Combating fungi with 1-(azol-1-yl)-2-hydroxy-or-keto-1-pyridinyloxy-alkanes

1-(Azol-1-yl)-2-hydroxy-or-keto-pyridinyloxy-alkanes of the formula ##STR1## in which A is CH or N, PA0 R is alkyl PA0 X is --CO--or --CH(OH)-- PA0 Y is halogen, alkyl, halogenoalkyl, alkenyl, alkynyl, alkoxy, alkylthio, nitro, cyano, optionally substituted aryl or optionally substituted aryloxy, and PA0 n is 0, 1, 2 or 3, an acid addition salt thereof, or a metal salt complex thereof, which possess fungicidal properties.

The present invention relates to and has for its objects the provision of 
particular new 1-(azol-1-yl)-2-hydroxy-or-keto-pyridinyloxy-alkanes which 
possess fungicidal properties, active compositions in the form of mixtures 
of such compounds with solid and liquid dispersible carrier vehicles, and 
methods for producing such compounds and for using such compounds in a new 
way especially for combating pests, e.g. fungi, with other and further 
objects becoming apparent from a study of the within specification and 
accompanying examples. 
It has already been disclosed that trityl-imidazoles and -1,2,4-triazoles, 
such as 1-triphenylmethyl-imidazole and 1-triphenylmethyl-1,2,4-triazole, 
have a good fungicidal activity (see U.S. Pat. No. 3,321,366 and DT-OS 
(German Published Specification) No. 1,795,249). However, their action is 
not always completely satisfactory, especially when low amounts and 
concentrations are used. 
The present invention provides the azolylalkyl pyridinyl ethers of the 
general formula 
##STR2## 
in which A represents the CH group or a nitrogen atom, 
R represents alkyl, 
X represents a keto group or a CH(OH) grouping, 
Y represents halogen, alkyl, halogenoalkyl, alkenyl, alkynyl, alkoxy, 
alkylthio, nitro, cyano or optionally substituted aryl or aryloxy and 
n represents the number 0, 1, 2 or 3, 
and acid addition salts thereof and metal salt complexes thereof. They have 
powerful fungicidal properties. 
Preferaly, R represents straight-chain or branched alkyl with 1 to 4 carbon 
atoms, and Y represents fluorine, chlorine, bromine, iodine, 
straight-chain or branched alkyl with 1 to 4 carbon atoms, halogenoalkyl 
with up to 2 carbon atoms and up to 5 halogen atoms (especially with up to 
3 identical or different halogen atoms, preferred halogens being fluorine 
and chlorine; an example which may be mentioned is trifluoromethyl), 
alkenyl or alkynyl with in either case 2 to 4 carbon atoms, alkoxy or 
alkylthio with in either case 1 to 4 carbon atoms, nitro, cyano or 
optionally substituted aryl or aryloxy with in either case 6 to 10 carbon 
atoms (especially phenyl, naphthyl, phenyloxy or naphthyloxy) preferred 
substituents of these radicals being halogen (especially fluorine, 
chlorine or bromine), alkyl, alkoxy or alkylthio with in each case 1 to 2 
carbon atoms and halogenoalkyl with up to 2 carbon atoms and up to 3 
identical or different halogen atoms (preferred halogens being fluorine 
and chlorine). 
Those compounds of the formula (I) in which X represents the CH(OH) group 
possess two asymmetric carbon atoms; they can therefore exist in the form 
of the two geometric isomers (ervthro form and threo form), which can be 
obtained in various proportions. In both cases they exist in the form of 
optical isomers. The formula (I) embraces all the isomers. 
Surprisingly, the active compounds according to the invention exhibit a 
considerably higher fungicidal activity, in particular against cereal 
diseases, than the compounds 1-triphenylmethyl-imidazole and 
1-triphenylmethyl-1,2,4-triazole known from the state of the art, which 
are known substances of the same type of action. The active compounds 
according to the invention thus represent an enrichment of the art. 
The present invention also provides a process for the preparation of an 
azolylalkyl pyridinyl ether of the formula (I) in which 
(a) an azolylhalogenoketone of the general formula 
##STR3## 
in which A and R have the meanings stated above and 
Hal represents chlorine or bromine, 
is reacted with a pyridinol of the general formula 
##STR4## 
in which 
Y and n have the meanings stated aove, in the presence of an acid-binding 
agent and optionally in the presence of a diluent, or 
(b) a halogeno ether-ketone of the general formula 
##STR5## 
in which 
Hal, R, Y and n have the meanings stated above, is reacted with imidazole 
or 1,2,4-triazole in the presence of an acid-binding agent and optionally 
in the presence of a diluent, or 
(c) a dihalogenoketone of the general formula 
EQU (Hal).sub.2 CH--CO--R (V) 
in which 
R and Hal have the meanings stated above, is reacted with imidazole or 
1,2,4-triazole and with a pyridinol of the formula (III) in the presence 
of an acid-binding agent and optionally in the presence of a diluent, and 
the keto derivative obtained according to process variant (a), (b) or (c) 
is optionally reduced by known methods in the customary manner. 
An acid or a metal salt can then optionally be added onto the compound of 
the formula (I) thus obtained. 
