EP0561961A1 - Novel heterocyclic amidines and guanidines as plant fungicides - Google Patents

Abstract

Compounds of formula (I) all comprising geometric stereoisomers, agricultural compositions containing them and their use as fungicides.

Description

TITLE

NOVEL HETEROCYCLIC AMIDINES AND

GUANIDINES AS PLANT FUNGICIDES

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application U.S. Serial No.

07/626,887, filed December 13, 1990.

BACKGROUND OF THE INVENTION EP 0375414 A1 discloses as fungicides substituted guanidine and amidine compounds of the formula:

wherein:

R¹ is H or C₁-C₃ alkyl;

each R² is independently H or C₁-C₄ alkyl;

R³ is C₄-C₂₀ alkyl, C₄-C₂₀ alkenyl, phenyl, phenyl-C₁-C₃ alkylene, or phenyl-C₂-C₃ alkenylene wherein the phenyl ring can be substituted with 1-5 halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, trihalomethyl, phenyl or phenoxy;

R⁴ is H or C₁-C₄ alkyl;

Y is -(CR⁷R⁷)_n-, wherein n is 2, 3 or 4, each R⁷ is independently H or C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₂-C₄ alkoxyalkyl; or -(CH₂)_q-O(CO)-R⁸, wherein q is 1, 2 or 3, and R⁸ is methyl or ethyl; and

R⁴ is H or C₁-C₃ alkyl.

SUMMARY OF THE INVENTION

This invention pertains to compounds of Formula I including all geometric and stereoisomers, agricultural compositions containing them and their use as fungicides.

wherein:

W is H, C₁-C₄ alkyl or C₃-C₄ alkenyl;

n is 0 or 1;

X is O, S, CR⁵R⁶ or NR⁷;

Y is CR⁸R⁹ or CR⁸R⁹CR¹⁰R¹¹;

R¹, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹⁴ and R¹⁵ are independently H or

C₁-C₄ alkyl;

R² is C₄-C₂₀ alkyl, C₄-C₂₀ alkenyl or C₄-C₂₀ alkynyl each optionally

substituted with halogen or CN; C₃-C₂₀ cycloalkyl optionally substituted with C₁-C₆ alkyl; phenyl or thienyl substituted with R¹² and R¹³; or aralkyl or aralkenyl optionally substituted with R¹² and R¹³ on the aryl ring and R¹⁴ and R¹⁵ on the alkyl or alkenyl moiety;

R³ and R⁴ are independently C₁-C₁₀ alkyl; C₁-C₁₀ alkoxy; NR¹⁶R¹⁷;

phenyl, benzyl or phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl; or R³ and R⁴ may be taken together with the nitrogen to which they are attached to form heterocycles of the formulae:

R¹² and R¹³ are independently H; halogen; CN; C₁-C₆ alkyl; C₁-C₆

cyanoalkyl; C₁-C₃ haloalkyl; C₃-C₆ cycloalkyl; C₃-C₆

cycloalkylmethyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; silicon substituted with any three of the group consisting of C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl and C₁-C₃ haloalkyl; or R¹² and R¹³ are independently phenyl optionally substituted with halogen, CN or C₁-C₄ alkyl;

R¹⁶ and R¹⁷ axe independently C₁-C₁₀ alkyl; or phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹⁸ and R¹⁹ are independently H; CN; C₁-C₄ alkyl; C₂-C₄ alkenyl; C₁-C₄ alkoxy; C₁-C₄ hydroxyalkyl; or phenyl optionally substituted with 1-2 halogen;

R²⁰ and R²¹ are independently H, halogen, CN, C₁-C₄ alkyl or C₁-C₄

alkoxy;

R²²is H, OH, halogen, CN, C₁-C₄ alkyl or C₁-C₄ alkoxy;

Qis O orNR²³;

R²³ is H, OH, C₁-C₃ alkyl or C₁-C₃ alkoxy;

Zis O orNR²⁴;

R²⁴ is H or C₁-C₄ alkyl;

E is O or CH₂; or their agriculturally suitable salts thereof, including, but not limited to, halide, acetate, benzoate, dodecylbenzenesulfonate, methanesulfonate, sulfate and nitrate.

Provided that:

1) When R³ is NR¹⁶R¹⁷ or C₁-C₁₀ alkoxy, R⁴ cannot be NR¹⁶R¹⁷ or C₁-C₁₀ alkoxy; and

2) When R³ and R⁴ are taken together to form structure A-4, R¹⁸ and R¹⁹ are independently CN, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₁-C₄ alkoxy or C₁-C₄ hydroxyalkyl. Formula I, as illustrated, contains a single double bond. However, it will be clear to one skilled in the art that the double bond is actually delocalized over the two or three nitrogen atoms of compounds of Formula I. Further, the compounds of Formula I can exist in tautomeric forms. All of these forms are understood as being within the scope of the instant invention. Compounds preferred for greatest fungicidal activity and/or ease of synthesis are:

1 ) Compounds of Formula I wherein:

W is H;

Y is CH₂;

R¹ is H or CH₃; and

Q is O.

