1,2-dihaloazolylethane derivatives and crop protection agents containing them

1,2-Dihaloazolylethane derivatives of the general formula I ##STR1## where R.sup.1 and R.sup.2 are each substituted or unsubstituted phenyl, biphenyl, naphthyl or hetaryl, Z is chlorine or bromine, and X is CH or N, and their plant-tolerated acid addition salts and metal complexes, and fungicides and growth regulators containing these compounds.

The present invention relates to novel azolyl compounds, processes for 
their preparation and growth regulators and fungicides containing them. 
It is known that triazole derivatives, for example 
2,4'-difluoro-.alpha.-(1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, can 
be used as a fungicide (European Patent 15,756). However, its fungicidal 
action is unsatisfactory. 
We have found that 1,2-dihaloazolylethane derivatives of the general 
formula I 
##STR2## 
where R.sup.1 and R.sup.2 are identical or different and are each phenyl, 
biphenyl, naphthyl or hetaryl, and these radicals may be monosubstituted 
to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or 
haloalkyl, each of 1 to 4 carbon atoms, 
Z is chlorine or bromine and 
X is CH or N, and their plant-tolerated acid addition salts or metal 
complexes have a better fungicidal action than known azole compounds. 
The compounds of the formula I contain asymmetric carbon atoms and can 
therefore occur as enantiomers and diastereomers. In the case of the novel 
compounds, the mixtures of the diastereomers can be separated in a 
conventional manner, for example on the basis of their different 
solubilities or by column chromatography, and the isomers can be isolated 
in pure form. The racemates of the novel compounds can be resolved by 
known methods, for example by salt formation with an optically active 
acid, separation of the diastereomeric salts and liberation of the 
enantiomers by means of a base. 
Both the individual enantiomers or diastereomers and the mixtures thereof 
can be used as fungicidal and growth-regulating active ingredients. 
R.sup.1 and R.sup.2 are identical or different and are each, for example, 
1-naphthyl, 2-naphthyl, p-biphenyl, phenyl, halophenyl, 2-chlorophenyl, 
2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 3-bromophenyl, 
3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 
2,4-dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 
2,6-dichloropheny1,2-chloro-6-fluorophenyl, C.sub.1 -C.sub.4 
-alkoxy-phenyl 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 
2,4-dimethoxyphenyl, C.sub.1 -C.sub.4 -alkylphenyl, 4-ethylphenyl, 
4-isopropylphenyl, 4-tert-butylphenyl, 4-tertbutoxypheny, 
2-chloro-4-fluoropheny1,2-chloro-6-methylphenyl, 3,4-dimethoxyphenyl, 
3-phenoxyphenyl, 4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 
3-aminophenyl, 4-aminophenyl, 2-trifluoromethylphenyl, halo-C.sub.1 
-C.sub.4 -alkyl-phenyl, 3-trifluoromethylpheny1,4-trifluoromethylphenyl, 
pyridyl, 3-pyridyl, furyl, 2-furyl, thienyl, 2-thienyl, 3-thienyl, 
isoxazolyl or 5-isoxazolyl. 
Acid addition salts are, for example, the hydrochlorides, bromides, 
sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates. The 
activity of the salts is due to the cation, so that the anion is in 
general unimportant. The novel active ingredient salts are prepared by 
reacting the 1,2-dihaloazolylethane derivatives (I) with the acids. 
Metal complexes of the active ingredients I or of their salts may be formed 
with, for example, copper, zinc, tin, manganese, iron, cobalt or nickel, 
by reacting the 1,2-dihaloazolylethane derivatives with corresponding 
metal salts. 
The compounds of the formula I can be prepared, for example, by reacting a 
compound of the formula II 
##STR3## 
where R.sup.1, R.sup.2 and X have the abovementioned meanings, with 
chlorine or bromine in the presence of a Lewis acid, eg. zinc chloride or 
zinc bromide. 
The reaction is carried out in the presence or absence of a solvent or 
diluent, at from -30.degree. to 100.degree. C. The preferred solvents 
include, for example, esters, such as ethyl acetate, methyl acetate or 
butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, 
dimethoxyethane, dioxane or diisopropyl ether, and in particular 
hydrocarbons and chlorohydrocarbons, such as pentane, hexane, benzene, 
methylene chloride, chloroform, carbon tetrachloride or dichloroethane, or 
corresponding mixtures. 
