94 CF2H H CH3 F O N 4. 95 CF2H H CH3 +, O 4. 96 CF2H H CH3 0 w N 4. 97 CF2H H CH3 ci 0 N 4. 98 CF2H H CH3 0 N Table 5 : Compounds of the formula I, wherein A = A24 = Compd. Rt R2 R3 R4 Rs X Phys. data No. No. [m. p.] 5. 1 CH3 H CH3 H 0 5. 2 CH3 H CH3 < H S 5. 3 CH3 H CH3 H 5. 4 CH3 H CH3 H 0 5. 5 CH3 H CH3 oCH, H O 5. 6 CH3 H CH3 H 0 5. 7 CH3 H CH3 F H O 5. 8 CH3 H CH3'H O 5. 9 CH3 H CH3 F H O 5. 10 CH3 H CH3 oc, H O 5. 11 CH3 H CH3 H S 5. 12 CH3 H CH3 t3F H O 5. 13 CH3 H CH3 t3F H S -F 5. 14 CH3 H CH3 5. 15 CH3 H CH3 ocCF, H O 5. 16 CH3 H CH3 c H 0 a 5. 17 CH3 H CH3 H 0 s cl 5. 18 CH3 H CH3 cl H 0 I I ci s 5. 19 CH3 H CH3 w043 H O 0 5. 20 CH3 H CH3 H 0 0' 5. 21 CH3 H CH3 H 0 o. N 5. 22 CH3 H CH3 CN H O 0 5. 23 CH3 H CH3 Ncl N, s ci sa 5. 24 CH3 H CH3 H O ZON 5. 25 CH3 H CH3 eC H O zon 5. 26 CH3 H CHs/° H S zon 5. 27 CH3 H CH3 CF, H O N 5. 28 CH3 H CH3 H 0 -Xb- 5. 29 CH3 H CH3 H O N 5. 30 CH3 H CH3 H 0 \ -N 5. 31 CH3 H CH3 H 0 )-N N ci 5. 32 CH3 H CH3 H 0 XbN 5. 33 CH3 H CH3 F H O N 5. 34 CH3 H CH3 H 0 5. 35 CH3 H CH3 H 0 N 5. 36 CH3 H CH3 cl ~ H O N 5. 37 CH3 H CH3 ß H O y N 5. 38 CH3 H CH3'H O -0 NJ 5. 39 CH3 H CH3 çN H O N-N 5. 40 CH3 H CH3 Ac, H O N-N 5. 41 A H CH3 h 0 5. 42 A H CH3 ,- H S 5. 43 IL H CH3 H 0 5. 44 A H CH, Q H 0 5. 45 A H CH3 H 0 5. 46 A H CH3 3 H O 5. 47 A H CH3'h O 5. 48 A H CH3 F H O 5. 49 A H CH3 oc H O 5. 50 A H CH3 <3 c H S 5. 51 A H CH3 oF H O 5. 52 A H CH3 H s 5. 53 A H CH3 oCF H O 5. 54 A H CH3 OCF, H O 5. 55 A H CH3 H 0 ci 5. 56 A H CH3 H O 5. 57 A H CH3 eC H O 5. 58 A H CH3 ci H S 5. 59 A H CH/ 0 zon 5. 60 A H CH3 H 0 zon 5. 61 A H CH3 H O zon 5. 62 A H CH3 H 0 N N 5. 63 A H CH3 H 0 ci 0 5. 64 A H CH3 H 0 N 5. 65 A H CH3 F H O N 5. 66 A H CH3 H 0 5. 67 A H CH3 H 0 N 5. 68 A H CH3 ci H O N N 5. 69. A H CH3 ß H O N 5. 70 CF2H H CH3 < H O 5. 71 CF2H H CH3 H S 5. 72 CF2H H CH3 H 0 5. 73 CF2H H CH3 H 0 5. 74 CF2H H CH3 H 0 5. 75 CF2H H CH3 H 0 5. 76 CF2H H CH3'H O 5. 77 CF2H H CH3 F H O 5. 78 CF2H H CH3 o H O 5. 79 CF2H H CH3 oc, H S 5. 80 CF2H H CH3 H 0 5. 81 CF2H H CH3 oF H S 5. 82 CF2H H CH3 CF, H 0 5. 83 CF2H H CH3--5OCF, H O 5. 84 CF2H H CH3 c H O 5. 85 CF2H H CH3 H O N 5. 86 CF2H H CH3 eQ H O -C- 5. 87 CF2H H CH3 N'ci H s N 5. 88 CF2H H CH3 cF, H 0 N 5. 89 CF2H H CH3 H 0 w N 5. 90. CF2H H CH3 H O N 5. 91 CF2H H CH3 H 0 N 5. 92 CF2H H CH3 H 0 -N N cl 5. 