Microbicidal and growth-regulating compositions

Fluoroazolylpropane derivatives of the formula I ##STR1## are described, in which Az is imidazolyl or triazolyl, R.sup.1 is hydrogen, alkyl or aralkyl which is unsubstituted or substituted by halogen, alkyl, alkoxy, halogenoalkyl, nitro, cyano, carboxyl or alkoxycarbonyl, R.sup.2 is C.sub.1 -C.sub.10 -alkyl which is unsubstituted or substituted by alkoxy, aralkoxy or phenyl, it being possible for the aromatic nuclei of aralkoxy and phenyl in turn to be unsubstituted or substituted by halogen, alkyl, alkoxy, halogenoalkyl, cyano, carboxyl or alkoxycarbonyl, R.sup.3 is hydrogen, alkyl, alkylcarbonyl or aralkyl which is unsubstituted or substituted by halogen, alkoxy, alkyl, halogenoalkyl, cyano, carboxyl or alkoxycarbonyl, R.sup.5 is an unsubstituted or monosubstituted or polysubstituted radical selected from the series comprising C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl, phenyl, naphthyl, biphenyl, benzylphenyl, benzyloxyphenyl, phenoxyphenyl and aralkyl, and X is oxygen or sulfur; including the acid addition salts, quaternary azolium salts and metal complexes. Methods of preparing these products are also disclosed, as are agrochemical compositions containing one of these compounds as the active substance. A process for controlling phytopathogenic microorganisms and/or for regulating plant growth by means of these substances is also described.

The present invention relates to novel, substituted fluoroazolylpropane 
derivatives and to acid addition salts, quaternary azolium salts and metal 
complexes thereof. The invention also relates to the preparation of these 
substances and to microbicidal and growth-regulating compositions 
containing at least one of these compounds as the active substance. The 
invention also relates to the preparation of the said compositions and to 
the use of the active substances or the compositions for regulating plant 
growth and for controlling harmful microorganisms. The invention also 
relates to fluoroazolylmethyloxiranes and fluoroazolyl ketones which have 
been prepared as intermediates. 
The fluoroazolylpropane derivatives according to the invention have the 
formula I 
##STR2## 
in which Az is imidazolyl or triazolyl, R.sup.1 is hydrogen, alkyl or 
aralkyl which is unsubstituted or substituted by halogen, alkyl, alkoxy, 
halogenoalkyl, nitro, cyano, carboxyl or alkoxycarbonyl, R.sup.2 is 
C.sub.1 -C.sub.10 -alkyl which is unsubstituted or substituted by alkoxy, 
aralkoxy or phenyl, it being possible for the aromatic nuclei of aralkoxy 
and phenyl in turn to be unsubstituted or substituted by halogen, alkyl, 
alkoxy, halogenoalkyl, cyano, carboxyl or alkoxycarbonyl, R.sup.3 is 
hydrogen, alkyl, alkylcarbonyl or aralkyl which is unsubstituted or 
substituted by halogen, alkoxy, alkyl, halogenoalkyl, cyano, carboxyl or 
alkoxycarbonyl, R.sup.5 is an unsubstituted or monosubstituted or 
polysubstituted radical selected from the series comprising C.sub.1 
-C.sub.8 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.3 -C.sub.6 -alkenyl, 
C.sub.3 -C.sub.6 -alkynyl, phenyl, naphthyl, biphenyl, benzylphenyl, 
benzyloxyphenyl, phenoxyphenyl and aralkyl, and X is oxygen or sulfur; 
including the acid addition salts, quaternary azolium salts and metal 
complexes. 
The term azolyl characterises a five-membered heterocyclic five-ring 
containing nitrogen as the hetero-atom and having aromatic character. 
Typical representatives are 1H-1,2,4-triazole, 4H-1,2,4-triazole and 
1H-imidazole. The term alkyl itself or as a constituent of another 
substituent, such as alkoxy, alkylthio, halogenoalkyl, aralkyl or 
alkylcarbonyl, is to be understood, depending on the number of carbon 
atoms indicated, as meaning, for example, the following groups: methyl, 
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and 
isomers thereof, for example isopropyl, isobutyl, sec.-butyl, tert.-butyl, 
isopentyl etc. Halogenoalkyl is a monohalogenated to perhalogenated alkyl 
substituent, for example CHCl.sub.2, CHF.sub.2, CH.sub.2 Cl, CCl.sub.3, 
CH.sub.2 F, --CH.sub.2 CH.sub.2 Cl, CHBr.sub.2 etc. Here and in the 
following text, halogen is to be understood as meaning fluorine, chlorine, 
bromine or iodine, preferably fluorine, chlorine or bromine and especially 
fluorine and chlorine. Naphthyl is .alpha.-naphthyl or .beta.-naphthyl, 
preferably .alpha.-naphthyl. Alkenyl is, for example, 1-propenyl, allyl, 
1-butenyl, 2-butenyl or 3-butenyl, and alkynyl is, for example, 1-propynyl 
or propargyl. Aryl is, for example, naphthyl, particularly phenyl, and 
aralkyl is a lower alkyl radical which is substituted by an aromatic 
group, for example benzyl or phenylethyl. Depending on the number of 
carbon atoms, cycloalkyl is, for example, cyclopropyl, cyclobutyl, 
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc. 
The present invention relates both to the free organic molecules of the 
formula I and to acid addition salts, quaternary azolium salts and metal 
complexes thereof. The free molecules are preferred. Examples of 
salt-forming acids are inorganic acids: a hydrogen halide acid, such as 
hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, 
and sulfuric acid, phosphoric acid, phosphorous acid and nitric acid, and 
organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic 
acid, propionic acid, glycollic acid, thiocyanic acid, lactic acid, 
succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, 
formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic 
acid, trifluoromethanesulfonic acid, salicylic acid, p-aminosalicylic 
acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid. 
Metal complexes of the formula I consist of the parent organic molecule and 
an inorganic or organic metal salt, for example the halides, nitrates, 
sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, 
propionates, tartrates, sulfonates, salicylates, benzoates etc., of the 
elements of the third and fourth main groups, such as aluminium, tin or 
lead, and of the first to eighth subgroups, such as chromium, manganese, 
iron, cobalt, nickel, copper, zinc, silver, mercury etc. The subgroup 
elements of the 4th period are preferred. The metals can be present in 
these complexes in the various valencies appropriate to them. The metal 
complexes of the formula I can exist in a mononuclear or polynuclear form, 
i.e. they can contain one or more organic molecular moieties as ligands. 
Complexes containing the metals copper, zinc, manganese and tin are 
preferred. 
1-Hydroxyethylazole derivatives are known as plant growth-regulators and 
fungicides from the literature, for example from European Patent 
Application No. 40,345. 
The compounds, according to the invention, of the formula I are oils, 
resins or, mainly, solids which are stable at room temperature and which 
are distinguished by very valuable microbicidal and growth-regulating 
properties. They can be employed in a preventive or curative manner in the 
agricultural sector or related fields, for controlling microorganisms 
which damage plants and for regulating plant growth, the triazolylmethyl 
derivatives within the scope of the formula I being preferred. The active 
substances, according to the invention, of the formula I are distinguished 
by being very well tolerated by crop plants. 
Compounds which are preferred by virtue of their pronounced 
growth-regulating and/or microbicidal action are those in which Az is 
imidazolyl or 1,2,4-triazolyl, R.sup.1 is hydrogen, C.sub.1 -C.sub.6 
-alkyl which is unsubstituted or substituted by halogen or cyano, or 
C.sub.1 -C.sub.3 -phenylalkyl which is unsubstituted or substituted by 
halogen, C.sub.1 -C.sub.3 -alkyl, C.sub.1 -C.sub.3 -alkoxy, C.sub.1 
-C.sub.3 -halogenoalkyl, nitro, cyano, carboxyl or C.sub.1 -C.sub.6 
-alkoxycarbonyl, R.sup.2 is C.sub.1 -C.sub.10 -alkyl which is 
unsubstituted or substituted by C.sub.1 -C.sub.3 -alkoxy, phenyl or 
C.sub.1 -C.sub.3 -phenylalkyl, it being possible for the phenyl nuclei in 
turn to be unsubstituted or substituted by halogen, C.sub.1 -C.sub.3 
-alkyl, C.sub.1 -C.sub.3 -alkoxy, C.sub.1 -C.sub.3 -halogenoalkyl, nitro, 
cyano, carboxyl or C.sub.1 -C.sub.6 -alkoxycarbonyl, R.sup.3 is hydrogen, 
C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkylcarbonyl or C.sub.1 
-C.sub.3 -phenylalkyl which is unsubstituted or substituted by halogen, 
C.sub.1 -C.sub.3 -alkoxy, C.sub.1 -C.sub.3 -alkyl, C.sub.1 -C.sub.3 
-halogenoalkyl, cyano, carboxyl or C.sub.1 -C.sub.6 -alkoxycarbonyl, 
R.sup.5 is an unsubstituted or monosubstituted or polysubstituted radical 
selected from the series comprising C.sub.1 -C.sub.8 -alkyl, C.sub.3 
-C.sub.8 -cycloalkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 
-alkynyl, phenyl, naphthyl, biphenyl, benzylphenyl, benzyloxyphenyl, 
phenoxyphenyl and aralkyl, the substituents being selected from the series 
comprising halogen, cyano, C.sub.1 -C.sub.3 -alkyl, C.sub.1 -C.sub.5 
-alkoxy, C.sub.1 -C.sub.5 -halogenoalkyl, C.sub.1 -C.sub.3 -alkylthio, 
C.sub.1 -C.sub.3 -halogenoalkyl, C.sub.1 -C.sub.3 -halogenoalkylthio, 
nitro and/or thiocyano, and X is oxygen or sulfur. 