If 1-bromo-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 
6-chloro-pyridin-2-ol are used as starting materials in process variant 
(a), the course of the reaction can be represented by the equation which 
follows: 
##STR6## 
If 1-bromo-1-(6-chloro-pyridin-2-yl-oxy)-3,3-dimethylbutan-2-one and 
imidazole are used as starting materials in process variant (b), the 
course of the reaction can be represented by the equation which follows: 
##STR7## 
If 6-chloro-pyridin-2-ol, dichloropinacolin and 1,2,4-triazole are used as 
starting materials in process variant (c), the course of the reaction can 
be represented by the equation which follows: 
##STR8## 
If 
1-(6-chloro-pyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2- 
one is used as the ketone and sodium borohydride is used as the reducing 
agent, the course of the reduction reaction can be represented by the 
equation which follows: 
##STR9## 
The azolylhalogenoketones of the formula (II) have not hitherto been 
described in the literature but they can be prepared by known processes by 
reacting known halides (see U.S. application Ser. No. 782,263, filed Mar. 
25, 1977) of the general formula 
EQU Hal--CH.sub.2 --CO--R (VI) 
with imidazole or 1,2,4-triazole in the presence of an acid-binding agent, 
such as, for example, potassium carbonate, and in the presence of an inert 
organic solvent, such as, for example, acetone, at temperatures between 
60.degree. and 120.degree. C. One of the two active hydrogen atoms is then 
replaced by chlorine or bromine in the customary manner. 
Examples which may be mentioned of the starting materials of the formula 
(II) are: 1-bromo-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one, 
1-chloro-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one, 
1-bromo-3,3-dimethyl-1-imidazol-1-yl-butan-2-one, 
1-chloro-3,3-dimethyl-1-imidazol-1-yl-butan-2-one, 
1-bromo-1-(1,2,4-triazol-1-yl)-propan-2-one, 
1-bromo-1-imidazol-1-yl-propan-2-one, 
1-bromo-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one, 
1-bromo-1-imidazol-1-yl-3-methyl-butan-2-one, 
1-bromo-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-pentan-2-one and 
1-bromo-3,3-dimethyl-1-imidazol-1-yl-pentan-2-one. 
The pyridinols of the formula (III) are generally known compounds of 
organic chemistry. Examples which may be mentioned are: 
2-hydroxy-pyridine, 3-hydroxy-pyridine, 4-hydroxy-pyridine, 
2-hydroxy-6-chloro-pyridine, 2-hydroxy-5-chloro-pyridine, 
2-hydroxy-4-chloro-pyridine, 2-hydroxy-3-chloro-pyridine, 
2-hydroxy-6-bromo-pyridine, 2-hydroxy-5-bromo-pyridine, 
2-hydroxy-4-bromo-pyridine, 2-hydroxy-3-bromo-pyridine, 
2-hydroxy-6-methyl-pyridine, 2-hydroxy-5-methyl-pyridine, 
2-hydroxy-4-methyl-pyridine, 2-hydroxy-3-methyl-pyridine, 
2-hydroxy-6-fluoro-pyridine, 2-hydroxy-5-fluoro-pyridine, 
2-hydroxy-4-fluoro-pyridine, 2-hydroxy-3-fluoro-pyridine, 
3-hydroxy-2-chloro-pyridine, 3-hydroxy-2-bromo-pyridine, 
3-hydroxy-2-fluoro-pyridine, 3-hydroxy-2-iodo-pyridine, 
3-hydroxy-2-methoxy-pyridine, 3-hydroxy-6-chloro-pyridine, 
3-hydroxy-5-chloro-pyridine, 4-hydroxy-2-chloro-pyridine and 
4-hydroxy-3-chloro-pyridine. 
The halogeno ether-ketones of the formula (IV) have not yet been described 
in the literature, but they can be prepared by known processes by reacting 
pyridinols of the formula (III) with halogenoketones of the formula (VI) 
in the presence of an acid-binding agent, such as, for example, potassium 
carbonate, and in the presence of an inert organic solvent, such as, for 
example, acetone, at temperatures between 60.degree. and 120.degree. C. 
One of the two active hydrogen atoms is then replaced by chlorine or 
bromine in the customary manner. 
Examples which may be mentioned of starting materials of the formula (IV) 
are: 1-bromo-3,3-dimethyl-1-pyridin-2-yl-butan-2one, 
1-bromo-3,3-dimethyl-1-pyridin-3-yl-butan-2-one, 
1-bromo-3,3-dimethyl-1-pyridin-4-yl-butan-2-one, 
1-bromo-1-(6-chloro-pyridin-2-yl)-3,3-dimethyl-butan-2-one, 
1-chloro-1-(6-chloro-pyridin-2-yl)-3,3-dimethyl-butan-2-one, 
1-bromo-1-(5-chloro-pyridin-2-yl)-3,3-dimethyl-butan-2-one, 
1-bromo-1-(2-chloro-pyridin-3-yl)-3,3-dimethyl-butan-2-one, 
1-bromo-1-(2-bromo-pyridin-3-yl)-3,3-dimethyl-butan-2-one and 
1-bromo-1-(3,4,5-trichloro-pyridin-2-yl)-3,3-dimethyl-butan-2-one. 
