3-Phenyl-4-cyanopyrrole derivatives, the preparation thereof, and method of use thereof as microbicides

The invention relates to novel N-alkylated 3-phenyl-4-cyanopyrrole derivatives of the formula I ##STR1## wherein R.sub.1 and R.sub.2, each independently of the other, are hydrogen, halogen, methoxy or methylthio, PA1 R.sub.3 is hydrogen or C.sub.1 -C.sub.8 haloalkyl, PA1 Y is hydroxy, halogen or the --O--C(O)--R.sub.4 group, and PA1 R.sub.4 is hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, C.sub.2 -C.sub.6 alkenyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C.sub.1 -C.sub.6 alkoxycarbonyl or the --CH(R.sub.5)--XR.sub.6 group, wherein PA1 X is oxygen or sulfur, PA1 R.sub.5 is hydrogen or C.sub.1 -C.sub.3 alkyl, and PA1 R.sub.6 is C.sub.1 -C.sub.6 alkyl, (C.sub.1 -C.sub.6 alkoxy)-C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, phenyl or phenyl which is substituted by halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, or C.sub.1 -C.sub.6 alkoxycarbonyl. The invention also relates to the preparation of these compounds by N-alkylation of the starting pyrroles, as well as to microbicidal compositions which contain a compound of formula I as active ingredient. Also disclosed is a method of controlling phytopathogenic micro-organisms which comprises the use of the novel compounds.

The present invention relates to novel N-alkylated 3-phenyl-4-cyanopyrrole 
derivatives of the formula I below, to the preparation thereof, and to 
microbicidal compositions which contain at least one of the novel 
compounds. The invention further relates to the preparation of said 
compositions and to the use of the novel compounds and compositions for 
controlling harmful micro-organisms, in particular phytopathogenic fungi. 
Specifically, the invention relates to novel compounds of the general 
formula I 
##STR2## 
wherein R.sub.1 and R.sub.2, each independently of the other, are 
hydrogen, halogen, methoxy or methylthio, 
R.sub.3 is hydrogen or C.sub.1 -C.sub.8 haloalkyl, 
Y is hydroxy, halogen or the --O--C(O)--R.sub.4 group, and 
R.sub.4 is hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, 
C.sub.2 -C.sub.6 alkenyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C.sub.1 
-C.sub.6 alkoxycarbonyl or the --CH(R.sub.5)--XR.sub.6 group, wherein 
X is oxygen or sulfur, 
R.sub.5 is hydrogen or C.sub.1 -C.sub.3 alkyl, and 
R.sub.6 is C.sub.1 -C.sub.6 alkyl, (C.sub.1 -C.sub.6 alkoxy)-C.sub.1 
-C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, phenyl 
or phenyl which is substituted by halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 
-C.sub.6 alkoxy or C.sub.1 -C.sub.6 alkoxycarbonyl. 
Depending on the indicated number of carbon atoms, alkyl by itself or as 
moiety of another substituent comprises e.g. the following groups: methyl, 
ethyl, propyl, butyl, pentyl, hexyl etc., and the isomers thereof, e.g. 
isopropyl, isobutyl, tert-butyl, isopentyl etc. Haloalkyl denotes a mono- 
to prehalogenated alkyl substituent, e.g. CH.sub.2 Cl, CHCl.sub.2, 
CCl.sub.3, CH.sub.2 Br, CHBr.sub.2, CBr.sub.3, CHF.sub.2, CF.sub.3, 
CCl.sub.2 F, CCl.sub.2 --CHCl.sub.2, CH.sub.2 CH.sub.2 F, CI.sub.3 etc. In 
formula I and throughout this specification halogen denotes fluorine, 
chlorine, bromine or iodine, with fluorine, chlorine or bromine being 
preferred. Alkenyl is e.g. vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 
3-butenyl etc., as well as alkyl chains which are interrupted by several 
C.dbd.C double bonds. Alkenyl is e.g. 2-propynyl, propargyl, 1-butynyl, 
2-butynyl etc., with propargyl being preferred. 
The compounds of formula I are oils, resins or mainly crystalline solids 
which are stable under normal conditions and have extremely valuable 
microbicidal properties. They can be used in particular under field 
conditions in agriculture or related fields curatively and, most 
particularly, preventively for controlling phytopathogenic 
micro-organisms. The compounds of formula I exhibit excellent fungicidal 
properties when applied in wide ranges of concentration and their use in 
the field poses no problems. 
In increasing order of preference, the following groups of compounds are 
preferred on account of their pronounced microbicidal activity: 
(a) compounds of the formula I, wherein R.sub.1 is in the 2-position and 
R.sub.2 is in the 3-position of the phenylring and each independently of 
the other is hydrogen, halogen, methoxy or methylthio; R.sub.3 is hydrogen 
or C.sub.1 -C.sub.4 haloalkyl; and Y is hydroxy, halogen or the 
--O--C(O)--R.sub.4 group, wherein R.sub.4 is C.sub.1 -C.sub.6 alkyl, 
C.sub.1 -C.sub.6 haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 
C.sub.1 -C.sub.2 alkoxycarbonyl or the --CH(R.sub.5)--XR.sub.6 group, 
wherein X is oxygen or sulfur, R.sub.5 is hydrogen or methyl and R.sub.6 
is C.sub.1 -C.sub.6 alkyl, (C.sub.1 -C.sub.3 alkoxy)-C.sub.1 -C.sub.3 
alkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, phenyl or 
phenyl which is substituted by fluorine, chlorine, bromine, methyl, 
methoxy and/or C.sub.1 -C.sub.3 alkoxycarbonyl; 
(b) compounds of the formula I, wherein R.sub.1 is hydrogen, 2-Cl, 
2-methoxy or 2-methylthio; R.sub.2 is hydrogen or 3-Cl; R.sub.3 is 
hydrogen or C.sub.1 -C.sub.4 haloalkyl; and Y is OH, chlorine or the 
--O--C(O)--R.sub.4 group, wherein R.sub.4 is C.sub.1 -C.sub.4 alkyl, 
C.sub.1 -C.sub.3 haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 
C.sub.1 -C.sub.2 alkoxycarbonyl or the --CH.sub.2 --OR.sub.6 group, 
wherein R.sub.6 is C.sub.1 -C.sub.4 alkyl, (C.sub.1 -C.sub.3 
alkoxy)-C.sub.1 C.sub.3 alkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 
alkynyl, phenyl or phenyl which is substituted by fluorine, chlorine, 
bromine, methyl, methoxy, ethoxycarbonyl and/or methoxycarbonyl; 
(c) compounds of the formula I, wherein R.sub.1 is hydrogen, 2-Cl, 
2-methoxy or 2-methylthio; R.sub.2 is hydrogen or 3-Cl; R.sub.3 is 
hydrogen or CCl.sub.3 ; and Y is OH, chlorine or the --O--C(O)--R.sub.4 
group, wherein R.sub.4 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.2 
haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, methoxycarbonyl or the 
--CH.sub.2 OR.sub.6 group, wherein R.sub.6 is C.sub.1 -C.sub.4 alkyl, 
methoxymethyl, ethoxymethyl, methoxyethyl, allyl, propargyl, phenyl or 
phenyl which is substituted by fluorine, chlorine, bromine, methyl, 
methoxy and/or methoxycarbonyl. 
The following individual compounds (a) to (u) are particularly preferred on 
account of their marked fungicidal properties under field conditions: 
(a) N-(hydroxymethyl)-3-(3-chlorophenyl)-4-cyanopyrrole, 
(b) 
N-(1-acetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole 
(c) 
N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2-methylthiophenyl)-4-cyanopyrrole, 
(d) 
N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole, 
(e) N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2-methoxyphenyl)-4-cyanopyrrole, 
(f) 
N-(1-methoxyacetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyano 
pyrrole, 
(g) N-(1-hydroxy-2,2,2-trichloroethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, 
(h) N-(methoxyacetyloxymethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole, 
(i) N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2-chlorophenyl)-4-cyanopyrrole, 
(k) N-(chloromethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, 
(l) 
N-[1-(n-butylcarbonyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-c 
yanopyrrole, 
(m) N-(1,2,2,2-tetrachloroethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, 
(n) 
N-[1-(n-propoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-c 
yanopyrrole, 
(o) N-(1,2,2,2-tetrachloroethyl)-3-(3-bromophenyl)-4-cyanopyrrole, 
(p) 
N-[1-(n-butoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cy 
anopyrrole, 
(q) 
N-[1-(isopropoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2-chlorophenyl)-4-cyan 
opyrrole, 
(r) N-[1-(n-butoxyacetyloxy)ethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole, 
(s) 
N-[1-(methoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2-methylthiophenyl)-4-cya 
nopyrrole, 
(t) 
N-[1-(propargyloxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)- 
4-cyanopyrrole, 
(u) N-(methoxyacetyl)-3-(2-chlorophenyl)-4-cyanopyrrole. 