Subgroups which may be mentioned as enjoying a further preference are those 
comprising compounds of the formula I in which (a) Az is 1,2,4-triazolyl 
or (b) R.sup.2 is C.sub.1 -C.sub.6 -alkyl or benzyl which is unsubstituted 
or substituted by halogen or (c) R.sup.1 and R.sup.3 are hydrogen or 
C.sub.1 -C.sub.4 -alkyl or (d) R.sup.5 is phenyl which is substituted by 
halogen or (e) X is oxygen. 
Within the subgroup (b), preferred compounds are those in which R.sup.2 is 
tert.-butyl or i-propyl. 
Within subgroup (d), preferred compounds are those in which R.sup.5 is 
phenyl which is substituted in the 4-position by halogen. 
Compounds which should be mentioned as a particularly preferred subgroup of 
compounds of the formula I are those in which Az is 1,2,4-triazolyl, 
R.sub.1 and R.sub.3 are hydrogen or C.sub.1 -C.sub.4 -alkyl, R.sub.2 is 
tert.-butyl or i-propyl, R.sub.5 is phenyl which is substituted in the 
4-position by halogen and X is oxygen. 
The following are examples of preferred individual compounds: 
1-(4-fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-(1H-1,2,4-triazol-1 
-yl)-propane, 
1-(4-fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-methyl-3-(1H-1,2,4- 
triazol-1-yl)-propane, 
1-(4-chlorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-(1H-1,2,4-triazol-1 
-yl)-propane, 
1-(4-chlorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-methyl-3-(1H-1,2,4- 
triazol-1-yl)-propane and 
1-(4-methylphenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-methyl-3-(1H-1,2,4- 
triazol-1-yl)-propane. 
The compounds of the formula I are prepared by processes known per se. 
Thus the compounds of the formula I are obtained by reacting an 
azolylmethyloxirane of the formula II 
##STR3## 
in which R.sup.1, R.sup.2 and Az are as defined under formula I, in the 
presence of a base and in an inert solvent, with an alcohol or thioalcohol 
of the formula III 
EQU H--X--R.sup.5 (III) 
in which X and R.sup.5 are as defined under formula I, and, if desired, by 
etherifying or esterifying the resulting product of the formula Ia 
##STR4## 
by reacting it with an etherifying or esterifying agent of the formula IV 
EQU Y--R.sup.3 (IV) 
in which R.sup.3 is as defined under formula I and Y is a halogen atom or 
an organic or inorganic acid radical. 
The reactions (II with III) is advantageously carried out in the presence 
of catalytic amounts of bases as condensation agents. Suitable 
condensation agents are organic and inorganic bases, for example tertiary 
amines, such as trialkylamines (trimethylamine, triethylamine, 
tripropylamine etc.), pyridine and pyridine bases 
(4-dimethylaminopyridine, 4-pyrrolidylaminopyridine etc.), oxides, 
hydrides and hydroxides, carbonates and bicarbonates of alkali and 
alkaline earth metals (CaO, BaO, NaOH, LiOH, CaH.sub.2, KOH, NaH, 
Ca(OH).sub.2, KHCO.sub.3, NaHCO.sub.3, Ca(HCO.sub.3).sub.2, K.sub.2 
CO.sub.3 and Na.sub.2 CO.sub.3), and alkali metal acetates, such as 
CH.sub.3 COONa or CH.sub.3 COOK. In addition, alkali metal alcoholates, 
such as C.sub.2 H.sub.5 ONa, n--C.sub.3 H.sub.7 ONa, (CH.sub.3).sub.3 
CO--K etc., are also suitable. 
The reaction (II with III) is preferably carried out in an organic solvent 
which is relatively polar, but inert towards the reaction, for example 
N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 
acetonitrile, benzonitrile, ethylene glycol dimethyl ether, diethylene 
glycol dimethyl ehter, triethylene glycol dimethyl ether, dioxane, 
tetrahydrofuran and others. Reactions of this type can, however, also be 
carried out in combination with other solvents which are inert towards the 
reaction, for example benzene, toluene, xylene, hexane, petroleum ether, 
chlorobenzene, nitrobenzene and others. The reaction temperatures are 
within a temperature range from 20.degree. C. to 250.degree. C., 
preferably 80.degree. C. to 180.degree. C. 
The optional conversion of the compounds of the subformula Ia into the 
compounds of the formula I in which R.sup.3 has a definition other than 
hydrogen is advantageously carried out in an inert organic solvent. 
Suitable solvents are aprotic solvents, such as N,N-dimethylformamide, 
N,N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, benzonitrile, 
N-methylpyrrolidone, N-methylpiperidone, benzene, toluene, xylene, hexane, 
cyclohexane, chlorobenzene, nitrobenzene and others. 
In the event that the --O--R.sup.3 group is an ether group, Y is usually 
halogen, such as chlorine, bromine and iodine, or acid radicals derived 
from strong acids, such as sulfuric acid, phosphoric acid, sulfonic acids, 
preferably halogenoalkylsulfonic acids, or halogenoalkanecarboxylic acids, 
such as trifluoroacetic acid. Typical representatives of such acid 
derivatives are dimethyl sulfate, diethyl sulfate and methyl 
trifluoromethanesulfonate. In the event that the --O--R.sup.3 group is an 
ester group, Y is generally halogen, such as chlorine or bromine, or acid 
radicals of acids which can form an anhydride with the acyl radical which 
is transferred. This is preferably an anhydride containing the same acid. 
Consequently, the reagent Y--R.sup.3 is then, for example, acetic 
anhydride, propionic anhydride, benzoic anhydride, benzenesulfonic 
anhydride or trifluoromethanesulfonic anhydride. 
The etherification or esterification of the compounds of the subformula Ia 
is advantageously effected in the presence of bases, such as alcoholates, 
hydroxides, hydrides, carbonates or bicarbonates of alkali or alkaline 
earth metals. The reaction temperatures are 20.degree.-150.degree. C., 
preferably 60.degree.-120.degree. C. 
The compounds of the formula I are obtained in the form of mixtures of 
diastereomers. The invention relates to all the diastereomeric forms of 
the active substances of the formula I and to mixtures thereof. It 
therefore embraces both the pure diastereomers and the individual optical 
isomers of the enantiomer pairs which are embraced. 
The alcohols or thioalcohols of the formula III and also the etherifying 
and esterifying agents of the formula IV are known or are prepared by 
methods known per se. 
The oxiranes of the formula II are novel; they are intermediates which have 
been specially developed for the preparation of the valuable active 
substances of the formula I. Because of their structure, they can be 
converted in a simple manner into the compounds of the formula I. The 
compounds of the formula II thus represent a further aspect of the present 
invention. 
The oxiranes of the formula II can be prepared by reacting the parent 
ketones of the formula V 
##STR5## 
in which R.sup.1, R.sup.2 and Az are as defined under formula I, in the 
presence of strong bases, such as alkali and alkaline earth metal 
alcoholates, alkali metal hydroxides or alkali or alkaline earth metal 
hydrides, in dimethyl sulfoxide or one of the other solvents described for 
the reaction of II with III, with dimethylsulfonium methylide, 
dimethyloxosulfonium methylide or the corresponding salts, such as 
trimethylsulfonium iodide or trimethyloxosulfonium iodide. Under suitable 
circumstances, it is also possible to effect the production of the 
sulfonium ylide or the reaction of the sulfonium salt with the base by the 
phase transfer process. The following could be used as suitable phase 
transfer catalysts: quaternary ammonium salts, such as 
trialkylphenylalkylammonium salts or tetraalkylammonium salts, quaternary 
phosphonium salts, such as tetraalkylphosphonium salts, or crown ethers, 
such as 15-crown-5 or 18-crown-6. In this reaction, the sulfonium ylide is 
formed in situ and reacts directly with the ketone of the formula V to 
give the oxirane of the formula II. The reaction is carried out at 
temperatures from 0.degree. to 120.degree. C. 
