AU2002223668A1

AU2002223668A1 - Pyrrolcarboxamides and pyrrolcarbothioamides and their agrochemical uses

Info

Publication number: AU2002223668A1
Application number: AU2002223668A
Authority: AU
Inventors: Harald Walter
Original assignee: Syngenta Participations AG
Current assignee: Syngenta Participations AG
Priority date: 2000-11-08
Filing date: 2001-11-06
Publication date: 2002-05-21
Also published as: PT1341757E; BR0115200A; EP1341757B1; CA2426033A1; US20060189676A1; DE60123274T2; US7105565B2; PL362930A1; DE60123274D1; CR6959A; CN1221532C; US20050119130A1; IL155623A0; US7652059B2; EP1341757A1; HUP0302471A3; EG23122A; ATE340158T1; WO2002038542A1; HUP0302471A2

Description

PYRRO CARBOXYAMIDES AND PYRROLCARBOTHIOAMIDES AND THEIR AGROCHEMICAL USES

The present invention relates to novel pyrrolecarboxylic acid amides and pyrrolecarbothioic acid amides which have microbicidal activity, in particular fungicidal activity. The invention ilso 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 )ompositions mentioned and to the use of the active ingredients or compositions in agriculture and horticulture for controlling or preventing infestation of plants by hytopathogenic microorganisms, preferably fungi.

The 3-pyrrolecarboxylic acid amides and 3-pyrrolecarbothioic acid amides of the present invention have the general formula )

'X

wherein

X is oxygen or sulfur;

Ri is CF₃, CF₂H or CFH₂;

R₂ is C C₃alkyl, CrC₃haloalkyl, d-Csalkoxy-C Caalkyl or C Cahaloalkoxy-C Caalkyl;

R₃ is hydrogen, methyl, CF₃ or fluoro;

R₄ is C₆-Cι₄bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; C₆-Cι₄bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; C₆-Cι₄bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or a group of the form wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; or a group

wherein Rι₀ and Rn are independently of each other hydrogen or halogen and n = 1 or 2; and

R₅ and R₆ are independently of each other hydrogen or halogen.

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 I, 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 and isopropyl. Non- branched alkyl is preferred. Alkyl as part of other radicals such as alkoxy, haloalkyl, 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, etc. is understood in an analogous way.

Bicycloalkyl is, depending on the ring size, bicyclo[2.1.1]hexane, bicyclo[2.2.1 ]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[4.2.2]decane, bicyclo[4.3.2]undecane, adamantane and the like.

Bicycloalkenyl is bicyclo[2.1.1]hex-4-ene, bicyclo[2.2.1]hept-2-ene, bicyclo[2.2.2]oct-2-ene and the like.

Bicycloalkadienyl is bicyclo[2.2.1]hepta-2,5-diene, bicyclo[2.2.2]octa-2,5-diene, and the like.

One specific subgroup of the compounds of formula I is the group wherein X is oxygen. Another specific subgroup of the compounds of formula I is the group wherein X is sulfur.

Preferred subgroups of compounds of formula I are those wherein

X is oxygen; or

X is sulfur; or

R, is CF₃; or

R₂ is CrC₃alkyl; or

R₂ is C C₃haloalkyl; or

R₂ is d-Csalkoxy-C Csalkyl; or

R₂ is d-Cshaloalkoxy-C Caalkyl; or

R₂ is Cι-C₃alkyl or d-Cshaloalkyl; or

R₂ is C C₃alkyl, Cι-C₃haloalkyl or CrC3alkoxy-CrC₃alkyl; or

R₂ is methyl or CH₂OCH₃; or

R₂ is methyl; or

R₃ is hydrogen; or

R₃ is methyl; or

R₃ is CF₃; or

R₃ is fluoro; or

R₃ is hydrogen or fluoro; or

Q is Q1 ; or

Q is Q2, Q3 or Q4; or

Q is Q2; or

Q is Q3; or

Q is Q4; or

R is C₆-C₁₀bicycloaikyl unsubstituted or substituted by methyl, ethyl or CF₃; or

C₆-C₁₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or

C-₆-Cιobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or a group of the form

f I wherein R₇, R₈ and R₉ are independently of each other CrC alkyl or

R₇ R₈ C C₃haloalkyl; or a group

wherein R10 and Rn are independently of each other hydrogen or halogen and n = 1 or 2; or

R₄ is C₆-C₁₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃ , C₆-Cι₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ , C₆-Cιobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ , or a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

C C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro, bromo or fluoro; or

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or

R₅ is hydrogen and R₆ is chloro or fluoro.

Further preferred subgroups are those wherein a) X is oxygen;

R₂ is C C₃alkyl or C Csalkoxy-d-Caalkyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R is C₆-C₁₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; or

C₆-Ci₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or

C₆-Cιobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or a group of the form

wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or d-Cshaloalkyl; or a group wherein R₁₀ and Rn are independently of each other hydrogen or halogen and n = 1 or 2; and

R₅ and R₆ are independently of each other hydrogen, fluoro, chloro or bromo; or b) X is oxygen;

R is C C₃alkyl or d-Cjjhaloalkyl;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R₄ is C₆-C₁₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; or

C₆-C₁₀bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; or a group

wherein R₁₀ and Rn are independently of each other hydrogen or halogen and n = 1 or 2; and

R₅ and R₆ are independently of each other hydrogen, fluoro, chloro or bromo; and among this subgroup Q = Q2 is preferred; or ab) X is oxygen;

R₂ is methyl or CH₂OCH₃;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is a group of the form wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, fluoro, chloro or bromo; or c) X is oxygen;

R₂ is methyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is a group of the form

wherein R₇, R₈ and R₉ are independently of each other CF₃, methyl or ethyl, preferably methyl; and

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro; or d) X is oxygen;

Ri is CF₃;

R₂ is methyl;

R₃ is hydrogen;

Q is Q1 ;

R₄ is a group of the form

wherein R₇, R₈ and R₉ are independently of each other methyl or ethyl, preferably methyl; and

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro; or e) X is oxygen;

R₂ is methyl;

R₃ is fluoro;

Q is Q1 ;

R₄ is a group of the form wherein R₇, R₈ and R₉ are independently of each other methyl or ethyl, preferably methyl; and

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro.

