CA1145253A

CA1145253A - Fungicidal agents, a process for their preparation and their use as fungicides

Info

Publication number: CA1145253A
Application number: CA000352114A
Authority: CA
Inventors: Erik Regel; Karl H. Buchel; Wilhelm Brandes; Paul-Ernst Frohberger
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1979-05-19
Filing date: 1980-05-16
Publication date: 1983-04-26
Also published as: JPS55154907A; PL121128B1; DK216380A; DD151039A5; DK150591B; EG14294A; IL60098A; DE3060698D1; DE2920374A1; ATE1360T1; ZA802936B; JPS6337764B2; TR20400A; PT71210A; PH16068A; BG31792A3; IL60098A0; EP0019189A1; NZ193745A; PL224311A1

Abstract

Fungicidal agents, a process for their preparation and their use as fungicides ABSTRACT OF THE DISCLOSURE
A method of combating fungi which comprises applying to the fungi or a habitat thereof a fungicidally effective amount of a hydroxyalkyl-triazole of the formula

Description

- 1 - T~pe IIa The present invantion relates to the u~e of certain hydroxyalkyl-triazole~ as fungicides.
It has already been di~closad khat l-phenyl-2-triazol-l-yl-ethanols substituted in the phenyl part have good fungicidal properties (Qee DE-OS (German Published Specification) 2,431,407 [Le A 15 735]). However, their activity is not always completely satisfactory, especially when small amounts and low concentrations are applied.
It has now been found that the hydroxyalkyl-triazoles of the general formula Rl OH
R2~3 C - ( CH2 ) m ~ R ( I ) R3n Az in which Az represents triazolyl, R represents an optionally substituted phenyl, naphthyl or tetrahydronaphthyl radical, Rl represents an optionally slubstituted phenyl or cycloalkyl radical and R2 represants hydrogen,or Rl and R2 together, in an o-position relati~e to one another, reprPsent an optionally eubQtituted, multi-membsred methylene bridge, or together with the phenyl ring represent naphthyl, R3 represents halogen, alkyl, alkoxy or halogeno- :
alkyl, n rapresents 0, 1, 2 or 3~ the substituants R3 being selected independently when n i8 2 or 3, and : m represents 0 or 1, and physiologically acceptable acid-addition salta there-of have good fungicidal properties.

Le A 19 636 ~5~253 Accorclingly 9 the present invention provideQ a fiungicidal composition containing as active ingredient a compound of the formula (I), or a physiologically acceptable acid-addition salt thereof, in admixture with a solid or liquafied gaseous diluent or csrrier or in admixturo with a liquid diluent or carrier containing a surface-active agent.
The invention also providas a method of combating fungi which compri~es applying to the fungi, or to a habitat thereof~ a compound of the formula (I), or a physiologically acceptable acid-addition Ralt thereof, alone or in the form of a composition containing as active ingredient such a compound or qalt, in admixture with a diluent or carrier.
Surprisingly, th~ hydroxyalkyl-triazoles of thc formula (I) which can be used according to the invention exhibit a b~tter fungicidal activity than the substitut-ed l-phenyl-2-triazol-1-yl-ethanols known from the state of the art, which are closely related compounds chem-cally and from the point of view of their action. The substances which can be used according to the inYention thus represent an enrichment of the art.
Preferred hydroxyalkyl-triazoles of the formula (I) which can be used according to the invention are thoee in which Az repr~santq 1,2,4-triazol-1-yl or 1,2,4-triazol-4-yl, R reprosents optionally substituted phenyl, n2phthyl or tetrahydronaphthyl, the or each substituent being selected from halcgen (especially fluorine, chlorine and bromine), straight-chain or branchad alkyl and alkoxy with in either caqe 1 to 4 carbon ato~s and halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms (e~pecially with 1 or 2 carbon atoms and up to 3 identical or different hslogen atome, preferred halogens being fluorine and chlorin~, Le A 19 636 ~L4~ii3 and trifluoromsthyl being mentioned as an example), R r~presents optionally substituted phenyl or cycloalkyl with 3 to 7 carbon atoms, the or each substituent being selected from halogen (especially fluorine, chlorine or bromine), alkyl with 1 to 4 (aspecially with 1 to 2) carbon atoms and alkonyl with 2 to 4 carbon atoms, and R2 r2prssents hydrogen9 or Rl and R~ together, in an ortho-position ralativa to one another, represent an optionally mono~ubstituted or polysubstitutcd methylene bridge with 3 to 5 methy~ene groups, the or each substituent being selected from halogen (especially fluorine7 chlorine or bromine) and alkyl with 1 to 4 (especially with 1 to 2) carbon atome,or together with the phenyl ring represent naphthyl, R3 represents halogen (especially fluorine, chlorine or bromine), straight-chain or branched alkyl or alkoxy with in aither case 1 to 4 carbon atoms, or halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atomR (especially with 1 or 2 carbon atoms and up to 3 identical or different halogen atoms, preferr~d halogens being fluorine and chlorine, and trifluoromethyl being mentioned as an example), n represents 0, 1 or 2 and m represents n or 1.
Very particularly preferred compounde of the formula (I) are thos~ in which Az has the preferrsd meaning indicated above, R represents phenyl which is optionally mono-substitutsd or disubstituted, by identical or differ~nt substituents, by chlorine, fluorine or methyl, or naphthyl or tetrahydronaphthyl;
Rl repreqents phenyl, cyclopentyl or cyclohexyl, and thcse radicals can optionally be monosubstituted or disubstituted by chlorine9 bromine, fluorine, mothyl, ethyl, isopropyl or isopropenyl; and Le A 19 636 ~5~53 R2 represents hydrogen; or R and R~ together, in anortht,-position relative to one another, reprasent a tri-, tetra- or penta-methylene bridge, which is optionally substituted by chlorine or methyl, or togethar with the phenyl ring represent naphthyl;
R3 represents chlorine, fluorine or methyl; n represent~
O or l; and m represents 0 or 1.
The following compounds of tha general formula (I) (Az in each case representing 1,2,4- or 1,3,4-triazol-1-yl) may be mentioned specifically, in addition to the compounds mention~d later in the proparative examples:

CHz n ~z R R1 R2 R3 m Cl ~Cl 4~) H - O

~Cl 4- <~ H - O

4-~ H - O

4-~ H - O

Cl 4-@ H - O

Cl~ 4-~ H -- O

Le A 19 636 f~ Rl R2 R3 m n ~Cl 4-~ H - O

F Cl 3,4-(CH2)3- - O

~3 4~-CH3 H - O
Cl, Cl -OE) 4~ H - O
F~ Cl -~ 4-:~ H - 0 ~ 4~CH3 H - 0 Cl~ 4~0CH3 H - 0 C1 4~!C(CH3 )3 H - O
Cl ~F 4~-Cl H - 0 _~ Cl H - O

~Cl 3,4-(CH2 )~- -4~Cl H - 0 ~Cl 4~-Cl H - 0 4~ H - 0 ,Cl Cl 4~-C1 4~ H - O
Cl Cl ~-Cl 4~> H - O

L~ A 19 636 ,.

`

~5~53 R Rl F~2 R3 m _ _ _ n ,~ 4~ H - O

4~ H ~ O
Cl ~-Cl 4- ~ H - O

Cl 3,4-(CH2 ~ O

Cl~ 3,4-(CH2 ),~, - O
~Cl 4-~ H - O

~-F 4~)-F H - O

~F 4- (~> H - O

Cl 4~ H - O

~F 4~ H - O
Cl ~Cl 4~Cl H - Q

C~-F 4~> H - O
~})-Cl 4- <~ H - 1 ~ 4 ~) H - 1 Cl, Cl~ ~ H ~ 1 -~ 4-@ H - 1 Cl Le A 19 636 R Rl R2 R3n m Cl 4- ~ H

-~ 4-~ H - 1 4~ C~I3 H

~' 4~C2 Hg H - 1 F` 4~C3 H7 -i H
Fc~l~ 4~) C~CH2 H - 1 -~ 4~)-CH3 H

Cl~ 4~C2 H5 H

Cl~ 4-~C3 H7~ -i H
Cl~ 4~> C~ H - 1 ~3-C1 4-~-Cl 3,4-(CH2 )3- _ ~Cl 3,4-(CH2 )~

~ 4~-Cl H

j~F 4~ H - 1 :

~3 4~Cl H

Le A 19 636 ~5'~3 - a R ~1 R2 R3n m Cl~F 4~oc~

~Cl 4~C H - 1 4~-C1 4~ H
Cl 4~> 4~ H - 1 Cl ~-Cl 4~Cl H - 1 F 4C~) H

~)-F 4~)-Cl H - 1 Cl Cl ~-Cl 4~ H
Cl Cl ~)-Cl 4~ H - 1 Cl Cl ~ 4~ H
Cl Cl ~) 4~-Cl H
Cl' Cl -$~Cl 4-~Cl H

4~Cl H - 1 ~) 4 3 H - 1 ,~ 4-~ H - 1 L~ A 19 636 .