The dihalogenoketones of the formula (V) are generally known compounds of 
organic chemistry. Examples which may be mentioned are: dichloropinacolin 
and dibromopinacolin. 
Possible diluents for the reactions according to the invention of process 
variants (a) and (b) are inert organic solvents, especially ketones, such 
as diethyl ketone, and in particular acetone and methyl ethyl ketone; 
nitriles, such as propionitrile, and in particular acetonitrile; alcohols, 
such as ethanol or isopropanol; ethers, such as tetrahydrofuran or 
dioxane; benzene; formamides, such as, in particular, dimethylformamide; 
and halogenated hydrocarbons. 
The reactions according to process variants (a) and (b) are carried out in 
the presence of an acid-binding agent. It is possible to add any of the 
inorganic or organic acid-binding agents which can usually be employed, 
such as alkali metal carbonates, for example sodium carbonate and 
potassium carbonate, and sodium bicarbonate, or such as lower tertiary 
alkylamines, cycloalkylamines and or aralkylamines, for example 
triethylamine and dimethylbenzylamine; or such as pyridine and 
diazabicyclooctane. 
In the case of process variant (b), it is also possible to use an 
appropriate excess of azole. 
The reaction temperatures in process variants (a) and (b) can be varied 
within a substantial range. In general, the processes are carried out at 
from 20.degree. to 150.degree. C., preferably at from 60.degree. to 
120.degree. C. If a solvent is present, the processes are appropriately 
carried out at the boiling point of the particular solvent. 
In carrying out process variants (a) and (b) according to the invention, 1 
to 2 moles of the pyridinol of the formula (III) or, respectively, 1 to 2 
moles of the azole and in each case 1 to 2 moles of acid-binding agent are 
preferably employed per mole of the compound of the formula (II) or (IV) 
respectively. In order to isolate the compound of the formula (I), the 
solvent is distilled off and either water is added to the residue and the 
mixture is stirred vigorously, whereupon the reaction product crystallizes 
completely, or the residue is taken up in a mixture of an organic solvent 
and water and the organic phase is separated off, washed with water, dried 
over sodium sulphate and freed from solvent in vacuo. The residue is 
appropriately purified by distillation or recrystallization. 
Preferred diluents for the reaction according to the invention of process 
variant (c) are polar organic solvents, especially chlorinated 
hydrocarbons, such as dichloroethane; alcohols, such as ethanol, propanol 
and n-butanol; ketones; such as acetone, methyl ethyl ketone and methyl 
butyl ketones; ethers, such as tetrahydrofuran and dioxane; and nitriles, 
such as acetonitrile. 
The reaction according to process variant (c) is carried out in the 
presence of an acid-binding agent. The preferred acid-binding agents 
include the inorganic and organic acid-binding agents which have already 
been mentioned as preferred in the case of process variants (a) and (b). 
The reaction temperatures in process (c) can be varied within a substantial 
range. In general, the process is carried out at from 0.degree. to 
150.degree. C., preferably from 50.degree. to 90.degree. C. 
In carrying out process variant (c) according to the invention, 1 mole of 
pyridinol, 1 to 1.2 moles of azole and 2 to 3 moles of acid-binding agent 
are preferaly employed per mole of dihalogenoketone of the formula (V). In 
order to isolate the compound of the formula (I), the solvent is largely 
distilled off in vacuo. A little dilute hydrochloric acid is added to the 
residue in the presence of an inert water-immiscible solvent, such as, for 
example, toluene, xylene or dichloroethane, in order to remove excess 
azole as the hydrochloride. Thereafter, the organic phase is washed with 
dilute alkali metal hydroxide solution until neutral and the solvent is 
distilled off in vacuo. The residue is approximately purified by 
distillation or recrystallization. 
The reduction according to the invention is carried out in the customary 
manner, such as, for example, by reaction with complex hydrides, 
optionally in the presence of a diluent, or by reaction with aluminum 
isopropylate in the presence of a diluent. 
If complex hydrides are used, possible diluents for the reaction according 
to the invention are polar organic solvents, especially alcohols, such as 
methanol, ethanol, butanol and isopropanol, and ethers, such as diethyl 
ether or tetrahydrofuran. In general, the reaction is carried out at from 
0.degree. to 30.degree. C., preferably at 0.degree. to 20.degree. C. For 
the reaction, about 1 mole of a complex hydride, such as sodium hydride or 
lithium alanate, is employed per mole of the ketone of the formula (I). In 
order to isolate the reduced compound of the formula (I), the residue is 
taken up in dilute hydrochloric acid and the mixture is then rendered 
alkaline and extracted with an organic solvent. Further working up is 
carried out in the customary manner. 
If aluminum isopropylate is used, preferred diluents for the reaction 
according to the invention are alcohols, such as isopropanol, or inert 
hydrocarbons, such as benzene. The reaction temperatures can again be 
varied within a substantial range; in general, the reaction is carried out 
at from 20.degree. to 120.degree. C., preferably at from 50.degree. to 
100.degree. C. For carrying out the reaction, about 1 to 2 moles of 
aluminum isopropylate are employed per mole of the ketone of the formula 
(I). In order to isolate the reduced compounds of the formula (I), the 
excess solvent is removed by distillation in vacuo and the aluminum 
compound formed is decomposed with dilute sulphuric acid or sodium 
hydroxide solution. Further working up is carried out in the customary 
manner. 
