1,1-Diaryl-2-azolylethanes and preparations containing these compounds

Substituted ethanols of the general formula ##STR1## in which Ar.sub.1 is a carbocyclic or heterocyclic ring and Az is a triazolyl, benzimidazolyl, pyrazolyl or imidazolyl radical, are reacted with aryl hydrocarbons Ar.sub.2 --H, in which Ar.sub.2 has the same meaning as Ar.sub.1, in the presence of an acidic catalyst, to give 1,1-diaryl-2-azolylethanes. The substances, which, apart from the imidazolyl derivatives, are new, can be used as biocides, in particular fungicides.

The invention relates to new 1,1-diaryl-2-azolylethyl derivatives, a 
process for the preparation of this substance class, and their use as 
biocides, in particular as fungicides. 
It is known that compounds from the class comprising the 
1,1-diaryl-2-imidazolylethanes possess fungicidal properties (U.S. Pat. 
No. 4,115,578 and German Offenlegungsschrift No. 2,604,047). However, more 
detailed data concerning their activity, in particular when low amounts 
are used, their spectrum of action, and the focal point of their action 
are not available. 
It has been found that certain 1,1-diaryl-2-azolylethanes not described 
hitherto surprisingly have a substantially higher fungicidal power 
compared to those already known, in particular against rust and powdery 
mildew, are herbicidally active, and can also be employed as antimycotics. 
The invention therefore relates to new 1,1-diaryl-2-azolylethanes of the 
general formula (I) 
##STR2## 
in which Ar.sub.1 and Ar.sub.2 represent identical or different radicals 
which have the meaning of naphth-1-yl or naphth-2-yl, 
tetrahydronaphth-1-yl or tetrahydronaphth-2-yl, indan-5-yl, five-membered 
or six-membered or benzo-fused five-membered or six-membered heterocyclic 
rings having up to two hetero-atoms which can be N, O or S, or in 
particular have the meaning of radicals of the formula (II) 
##STR3## 
and in this formula, R.sup.1 to R.sup.5 are identical or different and 
preferably represent hydrogen, halogen, CF.sub.3, C.sub.1 - to C.sub.8 
-alkyl, C.sub.2 - to C.sub.8 -alkenyl, C.sub.5 - or C.sub.6 -cycloalkyl, 
C.sub.1 - to C.sub.6 -alkoxy or C.sub.2 - or C.sub.6 -alkenoxy, or also 
phenoxy or phenyl radicals which can be substituted by up to 5 halogen 
atoms, preferably chlorine atoms, but in particular represent H, Cl, Br 
and C.sub.1 - to C.sub.8 -alkyl. 
Z is a radical of the formula (III) 
##STR4## 
in which R.sup.6 denotes hydrogen or an alkyl or alkenyl radical which has 
up to 8, preferably 1 or 2, C atoms and which can be substituted by up to 
two alkoxy or amino groups which have 1 or 2 C atoms and which may also be 
different, but in particular is H, methyl or ethyl. 
Az particularly represents 1,2,4-triazol-1-yl or 1,2,4-triazol-4-yl, or can 
also be benzimidazol-1-yl or pyrazol-1-yl. 
The salts, complex salts and quaternization products of 
1,1-diaryl-2-azolylethanes are also included. 
The new compounds are obtained from compounds which carry an alcoholic OH 
group and are of the formula 
##STR5## 
in which Ar.sub.1, R.sup.6 and Az have the meanings given above, by 
reaction with aryl hydrocarbons of the formula (VI) 
EQU H--Ar.sub.2 (VI) 
in which Ar.sub.2 is one of the radicals given above. 
The reaction is carried out in the temperature range from -15.degree. to 
+150.degree. C., preferably from -10.degree. to 110.degree. C., in the 
presence of an acidic catalyst, if appropriate in the presence of a 
diluent. In this context, acidic catalysts are understood as meaning the 
conventional Friedel-Crafts catalysts, as described--like the suitable 
diluents--for example in Houben-Weyl, Methoden der org. Chemie, Vol. 7/2a, 
pages 17 to 21. Tetrachloroethane and aluminum trichloride are preferred. 
1.1 to 2.5 equivalents of the catalyst and at least one equivalent of the 
aryl hydrocarbon H--Ar.sub.2, relative to the compound of the formula (V), 
are employed. 