Other preferred subgroups are those wherein f) X is sulfur;

R₂ is C_rC₃alkyl or C C₃haloalkyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is Ce-Ciobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; or

C₆-Ciobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; or a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; or a group

R₅ and R₆ are independently of each other hydrogen, fluoro, chloro or bromo; or g) X is sulfur;

R₂ is CrC₃alkyl or Cι-C₃haloalkyl;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R₄ is C₆-Cι₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; or

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; or a group

R₅ and R₆ are independently of each other hydrogen, fluoro, chloro or bromo.

Other subgroups of compounds of formula I are those wherein h) X is oxygen or sulfur;

R₂ is C C₃alkyl, CrC₃haloalkyl or d-Csalkoxy-d-d-alkyl ;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R is Ce-dobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C-e-dobicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ;

Ce-dobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or

C C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or i) X is oxygen or sulfur;

R₂ is C C₃alkyl, C C₃haloalkyl or d-dalkoxy-d-d-alkyl ;

R₃ is hydrogen or fluoro;

Q is Q1 ;

C_rC₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or j) X is oxygen or sulfur;

R₂ is d-C₃alkyl, d-C₃haloalkyl or CrC₃alkoxy-C_rC₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R is Ce-dobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C_e-Ci₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ;

C₆-C₁₀bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

Cι-C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or k) X is oxygen or sulfur;

R₂ is C C₃alkyl, C C₃haloalkyl or d-C₃alkoxy-C_rC₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q2;

R₄ is drdobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C₆-Cι₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ;

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

C C₃haloalkyl; and

R_. is CH₂F or CF₂H;

R₂ is d-C₃alkyl, C C₃haloalkyl or Cι-C₃alkoxy-d-C₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is Ce-Ciobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C₆-Cι₀bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or

C_rC₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or m) X is oxygen;

R₂ is methyl or CH₂OCH₃;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

CrC₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or n) X is oxygen or sulfur;

R₂ is CrC₃alkyl, C C₃haloalkyl or C C₃alkoxy-Cι-C₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R₄ is C₈-C₁₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

Ce-Ciobicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; C₆-Cι₀bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other d-C₃alkyl or d-C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro; or o) X is oxygen;

R₂ is methyl or CH₂OCH₃;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R₄ is a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

C C₃haioalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

Preferred individual compounds are :

1 -methyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3-dimethylbutyl)phenyl]amide;

1 -methoxymethyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3- dimethylbutyl)phenyl]amide;

1 -methyl-2-fluoro-4-trifluoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3- dimethylbutyl)phenyl]amide;

1 -methoxymethyl-2-fluoro-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3- dimethylbutyl)phenyl]amide;

1 -methyl-4-trif luoromethyl-1 H-pyrrole-3-carbothioic acid [2-(1 ,3-dimethylbutyl)phenyl] amide.

The compounds according to formula I wherein X is oxygen may be prepared according to the following reaction Scheme 1 A. Scheme 1A

The compounds of the formula I wherein X is oxygen may also be prepared from the corresponding esters according to reaction Scheme 1 B. Scheme 1 B

t = 15 min. - 24 hours

R = C,-C₆-alkyl / SiR₃ ^* (R^* = C_rC₆ •alkyl)

A further method for the synthesis of compounds of the formula I is outlined in Scheme 1 C. Scheme 1C

The synthesis of the pyrrole carboxylic acids of formula II wherein R₃ is not hydrogen may be conducted according to Scheme 2A. Scheme 2A

R₃ -reagents : F^t'= N-fluoro-bis(phenylsulfonyl)amine, N-fluoro-N-methyl-toluene-4-sulfonamide, 2-fluoro-3,3-dimethyl-2,3-dihydro-1 ,2-benzisothiazole-1 ,1 -dioxide, 1-fluoro-sym.-collidiniumtetrafluoroborate

Me = Mel, MeBr, DMS (dimethylsulfate) CF= NCS, Cl₂, hexachloroethane LDA = lithiumdiisopropylamide

The synthesis of the pyrrole carboxylic acids of formula II wherein R₃ = H is described in WO-00/09482.

Alternatively the pyrrole carboxylic acid fluorides wherein R₃ is fluoro may be obtained as outlined in Scheme 2B. Scheme 2B

The synthesis of the pyrrole carboxylic acids II may also be conducted according to the Schemes 2C or 2D. Scheme 2C

Scheme 2D

LiAIH(0-t-butyl)₃

-78" - -30°C THF or hexane

The amine intermediates NH₂-Q of formula IV may be prepared according to the following reactions as outlined in Scheme 3. Scheme 3 Route a) strong base -100 to -110 °C

W-NH-CHO + a keton IX WY-NH-CHO solvent (X) (XI)

acid / solvent

NaOH or KOH and/or ^"a H₂N-WY ^_ H_PN-Q (IV) in alcohol Pd or Pt on charcoal/

(VI) H₂ / solvent wherein Q, R₅ , R₆ , R₇ , R₈ , R₉ , R₁₀ , R^ and n are as described for the compounds of formula I, Hal is Br or I; strong base is n-BuLi, sec.-BuLi, tert.-BuLi, PhLi; and wherein

and n+m=2-10

or Route b)