Preferred Lewis acids are metal halides, eg. zinc chloride, zinc bromide, 
tin chloride, tin bromide, iron tribromide, aluminum trichloride or 
titanium tetrachloride. 
The reaction is generally carried out at from -30.degree. to 100.degree. C, 
under atmospheric or superatmospheric pressure, continuously or batchwise. 
The starting compounds II may be prepared, for example, by reacting a 
compound of the formula III 
##STR4## 
where A, B, X and Z have the abovementioned meanings, with a base. 
The reaction is carried out in the presence or absence of a solvent or 
diluent, with the addition of an inorganic or organic base and with or 
without the addition of a reaction accelerator, at from 10.degree. to 
150.degree. C. The preferred solvents and diluents include ketones, such 
as acetone, methyl ethyl ketone or cyclohexanone, nitriles, such as 
acetonitrile or propionitrile, alcohols, such as methanol, ethanol, 
isopropanol, n-butanol or glycol, esters, such as ethyl acetate, methyl 
acetate or butyl acetate, ethers, such as tetrahydrofuran, diethyl ether, 
dimethoxyethane, dioxane or diisopropyl ether, and amides, such as 
dimethylformamide or N-methylpyrrolidone, as well as dimethyl sulfoxide, 
sulfolane and corresponding mixtures. 
Suitable bases, which may also be used as acid acceptors in the reaction, 
are, for example, alkali metal hydroxides, such as lithium hydroxide, 
sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as 
sodium carbonate or cesium carbonate, alkali metal hydrides, such as 
lithium hydride, sodium hydride or potassium hydride, alkali metal amides, 
such as sodium amide or potassium amide, and pyridine and 
4-dimethylaminopyridine. However, it is also possible to use other 
conventional bases. 
Preferred reaction accelerators are metal halides, such as sodium iodide or 
potassium iodide, and quaternary ammonium salts, such as 
tetrabutylammonium bromide or iodide. 
However, the compounds of the formula II can also be prepared by known 
processes (cf. European Patent 60,223). 
The compounds of the formula III can be prepared by reacting a compound of 
the formula IV 
##STR5## 
where R.sup.1 and R.sup.2 have the abovementioned meanings, with a 
compound of the formula V 
##STR6## 
where X has the abovementioned meaning, in the presence of an appropriate 
thionyl halide (SOZ.sub.2). 
The reaction is carried out in the presence or absence of a solvent or 
diluent, at from -30.degree. to 80.degree. C. The preferred solvents and 
diluents include nitriles, such as acetonitrile or propionitrile, ethers, 
such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or 
diisopropyl ether, and in particular hydrocarbons and chlorohydrocarbons, 
such as pentane, hexane, toluene, methylene chloride, chloroform, carbon 
tetrachloride or dichloroethane, and corresponding mixtures. 
The compounds of the formula IV can be prepared by generally known 
processes for aldehyde synthesis (Houben-Weyl-Muller, Methoden der 
Organischen Chemie, Georg Thieme Verlag, Stuttgart 1983, Vol. E3). 
The compounds of the formula I can also be prepared by reacting a compound 
of the formula 
##STR7## 
where R.sup.1, R.sup.2 and Z have the abovementioned meanings, with a 
compound of the formula 
##STR8## 
where X has the abovementioned meanings, in the presence of a thionyl 
halide (SOZ.sub.2). 
The reaction is carried out in the presence or absence of a solvent or 
diluent at from -30.degree. to 80.degree. C. The preferred solvents and 
diluents include nitriles, such as acetonitrile or propionitrile, ethers, 
such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or 
diisopropyl ether, and in particular hydrocarbons and chlorohydrocarbons, 
such as pentane, hexane, toluene, methylene chloride, chloroform, carbon 
tetrachloride or dichloroethane, and corresponding mixtures. 
The Examples which follow illustrate the preparation of the active 
ingredients. 