All the physiologically acceptable acids can be used for the preparation of 
acid addition salts of the compounds of the formula (I). Preferred acids 
include the hydrogen halide acids (for example hydrobromic acid and 
especially hydrochloric acid), phosphoric acid, nitric acid, sulphuric 
acid, monofunctional and bifunctional carboxylic acids and 
hydroxycarboxylic acids (for example acetic acid, maleic acid, succinic 
acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic 
acid and lactic acid) and sulphonic acid (for example p-toluenesulphonic 
acid and 1,5-naphthalenedisulphonic acid). 
The salts of the compounds of the formula (I) can be obtained in a simple 
manner by conventional salt-formation methods, for example by dissolving a 
compound of the formula (I) in a suitable inert solvent and adding the 
acid, for example hydrochloric acid, and can be isolated in a known 
manner, for example by filtration, and appropriately purified by washing 
with an inert organic solvent. 
Salts which can be used for the preparation of metal salt complexes of the 
compounds of the formula (I) are preferably salts of metals of main groups 
II to IV and of sub-groups I and II and IV to VIII, examples of metals 
which may be mentioned being copper, zinc, manganese, magnesium, tin, iron 
and nickel. Possible anions of the salts are those which are derived from 
physiologically acceptable acids, preferably the hydrogen halide acids 
(for example hydrochloric acid and hydrobromic acid), phosphoric acid, 
nitric acid and sulphuric acid. 
The metal salt complexes of the compounds of the formula (I) can be 
obtained in a simple manner by customary processes, for example by 
dissolving the metal salt in alcohol, for example ethanol, and adding the 
solution to the compound of the formula (I). The metal salt complexes can 
be isolated in a known manner, for example by filtration and appropriately 
purified by recrystallization. 
Examples which may be mentioned of particularly active compounds according 
to the invention (in addition to those given later in the preparative 
examples) are (the expression azol-1-yl representing 1,2,4-triazol-1-yl 
and imidazol-1-yl); 
1-(4-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(5-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(6-bromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(6-fluoropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(6-iodopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(4-bromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(5-bromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(4,6-dichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(3,6-dichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(3,5,6-trichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(3,6-dibromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 
1-(3,5,6-tribromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(4,6-dimethylpyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 
1-(6-trifluoromethylpyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(4-phenylpyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(5-phenylpyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-phenylpyridin-2-yl-oxy)-3,3dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(4-phenoxypyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(5-phenoxypyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-methoxypyridin-2-yl-oxy)-3,3-dimethyl-1 
-azol-1-yl-butan-2-one and -ol, 
1-(3-cyanopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(6-cyanopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(2-fluoropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(2-iodopyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(2-methoxypyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2-methylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2-phenylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2-phenoxypyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(4-chloropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(5-chloropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-chloropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(2,6-dichloropyridin-2 
-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol, 
1-(2,4,6-trichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(4,5,6-trichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(2,4,5-trichloropyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(4-bromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(5-bromopyridin-2-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-bromopyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(5-iodopyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-iodopyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(2,6-dibromopyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(5-fluoropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(6-fluoropyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(5-phenylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(6-phenylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(4-phenylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(5-phenoxypyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(6-phenoxypyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2-cyanopyridin-3-yl-oxy)-3,3-dimethyl-1 -azol-1-yl-butan-2-one and 
-ol, 
1-(2-trifluoromethylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(6-trifluoromethylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(6-methylpyridin-3-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(2-chloropyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(2-bromopyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(2,6-dichloropyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2,6-dibromopyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 1-(2-phenylpyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, 
1-(2,6-dimethylpyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and 
-ol, 1-(2,6-difluoropyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one 
and -ol, and 
1-(2-fluoropyridin-4-yl-oxy)-3,3-dimethyl-1-azol-1-yl-butan-2-one and -ol. 
The active compounds according to the invention exhibit a powerful 
fungitoxic action. They do not damage crop plants in the concentrations 
required for combating fungi. For these reasons they are suitable for use 
as plant protection agents for combating fungi. Fungitoxic agents are 
employed in plant protection for combating Plasmodiophoromycetes, 
Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and 
Deuteromycetes. 
The active compounds according to the invention have a broad spectrum of 
action and can be used against parasitic fungi which infect above-ground 
parts of plants or attack the plants through the soil, as well as against 
seed-borne pathogens. They develop a particularly good activity against 
parasitic fungi on above-ground parts of plants. 
As plant protection agents, the active compounds according to the invention 
can be used with particularly good success for combating powdery mildew 
fungi, for example for combating powdery mildew of cucumbers (Erysiphe 
cichoriacearum), powdery mildew of cereals as well as against other cereal 
diseases, such as cereal rust and stripe disease of barley; they can also 
be used for combating species of Venturia, for example against the apple 
scab causative organism (Fusicladium dendriticum), and the fungi 
Pyricularia and Pellicularia. It should be particularly emphasized that 
the active compounds according to the invention not only develop a 
protective action, but in some cases also have a curative action, that is 
to say when used after infection has taken place. The systemic action of 
some of the substances should also be emphasized. Thus, it is possible to 
protect plants against fungal attack when the active compound is fed to 
the above-ground parts of the plant via the soil and the root or via the 
seed. 