2) Compounds of Preferred 1 wherein:

R³ and R⁴ are independently C₁-C₁₀ alkyl; phenyl, benzyl or

phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl; or R³ and R⁴ may be taken together with the nitrogen to which they are attached to form heterocycles of the formulae A-1 , A-2, A-3, A-4, A-6, A-9, A-11, A-12, A-13 or

A-16;

R¹² and R¹³ are independently H, halogen, CN, C₁-C₆ alkyl, C₁-C₆ cyanoalkyl, C₁-C₆ haloalkyl or C₃-C₆ cycloalkyl;

R¹⁸ and R¹⁹ are independently H, CN, C₁-C₄ alkyl, C₁-C₄ alkoxy or C₁-C₄ hydroxyalkyl;

R²⁰ and R²¹ are independently H, CN or CH₃; and

R²² is H or OH.

3) Compounds of Preferred 2 wherein:

X is O, CH₂ or NCH₃; and

R¹, R⁸, R⁹, R¹⁰, R¹¹, R¹⁴ and R¹⁵ are H.

4) Compounds of Preferred 3 wherein:

R³ and R⁴ are taken together with the nitrogen to which they are attached to form heterocycles of the formulae A-1 , A-3, A-4,

A-6, A-9, A-11, A-12, A-13 or A-16. 5) Compounds of Preferred 4 wherein:

R² is C₄-C₁₀ alkyl; C₃-C₆ cycloalkyl optionally substituted with

C₁-C₆ alkyl; phenyl or thienyl substituted with R¹² and R¹³; or benzyl optionally substituted with R¹² and R¹³ on the aryl ring; R¹² and R¹³ are independently H, CN, C₁-C₆ alkyl, CF₃ or C₃-C₄ cycloalkyl; and for salts, chloride.

Specifically preferred for greatest fungicidal activity and/or ease of synthesis are

1) 3-[4-(1,1-dimethyIethyl)phenyl]-3,4-dihydro-5-(1-pvrrolidinyl)-2H- pyrrole hydrochloride

2) 1-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol-5-yl]-3,5- dimethyl-piperidine

3) 2-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol-5-yl]- decahydroisoquinoline

4) 2-[3,5-dihydro-3-(4-(1-methylethyl)phenyl-2H-pyrrol-5-yl]- 1,2,3,5,6,7,8a-octahydro-5,5,8a-trimethyl-6-isoquinolinol.

Having briefly summarized the invention, the invention will now be described in detail by reference to the following specification and non-limiting examples. Unless otherwise specified, all percentages are by weight and all temperatures are in degrees Celsius.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

Compounds of Formula I wherein n is 1 and W is C₁-C₄ alkyl or C₃-C₄ alkenyl can be prepared by the displacement of a leaving group L in 2 where W¹ is C₁-C₄ alkyl or C₃-C₄ alkenyl with Formula I compounds in which n is O. Typical leaving groups in 2 include halides and sulfonates. The reaction is run in polar solvents such as acetone or dimethylformamide (DMF), in ethereal solvents such as diethyl ether or tetrahydrofuran (THF) or in hydrocarbons such as benzene or toluene. Temperatures for the reaction range from 0 - 150°C. Compounds of

Formula I wherein n is 1 and

W is H are recognized as the conjugate acids of la wherein n is 0 and are prepared by treatment of la with an acid such as HCl, acetic acid, benzoic acid or a sulfonic acid.

Compounds of Formula la can be prepared by displacement of a leaving group, LG, in 2 with an amine 4. Typical values for LG include halides, alkoxyls, alkylthios, sulfenates and sulϋnates. The reaction is run with one or more equivalents of the amine with or without an added base such as potassium carbonate, triethylamine or butyllithium. Appropriate solvents includes ethereal solvents such as ether or THF, hydrocarbons such as benzene or toluene or the amine itself may be used as solvent.

Compounds of Formula 2 in which LG is a halide can be prepared from compounds of Formula 5 by standard methods for the conversion of amides, ureas, carbamates and thiocarbamates to the corresponding iminoyl halide compounds. Typical reagents for the conversion include PCI₅, POCI₃, PBr₅, SOCI₂, SOBr₂. Appropriate solvents include hydrocarbons such as benzene or toluene or

chlorocarbons such as methylene chloride or 1,2-dichloroethane. Temperatures for the reaction range from 25 - 150°C.

Compounds of Formula 3 in which LG is alkoxyl also can be prepared from 5 by treatment with an alkylating reagent such as trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate, dimethyl sulfate or methyl iodide. The alkylation is run in hydrocarbons such as benzene or toluene or in chlorocarbons such as methylene chloride or chloroform at temperatures of 25 - 150°C.

Compounds of Formula 5a, a subset of 5 in which X is a heteratom and Y is CR⁸R⁹, can be made from 6 and phosgene or a phosgene equivalent such as carbonyldiimidazole or diethylcarbonate in a nonprotic solvent such as THF or methylene chloride with base catalysis.

Compounds of Formula 6 are available by a variety of methods set out in the literature. For example, reduction of cyanohydrins of Formula 2 with lithium aluminum hydride affords the aminoalcohol of Formula 6a.