I. PREATION OF THE STARTING MATERIALS METHOD 1 
1-Chloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethan 
e 
51.55 g of thionyl chloride are added to a solution of 119.6 g of triazole 
in 500 ml of dichloromethane at 0.degree. C. After the end of the 
addition, the mixture is stirred for 30 minutes at room temperature 
(20.degree. C), after which 67 g of 
2-fluorophenyl-4-fluorophenylacetaldehyde are added. After the reaction 
mixture has been stirred for 12 hours at room temperature, 300 ml of water 
are added to the solution and the organic phase is separated off. The 
remaining aqueous phase is extracted twice by shaking with 
dichloromethane, and the collected organic phases are washed twice with 
saturated sodium bicarbonate solution. The organic phase separated off is 
then dried over sodium sulfate and evaporated down, 84.7 g (92%) of 
1-chloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-etha 
ne being obtained as a 1:1 diastereomer mixture, in the form of an oil. 
METHOD 2 
1-(1,2,4-Triazol-1-yl)-2-(2-fluorophenyl)-2-(4 -fluoro-phenyl)-ethene 
28.6 g of sodium methylate and 0.2 g of potassium iodide are added to a 
solution of 84.7 g of 
1-chloro-1(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethan 
e in 500 ml of methanol. After the reaction mixture has been refluxed for 
one hour, 300 ml of water are added to the solution, which is extracted 
several times by shaking with methyl tert-butyl ether. The organic phase 
separated off is washed twice with water, then dried over sodium sulfate 
and evaporated down, 67 g (89%) of 
1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethene being 
obtained in the form of an oil. 
PREATION OF THE END PRODUCTS

EXAMPLE 1 
1,2-Dichloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-e 
thane (active ingredient No. 1) 
1.1 g of zinc chloride are added to a solution of 22.4 g of 
1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethene in 80 
ml of carbon tetrachloride, after which 8.4 g of chlorine are passed in 
gaseous form. After the reaction mixture has been stirred for two hours at 
room temperature, the resulting precipitate is filtered off under suction 
and taken up in methylene chloride, and the solution is washed several 
times with saturated sodium bicarbonate solution, dried over sodium 
sulfate and evaporated down. 17.8 g (63%) of 
1,2-dichloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)- 
ethane are obtained as a 1:1 diastereomer mixture. 
The compounds listed in the Table can be prepared similarly to Example 1. 
TABLE 
__________________________________________________________________________ 
##STR9## I 
Ex. R.sup.1 R.sup.2 X Z m.p./IR Isomer* 
__________________________________________________________________________ 
1 4-FC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
1604, 1507, 1237, 816 
D.sub.1 :D.sub.2 = 1:1 
754 cm.sup.-1 
2 4-FC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
CH Cl 
3 4-FC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Br 
1602, 1509, 1226, 836 
D.sub.1 :D.sub.2 = 1:1 
760 cm.sup.-1 
4 4-FC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
CH Br 
5 4-FC.sub.6 H.sub.4 
3-FC.sub.6 H.sub.4 
N Cl 
6 4-FC.sub.6 H.sub.5 
4-FC.sub.6 H.sub.4 
N Cl 
127-129.degree. C. 