As plant protection agents, the active compounds according to the invention 
can be used for the treatment of seed or soil and for the treatment of 
above-ground parts of plants. 
The active compounds can be converted into the customary formulations, such 
as solutions, emulsions, wettable powders, suspensions, powders, dusting 
agents, foams, pastes, soluble powders, granules, aerosols, 
suspension-emulsion concentrates, seed-treatment powders, natural and 
synthetic materials impregnated with active compound, very fine capsules 
in polymeric substances, coating compositions for use on seed, and 
formulations used with burning equipment, such as fumigating cartridges, 
fumigating cans and fumigating coils, as well as ULV cold mist and warm 
mist formulations. 
The formulations may be produced in known manner, for example by mixing the 
active compounds with extenders, that is to say liquid or liqueified 
gaseous or solid diluents or carriers, optionally with the use of 
surface-active agents, that is to say emulsifying agents and/or dispersing 
agents and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. 
As liquid solvents diluents or carriers, especially solvents, there are 
suitable in the main, aromatic hydrocarbons, such as xylene, toluene or 
alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic 
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene 
chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or 
paraffins, for example mineral oil fractions, alcohols, such as butanol or 
glycol as well as their ethers and esters, ketones, such as acetone, 
methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly 
polar solvents, such as dimethylformamide and dimethylsulphoxide, as well 
as water. 
By liquefied gaseous diluents or carriers are meant liquids which would be 
gaseous at normal temperature and under normal pressure, for example 
aerosol propellents, such as halogenated hydrocarbons as well as butane, 
propane, nitrogen and carbon dioxide. 
As solid carriers they may be used ground natural minerals, such as 
kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as 
highly-dispersed silicic acid, alumina and silicates. As solid carriers 
for granules there may be used crushed and fractionated natural rocks such 
as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, corn cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkylsulphates, aryl sulphonates as well as 
albumin hydrolysis products. Dispersing agents include, for example, 
lignin sulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, 
and trace nutrients, such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain from 0.1 to 95 percent by weight of 
active compound, preferably from 0.5 to 90 percent by weight. 
The active compounds according to the invention can be present in the 
formulations as a mixture with other active compounds, such as fungicides, 
insecticides, acaricides, nematicides, herbicides, bird repellents, growth 
factors, plant nutrients and agents for improving soil structure. 
The active compounds can be used as such, as their formulations or as the 
use forms prepared therefrom by further dilution, such as ready-to-use 
solutions, emulsions, suspensions, powders, pastes and granules. They may 
be used in the customary manner, for example by watering, spraying, 
atomising, dusting, scattering, dry dressing, moist dressing, wet 
dressing, slurry dressing or encrusting. 
Especially when used as leaf fungicides, the active compound concentrations 
in the use forms can be varied within a substantial range. They are, in 
general, from 0.1 to 0.00001 percent by weight, preferably from 0.05 to 
0.0001 percent. 
In the treatment of seed, amounts of active compound of generally 0.001 to 
50 g, preferably 0.01 to 10 g, are employed per kilogram of seed. 
For the treatment of soil, amounts of active compound of generally 1 to 
1000 g, especially 10 to 200 g, are employed per cubic meter of soil. 
The present invention also provides a fungicidal composition containing as 
active ingredient a compound of the present invention in admixture with a 
solid or liquefied gaseous diluent or carrier or in admixture with a 
liquid diluent or carrier containing a surface-active agent. 
The present invention also provides a method of combating fungi which 
comprises applying to the fungi, or to a habitat thereof, a compound of 
the present invention alone or in the form of a composition containing as 
active ingredient a compound of the present invention in admixture with a 
diluent or carrier. 
The present invention further provides crops protected from damage by fungi 
by being grown in areas in which immediately prior to and/or during the 
time of the growing a compound of the present invention was applied alone 
or in admixture with a diluent or carrier. 
It will be seen that the usual methods of providing a harvested crop may be 
improved by the present invention.

The following examples illustrate the preparation of the novel compounds of 
the invention: 
EXAMPLE 1 
##STR10## 
a (Process variant a) 
(I) Preparation of the precursor 
##STR11## 
13.45 g (1 mol) of 1-chloro-3,3-dimethyl-butan-2-one, 69 g (1 mol) of 
1,2,4-triazole and 140 g (1 mol) of powdered potassium carbonate were 
heated under reflux in 500 ml of acetone for 6 hours, while stirring. 
Thereafter, the mixture was allowed to cool, the inorganic salt was 
filtered off and the filtrate was concentrated in vacuo. After treatment 
with diisopropyl ether, the oily residue crystallized out. After drying, 
123.6 g (74% of theory) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one 
of melting point 63.degree.-65.degree. C. were obtained. 