Compounds of Formula 5b, a subset of Formula 5 compounds in which X is CR⁵R⁶ and Y is CR⁸R⁹ are prepared from compounds of Formula 8 wherein R is lower alkyl by catalytic reduction of the nitro group to an amine followed by cyclocondensation. The catalytic reduction may be carried out over a palladium or platinum catalyst on carbon in acetic acid or over Raney nickel in ethanol.

Hydrogen pressures of 1-50 psi and temperatures of 25-100°C may be used. The cyclization is carried out in a hydrocarbon solvent such as benzene or toluene with or without heating at reflux, with or without an acid catalyst such as HCl or

p-toluenesulfonic acid. Compounds of Formula 8 are available by addition of the anion of compounds of

Formula 2 to compounds of Formula 10 followed by addition of an electrophile R⁹-L wherein L is a halide or sulfonate leaving group. The anion of 9 may be generated with a strong base such as potassium-t-butoxide or lithium diisopropylamide in an ethereal solvent such as THF. Formula 9 compounds are generally commercially available or synthesized by procedures set out in the literature. Formula 10 compounds are generally made by condensation between carbonyl compounds R¹(C=O)R² and nitro compounds R⁸-CH₂-NO₂ with a base catalyst such as sodium ethoxide or Triton B^® followed by dehydration by methanesulfonyl chloride or acetic anhydride in pyridine. Alternatively 8a (a subset of 8) may be made by reaction of nitro compound 11 with 12 where R is lower alkyl in the presence of catalytic amount of base such as Triton B^® or potassium-t-butoxide.

Compounds of Formula 5c, a subset of 5 wherein X is a heteroatom and Y is CR⁸R⁹CR¹⁰R¹¹, can be made from 12 and phosgene or a phosgene equivalent as in the preparation of 5a (vide supra).

Compounds of Formula 13 can be prepared by a variety of methods. For example, treatment of 14 with 15 in the presence of a base such as potassium-t- butoxide or Triton B^® affords 16 which may be reduced with lithium aluminum hydride, palladium on charcoal in acetic acid or Raney nickel in ethanol to form 13. Formula 14 compounds may be prepared by standard literature procedures for the

preparation of epoxides, aziridines and episulfides (see J. March in Advanced Organic Chemistry, 3rd Ed., J. Wiley & Sons, New York, 1985, pp. 1156, 1161).

Compounds of Formula 5d, a subset of 5 wherein Y is CR⁸R⁹CR¹⁰R¹¹, may be prepared by reaction of a compound of Formula 12, wherein R is lower alkyl and L is a leaving group such as a halide in a hydrocarbon solvent such as benzene at elevated pressures and temperature (25 - 150°C). Compounds of Formula 12 are in turn obtained by treatment of compounds of Formula 18 with HBr or HCl in a lower alcohol solvent.

Compounds of Formula 18 are available by a variety of methods set out in the literature. For example, reduction of anhydride 12 with sodium borohydride affords 18a. Anhydride 19 in turn is available by reaction of 21

with a strong base such as lithium diisopropyl amide, followed by addition of aciylate 20, and then by addition of R⁶L to afford 22 as an intermediate. R in 20, 21 and 22 is lower alkyl and L is a leaving group such as a halide or p-toluenesulfonate. The conversion of 22 to 19 is carried out by standard literature methods of ester hydrolysis followed by cyclization to the anhydride.

Amines 4 are generally available commercially or else are known in the literature. The synthesis of amines 4 in which R³ and R⁴ are taken together with the nitrogen to form the heterocycle of A-9 has been described (Rahier, A. et al.,

Phytochemistry. vol. 24, No. 6, pp 1223-1232, 1985). Amines 4 in which R³ and R⁴ taken together with the nitrogen to form the heterocycle of A-11 or A-12 may be synthesized from amines such as 22 (Rahier, A., et al., Phytochemistry. vol. 24, No. 6, pp 1223-1232, 1985) by methods known to those skilled in the art.

For example, removal of the benzyl protecting group of 22 by heating with benzyl chloroformate followed by hydrolysis with NaOH or KOH affords 24 which may be reduced with a hydride reagent (such as lithium aluminum hydride or sodium borohydride) or else reacted with an organometallic reagent to afford heterocycles of Formula A-12a (a subset of A-12).

Alternatively, reaction of 22 with a base such as potassium t-butoxide and an alkylating reagent or an acid affords 25 which may in turn be converted to heterocycles of Formula A-11a (a subset of A 11) as described for the conversion of 22 to A-12a.

Those skilled in the art will recognize that Formula 1 compounds can contain two or more asymmetric carbon atoms. The stereoisomers that result can be separated using standard methods known in the art if desired.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. In the following examples, all temperatures are set forth in degrees Celsius; unless otherwise indicated, all parts and percentages are by weight.

EXAMPLES

Example 1

Synthesis of 1-[3-[4-(1,1-dimethylethyl)phenyl]- 3,4-dihydro-2H-pyrrol-5-yl]-cis-3.5-dimethylpiperidine A 60% oil dispersion of sodium hydride (6.0 g, 0.148 mol) was rinsed three times with hexanes, suspended in 200 mL dimethoxyethane and cooled to 0°C.