enantiomer mixture 
7 4-FC.sub.6 H.sub.4 
4-FC.sub.6 H.sub.4 
CH Cl 
8 4-FC.sub.6 H.sub.4 
4-FC.sub.6 H.sub.4 
N Br 
9 4-FC.sub.6 H.sub.4 
4-FC.sub.6 H.sub.4 
CH Br 
10 4-FC.sub.6 H.sub.4 
C.sub.6 H.sub.5 
N Cl 
resin D.sub.1 :D.sub.2 = 1:1 
11 4-FC.sub.6 H.sub.4 
C.sub.6 H.sub.5 
N Br 
12 4-FC.sub.6 H.sub.4 
C.sub.6 H.sub.5 
CH Cl 
13 4-FC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
1506, 1277, 1236, 816, 
D.sub.1 :D.sub.2 = 1:1 
750 cm.sup.-1 
14 4-FC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
CH Cl 
15 4-FC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Br 
16 4-FC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
CH Br 
17 4-FC.sub.6 H.sub.4 
3-ClC.sub.6 H.sub.4 
N Cl 
18 4-FC.sub.6 H.sub.4 
4-ClC.sub.6 H.sub.4 
N Cl 
19 4-FC.sub.6 H.sub.4 
4-ClC.sub.6 H.sub.4 
N Br 
20 4-FC.sub.6 H.sub.4 
4-ClC.sub.6 H.sub.4 
CH Cl 
21 4-FC.sub.6 H.sub.4 
2-BrC.sub.6 H.sub.4 
N Cl 
22 4-FC.sub.6 H.sub.4 
p-biphenyl 
N Cl 
23 4-FC.sub.6 H.sub.4 
2-naphthyl 
N Cl 
24 4-FC.sub.6 H.sub. 4 
1-naphthyl 
N Cl 
25 4-FC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
26 4-FC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Br 
27 4-FC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
CH Cl 
28 4-FC.sub.6 H.sub.4 
4-CH.sub.3C.sub.6 H.sub.4 
N Cl 
29 4-FC.sub.6 H.sub.4 
2,4-di-CH.sub.3C.sub.6 H.sub.3 
N Cl 
30 4-FC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
31 4-FC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Br 
32 4-FC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
CH Cl 
33 4-FC.sub.6 H.sub.4 
3-CF.sub.3C.sub.6 H.sub.4 
N Cl 
34 4-FC.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
N Cl 
35 4-FC.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
N Br 
36 4-FC.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
CH Cl 
37 4-FC.sub.6 H.sub.4 
3-NO.sub.2C.sub.6 H.sub.4 
N Cl 
38 4-FC.sub.6 H.sub.4 
3-NH.sub.2C.sub.6 H.sub.4 
N Cl 
39 4-FC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
40 4-FC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Br 
41 4-FC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
CH Cl 
42 4-FC.sub.6 H.sub.4 
3-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
43 4-FC.sub.6 H.sub.4 
3-OCH.sub.3C.sub.6 H.sub.4 
N Br 
44 4-FC.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
45 4-FC.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Br 
46 4-FC.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
CH Cl 
47 4-FC.sub.6 H.sub.4 
2-pyridyl N Cl 
48 4-FC.sub.6 H.sub.4 
3-pyridyl N Cl 
49 4-FC.sub.6 H.sub.4 
4-pyridyl N Cl 
50 4-FC.sub.6 H.sub.4 
2-thienyl N Cl 
51 4-FC.sub.6 H.sub.4 
3-thienyl N Cl 
52 4-FC.sub.6 H.sub.4 
2-furyl N Cl 
53 4-FC.sub.6 H.sub.4 
5-isoxazolyl 
N Cl 
54 C.sub.6 H.sub.5 
2-FC.sub.6 H.sub.4 
N Cl 
55 C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
N Cl 
56 C.sub. 6 H.sub.5 
2-ClC.sub.6 H.sub.4 
N Cl 
1502, 1277, 1133, 752 cm.sup.-1 
D.sub.1 :D.sub.2 = 1:1 
57 C.sub.6 H.sub.5 
4-ClC.sub.6 H.sub.4 
N Cl 
1494, 1276, 1096, 1014 
D.sub.1 :D.sub.2 = 1:1 
756, 701 cm.sup.-1 
58 C.sub.6 H.sub.5 
2-BrC.sub.6 H.sub.4 
N Cl 
59 C.sub.6 H.sub.5 
4-BrC.sub.6 H.sub.4 
N Cl 
60 C.sub.6 H.sub.5 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
61 C.sub.6 H.sub.5 
4-CH.sub.3C.sub.6 H.sub.4 
N Cl 
62 C.sub.6 H.sub.5 
4-tert.-C.sub.4 H.sub.9C.sub.6 H.sub.4 
N Cl 
63 C.sub.6 H.sub.5 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
64 C.sub.6 H.sub.5 
4-CF.sub.3C.sub.6 H.sub.4 
N Cl 
65 C.sub.6 H.sub.5 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
66 C.sub.6 H.sub.5 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
67 C.sub.6 H.sub.5 
2-naphthyl 
N Cl 
68 C.sub.6 H.sub.5 
2-pyridyl N Cl 
69 C.sub.6 H.sub.5 
3-pyridyl N Cl 
70 C.sub.6 H.sub.5 
2-thienyl N Cl 
71 C.sub.6 H.sub.5 
3-thienyl N Cl 
72 4-ClC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
73 4-ClC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
74 4-ClC.sub.6 H.sub.4 
4-ClC.sub.6 H.sub.4 
N Cl 
1502, 1490, 831, 764 cm.sup.-1 
enantiomer mixture 
75 4-ClC.sub.6 H.sub.4 
2-BrC.sub.6 H.sub.4 
N Cl 
76 4-ClC.sub.6 H.sub.4 