53~

Rl R2 R3ll m Cl _ ~ Cl 4- ~ 3-l - 1 Cl 3,4-(CH2)4-Cl -~) 3,4-(CH2)3-Cl Cl~
- ~ Cl 4 ~ H

; _ ~ F 4 ~ F H

- ~ F 4 ~ H

The active compounds of the :Eormula (I~ and acid addition salts thereof have not hitherto been described in the literature. I-lowever, the sub-stances, their preparations and medicinal use are the subject of our Canadian Patent Applications 340~546 LLe A 19 272] ~nd 340,547 ILe A 19 273] both of 23.11.1979. They can be prepared by the processes described in these applica-tions, by ~a) reacting triazolylmethyl phenyl ketones of the general formula R ~ ,_ 0 in which Az, Rl, R2, R3 and n have the meanings ~ndicated above, "-' .' , .

;i3 with a Grignard compound of the general formula R ~ (CH~ ~m ~ Mg - X ( III), in which R and m have the meanings indicated above and X reprsssnt~ halogen, e~pecially chlorine or bromine, in the prcsence of a sGlvent customary for a Grignard reaction, praferably an ether, at a tsmperature between 30 and 80C, or (b) reacting l-halogeno~alkyl alcohols of the general formula R~ OH
R2 ~ C - (CH2)~ - R (IV), R3n l H2 y in which R, Rl, R2, R3, n and m have the meanings indicated above and Y represents halogen, e~pecially chlorine or bromine, with triazole, if appropriate in the presence of an acid-binding ag~nt, for example an exce~ of triazole, and if appropriatc in ths presence of an inert organic aolvent ~

fo~ sxample acetonitrile, at temperature~ betweon 30n and 200C, preferably at the boiling point of tho colvent.
In some cases, it proves advantageous to employ the triazoles in the form of their alkali metal ~alts, such as the 30dium salt or potaa~ium salt.
The actiYa compounds to be used according to the invention in which the index m rapre~cnts 0 can al~o be obtained by a furthar process, which, however~ has al80 Le A 19 636 , . , - : . .

i%53 been described in published European Patent Application Serial No. 0,017,080, by (c) reacting oxiranes of the general formula Rl ~ ~ R V

in which R, Rl, R2, R3 and n have the meanings indicated above, with triazole in the presence of an alkali metal alcoholate, for example sodium methylate, and in the presence of an inert organic solvent, for example dimethylformamide, at temperatures between 30 and 100C.
The triazolylmethyl phenyl ketones of the formula II have not hitherto been described in the literature. However, they can be prepared in a generally customary and known manner by reacting corresponding phenacyl halides ~that is to say ~-halogenoacetophenone derivatives) with triazole in the presence of a diluent, for example dimethylformamide, and in the presence of an acid-binding agent, especially an excess of triazole, at temperatures between 20 and 80C.
The Grignard compounds of the formula III are generally known com-pounds of organic chemistry.
The l-halogeno-alkyl alcohols of the formula IV have not yet been described in the literature. However, they can be prepared in a generally customary and known manner, by reacting corresponding phenacyl halides with Grignard compounds of the formula III according to process (a) above.
The oxiranes of the formula V have not yet been described in the literature. They are also the subject of the abovementioned European Patent Application No. 0,017,080, and can be obtained by reacting corresponding ketonea eith~r with dimethyloxosulphonium methylide in a manr.er which is in itself known in tha presence of a diluent, for examplo dimethylsulphoxide, at temperatures betwaen 20 and 80C, or with trimethylsulphonium mathyl sulphate in a manner which is in itself known in the presence of a two-phase system and if appropriate in tha presencs of a phase transfer catalyst, at temperatures between O and 100C.
Any of the physiologically acceptable acids can be used for the preparation of acid addition salt~ of th~
compounds of the fDrmula (I). These acids include, as preferences, hydrogen halide acids tfor example hydrobromic acid and in particular hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, mono-functional and bifunctional carboxylic acids and hydroxy-carboxyl:ic acids(for example acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and sulphanic acid~ (for example p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid).
The salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt forma-tion methcds, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the