93 CF2H H CH3 H 0 N 5. 94 CF2H H CH3 F H O N 5. 95 CF2H H CH3 H 0 N 5. 96 CF2H H CH3 H 0 N 5. 97 CF2H H CH3 ci H O N, 5. 98 CF2H H CH3 $ H O w N Table 6 : Compounds of formula 1, wherein A = A25 = Compd. R, R2 R3 R4 R5 X Phys. data No. No. [M. P.] 6. 1 CH3 H CH3 H 0 6. 2 CH3 H CH3 ,- H S 6. 3 CH3 H CH3 H 0 6. 4 CH3 H CH3 H 0 6. 5 CH3 H CH3-0-H, H 0 6. 6 CH3 H CH3 H 0 6. 7 CH3 H CH3 F H O 6. 8 CH3 H CH3'H O w 6. 9 CH3 H CH3 F H O w 6. 10 CH3 H CH3 H 0 203-205 6. 11 CH3 H CH3 oc, H S 6. 12 CH3 H CH3 H 0 200-202 6. 13 CH3 H CH3 3-F H S 6. 14 CH3 H CH-3 CF, H 0 CFy 6. 15 CH3 H CH3 t CCF, H O 6. 16 CH3 H CH3 0 6. 17 CH3 H CH3 H 0 s cl 6. 18 CH3 H CH3 cl H 0 cl s ci s 6. 19 CH3 H CH3 H 0 0 6. 20 CH3 H CH3 N-H O 6. 21 CH3 H CH3 H O o, N 6. 22 CH3 H CH3 N H O 0 6. 23 CH3 H CHs/H 0 11 6. 24 CH3 H CH3 H O -" 6. 25 CH3 H CHs/° H 0 6. 26 CH3 H CH3 ci H S ZON 6. 27 CH3 H CH3 ACFz H ° N 6. 28 CH3 H CHg H 0 N 6. 29 CH3 H CH3 H O 6. 30 CH3 H CH3 H 0 N 6. 31 CH3 H CH3 H 0 -N ci 6. 32 CH3 H CHg H 0 -N N 6. 33 CH3 H CH3 F H O N 6. 34 CH3 H CH3 H 0 -N 6. 35 CH3 H CH3 H 0 N 6. 36 CH3 H CH3 c, ~ H O 0 N 6. 37 CH3 H CH3 P. H O N 6. 38 CH3 H CH3 H 0 N 6. 39 CH3 H CH3 H 0 N-N 6. 40 CH3 H CH3 H 0 N-N 6. 41 A H CH3 H 0 6. 42 A H CH3 H 3 6. 43 A H CH3 < H O 6. 44 A H CH3 H 0 6. 45 A H CH3) O 6. 46 A H CH3 F H O 6. 47 A H CH3 H 0 6. 48 A H CH3 F H O 6. 49 A H CH3 resin ; MS, 'H-NMR 6. 50 A H CH3 ec, H S 6. 51 A H CH3 0 resin. MS, 'H-NMR 6. 52 A H CH3 t3F H S 6. 53 A H CH3 H O 6. 54 A H CH3 43CCF, 6. 55 A H CH3 c H O a 6. 56 A H CH3 H O 6. 57 A H CH3 ci H O 6. 58 A H CH3 ci H s zon 6. 59 A H CH3 cF, H O 6. 60 A H CH3 H 0 w N 6. 61 A H CH3 H O N 6. 62 A H CH3 H 0 N 6. 63 A H CH3 H O N' N Ci 6. 64 A H CH3 H 0 -N N 6. 65 A H CH3 F H O N 6. 66 A H CH3 H 0 -N 6. 67 A H CH3 H 0 N 6. 68 A H CH3 ? H 0 "U 6. 69 IL H CH3 ß H O '"U N 6. 70 CF2H H CH3 H 0 6. 71 CF2H H CH3 < H S 6. 72 CF2H H CH3 H 0 6. 73 CF2H H CH3 H 0 6. 74 CF2H H CH3 H 0 6. 75 CF2H H CH3 F H O 6. 76 CF2H-H CH3'H O -d 6. 77 CF2H H CH3 H 0 -d 6. 78 CF2H H CH3 oc H O 6. 79 CF2H H CH3 oc, H S 6. 80 CF2H H CH3 H 0 F 6. 81 CF2H H CH3 oF H S F 6. 82 CF2H H CH3 oCF, H O 6. 83 CF2H H CH3 SCCP H O 6. 84 CF2H H CH3 9 H O a 6. 85 CF2H H CH3 H O zon 6. 86 CF2H H CH3 cl H 0 N 6. 87 CF2H H CH3 'H S N 6. 88 CF2H H CH3 CF3 H 0 N 6. 89 CF2H H CH3 H 0 N 6. 