Analogous reactions are known from the literature; cf. JACS, 87, 1353 
(1965). In principle, the reaction can be carried out analogously to the 
reactions described therein. 
Ketones of the formula V can be prepared from the .alpha.-halogenoketones, 
which are known per se, of the formula VI 
##STR6## 
in which R.sup.1 and R.sup.2 are as defined under formula I and Hal is 
chlorine or bromine, by reacting these compounds, in the presence of a 
base, with azoles of the formula VII 
EQU H--Az (VII) 
in which Az is as defined under formula I. 
The ketones of the formula V can also be obtained by reacting an 
azolylmethyl ketone of the formula VIII 
##STR7## 
in the presence of a base with a compound of the formula IX 
EQU Z--R.sup.1 (IX) 
in which R.sup.1 is as defined under formula I and Z is a halogen atom or 
an organic or inorganic acid radical. 
The preparation of the ketones of the formula V is effected in the 
conventional inert solvents and, if desired, at an elevated temperature. 
The compounds of the formulae VI, VII, VIII and IX are known and are in 
some cases commercially available or can be prepared by known methods. 
The intermediates of the formula V, which have been developed specially for 
the synthesis of the compounds of the formula I, form a further subject of 
the present invention. 
In principle, unless expressly specified in an individual case, one or more 
solvents or diluents, inert to the reaction, can be present when any of 
the starting materials, intermediates and end products mentioned herein 
are prepared. Suitable examples are aliphatic and aromatic hydrocarbons, 
such as benzene, toluene, xylenes or petroleum ether; halogenated 
hydrocarbons, such as chlorobenzene, methylene chloride, ethylene 
chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ethers 
and ether-like compounds, such as dialkyl ethers (diethyl ether, 
diisopropyl ether, tert.-butyl methyl ether etc.), anisole, dioxane or 
tetrahydrofuran; nitriles, such as acetonitrile or propionitrile; 
N,N-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; 
ketones, such as acetone, diethyl ketone or methyl ethyl ketone, and 
mixtures of such solvents with one another. In some cases it can also be 
advantageous if the reaction is, or partial stages of a reaction are, 
carried out under an atmosphere of a protective gas and/or absolute 
solvents. Suitable protective gases are inert gases, such as nitrogen, 
helium or argon, or in certain cases also carbon dioxide. 
The process of preparation described, including all its partial stages, is 
an important part of the present invention. 
It has now been found, surprisingly, that the new active substances of the 
formula I or compositions containing these active substances are 
especially distinguished by the fact that they intervene in a controlled 
manner in the metabolism of plants. This controlled intervention in the 
physiological processes of plant development makes it possible to use the 
active substances of the formula I for various purposes, in particular for 
purposes associated with increasing the yield of useful plants, 
facilitating harvesting and saving labour in the course of measures taken 
for crops of plants. 
According to experience hitherto, it is a fact relevant to the mode of 
action of plant growth regulators that an active substance can exert one 
or more different effects on plants. The effects of the substances depend 
essentially on the time of the application, relative to the stage of 
development of the seed or of the plant, and on the quantities of active 
substances applied to the plants or their habitat, and on the mode of 
application. In every case growth regulators are intended to have a 
favourable effect on the crop plants in the manner desired. 
Plant growth-regulating substances can be employed, for example, for 
inhibiting vegetative plant growth. Inhibition of growth in this way is of 
economic interest, inter alia, in the case of grasses, since it makes it 
possible, for example, to reduce the frequency of cutting the grass in 
ornamental gardens, parks and sports grounds or on road verges. Another 
important aspect is inhibition of the growth of herbaceous and woody 
plants on road verges and in the neighbourhood of overhead transmission 
lines or very generally in areas in which considerable ground vegetation 
is undesirable. 
The use of growth regulators for inhibiting the growth in height of cereals 
is also important, since the risk of the plants bending over ("lodging") 
before the harvest is reduced or completely eliminated by shortening the 
stems. In addition, growth regulators can cause a strengthening of the 
stems of cereals, which also counteracts lodging. 
In the case of many crop plants, inhibition of vegetative growth permits 
the crop to be cultivated more densely, so that an increased yield based 
on the area of soil can be achieved. 
A further mechanism for increasing yields by means of growth inhibitors 
depends on the fact that the nutrients benefit the formation of flowers 
and fruit to a greater extent, while vegetative growth is restricted. 
Growth regulators frequently also make it possible to achieve promotion of 
vegetative growth. This is of great benefit when the vegetative parts of 
the plants are harvested. Promoting vegetative growth can, however, also 
result at the same time in promotion of generative growth so that, for 
example, more fruit or larger fruit is formed. 
In some cases increases in yield can also be achieved by intervention in 
the plant metabolism, for example by increasing the efficiency of 
photosynthesis, without changes in vegetative growth manifesting 
themselves. Growth regulators can also cause a change in the composition 
of plants, so as to produce a better quality of harvested products. Thus 
it is possible, for example, to increase the content of sugar in sugar 
beet, sugar cane, pineapples and citrus fruits or to raise the protein 
content in soya or cereals. 
The development of parthenocarpic fruit can also take place under the 
influence of growth regulators. It is also possible to affect the sex of 
the flowers. 
Growth regulators also make it possible to exert a favourable influence on 
the production or outflow of secondary plant substances. Stimulating the 
flow of latex in rubber trees may be mentioned as an example. 
Lateral branching can also be increased by breaking the apical dominance by 
chemical means as the result of using growth regulators during plant 
growth. This is of interest, for example, in the propagation of plants by 
cuttings. However, it is also possible to inhibit the growth of side 
shoots, for example in order to prevent the formation of side shoots in 
tobacco plants after the latter have been decapitated, and thus to promote 
leaf growth. 
The premature falling of fruit can be prevented by using growth regulators. 
However, it is also possible to promote the fall of fruit to a certain 
extent--for example in the case of table fruit--in the sense of thinning 
out by chemical means. Growth regulators can also be used to reduce the 
force required to detach the fruit of crop plants at the time of 
harvesting, so as to enable the plants to be harvested mechanically or to 
facilitate manual harvesting. 
Growth regulators also make it possible to accelerate or to retard ripening 
of the harvested crop before or after harvesting. This is particularly 
advantageous, because it makes it possible to produce optimum adjustment 
to the demands of the market. Furthermore, growth regulators can improve 
the colouration of fruit in some cases. In addition, it is also possible 
to concentrate ripening to a particular point in time by means of growth 
regulators. This provides the conditions necessary to enable complete 
mechanical or manual harvesting of, for example, tobacco, tomatoes or 
coffee, to be carried out in only a single process. 
The use of growth regulators also makes it possible to affect the dormant 
period of seeding or budding in plants, i.e. the endogenous annual rhythm, 
so that the plants, for example pineapples or ornamental plants in 
nurseries, germinate, sprout or flower at a time at which they normally 
show no readiness to do so. 
Growth regulators also make it possible to retard the sprouting of buds or 
the germination of seeds, for example in order to avoid damage caused by 
late frosts in regions subject to frost. On the other hand, it is possible 
to stimulate the growth of roots and/or the formation of shoots, so that 
growth can be limited to a shorter period of time. 
Growth regulators can also render crop plants halophilic. This provides the 
conditions necessary to enable the cultivation of plants to be carried out 
on soils containing salt. 
Resistance to frost and drought can also be induced in plants by means of 
growth regulators. 
The aging (senescence) of plants or parts of plants can be inhibited or 
retarded under the influence of growth regulators. An effect of this type 
can be of great economic interest, because it is possible to improve or 
prolong the capacity of treated parts of plants or whole plants, such as 
fruit, berries, vegetables, lettuce or ornamental plants, to be stored 
after harvesting. It is also possible to achieve a considerable increase 
in yield via prolonging the phase of photosynthetic activity by treating 
crop plants. 
A further important field of application for growth inhibitors is their use 
for inhibiting excessive growth in tropical soil-covering plants, cover 
crops as they are called. In tropical and subtropical monocultures, for 
example in palm plantations, cotton fields, maize fields etc., 
soil-covering plants, especially species of leguminosae, are frequently 
planted alongside the actual crop plants and serve to maintain or improve 
the quality of the soil (prevention of desiccation and provision of 
nitrogen) and to prevent erosion (denudation by wind and water). By 
applying the active substances according to the invention, it is now 
possible to control the growth of these cover crops and thus to keep the 
height to which these soil-covering plants grow at a low level, so as to 
ensure that the crop plants grow in a healthy manner and the soil is 
maintained in a favourable condition. 