ΓUIKJ, Π₂, solvent(ether.THF)

H₂N-T + XV (IV) ignard) 0°C to reflux

(XII) (Gr

acid

(XIV)

wherein

and wherein isomeric mixtures are possible at the double bond

or Route c)

strong base SOCI₂ or POCI_g _n ... , , solvent N0₂-W + a ketone N0₂-WY N0₂-TG °C pyridine

(XIII) (IX) -105 (VII) (VIII) 0°C to reflux

Raney-Ni /H₂

H₂N-Q (IV) alcohol 50-200 bar/ 50-150°C

Specific amines of the formula IV can be prepared as follows: - The amines H₂N-Q of formula IV, wherein Q = Q1 as defined in formula I and R₄ is bicycloalkyl, bicycloalkenyl or bicycloalkadienyl and R₅ and R₆ are hydrogen may be obtained according to Scheme 3A (Route a). Scheme 3A

(exo/endo-isomers for n = 1 ,2 or 3)

For the synthesis of 2-bicyclo[2.2.1]hept-2-yl phenylamine and other bicyclosystems see for example EP-1 16044.

According to Scheme 3A the following compounds are also available :

wherein R₅ and R₆ are hydrogen and R₇, R₁₀, Rn and n are as defined for formula I. -- The amines H₂N-Q wherein Q is Q1 and R₄ is a group of the form

R₅ and R₆ are hydrogen and R₇, R₈ and R₉ are as defined for formula I may be obtained according to Scheme 3B (Route b).

Scheme 3B

(excess) NH₂

THF or ether, 0°C-reflux ^{Ry R9}

(XI lb)

+ other double bound isomers

(other syntheses of ortho-alky Isubstituted anilines are also described in EP-824099) or in a one step hydrogenation of the OH-group of compounds of formula VI

Pd on charcoal / H₂/ H₂S0₄

(VI) IVb alcohols

- Another synthesis of the amine intermediates is outlined in Scheme 3C (Route c). Scheme 3C

for compounds of formula IVb1

wherein R₇ is CF₃, R₅ and R₆ are hydrogen and R₈ and R_g are as defined for formula I strong base: n-BuLi, sec-BuLi, tert-BuLi, PhLi or others

Using the reaction sequence outlined in Scheme 3C the compounds of formula IVc2 wherein R₅ and R₆ are hydrogen, R₇ is CF₃, n=1 and R_i0 and Rn are as defined for formula are also available

- The synthesis of the amines IV wherein Q is Q2, Q3 or Q4, R₅ and R₆ are hydrogen and

R₄ is bicycloalkyl, bicycloalkenyl, bicycloalkadienyl or a group of the form and wherein R₇, R₈ and R₉ are as defined for formula I may be obtained according to scheme 3A) or 3B) starting from the following corresponding thienyl derivatives

(protected aminothiophenes)

BOC = -C(0)OC(CH₃)₃

and reacting either with the ketone IXa or IXb

or the Grignard-reagent XVb (XVb)

The present invention also relates to novel ketones of formula IX.

The carbothioic acid amides of formula I, wherein X=S may be obtained from the compounds of formula I wherein X=O according to Scheme 4. Scheme 4

The following phenylamine derivatives of formula IV are new and part of the invention :

2-bicyclo[2.2.2]oct-2-yl-phenylamine;

2-bicyclo[2.2.2]oct-2-en-2-yl-phenylamine;

2-bicyclo[2.2.2]octa-2,5-dien-2-yl-phenylamine;

2-(2-aminophenyl)-1 ,1 ,1-trifluoromethyl-4-methyl-pentan-2-ol;

2-(2-aminophenyl)-1 -cyclopropyl-propan-2-ol;

2-(2-aminophenyl)-1-cyclopropyl-butan-2-ol;

2-(3-methyl-1 -trifluoromethyl-but-1 -enyl)-phenylamine;

2-(3-methyl-1 -trifluoromethyl-butyl)phenylamine;

2-(2-cyclopropyl-1 -methyl-ethyl)phenylamine; and

2-(1-cyclopropylmethyl-propyl)phenylamine.

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

Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, 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 formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890. The compounds of formula I 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, fluthafoi, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazoie, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles 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, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines 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-[α{[(α-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, kasuga- mycin, 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-dimethyl- propyl)-2-(2,4-dichlorophenoxy)-propionamide (AC 382042), or iprovalicarb (SZX 722).

A preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, 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 I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and from 0 to 25 % by weight, preferably from 0.1 to 25 % by weight, of a surfactant.

Advantageous rates of application are normally from 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

2-Fluoro-1 -methyl-4-trifluoromethyl-1 H-pyrrole-3-carboxylic acid

A solution of 1.25g (11 mmol) lithiumdiisopropylam.de (LDA) a 95% in 20ml absolute THF is dropwise added to a solution of 1.0g (5.2mmol) 1 -methyl-4-trifluormethyl-1 H-pyrrole-3- carboxylic acid in 60ml THF in such a manner that the temperature remains constant at -75°C. After 3 hours stirring at -75°C, a solution of 1.95g (6.2mmol) N-fluoro- bis(phenylsulfonyl)amine in 20ml absolute THF is added in ca. 30 minutes at a constant temperature of -75°C. Then the cooling is stopped and the reaction mixture is stirred for 16 hours, thereby slowly warming up to room temperature. Then the solvent is removed in a water jet vacuum and the residue is solved in water. After addition of 1 N hydrochloric acid (pH = 1 ) ethylacetate is added and the organic phase extracted twice with additional water. After separation of the organic phase, drying over sodium sulfate and evaporation of the solvent in a water jet vacuum the raw material is obtained. The crude product is purified by column chromatography over silica-gel (eluant : hexane/ethylacetate = 1 :1). Yield : 0.65g 2-Fluoro-1 -methyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid in the form of white crystals; m.p. : 190-191 °C. 2-Chloro-1 -methyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid can be obtained in analogous manner using for example N-chlorsuccinimide as halogenation agent in the reaction described above, m.p. 197-198°C.