Examples of starting compounds of the formula (V) which are suitable for 
the preparation of the 1,1-diaryl-2-azolylethanes are: 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-propane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-hexane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-octane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(imidazolyl-1-yl)-ethane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(imidazolyl-1-yl)-propane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(imidazolyl-1-yl)-hexane, 
1-(2,4-dichlorophenyl)-1-hydroxy-2-(imidazolyl-1-yl)-octane, 
1-(3,4-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-(2,5-dichlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-(2-methyl-4-chlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-(4-methoxyphenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-(4-phenylphenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane, 
1-phenyl-1-hydroxy-2-(1,2,4-triazol-1-yl)-3-methoxy-propane, 
1-phenyl-1-hydroxy-2-(1,2,4-triazol-1-yl)-4-methoxy-butane, 
1-phenyl-1-hydroxy-2-(imidazol-1-yl)-4-(2,6-dimethylmorpholin-4-yl)-butane 
and 1-pentamethylphenyl-1-hydroxy-2-(1,2,4-triazol-1-yl)-propane. 
The aromatics of the formula H--Ar.sub.2 (VI) are understood as meaning, 
for example: chlorobenzene, bromobenzene, 1,3-dichlorobenzene, 
1,2-dichlorobenzene, 1,4-dichlorobenzene, toluene, xylene, mesitylene, 
3-chlorotoluene, 4-chlorotoluene, anisole, pyridine, thiophene, 
benzothiophene, benzoxazole, benzthiazole, naphthalene, 
tetrahydronaphthalene and indane. 
In the synthesis, the procedure is carried out, in particular, as follows: 
the compounds of the formula (V), the aryl hydrocarbon H--Ar.sub.2 (VI) 
and, if appropriate, a diluent are initially introduced, and the catalyst 
is slowly metered in at approx. -10.degree. C. The mixture is allowed to 
reach room temperature in the course of 30 minutes, and is then heated 
until the evolution of gas begins. When this has ended, the mixture is 
heated for a further 30 minutes, allowed to cool to room temperature, 
poured onto ice, and rendered strongly alkaline with 50% strength NaOH, 
while cooling with ice, and the organic phase is then worked up in the 
conventional manner. 
Using the same method, the products belonging to the same compound class 
and described in German Offenlegungsschrift No. 2,604,047 and U.S. Pat. 
No. 4,115,578 can also be prepared; these are those compounds of the 
formula (I) in which, in the radical Z the structure of which is 
illustrated by formula (III), Az represents an imidazolyl radical of the 
formula (IV) 
##STR6## 
in which Y denotes C.sub.1 - to C.sub.4 -alkyl, a halogen atom or nitro, 
and n can be 0 to 3, which compounds are obtainable by the process 
described in these publications only in minimal yields, via 8 reaction 
steps. In contrast, the process according to the invention is carried out 
in 4 stages with a total yield of more than 50%. 
The course of the reaction leading to the products according to the 
invention may be illustrated by the example, given below, of the reaction 
of 1,3-dichlorobenzene with 
1-(4-chlorophenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethane: 
##STR7## 
This is surprising and could not be foreseen, since, under the process 
conditions, it was to be expected that water would be split off to give 
.omega.-(1,2,4-triazol-1-yl)-styrene, as is known to take place in the 
case of 1-phenylethanolene [Journ. Am. Chem. Soc. 73 (1951), page 455; and 
Journ. Chem. Soc. 87, page 672], and splitting off of triazole, or a 
polymerization, are also possible. 
The 1,1-diaryl-2-azolylethanes according to the invention can occur in the 
E form and Z form. As basic compounds, they are furthermore capable of 
forming salts, complex salts and quaternization products. Salts of organic 
and inorganic acids may be mentioned, such as, for example, acetates, 
fumarates, oxalates, benzoates, nitrates, bromides, chlorides and 
sulfates, salts of naphthalenesulfonic acids, complexes with metals of 
group 1b, 2b, 4b or 8b of the periodic table, for example copper, zinc and 
tin, and quaternization products with alkyl halides and phenacyl halides. 
The preparation of such compounds is effected according to generally 
customary methods. 
The compounds according to the invention, of the formula I, are 
distinguished by an outstanding fungicidal action, in particular, for 
example, when used in plant protection. In this context, fungal pathogens 
which have already penetrated the plant tissue can be successfully 
controlled by curative measures. This is particularly important and 
advantageous in the case of those fungal diseases which, after infection 
has occurred, can no longer be effectively controlled with the fungicides 
otherwise customarily used. The spectrum of action of the claimed 
compounds includes, for example, in addition to various rust species, 
Phytophthora infestans, Plasmopara viticola and Piricularia oryzae, but in 
particular powdery mildew fungi in the cultivation of fruit, vegetables, 
cereal and decorative plants. The excellent action of the compounds 
against powdery mildew species which are resistant to benzimidazole 
derivatives (for example Benomyl and Carbendazim) should be particularly 
singled out. 
Moreover, the substances are suitable for use in industrial fields, for 
example as wood preservatives, as preservatives in paints, in cooling 
lubricants for metalworking, or as preservatives in drilling oils and 
cutting oils. 
