CA1255684A - Substituted azolyl-ketones and - alcohols - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An azolyl-ketone of the formula IIa, or an acid addition salt thereof, (IIa) in which A is a nitrogen atom or the CH group, and R4 is the CHO
group, or a -CH=O derivative selected from the group consisting of -CH=N-OH, alkoximinomethyl with 1 to 4 carbon atoms in the alkoxy group, di-(C1-4)-alkoxymethyl, dioxolane and dioxane. These compounds are useful in the preparation of substituted azolyl-ketones and -alcohols which exhibit plant growth regulating and fungicidal properties.

Description

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The present invention relates to intermediates useful in the preparation of new substituted azolyl-ketones and -alcohols, which are useful as fungicides and plant growth regulators, and a process for preparing them.
The parent application serial no. 431,352 relates to new substituted azolyl-ketones and -alcohols, several processes for their preparation and their use as fungicides and plant growth regulators.
It has already been disclosed that certain azolyl-penta-nones, such as, for example, 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one, possess good fungicidal properties (see DE-OS (German Published Specification) 2,734,426).
Furthermore, it has been disclosed that certain azolyl-butanones and -ols, such as, for example, alkylated 3,3-dimethyl-4-fluoro-(chloro)-1-(1,2,~-triazol-1-yl)-butan-2-ones and -019, have good ~ungicidal and plant growth-regulating properties (see DE-OS
(German Published Specification) 2,951,164 [Le A 20 067] and DE-OS
(German Published Specification) 2,951,163 /Le A 20 068/).
However, the action of all these compounds in certain fields of indication is not always completely satisfactory, particularly when low amounts and concentrations are used.
According to one aspect of the parent application there is provided substituted azolyl-ketones and -alcohols of the general formula . ,

- 2 -Rl - CH - B - R2 (I) N~

in which A represents a nitrogen atom or the CH group, B represents the keto or CH~OH) group, Rl represents alkyl, alkenyl, alkinyl, optionally substituted phenylalkyl, optionally substituted cycloalkyl or optionally sub-stituted cycloalkylalkyl, and R2 represents substituted cyclo-alkyl or the grouping -C(CH3)2R3, wherein R3 represents alkyl having more than 2 carbon atoms, alkenyl, alkinyl and the -CH=O group and its derivatives, ar.d their acid addition salts and metal salt complexes have been found.
Those compounds of the formula (I) in which B represents a CH(OH) group possess two asymmetric carbon atoms: they can therefore occur as the two geometric isomers (erythro and threo form), which may be obtained in varying proportions. In all cases, they are present as enantiomer pairs.
Furthermore, it has been found that the new substituted azolyl-ketones and -alcohols of the formula ( I ) are obtained when a) azolyl-ketones of the formula :~25~Çi8~
~ 2a -H2f - CQ - R2 (II) ~ N~

N
in which A and R2 have the meaning given above, are reacted with an alkylating agent of the formula Rl _ z (III) in which Rl has the meaning given above and Z represents an electron-attracting leaving grouping, in the presence of a base and in the presence of an organic dilu-ent, or in an aqueous-organic two-phase system in the presence of a phase-transfer catalyst;

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or b) halogenoketones of the formula I (IV) Hal in which S R1 and R2 have the meaning given above and Hal represents halogen, in particular chlorine or bromine, are reac~ed with azoles of the formula ~A==~
H - N l (V) in which A has the meaning given above, in the presence of a diluent and in the presence of an acid-b;nding agent: and, if aopropriate, c) the compounds obtained by processes (a) and ~b), of the formula R1 - CH - C0 - R2(Ia) ~N`A
N l¦
in wh;ch A, R1 and R2 have the meaning given above, are reduced in a customary manner, according to known methods.
The resulting compounds of the formula (I) can, if desired, then be subjected to an addition reaction with an acid or a metal salt. In some cases, it proves advantageous to obtain the compounds of the formula (I) in pure form via ~heir salts.
Le A 21 717 _ ~55~

According -to one aspect of the present invention, there i5 provided an azolyl-ketone of the formula IIa, or an acid addi--tion sal-t thereof, CH2 - CO - C - R4 (IIa) N~ CH3 ~ A
N
in which is a nitrogen atom or the CH group, and R4 i5 the CHO group, or a -CH=O derivative selected from the group consisting of -CH-N-OH, alkoximinomethyl with 1 to 4 carbon atoms in the alkoxy group, di-(Cl_4)-alkoxymethyl, dioxolane and dioxane.
According to anothe.r aspect of the present invention there is provided a process for preparing the above compounds of formula IIa which process comprises a process for preparing a compound of formula IIa as defined above, or an acid addition salt therefor which comprises reacting 1,2,4-triazole or imidazole with a halogenmethyl ketone of formula V:[

fH3 Hal' CH2-Co-C-R4 wherein R4 is as defined above and Hal' is chlorine or bromine, and where required, forming an acid addition salt thereof.