Example 2

1 -Methyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid[2-(1 ,3-dimethylbutyl)phenyl]amide

A solution of 0.5g (2.6mmol) 1-methyl-4-trifuoromethylpyrrole-3-carboxylic acid and 0.37g (2.85mmol) oxalylchloride in 20ml 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 0.46g (2.6mmol) 2-(1 ,3-dimethylbutyl)phenylamine, 0.33g (3.4mmol) triethylamine and 15ml methylene chloride. The resulting mixture is then stirred for 16 hours at room temperature. After removal of the solvent in a water jet vacuum, the raw material is taken up in ethylacetate. The ethylacetate phase is washed twice with water and then the organic phase is dried over sodium sulfate. After evaporation of the solvent in a water jet vacuum, the obtained residue is purified by column chromatography over silica- gel (eluant: hexane/ethylacetate = 3:1 ). Yield: 0.45g 1 -Methyl-4-trif luoromethyl-1 H-pyrrole-3- carboxylic acid[2-(1 ,3-dimethylbutyl)phenyl]amide in the form of brownish crystals; m.p. : 83-85°C. Example 3 1 -Methyl-4-trifluoromethyl-1 H-pyrrole-3-carbothioic acid[2-(1 ,3-dimethylbutyl)phenyl]amide

ln a sulfonation flask a mixture of 0.6 g 1 -Methyl-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid[2-(1 ,3-dimethylbutyl)phenyl]amide, 0.45 g P₂S₅ and 30 ml dioxane is heated at 70- 75°C for 3 hours. After filtration, the solvent is removed in a water jet vacuum and the residue taken up in ethylacetate. The organic phase is washed twice with water and ethylacetate is removed in a water jet vacuum. The crude material is purified by column chromatography over silica gel (eluant: ethylacetate/n-hexane = 1 :1 ). Yield: 0.53 g 1 -Methyl- 4-trifluoromethyl-1 H-pyrrole-3-carbothioic acid[2-(1 ,3-dimethylbutyl)phenyl]amide in the form of a reddish resin (¹H-NMR). Example 4 (amine intermediate) 2-(2-cyclopropyl-1-methyl-ethyl)phenylamine

To a solution of 2.96 g (15.5 mmol) of 2-(2-aminophenyl)-1-cyclopropyl-propan-2-ol in 70 ml methanol is added 4.43 g (43.4 mmol) cone, sulfuric acid (96%). The resulting mixture is hydrogenated over 600 mg Pd/C(10%) for 20 hours at 30-35°C. After that time no more hydrogen uptake is detected. The catalyst is filtered off and the solvent removed in a water- jet vacuum. The residue is taken up in ethyl acetate/water and the water phase is neutralised by the addition of sodium carbonate. The water phase is extracted twice with ethylacetate, then the combined organic phase is dried over sodium sulfate. After removal of the solvent in a water-jet vacuum, the crude amine is obtained. The obtained raw material is purified by column chromagraphy over silica gel (eluant: hexane/ether = 5:1 ). Yield: 2.1 g 2-(2-cyclopropyl-1-methyl-ethyl)phenylamine in the form of a brown oil (¹H-NMR). Example 5 (amine intermediate) 2-(3-methyl-1 -trif luoromethyl-but-1 -enyl)phenylamine, E/Z-isomeric mixture

A solution of 1.14 g (4.4 mmol) 1-(3-methyl-1-trifluoromethyl-but-1 -enyl)-2-nitrobenzene in 20 ml methanol is hydrogenated over 10% Pd/C (230 mg) at room temperature for 20 minutes. Then the catalyst is filtered off and the solvent removed in a water-jet vacuum. The crude product is purified by column chromatography over silica gel (eluant: methylenechloride/hexane = 2:1 ). Yield: 0.6 g((sum E + Z isomer) 2-(3-methyl-1 - trifluoromethyl-but-1 -enyl)phenylamine in the form of a brown oil. After column chromatography both isomers are obtained in pure form (¹H-NMR). Example 6 1 ,1 ,1 -trif luoromethyl-4-methyl-2-(2-nitrophenyl)-pentan-2-ol

To a solution of 20.2 g (0.1 mol) 2-bromonitrobenzene in 300 ml abs. tetrahydrofurane is added 81 ml of sec. BuLi (0.105 mol) over a period of 30 minutes in such a manner that the internal temperature remains constant at -103 to -107°C. After stirring for 70 minutes at - 103 to -107°C a solution of 20.0 g (0.13 mol) of trifluoromethylisobutylketone in 150 ml abs. tetrahydrofurane is added over a period of 20 minutes in such a manner that the temperature remains constant at -105°C (+ 2°C). After stirring for 4 hours at -105°C the temperature is raised to -20°C and a solution of 150 ml of saturated ammoniumchloride solution is added. Then 1 I of ethylacetate is added and the organic phase is washed 3 times with water. After drying the organic phase over sodium sulfate and distilling off the solvent in a water-jet vacuum the raw-material is obtained. Purification is achieved by column chromatography over silica gel (eluant: hexane/ethylacetate = 5:1). Yield: 8.2 g 1 ,1 ,1 -trif luoromethyl-4-methyl-2-(2-nitrophenyl)pentan-2-ol in the form of a brownish powder; m.p.: 103-105°C. Example 7 1 -(3-methyl-1 -trif luoromethyl-but-1 -enyl)-2-nitrobenzene (E/Z-mixture)