The novel compounds of the formula I are prepared by converting a 
3-phenyl-4-cyanopyrrole derivative of the formula II 
##STR3## 
by reaction with an aldehyde of the formula III 
EQU R.sub.3 --CHO (III) 
into a hydroxy derivative of the formula Ia 
##STR4## 
and, if desired, converting said derivative into another compound of the 
formula I by replacing the free OH group by another radical Y, said 
replacement being effected by converting either a compound of the formula 
Ia with an acid of the formula IV 
EQU R.sub.4 --COOH (IV) 
or preferably with a reactive acid derivative thereof, in particular an 
acid halide, e.g. an acid chloride or acid bromide, or with the acid 
anhydride thereof, into an acyloxy compound of the formula Ib 
##STR5## 
or, in a compound of the formula Ia, replacing the free OH group first by 
a halogen atom, preferably a chlorine or bromine atom, in conventional 
manner and, if desired, converting the so halogenated compound by reaction 
with a salt of the formula V 
EQU R.sub.4 --COO.sup..crclbar. M.sup.+ (V) 
into a compound of the formula Ib, in which formulae above the substituents 
are as defined for formulae Ia, Ib, II, III, IV and V, M.sup..sym. is a 
metal cation, preferably the cation of an alkaline earth metal or, 
preferably, of an alkali metal, and is e.g. Ca.sup..sym..sym., 
Mg.sup..sym..sym., Na.sup..sym. or K.sup..sym.. 
The reaction of a compound of formula II with an aldehyde of the formula 
III can be carried out in the presence or absence of an inert solvent or 
mixture of solvents. Examples of suitable solvents are: aromatic 
hydrocarbons such as benzene, toluene or xylenes; halogenated hydrocarbons 
such as chlorobenzene; aliphatic hydrocarbons such as petroleum ether; 
ether and ethereal compounds such as dialkyl ethers (diethyl ether, 
diisopropyl ether, tert-butylmethyl ether etc.), furan, dimethoxyethane, 
dioxan, tetrahydrofuran; and dimethylformamide and the like. 
The reaction of the compounds of formula II with compounds of formula III 
is conveniently carried out without a solvent but using an excess of the 
aldehyde of formula III. Depending on the nature of the aldehyde of the 
formula III, the reaction is carried out in solution or in the melt. The 
reaction rate can be speeded up by adding an acid or basic catalyst. 
Examples of suitable acid catalysts are non-aqueous hydrogen halides and 
mineral acids such as HCl, HBr or H.sub.2 SO.sub.4, and also concentrated 
hydrochloric acid. Examples of suitable basic catalysts which can be used 
are: trialkylamines such as trimethylamine, triethylamine, 
dimethylethylamine etc., alkali metal carbonates and alkaline earth metal 
carbonates such as Na.sub.2 CO.sub.3, BaCO.sub.3, MgCO.sub.3, K.sub.2 
CO.sub.3 etc., or alkali metal alcoholates such as NaOCH.sub.3, NaOC.sub.2 
H.sub.5, KO(iso-C.sub.3 H.sub.7), KO(tert-butyl). The reaction 
temperatures are normally in the range from 0.degree. to +200.degree. C., 
preferably from 0.degree. to +160.degree. C., and the reaction time is 
from 1 to 24 hours, preferably from 1 to 4 hours. 
The reaction to replace the free hydroxyl group in the compounds of formula 
Ia by a group Y is preferably carried out in an inert solvent. Examples of 
such solvents are: aromatic and aliphatic hydrocarbons such as benzene, 
toluene, xylenes, petroleum ether, ligroin or cyclohexane; halogenated 
hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, 
chloroform, carbon tetrachloride or tetrachloroethylene; ethers and 
ethereal compounds such as diethyl ether, diisopropyl ether, 
tert-butylmethyl ether, dimethoxyethane, dioxan, tetrahydrofuran or 
anisole; esters such as ethyl acetate, propyl acetate or butyl acetate; 
nitriles such as acetonitrile; or compounds such as dimethylsulfoxide, 
dimethylformamide, and mixtures of such solvents with one another. 
The introduction of the group Y is effected by conventional methods. If Y 
is chlorine, the reagent employed is e.g. phosphoroxy chloride, phosphorus 
trichloride, phosphorous pentachloride or, preferably, thionyl chloride. 
The reaction is normally carried out in the temperature range from 
0.degree. to +120.degree. C. If Y is bromine, the preferred reagent is 
phosphorus tribromide or phosphorus pentabromide and the reaction is 
carried out in the temperature range from 0.degree. to +50.degree. C. If Y 
is the --O--C(O)--R.sub.4 group, the reagent employed will normally be the 
corresponding acid halide, preferably acid chloride. In this case it is 
best to carry out the reaction in the temperature range from -20.degree. 
to +50.degree. C., preferably from -10.degree. to +30.degree. C., and in 
the presence of a weak base such as pyridine or triethylamine. To speed up 
the reaction it is also possible to add a 4-dialkylaminopyridine such as 
4-dimethyl- or 4-dimethylaminopyridine as catalyst. 
The reaction of compounds of formula I, wherein Y is halogen, preferably 
chlorine or bromine, with salts of formula V is usually carried out in the 
presence of a commonly employed inert solvent or mixture of solvents. 
Examples of such solvents are: aromatic and aliphatic hydrocarbons such as 
benzene, xylenes, petroleum ether, ligroin or cyclohexane; ethers and 
ethereal compounds such as dialkyl ethers, e.g. diethyl ether, diisopropyl 
ether, tert-butylmethyl ether, dimethoxyethane, dioxan, tetrahydrofuran or 
anisol; esters such as ethyl acetate, propyl acetate or butyl acetate; 
nitriles such as acetonitrile; or compounds such as dimethylsulfoxide, 
dimethylformamide and mixtures of such solvents with one another. 
The course of this reaction can be advantageously influenced by addition of 
catalytic amounts of a crown ether, e.g. 18-crown-6 or 15-crown-5. The 
reaction temperature is generally in the range from 0.degree. to 
+150.degree. C., preferably from +20.degree. to +80.degree. C. The 
reaction time is from 1 to 24 hours. 
In a preferred embodiment, the preparation of compounds of formula Ib, in 
particular those in which R.sub.3 is CCl.sub.3 or R.sub.3 is H, starting 
from compounds of formula II, is effected by carrying out the reaction 
continuously without isolation of the intermediate formed. This reaction 
is conveniently carried out in one of the solvents or diluents referred to 
above, most suitably e.g. an ethereal compound such as tetrahydrofuran, 
and in the presence of a weak base such as a trialkylamine, e.g. 
triethylamine, or pyridine. Chloral or paraformaldehyde is used as 
reagent. The reaction can be speeded up by adding a catalyst such as 
1,8-diazabicyclo[5.4.0]undec-7-ene. The temperature in this first reaction 
step is in the range from -20.degree. to +100.degree. C., preferably from 
0.degree. to +50.degree. C., and the reaction time is from 1/2 hour to 2 
hours. A hydroxy derivative of the formula Ia is obtained as intermediate. 
This intermediate is not isolated, but is reacted with a compound of the 
formula IV, in the same reaction solution, in the temperature range from 
-30.degree. to +30.degree. C., preferably from -10.degree. to 0.degree. 
C., and in the presence of catalytic amounts of a 4-dialkylaminopyridine, 
preferably 4-dimethylaminopyridine. The reaction time of this second step 
is from 1/2 hour to 16 hours. 
The starting materials of the formulae III, IV and V are generally known or 
they can be prepared by methods which are known per se. 
Some of the pyrroles of the formula II are known from the literature. Thus, 
for example, the method of preparing 4-cyano-3-phenylpyrrole and the 
chemical properties thereof are described in Tetrahedron Letters No. 52. 
pp. 5337-5340 (1972). No mention is made of the biological properties of 
this compound. 
N-Acetylated, substituted 3-phenyl-4-cyanopyrroles are known from the 
literature. For example, pyrroles of the formula VI 
##STR6## 
wherein X is a halogen atom, a lower alkyl group or lower haloalkyl group, 
and n is 0, 1 or 2, are described as fungicides in DE-OS 2 927 480. 
Pyrrole derivatives of the formula VII 
##STR7## 
wherein R.sub.7 =acyl, alkoxycarbonylalkyl . . . 
R.sub.8, R.sub.9 =H, aryl . . . 
R.sub.10 =hydroxy, mercapto 
are known as heat and light stabiliers for PVC plastics from GB Pat. No. 2 
078 761. 
Further pyrrole derivatives of the formula VIII 
##STR8## 
wherein R.sub.1 =alkyl, unsubstituted or substituted by acyloxy . . . 
R.sub.5 =H, alkyl, CN . . . 
are known as polymerisation catalysts for vinyl chloride from DE-OS No. 2 
028 363. 