90 CF2H H CH3 H O N N 6. 91 CF2H H CH3 H 0 \ N 6. 92 CF2H H CH3 H 0 / N ci 6. 93 CF2H H CH3 H 0 N 6. 94 CF2H H CH3 H 0 N 6. 95 CF2H H CH3 +, H O 6. 96 CF2H H CH3 H 0 N I 6. 97 CF2H H CH3 ci H O N 6. 98 CF2H H CH3 ß H O "U Table 7 : Compounds of the formula 1, wherein A = A26 = Compd. R, R2 R3 R4 R5 X Phys. data No. No. [M. P.) 7. 1 CH3 H CH3 < H O 7. 2 CH3 H CH3 3 H S 7. 3 CH3 H CH3 + H O 7. 4 CH3 H CH3 H 0 7. 5 CH3 H CH3 +,, 7. 6 CH3 H CH3 H 0 7. 7 CH3 H CH3 F H O if 7. 8 CH3 H CHs'H O 7. 9 CH3 H CH3 F H O 7. 10 CH3 H CH3 oc H O 7. 11 CH3 H CH3 ec, H S 7. 12 CH3 H CH3 < H O F 7. 13 CH3 H CH3 oF H S F 7. 14 CH3 H CH3 H 0 7. 15 CH3 H CH3 bOCF, O 7. 16 CH3 H CH3 I H O 7. 17 CH3 H CHg r-n H O -sa 7. 18 CH3 H CH3 H O I I ci s 7. 19 A H CH3 < H O 7. 20 A H CH3 H s 7. 21 A H CH3 H 0 7. 22 A H CH, H 0 7. 23 A H CH3 H 0 if 7. 24 H CH3 F H O 7. 25 A H CH3'H O if 7. 26 A H CH3 F H O if 7. 27, H CH3 H 0 7. 28 A H CH3 oc, H S 7. 29 A H CH3 H 0 7. 30 _ H CH3 oF H S 7. 31 A H CH3 ° 7. 32 A H CH3 oCCF, H O 7. 33 A H CH3 0 7. 34 CF2H H CH3 < H O 7. 35 CF2H H CH3 <, H S 7. 36 CF2H H CH3 H 0 7. 37 CF2H H CH3 q H O 7. 38 CF2H H CH3 H 0 if 7. 39 CF2H H CH3 F H O 7. 40 CF2H H CH3'H O 7. 41 CF2H H CH3 F H O 7. 42 CF2H H CH3 oc H O 7. 43 CF2H H CH3 oc) H S 7. 44 CF2H H CH3 H O 7. 45 CF2H H CH3 oF H S H s 7. 46 CF2H H CH3 CF H O 7. 47 CF2H H CH3 ocCF, O 7. 48 CF2H H CH3-c I _ H O Table 8 : Compounds of the formula 1, wherein A = A27 = Compd. R, R2 R3 R4 Rs X Phys. data No. (M. P.] Lm. P. l 8. 1 CH3 H CH3 H 0 8. 2 CH3 H CH3 < H S 8. 3 CH3 H CH3 H 0 8. 4 CH3 H CH3 {) H O 8. 5 CH3 H CH3 _ 0t H O 8. 6 CH3 H CH3 H 0 8. 7 CH3 H CH3 H 0 8. 8 CH3 H CH3 H 0 i 8. 9 CH3 H CH3 F H O 8. 10 CH3 H CH3 oc H O 8. 11 CH3 H CH3 oc, H S 8. 12 CH3 H CH3 H 0 8. 13 CH3 H CH3 oF H S 8. 14 CH3 H CH3 o CF, O 8. 15 CH3 H CH3 H 0 8. 16 CH3 H CH3 9 H O ci 8. 17 CH3 H CH3 I I H O s cri 8. 18 CH3 H CH3 H O I i ci s 8. 19 A H CH3 q3 H O 8. 20 A H CH3 H s 8. 21 A H CH3 H 0 8. 22 A H CH3 H 0 8. 23 A H CH3 H 0 if 8. 24 A H CH3 H 0 8. 25 A H CH3 H 0 if 8. 26 A H CH3 H 0 8. 27, H CH3 oc, H O 8. 28 A H CH3 oc, H S 8. 29 A H CH3 w f H O 8. 30 A H CH3 H S 8. 31 A H CH3 <3CF, H O 8. 32 H CH3 43CCF, H O 8. 33 A H CH3 c, H O cl 8. 34 CF2H H CH3 < H O 8. 35 CF2H H CH3 H S 8. 36 CF2H H CH3 H 0 8. 37 CF2H H CH3 CH, H 0 8. 38 CF2H H CH3 H 0 8. 