Triethylphosphonoacetate (29.4 mL, 0.148 mol) was added dropwise. The solution was warmed to room temperature and stirred until gas evaluation ceased. 4-t-Butylbenzaldehyde (20.0 g, 0.124 mol) was added dropwise and the reaction mixture was heated at 65°C for 1 h and stirred at room temperature overnight. After quenching with aqueous NH₄CI, solvent was removed and the aqueous residue was taken up in ether. The ether was washed twice with water and once with brine. Drying

(MgSO₄) and removal of solvent gave 31.6 g of ethyl 3-(4-t-butylphenyl)-propenoate.

Solvent from a solution of 4.0 g N-benzyltrimethyl ammonium hydroxide (40%) in methanol was evaporated away. n-Butanol (10 mL) was added and solvent was again evaporated. The residue was dissolved in 2-3 mL n-butanol and added to a solution of 20.0 g (86 mmol) of the preceding compound in 250 mL nitromethane.

The mixture was heated at 68°C overnight. A solution of 2 g of N-benzyltrimethyl- ammonium hydroxide was added and heating at 68°C was continued another 24 h.

The reaction mixture was acidified with aqueous HCl, and extracted with methylene chloride. The organic layer was washed with water and brine, dried (MgSO₄) and solvent was removed to afford 24.4 g of ethyl-3-(4-t-butylphenyl)-4-nitrobutyrate as an oil.

The preceding compound (24.1 g, 82 mmol) dissolved in 200 mL acetic acid was hydrogenated over 5.0 g of 10% palladium on carbon at 40 psi overnight. The reaction mixture was filtered through Celite^® and washed through with ethyl acetate.

Solvent was removed and the residue was dissolved in 200 mL toluene along with

3.0 g p-toluenesulfonic acid. The solution was heated with azeotropic removal of water overnight. Solvent was removed and the residue was taken up in ethyl acetate which was washed with aqueous Na₂CO₃, water and brine. The combined aqueous washings were reextracted with ethyl acetate three times. The organic extracts were dried (MgSO₄) and evaporated to give 17.1 g of 4-(4-t-butylphenyl)-pyrrolidin-2-one.

A solution of 11.6 g (53.5 mmol) of the preceding compound and 10.3 g

(69.6 mmol) of trimethyloxonium tetrafluoroborate in 200 mL dry methylene chloride was stirred at room temperature for 4 days. The mixture was washed with aqueous Na₂CO₃, water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was dissolved in hexanes. Filtering of insoluble material and removal of solvent from the filtrate gave 10.7 g of 3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-methoxy-2H-pyrrole as a viscous oil.

A solution of 3.0 g ( 13 mmol) of the preceding compound, cis-3 ,5-dimethylpiperidine hydrochloride (1.94 g, 13 mmol) and triethylamine (1.8 mL, 13 mmol) in 30 mL methylene chloride was stirred at room temperature for 2 days. The solution was diluted with methylene chloride and washed with 1N HO. The aqueous washing was reextracted with methylene chloride, and the combined extracts were washed with brine. Drying (MgSO₄) and removal of solvent gave a solid which was triturated with hot n-butyl chloride. The insoluble solids were filtered and partitioned between aqueous Na₂CO₃ and ethyl acetate. The organic layer was washed with brine, dried (MgSO₄) and solvent was removed to give 2.5 g of the title compound as an oil. Example 2

Synthesis of 3-[4-(1,1-dimethylethyl)phenyl]-3,4- dihydro-5-(1-pyrrolidinyl)-2H-pyrrole hydrochloride

A solution of 1.79 g (7.75 mmol) of 3-[4-(1, 1-dimethylethyl)phenyl]-3,4- dihydro-5-methoxy-2H-pyrrole, triethylamine (1.1 mL, 7.75 mmol) and pyrrolidine (0.6 mL, 7.75 mmol) in 20 mL methylene chloride was stirred at room temperature overnight. The reaction mixture was diluted with methylene chloride and washed with 1 N HCl. The aqueous washing was extracted a second time with methylene chloride and the combined extracts were dried (MgSO₄) and evaporated. Trituration of the residue with n-butylchloride gave 1.0 g of the title compound as a white solid.

Example 3

Synthesis of 2-[3,5-dihydro-3-(4-(1-methylethyl)phenyl)-2H- pyrrole-5-yl]-1,2,3,5,6,7,8,8a-octahydro-5,5,8a-trimethyl-6-isoquinolinol 12.5 g (41.3 mmol) of N-benzyl-1,3,4,7,8,8a-hexahydro-5,8a-dimethyl- 6(2H)-iso-quinolinone [Rahier, A. et al., Phytochemistry. vol. 24, No. 6, pp. 1223- 1232, 1985] was added to 13.9 g (0.124 mol) of potasium t-butoxide dissolved in 125 mL t-butanol. The mixture was heated to reflux for 15 min. and cooled to room temperature before 7.7 mL (0.124 mol) of methyl iodide was added. After heating to reflux for 15 min the mixture was quenched with aqueous NH₄CI and solvent was removed. The residue was dissolved in ethyl acetate and washed with water and brine. Drying (MgSO₄), removal of solvent and chromatography on silica gel (9:1 hexanes:diethyl ether) gave 4.8 g of N-benzyl-1,3,5,7,8,8a-hexahydro-5,5,8a-trimethyl-6(2H)-iso-quinolinone.

