A description is given of new compounds of the formula defined herein: ##STR1## which display valuable microbicidal properties. The compounds can be used for combatting microorganisms harmful to plants, especially phytopathogenic fungi. The compounds of formula I thus possess a curative, systemic, and preventive action very useful for practical requirements for the protection of cultivated plants, without causing these to suffer any undesirable side effects. In practice, the compounds can be used by themselves or in the form of pesticides.

The present invention relates to substituted 
1-[2-(4-diphenyl)ethyl]-1H-azolylketals of formula I and their 
plant-compatible salts with inorganic or organic acids and their metal 
complexes, to the manufacture of compounds of this type, and moreover to 
microbicidal agents containing the compounds of formula I as the active 
principles and to the use of compounds of formula I for combatting plant 
diseases. 
The invention comprises compounds of formula I 
##STR2## 
in which Y represents CH or N and A represents one of the following 
alkylene bridges 
##STR3## 
where Z stands for oxygen or sulfur, R.sub.1 for hydrogen or possibly a 
halogen-substituted C.sub.1 -C.sub.4 alkyl, R.sub.2 represents methyl or 
ethyl, R.sub.3 represents methyl, ethyl, or propyl, or R.sub.2 and R.sub.3 
together form a tetramethylene bridge, and R.sub.4, R.sub.5, and R.sub.6 
represent independently of one another hydrogen or C.sub.1 -C.sub.4 alkyl, 
the total number of carbon atoms in R.sub.4, R.sub.5, and R.sub.6 not 
exceeding 6, and R.sub.7 represents hydrogen or possibly C.sub.1 -C.sub.2 
-alkoxy-substituted C.sub.1 -C.sub.6 alkyl and in addition C.sub.3 
-C.sub.4 alkenyl, 2-propinyl, 3-halo-2-propinyl, or possibly a halogen-, 
alkyl-, alkoxy-, nitro- or trifluoromethyl-substituted phenyl or 
substituted benzyl, with the inclusion of their plant-compatible acid 
addition salts with organic and inorganic acids and their metal complex 
salts. 
Depending on the number of the carbon atoms given, by alkyl or alkyl 
fraction the following groups, for example, are meant: methyl, ethyl, 
propyl, butyl, pentyl, or hexyl and their isomers such as isopropyl, 
isobutyl, tert.butyl, isopentyl, etc. Alkenyl stands for propenyl-(1), 
allyl, butenyl-(1), butenyl-(2), and butenyl-(3). Here and in what follows 
the term halogen represents fluorine, chlorine, bromine, or iodine, and 
preferably chlorine or bromine. 
Examples of inorganic acids are hydrochloric acid, hydrobromic acid, 
hydroiodic acid, sulfuric acid, phosphoric acid, phosphorous acid, and 
nitric acid. 
Examples of organic acids are acetic acid, trichloroacetic acid, oxalic 
acid, benzenesulfonic acid, and methanesulfonic acid. 
The metal complexes of formula I consist of the basic organic molecule and 
an inorganic or organic metal salt, such as the halide, nitrate, sulfate, 
phosphate, tartrate, etc. of copper, manganese, iron, zinc, and other 
metals. The metal cations can be present in the various valences 
appropriate to them. 
The compounds of formula I exhibit a very useful microbicidal spectrum. 
They can be used, for example, against phytopathogenic microorganisms, in 
particular against fungi that are harmful to plants. The 1,2,4-triazolyl 
derivatives encompassed by formula I are preferred. 
The compounds of formula I, with the inclusion of their salts and metal 
complexes, in which Y represents nitrogen and Z represents oxygen, R.sub.1 
stands for C.sub.1 -C.sub.4 alkyl, R.sub.2 for methyl or ethyl, R.sub.3 
for methyl or ethyl, R.sub.4, R.sub.5, and R.sub.6 represent independently 
of one another hydrogen or a methyl group, and R.sub.7 stands for 
hydrogen, methyl, or ethyl (this group shall be known as Ia) constitute a 
preferred group of microbicides. Particularly preferred are the copper 
salt complexes of this group Ia. 
The compounds of formula I, with the inclusion of their salts and metal 
complexes, in which Y stands for --CH and Z stands for oxygen, R.sub.1 
stands for C.sub.1 -C.sub.4 alkyl, R.sub.2 for methyl or ethyl, R.sub.3 
for methyl or ethyl, R.sub.4, R.sub.5, and R.sub.6 represent independently 
of one another hydrogen or a methyl group, and R.sub.7 stands for 
hydrogen, methyl, or ethyl (this group shall be referred to as Ib) 
constitute a further group of microbicides. 
In addition, the following individual compounds are particularly preferred: 
1-[2-(4-diphenyl)-4,5-dimethyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole, 
including its acid addition salts and metal complexes, especially in view 
of its strong action against Alternaria. Copper complexes of this compound 
are particularly preferred, e.g., compound no. 2.24 which is named 
hereinafter. 
1-[2-(4-diphenyl)-4-methyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole, 
including its acid addition salts and metal complexes. 
The following imidazole compounds are also of interest: 
1-[2-(4-diphenyl)-4,5-dimethyl-1,3-dioxolan-2-yl-methyl]-1H-imidazole, 
including its acid addition salts and metal complexes. 
1-[2-(4-diphenyl)-4-ethyl-1,3-dioxolan-2-yl-methyl]-1H-imidazole, including 
its acid addition salts and metal complexes. 
The compounds of formula I can be manufactured by a whole series of 
reaction variants, such as are outlined below in a reaction scheme and 
which are listed in detail below. In formulas II to XIII R.sub.7, A, Y, 
and Z have the meanings stated in formula I. Me stands for hydrogen or 
preferably a metal atom and in particular an alkali metal atom. X 
represents one of the usual leaving groups such as a halogen, in 
particular chlorine, bromine, or iodine or benzenesulfonyl, p-tosyl, 
trifluoroacetyl, or preferably a lower alkylsulfonyl group such as mesyl. 
Ar stands for 
##STR4## 
Y representing --CH.dbd. or .dbd.N.dbd.. 