(II) Preparation of the starting material 
##STR12## 
80 g (0.5 mol) of bromine were slowly added dropwise to 83.5 g (0.5 mol) of 
3,3dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 41 g (0.5 mol) of 
anhydrous sodium acetate in 250 ml of glacial acetic acid at 40.degree. to 
50.degree. C., while stirring. The mixture was further stirred at 
40.degree. C. until it was completely decolorized. Thereafter, the 
reaction mixture was discharged onto 400 ml of water and extracted three 
times with 100 ml of chloroform each time. The combined organic phases 
were washed first with sodium bicarbonate solution until the evolution of 
CO.sub.2 had ended, and then with water, and were dried over sodium 
sulphate and concentrated in vacuo by distilling off the solvent. Crude 
1-bromo-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one, which was further 
reacted directly, was obtained quantitatively. 
(III) 50.5 g (0.5 mol) of triethylamine were added dropwise to 123 g (0.5 
mol) of crude 1-bromo-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 
65 g (0.5 mol) of 6-chloro-2-hydroxy-pyridine in 250 ml of absolute 
acetonitrile at 24.degree. to 30.degree. C., while stirring. The mixture 
was stirred at room temperature for 3 hours and filtered and the filtrate 
was concentrated in vacuo. After treatment with water, the residue 
crystallized out. 76.6 g (52% of theory) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne of melting point 103.degree.-105.degree. C. were obtained. 
b (Process variant b) 
(I) Preparation of the precursor 
##STR13## 
27 g (0.2 mol) of monochloropinacolin, 26 g (0.2 mol) of 
6-chloro-2-hydroxy-pyridine and 28 g (0.2 mol) of powdered potassium 
carbonate were heated under reflux in 150 ml of acetone for 3 hours, while 
stirring. Thereafter, the mixture was allowed to cool, the salt which had 
precipitated was filtered off and the filtrate was concentrated in vacuo. 
The oily residue was taken up in petroleum ether, the solution was cooled 
to -10.degree. C. and the crystalline precipitate which thereby separated 
out was filtered off and dried. 24.5 g (54% of theory) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-butan-2-one were obtained. 
(II) Preparation of the starting material 
##STR14## 
22.7 g (0.1 mol) of 1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-butan-2-one 
and 8.2 g (0.1 mol) of anhydrous sodium acetate were suspended in 100 ml 
of galcial acetic acid, and 16 g (0.1 mol) of bromine were slowly added at 
40.degree. to 50.degree. C. The mixture was further stirred at 40.degree. 
C. until it was completely decolorized. Thereafter, the reaction mixture 
was discharged onto 200 ml of water and extracted twice with 100 ml of 
chloroform each time. The combined organic phases were washed first with 
sodium bicarbonate solution until the evolution of CO.sub.2 had ended, and 
then with water, and were dried over sodium sulphate and concentrated in 
vacuo by distilling off the solvent. Crude 
1-bromo-1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-butan-2-one, which was 
further reacted directly, was obtained quantitatively. 
(III) 39.5 g (0.1 mol) of crude 
1-bromo-1-(6-chloropyidin-2-yl-oxy)-3,3-dimethyl-butan-2-one in 100 ml of 
acetonitrile were slowly added to a solution of 6.9 g (0.1 mol) of 
1,2,4-triazole and 10.1 g (0.1 mol) of triethylamine in 100 ml of 
acetonitrile at 20.degree. C. Thereafter, the mixture was stirred under 
reflux for 1 hour and concentrated by distilling off the solvent and the 
residue was taken up in water and thereby crystallized. After 
recrystallizing from ethyl acetate/petroleum ether, 13.5 g (45% of theory) 
of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne of melting point 105.degree. C. were obtained. 
c (Process variant c) 
33.8 g (0.2 mol) of 1,1-dichloro-3,3-dimethyl-butan-2-one, 26 g (0.2 mol) 
of 6-chloro-2-hydroxy-pyridine, 21 g (0.3 mol) of 1,2,4-triazole and 56 g 
(0.4 mol) of potassium carbonate were heated under reflux in 250 ml of 
acetone for 12 hours, while stirring. Thereafter, the mixture was allowed 
to cool, the salt which had precipitated was filtered off and the filtrate 
was concentrated in vacuo. Isopropanol was added to the oily residue, it 
being possible to isolate successively three crystal fractions. The first 
two contained mainly 1,1-bis-(1,2,4-triazol-1-yl)-3,3-dimethylbutan-2-one 
of melting point 157.degree.-158.degree. C. and 
1,1-bis-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-butan-2-one of melting 
point 102.degree.-104.degree. C. 4 g of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne of melting point 102.degree. C. were obtained from the third fraction. 
EXAMPLE 2 
##STR15## 
Reduction 
11.8 g (0.04 mol) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne (Example 1) were dissolved in 100 ml of methanol, and 1.8 g (0.04 mol) 
of sodium borohydride were added in portions at 20.degree.-30.degree. C., 
while stirring. After the exothermic reaction had ended, 5 ml of 
concentrated hydrochloric acid were added dropwise and the mixture was 
stirred at room temperature for 1 hour. Thereafter, 200 ml of water were 
added and the mixture was neutralised with sodium bicarbonate solution. 
The reaction mixture was extracted by shaking with ether and the organic 
phase was dried over sodium sulphate and concentrated. 5.3 g (54% of 
theory) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-ol 
were obtained as a viscous oil in the form of a diastereomer mixture. 