To a solution of 10.8 g (39 mmol) 1 ,1 ,1-trifluoromethyl-4-methyl-2-(2-nitrophenyl)pentan-2-ol in 110 ml of abs. pyridine is added slowly 13.9 g (117 mmol) thionylchloride at a temperature of 0-5°C. Then the mixture is heated at 90-95°C for 1 hour. After cooling the reaction mixture is added to ice water. The resulting solution is extracted carefully with ethylacetate and after drying of the organic phase over sodium sulfate and distilling off the solvent in a water-jet vacuum, the crude product is obtained. Purification is achieved by column chromatography over silica gel (eluant: methylene chloride/hexane = 1 :1). Yield: 5.2 g 1-(3-methyl-1-trifluoromethyl-but-1-enyl)-2-nitrobenzene in the form of a brownish oil (¹H-

NMR).

Example 8 (amine intermediate)

2-(3-methyl-1-trifluoromethyl-butyl)phenylamine

A solution of 2.98 g (12.9 mmol) 1-(3-methyl-1-trifluoromethyl-but-1 -enyl)-2-nitrobenzene in 30 ml methanol is hydrogenated over Raney-Nickel (ethanol) at 100°C and 150 bar for 10 hours. Then the catalyst is filtered off and the solvent removed in a water-jet vacuum. The obtained crude product is purified by column chromatography over silica gel (eluant: hexane/methylene chloride = 1 :2). Yield: 1.9 g 2-(3-methyl-1 -trif luoromethyl- butyl)phenylamine in the form of a brown oil (¹H-NMR).

o Φ CD CD U- ._ ^ CD CD __ Φ CD CD CD Φ U_ Φ Φ

Φ ^. cc ϋ UJ 111 Ε LU 2 LU UJ LU S O

=5 ><

Έ Φ CD CD CD CD CD Φ Φ Φ Φ u_ Φ ω

II cc ϋ 2 2 2 E 2 2 _> 2 2 ι≥ o Έ Έ ~σ

Φ Φ U. Φ Φ Φ Φ Φ Φ Φ Φ if L Φ Φ U- Φ LJ Φ

DC Ε ϋ ϋ ϋ 2 -- ϋ 2 ϋ s O cc DC X X X X X X X X X X X X X X X X X X X

o CO

90 2! o

00 CD

CO

X u 3 ϋ o II CΛ o

CD

---- >> O ω c 00 + c ^'n II Έ o. fc

H <ι> + U α. CC _≥ o

X m

X

Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ

2.2 CF₃ Me H

2.14 CF₃ CHpOMe H H H

2.20 CF₃ CHpOMe F H H

2.21 CF₃ CHpOMe F H H

2.24 CF₃ CHoOMe F H H

Table 3

Cmpd. Ri R_{2 3} R₅ Re R₇ R₈ R₉ Phys. data no. m.p.^DC

3.1 CF₃ Me H H H Me Me Me 92-93

3.2 CF₃ CH₂OMe H H H Me Me Me

3.3 CF₃ Me H H H CF₃ Me Me

3.4 CF₃ Me H H H Me CF₃ CF₃

3.5 CF₃ Me H H H Me Me Et 3.6 CF₃ CH₂OMe H H H Me Me Et

3.7 CF₃ Me H 6'-F H Me Me Me

3.8 CF₃ Me H 5'-F H Me Me Me

3.9 CF₃ Me H H H Me Et Et

3.10 CF₃ Me F H H Me Me Me Oil

3.11 CF₃ CHsOMe F H H Me Me Me

3.12 CF₃ Me F H H Me Me Et

3.13 CF₃ Me F H H CF₃ Me Me

3.14 CF₃ Me F H H CF₃ Me Et

3.15 CF₂H Me H H H Me Me Me Oil

3.16 CF₂H Me H H H Me Me Et

3.17 CF₂H Me H H H CF₃ Me Me

3.18 CF₂H Me H H H Me Me Me

3.19 CFH₂ Me H H H Me Me Me

3.20 CFH₂ Me H H H Me Me Et

3.21 CFH₂ Me H H H CF₃ Me Me

3.22 CFH₂ Me H H H Me Me Me

Table 4

Cmpd. Ri R₂ R₃ RB phys.data no. ιm.p.°C

4.2 CF₃ Me H H H Resin

4.4 CF₃ Me H H H Resin

Table 5

Cmpd. Ri R₂ R₃ R₅ Re R₇ Rio R11 phys. data no. m.p.°C

5.1 CF₃ Me H H H Me H H 109-110

5.2 CF₃ CH₂OMe H H H Me H H

5.3 CF₃ Me H H H CF₃ H H

5.4 CF₃ Me H H H Me Cl Cl

5.5 CF₃ CH₂OMe H H H CF₃ H H o

90 o

---- ω

H U co α. w

X X X X X ϋ X X X X X X X X ϋ ϋ X X X X X X X

Φ Φ U- ω LL Φ Φ LL Φ LL Φ LL Φ LL Φ Φ Φ -^ Φ ^ -,., ^ *. 2 -Σ ϋ 2 ϋ S S ϋ -S ϋ 2 ϋ 2 ϋ -2 S S iϊj S LlJ LLJ UJ UJ