##STR5## 
Specifically, it is possible to proceed as follows: 
A. Ketals of formula I can be manufactured by reacting an azole of formula 
II: 
##STR6## 
where Y stands for --CH.dbd. or --N.dbd. and Me stands for hydrogen or 
preferably a metal atom, and particularly an alkali metal atom, with a 
compound of formula III: 
##STR7## 
where A has the same meaning as under formula I and X represents one of 
the usual leaving groups, for example a halogen, especially chlorine, 
bromine, or iodine, or benzenesulfonyl, p-tosyl, trifluoroacetyl, or 
preferably a low alkylsulfonyl group such as mesyl. 
The reaction of II with III is preferably performed in a relatively polar 
but reaction-inert organic solvent such as N,N-dimethylformamide, 
N,N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, benzonitrile, 
etc. Solvents of this kind can be used in combination with other 
reaction-inert solvents, such as aliphatic or aromatic hydrocarbons, for 
example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, 
nitrobenzene, and so on. 
If X represents chlorine or bromine it is expedient to use an alkali metal 
iodide (such as NaI or KI) to accelerate the reaction. Elevated 
temperatures of 0.degree. to 220.degree. C., and preferably 80.degree. to 
170.degree. C., are advantageous. It is expedient for the reaction mixture 
to be heated under reflux. 
If, in formula II, Me stands for hydrogen, the process is performed in the 
presence of a base. Examples of such bases are inorganic bases such as the 
oxides, hydroxides, hydrides, carbonates, and hydrogen carbonates of 
alkali metals and alkaline earth metals, and also for example tertiary 
amines like triethylamine, triethylenediamine, piperidine, pyridine, 
4-dimethylaminopyridine, 4-pyrrolidylpyridine, etc. 
In the case of these and the following preparation variants the 
intermediate products and the end products can be isolated from the 
reaction medium and, if desired, be purified using one of the methods in 
general use, e.g. by extraction, crystallization, chromatography, 
distillation, etc. 
B. Another variant for the manufacture of the compounds of formula I 
consists in a ketalization reaction of a ketone of formula IV: 
##STR8## 
in which Y stands for --CH.dbd. or --N.dbd., in the presence of an acid, 
with a diol of formula V: 
EQU HO--A--OH (V) 
where A has the same meaning as given in formula I. 
This ketalization reaction can be performed analogously to ketalizations 
already known, for example in the same way as the manufacture of 
2-bromomethyl-2,4-diphenyl-1,3-dioxolane [Synthesis, 1974, (I), 23]. 
In the preferred embodiment of the ketalization the two reaction partners 
are refluxed for several hours together with an azeotrope-former in one of 
the customary organic solvents. Suitable azeotrope-formers are, for 
example, benzene, toluene, xylene, chloroform, or carbon tetrachloride. In 
this case the reaction is performed, for example, in the presence of a 
simple alcohol such as ethanol, propanol, butanol, pentanol, etc., an 
addition of a strong acid such as p-toluenesulfonic acid being sometimes 
advantageous to accelerate the reaction. Organic solvents that can be used 
in this case are, for example, aromatic hydrocarbons such as benzene, 
toluene, xylene, etc. and saturated hydrocarbons such as n-hexane. 
Other methods of ketalization are also possible, such as ketalization of 
the ketone IV with another diol or alkanol and then trans-ketalization of 
the ring-ketal or open ketal thus obtained to I by reaction with an excess 
of the diol V. 
C. Especially when in compounds of formula I the substituent A stands for 
--CH.sub.2 --CH(CH.sub.2 ZR.sub.7)--, the latter can be prepared by 
reaction of a compound of formula VI: 
##STR9## 
with a reactive compound of formula VII suitable for O-alkylation or 
S-alkylation, where Y, Z, and R.sub.7 have the meanings given under 
formula I and X has the meaning given in variant A. 
The reaction is preferably performed in reaction-inert organic solvents. 
Suitable solvents for this purpose are, for example, 
N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphorus 
triamide, dimethyl sulfoxide, 4-methyl-2-pentanone, etc. It is also 
possible to use mixtures with other reaction-inert solvents, for example 
with aromatic hydrocarbons like benzene, toluene, xylene, etc. In many 
cases it can prove advantageous to accelerate the reaction rate by working 
in the presence of a base. Suitable bases of this type are, for example, 
alkali metal hydrides or alkali metal carbonates. In certain cases it can 
also be beneficial first to convert the compound VI in a known manner into 
a suitable metal salt. This is preferably done by reacting VI with an Na 
compound such as sodium hydride, sodium hydroxide, etc. This salt of VI is 
thereafter reacted with the compound of formula VII. To accelerate the 
reaction rate it is possible in many cases to work at an elevated 
temperature, preferably 80.degree. to 130.degree. C., or at the boiling 
point of the solvent. 
D. For the manufacture of the compounds of formula I, in which A stands for 
--CH.sub.2 --CH(CH.sub.2 ZR.sub.7)--, a ketal of formula VIII: 
##STR10## 
can also be allowed to react with a compound of formula IX; in this case 
R.sub.7, X, Y, and Z have the meanings described under variant C. 
E. If Z in the products of formula I represents oxygen, these products can 
also be obtained by condensation of an alcohol of formula X with an 
alkanol of formula XI. 
##STR11## 
In this case R.sub.7 and Y have the same meanings as in formula I. 
In this condensation the reactants can be heated in a suitable solvent 
under reflux, the water azeotrope produced being simultaneously distilled 
off from the reaction mixture. Suitable solvents are aromatic hydrocarbons 
such as n-hexane or the alcohol XI itself. In this reaction it is 
expedient to work in the presence of a strong acid such as 
p-toluenesulfonic acid. 
If the compounds of formula I are obtained as bases they can be converted 
into corresponding salts by inorganic or organic acids or into metal 
complexes of formula I by preferably equimolar amounts of metal salts. 
Conversely, salts of formula I can be converted into the free bases of 
formula I, for example by reacting them with an alkali metal (hydrogen) 
carbonate or alkali metal hydroxide. 