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Furthermore, it has been found that -the new substituted azolyl-ketones and -carbinols of the formula (I) have powerful ungicidal and plan-t growth-regulating properties. In this context, -the compounds according to the invention, of the formula (I), surprisingly show better fungicidal and be-tter plan-t gro~,lth-regulating actions than the abovementioned triazolylalkanones and -ols, which are known from -the prior art and are similar compounds chemically and in terms of their action. The active compounds according to the inven-tion thus represent an enrichment of the art.
Furthermore, the new substituted azolylketones and -carbinols of the formula (I) are interesting intermediate products. Thus, by appropriate reactions, it is possible to obtain functional derivatives of the keto group, such as, for example, oximes and oxime-ethers, hydrazones and ketals. Further-more, the compounds of the formula (I) can be converted at the hydroxyl group in a customary manner to give the corresponding ethers, or acyl or carbamoyl derivatives of the compounds of the formula (I) can be obtained by reaction with, for example, acyl halides or carbamoyl chlorides, in a manner which is known in prlnclple .
Formula (I) gives a general definition of the substi-tuted azolyl-ketones and -alcohols according to the invention. In this formula:
Rl preferably represents straight-chain or branched alkyl having 1 to 12 carbon atoms, straigh-t-chain or branched alkenyl and alkinyl, each having 2 to 12 carbon atoms, or phenyl-alkyl s5~

which has 1 to ~ carbon atoms in the alkyl part and is optionally monosubstituted to trisubstituted by identical or different sub-stituents, the Eollowing being mentioned as phenyl substituents:
halogen, alkyl, alkoxy and alkylt~io, each having 1 to 4 carbon atoms, or preferably represents cyclohexyl; dialkylamino having 1 to 4 carbon atoms in each alkyl part; halogenoalkyl, halogeno-alkoxy and halogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine atoms and chlorine atoms, nitro and cyano; alkoxycarbonyl having 1 to 4 carbon atoms in the allcyl part; and op-tionally halogen-substituted phenyl and phenoxy; and also cycloalkyl and cycloal-kylalkyl, each of which has 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part and is optionally monosubstituted to trisubstituted by identical or different alkyl radicals having 1 to ~ carbon atoms;
R2 preferahly represents cycloalkyl which has 3 to 7 carbon atoms and is monosubstituted to trisubstituted by identical or different alkyl radicals having 1. to 4 carbon atoms; and the grouping -C(CH3)2R3, wherein R3 preferably represents strai~ght-chain or branched alkyl having 3 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to ~ carbon atoms, alkinyl having 3 to 5 carbon atoms or the -CH=0 group and its derivatives, such as oximes, oxime-ethers and acetals, for e~ample alkoxyiminomethyl having 1 to 4 carbon atoms in the alkyl part, dialkoxymethyl having 1 to 4 carbon atoms in each alkyl part and optionally substituted dioxolanes and ~2~