It has also been found, surprisingly, that the active substances of the 
formula I or corresponding compositions not only have advantageous 
growth-regulating properties, but also have a microbicidal spectrum which 
is very advantageous for practical requirements. A further field of use of 
compounds of the formula I is, therefore, the control of harmful 
microorganisms, especially phytopathogenic fungi. Thus the compounds of 
the formula I possess a curative, preventive and systemic action for the 
protection of plants, in particular crop plants, which is very 
advantageous for practical requirements, without affecting these plants 
adversely. 
The active substances of the formula I make it possible to inhibit or 
destroy the microorganisms which occur on plants or parts of plants 
(fruit, flowers, foliage, stalks, tubers or roots) of various useful 
crops, and parts of the plants which grow later also remain protected from 
microorganisms of this type. 
The active substances are effective against phytopathgenic fungi belonging 
to the following classes: Ascomycetes (for example Venturia, Podosphaera, 
Erysiphe, Monilinia and Uncinula); Basidiomycetes (for example the genera 
Hemileia, Rhizoctonia and Puccinia); and Fungi imperfecti (for example 
Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and 
Alternaria). In addition, the compounds of the formula I have a systemic 
action. They can also be employed as dressing agents for treating seed 
(fruit, tubers or grain) and plant cuttings to protect them against fungal 
infections and can also be employed against phytopathogenic fungi which 
occur in the soil. The active substances according to the invention are 
distinguished by being particularly well tolerated by plants. 
The invention also relates, therefore, to microbicidal compositions and to 
the use of the compounds of the formula I for controlling phytopathogenic 
microorganisms, in particular fungi which damage plants, and to the 
prophylactic prevention of attack on plants. 
In addition, the present invention also includes the preparation of 
agrochemical compositions, which comprises mixing the active substance 
intimately with one or more substances or groups of substances described 
herein. It also includes a process for treating plants which is 
distinguished by the application of the compounds of the formula I and/or 
of the novel compositions. 
Within the scope of this invention, the following species of plants rank as 
examples of target crops for the fields of indication disclosed herein: 
cereals: (wheat, barley, rye, oats, rice, sorghum and related crops); 
beet: (sugar beet and fodder beet); pome, stone and soft fruit: (apples, 
pears, plums, peaches, almonds, cherries, strawberries, raspberries and 
blackberries); leguminous plants: beans, lentils, peas and soya); oil 
crops: (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil 
plants, cocoa and ground nuts); cucurbitaceae: (pumpkins, cucumbers and 
melons); fibre plants: (cotton, flax, hemp and jute); citrus fruit: 
(oranges, lemons, grapefruit and mandarins); varieties of vegetables: 
(spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, 
potatoes and capsicum); lauraceae: (avocado, cinnamon and camphor); or 
plants such as maize, tobacco, nuts, coffee, sugar cane, tea, grapes, hops 
and banana and natural rubber plants. Within the scope of the present 
invention, however, plants are also any species of other green flora, 
either ornamental plants (composites), grasslands, embankments or general 
low cover crops which counteract erosion or desiccation of the soil, or 
cover crops such as are desirable in plantations of trees and shrubs 
(fruit plantations, hop fields, maize fields, vineyards etc.). 
Active substances of the formula I are customarily used in the form of 
compositions and can be applied to the area or plant to be treated 
together with further active substances, simultaneously or successively. 
These further active substances can be either fertilisers, trace element 
donors or other preparations which affect plant growth. They can, however, 
also be selective herbicides, insecticides, fungicides, bactericides, 
nematocides, molluscicides or mixtures of several of these preparations, 
together with, if appropriate, further carriers, surfactants or other 
application-promoting additives which are conventionally used in the art 
of formulation. 
Suitable carriers and additives can be solid or liquid and correspond to 
the substances which are serviceable in the art of formulation, for 
example natural or regenerated mineral substances, solvents, dispersing 
agents, wetting agents, tackifiers, thickeners, binders or fertilisers. 
A preferred process for applying an active substance of the formula I or an 
agrochemical composition containing at least one of these active 
substances is application to the foliage (leaf application). In this case 
the number of applications depends on the intensity of attack by the 
corresponding pathogen (variety of fungus) or the mode of influencing 
growth. The active substances of the formula I can, however, also reach 
the plants via the soil through the roots (systemic action), by the 
habitat of the plants being impregnated with a liquid preparation or the 
substances being introduced into the soil in a solid form, for example in 
the form of granules (soil application). The compounds of the formula I 
can, however, also be applied to seed grains (coating), either by 
impregnating the grains with a liquid preparation of the active compound 
or by coating them with a solid preparation. In addition, further modes of 
application are possible in special cases, for example controlled 
treatment of the plant stalks or the buds. 
The compounds of the formula I are employed in an unaltered form or, 
preferably, together with the adjuncts which are conventional in the art 
of formulation, and are, therefore, processed in a known manner to give, 
for example, emulsion concentrates, brushable pastes, solutions which can 
be atomised or diluted without further treatment, dilute emulsions, 
wettable powders, soluble powders, dusts, granules and encapsulations in, 
for example, polymeric substances. The application processes, such as 
atomising, nebulising, dusting, sprinkling, brushing or watering, are 
selected to suit the intended aims and the given circumstances, as is also 
the type of composition. Advantageous application rates are, in general, 
10 g to 5 kg of active substance (AS) per hectare; preferably 100 g to 2 
kg of AS per hectare and particularly 200 g to 600 g of AS per hectare. 
The formulations, that is to say the compositions, preparations or 
combinations containing the active substance of the formula I and, if 
appropriate, a solid or liquid adjuvant, are prepared in a known manner, 
for example by intimately mixing and/or grinding the active substances 
with diluents, for example solvents, solid carriers and, if appropriate, 
surface-active compounds (surfactants). 
The following can be suitable as solvents: aromatic hydrocarbons, 
preferably the fractions from C.sub.8 to C.sub.12, for example mixed 
xylenes or substituted naphthalenes, phthalic acid esters, such as dibutyl 
or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or 
paraffins, alcohols and glycols and also ethers and esters thereof, such 
as ethanol, ethylene glycol or ethylene glycol monomethyl or monoethyl 
ether, ketones, such as cyclohexanone, strongly polar solvents, such as 
N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and 
vegetable oil which can be epoxidised, such as epoxidised coconut oil or 
soya oil; or water. 
The solid carriers used, for example for dusts and dispersible powders, 
are, as a rule, natural ground minerals, such as calcite, talc, kaolin, 
montmorillonite or attapulgite. It is also possible to add highly disperse 
silica or highly disperse absorbent polymers in order to improve the 
physical properties. Suitable particulate, adsorptive granular carriers 
are porous types, for example pumice stone, broken brick, sepiolite or 
bentonite, while examples of suitable non-sorptive carriers are calcite or 
sand. In addition, it is possible to use a large number of pregranulated 
materials of an inorganic or organic nature, such as, in particular, 
dolomite or comminuted plant residues. 
Depending on the nature of the active substance of the formula I to be 
formulated, suitable surface-active compounds are nonionic, cationic 
and/or anionic surfactants having good emulsifying, dispersing and wetting 
properties. Surfactants are also to be understood as meaning mixtures of 
surfactants. 
Suitable anionic surfactants can be so-called water-soluble soaps as well 
as water-soluble synthetic surface-active compounds. 
Suitable soaps are the alkali metal salts, alkaline earth metal salts or 
substituted or unsubstituted ammonium salts of higher fatty acids 
(C.sub.10 -C.sub.22), for example the Na or K salts of oleic or stearic 
acid, or of natural mixtures of fatty acids, which can be obtained, for 
example, from coconut oil or tallow oil. Furthermore, mention should also 
be made of the salts of fatty acid methyl taurides. 
More frequently, however, so-called synthetic surfactants are used, in 
particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole 
derivatives or alkylarylsulfonates. 
The fatty sulfonates or sulfates are, as a rule, in the form of alkali 
metal salts, alkaline earth metal salts or substituted or unsubstituted 
ammonium salts, and contain an alkyl radical having 8 to 22 C atoms, in 
which connection alkyl also includes the alkyl moiety of acyl radicals, 
for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric 
acid ester or of a mixture of fatty alcohol sulfates prepared from natural 
fatty acids. These products also include the salts of the sulfuric acid 
esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The 
sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid 
groups and a fatty acid radical having 8-22 C atoms. Examples of 
alkylarylsulfonates are the Na, Ca or triethanolamine salts of 
dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a 
naphthalenesulfonic acid/formaldehyde condensation product. 
Furthermore, corresponding phosphates, for example salts of the phosphoric 
acid ester of a p-nonylphenol/(4-14)-ethylene oxide adduct, and 
phospholipids are also suitable. 
Suitable nonionic surfactants are primarily polyglycol ether derivatives of 
aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids 
and alkylphenols, and these derivatives can contain 3 to 30 glycol ether 
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 
6 to 18 carbon atoms in the alkyl radical of the alkylphenols. 