The starting ketals of formula III can be obtained from the basic 
4-acetylbiphenyl of formula XII: 
##STR12## 
by reaction with the desired diol in an inert solvent, e.g. a halogenated 
hydrocarbon (such as methylene chloride, ethylene chloride, chloroform, 
carbon tetrachloride, etc.) and by simultaneous or subsequent 
halogenation. To accelerate the reaction it is advantageous to add 
p-toluenesulfonic acid. 
The ketones of formula IV can be manufactured by halogenation of the 
starting ketones XII to XIII: 
##STR13## 
and by further reacting XIII in the same way as in variant A with an azole 
of formula II. In this case Hal is preferably chlorine or bromine. 
The ketals VI, VIII, and X are obtained in the same way as in variant B by 
reacting the starting ketone IV with a suitable .alpha.,.beta.-diol. 
The preparation variants described are an essential component of the 
invention. 
In all the described ketalizations of a ketone with a substituted 
.alpha.,.beta.-diol mixtures of diastereomers of the resultant ketal can 
be produced. Correspondingly, diastereomeric end products of formula I are 
then formed from the starting ketones. The individual isomers exhibit 
different microbicidal actions. The invention relates to all the isomeric 
compounds, to their salts, and to their metal complexes. 
The manufacturing processes of compounds of formula I in its described 
variants A, B, C, D, and E is an essential component of the invention. 
Some of the starting substances and intermediate products used in processes 
A, B, C, D, and E are familiar, and others can be prepared by methods 
known in themselves. Some are new; their preparation is described here. 
1-(.beta.-Aryl)-ethylimidazolylketals, in which the aryl stands for 
substituted phenyl or naphthyl are cited in the following references as 
fungicides and bactericides: U.S. Pat. Nos. 3,575,999; 3,936,470; 
4,101,664; 4,101,666; and 4,156,008. 
Surprisingly, it has been found that compounds of formula I display a 
microbicidal spectrum very favorable for practical requirements. For 
example, they can be used to protect cultivated plants. 
The main field of application of compounds of formula I lies in combatting 
harmful microorganisms, above all phytopathogenic fungi. Accordingly, the 
compounds of formula I possess a curative, preventive, and systemic action 
for the protection of cultivated plants that is very favorable for 
practical requirements and that does not have any side effects on the 
plants. The cultivated plants within the scope of the present invention 
are, for example: cereal crops (wheat, barley, rye, oats, rice), beets 
(sugar beet and fodder beet), pip and stone fruits and small fruits 
(apples, pears, plums, peaches, almonds, cherries, strawberries, 
raspberries, and blackberries), leguminous plants (beans, lentils, peas, 
soya beans), oil cultures (rape, mustard, poppy, olives, sunflowers, 
coconuts, castor-oil plants, cocoa, peanuts), cucumber-like plants 
(pumpkins, cucumbers, melons), fibrous plants (cotton, flax, hemp, jute), 
citrus fruits (oranges, lemons, grapefruits, tangerines), vegetables 
(spinach, cabbage lettuce, asparagus, cabbages, carrots, onions, tomatoes, 
potatoes, paprika), or plants such as maize, tobacco, nuts, coffee, sugar 
cane, tea, grapevines, hops, bananas, and natural rubber plants and 
ornamental plants. 
By using the active principles of formula I the microorganisms occurring on 
plants or parts of plants (fruit, blossom, foliage, stem, tuber, roots) of 
these and relates useful cultures can be checked or destroyed, the 
subsequently growing parts of the plants being unaffected by such 
microorganisms. The active principles are effective against the 
phytopathogenic fungi belonging to the following classes: Ascomycetes 
(e.g. Venturia, Podosphaera, Erysiphaceae, Fusarium, Helminthosporium), 
Basidiomycetes such as above all rust fungi (e.g. Puccinia), fungi 
imperfecti (e.g. Moniliales etc., Botrytis, and the Cercospora and 
Alternaria pathogens belonging to the family of Dematiaceae and the 
Oomycetes belonging to the Phycomycetes, such as Plasmopara. Moreover, the 
compounds of formula I exert a systemic action. They can also be used as 
disinfectants for the treatment of seed (fruits, tubers, grain) and of 
plant cuttings for protection against fungal infections and against 
phytopathogenic fungi occurring in the soil. 
The invention thus relates in addition to the use of the compounds of 
formula I for combatting phytopathogenic microorganisms and for the 
preventive inhibition of plant disease. 
To combat these microorganisms the compounds of formula I can be used by 
themselves or together with suitable carriers and/or other additions. 
Suitable carriers and additives can be solid or liquid and correspond to 
the substances usual in formulation technology, such as natural or 
regenerated inorganic substances, solvents, dispersing agents, 
cross-linking agents, adhesives, thickeners, bonding agents, or 
fertilizers. The active principles of formula I can also be used in 
mixtures, for example with pesticidal or plant-growth promoting 
preparations.

The following examples are intended to illustrate more closely the nature 
of agents of this kind. 
The contents of the active principle in the commercial preparations is 
between 0.0001 and 90%. 
The 1-(.beta.-diphenyl)ethylazolylketals of formula I in accordance with 
the invention exhibit, in comparison with the cited compounds, a better 
microbicidal spectrum for the protection of cultivated plants and are 
characterized by the absence of phytotoxicity while entailing the dosages 
usual in plant protection, so that they protect cultivated plants from 
harmful microorganisms without damaging them in the process. 
In the following examples the temperatures are given in degrees Celsius and 
the parts refer to parts by weight. 
EXAMPLE 1 
Preparation of 
##STR14## 
1-[2-(4-diphenyl)-4,5-dimethyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole 
13.8 parts of 1,2,4-triazole, 27.6 parts of potassium carbonate, and a 
catalytically active quantity of sodium iodide are mixed in 70 ml of 
dimethyl sulfoxide and treated to a dropwise addition of 64.2 parts of 
2-(4-diphenyl)-2-bromomethyl-4,5-dimethyldioxolane(1,3) in 50 ml of 
dimethyl sulfoxide, after which the reaction mixture is stirred for 48 h 
at an internal temperature of 130.degree. C. After cooling to room 
temperature, 250 ml of water are added and the crude product precipitated 
is filtered off and recrystallized from isopropanol. The beige-colored 
crystals melt at 125.degree.-133.degree. C. 