dioxanes, and A and B preferably have the meanings given in the definition of the invention.
Particularly preferred compounds of the formula (I) are those in which Rl represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl and alkinyl, each having 2 to 6 carbon atoms, and phenylalkyl which has 1 to 2 car-bon atoms in the alkyl part and is optionally monosubstituted or disubstituted by identical or different substituents, the fol-lowing being mentioned as phenyl substituents: fluorine, chlor-ine, methyl, ethyl, isopropyl, tert.-butyl, methoxy, methylthio, cyclohexyl, dimethylamino, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, methoxycarbonyl, or phenyl and phenoxy, each oE which is optionally substitu-ted by chlorine and fluorine; and also represents cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl and cycloheptyl, each of which is optionally monosubstituted or disub-stituted by identical or different substituents from amongst methyl, ethyl, isopropyl and tert.-butyl;
R2 represents cyclopropyl, cyclopentyl and cyclohexyl, each of which is monosubstituted or disubstituted by identical or different substituents from amongst methyl, ethyl, isopropyl and tert.-butyl, and represents the grouping -(CH3)2R3, wherein R3 represents straight-chain or branched alkyl having 3 to 6 2556~
- 7a -carbon atoms, vinyl, propargyl or t'ne -CH=0 group, methoxyimino-methyl, dimethoxymethyl, or the dioxolane and 1,3-dioxane radi-cals; and A and ~ have the meaning given in the definition of the invention.
Preferred compounds according to the invention are also addition products of acids and those substituted azolyl-ketones and -alcohols of the formula (I) in which the substituents A, B, Rl and R2 have the meanings which have already been ~entioned as being preferred for these substituents.
The acids with which addition products can be formed preEerably include hydrohalic acids, such as, for example, hydro-chloric acid and hydrobromic acid, in particular hydrochloric acid, and also phosphoric acid, nitric acid, sulphuric acid, mono-functional and hifunctional carboxylic acids and hydroxycarboxylic acids, such as, Eor example, acetic acicl, maleic acid, succinic acid, fumaric acid, tartaric acid, salicylic acid, sorbic acicl and lactic acid, as well as su].phonic acids, such as, for example, p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid.
Further preferred compounds are addition products o~
salts of metals of main groups II to IV and of sub-groups I and II
and IV to VIII and those substituted azolyl-ketones and -alcohols of the -formula (I) in which the substituents Ar, B and ~1 have the meanings which have already been mentioned as being preferred for these radicals. In this context, salts of copper, zinc, manga-nese, magnesium, -tin, iron and nickel are particularly preferred.

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- 7b -Sui~able anions of these salts are those which are derived from those acids which lead to physiologically tolerated addition products. Particularly preferred acids of this type in this connection are the hydrohalic acids, such as, for example, hydro-chloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulphuric acid.
If, for example, 3-(dioxolan-2-yl)-3-methyl-1-(1,2,4-triazol-l-yl)-butan-2-one and 2,4-dichloro-benzyl bromide are used as starting materials, the ~2S5~

course of the rea`ction can be represented by the fol-lowing equation (process a):

H2C-C0-C ( ~ + Cl ~ 2 _ HBr ~ ~`N CH3 N ll / N~N CH3 If, for example, 4-bromo-2-(dioxolan 2-yl~-S 5-(2,4-dichlorophenyl)-2-methyl-pentan-3-one and 1,2,4-triazole are used as s~arting materials, the course of the reaction can be represented by the fol-lo~ing equation (process b):

Cl- ~ -CH2-1CH-C0- ~ ~ N ~ + 8ase >
Br CH3 - H3r C l ~ - C H 2 - Cl H - C O - C - /

N

If, for example, 1-(2,4-d;chlorophenyl)-4-(di-oxolan-2-yl)-4-methyl-2-(1,2,4-triazol-1-yl)-pentan-

3-one and sodium borohydride are used as starting mat-erials, the course of the reaction can be represented by the following equation (process c):

Le A 21 717 ~5~8~
.

g Cl~ CH2-fH-CO- ~ ] + ~aBH4 - >
N I O
CH
ll ,N 3 N

Cl ~ Cl 03 CH3 ~ N~ CH3 U ~I
Formula (II) gives a general definition of the azolyl-ketones to be used as starting materials in carrying out process (a) according to the invention. In this formula, A and R2 prefer-ably represent the radicals which have already been mentioned in connection with the description of the substances according to the invention, of the formula (I), as being preferred for these sub-stituents.
Some of the azolyl-ketones of the Eormula (II) are known ~see, for example, DE-OS (German Published Specification~
2,431,407 [Le A 15 735] and DE-OS (German Published Speci-Eication) 3,028,330 [Le A 20 458]); they are obtained, for example, by reacting the corresponding halogenoketones with imidazole or 1,2,4-triazole. Azolyl-ketones of the general formula H2f - CO - C - R4 (IIa) N ~

~2~i5~
, . .