Further suitable nonionic surfactants are the water-soluble adducts, 
containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene 
glycol ether groups, of polyethylene oxide with polypropylene glycol, 
ethylenediaminopolypropylene glycol and an alkylpolypropylene glycol 
having 1 to 10 carbon atoms in the alkyl chain. The said compounds usually 
contain 1 to 5 ethylene glycol units per unit of propylene glycol. 
Examples of nonionic surfactants which may be mentioned are 
nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, 
polypropylene/polyethylene oxide adducts, 
tributylphenoxypolyethoxyethanol, polyethylene glycol and 
octylphenoxypolyethoxyethanol. 
Furthermore, fatty acid esters of polyoxyethylenesorbitan, such as 
polyoxyethylenesorbitan trioleate, are also suitable. 
The cationic surfactants are, in particular, quaternary ammonium salts 
which contain, as N-substituents, at least one alkyl radical having 8 to 
22 C atoms and, as further substituents, lower alkyl radicals which can be 
halogenated, benzyl radicals or lower hydroxyalkyl radicals. The salts are 
preferably in the form of halides, methylsulfates or ethylsulfates, for 
example stearyltrimethylammonium chloride or 
benzyl-di-(2-chloroethyl)-ethylammonium bromide. 
The surfactants which are customary in the art of formulation are 
described, inter alia, in the following publications: "McCutcheon's 
Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., 
1981; H. Stache, "Tensid-Taschenbuch" ("Surfactants Handbook"), 2nd 
edition, C. Hanser Verlag, Munich, Vienna, 1981; M. and J. Ash, 
"Encyclopedia of Surfactants", vol. I-III, Chemical Publishing Co., New 
York, 1980-1981. 
The pesticidal preparations contain, as a rule, 0.1 to 99%, in particular 
0.1 to 95%, of an active substance of the formula I, 1 to 99% of a solid 
or liquid adjuvant and 0 to 25%, in particular 0.1 to 25%, of a 
surfactant. 
In particular, preferred formulations have the following compositions: 
(%=percent by weight) 
______________________________________ 
Solutions 
Active substance: 
5 to 95%, preferably 10 to 80% 
Solvent: 95 to 5%, preferably 90 to 20% 
Surface-active agent: 
1 to 30%, preferably 2 to 20%. 
Emulsifiable concentrates 
Active substance: 
10 to 50%, preferably 10 to 40% 
Surface-active agent: 
5 to 30%, preferably 10 to 20% 
Liquid carrier: 
20 to 95%, preferably 40 to 80%. 
Dusts 
Active substance: 
0.5 to 10%, 
preferably 2 to 8% 
Solid carrier: 99.5 to 90%, 
preferably 98 to 92%. 
Suspension concentrates 
Active substance: 
5 to 75%, preferably 10 to 50% 
Water: 94 to 25%, preferably 90 to 30% 
Surface-active agent: 
1 to 40%, preferably 2 to 30%. 
Wettable powders 
Active substance: 
5 to 90%, preferably 10 to 80% 
and 
particularly 20 to 60% 
Surface-active agent: 
0.5 to 20%, 
preferably 1 to 15% 
Solid carrier: 5 to 90%, preferably 30 to 70%. 
Granules 
Active substance: 
0.5 to 30%, 
preferably 3 to 15% 
Solid carrier: 99.5 to 70%, 
preferably 97 to 85%. 
______________________________________ 
Whereas concentrated compositions are more likely to be preferred as 
commercial products, the final consumer generally uses dilute 
compositions. The applications can be diluted down to 0.001% of active 
substance. 
The compositions can also contain further additives, such as stabilisers, 
anti-foaming agents, viscosity regulators, binders, tackifiers and 
fertilisers or other active substances for achieving special effects. 
Agrochemical compositions of this type are a part of the present invention. 
The examples which follow serve to illustrate the invention in greater 
detail, without limiting the latter. Temperatures are quoted in degrees 
centigrade.

PREATION EXAMPLES 
Example 1 
##STR8## 
1-(4-Fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-(1H-1,2,4-triazol-1 
- 
yl)-propane (Compound 5.6) 
(a) 1-Fluoro-1-(1H-1,2,4-triazol-1-yl)-3,3-dimethyl-2-butanone: 
63.0 g of 1-bromo-1-fluoro-3,3-dimethyl-2-butanone are added slowly to a 
mixture of 23.0 g of 1,2,4-triazole and 44.2 g of potassium carbonate in 
280 ml of ethyl methyl ketone. The reaction mixture is stirred for 18 
hours at 45.degree.-50.degree. C. and is then filtered and evaporated. The 
residue is taken up in methylene chloride and washed with water. Drying 
and evaporating the organic phase gives 50.0 g of 
1-fluoro-1-(1H-1,2,4-triazol-1-yl)-3,3-dimethyl-2-butanone, melting point 
54.degree.-55.degree. C. 
(b) 2-tert.-Butyl-2-[(1H-1,2,4-triazol-1-yl)-fluoromethyl]oxirane: 
A mixture of 20 g of 
1-fluoro-1-(1H-1,2,4-triazol-1-yl)-3,3-dimethyl-2-butanone, 13.5 g of 
potassium tertiary butylate, 24.0 g of trimethylsulfoxonium iodide, 80 ml 
of tetrahydrofuran and 20 ml of dimethyl sulfoxide is stirred at 
60.degree. C. for 6 hours. The reaction mixture is then taken up in ice 
water and extracted with ethyl acetate. The combined organic phases are 
washed with water and saturated sodium chloride solution, dried over 
sodium sulfate and evaporated. Crystallisation from petroleum ether gives 
6.9 g of 2-tert.-butyl-2-[(1H-1,2,4-triazol-1-yl)-fluoromethyl]-oxirane, 
melting point 72.degree.-74.degree. C. 
(c) 3.0 g of 2-tert.-butyl-2-[(1H-1,2,4-triazol-1-yl)fluoromethyl]-oxirane, 
1.7 g of 4-fluorophenol and 0.3 g of potassium p-fluorophenate in 10 ml of 
diethylene glycol dimethyl ether are stirred at 140.degree. C. for 5 
hours. After cooling, the mixture is taken up in ice water and extracted 
with ethyl acetate. The combined organic phases are washed with water, 
saturated sodium chloride solution and 2N sodium hydroxide solution and 
again with saturated sodium chloride solution, dried over sodium sulfate 
and evaporated. Crystallisation from a 1:4 ether/hexane mixture gives 2.3 
g of 
1-(4-fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-(1H-1,2,4-triazol-1 
-yl)-propane, melting point 89.degree.-90.degree. C. 
EXAMPLE 2 
##STR9## 
1-(4-Fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-methyl-3-(1H-1,2,4- 
t 
riazol-1-yl)-propane (Compound 5.7). 
(a) 2-Fluoro-2-(1H-1,2,4-triazol-1-yl)-4,4-dimethyl-3-pentanone: 
20.0 g of 1-fluoro-1-(1H-1,2,4-triazol-1-yl)-3,3-dimethyl-2-butanone are 
added dropwise to a solution of 13.5 g of potassium tertiary butylate in 
100 ml of tetrahydrofuran. After the mixture has been stirred for 0.5 
hour, 15.6 g of methyl iodide are added dropwise and the mixture is 
stirred for 18 hours at 60.degree. C. After cooling, the reaction mixture 
is taken up in ice water and extracted with ethyl acetate. The combined 
organic phases are washed with water and saturated sodium chloride 
solution, dried over sodium sulfate and evaporated. Distillation of the 
oily residue gives 14.0 g of 
2-fluoro-2-(1H-1,2,4-triazol-1-yl)-4,4-dimethyl-3-pentanone, boiling point 
48.degree.-50.degree. C./0.013 mbar. 
(b) 2-tert.-Butyl-2-[1-fluoro-1-(1H-1,2,4-triazol-1-yl)ethyl]-oxirane: 
12.0 g of 2-fluoro-2-(1H-1,2,4-triazol-1-yl)-4,4-dimethyl-3-pentanone are 
added dropwise to a mixture of 13.2 g of trimethylsulfoxonium iodide, 7.3 
g of potassium tertiary butylate, 20 ml of dimethyl sulfoxide and 80 ml of 
tetrahydrofuran, and the reaction mixture is stirred for 18 hours at 
80.degree. C. After cooling, the mixture is taken up in ice water and 
extracted with ethyl acetate. The combined organic phases are washed with 
water and saturated sodium chloride solution, dried over sodium sulfate 
and evaporated. Distillation of the oily residue gives 6 g 
2-tert.-butyl-2-[1-fluoro-1-(1H-1,2,4-triazol-1-yl)-ethyl]-oxirane, 
boiling point 60.degree.-61.degree. C./0.013 mbar. 