CM

X X X X X X X X X X X X X X X X X X X X X X X x x x x x x x x x x x x x x x x x x x x x x x

LL LL LL LL U. X X X X LL LL X X X LL LL φ Φ Φ φ φ φ Φ φ

O O O O O O O O

Φ X Φ X X Φ Φ Φ X X Φ Φ X X Φ X Φ Φ Φ Φ Φ Φ Φ

S ϋ S ϋ ϋ ^ S 2 ϋ ϋ 2 S ϋ θ 2 ϋ 2 2 S 2 S 2 S

X X X X X X X X X X -^ -^ X X X

U_ LL LL LL LL LL LL U_ LL LL LL LL U_ LL LL LL LL LL LL LL LL LL LL ϋ ϋ ϋ ϋ ϋ O ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ O ϋ ϋ ϋ ϋ O O

90 o O O τ- CM CO -^- in CD I^*-~ CO CΛ O τ- CM CO ^*sr in CD ^"*^ 00

^•O N CO ffi r r r r- r r r r - r N N W N N αi W IN W

-n . -'j in i. -o -n -n in -n .n -n i .n -O -n

o w CM

90 00

Φ CO co o E CD α. o CO ω -2 II O X

H Φ CD U 00 a. -_* Φ— * X 00 co O CO CO Z

Q o ϋ X o en r φ φ >» D. ^'ω O

Φ X D_ b Φ X

Έ

II TJ Φ Φ LL .^ ^ ^ Φ ₊. ^ Φ ^. Φ Φ

E X

CO φ φ φ φ φ φ φ φ φ φ φ φ φ

X ϋ 2 UJ

Table 7: Amine-lntermediates

¹H-NMR Table

Compd. ¹H-NMR-data (ppm/multiplicity/number of protons; solvent CDCI₃)

No.

6.1 0.82/2xd/6H; 1.19/d/3H; 1.35-1.60/m/1H; 3.70/s/3H; 6.99/d/1H;

7.2-7.4/m/4H; 7.61/d/1H; 8.70/s(broad)/1 H

6.5 0.75-0.88/m/12H; 1.0-1.65/m/6H; 1.18/d/3H; 1.20/d/3H; 3.0/m/2H;

3.70/s/6H; 7.0/d/2H; 7.2-7.4/m/8H; 7.61/d/2H; 8.7/s/2H

7.2 0.1/m/2H; 0.45/m/2H; 0.65/m/1H; 1.69/s/3H; 1.80/m/1H; 2.0/m/1H;

3.7/s(broad)/3H(OH+NH₂); 6.60-6.70/m/2H; 6.98-7.11/m/2H

7.3 0.01/m/2H; 0.35/m/2H; 0.55/m/2H; 0.75/t/3H; 1.51/m/1H; 1.8-2.05/m/3H;

3.72/s(broad)/3H(OH+NH₂); 6.47-6.59/m/2H; 6.91 /m/2H

7.4.1 1.09/d/6H; 3.02/m/1H; 3.60/s(broad)/2H(NH₂); 5.81 /d/1H; 6.72/m/2H;

(E-isomer) 6.99/dxd/1H;7.15/txd/1H

7.4.2 0.91/d/3H; 1.03/d/3H; 2.25/m/1H; 3.58/s(broad)/2H; 6.36/dxd/1H;

(Z-isomer) 6.78/m/2H; 6.99/dxd/1H; 7.18/txd/1H

7.5 0.83/d/3H; 0.87/d/3H; 1.40/m/1H; 1.69/m/1H; 1.99/m/1H;

3.6/m/3H(NH_z+H-benzylic); 6.75/dxd/1 H; 6.85/t/1 H; 7.09-7.2/m/2H

7.6 0.05/m/2H; 0.4/m/2H; 0.69/m/1H; 1.29/d/3H; 1.35/m/1H; 1.60/m/1H;

2.88/m/1H; 3.65/s(broad)/2H(NH₂); 6.68/d/1H; 6.85/t1H; 7.0/txd/1H;

7.1/dxd/1H

7.7 0.01/m/2H; 0.38/m/2H; 0.60/m/1H; 0.82/t/3H; 1.32/m/1H; 1.52-1.80/m/3H;

2.68/m/1H; 3.65/s(broad)/2H(NH₂); 6.69/d/1H; 6.78/t/1H; 7.0/txd/1H;

7.08/dxd/1H

1.28 0.78-0.85/t+d/9H; 1.35-1.69/m/5H; 2.85/m/1H; 3.70/s/3H; 7.0/d/1H;

7.20/m/3H; 7.37/d/1H; 7.58/s(broad)/1 H; 7.7/m/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: Funqicidal 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 6 show good activity in these tests (< 20% infestation).

Example B-2: Action against Podosphaera leucotricha I apple (Powdery mildew on apple) 5 week old apple seedlings cv. Mclntosh 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 6 show good activity in this test.

Example B-3: Action against Venturia inaequalis I apple (Scab on apple)

4 week old apple seedlings cv. Mclntosh are treated with the formulated test compound

(0.02% active ingredient) in a spray chamber. One day after application 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 6 show good activity in this test.

Example B-4: Action against Erysiphe αraminis I 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 6 show good activity in this test. Example B-5: Action against Botrytis cinerea I apple (Botrytis on apple fruits)

In an apple fruit cv. Golden Delicious 3 holes are drilled and each filled with 30 μl droplets of the formulated test compound (0.002% active ingredient). Two hours after application 50 μl 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 6 show good activity in this test.

Example B-6: Action against Botrytis cinerea I 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 6 show good activity in this test.

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 6 show good activity in this test.