The following end products of formula I are prepared in a similar manner: 
TABLE 1 
______________________________________ 
##STR15## 
Com- 
pound 
No. R.sub.1 Y Salt Physical constants 
______________________________________ 
1.1 H N -- m.p. 129-132.degree. 
1.2 H N HNO.sub.3 
1.3 H CH -- 
1.4 CH.sub.3 N -- m.p. 103-105.degree. 
1.5 CH.sub.3 N HNO.sub.3 
m.p. 131-133.degree. 
1.6 CH.sub.3 N CuCl.sub.2 
1.7 CH.sub.3 CH -- 
1.8 CH.sub.3 N Mn(NO.sub.3).sub.2 
1.9 C.sub.2 H.sub.5 
N -- m.p. 93-115.degree. 
1.10 C.sub.2 H.sub.5 
N HNO.sub.3 
m.p. 126-127.degree. 
1.11 C.sub.2 H.sub.5 
N ZnCl.sub.2 
1.12 C.sub.2 H.sub.5 
N Mn(NO.sub.3).sub.2 
1.13 C.sub.2 H.sub.5 
N FeCl.sub.3 
1.14 C.sub.2 H.sub.5 
CH -- m.p. 109-117.degree. 
1.15 C.sub.2 H.sub.5 
CH CuCl.sub.2 
1.16 C.sub.3 H.sub.7n 
CH -- 
1.17 C.sub.3 H.sub.7 n 
N -- m.p. 66-73.degree. 
1.18 C.sub.3 H.sub.7n 
N ZnCl.sub.2 
1.19 C.sub.3 H.sub.7n 
N HNO.sub.3 
m.p. 141-144.degree. (dec) 
1.20 C.sub.4 H.sub.9n 
N -- 
1.21 C.sub.4 H.sub.9n 
CH -- 
1.22 CH.sub.2 Cl 
N -- 
______________________________________ 
TABLE 2 
______________________________________ 
##STR16## 
Com- 
pound 
No. R.sub.2 
R.sub.3 Y Salt Physical constants 
______________________________________ 
2.1 CH.sub.3 
C.sub.2 H.sub.5 
CH -- 
2.2 CH.sub.3 
C.sub.2 H.sub.5 
N -- m.p. 52-68.degree. 
2.3 CH.sub.3 
C.sub.2 H.sub.5 
CH HNO.sub.3 
2.4 CH.sub.3 
C.sub.2 H.sub.5 
N HNO.sub.3 
m.p. 86-88.degree. 
2.5 CH.sub.3 
C.sub.3 H.sub.7n 
CH -- 
2.6 CH.sub.3 
C.sub.3 H.sub.7n 
N -- 
2.7 CH.sub.3 
C.sub.3 H.sub.7n 
N HNO.sub.3 
2.8 CH.sub.3 
C.sub.3 H.sub.7n 
N Mn(NO.sub.3).sub.2 
2.9 CH.sub.3 
CH.sub.3 CH -- m.p. 74-78.degree. 
2.10 CH.sub.3 
CH.sub.3 CH CuCl.sub.2 
2.11 CH.sub.3 
C.sub.2 H.sub.5 
CH Mn(NO.sub.3).sub.2 
2.12 CH.sub.3 
C.sub. 2 H.sub.5 
CH CuCl.sub.2 
2.13 CH.sub.3 
C.sub.2 H.sub.5 
N CuCl.sub.2 
m.p. 138-142.degree. 
2.14 CH.sub.3 
C.sub.2 H.sub.5 
N ZnCl.sub.2 
2.15 CH.sub.3 
C.sub.2 H.sub.5 
N Mn(NO.sub.3).sub.2 
2.16 CH.sub.3 
C.sub.2 H.sub.5 
N FeCl.sub.3 
2.17 CH.sub.3 
CH.sub.3 N -- m.p. 125-133.degree. 
2.18 CH.sub.3 
CH.sub.3 N HNO.sub.3 
m.p. 153-154.degree.(dec) 
2.19 C.sub.2 H.sub.5 
CH.sub.3 CH MnCl.sub.2 
2.20 C.sub.2 H.sub.5 
CH.sub.3 N MnCl.sub.2 
2.21 C.sub.2 H.sub.5 
CH.sub.3 N CuCl.sub.2 
2.22 C.sub.2 H.sub.5 
CH.sub.3 N ZnCl.sub.2 
2.23 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH -- 
2.24 CH.sub.3 
CH.sub.3 N CuCl.sub.2 
m.p. 208-212.degree. 
2.25 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N -- 
2.26 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N HNO.sub.3 
2.27 CH.sub.3 
CH.sub.3 N ZnCl.sub.2 
m.p. 191-192.degree. 
2.28 C.sub.2 H.sub.5 
C.sub.3 H.sub.7n 
N -- 
2.29 C.sub.2 H.sub.5 
C.sub.3 H.sub.7i 
N -- 
2.30 C.sub.2 H.sub.5 
C.sub.3 H.sub.7n 
CH -- 
2.31 C.sub.2 H.sub.5 
C.sub.3 H.sub.7n 
N HCl 
2.32 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N Mn(NO.sub.3).sub.2 
2.33 CH.sub.3 
C.sub.2 H.sub.5 
N (COOH).sub.2 
2.34 CH.sub.3 
C.sub.2 H.sub.5 
CH (COOH).sub.2 
2.35 CH.sub.3 
C.sub.3 H.sub.7i 
N -- 
2.36 CH.sub.3 
C.sub.3 H.sub.7i 
N H.sub.2 SO.sub.4 
2.37 (CH.sub.2).sub.4 
CH -- 
2.38 (CH.sub.2).sub.4 
CH HNO.sub.3 
2.39 (CH.sub.2).sub.4 
N -- m.p. 121-122.degree. 