(c) 6.0 g of 
2-tert.-butyl-2-[1-fluoro-1-(1H-1,2,4-triazol-1-yl)-ethyl]-oxirane, 3.1 g 
of 4-fluorophenol and 0.4 g of potassium p-fluorophenate in 20 ml of 
diethylene glycol dimethyl ether are heated at 140.degree. C. for 6 hours. 
After cooling, the reaction mixture is taken up in ice water and extracted 
with ethyl acetate. The combined organic phases are washed successively 
with water, saturated sodium chloride solution, 2N sodium hydroxide 
solution, water and saturated sodium chloride solution, dried over sodium 
sulfate and evaporated. Chromatography over silica gel using a 4:1 
hexane/ethyl acetate mixture gives 1.6 g of 
1-(4-fluorophenoxy)-2-tert.-butyl-2-hydroxy-3-fluoro-3-methyl-3-(1H-1,2,4- 
triazol-1-yl)-propane as a mixture of diastereomers, melting point 
90.degree.-93.degree. C. 
The compounds listed in the following tables are prepared analogously. 
TABLE 1 
______________________________________ 
##STR10## 
No. R.sup.1 
R.sup.2 Physical data 
______________________________________ 
1.1 H C.sub.4 H.sub.9t 
m.p. 54-55.degree. C. 
1.2 H C.sub.3 H.sub.7i 
1.3 CH.sub.3 
C.sub.4 H.sub.9t 
b.p. 48-50.degree. C./0.013 mbar 
1.4 CH.sub.3 
C.sub.3 H.sub.7i 
1.5 H 4-ClC.sub.6 H.sub.4CH.sub.2 
1.6 H 4-FC.sub.6 H.sub.4CH.sub.2 
______________________________________ 
TABLE 2 
______________________________________ 
##STR11## 
No. R.sup.1 R.sup.2 Physical data 
______________________________________ 
2.1 H C.sub.4 H.sub.9t 
2.2 H C.sub.3 H.sub.7i 
2.3 CH.sub.3 
C.sub.4 H.sub.9t 
2.4 CH.sub.3 
C.sub.3 H.sub.7i 
2.5 H 4-ClC.sub.6 H.sub.4CH.sub.2 
2.6 CH.sub.3 
4-ClC.sub.6 H.sub.4CH.sub.2 
______________________________________ 
TABLE 3 
______________________________________ 
##STR12## 
Physical 
No. R.sup.1 R.sup.2 data 
______________________________________ 
3.1 H C.sub.4 H.sub.9t 
m.p. 
72-74.degree. C. 
3.2 H C.sub.3 H.sub.7i 
3.3 CH.sub.3 C.sub.4 H.sub.9t 
b.p. 
60-61.degree. C./ 
0.013 mbar 
3.4 CH.sub.3 C.sub.3 H.sub.7i 
3.5 H 4-ClC.sub.6 H.sub.4CH.sub.2 
3.6 H 4-FC.sub.6 H.sub.4CH.sub.2 
3.7 C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
3.8 C.sub.6 H.sub.5CH.sub.2 
C.sub.4 H.sub.9t 
3.9 4-ClC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
3.10 4-FC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
3.11 C.sub.3 H.sub.7n 
C.sub.4 H.sub.9 t 
______________________________________ 
TABLE 4 
______________________________________ 
##STR13## 
No. R.sup.1 R.sup.2 Physical data 
______________________________________ 
4.1 H C.sub.4 H.sub.9t 
4.2 H C.sub.3 H.sub.7i 
4.3 CH.sub.3 
C.sub.4 H.sub.9t 
4.4 CH.sub.3 
C.sub.3 H.sub.7i 
4.5 H 4-ClC.sub.4 H.sub.6CH.sub.2 
4.6 CH.sub.3 
4-ClC.sub.4 H.sub.6CH.sub.2 
4.7 C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
______________________________________ 
TABLE 5 
__________________________________________________________________________ 
##STR14## 
No. 
R.sup.1 R.sup.2 
R.sup.3 R.sup.4 
R.sup.5 X Physical 
__________________________________________________________________________ 
data 
5.1 
H C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O m.p. 100-101.degree. C. 
5.2 
CH.sub.3 C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O m.p. 98-99.degree. C. 
5.3 
C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O 
5.4 
4-ClC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O 
5.5 
4-FC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O 
5.6 
H C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O m.p. 89-90.degree. C. 
5.7 
CH.sub.3 C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O m.p. 90-93.degree. C. 
5.8 
C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
5.9 
4-ClC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
5.10 
4-FC.sub.6 H.sub.4CH.sub.2 
C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
5.11 
H C.sub.4 H.sub.9t 
CH.sub.3 H 4-FC.sub.6 H.sub.4 
O 
5.12 
H C.sub.4 H.sub.9t 
C.sub.6 H.sub.5CH.sub.2 
H 4-FC.sub.6 H.sub.4 
O 
5.13 
H C.sub.4 H.sub.9t 
H H 4-BrC.sub.6 H.sub.4 
O m.p. 108-109.degree. C. 
5.14 
H C.sub.4 H.sub.9t 
H H 4-CH.sub.3C.sub.6 H.sub.4 
O m.p. 96-98.degree. C. 
5.15 
H C.sub.4 H.sub.9t 
H H C.sub.6 H.sub.5 
O 
5.16 
H C.sub. 4 H.sub.9t 
H H 2-Cl3-ClC.sub.6 H.sub.3 
O m.p. 127-128.degree. C. 
5.17 
H C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
S 
5.18 
CH.sub.3 C.sub.4 H.sub.9t 
H H 4-BrC.sub.6 H.sub.4 
O 
5.19 
C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
H H 4-BrC.sub.6 H.sub.4 
O 
5.20 
CH.sub.3 C.sub.4 H.sub.9t 
H H 4-CH.sub.3C.sub.6 H.sub.4 
O m.p. 136-137.degree. C. 
5.21 
CH.sub.3 C.sub.4 H.sub.9t 
H H C.sub.6 H.sub.5 
O 
5.22 
CH.sub.3 C.sub.4 H.sub.9t 
CH.sub.3 H 4-FC.sub.6 H.sub.4 
O 
5.23 
CH.sub.3 C.sub.4 H.sub.9t 
CH.sub.3 H 4-ClC.sub.6 H.sub.4 
O 
5.24 
CH.sub.3 C.sub.4 H.sub.9t 
C.sub.6 H.sub.5CH.sub.2 
H 4-FC.sub.6 H.sub.4 
O 
5.25 
CH.sub.3 C.sub.4 H.sub.9t 
4-ClC.sub.6 H.sub.4CH.sub.2 
H 4-FC.sub.6 H.sub.4 
O 
5.26 
CH.sub.3 C.sub.4 H.sub.9t 
C.sub.6 H.sub.5CH.sub.2 
H 4-ClC.sub.6 H.sub.4 
O 
5.27 
CH.sub.3 C.sub.4 H.sub.9t 
4-ClC.sub.6 H.sub.4CH.sub.2 
H 4-FC.sub.6 H.sub.4 
O 
5.28 
C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
CH.sub.3 H 4-FC.sub.6 H.sub.4 
O 
5.29 
CH.sub.3 C.sub.4 H.sub.9t 
COCH.sub.3 H 4-FC.sub.6 H.sub.4 
O 
5.30 
CH.sub.3 C.sub.4 H.sub.9t 
COCH.sub.3 H 4-ClC.sub.6 H.sub.4 
O 
5.31 
H C.sub.4 H.sub.9t 
H H 2-ClC.sub.6 H.sub.4 
O m.p. 121-122.degree. C. 
5.32 
H C.sub.4 H.sub.9t 
H H 2-ClClC.sub.6 H.sub.5 
O m.p. 163-165.degree. C. 
5.33 
H C.sub.4 H.sub.9t 
H H 2-Cl3-ClC.sub.6 H.sub.5 
O m.p. 135-136.degree. C. 
5.34 
H C.sub.4 H.sub.9t 
H H C.sub.4 H.sub.9n 
S m.p. 150-160.degree. C./ 
0.06 mb 
5.35 
CH.sub.3 C.sub.4 H.sub.9t 
H H 2-CH.sub.33-CH.sub.3C.sub.6 H.sub.3 
O m.p. 147-148.degree. C. 
5.36 
CH.sub.3 C.sub.4 H.sub.9t 
H H 2-ClC.sub.6 H.sub.4 
O m.p. 158-159.degree. C. 