39 CF2H H CH3 F H O -b 8. 40 CF2H H CH3 H 0 8. 41 CF2H H CH3 F H O -d 8. 42 CF2H H CH3 oc H O 8. 43 CF2H H CH3 oc, H S 8. 44 CF2H H CH3 H O 8. 45 CF2H H CH3 H S \-Ir 8. 46 CF2H H CH3 bCF, O 8. 47 CF2H H CH3 t3-OCF, H O 8. 48 CF2H H CH3 0 Table 9 : Compounds of the formula I, wherein A = A31 = Compd. R, R2 R3 Rs X Phys. data No. m. p. °C 9. 1 CH3 H CH3 H O resin, MS 9. 2 CH3 H CH3 H S 9. 3 CF2H H CH3 H O 9. 4 CF2H H CH3 H S 9. 5 CFH2 H CH3 H O 9. 6 CFH2 H CH3 H S 9. 7 A H CH3 H O 9. 8 A H CH3 H S 9. 9 A H CH2OCH3 H O 9. 10 H CH2OCH3 H S L 9. 11 CH2CH3 H CH3 H O resin, MS Table 10 : Compounds of formula 1, wherein A = A33 = Compd. R1 R2 R3 R5 X Phys. data No. m. p. °C 10. 1 CH3 H CH3 H O 10.2 CH2CH3 H CH3 H O 10. 3 CF2H H CH3 H O 10. 4 CF2H H CH2OCH3 H O 10. 5 CF2CF3 H CH3 H O 168-169 Table 11 : Pyrrole carboxylic acid of the formula X (X), wherein R2 is hydrogen Compd. R, R3 Phys. data No. m. p. °C 11. 1 CH3 CH3 166-168 11. 2 CH3 CH2CH3 11. 3 CH3 CHF2 11. 4 CH3 CH2OCH3 11. 5 CH3 CH20CF3 11. 6 CHF2 CH3 11. 7 CHF2 CH2CH3 11. 8 CHF2 CH20CH3 11. 9 CH2F CH3 11. 10 CH2F CH2CH3 1 1. 1 1 CH2F CH20CH3 11. 12 CH2CH3 CH3 164-165 11. 13 CH2CH3 CH2OCH3 11. 14 CF2CF3 CH3 180-181 11. 15ACHs 182-183 11. 16 CH2CH3 11. 17 tS CHF2 11. 18 A CH2OCH3 11. 19 A CH2OCF3 L 11. 20 CH2CH3 CH2CH3 68 11. 21 (CH3) 2CH CH3 158-159 11. 22 (CH3) 2CH CHCH 99-100 Table 12 :'H-NMR of selected compounds Cmpd. No.'H-NMR-data (ppm/multiplicity/number of H's) ; solvent=CDCI3 1. 5 1. 60-1. 85/m/4H ; 2. 15-2. 30/m/4H ; 3. 62/s/3H ; 5. 80/ml1 H ; 6. 39/m/1H ; 6. 95-7. 15/m/3H ; 7. 20-7. 30/m/1H ; 7. 94/s/1H ; 8. 46/d/1H 1. 206 0. 68-0. 74/m/2H ; 0. 91-0. 98/m/2H ; 1. 29-1. 94/m/11 H ; 2. 72/m/1 H ; 3. 55/s/SH ; 6. 35/m/1H ; 7. 13-7. 34/m/4H ; 7. 75/m/1H ; 8. 19/s/1H (NH) 1. 220 0. 22-0. 29/m/4H ; 1. 20/m/1H ; 3. 57/s/3H ; 6. 22/m/1H ; 7. 10-7. 28/m/4H ; 7. 32-7. 45/m/4H ; 8. 15/s/1H ; 8.35/d/1H 6. 49 0. 29/m/4H ; 1. 23/m/1 H ; 3. 58/s/3H ; 6. 24/m/1 H ; 6. 98-7. 50/m/5H ; 8. 06/d/1H ; 8. 15/m/2H (NH+1 pyridin-H) ; 8. 42/d/1H 6. 51 0. 27/m/4H ; 1. 25/m/1H ; 3. 59/s/3H ; 6. 23/ml1H ; 6. 99-7. 48/m/7H ; 8. 15/s/1H ; 8. 42/d/1H ; Formulation Examples for compounds of formula I Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable concentrates, Solutions, Granulates, Dusts and Wettable powders are described in WO 97/33890.