4-BrC.sub.6 H.sub.4 
N Cl 
77 4-ClC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
78 4-ClC.sub.6 H.sub.4 
4-CH.sub.3C.sub.6 H.sub.4 
N Cl 
79 4-ClC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
80 4-ClC.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
N Cl 
81 4-ClC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
82 4-ClC.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
83 4-BrC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
84 4-BrC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
85 4-BrC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
86 4-BrC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
87 4-BrC.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
N Cl 
88 4-BrC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
89 4-BrC.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
90 4-CH.sub.3C.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
91 4-CH.sub.3C.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
92 4-CH.sub.3C.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
93 4-CH.sub.3C.sub.6 H.sub.4 
4-CH.sub.3C.sub.6 H.sub.4 
N Cl 
94 4-CH.sub.3C.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
95 4-CH.sub.3C.sub.6 H.sub.4 
4-CF.sub.3C.sub.6 H.sub.4 
N Cl 
96 4-CH.sub.3C.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
97 4-CH.sub.3C.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
98 4-CF.sub.3C.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
99 4-CF.sub.3C.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
100 4-CF.sub.3C.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
101 4-CF.sub.3C.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
102 4-CF.sub.3C.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
103 4-OCH.sub.3C.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
104 4-OCH.sub.3C.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
105 4-OCH.sub.3C.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
106 4-OCH.sub.3C.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
107 4-OCH.sub.3C.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
108 4-OCH.sub.3C.sub.6 H.sub.4 
4-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
109 2-FC.sub.6 H.sub.4 
2-ClC.sub.6 H.sub.4 
N Cl 
110 2-FC.sub.6 H.sub.4 
2-FC.sub.6 H.sub.4 
N Cl 
111 2-FC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub.4 
N Cl 
112 2-ClC.sub.6 H.sub.4 
2-CH.sub.3C.sub.6 H.sub. 4 
N Cl 
113 2-ClC.sub.6 H.sub.4 
2-CF.sub.3C.sub.6 H.sub.4 
N Cl 
114 2-ClC.sub.6 H.sub.4 
2-OCH.sub.3C.sub.6 H.sub.4 
N Cl 
__________________________________________________________________________ 
*D.sub.1 :D.sub.2 = ratio of the diastereomers formed 
Generally speaking, the novel compounds are extremely effective on a broad 
spectrum of phytopathogenic fungi, in particular those from the 
Ascomycetes and Basidiomycetes classes. Some of them have a systemic 
action and can be used as foliar and soil fungicides. 
The fungicidal compounds are of particular interest for controlling a large 
number of fungi in various crops or their seeds, especially wheat, rye, 
barley, oats, rice, Indian corn, lawns cotton, soybeans, coffee, sugar 
cane, fruit and ornamentals in horticulture and viticulture, and in 
vegetables such as cucumbers, beans and cucurbits. 
The novel compounds are particularly useful for controlling the following 
plant diseases: 
Erysiphe graminis in cereals, 
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, 
Podosphaera leucotricha in apples, 
Uncinula necator in vines, 
Puccinia species in cereals, 
Rhizoctonia species in cotton and lawns, 
Ustilago species in cereals and sugar cane, 
Venturia inaequalis (scab) in applies, 
Helminthosprium species in cereals, 
Septoria nodorum in wheat, 
Botrytis cinerea (gray mold) in strawberries and grapes, 
Cercospora arachidicola in groundnuts, 
Pseudocercosporella herpotrichoides in wheat and barley, 
Pyricularia oryzae in rice, 
Phytophthora infestans in potatoes and tomatoes, 
Fusarium and Verticillium species in various plants, 
Plasmopara viticola in grapes, 
Alternaria species in vegetables and fruit. 