5.37 
CH.sub.3 C.sub.4 H.sub.9t 
H H C.sub.4 H.sub.9n 
S m.p. 125.degree. C./ 
0.01 mb 
__________________________________________________________________________ 
TABLE 6 
______________________________________ 
##STR15## 
Phy- 
sical 
No. R.sup.1 
R.sup.2 R.sup.3 
R.sup.4 
R.sup.5 X data 
______________________________________ 
6.1 H C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O 
6.2 H C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
6.3 H C.sub.4 H.sub.9t 
H H 4-CH.sub.3C.sub.6 H.sub.4 
O 
6.4 H C.sub.4 H.sub.9t 
H H 4-BrC.sub.6 H.sub.4 
O 
6.5 H C.sub.4 H.sub.9t 
H H 4-OCF.sub.3C.sub.6 H.sub.4 
O 
6.6 H C.sub.4 H.sub.9t 
H H 2-Cl4-ClC.sub.6 H.sub.4 
O 
6.7 CH.sub.3 
C.sub.4 H.sub.9t 
H H 4-ClC.sub.6 H.sub.4 
O 
6.8 CH.sub.3 
C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
6.9 C.sub.2 H.sub.5 
C.sub.4 H.sub.9t 
H H 4-FC.sub.6 H.sub.4 
O 
______________________________________ 
FORMULATION EXAMPLES 
Example 3 
______________________________________ 
Examples of formulations of liquid active substances of the 
formula I (% = percent by weight) 
(a) Emulsion concentrates 
(a) (b) (c) 
______________________________________ 
Active substance 20% 40% 50% 
Ca dodecylbenzenesulfonate 
5% 8% 5.8% 
Castor oil polyethylene 
5% -- -- 
glycol ether (36 moles of EO) 
Tributylphenol polyethylene 
-- 12% 4.2% 
glycol ether (30 moles of EO) 
Cyclohexanone -- 15% 20% 
Mixed xylenes 70% 25% 20% 
______________________________________ 
Emulsions of any desired concentration can be prepared from such 
concentrates by dilution with water. 
______________________________________ 
(b) Solutions (a) (b) (c) (d) 
______________________________________ 
Active substance 80% 10% 5% 95% 
Ethylene glycol monomethyl 
20% -- -- -- 
ether 
Polyethylene glycol MW 400 
-- 70% -- -- 
N--Methyl-2-pyrrolidone 
-- 20% -- -- 
Epoxidised coconut oil 
-- -- 1% 5% 
Petroleum ether (boiling 
-- -- 94% -- 
range 160-190.degree. C.) 
______________________________________ 
The solutions are suitable for application in the form of very fine drops. 
______________________________________ 
(c) Granules (a) (b) 
______________________________________ 
Active substance 5% 10% 
Kaolin 94% -- 
Highly disperse silica 
1% -- 
Attapulgite -- 90% 
______________________________________ 
The active substance is dissolved in methylene chloride, the solution is 
sprayed onto the carrier and the solvent is then removed by evaporation in 
vacuo. 
______________________________________ 
(d) Dusts (a) (b) 
______________________________________ 
Active substance 2% 5% 
Highly disperse silica 
1% 5% 
Talc 97% -- 
Kaolin -- 90% 
______________________________________ 
Ready-to-use dusts are obtained by mixing the carriers intimately with the 
active substance. 
Example 4 
______________________________________ 
Examples of formulations of solid active substances of the 
formula I (% = percent by weight) 
(a) Wettable powders 
(a) (b) 
______________________________________ 
Active substance 20% 60% 
Na ligninsulfonate 5% 5% 
Na laurylsulfate 3% -- 
Na diisobutylnaphthalene- 
-- 6% 
sulfonate 
Octylphenol polyethylene 
-- 2% 
glycol ether (7-8 moles 
of EO) 
Highly disperse silica 
5% 27% 
Kaolin 67% -- 
______________________________________ 
The active substance is thoroughly mixed with the adjuvants, and the 
mixture is thoroughly ground in a suitable mill. This gives wettable 
powders which can be diluted with water to give suspensions of any desired 
concentration. 
______________________________________ 
(b) Emulsion concentrate 
______________________________________ 
Active substance 10% 
Octylphenol polyethylene 
3% 
glycol ether (4-5 moles 
of EO) 
Ca dodecylbenzenesulfonate 
3% 
Castor oil polyglycol ether 
4% 
(36 moles of EO) 
Cyclohexanone 30% 
Mixed xylenes 50% 
______________________________________ 
Emulsions of any desired concentration can be prepared from this 
concentrate by dilution with water. 
______________________________________ 
(c) Dusts (a) (b) 
______________________________________ 
Active substance 5% 8% 
Talc 95% -- 
Kaolin -- 92% 
______________________________________ 
Ready-to-use dusts are obtained by mixing the active substance with the 
carrier and grinding the mixture on a suitable mill. 
______________________________________ 
(d) Extruder granules 
______________________________________ 
Active substance 10% 
Na ligninsulfonate 2% 
Carboxymethylcellulose 
1% 
Kaolin 87% 
______________________________________ 
The active substance is mixed with the adjuvants, and the mixture is ground 
and moistened with water. This mixture is extruded and then dried in a 
stream of air. 
______________________________________ 
(e) Coated granules 
______________________________________ 
Active substance 3% 
Polyethylene glycol (MW 200) 
3% 
Kaolin 94% 
______________________________________ 
The active substance is finely ground and applied uniformly, in a mixer, to 
the kaolin, which has been moistened with polyethylene glycol. Dust-free 
coated granules are obtained in this way. 
______________________________________ 
(f) Suspension concentrate 
______________________________________ 
Active substance 40% 
Ethylene glycol 10% 
Nonylphenol polyethylene 
6% 
glycol ether (15 moles 
of EO) 
Na ligninsulfonate 10% 
Carboxymethylcellulose 
1% 
37% aqueous formaldehyde 
0.2% 
solution 
Silicone oil in the form 
0.8% 
of a 75% aqueous emulsion 
Water 32% 
______________________________________ 
The active substance is finely ground and intimately mixed with the 
adjuvants. This gives a suspension concentrate from which suspensions of 
any desired concentration can be prepared by dilution with water. 
BIOLOGICAL EXAMPLES 
Example 5 
Action against Puccinia graminis on wheat 
(a) Residual protective action 
6 days after being sown, wheat plants are sprayed with a spray liquor 
(0.06% of active substance) prepared from a wettable powder of the active 
substance. After 24 hours, the treated plants are infested with a 
uredospore suspension of the fungus. After being incubated for 48 hours at 
95-100% relative humidity and approx. 20.degree. C., the infested plants 
are placed in a greenhouse at approx. 22.degree. C. Development of rust 
pustules is assessed 12 days after infestation. 
(b) Systemic action 
5 days after being sown, wheat plants are watered with a spray liquor 
(0.006% of active substance, based on the volume of soil) prepared from a 
wettable powder of the active substance. After 48 hours, the treated 
plants are infested with a uredospore suspension of the fungus. After 
being incubated for 48 hours at 95-100% relative humidity and approx. 
20.degree. C., the infested plants are placed in a greenhouse at approx. 
22.degree. C. Development of rust pustules is assessed 12 days after 
infestation. 
Compounds from Table 1 have a good action against Puccinia fungi. 
Untreated, but infested, control plants show a 100% attack by Puccinia. 
Inter alia, compounds 5.6 and 5.7 inhibit attack by Puccinia to 0 to 5%. 
Example 6 
Action against Cercospora arachidicola on groundnut plants 
(a) Residual protective action 
Groundnut plants 10-15 cm high are sprayed with a spray liquor (0.02% of 
active substance) prepared from a wettable powder of the active substance, 
and are infested, 48 hours later, with a conidia suspension of the fungus. 
The infested plants are incubated for 72 hours at approx. 21.degree. C. 
and a high humidity and are then placed in a greenhouse until the 
appearance of the typical leaf spots. The fungicidal action is assessed 12 
days after infestation, on the basis of the number and size of spots which 
have appeared. 
(b) Systemic action 
Groundnut plants 10-15 cm high are watered with a spray liquor (0.06% of 
active substance, based on the volume of soil) prepared from a wettable 
powder of the active substance. After 48 hours, the treated plants are 
infested with a conidia suspension of the fungus and are incubated for 72 
hours at approx. 21.degree. C. and a high humidity. The plants are then 
placed in a greenhouse, and the fungal attack is assessed after 11 days. 
In comparison with untreated, but infested, control plants (number and size 
of spots=100%), groundnut plants treated with active substances from Table 
1 show a greatly reduced attack by Cercospora. This compounds 5.6 and 5.7 
prevent the appearance of spots almost completely (0-10%) in the above 
tests. 
Example 7 
Action against Erysiphe graminis on barley 
(a) Residual protective action 
Barley plants approx. 8 cm high are sprayed with a spray liquor (0.02% of 
active substance) prepared from a wettable powder of the active substance. 
After 3-4 hours, the treated plants are dusted with conidia of the fungus. 
The infested barley plants are placed in a greenhouse at approx. 
22.degree. C., and the fungal attack is assessed after 10 days. 