EXAMPLE 3 
##STR16## 
Salt Formation 
10 g (0.034 mol) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne (Example 1) were dissolved in 50 ml of acetone, and a solution of 8 g 
(0.027 mol) of naphthalene-1,5-disulphonic acid in 50 ml of acetone was 
added. The salt which precipitated after some time was filtered off and 
dried. 14 g (94% of theory) of 
1-(6-chloropyridin-2-yl-oxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-o 
ne naphthalene-1,5-disulphonate of melting point 212.degree.-215.degree. C. 
(decomposition) were obtained. 
The compounds listed in the table which follows were obtained analogously. 
TABLE I 
______________________________________ 
##STR17## 
Com- Melting 
pound point 
No A R R' X (.degree.C.) 
______________________________________ 
4 N C(CH.sub.3).sub.3 
##STR18## CHOH 202-04(D. (.times. 1/2 NDS) 
5 N C(CH.sub.3).sub.3 
##STR19## CO 164 
6 CH C(CH.sub.3).sub.3 
##STR20## CO 214-18(D.) (.times. 1/2 NDS) 
7 CH C(CH.sub.3).sub.3 
##STR21## CO viscous oil 
8 CH C(CH.sub.3).sub.3 
##STR22## CO 195-200 (D.) (.times. 1/2 NDS) 
9 N C(CH.sub.3).sub.3 
##STR23## CO 81-83 
10 CH C(CH.sub.3).sub.3 
##STR24## CO viscous oil 
11 CH C(CH.sub.3).sub.3 
##STR25## CO 79-82 
12 CH C(CH.sub.3).sub.3 
##STR26## CHOH amorphous 
13 N C(CH.sub.3).sub.3 
##STR27## CO 92-95 
14 N C(CH.sub.3).sub.3 
##STR28## CO crystal mass 
15 N C(CH.sub.3).sub.3 
##STR29## CO 140 
______________________________________ 
The fungicidal activity of the compounds of this invention is illustrated 
by the following examples: 
EXAMPLE 4 
Erysiphe test (cucumbers)/systemic 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 
Water: 95.0 parts by weight 
The amount of active compound required to give the desired concentration of 
active compound in the watering liquid was mixed with the stated amount of 
solvent and the concentrate was diluted with the stated amount of water 
which contained the stated amount of emulsifier. 
Cucumber plants grown in standard soil, in the 1 to 2 leaf stage, were 
watered three times within one week with 10 ml of the watering liquid, of 
the desired concentration of active compound, per 100 ml of soil. 
The plants treated in this way were inoculated, after treatment, with 
conidia of the fungus Erysiphe cichoriacearum. The plants were then set up 
in a greenhouse at 23.degree. to 24.degree. C. and 70 percent relative 
humidity. After 12 days, the infection of the cucumber plants was 
determined. 
In this test, for example, compounds 1 and 6 showed a very good action 
which was distinctly superior to that of the compounds known from the 
prior art. 
EXAMPLE 5 
Fusicladium test (apple)/protective 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 
Water: 95.0 parts by weight 
The amount of active compound required for the desired concentration of the 
active compound in the spray liquid was mixed with the stated amount of 
solvent, and the concentrate was diluted with the stated amount of water 
which contained the stated amount of emulsifier. 
Young apple seedlings in the 4 to 6 leaf stage were sprayed with the spray 
liquid until dripping wet. The plants remained in a greenhouse for 24 
hours at 20.degree. C. and at a relative atmospheric humidity of 70 
percent. They were then inoculated with an aqueous conidium suspension of 
the apple scab causative organism (Fusicladium dendriticum) and incubated 
for 18 hours in a humidity chamber at 18.degree. to 20.degree. C. and at a 
relative atmospheric humidity of 100 percent. 
The plants were then brought into a greenhouse again for 14 days. 
15 days after inoculation, the infection of the seedlings was determined. 
In this test compounds 1 and 6 showed a very good action which was 
distinctly superior to that of the compounds known from the prior art. 
EXAMPLE 6 
Shoot treatment test/powdery mildew of cereal/protective/curative 
(leaf-destructive mycosis) 
To produce a suitable preparation of active compound, 0.25 part by weight 
of active compound was taken up in 25 parts by weight of dimethylformamide 
and 0.06 part by weight of alkylaryl polyglycol ether and then 975 parts 
by weigh of water were added. The concentrate was diluted with water to 
the desired final concentration of the spray liquor. 
To test for protective activity, single-leaved young barley plants of the 
Amsel variety were sprayed with the preparation of active compound until 
dew-moist. After drying, the barley plants were dusted with spores of 
Erysiphe graminis var. hordei. 
To test for curative activity the corresponding procedure was followed in 
converse sequence. The treatment of the single-leaved young barley plants 
with the preparation of active compound was carried out 48 hours after 
inoculation, when the infection was already manifest. 
After 6 days' dwell time of the plants at a temperature of 
21.degree.-22.degree. C. and 80-90 percent relative humidity the 
occurrence of mildew pustules on the plants was evaluated. The more active 
the compound, the lower the degree of mildew infection. 
In this test compounds 1, 3 and 6 showed a very good action which was 
distinctly superior to that of the compounds known from the prior art. 