The known pyrrole derivatives are either inactive to phytopathogens or in 
the greenhouse they have a marked fungicidal activity which is not 
reproduced under field conditions owing to their instability to 
environmental influences. They are therefore not suitable for practical 
application in agriculture, in horticulture or in related fields of use. 
In contradistinction thereto, the novel pyrrole derivatives of the formula 
I constitute a useful enlargement of technical knowledge, for it has 
surprisingly been found that they have, for practical field application 
purposes, a very advantageous microbicidal activity spectrum against 
phytopathogenic fungi and bacteria. They can be used not only in crop 
growing or similar fields of use for controlling harmful micro-organisms 
in cultivated plants, but additionally in storage protection for 
preserving perishable goods. Compounds of formula I have very advantageous 
curative, systemic and, in particular, preventive properties, and can be 
used for protecting numerous cultivated plants, in particular field crops. 
With the compounds of formula I it is possible to inhibit or destroy the 
micro-organisms which occur in plants or in parts of plants (fruit, 
blossoms, leaves, stems, tubers, roots) in different crops of useful 
plants, while at the same time the parts of plants which grow later are 
also protected from attack by such micro-organisms. 
The compounds of formula I are effective for example against the 
phytopathogenic fungi belonging to the following classes: Ascomycetes, 
e.g. Erysiphe, Sclerotinia, Fusarium, Monilinia, Helminthosporium; 
Basidiomycetes, e.g. Puccinia, Tilletia, Rhizoctonia; as well as the 
Oomycetes belonging to the class of Phycomycetes, e.g. Phytophthora. As 
plant protective agents, the compounds of formula I can be used with 
particular success against important noxious fungi of the Fungi imperfecti 
family, e.g. against Cercospora, Piricularia and, in particular, against 
Botrytis spp. (B. cinerea, B. allii) and the grey mould on vines, 
strawberries, apples, onions and other varieties of fruit and vegetables 
is a noxious fungus that causes considerable economic damage. Furthermore, 
some compounds of the formula I, e.g. compound 1.2, can be successfully 
used for protecting perishable goods of vegetable or animal origin. They 
control mould fungi such as Penicillium, Aspergillus, Rhizopus, Fusarium, 
Helminthosporium, Nigrospora and Alternaria, as well as bacteria such as 
butyric acid bacteria and yeast fungi such as Candida. 
As plant protective agents, the compounds of formula I have a very 
advantageous activity spectrum for practical application in agriculture 
for protecting cultivated plants, without damaging said plants by harmful 
side-effects. They can also be used as seed dressing agents for protecting 
seeds (fruit, tubers, grains) and plant cuttings against fungus infections 
and against phytopathogenic fungi which occur in the soil. 
Accordingly, the invention also relates to microbicidal compositions and to 
the use of the compounds of formula I for controlling phytopathogenic 
micro-organisms, in particular phytopathogenic fungi, and for the 
preventive treatment of plants and stored goods of vegetable or animal 
origin to protect them from attack by such micro-organisms. 
The present invention also relates to the preparation of agrochemical 
compositions, which comprises homogeneously mixing the active ingredient 
(compound of formula I) with one or more substances or groups of 
substances described herein. The invention further relates to a method of 
treating plants or storable goods, which comprises applying the compounds 
of formula I or the novel compositions to said plants, parts of plants or 
to the locus thereof, or to the substrate. 
Target crops to be protected within the scope of the present invention 
comprise e.g. the following species of plants: cereals (wheat, barley, 
rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder 
beet), drupes, pomes and soft fruit (applies, pears, plums, peaches, 
almonds, cherries, strawberries, rasberries and blackberries), leguminous 
plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, 
olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), 
cucumber plants (cucumber, marrows, melons), fibre plants (cotton, flax, 
hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), 
vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, 
tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or 
plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, 
bananas and natural rubber plants, as well as ornamentals (composites). 
For storage protection, the compounds of formula I are used in unmodified 
form or, preferably, together with the adjuvants conventionally employed 
in the art of formulation, and are therefore formulated in known manner to 
e.g. emulsifiable concentrates, brushable pastes, directly sprayable or 
dilutable solutions, dilute emulsions, wettable powders, soluble powders, 
dusts, granulates, and also encapsulations in e.g. polymer substances. The 
methods of application, such as spraying, atomising, dusting, scattering 
or pouring, and the formulation of the composition, are chosen in 
accordance with the intended objectives and the prevailing circumstances. 
Suitable rates of application are in general in the range from 0.01 to at 
most 2 kg of active ingredient per 100 kg of substrate to be protected. 
However, they depend very materially on the nature (surface area, 
consistency, moisture content) of the substrate and its environmental 
influences. 
Within the scope of this invention, storable goods will be understood as 
meaning natural substances of vegetable and/or animal origin and the 
products obtained therefrom by further processing, for example the plants 
listed below whose natural life cycle has been interrupted and the parts 
thereof (stalks, leaves, tubers, seeds, fruits, grains) which are in 
freshly harvested or further processed form (predried, moistened, crushed, 
ground, roasted). The following produce may be cited by way of example, 
without any restriction to the field of use within the scope of this 
invention: cereals (wheat, barley, rye, oats, rice, sorghum and related 
crops); beet (carrots, sugar beet and fodder beet); drupes, pomes and soft 
fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, 
rasberries and blackberries); leguminous plants (beans, lentils, peas, 
soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, 
castor oil plants, cocoa beans, groundnuts); cucmber plants (cucumber, 
marrows, melons); fibre plants (cotton, flax, hemp, jute, ramie); citrus 
fruit; vegetables (spinach, lettuce, asparagus, cabbages, carrots, anions, 
tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), or 
maize, tobacco, nuts, coffee, sugar cane, tea, vines, chestnuts, hops, 
bananas, grass and hay. 
Examples of natural products of animal origin are, in particular, dried 
meat and processed fish products such as dry-cured meat, dry-cured fish, 
meat extracts, bone meal, fish meal and animal dry feeds. 
The storable goods treated with compounds of the formula I are given 
lasting protection from attack by mould fungi and other harmful 
microorganisms. The formation of toxic and in some cases carcinogenic 
mould fungi (aflatoxins and ochratoxins) is inhibited, the goods are 
preserved from deterioration, and their quality is maintained over a 
prolonged period of time. The method of the invention is susceptible of 
application to all forms of dry and moist storable goods which are 
susceptible to attack by microorganisms such as yeast fungi, bacteria and, 
in particular, mould fungi. 
A preferred method of applying active ingredient comprises spraying or 
wetting the substrate with a liquid formulation, or mixing the substrate 
with a solid formulation, of the active ingredient. The invention also 
relates to the described method of preserving storable goods. 
The compounds of formula I are normally applied in the form of compositions 
and can be applied to the crop area, plant or substrate to be treated, 
simultaneously or in succession, with further compounds. These compounds 
can be both fertilisers or micronutrient donors or other preparations that 
influence plant growth. They can also be selective herbicides, fungicides, 
bactericides, nematicides, mollusicides 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. Suitable carriers and adjuvants can be solid or liquid and 
correspond to the substances ordinarily employed in formulation 
technology, e.g. natural or regenerated mineral substances, solvents, 
dispersants, wetting agents, tackifiers, thickeners, binders or 
fertilisers. 
A preferred method of applying a compound of the formula I or an 
agrochemical composition which contans at least one of said compounds, is 
foliar application. The number of applications and the rate of application 
depend on the risk of infestation by the corresponding pathogen (species 
of fungus). However, the compound of formula I can also penetrate the 
plant through the roots via the soil (systemic action) by impregnating the 
locus of the plant with a liquid composition, or by applying the compounds 
in solid form to the soil, e.g. in granular form (soil application). The 
compounds of formula I may also be applied to seeds (coating) by 
impregnating the seeds either with a liquid formulation containing a 
compound of the formula I, or coating them with a solid formulation. In 
special cases, further types of application are also possible, e.g. 
selective treatment of the plant stems or buds. 
The compounds of the formula I are used in unmodified form or, preferably, 
together with the adjuvants conventionally employed in the art of 
formulation, and are therefore 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 in e.g. polymer substances. As with the nature of 
the compositions, the methods of application, such as spraying, atomising, 
dusting, scattering or pouring, are chosen in accordance with the intended 
objectives and the prevailing circumstances. Advantageous rates of 
application are normally from 50 g to 5 kg of active ingredient (a.i.) per 
hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g 
to 600 g a.i./ha. 
The formulations, i.e. the compositions or preparations containing the 
compound (active ingredient) of the formula I and, where appropriate, a 
solid or liquid adjuvant, are prepared in known manner, e.g. by 
homogeneously mixing and/or grinding the active ingredients with 
extenders, e.g. solvents, solid carriers and, where appropriate, 
surface-active compounds (surfactants). 
Suitable solvents are: aromatic hydrocarbons, preferably the fractions 
containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted 
naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, 
aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and 
glycols and their ethers and esters, such as ethanol, ethylene glycol 
monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly 
polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or 
dimethylformamide, as well as epoxidised vegetable oils such as epoxidised 
coconut oil or soybean oil; or water. 