The agents can be used as wettable powders, emulsifiable concentrates, 
atomizable solutions, dusting agents, dressing agents, dispersions, 
granules or microgranules, in the conventional preparations. 
Wettable powders are understood as meaning preparations which are uniformly 
dispersible in water and which also contain, in addition to the active 
compound and in addition to any diluent or inert substance, wetting 
agents, for example polyoxyethylated alkylphenols, polyoxyethylated fatty 
alcohols, alkyl sulfonates or alkylphenyl sulfonates, and dispersants, for 
example sodium ligninsulfonate, sodium 
2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalene 
sulfonate or even sodium oleolylmethyl taurate. Their preparation is 
effected in a conventional manner, for example by grinding and mixing the 
components. 
Emulsifiable concentrates can be prepared, for example, by dissolving the 
active compound in an inert organic solvent, for example butanol, 
cyclohexanone, dimethylformamide, xylene or even high-boiling aromatics or 
hydrocarbons, with the addition of one or more emulsifiers. In the case of 
liquid active compounds, the solvent constituent can also be either 
completely or partially dispensed with. Examples of emulsifiers which can 
be used are: calcium salts of alkylarylsulfonic acid, such as Ca 
dodecylbenzenesulfonate, or non-ionic emulsifiers, such as fatty acid 
polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol 
ethers, propylene oxide/ethylene oxide condensation products, fatty 
alcohol/propylene oxide/ethylene oxide condensation products, alkyl 
polyglycol ethers, sorbitane fatty acid esters, polyoxyethylene sorbitane 
fatty acid esters or polyoxyethylene sorbitol esters. 
Dusting agents are obtained by grinding the active compound with finely 
divided solid substances, for example talc, natural clays, such as kaolin, 
bentonite or pyrophillite, or diatomaceous earth. 
Granules can be prepared either by spraying the active compound onto 
absorptive, granulated inert material, or by applying active compound 
concentrations onto the surface of carriers, such as sand or kaolinites, 
or of granulated inert material by means of binders, for example polyvinyl 
alcohol, sodium polyacrylic or even mineral oils. It is also possible to 
granulate suitable active compounds in the manner customary for the 
preparation of fertilizer granules--if desired as a mixture with 
fertilizers. 
In wettable powders, the active compound concentration is, for example, 
about 10 to 90% by weight, and the residual amount up to 100% by weight 
comprises conventional formulation constituents. In the case of 
emulsifiable concentrates, the active compound concentration can be about 
10 to 80% by weight. Dust-like formulations contain at most 5 to 20% by 
weight of active compound, and atomizable solutions contain about 1 to 20% 
by weight. In the case of granules, the active compound content depends in 
part on whether the active compound is present in liquid or solid form, 
and which granulation auxiliaries, fillers, etc. are used. 
In addition, the active compound formulations mentioned contain, if 
appropriate, the adhesives, wetting agents, dispersants, emulsifiers, 
penetrating agents, solvents, fillers or carriers customarily used in the 
particular case. 
For use, the concentrates present in the commercial form are diluted in the 
conventional manner if appropriate, for example in the case of wettable 
powders, emulsifiable concentrates and dispersions, and also in the case 
of some of the microgranules, by means of water. Dust-like and granulated 
preparations, and atomizable solutions, are customarily no longer diluted 
with further inert substances before use. 
Mixtures or mixed formulations with other active compounds, such as, for 
example, insecticides, acaricides, herbicides, fertilizers, growth 
regulators or further fungicides are also possible if required, and 
synergistic increases in action can also be achieved in certain 
circumstances. 
Some formulation examples are mentioned below: 
A dusting agent is obtained by mixing 10 parts by weight of active compound 
and 90 parts by weight of talc as the inert substance, and comminuting the 
mixture in a hammer mill. 
A wettable powder which is readily dispersible in water is obtained by 
mixing 25 parts by weight of active compound, 64 parts by weight of 
kaolin-containing quartz as the inert substance, 10 parts by weight of 
potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyl 
taurate as the wetting agent and dispersant, and grinding the mixture in a 
pinned disk mill. 
A dispersion concentrate which is readily dispersible in water is prepared 
by mixing 20 parts by weight of active compound with 6 parts by weight of 
alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of 
isotridecanol polyglycol ether (8 ethylene oxide units) and 71 parts by 
weight of paraffinic mineral oil (boiling range, for example, approx. 
255.degree. to above 377.degree. C.), and grinding the mixture in an 
attrition ball mill to a fineness of less than 5 microns. 
An emulsifiable concentrate can be prepared from 15 parts by weight of 
active compound, 75 parts by weight of cyclohexanone as the solvent and 10 
parts by weight of oxyethylated nonylphenol (10 ethylene oxide units) as 
the emulsifier.