5.7 g (21 mmol) of the preceding compound and 2.4 mL (23 mmol) of phenyl chloroformate were heated at reflux in 30 mL toluene overnight. Dilution with ethyl acetate, washing with water and brine, drying (MgSO₄) and removal of solvent gave a gummy oil. Crystallization from methanol afforded 3.1 g of

N-phenoxycarbonyl-1,3,5,7,8,8a-hexahydro-5,5,8a-trimethyl-6(2H)-iso-quinolinone.

4.2 g (14 mmol) of the preceding compound and 3.2 g (56 mmol) of KOH were stirred at room temperature for 4 d. The mixture was diluted with ether and washed with 1 N NaOH, water and brine. Drying (MgSO₄), removal of solvent and chromatography on silica gel (4:1 hexanes:ethyl acetate followed by 1:1

hexanes:ethyl acetate to remove impurities; then followed by 19:1 ethyl acetate.-triethylamine) afforded 1.4 g of 1,3,5,7,8,8a-hexahydro-5,5,8a-trimethyl- 6(2H)-isfi-quinolinone.

The preceding compound (1.2 g, 6.1 mmol) was dissolved in 30 mL ether and 3.1 mL (3.1 mmol) of 1 M lithium aluminum hydride in tetrahydrofuran was added by syringe. After stirring 10 min, a saturated aqueous solution of NaHSO₃ was added dropwise until white solids appeared and gas evolution ceased. Drying (K₂CO₃), filtration of solids and removal of solvent gave a solid which was triturated with ether to afford 490 mg of 1,2,3,5,6,7,8,8a-octahydro-5,8,8a-trimethyl-6-isoquinolinol.

The preceding compound (490 mg. 2.5 mmol) and 3-[4-(1-methylethyl)phenyl]-3,4-dihydro-5-methoxy-2H-pyrrole (545 mg, 2.5 mmol) in 30 mL dichloromethane were stirred at room temperature for 3 d. Solvent was removed and the residue was chromatographed on silica gel (9:1 ethyl acetate:triethylamine) to afford 540 mg of the title compound as a solid.

Examples of compounds of the invention are shown in Table 1. One skilled in the art will recognize that those compounds of Table 1 not designated as salts can readily be converted to their conjugate acid salts. Variables correspond to compounds of Formula I. Abbreviations are as follows:

t-Bu is tertiary butyl

i-Pr is isopropyl

Me is methyl

Et is ethyl

Pr is 1-τopyl

Hex is hexyl

Ph is phenyl

n-BU is normal butyl

Bnz is benzyl

Me-O is methoxy

CN is cyano

Et-O is ethoxy

HO is hydroxy

TMS is trimethylsilyl

t-Am is tertiary amyl.

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Weight Percent*

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10

Oil Suspensions, 3-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Aqueous Suspension 10-50 40-84 1-20

Dusts 1-25 70-99 0-5

Granules and Pellets 0.1-95 5-99.9 0-15 High Strength 90-99 0-10 0-2

Compositions

*Active ingredients plus at least one of a surfactant or a diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins et al., "Handbook of

Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell,

New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", MC

Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood,

"Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E.Browning, "Agglomeration",

Chemical Engineering. December 4, 1967, pp. 147ff and "Perry's Chemical

Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-59ff.

For further information regarding the art of formulation, see for example: H. M. Loux, US. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, Marchl4, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example A

Wettable Powder

3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyrrole hydrochloride 50%

sodium alkylnaphthalenesulfonate 2% sodium liginsulfonate 5% diatomaceous earth 43%

The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

Example B

Granule

Oily active ingredient 5% attapulgite granules 95%

(U.S.S.20- 40 mesh; 0.84-0.42 mm)

An oily active ingredient is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. Example C

Oil Suspension

1-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol- 5-yl]-3,5-dimethylpiperidine 25%

polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspensions may be applied directly, but preferably after being extended with oils or emulsified in water. Example D

Wettable Powder

3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyrrole hydrochloride 20% sodium alkylnaphthalenesulfonate 4% sodium liginsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example E

Low Strength Granule

3-[4-(1,1-dimethylethyl)ρhenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyrrole hydrochloride 1%

methylene chloride 9% attapulgite granule 90%

(U.S.S.20-40 sieve)

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period. The product is then gently dried to remove solvent and the granules are packaged.

Example F

Aqueous Suspension

3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolid-nyl)- 2H-pyrrole hydrochloride 10%

polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol 5.0% ether

disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 82.2%

The ingredients are blended and milled together in a homogenizer to produce particles essentially all under 5 microns in size.