Example B-8: Action against Pyrenophora feres/ 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 6 show good activity in this test. Example B-9: Action against Septoria trøαto m /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 Tables 1 to 6 show good activity in this test.

Claims

What is claimed is

1. A pyrrolecarboxylic acid amide or pyrrolecarbothioic acid amide of the formula I

wherein

X is oxygen or sulfur;

R₁ is CF₃, CF₂H or CFH₂;

R₂ is Cι-C₃alkyl, CrC₃haloalkyl, CrC₃alkoxy-CrC₃alkyl or C C₃haloalkoxy-CrC₃alkyl;

R₃ is hydrogen, methyl, CF₃ or fluoro;

R₄ is C₆-Cι₄bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; C₆-C₁₄bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; C₆-Cι₄bicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or

C C₃haloalkyl; or a group

wherein R_i0 and Rn are independently of each other hydrogen or halogen and n = 1 or 2; and

R₅ and R₆ are independently of each other hydrogen or halogen.

2. A compound of formula I according to claim 1 , wherein X is oxygen.

3. A compound of formula I according to claim 1 , wherein X is sulfur.

4. A compound of formula I according to claim 1 , wherein

R₂ is C C₃alkyl, C C₃haloalkyl or C Csalkoxy-Ci-Csalkyl ;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is C₆-Ciobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

wherein R₇, R₈ and R₉ are independently of each other d-C₃alkyl or

C_rC₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

5. A compound of formula I according to claim 4, wherein R₄ is a group of the form

wherein R₇, R₈ and R_g are independently of each other CrC₃alkyl or

C C₃haloalkyl.

6. A compound of formula I according to claim 1 , wherein

R₂ is C C₃alkyl, Cι-C₃haloalkyl or C C₃alkoxy-Cι-C₃alkyl; R₃ is hydrogen or fluoro; Q is Q2, Q3 or Q4; R is Ce-Ciobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃; C₆-Cι₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ; C₆-Ciobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

[ j wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or

R₇ R₈

C_rC₃haioalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

7. A compound of formula I according to claim 6, wherein Q is Q2.

8. A compound of formula I according to claim 2, wherein

R₂ is C C₃alkyl or Cι-C₃alkoxy-C C₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R₄ is C₆-Cι₀bicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C₆-Ciobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

Cι-C₃haloalkyl; or a group

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

9. A compound of formula I according to claim 8, wherein R₂ is methyl or CH₂OCH₃; R₄ is a group of the form

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro.

10. A compound of formula I according to claim 9, wherein R₂ is methyl.

11. A compound of formula I according to claim 9, wherein R₂ is methyl;

R₃ is hydrogen;

R is a group of the form

[ [ wherein R₇, R₈ and R₉ are independently of each other methyl or ethyl,

R₇ R₈

preferably methyl; and

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro.

12. A compound of formula I according to claim 9, wherein R₂ is methyl;

R₃ is fluoro;

R₄ is a group of the form

R₅ and R₆ are independently of each other hydrogen, fluoro or chloro.

13. A compound of formula I according to claim 1 , wherein R₂ is C C₃alkyl, C C₃haloalkyl or C C₃alkoxy-C C₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q1 ;

R is C₆-Ciobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

C₆-Ci₀bicycloalkenyl unsubstituted or substituted by methyl, ethyl or CF₃ ;

wherein R₇, R₈ and R₉ are independently of each other CrC₃alkyl or d-C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

14. A compound of formula I according to claim 13, wherein

X is oxygen;

R₂ is methyl or CH₂OCH₃;

R is a group of the form

wherein R₇, R₈ and R₉ are independently of each other C C₃alkyl or

C_rC₃haloalkyl.

15.A compound of formula I according to claim 1 , wherein

R_! is CF₂H or CFH₂;

R₂ is C C₃alkyl, Cι-C₃haloalkyl or Cι-C₃alkoxy-CrC₃alkyl;

R₃ is hydrogen or fluoro;

Q is Q2, Q3 or Q4;

R₄ is C₆-Cιobicycloalkyl unsubstituted or substituted by methyl, ethyl or CF₃;

Ce-Ciobicycloalkadienyl unsubstituted or substituted by methyl, ethyl or CF₃ ; a group of the form wherein R₇, R₈ and R₉ are independently of each other CrC₃alkyl or

C C₃haloalkyl; and

R₅ and R₆ are independently of each other hydrogen, chloro or fluoro.

16. A compound of formula I according to claim 15, wherein X is oxygen;

R₂ is methyl or CH₂OCH₃; R₄ is a group of the form

wherein R₇, R₈ and R₉ are independently of each other Cι-C₃alkyl or d-C₃haloalkyl.

17. A compound of formula I according to claim 1 selected from

1 -methyl-4-trifluoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3-dimethylbutyl)phenyl]amide;

1 -methyl-2-f luoro-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3- dimethylbutyl)phenyl]amide;

1 -methoxymethyl-2-f luoro-4-trif luoromethyl-1 H-pyrrole-3-carboxylic acid [2-(1 ,3- dimethylbutyl)phenyl]amide;

1 -methyl-4-trif luoromethyl-1 H-pyrrole-3-carbothioic acid [2-(1 ,3-dimethyibutyl)phenyl]amide.

18. A process for the preparation of compounds of formula I, which comprises in a first step preparing the compounds of formula I wherein X=O by converting the pyrrolecarboxylic acid II

to the acid chloride III

and by reacting the pyrrole acid chloride III with the amine IV H₂N-Q IV to the compounds of formula I

and optionally converting these compounds to the compounds of formula I wherein X=S by reacting with Lawesson-Reagent or P₂S₅ in dioxane, tetrahydrofurane or toluene at a temperature of 0° - reflux to

and wherein Ri, R₂, R₃ and Q are as defined for formula I in claim 1.