The solid carriers used e.g. for dusts and dispersible powders, are 
normally natural mineral fillers such as calcite, talcum, kaolin, 
montmorillonite or attapulgite. In order to improve the physical 
properties it is also possible to add highly dispersed silicic acid or 
highly dispersed absorbent polymers. Suitable granulated adsorptive 
carriers are porous types, for example pumice, broken brick, sepiolite or 
bentonite; and suitable nonsorbent carriers are materials such as calcite 
or sand. In addition, a great number of pregranulated materials of 
inorganic or organic nature can be used, e.g. especially dolomite or 
pulverised plant residues. Particularly advantageous application promoting 
adjuvants which are able to reduce substantially the rate of application 
are also natural (animal or vegetable) or synthetic phospholipids of the 
series of the cephalins and lecithins, e.g. phosphatidyl ethanolamine, 
phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphatidyl 
inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or 
cardiolipin, which can be obtained e.g. from animal or plant cells, in 
particular from the brain, heart, liver, egg yokes or soya beans. Examples 
of useful physical forms are phosphatidyl choline mixtures. Examples of 
synthetic phospholipids are dioctanoylphosphatidyl choline and 
dipalmitoylphosphatidyl choline. 
Depending on the nature of the compound of the formula I to be formulated, 
suitable surface-active compounds are nonionic, cationic and/or anionic 
surfactants having good emulsifying, dispersing and wetting properties. 
The term "surfactants" will also be understood as comprising mixtures of 
surfactants. 
Suitable anionic surfactants can be both water-soluble soaps and 
water-soluble synthetic surface-active compounds. 
Suitable soaps are the alkali metal salts, alkaline earth metal salts or 
unsubstituted or substituted ammonium salts of higher fatty acids 
(C.sub.10 -C.sub.22), e.g. the sodium or potassium salts of oleic or 
stearic acid, or of natural fatty acid mixtures which can be obtained e.g. 
from coconut oil or tallow oil. Mention may also be made of fatty acid 
methyltaurin salts. 
More frequently, however, so-called synthetic surfactants are used, 
especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole 
derivatives or alkylarylsulfonates. 
The fatty sulfonates or sulfates are usually in the form of alkali metal 
salts, alkaline earth metal salts or unsubstituted or substituted ammonium 
salts and contain a C.sub.8 -C.sub.22 alkyl radical which also includes 
the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of 
lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol 
sulfates obtained from natural fatty acids. These compounds also comprise 
the salts of sulfuric acid esters and sulfonic acids of fatty 
alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives 
preferably contain 2 sulfonic acid groups and one fatty acid radical 
containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the 
sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, 
dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic 
acid/formaldehyde condensation product. Also suitable are corresponding 
phosphates, e.g. salts of the phosphoric acid ester of an adduct of 
p-nonylphenol with 4 to 14 moles of ethylene oxide. 
Non-ionic surfactants are preferably polyglycol ether derivatives of 
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty 
acids and alkylphenols, said derivatives containing 3 to 30 glycol ether 
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 
6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. 
Further suitable non-ionic surfactants are the water-soluble adducts of 
polyethylene oxide with polypropylene glycol, ethylenediamine propylene 
glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in 
the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether 
groups and 10 to 100 propylene glycol ether groups. These compounds 
usually contain 1 to 5 ethylene glycol units per propylene glycol unit. 
Representative examples of non-ionic surfactants are 
nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, 
polypropylene/polyethylene oxide adducts, 
tributylphenoxypolyethoxyethanol, polyethylene glycol and 
octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan 
and polyoxyethylene sorbitan trioleate are also suitable non-ionic 
surfactants. 
Cationic surfactants are preferably quaternary ammonium salts which 
contain, as N-substituent, at least one C.sub.8 -C.sub.22 alkyl radical 
and, as further substituents, lower unsubstituted or halogenated alkyl, 
benzyl or lower hydroxyalkyl radicals. The salts are preferably in the 
form of halides, methylsulfates or ethylsulfates, e.g. 
stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium 
bromide. In the field of storage protection, the auxiliaries which are 
acceptable for human and animal nutrition are preferred. 
The surfactants customarily employed in the art of formulation are 
described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC 
Publishing Corp. Ridgewood, N.J., 1981; Helmut Stache 
"Tenside-Taschenbuch" (Tenside Handbook) Carl Hanser Verlag, 
Munich/Vienna, 1981. 
The agrochemical compositions usually contain 0.1 to 99%, preferably 0.1 to 
95%, of a compound of the formula I, 99.9 to 1%, preferably 99.8 to 5%, of 
a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a 
surfactant. 
Whereas commercial products are preferably formulated as concentrates, the 
end user will normally employ dilute formulations. 
The compositions may also contain further auxiliaries such as stabilisers, 
antifoams, viscosity regulators, binders, tackifiers as well as 
fertilisers or other active ingredients in order to obtain special 
effects. 
Such agrochemical compositions also constitute an object of the present 
invention. 
The invention is illustrated in more detail by the following Examples, 
without implying any restriction to what is described therein. Parts and 
percentages are by weight.

PREATORY EXAMPLES 
Example P1 
Preparation of 
##STR9## 
N-Hydroxymethyl-3-(2-chlorophenyl)-4-cyanopyrrole 
60.8 g of 3-(2-chlorophenyl)-4-cyanopyrrole, 9.9 g of paraformaldehyde and 
0.8 g of triethylamine are thoroughly mixed and and the mixture is then 
heated, with stirring, at a bath temperature of 90.degree. C. The 
resultant melt is cooled to room temperature after 11/4 hours, when it 
congeals to a glass-like solid. Recrystallisation from toluene yields the 
title compound in the form of brownish crystals of m.p. 
94.degree.-97.degree. C. 
Example P2 
Preparation of 
##STR10## 
N-Chloromethyl-3-(2-chlorophenyl)-4-cyanopyrrole 
With efficient stirring, 48 g of 
N-hydroxymethyl-3-(2-chlorophenyl)-4-cyanopyrrole are added in several 
portions to 60 ml of thionyl chloride such that moderate gas evolution is 
maintained. When the evolution of gas ceases, the mixture is stirred for 2 
hours at room temperature and then for 21/2 hours at 35.degree.-40.degree. 
C. After cooling to room temperature, toluene is added and the mixture is 
concentrated. The residue is recrystallised from diethyl ether/petroleum, 
affording the title compound in the form of beige crystals with a melting 
point of 97.degree.-99.degree. C. 
Example P3 
Preparation of 
##STR11## 
N-Acetyloxymethyl-3-(2-chlorophenyl)-4-cyanopyrrole 
41.4 g of N-hydroxymethyl-3-(2-chlorophenyl)-4-cyanopyrrole are dissolved 
in 350 ml of pyridine and 1.8 g of dimethylaminopyridine are added. Then 
21.4 ml of acetic anhydride are slowly added dropwise at 0.degree. to 
7.degree. C. and the mixture is stirred for 12 hours. The reaction mixture 
is then poured into ice-water and extracted twice with ethyl acetate. The 
extracts are washed twice with dilute ice-cold hydrochloric acid and twice 
with a semi-saturated aqueous solution of sodium chloride, dried over 
sodium sulfate and filtered. The filtrate is concentrated and the residue 
is recrystallised from diethyl ether/hexane to give the title compound in 
the form of colourless crystals with a melting point of 
91.degree.-95.degree. C. 
Example P4 
Preparation of 
##STR12## 
N-(1-Acetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyano pyrrole 
1.2 ml of chloral and 1.8 ml of triethylamine are added dropwise in 
succession to 2.4 g of 3-(2,4-dichlorophenyl)-4-cyanopyrrole in 50 ml of 
tetrahydrofuran. The reaction mixture is stirred for 11/2 hours at 
25.degree. C., then 0.1 g of 4-dimethylaminopyridine is added and the 
mixture is cooled to -10.degree. C. A solution of 0.9 ml of acetyl 
chloride in 10 ml of tetrahydrofuran is added very slowly dropwise at 
-10.degree. to -5.degree. C. and the reaction mixture is subsequently 
stirred for 30 minutes at 0.degree. C. and then for 1 hour at room 
temperature, and filtered. The filtrate is concentrated and the residue is 
dissolved in diethyl ether. The ethereal solution is washed twice with a 
semi-saturated solution of sodium chloride, dried over sodium sulfate, and 
filtered. The filtrate is concentrated and the crude product is 
recrystallised from diethyl ether/petroleum ether to give colourless 
crystals of the title compound with a melting point of 
111.degree.-113.degree. C. 