The compounds are applied by spraying or dusting the plants with the active 
ingredients, or treating the seeds of the plants with the active 
ingredients. They may be applied before or after infection of the plants 
or seeds by the fungi. 
Application rates of the fungicidal agents are from 0.02 to 3 kg or ore of 
active ingredient per hectare, depending on the type of effect desired. 
The novel compounds may also be used for protecting materials (wood), for 
example against Paecilomyces variotii. 
The novel compounds may exercise a variety of influences on practically all 
plant development stages and are therefore used as growth regulators. The 
diversity of action of growth regulators depends especially on 
(a) the type and variety of plant; 
(b) the time applied with reference to the development stage of the plants 
and the time of the Year; 
(c) the place and method of application seed treatment, soil treatment, or 
application to foliage; 
(d) climatic factors, e.g., average temperature, amount of precipitate, 
sunshine and duration; 
(e) soil conditions (including fertilization; 
(f) the formulation of the active ingredient; and 
(g) the concentration at which the active ingredient is applied. 
A description of some of the various possibilities of using the growth 
regulators according to the invention in agriculture and horticulture is 
given below. 
A. Vegetative plant growth can be inhibited to a considerable extent, a 
fact which is manifested particularly in a reduction in plant height. The 
treated plants thus have a compact habit; furthermore, the leaf color is 
darker. 
Of advantage in practice is for example the reduction in grass growth on 
roadsides, hedges canal embankments and on areas such as parks, 
sportsgrounds, fruit orchards, lawns and airfields, thus reducing 
expensive and time-consuming mowing. 
A further feature of economic interest is the increase in the rigor of 
crops which tend to lodge such as cereals, Indian corn, sunflowers and 
soybeans. The shortening and strengthening of the stem thus caused reduces 
or eliminates the danger of lodging under unfavorable weather conditions. 
Of practical importance is the reduction in vegetative growth in fruit 
trees and other woody plants, thus saving pruning costs. 
The use of growth regulators and also so important for inhibiting plant 
height and changing the time of ripening in cotton. It is thus possible 
for this important crop to be harvested completely mechanically. 
Growth regulators may also increase or inhibit lateral branching. This is 
of interest when, for instance in tobacco plants, it is desired to inhibit 
the formation of lateral shoots (suckers) in favor of leaf development. 
with the novel compounds, it is possible for instance in winter rape to 
considerably increase the resistance to freeze injury. On the one hand, 
upward growth and the development of a too luxuriant (and thus 
particularly frost-susceptible) leaf or plant mass are inhibited; on the 
other, the Young rape plants are kept in spite of favorabIe growth 
conditions, in the vegetative development stage before winter frosts 
begin. The danger of freeze injury is thus eliminated in plants which tend 
to lose prematurely their inhibition to bloom and pass into the generative 
phase. In other crops, too, e.g., winter cereals, it is advantageous if 
the plants are well tillered in the fall as a result of treatment with the 
compounds according to the invention, but enter winter with not too lush a 
growth. This is a Preventive measure against increased susceptibility to 
freeze injury and--because of the relatively low leaf or plant 
mass--attach by various (especially fungus) diseases. The inhibition of 
vegetative growth also makes closer planting possible in numerous crops, 
which means an increase in yield based on the area cropped. 
B. Better yields both of plant parts and plant materials may be obtained 
with the novel agents. It is thus for instance possible to induce 
increased formation of buds blossom leaves, fruit, seed grains, roots and 
tubers, to increase the sugar content of sugarbeets, sugarcane and citrus 
fruit, to raise the protein content of cereals and soybeans, and to 
stimulate the increased formation of latex in rubber trees. 
The compounds of the formula I may raise the yield by influencing plant 
metabolism or by promoting or inhibiting vegetative and/or generative 
plant growth. 
C. It is also possible with growth regulators to shorten or lengthen growth 
stages and to accelerate or retard the ripening process in plant parts 
either before or after harvesting. 