in which A has the meaning given above and R4 represents the -CH=0 group and its derivatives, are hitherto unknown, and are the subject of one aspect of the present invention.
The new azolyl-ketones of the formula (IIa) which are one aspect of this invention are generally interesting intermedi-ate products, and can be obtained by reacting halogenomethyl-ketones of the formula Hal'-CH2-CO~C R4 (VI) in which Hal' represents chlorine or bromine and R4 has the meaning given above, in a customary manner with 1,2,4-triazole or imidazole, in the presence of an inert organic solvent, such as, for example, ace-tone, and in the presence of an acid-binding agent, such as, for example, potassium carbonate, at temperatures between 20 and 150C. The above process of preparlng compounds of formula IIa is another aspect of the present invention.
The halogenomethyl-ketones of the formula (VI) likewise are hitherto unknown. They are obtained when l-(N-morpholino)-isobutene of the formula o ~-CH=C(CH3)2 (VII) is reacted with halogenoacetyl chlorides of the formula Hal'-CH2-C0-Cl (VIII) in which Hal' has the meaning given above, in the presence o-f a solvent, such as, for example, diethyl ether, at temperatures between 20 and 120C, and, if appropriate, the resulting halogenomethyl-ketones of the formula C~13 Hal'-CH2-C0- C - CH0 (VIa) in which Hal' has the meaning given above, are derivatised at the aldehyde group in a customary manner, such as, for example, by reaction with diols in the presence of an inert organic solvent, S-lCh as, for example, toluene, and in the presence of a strong acid as a catalyst, such as, for example, p-toluenesulphonic acid, at temperatures between 80 and 100C.
Formula (III) gives a general definition of the alkyl-ating agents additionally to be used as starting materials for process (a) according to the invention. In this formula, Rl preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I), as being preferred for these substituents. Z
represents an electron-attracting leaving grouping, selected from 6~

halogen, p-methylphenylsulphonyloxy, the group -0-S02-OR or -~R3 wherein R3 is as defined above and R represents alkyl having 1 to 4 carbon atoms.
The alkylating agen-ts of the formula (III) are generally known compounds.
Formula (IV) gives a general deEinition of the halogeno-ketones to be used as starting materials in carrying out process (b). In thi~ ~or~ula, Rl and R2 preferably represent the radicals which have already been men-tioned in connection with the descrip-tion of the substances of the formula (I), as being preferred for these substituents.
The halogenoketones of the formula (IV) are hitherto unknown; however, they can be obtained in a generally Xnown manner, by reacting, for example, the correspondin~ ke-tones with chlorine or bromine in the presence of an inert orgarlic solvent, such as, for example, chlorinated hydrocarbons, at room tempera-ture, or with cus-tomary chlorinatin~ agents, such as, for example, sulphuryl chloride, at temperatures between 20 and 60C.
Formula (V) gives a general definition of -the azoles additionally to be used as starting~ materials for process (b). In this formula, A has the preferred meanings given above.
The azoles of the formula (V) are generally known compounds.
Formula (Ia) gives a general definition of the compounds to be used as starting materials in carrying out process (c). The compounds of the formula (Ia) are substances according to the 5~

invention of the parent application.
Suitable diluents for process (a) are inert organic solvents. These preferably include aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chloro-benzene; esters, such as ethyl ace-tate: formamides, such as dimethylformamide; and dime-thylsulphoxide.
Process (a) i5 carried out in the presence of a base.
All customary organic and, in particular, inorganic bases, such as, preferably, alkali metal hydroxides or alkali metal carbon-ates, can be employed for this process, and sodium hydroxide and potassium hydroxide may be mentioned as examples.
In carrying out process (a) the reaction temperatures can he varied within a relatively wide range. In general, the reaction is carried out at between 0 and 100C, preferably between 20 and 100C.
In carrying out process (a) e~uimolar amounts are preferably employed. The end products of the formula (I) are isolated in a generally customary manner.
Process (a) can also be carried out in a two-phase sys-tem, such as, for example, aqueous~sodium hydroxide or potassium hydroxide solution/toluene or methylene chloride, if appropriate with the addition of 0.1 to 1 mol of a phase-transfer catalyst, such as, for example, ammonium or phosphonium compounds, benzyl-dodecyl-dimethyl-ammonium chloride and triethyl-benzyl-ammonium . ~ ~S~i~3~'~