Example P5 
Preparation of 
##STR13## 
N-Chloromethyl-3-(2,3-dichlorophenyl)-4-cyanopyrrole 
To a solution of 23.7 g of 3-(2,3-dichlorophenyl)-4-cyanopyrrole in 300 ml 
of tetrahydrofuran are added 7.5 g of paraformaldehyde and then 1.5 ml of 
1,8-diazabicyclo[5.4.0]undec-7-ene. The mixture is stirred for 3 hours at 
room temperature. With stirring, 21.7 ml of thionyl chloride are added 
dropwise at 20.degree.-30.degree. C. to the resultant hydroxymethyl 
derivative. The reaction mixture is stirred for 16 hours at room 
temperature, then poured into ice-water and extracted twice with ethyl 
acetate. The combined organic extracts are washed twice with a 
halogen-containing solution of sodium chloride, dried over sodium sulfate 
and filtered. The filtrate is concentrated and the residue is crystallised 
from ether/petroleum ether to give the title compound in the form of beige 
crystals with a melting point of 132.degree.-133.degree. C. 
Example P6 
Preparation of 
##STR14## 
N-(1-Hydroxy)-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole 
39.6 ml of chloral are added dropwise at 20.degree.-29.degree. C. to 64 g 
of 3-cyano-4-(2,3-dichlorophenyl)pyrrole and 1.2 ml of triethylamine in 
400 ml of tetrahydrofuran. Then a further 2.4 ml of triethylamine followed 
by 1.2 ml of diazabicyclo[5.4.0]undec-7-ene are added and the clear 
solution so obtained is stirred initially for 2 hours at room temperature 
and then for 14 hours at 0.degree.-5.degree. C. The solution is then 
poured into dilute hydrochloric acid and ice and the mixture is extracted 
twice with ethyl acetate. The organic extracts are washed three times with 
a cold semi-saturated solution of sodium chloride, dried over sodium 
sulfate and filtered. The filtrate is concentrated and the residue is 
crystallised from ether/petroleum ether to give colourless crystals of the 
desired compound with a melting point of 117.degree. C. (decompos.). 
Example P7 
Preparation of 
##STR15## 
N-[1-(Methoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyan 
opyrrole 
4.8 g of 3-cyano-4-(2,3-dichlorophenyl)pyrrole are dissolved in 50 ml of 
tetrahydrofuran and to the solution are added 0.2 ml of 
diazabicyclo[5.4.0]undec-7-ene and then 2.3 ml of chloral. The solution is 
cooled to -5.degree. C., then 3.3 ml of triethylamine are added dropwise. 
The reaction mixture is stirred for 1 hour at -5.degree. C. and then a 
solution of 2.2 ml of methoxyacetyl chloride in 10 ml of tetrahydrofuran 
is slowly added dropwise at -10.degree. to -5.degree. C. After it has been 
stirred for 1 hour in a thawing cooling bath, the reaction mixture is 
poured into ice-water and extracted twice with ethyl acetate. The organic 
extracts are washed twice with cold dilute hydrochloric acid and twice 
with a cold semi-saturated solution of sodium chloride, then dried over 
sodium sulfate and filtered. The filtrate is concentrated and the residue 
is crystallised from petroleum ether, affording colourless crystals of the 
title compound with a melting point of 88.degree.-90.degree. C. 
Example P8 
Preparation of 
##STR16## 
N-[1-(Methoxyacetyloxy)methyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole 
4.5 g of 3-cyano-4-(2,3-dichlorophenyl)pyrrole are dissolved in 50 ml of 
tetrahydrofuran and to the solution are added 0.65 g of paraformaldehyde, 
3.0 ml of triethylamine and 0.5 ml of diazobicyclo[5.4.0]undec-7-ene. The 
mixture is stirred for 2 hours at room temperature to form a clear 
solution. With stirring, 2.0 ml of ethoxyacetyl chloride are slowly added 
dropwise at 5.degree. C. The reaction mixture is kept for 21/2 hours at 
0.degree.-5.degree. C. and then filtered. The filtrate is concentrated and 
the residue is crystallised from ether/petroleum ether to give colourless 
crystals of the title compound with a melting point of 
72.degree.-75.degree. C. 
The compounds listed in the following tables can also be prepared in 
corresponding manner. 
TABLE 1 
______________________________________ 
Compounds of the formula 
##STR17## 
wherein Y is OH. 
Physical data 
Compound R.sub.1 R.sub.2 R.sub.3 
(.degree.C.) 
______________________________________ 
1.1 2-Cl H H m.p. 94-97.degree. 
1.2 H 3-Cl H m.p. 72-74 
1.3 2-Cl 3-Cl CCl.sub.3 
117.degree. decompos. 
1.4 H 2-SCH.sub.3 
CCl.sub.3 
85.degree. decompos. 
1.5 2-Cl H CCl.sub.3 
70-76.degree. decompos. 
1.6 2-Cl 3-Cl H m.p. 137-140.degree. 
1.7 H 3-Cl CCl.sub.3 
1.8 2-SCH.sub.3 
H H 
1.9 2-OCH.sub.3 
H H resin 
1.10 2-OCH.sub.3 
H CCl.sub.3 
1.11 H H H m.p. 81-84.degree. 
1.12 H 3-OCH.sub.3 
H 
1.13 H 3-OCH.sub.3 
CCl.sub.3 
resin 
1.14 H 3-SCH.sub.3 
CCl.sub.3 
1.15 H 3-SCH.sub.3 
H resin 
1.16 2-OCH.sub.3 
3-OCH.sub.3 
H 
1.17 2-OCH.sub.3 
3-OCH.sub.3 
CCl.sub.3 
1.18 H 3-Br H m.p. 65-69.degree. 
1.19 H 3-Br CCl.sub.3 
1.20 H 3-F H m.p. 75-77.degree. 
1.21 2-F H H 
1.22 H 3-F CCl.sub.3 
1.23 H 3-I CCl.sub.3 
1.24 H 3-I H 
______________________________________ 
TABLE 2 
______________________________________ 
Compounds of the formula 
##STR18## 
wherein Y is Cl. 
Physical data 
Compound R.sub.1 R.sub.2 R.sub.3 
(.degree.C.) 
______________________________________ 
2.1 2-Cl H H m.p. 97-99.degree. 
2.2 H 3-Cl H m.p. 77-79.degree. 
2.3 2-Cl H CCl.sub.3 
2.4 2-Cl 3-Cl H m.p. 132-133.degree. 
2.5 2-Cl 3-Cl CCl.sub.3 
m.p. 152-157.degree. 
2.6 H 3-Cl CCl.sub.3 
2.7 2-SCH.sub.3 
H H 
2.8 2-SCH.sub.3 
H CCl.sub.3 
2.9 2-OCH.sub.3 
H H 
2.10 2-OCH.sub.3 
H CCl.sub.3 
2.11 H 3-OCH.sub.3 
H resin 
2.12 H 3-OCH.sub.3 
CCl.sub.3 
resin 
2.13 H 2-SCH.sub.3 
H 
2.14 H 3-SCH.sub.3 
CCl.sub.3 
2.15 2-OCH.sub.3 
3-OCH.sub.3 
H 
2.16 2-OCH.sub.3 
3-OCH.sub.3 
CCl.sub.3 
2.17 H 3-Br H m.p. 71-74.degree. 
2.18 H 3-Br CCl.sub.3 
semi-crystalline 
2.19 H 3-F H m.p. 80-83.degree. 
2.20 2-F H H 
2.21 H 3-F CCl.sub.3 
2.22 H 3-I CCl.sub.3 
2.23 H 3-I H m.p. 59-65.degree. 
2.24 H 3-OCH.sub.3 
CHCl.sub.2 
2.25 H 3-OCH.sub.3 
CHCl.sub.2 
resin 
2.26 H 3-SCH.sub.3 
CH.sub.2 Cl 
______________________________________ 
TABLE 3 
__________________________________________________________________________ 
Compounds of the formula 
##STR19## 
wherein Y is OC(O)R.sub.4. 
Com- Physical data 
pound 
R.sub.1 
R.sub.2 
R.sub.3 
R.sub.4 (.degree.C.) 
__________________________________________________________________________ 
3.1 2-Cl H CCl.sub.3 
CH.sub.3 m.p. 100-108.degree. 
3.2 2-Cl H H CH.sub.3 m.p. 91-95.degree. 
3.3 H 3-Cl CCl.sub.3 
CH.sub.3 m.p. 118-120.degree. 
3.4 2-Cl 3-Cl CCl.sub.3 
CH.sub.3 m.p. 111-113.degree. 
3.5 2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH.sub.3 
m.p. 88-90.degree. 
3.6 2-SCH.sub.3 
H CCl.sub.3 
CH.sub.3 m.p. 139-141.degree. 
3.7 2-OCH.sub.3 
H CCl.sub.3 
CH.sub.3 m.p. 106-108.degree. 
3.8 2-Cl H H CCl.sub.3 
3.9 2-Cl H H CH.sub.2 OCH.sub.3 
m.p. 112-114.degree. 