2~ acid, for examplc hydrogen chloride, and they can be iso-lated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent.
The active compound~ to be used according to the invention exhibit a powerful microbicidal action end can be employed in practice for combating undesired micro-organisms. The active compounda are suitable for use as plant protection agents.
Fungicidal agents in plant protection ars cmployed for combating Pla~modioohoromycet~, Ocmycete3, Le A 19 636 ~5~i3 Chy~ridi~rnycetes, Zygomycetsq9 Ascumycstes, and D~utcromyc~t~s.
The good toleration, by plants, of the active compoun~s, at thc ~oncentrations requi~2d for combati~g plant di~ea~s, p~rmits treatment of above-ground parts o~
plants, of vegstativ~ propagation tock and ~eeds, and of the soil.
As plant protcction agents, the active compounds according to th~ invention can be u~ed with particularly good succ~ss for combating Podosphaera, Uromycc~ and Erysiphe sp~cies, such as the powdery mildcw of apple causative organism (_odosphaera l~ucotricha), the bean rust causative organism (Uromyce~ phaseoli) and the powdery mild~w of cucumber causative organism (EryQiphe cichoracearum). Good successes are also achieved in combating cereal diseases, such as powdery mildew of cereal and cereal rust.
When certain amounts are applied, the active com-pounds according to the inv~ntion al~o exhibit a growth-regulation action.
The active compounds can be converted into thecustomary formulations, such as solutions, emulsions, suspensions, powders, dusting agent~, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment~ such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers9 optionally with the use of surface-active Le A 19 636 agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case Or the use of water as an extenderg organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons J such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone~ methyl ethyl ketone, methyl isobutyl ~etone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide~ as well as water.
By lique.fied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, .for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-Le A 19 636 ~L5'~i3 fatty alcohol ethers 3 ~or example alkylaryl polyglycolethers, alkyl sulphonates b alkyl sulphates, aryl sul-phonates as well as albumin hydrolysis products. Dis-persing agents include9 for example9 lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizari~
dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations~ or in the various use forms,as a mixture with other active compounds, such as fungicides, bactericides 9 insecticides, acaricides~
nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such, as their formulations or as the use forms prepared therefrom by ~urther dilution~ such as ready-to-use solutions, emulsionsl suspensions, powders, pastes and granules.
m ey may be used in the customary manner, for example 3o by watering, immersion, spraying, atomi~ing, misting, vaporising, injecting9 brushing on3 dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be ~ `:

` Le A 19 636 5~3 varied within a substantial range. They are, in general, from 1 to 0.0001~ by weight3 preferably from 0.5 to O . 001 % .
In the treatment of seed, amounts of active compound of in general 0.001 to 50 g~ preferably 0.01 to 10 g3 are employed per kilogram of seed.
For the treatment of soil; active compound concen-trations of in general 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are employed at the place of action.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present i~vention.
The fungicidal activity of the compounds of this invention is lllustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
The known comparison compounds are identified as follows:

(A) ~ CH-CH2-N~

(B) Cl ~ CH-CHz-~

(C) Br ~ CH-CH2~N

(D) Cl- ~ CH-CH2-N

Le A 19 636 .

~5~3 (E) H3C ~ CH-CH2-N\ J

(F) Cl ~ CH-CH~-~ J x 1/2 Cl SO~H

Example A
test (apple)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount oP solvent, and the con-centrate was diluted with the stated amount of water which contained the stated amount of emulsifier.
Young apple seedlings in the 4 - 6 leaf ~tage were sprayed with the spray liquid until dripping wet. m e plants remained in a greenhouse f~or 24 hours at 20 deg.C
and at a relative atmospheric humidity of 70~. They were then inoculated by dusting the conidia of the apple powdery mildew causative organism ( ~ leuaatriaha) and placed in a greenhouse at a temperature o~ 21 23 deg.
C and at a relative atmospheric humidity of about 70~.
lO days after the inoculation, the infection of the seedlings was determined. The assessment data were con-verted to % infection. 0% meant no infection; lO0~ meant that the plants were completely infected.
In this test 3 for example, the following compounds ; showed a very good action which was significantly superior to that of the compounds (A) and (B) known from the prior art: compounds (l) and (3)~

: : ' Le A l9 636 :

.