chloride being mentioned as examples.
Suitable diluents for process (b) are inert organic solvents. These preferably include ketones, such as diethyl ketone and, in particular, acetone ancl methyl ethyl ketone;
nitriles, such as propionitrile, and in particular acetonitrile;
alcohols, such as ethanol or isopropanol; ethers, such as tetra-hydrofuran or dioxane; aromatic hydrocarbons, such as toluene, benzene or chlorobenzene; formamides, such as, in particular, dimethylformamide; and halogenated hydrocarbons.
Process (b) is carried out in the presence of an acid-binding agent. It J.S possible to add all customarily usable inor-ganic and organic acid-binding agents, such as alkali metal car-bonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or 5UC}I as lower tertiary alkylamines, cyclo-alkylamines or aralkylamines, Eor example triethylamine, N,~-di-methy]cyclohexylamine, dicyc]ohexylamine, N,N-dimethylbenzylamine, and fur-thermore pyridine and diazabicyclooctane. Preferably, an appropriate excess of azole is used.
In process (b) the reaction temperatures can be varied within a rela~ively wide range. In general, the reaction is carried out at between about 20 and about 150C, preferably at 40 to 100C. When a solvent is present, the reaction is advanta-geously carried out at the boiling point of the particular solvent.
In carrying out process (b) 2 to 4 mols of azole and 1 to 4 mols of the acid-binding agent are preferably employed per mol of the compounds of the formula (IV). To isolate the ~ ~ 5 compounds of the formula (I), the solvent is distilled off and the residue is worked up in the customary manner.
The reduction by process (c) is carried out in a custom-ary manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent, or by reaction with aluminium isopropylate in the presence of a diluent.
If complex hydrides are employed, suitable diluents for the reaction according to the invention are polar organic solvents. These preferably include alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. The reaction is carried out in general at 0 to 30C, preferably at 0 to 20C. For this purpose, about 1 mol of a complex hydride, such as sodium borohydride or lithium alanate, is employed per mol of the ketone of the formula (I). To isolate the reduced compounds oE the formula (I), the residue is taken up in dilute hydrochloric acid, and the solution is then rendered alkaline, and extracted with an organic solvent. Further working-up is effected in the customary manner.
If aluminium isopropylate is employed, preferred dilu-ents for the reaction are alcohols, such as isopropanol, or inerthydrocarbons, such as benzene. The reaction temperatures once again can be varied within a relatively wide range; in general, the reaction is carried out at between 20 and 120C, preferably at 50 to 100C. To carry out the reaction, about 0.3 to 2 mols of aluminium isopropylate are employed per mol of the ketone of the formula (I). To isolate the reduced compounds of the formula (I), ~255~

- 15a -the excess solvent is removed in vacuo, and the aluminium compounds formed are decomposed with dilute sulphuric acid or sodium hydroxide solution. Further working-up is effected in the customary manner.
The active compounds which can be used engage in the metabolism of the plants and can therefore be employed as growth regulators.
Experience to date of the mode of action of plant growth regulators has shown that an active compound can also exert several different actions on plants. The actions of the compounds depend essentially on the point in time at which they are used, relative to the stage of development of the plant, and on the amounts of active compound applied to the plants or their environ-ment and the way in which the compounds are applied. In every case, growth regulators are intended to influence the crop plants in the particular manner desired.
Plant growth-regulating compounds can be employed, for example, to inhibit vegetative growth of the plants. Such inhibi-tion of growth is inter alia of economic interest in the case of ~0 grasses, since it is thereby possible to reduce the frequency of cutting the grass in ornamental gardens, parks and sportsgrounds, at verges, at airports or in fruit orchards. The inhibition of growth of herbaceous and woody plants at verges " ~55~i8~

and in the vicinity of pipelines or overland lines or, quite generally, in areas in which heavy additional growth of plants is undesired, is also of importance.
The use of growth regulators to inhibit the growth in length of cereals is also important. The danger of lodging of the plants before harvesting is thereby reduced or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals, which again counteracts lodging. Use of growth regulators for shortening and strengthening the stem enables higher amounts of fertiliser to be applied to increase the yieldr without danger of the cereal lodging.
In the case of many crop plants, inhibition of the vegetative growth makes denser planting possible, so that greater yields per area of ground can be ach,eved.
An advantage of the smaller plants thus produced is also that the crop can be worked and harvested more easily.
Inhibition of the vegetative growth of plants can also lead to increases in yield, since the nutri-ents and assimilates benefit blossoming and fruit forma-tion to a greater extent than they benefit the vegetative parts of plants.
Promotion of vegetative growth can also fre-quently be achieved with growth regulators. This is of great utility if it is the vegetative pares of the plants which are harvested. Promoting vegetative growth can, however, also simultaneously lead to a promotion of generative growth, since more assimilates are formed~ so that more fruit, or larger fruit, is obtained.
Increases in yield can in some cases be achieved by affecting the plant metabolism, without noticeable changes in vegetative growth. A change in the composi-tion of plants, which in turn can lead to a better quality of the harvested products, can furthermore be achieved with growth regulators. Thus, it is possible, for example, to increase the content of sugar in sugar Le A 21 717 - ~5568L~
.