2.40 (CH.sub.2).sub.4 
N HNO.sub.3 
m.p. 171-172.degree. 
2.41 (CH.sub.2).sub.4 
N CuCl.sub.2 
m.p. 217-222.degree. 
2.42 (CH.sub.2).sub.4 
N ZnCl.sub.2 
m.p. 178-184.degree. 
2.43 (CH.sub.2).sub.4 
N HCl 
2.44 (CH.sub.2).sub.4 
CH ZnCl.sub.2 
______________________________________ 
TABLE 3 
__________________________________________________________________________ 
Compounds of the formula 
##STR17## 
including isomeric forms 
Com- 
pound Physical 
No. R.sub.8 
R.sub.9 
R.sub.10 
Y Salt constants 
__________________________________________________________________________ 
3.1 H CH.sub.3 
H N -- 
3.2 H C.sub.2 H.sub.5 
H N -- 
3.3 H CH.sub.3 
H CH -- 
3.4 CH.sub.3 
CH.sub.3 
H N -- 
3.5 CH.sub.3 
CH.sub.3 
H N HNO.sub.3 
3.6 CH.sub.3 
CH.sub.3 
CH.sub.3 
N -- 
3.7 CH.sub.3 
CH.sub.3 
CH.sub.3 
N HNO.sub.3 
3.8 CH.sub.3 
CH.sub.3 
CH.sub.3 
N ZnCl.sub.2 
3.9 CH.sub.3 
CH.sub.3 
CH.sub.3 
N Mn(NO.sub.3).sub.2 
3.10 
CH.sub.3 
CH.sub.3 
CH.sub.3 
N CuCl.sub.2 
3.11 
CH.sub.3 
CH.sub.3 
CH.sub.3 
N (COOH).sub.2 
3.12 
CH.sub.3 
CH.sub.3 
CH.sub.3 
CH HNO.sub.3 
3.13 
CH.sub.3 
CH.sub.3 
CH.sub.3 
CH CuCl.sub.2 
3.14 
CH.sub.3 
CH.sub.3 
CH.sub.3 
CH FeCl.sub.3 
3.15 
CH.sub.3 
H CH.sub.3 
N -- 
3.16 
CH.sub.3 
H C.sub.2 H.sub.5 
N -- 
3.17 
C.sub.2 H.sub.5 
H C.sub.2 H.sub.5 
N -- 
3.18 
CH.sub.3 
H H N -- m.p. 117-121.degree. 
3.19 
CH.sub.3 
H H N CuCl.sub.2 
m.p. 211.5- 
214.5.degree. 
3.20 
CH.sub.3 
C.sub.2 H.sub.5 
H N -- 
3.21 
CH.sub.3 
C.sub.2 H.sub.5 
H CH -- 
3.22 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH.sub.3 
N -- 
3.23 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N Mn(NO.sub.3).sub.2 
3.24 
C.sub.3 H.sub.7 -n 
H C.sub.3 H.sub.7 -n 
N -- 
3.25 
C.sub.3 H.sub.7 -n 
H C.sub.3 H.sub.7 -n 
CH -- 
3.26 
C.sub.3 H.sub.7 -n 
C.sub.3 H.sub.7 -n 
H N -- 
3.27 
C.sub.3 H.sub.7 -n 
C.sub.2 H.sub.5 
CH.sub.3 
N -- 
3.28 
C.sub.3 H.sub.7 -n 
C.sub.2 H.sub.5 
CH.sub.3 
CH -- 
3.29 
C.sub.3 H.sub.7 -n 
C.sub.2 H.sub.5 
CH.sub.3 
N ZnCl.sub.2 
3.30 
C.sub.3 H.sub.7 -n 
CH.sub.3 
C.sub.2 H.sub.5 
N -- 
3.31 
C.sub.2 H.sub.5 
C.sub.3 H.sub.7 -n 
CH.sub.3 
N -- 
3.32 
C.sub.4 H.sub.9 -n 
CH.sub.3 
H N -- 
3.33 
C.sub.4 H.sub.9 -n 
H CH.sub.3 
N FeCl.sub.3 
3.34 
C.sub.4 H.sub.9 -n 
H CH.sub.3 
CH -- 
3.35 
CH.sub.3 
H C.sub.4 H.sub.9 -n 
N -- 
3.36 
H H C.sub.4 H.sub.9 -n 
N -- 
3.37 
H H C.sub.4 H.sub.9 -n 
CH -- 
3.38 
H H C.sub.4 H.sub.9 -n 
N HNO.sub.3 
3.39 
H C.sub.4 H.sub.9 -n 
H N -- 
3.40 
H C.sub.4 H.sub.9 -n 
CH.sub.3 
CH HCl 
3.41 
CH.sub.3 
C.sub.4 H.sub.9 -n 
H N -- 
3.42 
H C.sub.4 H.sub.9 -sek 
H N HNO.sub.3 
3.43 
H C.sub.4 H.sub.9 -sek 
H N -- 
3.44 
H C.sub.4 H.sub.9 -sek 
CH.sub.3 
N -- 
3.45 
H C.sub.4 H.sub.9 -sek 
CH.sub.3 
CH -- 
3.46 
H C.sub.3 H.sub.7 -i 
CH.sub.3 
N -- 
3.47 
H C.sub.3 H.sub.7 -i 
CH.sub.3 
N Mn(NO.sub.3).sub.2 
3.48 
CH.sub.3 
C.sub.3 H.sub.7 -i 
CH.sub.3 
N -- 
3.49 
C.sub.2 H.sub.5 
C.sub.3 H.sub.7 -i 
H N -- 
__________________________________________________________________________ 
TABLE 4 
______________________________________ 
Compounds of the formula 
##STR18## 
including isomeric forms 
Com- 
pound 
No. R.sub.11 
R.sub.12 Y Salt Physical constants 
______________________________________ 
4.1 H CH.sub.3 N -- 
4.2 H CH.sub.3 CH -- 
4.3 CH.sub.3 
CH.sub.3 N -- m.p. 96-100.degree. 