~5~53 test (cucumber)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required ~or the desired concentration of active compound in the spray liquid was mixed with the stated amount of solYent and the concentrate was diluted with the stated amount o~
water containing the stated amount of emulsi~ier.
Young cucumber plants with about three foliage leaves were sprayed with khe spray liquid until dripping wet.
The cucumber plants remained in a greenhouse for 24 hours to dry. They were then3 for the purpose of inoculationJ
dusted with conidia of the fungus Erysiphe cichoracearum.
The plants were subsequently placed in a greenhouse at 23-24 degrees C and at a relative atmospheric humidity of about 75%.
After 12 days, the infection of the cucumber plants was determined. The assessment data were converted to percent infectlon. 0% meant no infection; 100% meant that the plants were totally infected.
In this test, for example, the following compound~
showed a very good action which was superior to that of the compounds (C) and (D) known from the prior art: compounds (1), (7), (10), (12), (14) and (5).
Example C
~ test (bean rust)~protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required ~or the desired concentration of active compound in the spray liquor Le A 19 636 . ~...... .

5~53 was mixed with the stated amount of the solvent and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.
The young bean plants, which were in the 2-leaf stage; were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse for 24 hours at 20-22 deg.C and a relative atmospheric humidity of 70~ in order to dry. They were then inoculated with an aqueous uredospore suspension of the causative organism of bean rust ( ~ phaseoli) and incubated for 24 hours in a dark humidity chamber at 20 - 22 deg.C and 100% relative atmospheric humidity.
The plants were then set up in a greenhouse under intensive illumination for 9 days at 20 - 22 deg.C and a relative atmospheric humidity of 70-80%.
10 days after the inoculation, the infection of the plants was determined. The assessment data were converted to % infection. 0% denoted no infection and 100% denoted that the plants were completely infected.
In this test, for example, the following compounds showed a very good action which was significantly superior to that of the compound (E) know~ from the prior art:
(12),(14) and (5).
~e~
Shoot treatment test/powdery mildew of cereals (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound~
0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part

3 by weight of alkylaryl polyglycol etherg 975 parts by weight o~ water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test for protective activity3 single-leaved young barley plants of the Amsel variety were sprayed Le A 19 636 ~S~53 with the preparation of active compound until dew-moist.
After drying, the barley plants were dusted with spores of ~ ~ var. hordei.
After 6 days' dwell time of the plants at a tempera-ture of 21-22 deg.C and 80-90~ atmospheric humidity the occurrence of mildew pustules on the plants was evaluated.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0%
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower was the degree of mildew infection.
In this test, for example, the following compound~
showed a very good action which was significantly superior to that of the compounds (D) and (F) known from the prior art: (1), (~), (7), (10), (12), (14) and (5).
Exa~ e E
Shoot treatment test/cereal rust (leaf-destructive mycosis)/protective To produce a suita~le preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
To test the protective activity, one-leaved young wheat plants of the Michigan Amber variety were inoculated with a uredospore suspension o~ Puc ~econdita in 0.1% strength aqueous agar. After the spore suspension had dried on, the wheat plants were sprayed with the preparation of active compound until dew-moist and were placed, for incubation, in a greenhouse for 24 hours at about 20 deg.C and 100% relativa atmospheric humidity.
After 10 daysl dwell time of the plants at a tempera-Le A 19 636 ture of 20 deg.C ~nd 80-90% atmospherio humidity, the occurrence o~ ru~t pustules on the plant was evaluated.
m e degree of infection wa~ expre~sed a~ a percentage of the infection of the untreated control plants. 0~
denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control.
The active compound was the more active, the lower wa~
the ~egree of rust infection.
In this test, for example, the following compounds showed a very good action which was significantly superior to that of the compound (D) known from the prior art:
(8), (12)J (14) and (5).