Biological Examples : Fungicidal actions Example B-1 : 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 wheat plants are inoculated by spraying a spore suspension (1 x 105 uredospores/ml) on the test plants. After an incubation period of 2 days at 20° C and 95% r. h. plants are kept in a greenhouse for 8 days at 20° C and 60% r. h. The disease incidence is assessed 10 days after inoculation.

Compounds of Tables 1 to 10 show good activity in these tests. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 5., 1 and 10. 5 exhibit strong efficacy (< 20% infestation).

Example B-2 : Action against Podosphaera leucotricha/apple (Powdery mildew on apple) 5 week old apple seedlings cv. Mcfntosh are treated with the formulated test compound (0. 002% active ingredient) in a spray chamber. One day after 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 14/10 h (light/dark) the disease incidence is assessed.

Compounds of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-3 : Action against Venturia inaequalis/apple (Scab on apple) 4 week old apple seedlings cv. Mcfntosh are treated with the formulated test compound (0. 02% active ingredient) in a spray chamber. One day after application apple plants are inoculated by spraying a spore suspension (4 x 105 conidia/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 of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-4 : Action against Erysiphe graminis/barley (Powdery mildew on barley 1 week old barley plants cv. Express are treated with the formulated test compound (0. 02% active ingredient) in a spray chamber. One day after application 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 of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-5 : Action against Botrytis cinerea/apple (Botrytis on apple fruits) In an apple fruit cv. Golden Delicious 3 holes are drilled and each filled with 301l1 droplets of the formulated test compound (0. 002% active ingredient). Two hours after application 501l1 of a spore suspension of B. cinerea (4 x 105 conidia/ml) are pipetted on the application sites.

After an incubation period of 7 days at 22° C in a growth chamber the disease incidence is assessed.

Compounds of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-6 : Action against Botrytis cinerea/grape (Botrytis on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0. 002% active ingredient) in a spray chamber. Two days after application grape plants are inoculated by spraying a spore suspension (1 x 106 conidia/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 of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-7 : Action against Botrytis cinerea I tomato (Botrytis on tomatoes) 4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0. 002% active ingredient) in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension (1 x 105 conidia/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 of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-8 : Action against Pyrenophora teres/barley Net blotch on barley) 1 week old barley plants cv. Express are treated with the formulated test compound (0. 002% active ingredient) in a spray chamber. Two days after application barley plants are inoculated by spraying a spore suspension (3 x 104 conidia/ml) on the test plants. After an incubation period of 2 days at 20° C and 95% r. h. plants are kept for 2 days at 20° C and 60% r. h. in a greenhouse. The disease incidence is assessed 4 days after inoculation.

Compounds of Tables 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.

Example B-9 : 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 wheat plants are inoculated by spraying a spore suspension (5 x 105 conidia/ml) on the test plants. After an incubation period of 1 day at 20° C and 95% r. h. 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 of Tabies 1 to 10 show good activity in this test. The compounds 1. 5, 1. 9, 1. 23, 1. 25, 1. 46, 1. 144, 1. 153, 1. 183, 1. 187, 1. 190, 1. 192, 1. 206, 1. 244, 1, 260, 1. 261, 1. 265, 1. 266, 1. 268, 1. 269, 1. 271, 1. 272, 2. 23, 2. 190, 2. 192, 4. 12, 6. 10, 6. 12, 6. 49, 6. 51 and 10. 5 exhibit strong efficacy.