4.4 CH.sub.3 
CH.sub.3 N HNO.sub.3 
m.p. 132-134.degree. 
4.5 CH.sub.3 
CH.sub.3 N Mn(NO.sub.3).sub.2 
4.6 CH.sub.3 
CH.sub.3 CH -- m.p. 132-140.degree. 
4.7 CH.sub.3 
CH.sub.3 CH ZnCl.sub.2 
4.8 CH.sub.3 
C.sub.2 H.sub.5 
N -- m.p. 132-139.degree. 
4.9 CH.sub.3 
C.sub.2 H.sub.5 
N CuCl.sub.2 
m.p. 203-211.degree. 
4.10 CH.sub.3 
C.sub.2 H.sub.5 
CH (COOH).sub.2 
4.11 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N HNO.sub.3 
4.12 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
N -- m.p. 106.5-108.5.degree. 
4.13 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH HCl 
4.14 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH FeCl.sub.3 
4.15 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
CH -- m.p. 109-112.degree. 
4.16 H C.sub.2 H.sub.5 
N -- 
4.17 H C.sub.2 H.sub.5 
N HNO.sub.3 
4.18 H C.sub.2 H.sub.5 
CH -- 
4.19 CH.sub.3 
C.sub.3 H.sub.7 -n 
N CuCl.sub.2 
m.p. 214-217.degree. 
4.20 H C.sub.3 H.sub.7 -n 
CH -- 
4.21 CH.sub.3 
C.sub.3 H.sub.7 -n 
N HNO.sub.3 
m.p. 188-189.degree. (dec) 
4.22 CH.sub.3 
C.sub.3 H.sub.7 -n 
CH (COOH).sub.2 
4.23 CH.sub.3 
C.sub.3 H.sub.7 -n 
N -- m.p. 130.5-133.degree. 
4.24 CH.sub.3 
C.sub.3 H.sub.7 -n 
CH -- 
4.25 H C.sub.4 H.sub.9 -n 
N -- 
4.26 CH.sub.3 
C.sub.4 H.sub.9 -n 
N -- 
4.27 CH.sub.3 
C.sub.4 H.sub.9 -n 
CH -- 
4.28 C.sub.2 H.sub.5 
C.sub.4 H.sub.9 -n 
N HNO.sub.3 
______________________________________ 
TABLE 5 
______________________________________ 
and the following compounds of the formula 
##STR19## 
including isomeric forms 
Com- 
pound 
No. Y Salt Physical constants 
______________________________________ 
5.1 N -- m.p. 124-127.degree. 
5.2 CH -- 
5.3 N HNO.sub.3 m.p. 161-163.degree. 
5.4 N Cl.sub.3 CCOOH 
5.5 N CuCl.sub.2 m.p. 202-210.degree. 
5.6 N ZnCl.sub.2 
5.7 N Mn(NO.sub.3).sub.2 
5.8 N HCl 
5.9 N (COOH).sub.2 
5.10 CH HNO.sub.3 
5.11 CH Cl.sub.3 CCOOH 
5.12 CH CuCl.sub.2 
5.13 CH ZnCl.sub. 2 
5.14 CH Mn(NO.sub.3).sub.2 
5.15 CH HCl 
______________________________________ 
TABLE 6 
______________________________________ 
##STR20## 
Com- 
pound 
No. ZR.sub.7 Y Salt Physical constants 
______________________________________ 
6.1 OCH.sub.3 N -- m.p. 112-114.degree. 
6.2 OCH.sub.3 CH -- 
6.3 OCH.sub.3 N HNO.sub.3 
m.p. 150-151.degree. 
6.4 OCH.sub.3 N CuCl.sub.2 
m.p. 185-186.degree. 
6.5 OCH.sub.3 N Mn(NO.sub.3).sub.2 
6.6 OC.sub.2 H.sub.5 
N -- m.p. 98-102.degree. 
6.7 OC.sub.2 H.sub.5 
CH -- 
6.8 OC.sub.2 H.sub.5 
N ZnCl.sub.2 
6.9 OC.sub.4 H.sub.9n 
N -- m.p. 65-68.degree. 
6.10 OC.sub.4 H.sub.9n 
CH -- 
6.11 OC.sub.4 H.sub.9n 
N CuCl.sub.2 
m.p. 137-138.degree. 
6.12 OC.sub.6 H.sub.4 Cl(4) 
N -- m.p. 139-140.degree. 
6.13 OC.sub.6 H.sub.4 Cl(4) 
N CuCl.sub.2 
m.p. 215-216.degree. 
6.14 SCH.sub.3 N -- 
6.15 OC.sub.6 H.sub.4 Cl(4) 
N HNO.sub.3 
m.p. 166-167.degree. 
6.16 SC.sub.3 H.sub.7n 
CH -- 
______________________________________ 
For application, the compounds of formula I can be used in the following 
working forms. 
FORMULATION EXAMPLES 
Solid working forms: 
Dusting and scattering materials generally contain up to 100% of the active 
principle. A 5% dusting agent may, for example, consist of 5 parts of the 
active principle and 95 parts of an additive such as talc or of 5 parts of 
active principle, 3 parts of highly dispersed silica, and 92 parts of 
talc. In addition, further mixtures with carrier materials and additives 
such as these and others usual in formulation technology are conceivable. 
In the preparation of these dusting agents the active principles are mixed 
and ground with the carriers and the additives and can be diluted in this 
form. 
Granulates such as covering granulates, impregnation granulates, 
homogeneous granulates and pellets usually contain 1 to 80% of the active 
principle. Thus, a 5% granulate can be composed, for example, of 5 parts 
of the active principle, 0.25 part of epichlorohydrin. 0.25 part of cetyl 
polyglycol ether, 3.50 parts of polyethylene glycol, and 91 parts of 
kaolin (preferred particle size 0.3 to 0.8 mm). The granulate can be 
prepared as follows: 
The active substance is mixed with the epichlorohydrin and dissolved in 6 
parts of acetone, after which the polyethylene glycol and the cetyl 
polyglycol ether are added. The solution thus obtained is sprayed onto 
kaolin and finally the acetone is evaporated off under vacuum. A 
microgranulate of this kind can be used advantageously for combatting soil 
fungi. 