Example G

Solution

3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyτrole hydrochloride 5%

water 95%

The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.

Example H

Low Strength Granule

3-[4-(14-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyrrole hydrochloride 0.1% attapulgite granules 99.9%

(U.S.S.20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged. Example I

Emulsion Concentrate

1-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol- 5-yl]-3,5-dimethylpiperidine 35%

blend of poly alcohol carboxylic 6% esters and oil soluble petroleum

sulfonates

xylene 59%

The ingredients are combined and stirred together to produce a solution. The product can be extended with oils, or emulsified in water. Example J

Dust

3-[4-(1,1-d-methylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)- 2H-pyrrole hydrochloride 10%

attapulgite 10% pyrophyllite 80%

The active ingredient is blended with attapulgite and pyrophyllite and then passed thorugh a hammer-mill to produce particles substantially all below 200 microns.

Example K

Emulsifiable Concentrate

1-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol-5- yl]-3,5-dimethylpiperidine 20%

chlorobenzene 74% sorbitan monostearate and polyoxy6% ethylene condensates thereof

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

UTILITY

The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include, Venturia inaequalis, Cercosporidium personatum, Cercospora arachidicola, Cercospora beticola, Pseudocercosporella herpotrichoides. Erysiphe graminis.

Uncinula necatur, Podosphaera leucotricha, Paccinia recondita, Puccinia gamminis,

Hemileia vastatrix. Puccinia strüformis. Puccinia arachidis. Pyricularia oryzae, Phytophthora infestans. Plasmopara viticola. Peronospora tabacina,

Pseudoperonospora cubensis. Pythium aphanidermatum. Botrytis cinerea. Monilinia fructicola, Altemaria brassicae. Septoria nodorum. and other species closely related to these pathogens. They also control seed pathogens.

The compounds of this invention can be mixed with various fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material. Suitable agents of this type are well-known to those skilled in the art. Some of these agents are listed below:

Fvmgigides

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1 ,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimid--zolecarbamate (benomyl)

2-cyano-N-ethylcarbamoyl-2-memoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan)

N-trichloromethylthiophthalimide (folpet)

dimethyl 4,4'-(o-phenylene) bis (3-thioallophanate) (thiophanate-methyl)

2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethylphosphonate)(phosethyl aluminum)

tetrachloroisσphthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl) cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene- 1,2-dicarbioximide (captafol)

3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidine carboxamide

(iprodione)

3-(3,5-dicMorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) kasugamycin

O-ethyl-S,S-diphenylphosphorodithioate (edifenphos)

4-(3-(4-(1,1-dimethylethyl)phenyl)-2-methyl)propyl-2,6-dimethylmorpholine

(fenpropimorph)

4-(3-4(1,1-dimethylethyl)phenyl)-2-methyl)propylpiperidine (fenpropidine)

1-(4-cMorophenoxy)-3,3-dimethyl-1-1H-1,2,4-triazol-1-yl)butanone (triadimefon) 2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yhnethyl)hexanenitrile (myclobutanil) 1-[2-(4-chlorophenyl)ethyl]-1-(1,1-dimethylethyl)-1-(1H-1,2,4-triazole- 1-yl)ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1-ylmethyl)-1,3-dioxolan-2-yl]phenyl- 4-chlorophenyl ether (difenoconazole)

1-[2-(2,4-dichlorophenyl)pentyl]1H-1,2,4-triazole (penconazole)

2,4'-difluoro-1-(1H-1,2,4-triazole-1-ylmethyl)benzhydryl alcohol (flutriafol) 1-[[[bis(4-fluorophenyl)]methylsilyl]methyl]-1H-1,2,4-triazole (flusilazole)

N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (prochloraz) 1-[2-(2,4-dichloroρhenyl)-4-propyl-1,3-dioxolan-2- ylmethyl]-1H-1,2,4-triazole

(propiconazole)

1-(2-chlorophenyl)-1-(4-chlorophenyl)-1-(5-pyrimidin)-methanol (fenarimol) 1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)butan-2-ol

(triadimenol)

1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol

(diclobutrazol)

copper oxychloride

methyl N-(2,6-d-methylphenyl)-N-(2-furanylcarbonyl)-DL-alaninate (furalaxyl) Bactericides tribasic copper sulfate

streptomycin sulfate

oxytetracycline

Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitro-phenol (binapacryl)

6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one (oxythio-quinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl)(dienochlor)

tricyclohexyltin hydroxide (cyhexatin)

hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide) Nematicides

2-[diethoxyphosphinylimino]-1,3-diethietane (fosthietan)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl) S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl]- diester (fenamiphos)

Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcaibamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol

(carbofuran)

O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoricacid, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid,- dimethyl ester (malathion)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with alpha-naphthol (carbaryl)

methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (methomyl)

N'-(4-chloro-O-tolyl)-N,N-dimethylfoimamidine (chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothioate (diazinon) octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

cyano(3-phenoxyphenyl)-methyl 4-chloro-alpha-(1-methylethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl 3-(2,2-dichloro-ethenyl)-2,2-dimethylcycIo- propanecarboxylate (permethrin)

dimethyl N,N-[thiob-s(N-methylimmo)carbonyloxy]]-bis[ethanimidothioate]

(thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester

(sulprofos)

alpha-cyano-3-phenoxybenzyl 3-(2,2-dicWorovinyl)-2,2-dimethylcyclo- propanecarboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-alpha-(methylethyl) benzeneacetate (flucythrinate)

O,O-diethyl-O-(3,5,6-tricωoro-2-pyridyl)phosphorothioate (chlorpyrifos)

O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)-methyl]phosphorodithioate (azinphos-methyl)

5,6-d-methyl-2-d-methylammo-4-pyrimidinyl dimethyl carbamate (pirimicarb) S-(N-forthyl-N-methylcarbamoylmethyl)-O,O-dimethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl)

(5)-alpha-cyano-3-phenoxybenzyl (1R,3R)-3-(2,2-dibromovmyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethylphenyl)alanine (fluvalinate) APPUCATION METHOD

Disease control is ordinarily accomplished by applying an effective amount of the compounds of the invention either pre-infection or post-infection to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound also may be applied to the seed, to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to

5000 g/ha, 10 g/ha to 10,000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed. The efficacy of the compounds for disease control is evaluated according to Tests A - E below.

Test A

The test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on wheat seedlings. The following day the seedlings are inoculated with a spore dust of Erysiphe graminis f. sp.tritici. (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings are made. Test B

The test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on wheat seedlings. The following day the seedlings are inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings are made.

Test C

The test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on tomato seedlings. The following day the seedlings are inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings are made.

Test D

The test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspendend at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on potato plants. The following day the plants are inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20° C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings are made.

Test E

The test compounds are dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension is sprayed to the point of run-off on grape seedlings. The following day the seedlings are inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings are made.

Results for Tests A to E are given in Table 1. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). NT indicates that no test was performed. The number compounds in Table 1 are identified in Index Table A.

TABLE 1

Cmpd Test Test Test Test Test

No. A B C D E

1 68 86 89 NT 100 2 96 97 58 NT 36 3 90 89 87 NT 100 4 78 63 87 NT 99 5 91 98 81 NT 100 6 95 63 23 NT 0 7 93 92 0 NT NT 8 94 98 48 NT NT 9 90 96 08 NT NT 10 74 89 40 NT 07 11 60 37 25 NT NT 12 96 98 38 NT 100 13 98 100 76 NT 99 14 100 96 76 43 100 15 80 59 76 92 100 16 90 10 63 76 96 17 58 10 97 95 99 18 96 90 76 23 58 19 54 32 76 82 84 20 94 62 62 NT 10021 72 30 97 96 100 22 92 87 97 99 10023 84 44 92 92 7324 82 44 86 100 10025 65 18 92 95 10026 96 44 76 08 9127 88 31 76 0 100 28 60 11 86 0 21 29 44 26 86 0 21 30 96 38 45 0 0 Cmpd Test Test Test Test Test

No. A B C D E

31 96 54 97 86 85

32 66 31 97 30 92

33 97 100 76 NT 92

34 95 92 25 NT 21

35 95 100 76 NT 97

36 97 83 76 NT 100 37 97 83 93 NT 9938 63 02 0 NT 7539 46 02 0 NT 21 40 92 13 46 NT 8541 95 61 63 NT 8542 98 13 46 NT 8543 100 100 76 NT 8544 100 83 0 NT 2145 97 13 0 NT 6146 95 61 0 NT 6147 79 61 25 NT 8548 95 66 75 NT 7549 77 65 85 68 9240 0 0 61 NT 10051 98 21 75 NT 8552 86 84 97 NT 8553 97 100 92 NT 10054 86 21 0 NT 2155 92 21 21 NT 056 62 99 92 NT 92 57 37 65 99 NT 9758 75 80 97 89 10059 98 100 21 NT 7560 95 100 21 NT 9261 97 100 75 NT 99 Cmpd Test Test Test Test Test

No. A B C D E

62 81 41 26 rn 39

63 68 74 26 NT 73

64 96 88 93 NT 73

Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification, or from practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the scope and spirit of the invention being indicated by the following claims.

Claims

CLAIMS What is claimed is:

1. Compounds of Formula I

wherein:

W is H, C₁-C₄ alkyl or C₃-C₄ alkenyl;

n is 0 or 1;

X is O, S, CR⁵R⁶ orNR⁷;

Y is CR⁸R⁹ or CR⁸R⁹CR¹⁰R¹¹;

R¹, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹⁴ and R¹⁵ are independently H or

C₁-C₄ alkyl;

R² is C₄-C₂₀ alkyl, C₄-C₂₀ alkenyl or C₄-C₂₀ alkynyl each optionally

substituted with halogen or CN; C₃-C₂₀ cycloalkyl optionally substituted with C₁-C(5 alkyl; phenyl or thienyl substituted with R¹² and R¹³; or aralkyl or aralkenyl optionally substituted with R¹² and R¹³ on the aryl ring and R¹⁴ and R¹⁵ on the alkyl or alkenyl moiety;