3.10 
H 3-Cl CCl.sub.3 
CH(CH.sub.3).sub.2 
3.11 
H 3-Cl CCl.sub.3 
(CH.sub.2).sub.3 CH.sub.3 
resin 
3.12 
H 3-Cl CCl.sub.3 
CH.sub.2 Br 
3.13 
H 3-Cl CCl.sub.3 
CF.sub.3 
3.14 
H 3-Cl H CH.sub.3 
3.15 
H 3-Cl H CHCl.sub.2 
3.16 
2-Cl 3-Cl CCl.sub.3 
C.sub.2 H.sub.5 
m.p. 137-141.degree. 
3.17 
2-Cl 3-Cl CCl.sub.3 
(CH.sub.2).sub.3 CH.sub.3 
n.sub.D.sup.50 1.5548 
3.18 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 Cl m.p. 143-151.degree. 
3.19 
2-Cl 3-Cl CCl.sub.3 
H resin 
3.20 
2-Cl 3-Cl H CH.sub.3 m.p. 95-99.degree. 
3.21 
2-Cl 3-Cl H C(CH.sub.3).sub.3 
m.p. 86-88.degree. 
3.22 
2-Cl 3-Cl H CH.sub.2 OCH.sub.3 
m.p. 72-75.degree. 
3.23 
2-Cl 3-Cl H CCl.sub.3 
3.24 
2-Cl 3-Cl H H 
3.25 
2-OCH.sub.3 
H CCl.sub.3 
C(CH.sub.3).sub.3 
3.26 
2-OCH.sub.3 
H CCl.sub.3 
CH.sub.2 Cl resin 
3.27 
2-OCH.sub.3 
H CCl.sub.3 
H 
3.28 
2-OCH.sub.3 
H H CCl.sub.3 
3.29 
2-OCH.sub.3 
H H CH.sub.3 
3.30 
2-OCH.sub.3 
H H CH.sub.2 OCH.sub.3 
semi-crystalline 
3.31 
2-SCH.sub.3 
H CCl.sub.3 
C.sub.2 H.sub. 5 
3.32 
2-SCH.sub.3 
H CCl.sub.3 
CH.sub.2 Cl 
3.33 
2-SCH.sub.3 
H CCl.sub.3 
CH.sub.2 OCH.sub.3 
semi-crystalline 
3.34 
2-SCH.sub.3 
H H CH.sub.3 
3.35 
2-SCH.sub.3 
H H C.sub.2 H.sub.5 
3.36 
2-SCH.sub.3 
H H CCl.sub.3 
3.37 
2-Cl 3-Cl H CH.sub.2 Cl m.p. 113-115.degree. 
3.38 
2-Cl 3-Cl H C.sub.2 H.sub.5 
resin 
3.39 
2-Cl 3-Cl H C.sub.4 H.sub.9n 
n.sub.D.sup.50 1.5571 
3.40 
2-Cl 3-Cl CCl.sub.3 
C(CH.sub.3).sub.3 
m.p. 146-147.degree. 
3.41 
H H CCl.sub.3 
CH.sub.2 OCH.sub.3 
m.p. 121-122.degree. 
3.42 
2-Cl 3-Cl CCl.sub.3 
C.sub.2 H.sub.5 
semi-crystalline 
3.43 
2-Cl 3-Cl H CH.sub.2 Br m.p. 88-90.degree. 
3.44 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 Br m.p. 132-135.degree. 
3.45 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.2 H.sub.5 
m.p. 115-117.degree. 
3.46 
2-Cl 3-Cl H CH.sub.2 OC.sub.2 H.sub.5 
m.p. 83-85.degree. 
3.47 
2-Cl H CCl.sub.3 
CH.sub.2 OCH.sub.3 
m.p. 116-118.degree. 
3.48 
H H H CH.sub.2 OCH.sub.3 
m.p. 78-79.degree. 
3.49 
2-Cl 3-Cl H CH.sub.2 OC.sub.3 H.sub. 7n 
m.p. 87-88.degree. 
3.50 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.3 H.sub.7n 
m.p. 76-78.degree. 
3.51 
2-Cl 3-Cl H CH.sub.2 OC.sub.4 H.sub.9n 
m.p. 71-74.degree. 
3.52 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.4 H.sub.9n 
m.p. 89-91.degree. 
3.53 
2-Cl 3-Cl H CH.sub.2 OC.sub.6 H.sub.13n 
3.54 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.6 H.sub.13n 
3.55 
2-Cl H H CH.sub.2 OCH(CH.sub.3).sub.2 
3.56 
2-Cl H CCl.sub.3 
CH.sub.2 OCH(CH.sub.3).sub.2 
m.p. 69-76.degree. 
3.57 
2-Cl 3-Cl H CH.sub.2 OCH(CH.sub.3).sub.2 
m.p. 74-75.degree. 
3.58 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH(CH.sub.3).sub.2 
m.p. 112-115.degree. 
3.59 
2-Cl 3-Cl H CH.sub.2 OCH(CH.sub.3)C.sub.2 H.sub.5 
m.p. 71-73.degree. 
3.60 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH(CH.sub.3)C.sub.2 H.sub.5 
m.p. 70-74.degree. 
3.61 
2-Cl 3-Cl H CH.sub.2 OC(CH.sub.3).sub.3 
3.62 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC(CH.sub.3).sub.3 
3.63 
2-Cl H H CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
3.64 
2-Cl H CCl.sub. 3 
CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
3.65 
2-Cl 3-Cl H CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
m.p. 99-101.degree. 
3.66 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
n.sub.D.sup.50 1.5472 
3.67 
2-Cl 3-Cl H CH.sub.2 OCH.sub.2 CHCH.sub.2 
m.p. 65-67.degree. 
3.68 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH.sub.2 CHCH.sub.2 
m.p. 86-88.degree. 
3.69 
2-Cl 3-Cl H CH.sub.2 OCH.sub.2 CCH 
m.p. 109-111.degree. 
3.70 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OCH.sub.2 CCH 
n.sub.D.sup.50 1.5732 
3.71 
2-Cl 3-Cl H CH.sub.2 OC.sub.6 H.sub.5 
m.p. 119-121.degree. 
3.72 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.6 H.sub.5 
n.sub.D.sup.50 1.5803 
3.73 
2-Cl 3-Cl H CH.sub.2 OC.sub.6 H.sub.3 Cl.sub.2 (3,5) 
m.p. 125-127.degree. 
3.74 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.6 H.sub.3 Cl.sub.2 (3,5) 
m.p. 154-156.degree. 
3.75 
2-Cl 3-Cl H CH.sub.2 OC.sub.6 H.sub.3 Cl.sub.2 (2,4) 
m.p. 102-104.degree. 
3.76 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 OC.sub.6 H.sub.3 Cl.sub.2 (2,4) 
m.p. 157-159.degree. 
3.77 
2-Cl H H 2-tetrahydrofuryl 
n.sub.D.sup.50 1.5672 
3.78 
2-Cl H CCl.sub.3 
2-tetrahydrofuryl 
m.p. 142-149.degree. 
3.79 
2-Cl 3-Cl H 2-tetrahydrofuryl 
m.p. 96-98.degree. 
3.80 
2-Cl 3-Cl CCl.sub.3 
2-tetrahydrofuryl 
m.p. 156-160.degree. 
3.81 
2-Cl H H CH.sub.2 SCH.sub.3 
3.82 
2-Cl H CCl.sub.3 
CH.sub.2 SCH.sub.3 
3.83 
H H H CH.sub.2 SCH.sub.3 
3.84 
H H CCl.sub.3 
CH.sub.2 SCH.sub.3 
3.85 
2-Cl 3-Cl H CH.sub.2 SCH.sub.3 
3.86 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 SCH.sub.3 
3.87 
2-Cl 3-Cl H CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5 
resin 
3.88 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5 
3.89 
2-Cl H H CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5 
3.90 
2-Cl H CCl.sub.3 
CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5 
3.91 
2-Cl 3-Cl H CH.sub.2 SC.sub.4 H.sub.9n 
3.92 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 SC.sub.4 H.sub.9n 
3.93 
2-Cl 3-Cl H CH.sub.2 SC(CH.sub.3).sub.3 
3.94 
2-Cl 3-Cl CCl.sub. 3 
CH.sub.2 SC(CH.sub.3).sub.3 
3.95 
2-Cl 3-Cl H C(O)OC.sub.2 H.sub.5 
m.p. 111-113.degree. 
3.96 
2-Cl H H CH.sub.2 SC.sub.6 H.sub.5 
3.97 
2-Cl H CCl.sub.3 
CH.sub.2 SC.sub.6 H.sub.5 
3.98 
2-Cl 3-Cl H CH.sub.2 SC.sub.6 H.sub.5 
3.99 
2-Cl 3-Cl CCl.sub.3 
CH.sub.2 SC.sub.6 H.sub.5 
3.100 
2-Cl H H CHCH.sub.2 
3.101 
2-Cl H CCl.sub.3 
CHCH.sub.2 
3.102 
2-Cl 3-Cl H CHCH.sub.2 
3.103 
2-Cl 3-Cl CCl.sub.3 
CHCH.sub.2 m.p. 106-108.degree. 