Liquid working forms 
A general distinction is drawn between active principle concentrates that 
are dispersable or soluble in water and aerosols. Among the active 
principle concentrates that are dispersable in water there are, for 
example, wettable powders and pastes which as a rule contain 25-90% of the 
active principle in the commercially available packs and 0.01 to 15% of 
the active principle in the ready-for-use solutions. Emulsion concentrates 
contain 10 to 50% and solution concentrates 0.0001 to 20% of the active 
substance in the ready-for-use solution. Thus, a 70% wettable powder 
consists, for example, of 70 parts of the active principle, 5 parts of 
sodium dibutylnaphthylsulfonate, and 3 parts of naphthalenesulfonic 
acids--phenolsulfonic acids--formaldehyde condensate (in the ratio of 
3:2:1), 10 parts of kaolin, and 12 parts of chalk, e.g. Champagne chalk. A 
40% wettable powder can, for example, consist of the following substances: 
40 parts of the active principle, 5 parts of sodium ligninsulfonate, 1 
part of sodium dibutylnaphthylsulfonate, and 54 parts of silica. A 25% 
wettable powder can be made in various ways. Thus, the latter can, for 
example, consist of 25 parts of the active substance, 4.5 parts of calcium 
ligninsulfonate, 1.9 parts of a mixture of chalk, such as Champagne chalk, 
and hydroxyethylethylenecellulose (1:1 ), 1.5 parts of sodium 
dibutylnaphthylsulfonate, 19.5 parts of silica, 19.5 parts of chalk, e.g. 
Champagne chalk, and 28.1 parts of kaolin. A 25% wettable powder can, for 
example, also consist of 25 parts of the active principle, 2.5 parts of 
isooctylphenoxypolyoxyethyleneethanol, 1.7 parts of a mixture of Champagne 
chalk and hydroxyethylcellulose (1:1), 8.3 parts of sodium silicate, 16.5 
parts of kieselguhr, and 46 parts of kaolin. A 10% wettable powder can be 
made, for example, from 10 parts of the active principle, 3 parts of a 
mixture of sodium salts of saturated fatty alcohol sulfonates, 5 parts of 
naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin. 
Other wettable powders can be mixtures of 5 to 30% of the active substance 
together with 5 parts of an absorbent carrier material such as silica, 55 
to 80 parts of a carrier material such as kaolin, and a dispersing agent 
consisting of 5 parts of sodium arylsulfonate and 5 parts of an alkylaryl 
polyglycol ether. A 25% emulsion concentrate can, for example, contain the 
following emulsifiable substances: 25 parts of the active principle, 2.5 
parts of epoxidized vegetable oil, 10 parts of an alkylaryl 
sulfonate/fatty alcohol polyglycol ether mixture, 5 parts of 
dimethylformamide, and 57.5 parts of xylene. 
Emulsions of the desired concentration which are particularly suitable for 
application to the leaves can be prepared from condensates of this type by 
dilution with water. In addition, other wettable powders can be prepared 
using different mixing ratios or other carrier materials and additives 
usual in formulation technology. The active principles are mixed 
thoroughly with the said additives in suitable mixers and ground using 
appropriate mills and rollers. Wettable powders of excellent wettability 
and buoyancy are obtained that can be diluted with water to give 
suspensions of the desired concentration and which are particularly 
suitable for application to the leaves. Such agents are also the object of 
the invention. 
Preparations that have been formulated in the above-described manner, and 
which contain as the active component a compound of formula I (e.g. 
compound 1.4, 1.9, 1.14, 1.17, 2.9, 2.17, 2.24, 3.18, 4.3, 4.6, 4.8, 4.12, 
4.15, or 4.23) can be used highly successfully for combatting 
phytopathogenic microorganisms. Other compounds from Tables 1 to 6 can 
also be used, with equally good or similar results. 
Biological examples 
The wettable mixtures used in the subsequent examples were formulated as 
described above. 
EXAMPLE 2 
Action against Cercospora arachidicola on peanut plants 
3-week-old peanut plants were sprayed with a spray (0.02% of the active 
substance) prepared from a wettable powder of the active principle. After 
about 12 h the treated plants were dusted with a conidium suspension of 
the fungus. The infected plants were incubated for about 24 h at 90% 
relative humidity and then placed in a greenhouse at about 22.degree. C. 
The incidence of the fungus infection was evaluated after 12 days. 
In comparison with the untreated controls, plants that had been treated 
with the active principles of formula I displayed little or no fungal 
infestation. 
Compounds 1.4, 1.9, 1.17, 2.17, 2.24, 2.9, 3.18, 4.12, 4.23, and 4.3 also 
inhibit the fungus infection in a concentration as low as 0.002%. 
EXAMPLE 3 
Action against Puccinia graminis on wheat 
(a) Residual protective action 
6 days after sowing wheat plants were sprayed with a spray (0.06% of the 
active substance) prepared from wettable powder of the active principle. 
After 24 h the treated plants were infected with a uredospore suspension 
of the fungus. After incubation for 48 h at 95-100% relative humidity and 
about 20.degree. C. the infected plants were placed in a greenhouse at 
about 22.degree. C. 
The development of the rust pustules was evaluated 12 days after the 
infection. Compounds of formula I displayed a strong action, as did 
compounds 1.4, 1.17, 2.17, 2.24, 4.3, and 4.8. 
(b) Systemic action 
5 days after sowing a spray solution made from wettable powder of the 
active principle (0.006% of the active substance referred to the soil 
volume) was poured over wheat plants. After 3 days the treated plants were 
infected with a uredospore suspension of the fungus. Following incubation 
for 48 h at 95-100% relative humidity and about 20.degree. C. the infected 
plants were placed in a greenhouse at about 22.degree. C. The development 
of the rust pustules was evaluated 12 days after the infection. Compounds 
of formula I exhibited a strong action. For example, compound 2.17 
prevented entirely any spread of the disease. 