beet, sugar cane, pineapples and citrus fruit or to increase the protein content in soya or cereals. Using growth-regulators it is also possible, for example, to inhibit the degradation of desired constituents, such as, for example, sugar in sugar beet or sugar cane, before or after harvesting. It is also possible favour-ably to influence the production or the efflux of secondary plant constituents. The stimulation of latex flux in rubber trees may be mentioned as an example.
Parthenocarpous fruit can be formed under the influence of growth regulators. Furthermore, the gender of the flowers can be influencedO Sterility of the pol-len can also be produced, which is of great importance in the breeding and preparation of hybrid seed.
Branching of plants can be controlled by using growth regulators. On the one hand, by breaking the apical dominance the development of side shoots can be promoted, which can be very desirable, especially in the cultivation of ornamental plants, also in connection with growth inhibition. On the other hand, however, it is also possible to inhibit the growth of side shoots.
There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes.
The amount of leaf on plants can be controlled, under the influence of growth regulators, so that defolia-tion of the plants at a desired point in time is achieved. Such defoliation is of great impor~ance in the mechanical harvesting of cotton, but is also of interest for facilitating harvesting in other crops, such as, for example, in viticulture~ Defoliation of the plants can also be carried out to lower the trans-piration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators. On the one hand, it is possible to prevent premature shedding of fruit. However, on the Le A 21 717 5SÇ;~3f~

other hand, shedding of fruit, or even the fall of blos-som, can be promoted up to a certain degree (thinning out) in order to interrupt the alternance. By alter-nance, there is understood the peculiarity of some vari-eties of fruit to produce very different yields from yearto year, for endogenic reasons. Finally, using growth regulators it is possible to reduce the force required to detach the fruit at harvest time so as to permit mechanical harvesting or facilitate manual harvesting.
Using growth regulators, it is furthermore pos-sible to achieve an acceleration or retardation of ripening of the harvest product, before or after harvest-ing. This is of particular advantage, since it is thereby possible to achieve optimum adaptation to mar-ket requirements. Furthermore, growth regulators can at times improve the coloration of fruit. In addition, con-centrating the ripening within a certain period of time is also achievable with the aid of growth regulators.
This prov~des the preconditions for being able to carry out complete mechanical or manual harvesting in only a single pass, for example ;n the case of tobacco, tomatoes or coffee.
Using growth regulators, it is furthermore pos-sible to influence the latent period of seeds or buds of plants, so that the plants, such as, for example, pine-apple or ornamental plants in nurseries, germinate, shoot or blossom at a time at which they normally show no readiness to do so. Retar`ding the shooting of buds or the germination of seeds with the aid of growth 3û regulators can be desirable in regions where frost is a hazard, in order to avoid damage by late frosts.
Finally, the resistance of plants to frost, drought or a high salt content in the soil can be induced with growth regulators. Cultivation of plants in regions which are usually unsuitable for this pur-pose thereby becomes possible.
Le A 21 717 ~2~5~

The active compounds exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant prokection agents.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
~ ac-terici~al agents are employed in plant pro-tection for combating Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
The good toleration, by plants, of -the active compounds, at the concentrations required for combating plant diseases, per-mits treatment o~ above-ground parts oE plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds can be used with particularly good success for combating those fungi which cause powdery mildew diseases; thus, ~or combating Erysiphe species, such as, for example, against the powdery mildew of barley or cereals causative organism (Erysiphe graminis), or ~O Sphaerotheca species, such as, for example, against the powdery mildew o cucumber causative organism (Sphaerotheca fuligenea), and also for combating further cereal diseases, such as Cochliobolus sativus and Pyrenophora teres, and rice diseases, such as Pyricularia oryzae and Pellicularia sasakii. The additional bactericidal action should be singled out.