3.104 
2-Cl 3-Cl H CHCHCH.sub.3 
3.105 
2-Cl 3-Cl CCl.sub.3 
CHCHCH.sub.3 
m.p. 107-109.degree. 
3.106 
2-Cl H H CHCHCH.sub.3 
3.107 
2-Cl H CCl.sub.3 
CHCHCH.sub.3 
3.108 
H H H CH.sub.2 Cl m.p. 83-84.degree. 
3.109 
H 3-OCH.sub.3 
H CH.sub.3 
3.110 
H 3-OCH.sub.3 
CCl.sub.3 
CH.sub.3 
3.111 
H 3-OCH.sub.3 
CCl.sub.3 
CH.sub.3 
3.112 
H 3-OCH.sub.3 
H CH.sub.3 resin 
3.113 
2-OCH.sub.3 
3-OCH.sub.3 
H CH.sub.2 OCH.sub.3 
resin 
3.114 
2-OCH.sub.3 
3-OCH.sub.3 
H CH.sub.3 
3.115 
H 3-Br CCl.sub.3 
CH.sub. 2 OCH.sub.3 
3.116 
H 3-Br H CH.sub.3 
3.117 
H 3-F H CH.sub.3 
3.118 
2-F H H CH.sub.2 OCH.sub.3 
3.119 
H 3-F CCl.sub.3 
CH.sub.3 
__________________________________________________________________________ 
FORMULATION EXAMPLES 
Formulation Examples for liquid active ingredients of the formula I 
(throughout, percentages are by weight) 
______________________________________ 
F1. Emulsifiable concentrates 
(a) (b) (c) 
______________________________________ 
a compound of tables 1 to 3 
25% 40% 50% 
calcium dodecylbenzenesulfonate 
5% 8% 6% 
castor oil polyethylene glycol ether 
5% -- -- 
(36 moles of ethylene oxide) 
tributylphenol polyethylene glycol ether 
12% 4% 
(30 moles of ethylene oxide) 
cyclohexanone -- 15% 20% 
xylene mixture 65% 25% 20% 
______________________________________ 
Emulsions of any required concentration can be produced from such 
concentrates by dilution with water. 
______________________________________ 
F2. Solutions (a) (b) (c) (d) 
______________________________________ 
a compound of tables 1 to 3 
80% 10% 5% 95% 
ethylene glycol monomethyl ether 
20% -- -- -- 
polyethylene glycol 400 
-- 70% -- -- 
N--methyl-2-pyrrolidone 
-- 20% -- -- 
epoxidised coconut oil 
-- -- 1% 5% 
petroleum distillate (boiling range 
-- -- 94% -- 
160-190.degree.) 
______________________________________ 
These solutions are suitable for application in the form of microdrops. 
______________________________________ 
F3. Granulates (a) (b) 
______________________________________ 
a compound of tables 1 to 3 
5% 10% 
kaolin 94% -- 
highly dispersed silicic acid 
1% -- 
attapulgite -- 90% 
______________________________________ 
The active ingredient is dissolved in methylene chloride, the solution is 
sprayed onto the carrier, and the solvent is subsequently evaporated off 
in vacuo. 
______________________________________ 
F4. Dusts (a) (b) 
______________________________________ 
a compound of tables 1 to 3 
2% 5% 
highly dispersed silicic acid 
1% 5% 
talcum 97% -- 
kaolin -- 90% 
______________________________________ 
Ready-for-use dusts are obtained by intimately mixing the carriers with the 
active ingredient. 
Formulation examples for solid active ingredients of the formula I 
(throughout, percentages are by weight) 
______________________________________ 
F5. Wettable powders (a) (b) (c) 
______________________________________ 
a compound of tables 1 to 3 
25% 50% 75% 
sodium lignosulfonate 5% 5% -- 
sodium lauryl sulfate 3% -- 5% 
sodium diisobutylnaphthalenesulfonate 
-- 6% 10% 
octylphenol polyethylene glycol ether 
-- 2% -- 
(7-8 moles of ethylene oxide) 
highly dispersed silicic acid 
5% 10% 10% 
kaolin 62% 27% -- 
______________________________________ 
The active ingredient is thoroughly mixed with the adjuvants and the 
mixtures is thorougly ground in a suitable mill, affording wettable 
powders which can be diluted with water to give suspensions of the desired 
concentration. 
______________________________________ 
F6. Emulsifiable concentrate 
______________________________________ 
a compound of tables 1 to 3 
10% 
octylphenol polyethlene glycol ether 
3% 
(4-5 moles of ethylene oxide) 
calcium dodecylbenzenesulfonate 
3% 
castor oil polyglycol ether 
4% 
(36 moles of ethylene oxide) 
cyclohexanone 30% 
xylene mixture 50% 
______________________________________ 
Emulsions of any required concentration can be obtained from this 
concentrate by dilution with water. 
______________________________________ 
F7. Dusts (a) (b) 
______________________________________ 
a compound of tables 1 to 3 
5% 8% 
talcum 95% -- 
kaolin -- 92% 
______________________________________ 
Ready-for use dusts are obtained by mixing the active ingredient with the 
carriers, and grinding the mixture in a suitable mill. T1 -F8. Extruder 
granulate? -a compound of tables 1 to 3 10% -sodium lignosulfonate 2% 
-carboxymethylcellulose 1% -kaolin 87%? - 
The active ingredient is mixed and ground with the adjuvants, and the 
mixture is subsequently moistened with water. The mixture is extruded and 
then dried in a strem of air. 
______________________________________ 
F9. Coated granulate 
______________________________________ 
a compound of tables 1 to 3 
3% 
polyethylene glycol 200 
3% 
kaolin 94% 
______________________________________ 
The finely ground active ingredient is uniformly applied, in a mixer, to 
the kaolin moistened with polyethylene glycol. Non-dusty coated granulates 
are obtained in this manner. 
______________________________________ 
F10. Suspension concentrate 
______________________________________ 
a compound of tables 1 to 3 
40% 
ethylene glycol 10% 
nonylphenol polyethylene glycol 
6% 
(15 moles of ethylene oxide) 
sodium lignosulfonate 10% 
carboxymethylcellulose 
1% 
37% aqueous formaldehyde solution 
0.2% 
silicone oil in the form of a 75% 
0.8% 
aqueous emulsion 
water 32% 
______________________________________ 
The finely ground active ingredient is intimately mixed with the aduvants, 
giving a suspension concentrate from which suspensions of any desired 
concentration can be obtained by dilution with water. 
BIOLOGICAL EXAMPLES 
EXAMPLE B1 
Action against Puccinia graminis on wheat 
(a) Residual-protective action 
Wheat plants were treated 6 days after sowing with a spray mixture prepared 
from a wettable powder formulation of the test compound (0.06%). After 24 
hours the treated plants were infected with a uredospore suspension of the 
fungus. The infected plants were incubated for 48 hours at 95-100% 
relative humidity and about 20.degree. C. and then stood in a greenhouse 
at about 22.degree. C. Evaluation of rust pustule development was made 12 
days after infection. 
(b) Systemic action 
Wheat plants were treated 5 days after sowing with a spray mixture prepared 
from a wettable powder formulation of the test compound (0.006% based on 
the volume of the soil). After 48 hours the treated plants were infected 
with a uredospore suspension of the fungus. The plants were then incubated 
for 48 hours at 95-100% relative humidity and about 20.degree. C. and then 
stood in a greenhouse at about 22.degree. C. Evaluation or rust pustule 
development was made 12 days after infection. 
Compounds of Tables 1 to 3 were very effective against Puccinia fungi not 
only in the above greenhouse test but also in field trials. Puccinia 
attack was 100% on untreated and infected control plants. Compounds No. 
1.2 to 1.5, 1.9, 1.13, 2.11, 2.12, 2.18, 3.2, 3.4 to 3.7, 3.37 to 3.40, 
3.42 to 3.46, 3.51, 3.52, 3.57, 3.70, 3.73 to 3.76 and 3.94 and others 
inhibited Puccinia attack to 0 to 10%. 
EXAMPLE B2 
Action against Cercospora arachidicola in groundnut plants 
Residual protective action 
Groundnut plants 10-15 cm in height were sprayed with a spray mixture 
(0.006%) prepared from a wettable powder formulation of the test compound, 
and infected 48 hours later with a conidia suspension of the fungus. The 
infected plants were incubated for 72 hours at about 21.degree. C. and 
high humidity and then stood in a greenhouse until the typical leaf specks 
occur. Evaluation of the fungicidal action was made 12 days after 
infection and was based on the number and size of the specks. 