Example 1 and 2 ~-C -CH 2 ~-Cl ~ N
Az = - ~ ¦ = Example l /==N
Az - -N\= ¦ ~ Example 2 N

Process (b) 7.6 9 (0.11 mol) of 1,2,4-triazola were added to a 901ution of 3.5 9 (0.065 mol) of sodium methylate in 18 ml of methyl alcohol; a solution of 19.5 9 $0.05 mol) 2n of 2-(4-biphenylyl)-3-chloro-1-(2,4-dichlorophonyl)-propan-2-ol in 38 ml of dimethylformamid~ was then add~d dropwis~ and the mixture was heated to 70C for 90 minutos.
The solvents were removed in v;acu~-in a rotary avaporator and the r~aidue was stirrad with water. Th~ resulting Le A 19 636 ~5~53 crystals were waahed with diethyl ether and r~crystalli~d from acetonitrile. 2.2 9 of 2-(4-biphenylyl)~ 2,4-dichlorophsnyl)-3-(1,2,4-triazol-4-yl)-propan-2-ol of mclting point 260C were obtained.
Ths acetonitrile solution (mother liquor) was evaporated and the re~ulting crystals were wa~hed with diathyl ether and ethyl acetate. 6.5 g of ~-(4-biphonylyl)-1-(2,4~dichlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol of melting point 124C were obtained.
Preparation of the startinq mstorial ~ C-C~2-~-Cl Cl 69.3 9 (0.3 mol) of 4-phenylphenacyl chloride were added in portions to a solution of 0.6 mol of 2,4-dichlorobenzyl-magneaium chloride, obtained from 15.9 9 ~0.65 mol) of magnesium and 117.3 g (0.6 mol) of 2,4-dichlorobenzyl chloride in 300 ml of ether. The reaction mixture was then poured onto aqueous ammonium chloride solution and the ~ther phase was separated off, washed with water, dried over sodium sulphate and evaporated.
The oil which remainad wa~ extracted with petroleum eth~r and the petroleum ethar solution waa evaporated. Th~
crystals were filtered off and dried. 62 g (53~ of theory) of 2-(4-biphenylyl)-3-chloro-1-(2,4-dichloro-phenyl)-propan-2-ol of m21ting poi'nt 84C w~re obtained.
~ 4 ~-C-C~2~
AZ

Le A 19 636 f~5~

f~N
A2 ~ Example 3 'N=J ' ~ N
AZ = -N I = Example 4 ~=:N

Process (b) , 38.3 9 (0.56 mol) of 1,2,4-triazole were added to a solution of 17.9 9 (0.33 mol) of sodium methylate in 90 ml of methyl alcohol; a solution of 82 9 (0.254 mol~
of 2-(4-biphenylyl)-3-chloro-1-phenyl-propan-2-ol in 191 ml of dimethylformamide wae then addsd dropwise and the mixture was heated to 60C for 90 minutes. The sol-vents wer~ removed in vacuo in a rotary evaporator; ther~siduo was dissolved in methylene chloride and the methy-lane chloride solution was washed with water. The methylene chloride solution wa~ dried o~er sodium sulphat~
and filtered and the filtrate was concentrated in vacuo.
The resulting oil was separated by chromatography.
13.8 9 of 2-(4-biphenylyl)-1-phe~nyl-3-(1,2,4-triazol-1-yl~-propan-2-ol of melting point 124C and 2.7 9 of 2-(4-biphenylyl)-l-phenyl-3-(1,2,~-triazol-4-yl)-propan-2-ol of molting point 246C wero obt~lined.
Preparation of the startinq mat~rial ~ ~ -C-CH2 Cl 115.3 9 (0.5 mol) of 4-phonylph~n~cyl chlnrido w~re ~dded in portions to a solution of benzyl-megne~ium chlorid~, obtainod from 24.3 9 (1 mol) of magn~ium ~nd 115 ml (1 mol) of b~nzyl chloride in 150 ml of diethyl ~ther. The reaction mixture was warmsd und~r reflux e A 19 636 L~ 5 3 _ 24 _ for 90 minut~s and then poured onto aqueouc ammonium chloride solution. The ether phase was separatad off, washed with water, dried over sodium sulphata snd con-centratsd. The oil which remained was made to cryetQl-lise by stirring with petroleum ether. 50 9 (31o of thaory) o~ 2-(4-biphenylyl)-3-chloro-1-phenyl-propan-2-ol of melting point 96C wera obtained.
~e.~