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- l9a -The active compounds can be converted to the customary Eormulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, very fine capsules in poly-meric substances and in ~255Ç;8~

coating composit10ns for seed, as well as ULV
formulations.
~ hese formulations are produced in known manner, for example by mixing the active compounds with exten-S ders, that is, liquid solvents, Liquefied gases underpressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated ali-phatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic 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 ace-tone~ methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water. By liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propel-lant, such as halogenated hydrocarbons as well asbutane, propane, nitrogen and carbon dioxide. As solid carriers there are suitable: for example, ground natu-ral minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmor-illonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there are suitable: for example, 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, Le A 21 717 ~255~

coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there are suitable: for example, non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxy-ethylene-fatty alcohol ethers, for example alkyl-aryl polyglycol ethers; alkylsulphonates, alkyl-sulphates, aryl-sulphonates as well as albumin hydrolysation products. As dispersing agents there are suitable for example, lignin-sul-phite waste liquors and methylcelluloseO
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 pig-ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90% .
The active compounds can be present in ~he formulation as a mixture with other known active compounds, such as fungi-cides, insecticides, acaricides and herbicidesl and also as mix-tures with fertilisers and other growth regulators.
The active compounds can be used as such, in the form of their formulations or as the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsion ~25S6~3~

foams, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. They are used in the customary manner, for example by watering, spraying, atomising, scattering, dusting, foaming, coating and the like. Furthermore, it is possible to apply the active compounds in accordance with the ultra-low volume process or to inject the active compound prepara-tion or the active compound itself into the soil. It is also possible to treat the seeds of plants.
When the active compounds are employed as plant growth regulators, the amounts applied can be varied within a substantial range. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of the active compound are employed per hectare of soil surface.
When the active substances are employed as plant growth regulators, the rule is that they are applied within a preferred period of time, the exact definition of which depends on the climatic and vegetative circumstances.
When the active substances are employed as fungicides, also, the amount employed can be varied within a substantial range, depending on the type of application. Thus, in the treat-ment of parts of plants, the active compound concentrations in theuse forms are in general between 1 ànd 0.0001% by weight, prefer-ably between 0.5 and 0.001%. In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required. In the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the place of action.
The following are examples relating to the compounds and methods of this application and the parent application.

~25~68~
,.

Preparation Exam`ples ~xample 1 Cl~-CH2-CH-C0-C-C~(c~3)2 j~N`N CH3 N

(Process a) 15.6 g (0.08 mol~ of 1-(1,2,4-triazol-1-yl)-3,3,4-trimethylpentan-2-one are clissolved in 100 ml of dimethylsulphoxide, and 4.5 g (0.08 mol) of potassium hydroxide, dissolved in 10 ml of water, are added, while cooling. 16.4 g (0.08 mol) of 4-chlorobenzyl bromide, 10 lissolved in S0 ml of dimethylsulphoxide, are added dropwise to the mixture at a rate such that the tempera-ture does not exceed 40C. Thereafter, the mixture is slowly warmed to 100C and stirred for a further 15 hours at this temperature, and the cooled solution is 15 poured onto 500 ml o~ water. The mixture is extracted with twice 250 ml of methylene chloride, the methy-lene chloride phase is then extracted with four times 100 ml of water, and the organic phase is evaporated down. The residue is taken up in 100 ml of acetone, and 20 14.4 9 of naphthalene-1,5-disulphonic acid, dissolved in 50 ml of acetone, are added. The 2,3,3-trimethyl-5-(1,2,4~triazol-1-yl)-6-(4-chlorophenyl)-hexan-3-one salt of naphthalene-1,5-disulphonic acid crystallises out. The precipitate is filtered off under suction and 25 taken up in 250 ml of saturated sodium bicarbonate solu-tion, the aqueous phase is extracted with four times 100 ml of methylene chloride, the methylene chloride phase is extracted with 10û ml of water, and the sol-vent is distilled off from the organ-ic phase. 17.3 9 30 (67.6% of theory) of 2,3,3-trimethyl-5-(1,2,4-triazol-1-yl)-6-t4-chlorophenyl)-hexan-4-one are obtained as Le A 21 717 ~55~

~ 24 -colourless crystals of melting point 91-94C.
Preparation of intermediate fH3 H2C - C0 - f - CH(CH3)2 N~ CH3 162.5 g (1 mol) of 1-chloro-3,3,4-trimethyl-pentan-2-one are added dropwise to a suspension of 84 g (1.2 mols) of 1,2,4-triazole and 165.6 g (1.2 mols) of potassium carbonate in 1 litre of ethanol. The mixture is stirred for 15 hours at 40C, the inorganic precipitate is filtered off under suction, the solvent is distilled off, the precipitate is taken up in 500 ml of methyl-ene chloride, the organic phase is extracted with 1 litre of water, the aqueous phase is extracted with 500 ml of methylene chloride, the methylene chloride phases are combined, and the combined phases are extracted with twice 1 litre of water. The solvent is distilled off from the organic phase. 154.6 g (79.3%
of theory) of l-(1,2,4-triazol-1-yl)-3, 3 4-trimethyl-pentan-2-one are obtained as a colourless oil of refractive index nD-1.4827.
\
fH3 Cl - CH2 - C0 - f CH(CH3)~