(b) Systemic action 
Groundnut plants 10-15 cm in height were sprayed with a spray mixture 
prepared from a wettable powder formulation of the test compound (0.06%, 
based on the volume of the soil). The treated plants were infected 48 
hours later with a conidia suspension of the fungus and then incubated for 
72 hours at about 21.degree. C. and high humidity. The plants were then 
stood in a greenhouse and evaluation of fungus attack was made 11 days 
later. 
Compared with untreated and infected control plants (number and size of the 
specks=100%), Cercospora attack on groundnut plants treated in the 
greenhouse or in the field with compounds of Tables 1 to 3 was 
substantially reduced. Thus compounds 1.3, 1.6, 3.4, 3.5, 3.17, 3.18, 
3.20, 3.49, 3.51, 3.52, 3.57, 3.67, 3.69, 3.70 and 3.95 inhibited 
Cercospora attack almost completely (8%). 
EXAMPLE B3 
Action against Botrytis cinerea on beans 
Residual protective action 
Bean plants about 10 cm in height were sprayed with a spray mixture (0.02%) 
prepared from a wettable powder formulation of the test compound. After 48 
hours the treated plants were infected with a conidia suspension of the 
fungus. The infected plants were incubated for 3 days at 95-100% relative 
humidity and 21.degree. C. and then evaluated for fungus attack. The 
compounds of Tables 1 to 3 inhibited the fungus infection very strongly 
not only in the above model test but also in field trials. At a 
concentration of 0.02%, compounds 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15, 1.18, 
1.20, 2.1, 2.2, 2.4, 2.5, 2.11, 2.12, 2.17, 2.18, 2.19, 2.23, 3.1 to 3.7, 
3.9, 3.16 to 3.22, 3.26, 3.30, 3.33, 3.37, 3.38, 3.39 to 3.52, 3.56 to 
3.60, 3.65 to 3.80, 3.95, 3.103, 3.105, 3.108, 3.112 and 3.113 were fully 
effective (0 to 5% attack). This activity was achieved with some 
representatives at half the rate of application. Fungus attack was 100% on 
untreated and infected bean plants. The intermediates 16 and 24 were 
equally effective. 
EXAMPLE B4 
Action against Botrytis cinerea on apples 
Artificially damaged apples were treated by dropping a spray mixture 
prepared from the respective test compound formulated as wettable powder 
onto the injury sites. The treated fruit was then inoculated with a spore 
suspension of Botrytis cinerea and incubated for 1 week at high humidity 
and about 20.degree. C. Evaluation was made by counting the number of 
injury sites attacked by rot and deducing the fungicidal action of the 
test compound therefrom. Compared with untreated controls (100% attack), 
compounds 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15, 1.18, 1.20, 2.1, 2.2, 2.4, 
2.5, 2.11, 2.12, 2.17, 2.18, 2.19, 2.23, 3.1 to 3.7, 3.9, 3.16 to 3.22, 
3.26, 3.30, 3.33, 3.37, 3.38, 3.39 to 3.52. 3.56 to 3.60, 3.65 to 3.80, 
3.95, 3.103, 3.105, 3.108, 3.112 and 3.113 and others inhibited fungus 
attack almost completely. The intermediates 16 and 24 were also equally 
effective. 
EXAMPLE B5 
Action against Piricularia on rice plants 
Residual protective action 
After a cultivation period of 2 weeks, rice plants were sprayed with a 
spray mixture (0.02%) prepared from a wettable powder formulation of the 
test compound. After 48 hours the treated plants were infected with a 
conidia suspension of the fungus. Evaluation of fungus attack was made 
after incubation for 5 days at 95-100% relative humidity and 24.degree. C. 
Compounds of formula I inhibited Piricularia attack effectively e.g. 
compounds 1.3, 1.6, 2.2, 2.4, 3.1 to 3.5, 3.7, 3.17, 3.18, 3.20, 3.21, 
3.44 to 3.47, 3.49, 3.51, 3.52, 3.57, 3.67, 3.70, 3.75 and 3.95. These 
compounds reduced attack to less than 10%. It was also possible to achieve 
this activity under field conditions. 
EXAMPLE B6 
Action against Rhizoctonia solani in cabbage 
Action after soil application 
The fungus was cultivated on sterile millet seeds and added to a mixture of 
soil and sand. Dishes were filled with the infected soil in which cabbage 
seeds were sown. Immediately after sowing, an aqueous suspension of the 
test compound formulated as wettable powder was poured onto the soil (20 
ppm, based on the volume of the soil). The dishes were then put into a 
greenhouse for 2-3 weeks at about 24.degree. C. and kept uniformly moist 
by light spraying. The test was evaluated by determining the number of 
emerged cabbage plants. After treatment with wettable powders which 
contained one of compounds 1.3, 2.1, 3.20 or 3.27, 80% of the cabbage 
seeds emerged and the plants had a healthy appearance. 
EXAMPLE B7 
Residual-protective action against Venturia inaequalis on apple shoots 
Apple cuttings with 10-20 cm long fresh shoots were sprayed with a spray 
mixture (0.006%) prepared from a wettable powder formulation of the test 
compound. The plants were infected 24 hours later with a conidia 
suspension of the fungus. The plants were then incubated for 5 days at 
90-100% relative humidity and stood in a greenhouse for a further 10 days 
at 20.degree.-24.degree. C. Evaluation of scab infestation was made 15 
days after infection. 
Compounds of formula I were very effective against Venturia pathogens. 
Compared with attack on untreated control plants, scab attack was 
inhibited to less than 20% with compounds 1.2, 1.3, 3.4, 3.5, 3.17, 3.18, 
3.20, 3.22, 3.37, 3.39, 3.71 and 3.95. This effect was achieved in field 
trials with compounds 1.2, 1.3, 3.4, 3.5 and 3.17 in field trials even at 
a concentration of 0.002%. 
EXAMPLE B8 
Action against Helminthosporium gramineum 
Wheat grains were contaminated with a spore suspension of the fungus and 
dried. The contaminated grains were dressed with a suspension of the test 
compound prepared from a wettable powder (600 ppm of test compound, based 
on the weight of the seeds). Two days later the grains were placed in 
suitable agar dishes and a count of the fungus colonies which had 
developed around the grains was made after another 4 days. The 
effectiveness of the test compounds was assessed on the basis of the 
number and size of the colonies. Compounds of Tables 1 to 3, in particular 
those of Table 3, inhibited fungus attack substantially (0 to 10%). 
EXAMPLE B9 
Action against Fusarium nivale 
Wheat grains were contaminated with a spore suspension of the fungus and 
dried. The contaminated grains were dressed with a suspension of the test 
compound prepared from a wettable powder (600 ppm of test compound, based 
on the weight of the seeds). Two days later the grains were placed in 
suitable agar dishes and a count of the fungus colonies which had 
developed around the grains was made after another 4 days. The 
effectiveness of the test compounds was assessed on the basis of the 
number and size of the colonies. The development of fungus colonies was 
almost completely inhibited (0 to 5%) on wheat grains treated with a 
wettable powder formulation of one of the compounds of Tables 1 to 3. 
EXAMPLE B10 
Grain preservative test 
(a) Short-term test against mould fungi on moist maize 
Dry maize kernels (80 g portions) intended for use as animal feed were 
thoroughly mixed in sealable platic beakers with compounds of all Tables 
in the form of an aqueous suspension, emulsion or solution. The 
application of test compound was made so as to give a concentration of 
0.06%, based on the dry weight of the maize. A moistened sheet of paper 
ensured a saturated moist atmosphere in the beakers, which were filled 
with the maize and then sealed. After an incubation of 2-3 weeks at about 
20.degree. C., a mixed population of mould fungi developed spontaneously 
on the maize samples treated only with water. There was no need to make an 
artificial infection. The effectiveness of the compounds of the formula I 
was evaluated by determining the extent of fungus development after 3 
weeks. 
(b) Long-term test against mould fungi on moist maize 
I The maize samples exhibiting no fungus attack after 3 weeks were 
incubated for a further two months. A visual assessment was made after 
each month, applying the same criteria as in test (a). 
II The test procedure was in principle the same as in (a) and (b), except 
that the test compound of the formula I or II' were used in concentrations 
of 2000, 600 and 200 ppm a.i. (based on the dry weight of the maize) over 
6 months. 
In all three tests (a), (bI) and (bII), the formation of mould fungi on 
moist maize was inhibited completely both short-term (3 weeks) and 
long-term (6 months) by treatment with compounds of the formula I of 
Tables 1 to 3. For example, compounds 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15, 
1.18 and a number of representatives of Tables 2 and 3 in all three tests 
(a), (bI) and (bII) inhibited mould fungus attack almost completely (0-5% 
attack) at a test concentration of 600 ppm a.i.. Treatment with compounds 
of the formula I in similar tests using, alternatively, cereals (oats), 
hay, carrot chips or broad beans instead of fodder maize, gave similar 
reuslts of long-term protection over several months.