~ ~ -C-<~-Cl ~1 C~2 ,N~
N
Proc0ss ~b) 14.96 9 (0.22 mol) of triazole were added to a solution of 7.02 9 (0.13 mol) oF sodium methylate in 36 ml of methyl alcohol. A solution of 40 9 tO.1 mol) of 1-(2'-chloro-4-biphenylyl)-2-chloro-1-~4-chloro-phenyl)-ethanol in 75 ml of dimethylformamide wa~ then added dropwise and the reaction rnixture was heated to 70C
for 3 hours. It was concentrated by distilling off th0 solvents in vacuo, and the re~idue was stirred with water7 The crystals which remained were washed with ac~tonitrile and recrystallieed. 16.2 9 (400D of theory) of 1-(2'-chloro-4-biphenylyl)-1-t4-chlorophenyl)-2-(1,2,4-tri~ol-l-yl)-ethanol of melting point 1~0C were obtained.
PreparatiDn of tho ~tarting mat~rial ~ ~ O ~

75 g of 1-(2'-chloro-4-biphenylyl)-2-chloro-1-(4-chlorophenyl)-ethanol were obtained from 10.69 9 (0.44 mol~ of magneQium, 76.6 9 (0.4 mol) of 4-bromo-Le A 19 636 ~5~25~

- 25 .
ehlorobsnzane and 53 9 (0.2 mol) of 4-(2-ehlorophenyl)-phenaeyl ehlorido analogou~ly to Example 1.

~ - COCH2 Cl 29~.7 9 (2.2 mol) of aluminium chloride wsre introdueed in portions into a solution of 377 9 (2 mol) of 2-ehlorobiphenyl in 160 ml (2 mol) of ehloroaeetyl ehloride and 1,000 ml of methylene ehloride. After 18 hours, the reaction mixture was poured onto iee and hydro-ehloric acid. The organic phas0 was separated off, washed, dried over sodium ~ulphate and concentrated in vaeuo by distilling off tha solvant. The oil whieh r~mained was purifiad by di~tillation. 478.7 g (90OD of theory) of 4-(2-chlorophenyl)-phenacyl ehloride of melt-ing point 47C were obtained.
The follnwing eompounds of the general formula R~ OH
R2 ~ C (Cll2)m - R (I) R3n l H2 Az eould be obtained analogously to Examples 1 to 5:

Le A 19 636 - 26 _ Meltin~
point( C) Example R Rl R R3n Az m tive index No .
~ . _ , _ .
r=~N
6 ~ Cl 4 ~ H ~ 1 250 f==N
7 ~ -Cl 4 ~ \N _1 1 104 8 ~ -Cl 4 ~ -Cl H - -N I 1 144 Cl~_ ,- N
9 ~ -Cl 4~2i H - N I 1 175 ~ Cl 4 ~ ,~ N 1 nD:1.5992 11 ~ Cl 4~ ~ -Cl H --N~ I 1 160 r==N
12 ~ Cl 4 ~ -Cl H - -N ~ 0 189 13 ~ -F 4 ~ Cl H _-N I 0 217 Cl ~ 4 ~ Cl H _ -N I 0 144 - ~ 4 ~ H - -N ~ 0 164 F , - N
16 ~ 4 ~ H - -N I 0 170 1 7 ~> 4 - ~ H -- N~ ~J O 1 6 0 Cl ~N
18 _~ 4_~ H - -N 1 0 220 La A 19 636

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fungicidal composition for u æ in plant protection characterised in that it contains as active ingredient a hydroxyalkyl-triazole of the general formula (I) in which A2 represents triazole, R represents an optionally substituted phenyl, naphthyl or tetrahydronaphthyl radical, R1 represents an optionally substituted phenyl or cycloalkyl radical and R2 represents hydrogen, or R1 and R2 together, in an o-position relative to one another, represent an optionally substituted, nulti-membered methylene bridge, or together with the phenyl ring represent naphthyl, R3 represents halogen, alkyl, alkoxy or halogenoalkyl, n represents 0, 1, 2 or 3, the substituents R3 being selected independently when n is 2 or 3, and m represents O or 1, or a non-phytotoxic acid-addition salt thereof, in admixture with a solid or liquefied normally gaseous diluent or carrier, or in admixture with a liquid diluent or carrier containing a surface-active agent.