(b) Systemic action 
Barley plants approx. 8 cm high are watered with a spray liquor (0.006% of 
active substance, based on the volume of soil) prepared from a wettable 
powder of the active substance. In doing so, care is taken that the spray 
liquor does not come into contact with the parts of the plants above 
ground. After 48 hours, the treated plants are dusted with conidia of the 
fungus. The infested barley plants are placed in a greenhouse at approx. 
22.degree. C., and the fungal attack is assessed after 10 days. 
Compounds of the formula I have a good action against Erysiphe fungi. 
Untreated, but infested, control plants show a 100% attack by Erysiphe. 
Amongst other compounds from Table 1, compound Nos. 5.6 and 5.7 inhibit 
fungal attack on barley to 0 to 5%. 
Example 8 
Residual protective action against Venturia inaequalis on apple shoots 
Apple cuttings having fresh shoots 10-20 cm long are sprayed with a spray 
liquor (0.06% of active substance) prepared from a wettable powder of the 
active substance. After 24 hours, the treated plants are infested with a 
conidia suspension of the fungus. The plants are then incubated for 5 days 
at 90-100% relative humidity and are kept for a further 10 days in a 
greenhouse at 20.degree.-24.degree. C. The scab attack is assessed 15 days 
after infestation. Compounds 5.6, 5.7 and others inhibit the attack of the 
disease to less than 10%. Untreated, but infested, shoots show 100% attack 
by Venturia. 
Example 9 
Action against Botrytis cinerea on beans Residual protective action 
Bean plants approx. 10 cm high are sprayed with a spray liquor (0.02% of 
active substance) prepared from a wettable powder of the active substance. 
After 48 hours, the treated plants are infested with a conidia suspension 
of the fungus. The fungal attack is assessed after the infested plants 
have been incubated for 3 days at 95-100% relative humidity and 21.degree. 
C. In many cases the compounds from Table 1 inhibit the fungal infestation 
very greatly. For example, compounds Nos. 5.5, 5.7 and 5.14 prove fully 
effective (0 to 5% attack by the disease) at a concentration of 0.02%. The 
attack by Botrytis on untreated, but infested, bean plants was 100%. 
Example 10 
Inhibition of growth in cereals 
The cereal species Hordeum vulgare (spring barley) and Secale (spring rye) 
are sown in plastic pots containing sterilised soil in a greenhouse and 
are watered as required. The shoots are sprayed with an aqueous spray 
liquor of an active substance of the formula I approx. 21 days after 
sowing. The quantity of active substance is equivalent to 0.3, 1 or 3 kg 
of active substance per hectare. The growth of the cereal is assessed 21 
days after the application. This makes it possible to establish that 
cereal plants treated with active substances of the formula I show a 
considerable reduction in growth in comparison with untreated control 
plants. 
Test results 
The growth in height of the cereal plants as a percentage of the growth in 
height of the untreated control plants. 
______________________________________ 
Com- 
pound 3 kg of AS/ha 
1 kg of AS/ha 
0.3 kg of AS/ha 
No. Rye Barley Rye Barley Rye Barley 
______________________________________ 
5.1 28 44 36 53 50 67 
5.6 5 6 23 21 38 53 
5.7 12 19 18 37 46 65 
5.14 43 67 57 84 80 86 
5.20 28 67 38 86 58 88 
______________________________________ 
Example 11 
Inhibition of growth in grasses 
A grass mixture containing Poa pratensis, Dactylis glomerata, Lolium 
perenne, Festuca rubra, Festuca ovina, Cynosurus crystatus, Agropyron 
repens and Bromus inermis is sown in plastic trays containing a 6:3:1 
soil/peat/sand mixture in a greenhouse, and the trays are watered as 
rerequired. The emergent grasses are cut back every week to a height of 
approx. 4 cm and, approx. 50 days after sowing and one day after the last 
cutting, are sprayed with an aqueous spray liquor of an active substance 
of the formula I. The quantity of active substance is equivalent to 0.3, 
1, or 3 kg of active substance per hectare. The average growth of the 
grasses is assessed 21 days after the application, and it is found that 
the active substances according to the invention from Tables 5 and 6 
effect a noticeable inhibition of growth. 
Test results 
The growth in height of the grasses as a percentage of the growth in height 
of the untreated control plants. 
______________________________________ 
Compound 3 kg of 1 kg of 0.3 kg of 
No. AS/ha AS/ha AS/ha 
______________________________________ 
5.1 39 39 61 
5.6 31 33 39 
5.7 32 36 50 
5.14 76 83 86 
5.20 64 79 89 
______________________________________ 
Example 12 
Increasing the yield of soya beans 
Soya beans of the "Hark" variety are sown in plastic vessels containing a 
6:3:1 soil/peat/sand mixture, and are put into an airconditioned chamber. 
As the result of an optimum choice of temperature, illumination, addition 
of fertiliser and watering, the plants develop to the 5-leaf to 6-leaf 
trefoil stage after approx. 5 weeks. At this point the plants are sprayed 
with an aqueous liquor of an active substance of the formula I until they 
are thoroughly wetted. The concentration of active substance is equivalent 
to up to 3 kg of active substance per hectare. Evaluation is carried out 
out approx. 5 weeks after the application of the active substance. The 
active substances, according to the invention, of the formula I cause a 
noticeable increase in the number and weight of pods harvested, in 
comparison with untreated control plants. 
Example 13 
Inhibiting the vegetative growth of soya 
Soya beans of the variety "Hark" are sown in plastic pots containing a 
6:3:1 soil/peat/sand mixture, and are placed in a greenhouse and watered 
as required. 15 days after sowing, the plants are sprayed with an aqueous 
spray liquor of an active substance of the formula I until they are 
wetted. The combination of active substances is equivalent to 0.1, 0.5 and 
1.5 kg of active substance per hectare. The growth of the plants is 
assessed 14 days after the application, and it is found that the active 
substances, according to the invention, from Tables 5 and 6 produce a 
noticeable inhibition of growth. 
Test results 
The growth in height of the soya plants as a percentage of the growth in 
height of the untreated control plants. 
______________________________________ 
Compound 1.5 kg of 0.5 kg of 
0.1 kg of 
No. AS/ha AS/ha AS/ha 
______________________________________ 
5.1 11 11 11 
5.6 5 5 11 
5.7 5 5 11 
5.14 19 19 48 
5.20 16 16 16 
______________________________________ 
Example 14 
Inhibition of growth in soil-covering plants (cover crops) 
Test plants of the varieties Psophocarpus palustris and Centrosema 
pubescens are grown from cuttings in plastic trays containing a 1:1:1 
soil/peat/sand mixture. After rooting, the small plants are transplanted 
into 9 cm pots and are watered as required. The plants are cultivated 
further in a greenhouse at a day temperature of 27.degree. C. and a night 
temperature of 21.degree. C., with an average duration of light of 14 
hours (6,000 lux) and a humidity of 70%. The test plants are cut back to a 
height of approx. 15 cm and are sprayed with a spray liquor of the active 
substance (equivalent to 0.1, 0.3, 1 and 3 kg of active substance per 
hectare) 5 days after being cut back. 4 weeks after the application, the 
growth of the treated plants is compared with that of pruned, but 
untreated, control plants. This makes it possible to establish that 
compounds from Tables 5 and 6 initiate a marked inhibition of the growth 
of the soil-covering plants. 
Test results 
New growth of cover crop plants as a percentage of the green weight and 
growth in height of the new growth of the untreated control plants. 
______________________________________ 
New growth of 
Com- Centrosema pubescens 
Psophocarpus palustris 
pound kg of green growth in 
green growth in 
No. AS/ha weight height weight height 
______________________________________ 
5.1 3 15 10 29 10 
1 26 10 35 10 
0.3 26 10 39 40 
0.1 59 30 59 30 
5.6 3 15 10 26 10 
1 14 10 35 10 
0.3 30 10 23 10 
0.1 41 10 58 40 
5.20 3 63 30 29 10 
1 59 40 58 40 
0.3 81 80 84 80 
0.1 85 80 97 100 
______________________________________ 
Example 15 
Terminating the growth of cotton 
Cotton plants of the variety "Delta Pine" are sown in plastic vessels 
containing a 2:1 soil/peat mixture, and are cultivated in a greenhouse at 
temperatures of 20.degree.-26.degree. C. After 2 months the plants have 
developed to the 6-Leaf stage. At this point in time, the plants are 
sprayed with an aqueous dispersion of an active substance of the formula I 
until they are thoroughly wetted. The concentration of active substance is 
equivalent to 2.0 kg of active substance per hectare. Evaluation is 
carried out approx. 1 month after the application of the active substance. 
The active substances, according to the invention, of the formula I effect 
a noticeable reduction in new growth in comparison with untreated control 
plants.