A factor of economic interest is for example the facilitation of harvesting 
made possible by a chemical, temporally concentrated loosening 
(abscission) of the adherence of stalks to the branches of citrus fruit, 
olive trees, and other kinds of pomes, drupes and indehiscent fruit. The 
same mechanism. i.e.. promotion of the formation of separation layers 
between fruit or leaf and stem of the plant is also essential for a 
readily controllable defoliation of crop plants e.g., cotton. 
D. Further, transpiration in crop plants may be reduced with growth 
regulators. This is particularly important for plants growing in 
agricultural areas which are expensive to irrigate. e.g., in arid or 
semi-arid areas. Irrigation frequency can be reduced by using the 
compounds according to the invention, making for lower costs. As a result 
of the use of growth regulators, the water available can be better 
utilized because inter alia, 
the size of the stomata opening is reduced: 
a thicker epidermis and cuticle are formed: 
penetration of the soil by the roots is improved: 
the micro-climate in the stand is favorably influenced by the more compact 
growth. 
The active ingredients according to the invention may be applied not only 
to the seed (as a disinfectant), but also to the soil, i.e., via the 
roots, and to the foliage by spraying. 
As a result of the good tolerance by crop plants, the application rate when 
the active ingredients are used as growth regulators may vary within wide 
limits. 
When the active ingredients are used for treating seed, amounts of from 
0.001 to 50, and preferably from 0.005 to 0.5, per kg of seed are 
generally required. For foliage and soil treatment, amounts of from 0.01 
to 10, and preferably from 0.05 to 1, kg/ha are generally considered to be 
sufficient. 
The novel substances may be converted into conventional formulations such 
as solutions, emulsions, suspensions, dusts, powders, pastes and granules. 
The application forms depend entirely on the purposes for which they are 
intended: they should at all events ensure a fine and uniform distribution 
of the active ingredient. The formulations are produced in known manner, 
for example by extending the active ingredient with solvents and/or 
carriers, with or without the use of emulsifiers and dispersants; if water 
is used as solvent, it is also possible to employ other organic solvents 
as auxiliary solvents. Suitable auxiliaries for this purpose are solvents 
such as aromatics (e.g., xylene), chlorinated aromatics e.g., 
chlorobenzenes, paraffins (e.g., crude oil fractions), alcohols e.g., 
methanol, butanol), amines (e.g. ethanolamine, dimethylformamide), and 
water; carriers such as ground natural minerals (e.g., kaolins, aluminas, 
talc and chalk) and around synthetic minerals (e.g., highly disperse 
silica and silicates); emulsifiers and other surfactants, such as nonionic 
and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl 
sulfonates); and dispersants such as lignin, sulfite waste liquors and 
methylcellulose. 
The fungicidal agents generally contain from 0.1 to 95, and preferably from 
0.5 to 90, wt % of active ingredient. 
The agents and the ready-to-use formulations prepared from them, such as 
solutions, emulsions, suspension, powders, dusts, pastes and granules, are 
applied in conventional manner, for example by spraying, atomizing, 
dusting, scattering, dressing or watering. 
Examples of formulations are given below. 
I. 90 parts by weight of compound no. 13 is mixed with 10 parts by weight 
of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable 
for application in the form of very fine drops. 
II. 20 parts by weight of compound no. 13 is dissolved in a mixture 
consisting of 80 parts by weight of xylene, 10 parts by weight of the 
adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic 
acid-N-monoethanolamide, 5 parts by weight of the calcium salt of 
dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 
moles of ethylene oxide and 1 mole of castor oil. By pouring the solution 
into water and uniformly distributing it therein, an aqueous dispersion is 
obtained. 
III. 20 parts by weight of compound no. 13 is dissolved in a mixture 
consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of 
isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide 
and b 1 mole of castor oil. By pouring the solution into water and finely 
distributing it therein, an aqueous dispersion is obtained. 
IV. 20 parts by weight of compound no. 13 id dissolved in a mixture 
consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a 
mineral oil fraction having a boiling point between 210.degree. C. and 
280.degree. C., and 10 parts by weight of the adduct of 40 moles of 
ethylene oxide and b 1 mole of castor oil. By pouring the solution into 
water and uniformly distributing it therein, an aqueous dispersion is 
obtained. 