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

20. Use of a compound of formula I according to claim 1 for protecting plants against infestation by phytopathogenic microorganisms.

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

22. The amine intermediates of formula IV H₂N-Q wherein Q and R₄, R₅, Rε, R₇, R₈, R9, R₁0 and Rn are as defined in claim 1.

23. A compound of formula IV according to claim 22 selected from 2-bicyclo[2.2.2]oct-2-yl-phenylamine; 2-bicyclo[2.2.2]oct-2-en-2-yl-phenylamine; 2-bicyclo[2.2.2]octa-2,5-dien-2-yl-phenylamine; 2-(2-aminophenyl)-1 ,1 ,1-trifluoromethyl-4-methyl-pentan-2-ol; 2-(2-aminophenyl)-1 -cyclopropyl-propan-2-ol; 2-(2-aminophenyl)-1-cyclopropyl-butan-2-ol;

2-(3-methyl-1 -trifluoromethyl-but-1 -enyl)-phenylamine; 2-(3-methyl-1 -trifluoromethyl-butyl)phenylamine; 2-(2-cyclopropyl-1 -methyl-ethyl)phenylamine; and 2-(1-cyclopropylmethyl-propyl)phenylamine.

24. A process for the preparation of compounds of the formula IV according to claim 22, characterized by

Route a) reacting the formyl derivate W-NHCHO of formula X with a ketone of formula IX in the presence of 2-3 equivalents of n-BuLi or sec-BuLi or another strong base in a solvent at a temperature of -100 to -110°C providing the compounds of formula XI (WY-NHCHO); converting the formyl derivative of formula XI to the amine compounds of formula VI (H₂N-WY) in a basic hydrolysis by reacting with NaOH or KOH in alcohols; and hydrogenation the amine VI to the compounds IV (H₂N-Q) with Pd/charcoal in the presence of a strong acid (f .e. sulfuric acid) or alternatively elimination of water and than hydrogenation; or

Route b) reacting the amine of formula XII (H₂N-T) with an excess of the Grignard reagent of formula XV in a solvent like THF or ether at a temperature 0°C to reflux to the amine of formula VI; and converting the amine VI to the amine XIV (H₂N-TG) by elimination of water; the hydrogenation of XIV with Pd or Pt on charcoal in a solvent like THF or alcohols at temperatures of 0°C to reflux provides the compounds of formula IV; or directly the compounds of formula VI by hydrogenation with Pd on charcoal in the presence of sulfuric acid in a solvent like an alcohol provides the amines IV; or .

Route c) reacting the nitro derivative NO₂-W (formula XIII) with a ketone of formula IX providing the nitro derivative NO₂-WY of formula VII; transforming the compound of formula VII by reaction with SOCI₂ or POCI₃ in pyridine at a temperature of 0°C to reflux to the derivative VIII (NO₂-TG); and hydrogenation of the compound of formula VIII with Raney-Ni in alcohol at a pressure of 50- 200 bar and a temperature of 50-150°C to the compound of formula IV; wherein Q, R₅, R₆, R₇, R₈, R₉, Rio, Rn are as defined in claim 1 for compounds of the formula I, Hal is Br or I and wherein

and wherein n+m=2-10

25. A process according to claim 24, Route a), for compounds of formula IV wberein Q is Q1 ; and

R is C₇-C₉bicycloalkyl unsubstituted or substituted by methyl or CF₃; C₇-Cgbicycloalkenyl unsubstituted or substituted by methyl or CF₃; C₇-C₉bicycloalkadienyl unsubstituted or substituted by methyl or CF₃; or a group

R₅ and R₆ are hydrogen; and wherein R₇, Rio, Rn and n are as defined in claim 1.

26. A process according to claim 24, Route a), wherein Q is Q2, Q3 or Q4; and

R₄ is C₇-Ci₀bicycloalkyl unsubstituted or substituted by methyl or CF₃; C₇-Ci₀bicycloalkenyl unsubstituted or substituted by methyl or CF₃; C₇-Cι₀bicycloalkadienyl unsubstituted or substituted by methyl or CF₃; or a group

R₅ and R₆ are hydrogen; and wherein R₇, R₈, R₉ and n are as defined in claim 1.

27. A process according to claim 24, Route b), wherein

Q is Q1 ; and

R is C₇-Cι₀bicycloalkyl unsubstituted or substituted by methyl or CF₃;

C₇-C obicycloalkenyl unsubstituted or substituted by methyl or CF₃;

C₇-Cιobicycloalkadienyl unsubstituted or substituted by methyl or CF₃;

or a group

28. A process according to claim 24; Route b), wherein

Q is Q2, Q3 or Q4; and

R₄ is C₇-Cιobicycloalkyl unsubstituted or substituted by methyl or CF₃; C₇-C₁₀bicycloalkenyl unsubstituted or substituted by methyl or CF₃; C₇-Cιobicycloalkadienyl unsubstituted or substituted by methyl or CF₃;

or a group

29. A process according to claim 24, Route c), wherein Q is Q1 ; and

R₄ is a group ^" | ;

R₇ R_g

R₅ and R₆ are hydrogen;

R₇ is CF₃; and wherein R₈, R₉ and n are as described in claim 1 .

30. A process according to claim 24, Route c), wherein Q is Q1 ;

R₄ is a group

R₅ and R₆ are hydrogen; n is 1 ;

R₇ is CF₃; and wherein R_i0 and Rn are as defined in claim 1.