EXAMPLE 7 
Powdery mildew of barley test (Erysiphe graminis var. hordei)/systemic 
(fungal disease of cereal shoots) 
The active compounds were used as pulverulent seed treatment agents. They 
were prepared by extending the particular active compound with a mixture 
of equal parts by weight of talc and kieselguhr to give a finely 
pulverulent mixture of the desired concentration of active compound. 
For the treatment of seed, barley seed was shaken with the extended active 
compound in a closed glass bottle. The seed was sown at the rate of 
3.times.12 grains in flowerpots, 2 cm deep in a mixture of one part by 
volume of Fruhstorfer standard soil and one part by volume of quartz sand. 
The germination and emergence took place under favorable conditions in a 
greenhouse. 7 days after sowing, when the barley plants had developed 
their fast leaf, they were dusted with fresh spores of Erysiphe graminis 
var. hordei and grown on at 21.degree.-22.degree. C. and 80-90 percent 
relative atmospheric humidity and 16 hours' exposure to light. The typical 
mildew pustules formed on the leaves over the course of 6 days. The more 
active the compound, the lower the degree of mildew infection. 
In this test compound 6 showed a very good action which was distinctly 
superior to that of the compounds known from the prior art. 
EXAMPLE 8 
Shoot treatment test/cereal rust/protective (leaf-destructive mycosis) 
To produce a suitable preparation of active compound, 0.25 part by weight 
of active compound was taken up in 25 parts by weight of 
dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether, 
and then 975 parts by weight of water were added. The concentrate was 
diluted with water to the desired final concentration of the spray liquor. 
To test the protective activity, one-leaved young wheat plants of the 
Michigan Amber variety were inoculated with a uredospore suspension of 
Puccinia recondita in 0.1 percent strength aqueous agar. After the spore 
suspension had dried on, the wheat plants were sprayed with the 
preparation of active compound until dew-moist and were placed, for 
incubation, in a greenhouse for 24 hours at about 20.degree. C. and 100 
percent relative humidity. 
After 10 days' dwell time of the plants at a temperature of 20.degree. C. 
and 80-90 percent relative humidity, the occurrence of rust pustules on 
the plant was evaluated. The more active the compound, the lower was the 
degree of rust infection. 
In this test compound 6 showed a very good action which was distinctly 
superior to that of the compounds known from the prior art. 
EXAMPLE 9 
Seed dressing test/stripe disease of barley (seed-borne mycosis) 
To produce a suitable dry dressing, the active compound was extended with a 
mixture of equal parts by weight of talc and kieselguhr to give a finely 
powdered mixture with the desired concentration of active compound. 
To apply the dressing, barley seed, which was naturally infected by 
Drechslera graminea (commonly described as Helminthosporium gramineum), 
was shaken with the dressing in a closed glass flask. The seed, on moist 
filter paper discs in closed Petri dishes, was exposed to a temperature of 
4.degree. C. for 10 days in a refrigerator. The germination of the barley, 
and possibly also of the fungus spores, was thereby initiated. 2 batches 
of 50 grains of the pregerminated barley were subsequently sown 2 cm deep 
in Fruhstorfer standard soil and cultivated in a greenhouse at 
temperatures of about 18.degree. C. in seed boxes which were exposed to 
light for 16 hours daily. The typical symptoms of the stripe disease 
developed within 3 to 4 weeks. 
After this time, the number of diseased plants was determined as a 
percentage of the total number of emerged plants. The fewer plants were 
diseased, the more effective was the active compound. 
In this test compounds 1 and 6 showed a very good action which was 
distinctly superior to that of the compounds known from the prior art. 
EXAMPLE 10 
Pyricularia and Pellicularia test 
Solvent: 11.75 parts by weight of acetone 
Dispersing agent: 0.75 part by weight of alkylaryl polyglycol ether 
Water: 987.50 parts by weight 
The amount of active compound required for the desired concentration of 
active compound in the spray liquor was mixed with the stated amount of 
the solvent and of the dispersing agent, and the concentrate was diluted 
with the stated amount of water. 
Rice plants about 2-4 weeks old were sprayed with the spray liquor until 
dripping wet. The plants remained in a greenhouse at temperatures of 
22.degree. to 24.degree. C. and a relative atmospheric humidity of about 
70 percent until they were dry. Thereafter, some of the plants were 
inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of 
Pyricularia oryzae and placed in a chamber at 24.degree. to 26.degree. C. 
and 100 percent relative atmospheric humidity. The other plants were 
infected with a culture of Pellicularia sasakii grown on malt agar and 
were set up at 28.degree. to 30.degree. C. and 100 percent relative 
atmospheric humidity. 
5 to 8 days after the inoculation, the infection of all the leaves present 
at the time of inoculation with Pyricularia oryzae was determined as a 
percentage of the untreated but also inoculated control plants. In the 
case of the plants infected with Pellicularia sasakii, the infection at 
the leaf sheaths after the same time was determined, again in relation to 
the untreated but infected control. 
In this test compounds 3 and 6 showed a very good action which was 
distinctly superior to that of the compounds known from the prior art. 
It will be appreciated that the instant specification and examples are set 
forth by way of illustration and not limitation, and that various 
modifications and changes may be made without departing from the spirit 
and scope of the present invention.