R³ and R⁴ are independently C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, NR¹⁶R¹⁷;

phenyl, benzyl or phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl; or R³ and R⁴ may be taken togedier with the nitrogen to which they are attached to form heterocycles of the formulae:

R¹² and R¹³ are independently H; halogen; CN;

C₁-C₆ alkyl; C₁-C₆ cyanoalkyl; C₁-C₃ haloalkyl; C₃-C₆ cycloalkyl;

C₃-C₆ cycloalkylmethyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; silicon substituted with any three of the group consisting of C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl and C₁-C₃ haloalkyl; or

R¹² and R¹³ are independently phenyl optionally substituted with halogen, CN or C₁-C₄ alkyl;

R¹⁶ and R¹⁷ are independently C₁-C₁₀ alkyl; or phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen,

CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹⁸ and R¹⁹ are independently H; CN; C₁-C₄ alkyl; C₂-C₄ alkenyl; C₁-C₄ alkoxy; C₁-C₄ hydroxyalkyl; or phenyl optionally substituted with 1-2 halogen;

R²⁰ and R²¹ are independently H, halogen, CN, C₁-C₄ alkyl or C₁-C₄

alkoxy;

R²² is H, OH, halogen, CN, C₁-C₄ alkyl or C₁-C₄ alkoxy;

Q is O orNR²³;

R²³ is H, OH, C₁-C₃ alkyl or C₁-C₃ alkoxy;

Z is O orNR²⁴;

R²⁴ is H or C₁-C₄ alkyl;

E is O or CH₂; Provided that:

1) When R³ is NR¹⁶R¹⁷ or C₁-C₁₀ alkoxy, R⁴ cannot be NR¹⁶R¹⁷ or C₁-C₁₀ alkoxy; and 2) When R³ and R⁴ are taken together to form structure A-4, R¹⁸ and R¹⁹ are independently CN, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₁-C₄ alkoxy or C₁-C₄ hydroxyalkyl; and die geometric and stereoisomers or their agriculturally suitable salts thereof.

2. Compounds of Claim 1 wherein:

WisH;

Y is CH₂;

R¹ is H or CH₃; and

Q is O.

3. Compounds of Claim 2 wherein:

R³ and R⁴ are independently C₁-C₁₀ alkyl; phenyl, benzyl or phenethyl each optionally substituted with 1-3 substitutents selected from the group consisting of halogen, CN, C₁-C₄ alkyl and C₁-C₄ haloalkyl; or R³ and R⁴ may be taken together with the nitrogen to which they are attached to form heterocycles of the formulae A-1, A-2, A-3, A-4, A-6, A-9, A-11, A-12, A-13 or A-16;

R¹² and R¹³ are independently H, halogen, CN, C₁-C₆ alkyl, C₁-C₆ cyanoalkyl, C₁-C₆ haloalkyl or C₃-C₆ cycloalkyl;

R¹⁸ and R¹⁹ are independently H, CN, C₁-C₄ alkyl, C₁-C₄ alkoxy or C₁-C₄ hydroxyalkyl;

R²⁰ and R²¹ are independently H, CN or CH₃; and

R²² is H or OH.

4. Compounds of Claim 3 wherein:

X is O, CH₂ or NCH₃; and

R¹, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹⁴ and R¹⁵ are H.

5. Compounds of Claim 4 wherein:

R³ and R⁴ are taken together with die nitrogen to which they are attached to form heterocycles of the formulae A-1, A-3, A-4, A-6, A-9, A-11, A-12, A-13 or A-16.

6. Compounds of Claim 5 wherein:

R² is C₄-C₁₀ alkyl; C₃-C₆ cycloalkyl optionally substituted with C₁-C₆ alkyl; phenyl or thienyl substituted with R¹² and R¹³; or benzyl optionally substituted with R¹² and R¹³ on the aryl ring;

R¹² and R¹³ are independently H, CN, C₁-C₆ alkyl, CF₃ or

C₃-C₄ cycloalkyl; and for salts, chloride.

7. A compound of Claim 1 which is 3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-5-(1-pyrrolidinyl)-2H-pyrrole hydrochloride.

8. A compound of Claim 1 which is 1-[3-[4-(1,1-dimethylethyl)phenyl]-3,4-dihydro-2H-pyrrol-5-yl]-3,5-dimethyl-piperidine.

9. A compound of Claim 1 which is 2-[3-[4-(1,1-dimethylethyl)phenyl]- 3,4-dihydro-2H-pyrrol-5-yl]decahydroisoquinoline.

10. A compound of Claim 1 which is 2-[3,5-dihydro-3-(4-Cl-methylethyl)phenyl)-2H-pyrrol-5-yl]-1,2,3,5,6,7,8,8a-octahydro-5,5,8a-trimethyl-6-isoquinolinol.

11. An agriculturally suitable composition comprising a fungicidally effective amount of a compound of Claims 1-10 and at least one of the following: surfactant, solid diluent or liquid diluent.

12. A method for controlling fungus disease in plants comprising applying to the locus of plants to be protected an effective amount of a compound of Claims 1-10.