EXAMPLE 4 
Residual protective action against Venturia inaequalis on apple shoots 
Apple saplings with fresh shoots 10 to 20 cm in length were sprayed with a 
spray (0.06% of the active substance) prepared from wettable powder of the 
active principle. After 24 h the treated plants were infected with a 
conidium suspension of the fungus. The plants were then incubated for 5 
days at 90-100% relative humidity and kept for a further 10 days in a 
greenhouse at 20.degree.-24.degree. C. The scab formation was evaluated 15 
days after the infection. Compounds 1.4, 1.9, 1.14, 1.17, 2.17, 3.18, and 
others inhibited the disease even in a concentration as low as 0.006%. 
EXAMPLE 5 
Residual protective action against Podosphaera leucotricha on apple shoots 
Apple saplings with fresh shoots some 15 cm in length were sprayed with a 
spray (0.06% of the active substance) prepared from wettable powder of the 
active principle. After 24 h the treated plants were infected with a 
conidium suspension of the fungus and kept in an air-conditioned chamber 
at a relative humidity of 70% and a temperature of 20.degree. C. The 
incidence of the fungal infection was evaluated 12 days later. Compounds 
of formula I displayed strong fungicidal action. Compounds 1.4, 1.9, 1.17, 
2.9, 2.17, and 3.8, among others, inhibited the disease even in a 
concentration of 0.006%. 
EXAMPLE 6 
Action against Erysiphe graminis on barley 
(a) Residual protective action 
Barley plants about 8 cm high were sprayed with a spray (0.02% of the 
active substance) prepared from wettable powder of the active principle. 
After 3-4 h the treated plants were dusted with conidia of the fungus. The 
infected barley plants were kept in a greenhouse at about 22.degree. C. 
and the incidence of the fungus infestation was evaluated after 10 days. 
(b) Systemic action 
A spray (0.006% of the active substance referred to the soil volume) 
prepared from wettable powder of the active principle was poured over 
barley plants about 8 cm high. Care was taken that the spray mixture did 
not come into contact with the parts of the plant above ground level. 
After 48 h the treated plants were dusted with conidia of the fungus. The 
infected barley plants were kept in a greenhouse at about 22.degree. C. 
and the incidence of the fungal infestation was evaluated after 10 days. 
In Experiments (a) and (b) the compounds of formula I displayed total 
action (fungal infection completely prevented). In Experiment (a) 
compounds 1.4, 1.9, 1.14, 1.17, 2.9, 2.17, 3.18, 4.3, 4.8, and 4.12 
exhibited total action even at a dilution of 0.002%. Compounds 1.4, 1.9, 
and 2.17, inter alia, also exhibited this action in Experiment (b) at a 
concentration of 0.002%. 
EXAMPLE 7 
Action against Botrytis cinerea on beans 
Residual protective action 
Bean plants about 10 cm in height were sprayed with a spray (0.02% of the 
active substance) prepared from wettable powder of the active principle. 
After 48 h the treated plants were infected with a conidium suspension of 
the fungus. Following incubation of the infected plants for 3 days at 
95-100% relative humidity and 21.degree. C., the incidence of the fungal 
infestation was evaluated. The compunds of formula I inhibited the fungal 
infection totally. Compounds 1.14 and 2.9, for example, proved to be still 
fully effective at a concentration of 0.006% (zero incidence of the 
disease). 
EXAMPLE 8 
Action against Plasmopara viticola on vines 
Residual preventive action 
"Chasselas" vine saplings were treated in a greenhouse. At the 10-leaf 
stage 3 plants were sprayed with a spray (0.06% of the active substance) 
prepared from the active substance formulated as wettable powder. After 
the spray coating had dried, the plants were uniformly infected on the 
underside of the leaves with a spore suspension of the fungus. The plants 
were then kept in a moisture chamber for 8 days. After this period clear 
symptoms of disease were visible on the control plants. The number and 
size of the fungus colonies were used to evaluate the test products, and 
it was found that among others compounds 1.14 and 2.9 exhibited a very 
good action. 
Compounds 1.4, 1.9, 1.14, 1.17, 2.9, 2.17, and 3.18, inter alia, inhibited 
the development of the fungus colonies almost entirely. 
EXAMPLE 9 
Action against Fusarium nivale on wheat 
Wheat grains were contaminated with a spore suspension of the fungus and 
dried. The contaminated grains were steeped in a suspension of the test 
substance prepared from wettable powder (600 ppm of the active principle 
referred to the weight of the seeds). After two days the grains were laid 
out on suitable agar dishes and after a further four days the development 
of fungal colonies around the grains was evaluated. The number and size of 
the fungal colonies were used to evaluate the test products, and among 
other compounds 1.14 and 2.9 were found to have a very good action. 
EXAMPLE 10 
Action against Helminthosporium gramineum 
Wheat grains were contaminated with a spore suspension of the fungus and 
dried. The contaminated grains were steeped in a suspension of the test 
substance prepared from wettable powder (600 ppm of the active principles 
referred to the weight of the seeds). After two days the grains were laid 
out on suitable agar dishes and after a further four days the development 
of fungal colonies was evaluated. The number and size of the fungal 
colonies were used to evaluate the test products. 
Among others, compounds 1.4, 1.9, 1.14, 1.17, 2.9, and 2.17 inhibited the 
development of the fungus colonies almost totally. 
EXAMPLE 11 
Action against Alternaria solani on tomatoes 
After 3 weeks of rearing tomato plants were sprayed with a spray (0.02% of 
the active substance) prepared from wettable powder of the active 
principle. After 24 h the plants were infected with a conidium suspension 
of the fungus. The fungicidal action was evaluated on the basis of the 
incidence of fungus infestation after incubation of the infected plants 
for 8 days at high relative humidity (95-100%) and at a temperature of 
18.degree.-22.degree. C. 
Compounds 2.17 and 2.24, among others, exhibited a very good action against 
Alternaria. 
The results of the biological Examples 2-11 are proof of the exceptional 
activity and the broad action spectrum of the compounds against 
biologically very varied phytopathogenic fungi.