V. 80 parts by weight of compound no. 13 is well mixed with 3 parts by 
weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 
10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained 
from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, 
and triturated in a hammer mill. By uniformly distributing the mixture in 
water, a spray liquor is obtained. 
VI. 3 parts by weight of compound no. 13 is intimately mixed with 97 parts 
by weight of particulate kaolin. A dust is obtained containing 3% by 
weight of the active ingredient. 
VII. 30 parts by weight of compound no. 13 is intimately mixed with a 
mixture consisting of 92 parts by weight of powdered silica gel and 8 
parts by weight of paraffin oil which has been sprayed onto the surface of 
this silica gel. A formulation of the active ingredient is obtained having 
good adherence. 
VIII. 40 parts by weight of compound no. 13 is intimately mixed with 10 
parts by weight of the sodium salt of a phenolsulfonic 
acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of 
water to give a stable aqueous dispersion. Dilution in water gives an 
aqueous dispersion. 
IX. 20 parts by weight of compound no. 13 is intimately mixed with 2 parts 
by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by 
weight of a fatty alcohol polyglycol ether, 2 parts by weight of the 
sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 
parts by weight of a paraffinic mineral oil. A stable oily dispersion is 
obtained. 
In these application forms, the agents according to the invention may also 
be present together with other active ingredients, for example herbicides, 
insecticides, growth regulators, and fungicides, and may furthermore be 
mixed and applied together with fertilizers. Admixture with other 
fungicides frequently results in an increase in the fungicidal spectrum. 
USE EXAMPLES 
For comparison purposes, the compound 
2,4'-difluoro-.alpha.-(1,2,4-triazol-1-yl-methyl)-benzhydryl alcohol (A) 
disclosed in EP 15,756 was used. 
USE EXAMPLE 
Action on Pyrenophora trees 
Barley seedlings of the "Igri" variety were sprayed to runoff at the 
two-leaf stage with aqueous suspensions consisting (dry basis) of 80% of 
active ingredient and 20% of emulsifier. After 24 hours of plants were 
inoculated with a spore suspension of the fungus Pyrenophora trees, and 
set up for 48 hours in a high-humidity climatic cabinet at 18.degree. C. 
The plants were then cultivated for a further 5 days in the greenhouse at 
20.degree. to 22.degree. C. and a relative humidity of 70.degree. C. The 
extent of fungus spread was then assessed. 
The results show that active ingredient 13, applied as a 0.0125 wt % spray 
liquor, has a better fungicidal action (100%) than prior art comparative 
agent A (80%). 
To determine the growth-regulating properties of the candidate compounds, 
the test plants were grown in plastic pots (approx. 12.5 cm in diameter, 
and having a volume of about 500 ml) in a substrate provided with 
sufficient nutrients. 
In the preemergence treatment method, the candidate compounds were sprayed 
as aqueous formulations onto the seedbed on the day of sowing. In the 
postemergence method, the compounds were sprayed as aqueous formulations 
onto the plants. 
The growth-regulating action observed was confirmed at the end of the 
experiment by measuring the height of the plants. The figures obtained 
were compared with the growth height of the untreated plants. The active 
ingredient CCC was used for comparison purposes. 
The reduction in growth height was also accompanied by a deeper leaf 
coloration. The increased chlorophyll content is indicative of an 
increased rate of photosynthesis, making for bigger yields. 
The individual data are given in the following tables. 
Comparative substances: 
##STR10## 
TABLE 1 
______________________________________ 
Spring rape, "Petranova" variety 
Preemergence (soil) treatment 
Conc. Growth height 
Active ingr. no. 
mg of a.i./vessel 
relative 
______________________________________ 
untreated -- 100 
CCC 6 95.9 
6 6 91.3 
10 6 88.7 
______________________________________ 
TABLE 2 
______________________________________ 
Spring rape, "Petranova" variety 
Postemergence (leaf) treatment 
Conc. Growth height 
Active ingr. no. 
mg of a.i./vessel 
relative 
______________________________________ 
untreated -- 100 
CCC 6 92.2 
1 6 88.3 
10 6 84.4 
74 6 75.6 
______________________________________