2. A composition according to claim 1, characterised in that in said com-pound of the formula (I) A2 represents 1,2,4-triazol-1-yl or 1,2,4-triazol 4-yl, R represents optionally substituted phenyl, naphthyl or tetrahydronaphthyl, the or each substituent being selected from halogen, straight-chain or branched alkyl and alkoxy with in either case 1 to 4 carbon atoms and halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms, R1 represents optionally sub-stituted phenyl or cycloalkyl with 3 to 7 carbon atoms, the or each substituent being selected from halogen, alkyl with 1 to 4 carbon atoms and alkenyl with 2 to 4 carbon atoms, and R2 represents hydrogen, or R1 and R2 together, in an ortho-position relative to one another, represent an op-tionally monosubstituted or polysubstituted methylene bridge with 3 to 5 methylene groups, the or each substituent being selected from halogen and alkyl with 1 to 4 carbon atoms, or together with the phenyl ring represent naphthyl, R represents halogen, straight-chain or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms, or halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms, n represents 0, 1 or 2 and _ represents O
or 1.

3. A composition according to claim 1 or 2, characterised in that it contains a salt of a compound of the formula (I) with an acid selected from hydrogen halide acids, phosphoric acid, nitric acid, sulphuric acid, mono-functional and bifunctional carboxylic or hydroxycarboxylic acids, and sul-phonic acids.

4. A composition according to claim 1 or 2 containing from 0.1 to 95%
of the active compound, by weight.

5. A composition according to claim 1 containing 2-(4-biphenylyl)-1-(2,4-dichlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol as said active ingredient.

6. A composition according to claim 1 containing 2-(4-biphenylyl)-1-phenyl-3-(1,2,4-triazol-1-yl)-propan-2-ol as said active ingredient.

7. A composition according to claim 1 containing 1-(2'-chloro-4-bi-phenylyl)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanol as said active ingredient.

8. A composition according to claim 1 containing 2-(4-biphenylyl)-1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol as said active ingredient.

9. A composition according to claim 1 containing 2-(4'-chloro-4-bi-phenylyl)-1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol as said active ingredient.

10. A composition according to claim 1 containing 2-(2'-chloro-4-bi-phenylyl)-l-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol as said active ingredient.

11. A composition according to claim 1 containing 1-(4'-chloro-4-bi-phenylyl)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanol as said active ingredient.

12. A composition according to claim 1 containing 1-(4'-chloro-4-bi-phenylyl)-1-(2-chlorophenyl)-2-(1,2,4-triazol-l-yl)-ethanol as said active ingredient.

13. A method of combating phytopathogerlic fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the formula (I), or a non-phytotoxic acid-addition salt thereof, as specified in claim 1.

14. A method according to claim 13 wherein said compound or salt is applied in the form of a composition containing said compound or salt as active ingredient, in admixture with a suitable diluent or carrier.

15. A method according to claim 14 in which a composition is used con-taining from 0.0001 to 1% of said compound or salt, by weight.

16. A method according to claim 14 in which a composition is used con-taining from 0.001 to 0.5% of said compound or salt, by weight.

17. A method according to claim 13, in which said compound is applied to soil in an amount of 0.00001 to 0.1% by weight.

18. A method according to claim 13, in which said compound is applied to soil in an amount of 0.0001 to 0.02% by weight.

19. A method according to claim 13, in which said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

20. A method according to claim 13, in which said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

21. A method according to claim 13, 18 or 20 in which said compound is 2-(4-biphenylyl)-1-(2,4-dichlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol.

22. A method according to claim 13, 18 or 20 in which said compound is 2-(4-biphenylyl)-1-phenyl-3-(1,2,4-triazol-1-yl)-propan-2-ol.

23. A method according to claim 13, 18 or 20 in which said compound is 1-(2'-chloro-4-biphenylyl)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanol.

24. A method according to claim 13, 18 or 20 in which said compound is 2-(4-biphenylyl)-1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol.

25. A method according to ciaim 13, 18 or 20 in which said compound is 2-(4'-chloro-4-biphenylyl)-1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol.

26. A method according to claim 13, 18 or 20 in which said compound is 2-(2'-chloro-4-biphenylyl)-1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol.

27. A method according to claim 13, 18 or 20 in which said compound is 1-(4'-chloro-4-biphenylyl)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanol.

28. A method according to claim 13, 18 or 20 in which said compound is 1-(4'-chloro-4-biphenylyl)-1-(2-chlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanol.