DE2556319A1 - SUBSTITUTED TRIAZOLE AETHER - Google Patents

Description

The present invention relates to substituted triazole ethers and their acid addition salts and processes for their preparation and their use as fungicides.

It is known to use imidazole-substituted ethers as fungicides for combating phytopathogenic fungi (DOS 2 63 857). However, when used as a dressing agent, for example, they often cause germination delays and emergence damage to the crop plants.

It has been found that substituted triazole ethers of the formula I

r \?

in the

R is an alkyl radical with 1-8 carbon atoms, optionally by a or several halogen atoms, an alkoxy or a cyano group is substituted,

an alkenyl radical with 3-6 carbon atoms which is optionally substituted by halogen,

an alkynyl group with 3-6 carbon atoms, optionally substituted by halogen,
or a benzyl radical of the general formula

h denotes, where m denotes the numbers 0-5 and R denotes chlorine, bromine, trifluoromethyl or alkyl with 1-4 carbon atoms, hydrogen, an alkyl group with 1-5 carbon atoms <

^546/75 709825/1014 " ² "

ρ
R is hydrogen, an alkyl group with 1-5 carbon atoms, a cyclo-

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denotes hexyl radical or a phenyl radical,

R ^ fluorine, chlorine or bromine, a methyl, trifluoromethyl or Denotes phenyl radical or an alkoxy group with 1-3 carbon atoms and

η denotes the numbers 0-3, where η equals 2 or 3, the radicals R ^ can be the same or different and their acid addition salts have a good fungicidal effect, no damage to crop plants comparable to the known active ingredients cause and also the well-known in their excellent effectiveness against a wide range of fungi Connections are superior.

The acid addition salts have the general formula II

² 3

II

12 3
in which R, R, R and η have the meaning given above and HS represents any organic or inorganic acid which, however, must not be phytotoxic and must be able to form salts with compounds of the formula I. Particularly suitable acids are sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, phosphoric acid, acetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid, dodecylbenzenesulfonic acid and the like.

The compounds of the formula II can by simple addition of the acids HS to the compounds of the formula I, optionally in one Solvents.

Compounds of the formulas are preferred

R is an alkyl, alkenyl or alkynyl radical with 1-6 carbon atoms, and their acid addition salts with organic and inorganic acids,

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in which X and Y are hydrogen, chlorine or bromine, with the Provided that X and Y are not simultaneously hydrogen and their acid addition salts with organic or inorganic acids,

-ch-ch / O V- Br

0-CH ₂ -CH = CH ₂

in which R has the meaning given in claim 1, as well as its acid addition salts,

IL

0-CH ₂ -CH = CH ₂

in which X and Y have the meanings given in claim 9, as well as their acid addition salts.

The compounds of the formula I can easily be prepared by reacting alkali metal salts of the formula III

III

NVN-CH-CH-C. OMe

2 "5
where R, R and η have the meaning given above and Me is sodium or potassium,

with a compound of the general formula IV

X-R-

IV

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in which R has the meaning given above and is preferably chlorine, bromine or iodine, but also methosulphate or toluenesulphonate can be received.

The alkali metal salts of the formula III are conveniently obtained from the 1-aryl-2- (triazolyl-1) alkanols of the general formula V

durph reaction with suitable strong bases such as alkali hydride, alkali amide or lower alkali alcoholates, in the latter case If the lower alcohols formed have to be removed by azeotropic distillation. Isolation of the alkali salts III is generally unnecessary. You can use a suitable inert solvent such as toluene, xylene, tetrahydrofuran or dimethylformamide are reacted immediately after their preparation with the compounds of formula IV.

To represent the alcohols of the formula V, one can use the corresponding Ketones of the general formula VI

VI

going out - by reducing the ketones. Suitable for reduction catalytically excited hydrogen or complex metal r hydrides, such as lithium aluminum hydride or sodium borohydride,

in a suitable solvent.

The triazole-containing ketones of type VI are obtained by using shark ketones of the formula VII, where Y is preferably chlorine or bromine

2 3
represents and R, R and η have the meaning given above, with 1,2,4-triazole in the presence of a base or excess triazole, in a suitable solvent, e.g. acetone, acetonitrile, dimethylformamide, lower alcohols, tetrahydrofuran, dioxane, chloroform, etc. implements, e.g.

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j. 2S56319

r = I ₂

N. N-H + R

₂ / r> η

H + R -CH-C-fßT) ^η ^ VI

^ • "J \ /

VII

The compounds are isolated by the customary working-up methods VI as such or in the form of their acid addition salts, from which they are isolated again in pure form by adding bases can be.

The halogen ketones of the formula VII are known.

The new fungicidal compounds fall depending on the conditions under which the reactions are carried out either in the form of the free bases I or their salts II. The salts can be converted into the free bases in the usual manner e.g. by reaction with alkali such as sodium or potassium hydroxide, sodium or potassium carbonate, ammonia or the like Alkalis. The compounds in base form can be prepared by reaction with suitable acids, for example inorganic acids, such as Hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, Nitric acid, phosphoric acid, organic acids such as acetic acid, propionic acid, butyric acid, glycolic acid, oxalic acid, Benzoic acid, toluenesulphonic acid or higher alkylbenzenesulphonic acids such as dodecylbenzenesulphonic acid in the application-technically valuable ones Acid addition salts are converted.

Some characteristic examples should describe the manufacturing process explain. In the following, all parts are parts by weight and all percentages are percentages by weight.

Manufacture of the preliminary products

la) are added to a solution of 69 parts of 1,2,4-triazole in 500 parts of methanol, 180 parts of a 30 lar methanolic sodium methylate solution (20 ⁰ C) and stirred for 10 minutes, then a solution of 206 is Teilenco-bromo-4- fluoroacetophenone in 200 parts of methanol was added dropwise. One warms up half a

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Hour at 50 C, the reaction solution ₅ evaporated to dryness, the residue is extracted with chloroform, washed with this water, dried with sodium sulfate and concentrated. The remaining oil is dissolved in acetone and 98 % ± gev nitric acid is added dropwise until no more precipitate separates out. It is filtered off with suction, washed with acetone and 126 parts of ^ - (J- '> ² '> ⁴ '-triazolyl- (I') J -4-fluoroacetophenone hydronitrate with a melting point of 153 ° C. are obtained.

Ib) 126 parts of (P- | _l ^f , 2 ', 4' -triazolyl- (I ¹ ) ~ j-4-fluoroacetophenone hydronitrate in 900 parts of methanol are mixed with 100 parts of concentrated ammonium hydroxide and stirred until it dissolves a, mixed with water, sucks the precipitate, washed it with water and obtained after drying 91 parts of OO - [1 ', 2', 4 '· triazolyl- (I ¹ ) -4-fluoroacetophenone with a melting point of 120 122 ° C.

Ic) 112 parts of Go-II ', 2', 4 '-triazolyl- (I') J -4-fluoroacetophenone in 900 parts of methanol are mixed with 1 part of 30 percent strength. methanolic sodium methylate solution and then 13 » 8 parts of sodium borohydride are added in ^{portions while cooling with ice (0} ° C.). The mixture is allowed to warm to room temperature, refluxed for 1 hour, 35O parts of water are added and the mixture is concentrated. The residue is extracted with methylene chloride, the methylene chloride solution is washed with water, dried over magnesium sulfate and evaporated. 87 parts of 1- (4-fluorophenyl) -2- '[l', 2 ', 4 ^f -triazolyl- (l') l-ethanol with a melting point of 91 ° -93 ° C. are obtained

2a) 16.6 parts 1,2,4-triazole, 40.4 parts 1- (4-bromophenyl) -2-bromohexanone- (1) and 12.6 parts of sodium carbonate are refluxed for 1 hour in 80 parts of methanol. It is mixed with water, filtered off, crystallized from ethanol μΐη and receives 20.5 parts of 1- (4-bromophenyl) -2-ri ', 2 ·, 4 • -triazolyl- (I') J-hexanone- (l) with a melting point of 103-105 ° C.

2b) 19.3 parts of l- (4-bromophenyl) -2- [l ^l, 2 ', 4'-triazolyl (l') ~ jhexanon- (l) is dissolved in methanol and treated at Räumtempera-

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1.25 parts of sodium borohydride are added in portions. After stirring for one hour, aqueous ammonium chloride solution is added, the mixture is extracted with ethyl acetate, and the organic phase is dried with sodium sulfate and evaporated. 20 parts of 1- (4-bromophenyl) -2- [T ', 2 ^f , 4'-triazolyl- (l' _) J hexanol- (l) are obtained in the form of an oil which, upon treatment with isopropyl ether / petroleum ether, gives crystals of melting point 46 - 48 ° C results.

3a) To a mixture of 13.8 parts of 1,2,4-triazole, 42 parts of sodium carbonate and 100 parts of methanol is added dropwise at room temperature (20 ⁰ C) 2,4-dichloroacetophenone CO-bromo-a solution of 53.6 parts of in 100 parts of methanol. The reaction mixture is refluxed for 2 hours and, after cooling, poured into 1000 parts of water. The oil is separated off, the water phase is shaken out with chloroform, the combined organic phases are washed with water, dried with sodium sulfate and concentrated to dryness. 48 parts of dark brown crystals are obtained, which are dissolved in 150 parts of acetone and, while cooling with ice, dropwise with 12 parts of 98 percent strength. Nitric acid are added. The precipitate is filtered off with suction, washed with acetone and dried. This gives 31 parts cjö- | jl ', 2', 4 '-Triazolyl- (l ^f) J-2.4-dichloroacetophenone as the hydrochloride mp nitrate, 14O ° C.

3b) 66 parts of 03- [1 ', 2', 4'-triazolyl- (I ') J-2.4-dichloroacetophenone hydronitrate, 400 parts of methanol and 50 parts of concentrated aqueous ammonia solution are stirred until completely dissolved, evaporated and mixed with water for crystallization brought. 49 parts of co- [T ', 2 », 4' -triazolyl- (I ') J-2,4-dichloroacetophenone of melting point III C. are obtained.

3c) 110 parts of ΟΟ-Γΐ ', 2', 4'-triazolyl- (I ') J-2.4-dichloroacetophenone, 800 parts of methanol and 1 ml of 30 percent strength. Sodium methylate solution 12 parts of sodium borohydride are added in portions while cooling with ice. After warming to room temperature heated to reflux for one hour, treated with 300 parts of water and largely evaporated. The residue is with

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Water added and sucked off. The piltrate is extracted with methylene chloride, the filter residue is dissolved in chloroform and the combined organic phases are washed with water and dried with magnesium sulfate. Evaporation of the solution remain behind 77 parts of l- (2.4-DichlorphenyD-2-Γΐ ^1, 2 ', 4'-triazolyl (1') ~] -ethanol of mp. 93 96 ⁰ C.

4a) 126 parts of 60- [V , 2 ', 4 ^f -triazolyl- (1 ^f _) J -4-chloroacetophenone, 1000 parts of methanol and 2 parts of sodium methylate are added in portions with 14.6 parts of sodium borohydride while cooling with ice. After warming to room temperature and boiling under reflux for one hour, 400 parts of water are added, the mixture is concentrated and the residue is extracted with methylene chloride. The methylene chloride solution is washed with water, dried with magnesium sulfate and concentrated. 105 parts of 1- (4-chlorophenyl) -2- [V , 2 ', 4' -triazolyl- (l ') I-ethanol with a melting point of 115 ° -117 ° C. are obtained

5a) To a mixture of 14 parts of 1- (4-bromophenyl) -2- [V , 2 ', 4'-triazolyl- (1') I-propanone- (1) and 16 parts of methanol are added in portions 1.2 Parts sodium borohydride. After stirring for one hour at room temperature, aqueous ammonium chloride solution is added, the mixture is extracted with ethyl acetate, and the combined organic phases are dried with sodium sulfate and concentrated. This gives 11 parts of l- (4-bromophenyl) -2- [I ^1, 2 ', 4'-triazolyl (l') -propanol- (1) of melting point 90-92 ⁰ C.

example 1

To a suspension of 5> 6 parts 80 percent. Sodium hydride in parts of dry tetrahydrofuran is added dropwise at 50 ⁰ C a solution of 15.4 parts of l- (4-Pluorphenyl) -2- [l ^l, 2 ', 4'-triazolyl (l ^f)] - ethanol in 50 parts of dry dimethylformamide. After two hours of stirring under reflux for 14.7 parts bromopropyne are added dropwise at 5O ⁰ C. The mixture is left to ^{stir at 50 °} C. for a further hour, and water is then carefully added. The mixture is extracted with ether, the ethereal solution dried and added dropwise with 98 percent.

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Nitric acid added. The precipitated crystals are filtered off and recrystallized from ethyl acetate. 6.4 parts of 1 - (- 4-fluorophenyl) -l-propargyloxy-2-II ', 2', 4 ^f -triazolyl - '(1 ^! ) I-ethane are obtained as hydronitrate with a melting point of 110-112 C.

Example 2

To a suspension of 5 »2 parts 80 percent. Sodium hydride in parts of tetrahydrofuran is added dropwise at 50 ⁰ C, 20 parts of 1- (2,4-Diehlorphenyl) -2- [jL ^f, 2 ', 4'-triazolyl (l'2J ethanol, dissolved in 50 parts of dry dimethylformamide. after two hours of stirring under reflux for 15.8 parts was added dropwise 3-bromopropene. The mixture is stirred for 1 hour at 50 ⁰ C, decomposed with water and extracted with ether. The extract is added dropwise under ice cooling with 98 percent strength. nitric acid added. There are 19 parts of crystals the recrystallized from from Essigsäureäthlester, 12 parts of l- (2.4-dichlorophenyl) -l-allyloxy-2-I ^1, 2 ', ^4! give -triazolyl- (l') -ethane as a hydraulic nitrate of melting point 129 C.

Example 3

To a suspension of 5 * 2 parts 80 percent. Sodium hydride in parts of tetrahydrofuran is added dropwise at 50 ^° C. 20 parts of 1- (2,4-di-chlorophenyl) -2- | l ^l , 2 ^! , 4 ^f -triazolyl - '(l ^l ) I-ethanol, dissolved in 50 parts of dry dimethylformamide. After stirring for two hours under reflux, 15.5 parts of 3-bromopropine are added dropwise. After one hour of heating at 50 ⁰ C, water is added, the mixture was extracted with ether and ethereal solution dropwise to 98 per cent. Nitric acid. The precipitated crystals are recrystallized from ethyl acetate and give 11 parts of 1- (2,4-dichlorophenyl) - * l-propargyloxy-2-Jl ', 2' ^ '- triazolyl-d ¹ n -ethane hydronitrate with a melting point of 128 ⁰ C,

Example 4

To a suspension of 5 »5 parts 80 percent, sodium hydride in Parts of tetrahydrofuran are added dropwise to a solution of 16.5 at 50.degree

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Parts of 1- (4-chlorophenyl) -2- Fl ', 2 ^r , 4'-triazolyl- (1 *) 1 -ethanol in 50 parts of dimethylformamide. After two hours of stirring at reflux is added dropwise 16.9 parts of 1-bromobutane to at 5O ⁰ C. After one hour of warming to 50 ° C., the mixture is mixed with water and extracted with ether. The ethereal solution is added dropwise with 98 percent. Nitric acid added. The precipitated crystals are recrystallized from ethyl acetate and give 10.5 parts of 1-butyloxy-1- (4-chlorophenyl) -2-il », 2 ', 4 · -triazolyl- (1» I) -ethane hydronitrate with a melting point of 10d C.

Example 5

In a suspension of 4 parts 80 percent. Sodium hydride in 90 parts of tetrahydrofuran is added dropwise at 20 ^° C. to a solution of 13.9 parts of 1- (2,4-dichlorophenyl) -2- [l ', 2 », 4' -triazoly 1- (1 ') I-ethanol in 40 parts of dry dimethylformamide. After two hours of stirring and refluxing is added dropwise at 50 ⁰ C 23 _s 9 parts of 4-trifluoromethylbenzyl bromide dissolved in 30 parts of dimethylformamide and heated for 2 hours at reflux. After decomposition with water, it is extracted with ether and the extract with 98 percent. Nitric acid precipitated. The precipitate obtained is recrystallized from alcohol and gives 14.7 parts of 1- (2.4-dichlorophenyl) -l- (4 "-trifluorobenzyloxy) -2- [I ', 2', 4'-triazoly 1- (1 ')] - Ethane hydronitrate with a melting point of 190 - 191 ° C

Example 6

2.7 parts of 1- (4-bromophenyl) -2- [l ¹ , 2 ', 4' -triazoly 1- (I ¹ ) I -ethanol and 0.5 part of sodium hydride are stirred together in dimethylformamide until the evolution of gas has ceased . 0.7 parts of allyl chloride in 20 parts of dimethylformamide are added dropwise with ice cooling. After stirring for one hour at room temperature (20 ^° C.), the mixture is hydrolyzed, extracted with ethyl acetate, the extract is concentrated, dissolved in ethanol and a solution of hydrogen chloride in isopropyl ether is added. The solution obtained is concentrated, precipitated by adding ether and the precipitate is recrystallized from a mixture of isopropyl ether and isopropanol. Man

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holds 1.6 parts of l-allyloxy-l- (4-bromophenyl) -3- [l ¹ , 2 ', 4 ^f -triazolyl- (l ^! ) j-ethane as hydrochloric! from melting point 142 - 145 ⁰ C.

Example 7

14.1 parts of 1- (4-bromophenyl) -2-F "i ^f , 2 ', 4'-triazolyl- (l')] -propanol- (1) and 1.5 parts of sodium hydride in 50 parts of dimethylformamide are up to 8 parts of allyl chloride are then added dropwise in the cold. After two hours of stirring, water is added, the mixture is extracted with ethyl acetate, the extract is dried, concentrated and distilled. 13.1 parts of 1-allyloxy-1 are obtained. (4-bromophenyl) -2-Q. ^F , 2 ', 4 »-triazolyl- (l') J-propane with a boiling point of 152-154 ° C. at 0.08 torr.

Example 8

3.2 parts of 1- (4-bromophenyl) -2-jl _; ^l, 2 ', 4'-triazolyl ^(l!) J-hexanol (l) and 0.5 parts of sodium hydride in 60 parts of dimethylformamide are until completion of the gas evolution stirred together. A solution of 1.6 parts of allyl chloride in 10 parts of dimethylformamide is added dropwise and, after 2 hours, the mixture is mixed with water and extracted with ethyl acetate. The extract is dried and concentrated and the remaining oil is treated with a solution of nitric acid in isopropyl ether. After recrystallization from butyl acetate, the precipitated crystals give 1.8 parts of 1-allyloxy-1- (4-bromophenyl) -2-Q ^f , 2 ^f , 4 -triazoly1- (1'jj-hexane

hydronitrate with a melting point of 143 - 144 ° C.

Example 9

2.2 parts of 1- (4-chlorophenyl) -2- [I ¹ , 2 '^' - triazolyl-d '^ j -ethanol, 0.5 part of sodium hydride and 10 parts of dimethylformamide are stirred together until the evolution of gas has ceased. Then, while cooling with ice, a solution of 2 parts of 3,4-dichlorobenzyl chloride in 20 parts of dimethylformamide is added dropwise. After stirring for one hour at room temperature, water is added, vinegar

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extracted ester, the extract dried, concentrated and made from isopropyl ether recrystallized. 1.7 parts of 1- (4-chlorophenyl) -l- (3,4-dichlorobenzyloxy) -2- [l ' , 2 ', 4'-triazolyl- (l') "] -ethane with a melting point of 55 - 56 C.

Example 10

2.7 parts of 1- (4-bromophenyl) -2-fl ^t , 2 ', iJ'-triazolyl-d'I -ethanol, 0.5 part of sodium hydride and 20 parts of dimethylformamide are stirred together until the evolution of gas has ceased. A solution of 2 parts of 3,4-dichlorobenzyl chloride in a little dimethylformamide is then added dropwise at 10 ^° C. After one hour, water is added, extracted with ethyl acetate, the extract is dried and concentrated. The oil that remains is dissolved in ether and mixed with a solution of hydrogen chloride added to isopropyl ether. The resulting precipitate gives after recrystallization from ethanol 3.3 parts of 1- (4-bromophenyI) -I- (3.4-dichlobenzyloxy) -2-II ', 2 ·, 4'-triazolyl- (l') l-ethane- hydrochloride, melting point 178 - 180 ⁰ C.

The following table shows a selection of the new fungicidal triazole-containing products Ethers of the general formula I or their acid additives II, which were prepared in a corresponding manner. 2 2

N ⁷ . N ^ -CH-CH- (U; or, N. ^ -CH-QH-Z (VP "^; n. HS

,1

\\ mm

0-R-

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Active ingredient no,

(R ³ J

0.2. 31 727

HS melting point ( ⁰ C)

1 · - (CHg) ₂ -CHj

11 -CH,

- (CHg) ₅ -CHj -CH ₀ -CH = CH ₀

CHg-C ^ CH

CHg-CH = CH-CHj

Cl

H
H
H
H
H
H
H
H

H
H

4-P 4-F 4-P 4-P 4-P 4-F 4-P 4-P

4-P 4-F

4-P

ENT 97-98

HNOj 98-100

ENT 100-103

ENT IO5-IO7 ENT 110-112 ENT 111-112 - 86-87 - 120-121 ENT II7-II9

ENT.

95-96

138-140

Cl H 4-Cl ENT 103-104 12th - (CHg) ₃ -CH ₃ H 4-Cl ENT 13th - (CHg) ₅ -CH ₃ H 4-Cl ENT 97-98 14th -CHg-CH = CHg H 4-Cl HCl 133-135 15th -CHg-CH = CHg H 4-Cl ENT IO9-IIO 16 -CH ₂ -CSCH

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Active ingredient

(R ³ )

O 7 Til 7 °?

HS melting point

17 —CH ^ -CH ⁼ CH — CH-

Cl

Cl '
-CH _n -CH = CH,

■ CH ₂ - / OVci

^C1

-CH ₂ -CH = CH ₂

Cl

Cl

Cl

4-Cl 4-Cl

H H H 4-Cl

H 4-Cl 4-Cl

₃ -CH ₃ 4-Cl ₃ ~ CH ₃ 4-Cl - (CH ₂ J ₃ -CH ₃ 4-Cl

₃ -CH ₃ 4-Cl 4-Br 4-Br

4-Br 4-Br

4-Br

-CH ₂ -CH = CH ₂ -CH ₃ 4-Br

-CH-

4-Br ENT ₃ IO7-IO9

ENT ₃ 114-116

116-117

72-74
119-120

ENT 132-133

ENT ₃ I63-I65

ENT ₃ 146-148

ENT ₃ 156-159

HCl

HCl

142-145

90-92

139-140

175-177

HCl I78-180

^K P

ENT

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0.08

163-164 - 15 -

Active ingredient
No,

R-

R ^£

0. HS Line 11 707
2556319 ENT ₃ Melting point
( ⁰ C) ENT, 145-148 ENT ₃ 143-144 HCl 146-147 ENT ₃ 175-178 142-144

33 -CH ₂ - (O) -Cl

34 -CH ₂ -CH = CH ₂

Cl

37 -CH ₂ - (O> C1

-CH-

- (CH ₂ J ₃ -CH ₃ 4-Br - (CH ₂ J ₃ -CH ₃ 4-Br - (CH ₂ J ₃ -CH ₃ 4-Br

(CH ₂ J ₃ -CH ₃ 4-Br

ENT.

39 - (CH ₂ J ₃ -CH ₃ H 3-Br 40 - (CH ₂ J ₅ -CH ₃ H 3-Br 41 -CH (CH ₃ J ₂ H 3-Br 42 -CH ₂ -CH = CH ₂ H 3-Br

ENT.

ENT.

ENT-ENT.

119-120

43 -CH ₂ -CH = CH-CH ₃

ENT

44 -CH ₂ -C ^- CH

ENT.

ENT

113-114

CX
Cl

70982S / 10U

ENT

ENT,

ENT

140-141

155-156 - 16 -

Active ingredient

(R ³ )

O. Z. 21

HS melting point

- (CHg) ₂ -CH ₃

-CH (CHg) ₃

52 - (CH ₂ J ₅ -CH ₃

53 -CH ₂ -CH = CHg

54 -CH ₂ -CH = CH ₂

55 -CII ₂ -CH = CH-CH ₃

56 -CHg-C = C

-CH,

-CH ₂ - (O) -Cl

-CHp- (CO-Cl 'Cl

'Cl - ^CH 2 <Q)

Cl

-CH

-CH

Cl

Cl Cl

H H H H H

H II

H H H

H H

HH 2,4-Clg HNO ₃ 187-188

2,4-Cl ₂

2,4-Cl,

2,4-Cl,

2,4-Cl ₂

2,4-Cl ₂
2,4-Cl ₂

ENT.

ENT.

2,4-Cl ₂ HNO ₃

ENT

2,4-Cl ₂ HCl

ENT

2,4-Clg HNO 2,4-Clg HNO ₃

2,4-Cl ₂

ENT

ENT.

135-137 135-136 129

110-112

115

128

100-102

176

159-161

2,4-Cl ₂

2,4-Cl,

2,4-Cl ₂

2,4-Cl ₂ HNO ₃ 160-162

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Active ingredient no, (R ³ )

HS Melting point 120-122 ENT ₃ 190-191 ENT, I6I-I63 98-99 142-143

er 65 -CH ₉ - (O,

67 68 69 70 71

Cl

P,

Cl

Cl

Cl

72 -CH ₂ -CH = CH ₂ 73 -CH ₂ -CH = CH ₂ 74 -CH ₂ -CH-CH ₂ Br Br 75 -CH ₂ -CH = CH ₂ 76 -CH ₂ -CH = CH ₂ 77 -CH ₂ -CH = CH ₂ 78 -CH ₂ -CH = CH ₂ 79 -CH ₂ -CH = CH ₂ 80 -CH ₂ -CH = CH ₂

H H H H

H H H H

H H H H H H

2,4-Cl,

2,4-Cl ₂
2,4-Cl ₂

2-Cl, 4-Br

2-Cl, 4-Br

2-Cl, 4-Br HCl

2-Cl, 4-Br HCl

ENT.

4-OCH ₃ ENT ₃

4-Cl

4-Cl

4-CH,

2,4-Cl ₂

ENT.

ENT

184-185

I8I-192

96-98 120-121 I29-I3I

122-123

ng ² 1,556]

2,4-Cl ₂ 0.5 H ₂ SO ₄ 80 2,4-Cl ₂ H ₂ SO ₄ 2,4-Cl ₂ H ₃ PO ₄

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105

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Active ingredient
No.

R-

(R ³ )

η "31

HS melting point

81 -CH ₂ -CH = CH ₂ H 82 -CH ₂ -CH = CH ₂ H 83 -CH ₂ -CH = CH ₂ H 84 -CH ₂ -CH = CHCl H 85 -CH ₀ -CH-CH-
Br Br H

86 -CH ₂ -CH = C (CH,) ₂

87 -CH ₂ -CH ₂ -O-CH ₃

-CH ₂ -C = C-CH ₃

89 -CH (CH ₃ ) (CH ₂ P)

90 -CH (CH ₃ ) = CH ₂

91 -CH ₂ -C = CH ₂

Cl

92 -CH ₀ -C = CHCl
Cl

93 -CH ₀ -C = CH

H H H H H H

2,4-Cl ₂
2,4-Cl ₂
2,4-Cl ₂
2,4-Cl ₂
2,4-Cl ₂

2,4-Cl ₂
2,4-Cl ₂

0.5

2,4-Cl ₂ C ₆ H ₅

2,4-Cl ₂

2,4-Cl ₂

COOH

ENT

2,4-Cl ₂ HNO ₃

ENT.

ENT

ENT.

ENT.

ENT.

ENT

ENT.

102-103

127-128 150-151

134-135 138-140 133-134

131-132

128-130

94 -CH ₀ -C = CH

2,4-Cl ₂

ENT.

95 -CH ₂ -CH = C-CH;

Cl

96 - (CH ₂ J ₆ -CH ₃

2,4-Cl ₂ HNO ₃

2,4-Cl ₂

70982B / 10U

ENT.

- 19. -

Active ingredient
No.

- iS - R ² (R ³ ) _n o.z. 31 727 -Xl. 2556319 HS melting point

97 -CHg-CH = CHg

3,4,5- (OCH ₃ ) ₃ HNO ₃

98 -CHg- (O) -Cl

99 -CH,

1 cl

100 -CHg-CH = CHg 101 -CH,

H H H

3,4,5- (OCH ₃ ) ₃ HNO ₃

ENT

2,3,4- (OCH ₃ ) ₃ HNO ₃

102 -CH,

103 -CH ₂ -CP ₃

104 -CH ₀ -CH = CH,

105 -CHg-C = CH

106 -CH ₂ -CH = CH ₂ 107 -CH ₂ -

CH = CH,

2,4-Cl ₂

4-Br

4-Br

H 2,4- (OCH ₃ ) ₂

2,5- (OCH ₃ ) ₂

ENT.

ENT.

I55-I56

99-100

ENT ₃ 119-120

ENT.

ENT.

The triazole ethers according to the invention and their acid addition salts are characterized by an excellent effectiveness against a broad spectrum of phytopathogenic fungi. You are to Partly systemically effective and can be used as foliar and soil fungicides, but especially also as dressing agents.

The fungicidal compounds are of particular interest for combating a variety of fungi on different crops.

709825/1014

- 20 -

-20-- OZ Jl (έ (

In this context we understand cultivated plants in particular special wheat, rye, barley, oats, rice, corn, cotton, soy, Coffee, sugar cane, fruits and ornamental plants in horticulture, as well as vegetables such as cucumbers, beans and cucurbits.

The new compounds are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoriacearum (powdery mildew) on cucurbits, Podosphaera leucotricha on apples,

Uncinula necator on vines,

Erysiphe polygoni on beans,

Sphaerotheca pannosa on roses,

Puccina species on grain,

Rhizoctonia solani on cotton,

Botrytis cinerea on strawberries and vines as well as Helminthosporium and Fusarium species on grain, Ustilago species on grain and sugar cane, Rhynchosporium secale on grain,

Septoria nodorum and Septoria tritici on wheat.

The substances according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granulates. The application forms depend entirely on the intended use; they should be in everyone Case ensure a fine and even distribution of the active substance. The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and / or carriers, optionally using emulsifiers and dispersants, in the case of use In addition to water as a diluent, other organic solvents can also be used as auxiliary solvents. As auxiliary materials The following essentially come into question: Solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), Paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural rock flour (e.g. kaolins, clays,

709826/1014 ' ²¹ '

G.Z. 31 727

Talc, chalk) and synthetic stone powder (e.g. highly dispersed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene - petroleum alcohol - fither, Alkyl sulfonates and aryl sulfonates) and dispersants, such as lignin, sulfite waste liquors and methy! Cellulose.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90.

The formulations or the ready-to-use ones made from them Preparations such as solutions, emulsions, suspensions, powders, dusts, pastes or granules are used in a known manner.

Depending on the type of effect desired, the application rates are between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.

The agents according to the invention can be used in these forms are also present together with other active ingredients, such as herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied. When mixed with fungicides, an enlargement is obtained in many cases the spectrum of fungicidal activity in a number of these fungicide mixtures synergistic effects also occur, i.e. the fungicidal effectiveness of the combination product is greater than that of the added effectiveness of the individual components.

The following list of fungicides with which the invention Connections can be combined, should explain the combination possibilities, but not restrict them.

Fungicides combined with the triazole ethers according to the invention can be, for example:

Dithiocarbamates and their derivatives, such as
Ferridimethyldithiocarbamate (Ferbam),
Zinc dimethyldithiocarbamate (Ziram),

70982B / 10U " ²² "

- £ 2- - O.Z. 31 727

Manganese-ethylene bisdithiocarbamate (Maneb), manganese-zinc-ethylenediamine-bis-dithiocarbamate (Mancoceb), Zinc ethylene bisdithiocarbamate (Zineb),

Tetramethylthiuram sulfide (thiram),

3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazin-2-thione, Ammonia complex of zinc-CNjN'-ethylene-bis-dithiocarbamate) and NjN'-polyethylene-bis-CthiocarbamoyD-disulfide (Metiram), Zinc-CNjN'-propylene-bis-dithiocarbamate) (Propineb), Ammonia complex of zinc-CNjN'-propylene-bis-dithiocarbamate) and NjN'-polypropylene-bis-CthiocarbamoyD-disulfide (methyl-metiram);

Nitrophenol derivatives, such as

Dinitro (1-methylheptyl) pheny1-crotonate (dinocap) _s 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate (binapacryl), 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

heterocyclic structures such as

N-trichloromethylthio-tetrahydrophthalimide (captan), N-trichloromethylthio-phthalimide (Folpet), N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide (captaf oil), 2-heptadecyl-3-imidazoline acetate (gylodin), 2,4-dichloro-6- (o-chloroanilino) -s-triazine (anilazine) diethylphthalimidophosphorothioate (Plondrel), 5-Amino-1-J bis (dimethylamino) -phosphiny1 -3-pheny1-1,2,4-triazo i, 5-ethoxy-3-trichloromethy1-1,2,4-thiadiazole, 2,3-Dicyano-1,4-dithiaanthraquinone (Dithianon), 2-Thio-1,3-dithio- (4,5-b) -quinoxaline (Thioquinox), 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester (benomyl), 2-methoxycarbonylamino-benzimidazole,

2-Rhodanmethylthio-benzothiazole (Busan), 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, 2- (0,0-diethyl-thionophosphoryl) -5-methyl-6-carbethoxy-pyrazolo- (1,5a) -pyrimidine (Pyrazaphos),

Pyridine-2-thiol-1-oxide,

2-chloro-4-trichloromethyl-6-methoxypyridine (pyroxychlor), 8-hydroxyquinoline or its copper salt, 5,5-dimethyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,

70ΘΒ2Β / 10Η " ²³ '

5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2, ¹ i-dioxo-1,3-oxazolidine,

2- KFury 1- (2) | -benziraidazole,

Piperazine-1,4-diyl-bis- [1- (2,2,2-trichloro-ethyl) -formamide] (Triforine)

2- [thiazolyl- (4) -benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine (Dimethirimol),

Bis (p-chlorophenyl) -3-pyridinemethanol,

5,6-dihydro-3-niethyl-l, 4-oxathiin-3-carboxanilide (carboxin), 5,6-dihydro-3 ~ niethyl-l, l ^{i-oxathiin-3-carboxanilide-4,4-dioxide} ( Oxicarboxin),

2-methyl-5,6-dihydro-4-H-pyran-3-carboxylic acid anilide (pyracarbolide), 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, and various fungicides, such as

1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene (thiophanate), 1,2-bis- (3-methoxycarbonyl-l-thioureido) benzene (Thiophanate M), (S-Ethyl-N- (3-dimethylaminopropyl)) thiol carbamate hydrochloride (Prothiocarb),

Dodecylguanidine acetate (Dodine),

3- 2- (3,5-Dimethyl-2-oxycyclohexyl) -2-hydroxyethylj-glutarimide (Cycloheximide),

2-methylbenzoic anilide (Mebenil),

2-iodobenzoic acid anilide (benodanil)

N-dichlorofluorine thylthio-N ¹ , N'-dimethyl-N-phenyl-sulfuric acid diamide (dichlofluanid),

2 » 4 » 5 » 6-tetrachloroisophthalonitrile (Daconil), 1- (3 s 4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane (chloroaniformethane),

2,6-dimethyl-N-tridecyl-morpholine or its salts 2,6-dimethyl-N-eyclododecyl-morpholine or its salts, 2,3-DiChIOr-1,4-naphthoquinone,

1, 'I-dichloro-3,5-dimethoxybenzene,

p-dimethylaminobenzene diazo sodium sulfonate, 2-chloro-l-nitro-propane,

Polychloronitrobenzenes such as

Pentachloronitrobenzene,

Methyl isothiocyanate,

- 24 -

709825/1014

O. Z,> 1,727

fungicidal antibiotics, such as

Griseofulvin or kasugamycin,

Tetrafluorodichloroacetone,

1-phenylthiosemicarbazide,

Bordeaux mixture,

compounds containing nickel and sulfur.

The admixture of these agents to the fungicides according to the invention can be done in a weight ratio of 1:10 to 10: 1.

If necessary, they can also be added immediately before use (tank mixing).

The following examples illustrate the biological effectiveness of the new compounds.

The comparison substance described in DOS 2,063,857 was used Compound of the following formula

A,

QrCH ₂ -CH = CH ₂

which is designated in the following for the sake of simplicity with A, is used,

Example 11
Effect against wheat powdery mildew

Leaves of potted wheat seedlings of the "Caribo" variety are sprayed to runoff with 0.05 and 0.025% (% by weight ) aqueous broths containing 80 % active ingredient and 20 % lignosulphonate in the dry matter. After the spray coating has dried on, the plants are dusted with oidia (spores) of wheat powdery mildew (Erysiphe graminis var. Tritici). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ^° C. and 65-70 % relative humidity. After 10 days, the extent of powdery mildew development is determined, _nc -

709B25 / 10U - 25 -

ο.ζ. 31 727

Active ingredient no.

Infestation of the leaves after spraying with active substance stock

+ = 0.05 0.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 0 1 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

5 6 8

10 Ik 15 20 26 27 30 31 53 54 55 56 58 59 66 67 76

(known)

Control (untreated)

0 5 no infestation, graded up to 5 = total infestation

Example 12 Action against brown rust

Leaves of potted wheat seeds of the cultivar "Caribo" are made with spores of brown rust (Puccinia recondita)

709825 / 10U

- 26 -

ο.ζ. 51 727

pollinated. The pots are then placed in a chamber with high humidity ( 90-95%) for 2k hours at 20-22 ° C.
During this time, the spores germinate and the germinal claws penetrate the leaf tissue. The infected plants are then with 0.1 % ₃ . 0.05 and 0.05 # strength (% by weight ) aqueous
Spray mixtures »containing 80 % active ingredient and 20 % lignosulphonate in the dry substance» sprayed dripping wet. After the spray coating has dried on, the test plants are placed in a greenhouse at temperatures between 20 and 22 ° C. and 65-70% relative humidity. After 8 days, the extent of the rust fungus development on the leaves is determined.

Active ingredient Infestation of the leaves after spraying

No. with % ± ser active ingredient broth

+ = 0.1 0.05 0.025

10 Ik .

15 20 30 31 53 54 55 56 58 59 66 61 16

A.
(known)

Control 5 5

,, 7 ü 9 8 Z b / 1 U "K

0 1 3 0 1 3 0 1 3 0 2 3 0 0 0 0 0 0 1 2 3 1 2 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

ο.ζ. 51 727

Example 13
Striped sick witch on barley (Helrninthosporium sativum)

100 g samples of a strongly contaminated Helminthosporium sativum fungus Infested barley seeds of the variety "Asse" are in glass bottles for about 5 minutes with 250 mg (= 0.25% by weight) of the in the The pickling agents listed in the table are carefully pickled. Then on a 2% malt extract agar in Petri dishes per Petri dish 10 pickled grains each laid out; A total of 10 Petri dishes are used for each test series. The shells will placed at temperatures between 8 and 10 ° C. After a one-week trial period, the grains that are infected with Helminthosporium are counted exhibit.

Active ingredient ..% active ingredient. .% Active ingredient

fungal attack in the dressing agent

53 5 5

10 0

A (known) 5 10

10 2

Control (untreated) - 100

example Ik

Effect against vine peronospora

Leaves of potted vines of the Müller-Thurgau variety are sprayed with aqueous dispersions containing 80% active ingredient and 20 % sodium lignosulfonate in the dry matter. 0.1 solution spray liquors (% by weight , based on the dry substance) are used. After the spray coating has dried on, the leaves are infected with a zoospore suspension of Plasmopara viticola. The plants are then first placed in a water vapor-saturated (humid) chamber at 20 ° C for 16 hours and then in a greenhouse with temperatures between 20 and 30 ° C for 8 days. After this time the plants will accelerate and strengthen the

- 28 -

709825 / 10U

O.Z. Jl

Against the outbreak of the sporangia carrier, set up in the humid chamber for 16 hours. Then the counting takes place Spore bearing on the underside of the leaves. Untreated infected control plants serve as a comparison.

Active ingredient commanded the leaves after spraying

with active ingredient broth

+ = 0.1

20 0

53 1

A (known) 3

Control untreated) 4

0 = no fungal infestation, graduated to 5 = total infestation

Example 15 Piltrate Papers Tests

Pilgrim paper disks with a diameter of 13 mm and a thickness of 1 mm are impregnated with 0.2 ml solutions each containing 800, 400 and 200 parts of active ingredient per million parts of solution (ppm). The discs are then placed on a 5% malt extract agar in Petri dishes which have previously been inoculated separately with spores (conidia) of the fungi Alternaria solani, Helminthosporium gramineum, Fusarium culmorum, Botrytis cinerea, Septoria nodorum and with the mycelium of the fungus Rhizoctonia solani. The dishes are then ^{incubated at 22-24 °} C. for 3 days. After this time, the fungi in the control dishes have developed very well j the fungicidal effectiveness of the active ingredients is assessed on the basis of the fungus-free zones (zones of inhibition) created around the pilgrim paper disks as follows:

no inhibition zone (no fungicidal effectiveness)

+ small inhibition zone <1 mm (low fungicidal effectiveness) ++ medium zone of inhibition 1-5 mm (good fungicidal effectiveness) +++ very large zone of inhibition > 5 mm (very good fungicidal effectiveness)

- 29 -

709825 / 10U

ο.ζ. 31

a) Alternaria solani

Active ingredient ... ppm active ingredient in the impregnation solution

800 400

Control (untreated) -

b) Helminthosporium gramineum

Active ingredient ... ppm active ingredient in the impregnation solution

800 400

Control (untreated) -

c) Pusarium culmorum

Active ingredient ... ppm active ingredient in the impregnation solution

800 400

Control (without active ingredient)

70982B / 10U

- 5-Θ-- ° ^ζ 2 ¹

d) Botrytis cinerea ^ bODo IcI

Active ingredient ... ppm active ingredient in the impregnation solution

800 400

Control (without active ingredient) -

e) Septoria nodorum

Active ingredient.,. Ppm active ingredient in the impregnation solution

800 400

Control (without active ingredient) - -,

f) Rhizoctonia solani

Active ingredient ... ... ppm active ingredient in the impregnation solution

800 400

Control (without active ingredient) -

example

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-0V-pyrrolidone and a solution is obtained which is suitable for use in the form of the smallest drops is suitable.

709825/1014

- CZ. 31 727

.ir *

Example 17 2556319

20 parts by weight of compound 2 are dissolved in a mixture from 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 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 out and Finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02 percent by weight of the Contains active ingredient.

Example l8

20 parts by weight of compound 3 are dissolved in a mixture those from 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of the Addition product of 40 moles of ethylene oxide and 1 mole of castor oil consists. By pouring the solution into and finely distributing it 100,000 parts by weight of water give an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 19

20 parts by weight of compound 4 are dissolved in a mixture which consists of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 28O ⁰ C and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 20

20 parts by weight of active ingredient 5 are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-cfe-sulfonic acid, 17 parts by weight

709825/1014

o.ζ. 51 727

parts of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 6ü parts by weight of powdered silica gel are mixed well and ground in a hammer mill. By fine distribution the mixture in 20,000 parts by weight of water gives a spray mixture which contains 0.1 percent by weight of the active ingredient.

Example 21

3 parts by weight of compound 6 are intimately mixed with 97 parts by weight of finely divided kaolin. One gets in this way a dust containing 3 percent by weight of the active ingredient.

Example 22

30 parts by weight of compound 7 are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight * share paraffin oil, which has been sprayed onto the surface of this silica gel, intimately mixed. This is how you get a Preparation of the active ingredient with good adhesion.

Example 23

40 parts by weight of the active ingredient 8 are mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts Silica gel and 48 parts of water are intimately mixed. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which is 0.04 percent by weight Contains active ingredient.

Example 24

20 parts of active ingredient 9 are mixed with 2 parts of the calcium salt of dodecylbenzsulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol sulfonic acid urea formaldehyde «· hyd condensate and 68 parts of a paraffinic mineral oil intimately mixed. A stable oily dispersion is obtained.

- 33 -

709825/1014

Claims (17)

- · & - ο.ζ. 31 claims 2bbbol9 Substituted triazole ethers of the formula I. , 2 in the R is an alkyl radical which is optionally substituted by 1 or more halogen atoms, an alkoxy or cyano group with 1-8 carbon atoms, an alkenyl radical with 3-6 carbon atoms which is optionally substituted by halogen, an alkynyl radical with 3-6 carbon atoms which is optionally substituted by halogen or a benzyl radical of the general formula R V means in the m the numbers 0-5 and R chlorine, bromine, trifluoro- methyl or alkyl with 1-4 carbon atoms, R denotes a hydrogen atom, an alkyl radical with 1-5 carbon atoms, denotes a phenyl or a cyclohexyl radical, η denotes the numbers 0-3 and
R denotes fluorine, chlorine, bromine, a methyl, trifluoromethyl, phenyl or alkoxy group with 1-3 carbon atoms, where in the case η = 2 and 3 the radicals R can be identical or different. 2. Acid addition salts of 1- (2-aryl-3-alkoxy-ethyl) -I, 2,1-triazoles according to claim 1. 3. 1-Alkoxy-α ~ (2,4-dichlorophenyl) -2- (1 ·, 2 ', 4'-triazolyl- (1 ») ■ ethane of formula 70982B / 10U ORIGINAL INSPECTED ■ γ = · ^ν ü.z. 31 ¹ 1 whereby R is an alkyl, alkenyl or alkynyl radical with 1-6 carbon atoms means and their acid addition salts with organic and inorganic acids. 4. l-Allyloxy-l- (2,4-dichlorophenyl) -2- (l ', 2', 4'-triazolyl- (I ')) ethane and its acid addition salts. 5. l-propargyloxyl- (2,4-dichlorophenyl) -2- (l ', 2', 4'-triazolyl- (l ')) ethane and its acid addition salts. 6. l-crotyloxy-l- (2,4-dichlorophenyl) -2- (l ', 2', 4'-triazolyl- (l ')) ethane and its acid addition salts. 7. 1-Propyloxy-1- (2,4-dichlorophenyl) -2- (1 ^T , 2 ', 4 »-triazolyl- (1')) - ethane and its acid addition salts. 8. l-Butyloxy-l- (2,4-dichlorophenyl) -2- (l ', 2', 4 »-triazolyl- (l ^f )) - ethane and its acid addition salts. 9. 1-Aryl-1- (3,4-dichlorobenzyloxy) -2- (1 ', 2', 4 »-triazolyl- (1»)) ethanes the formula in which X and Y are hydrogen, chlorine or bromine, with the proviso that X and Y are not hydrogen at the same time interpret, and their acid addition salts with organic or inorganic acids. 709825/1014 - 35 - - 3g - ο.ζ. 31 727 • 3. 2556313 10. 1- (4-bromophenyl) -l- (3,4-dichlorobenzyloxy) -2- (l ^!, 2 ', 4'-tri ~ azolyl- (l')) - ethane and its acid addition salts, 11. 1- (4-Chlorophenyl) -1- (3,4-dichlorobenzyloxy) -2- (1 ', 2 ·, 4 · -triazolyl- (I ¹ )) - ethane and its acid addition salts. 12. 1-Allyloxy-1- (4-bromophenyl) -2- (1 ·, 2 ', 4 · -triazoly1- (1') alkanes the formula R ²
K _n . N-CH-CH- ^ V Br 0-CH ₂ -CH = CH ₂ 2
in which R has the meanings given in claim 1, as well as their acid addition salts. 13. 1-Allyloxy-1- (4-bromophenyl) -2- (1 ·, 2 ', 4'-triazoly1- (1 *)) - ethane and its acid addition salts. 14.l-Allyloxy-1- (4-bromophenyl) -2- (l ', 2 ^f , 4'-triazolyl- (l ^f )) propane, 15. 1-Allyloxy-1-ary1-2- (1 ^!, 2 ', 4'-triazolyl- (l ^f )) - ethane of the general formula 0-CH ₂ -CH = CH ₂ in which X and Y have the meanings given in claim 9, as well as their acid addition salts. 16. Use of l- (2-aryl-2-alkoxy-ethyl) -l, 2,4-triazoles according to Claim 1 or its acid addition salts according to Claim 2 as fungicides. 17. Fungicides containing 1- (2-Ary1-2-alkoxy-athyI) -I, 2,4-triazoles according to claim 1 or their acid addition salts according to claim 2. 709825/1014 ~ ³⁶ " ο.ζ. 31 727 Process for the preparation of 1- (2-aryl-2-alkoxy-ethyl) -1,2,4-triazoles and their acid addition salts according to Claims 1 and 2, characterized in that 1,2,4-triazole is treated with a l- Aryl-2-halo-alkanone- (l) converts, the resulting l-aryl-2-triazolyl-alkanone- (l) is reduced to the l-aryl-2-tri- ^ azolyl-alkanol- (1), this in be Converted alkali salt and the alkali l-aryl-2-triazolyl alkanolate with a compound of the general formula where R has the meaning given in claim 1 and Z is chlorine, bromine, iodine, methosulphate or toluenesulphonate, reacted and the compound obtained, optionally by adding a stoichiometric amount of an organic or inorganic acid converted into its acid addition salt. BASF Aktiengesellschaft., 70982B / 10U