5~

- 24a -238 g (1 mol) of 1-chloro-2-phenoxy-3,3,4-'cri-methyl-pent-l-ene are stirred with 500 g of formic acid and 50 g of concentrated hydrochloric acid for 2 hours at 80C. The mixture is diluted with methylene chloride, and is washed once with water and four times wi~h dilute sodium hydroxide solution. After the mixture has been dried over sodium sulphate, the solvent is stripped ~255~

off in vacuo, and the residue is distilled over a column. 125 to 135 g (77-83% of theory) of 1-chloro-3,3,4-trimethyl-pentan-2-one of boiling point 88-93C/16 mbar are obtained.

CH3 \ CH3 ~ CHCl CH - C - C
CH3 CH \ O ~

487 g of sodium phenolate are introduced into 1.6 litres of N-methylpyrrolidone at about 100C, and dissolved by heating the mixture to 200C. 360 g (2 mols) of 1,1-dichloro-3,3,4-trimethyl-pent-l-ene are added dropwise in the course of 3 hours at a rate such that the temperature of the reaction mixture does not fall below 195C. Thereafter, the mixture is heated at 200-210C for 8 hours. Working-up is carried out by diluting the solution with methylene chloride and extracting it by shaking with dilute sodium hydroxide solution. After drying and stripping off the solven~, 406 g of crude product remain, this product being distilled at 105-120C/0.1 mbar. 337 g (71% of theory) of l-chloro-2-ph~noxy-3,3,4-trimethyl-pent-1-ene are obtained.

\ CH - C CH=CC12 20 g of anhydrous, powdered aluminium chloride are added in portions to 2,040 g (21 mols) of vinylidene chloride at -10C, in a dry apparatus equipped with a drying tube. 837 g (7 mols) of 2-chloro-2,3-dimethyl-butane are then added dropwise in the temperature range from 0 to 10C. The mixture is allowed :/:

to warm up to 20C, and further aluminium chloride portions (a maximum of 20 g) are added, while cooling, until the reaction is no longer exothermic. The mixture is stirred for a further 4 hours at room temperature, the catalyst is deactivated by dropwise addition of 70 ml of acetîc acid, and the mixture is filtered over sodium sulphate. The volatile constituents are separated from the sparingly volatile constituents by continuous-feed distillation under 1 mbar. The distillate is :Eractionated in a column. 824 to 1,226 g (65-95% of theory) of l,l-dichloro 3,3,4-trimethyl-pent-l-ene of boiling point 60-75C/20 mbar are obtained.

C~13\ CIH3 CH -C Cl About 440 g (12 mols) of hydrogen chloride from a cylinder are passed, in the course of 16 hours, into 840 g (10 mols) of 2,3-dimethyl-but-1 ene at 10 to 20C, while cooling with ice. According to IR, conversion is then complete. Excess hydrogen chloride is drawn off with a water jet pump. 1,103 g (91% of theory) of 2-chloro-2,3-dimethyl-butane are obtained.
Example 2 Cl ~ CH2- CH - CH - 1 CH(CH3)2 " N ~ CH3 N
(Process c) 13.8 g (0.043 mol) of 2,3,3-trimethyl-5-(1,2,4-triazol-,f ~.~

~55~8~

l-yl)-6-(4-chlorophenyl)-hexan~4-one (Example 1) are dissol~Jed in 100 ml of methol, and 2.1 g (0.056 mol) of sodium borohydride are added in portions a-t 0 to 10C, the mixture is then allowed to react for a further 15 hours at room temperature, 90 ml of 2N hydrochloric acid are added dropwise, and stirring is continued for a further 15 hours at room temperature.
300 ml of saturated sodium bicarbonate solution are added, the mixture is extracted with twice 250 ml of methylene chloride, and washed with 250 ml of methylene chloride in each case, the methylene chloride phase is washed with three times 50 ml of water, and the methylene chloride is distilled off. 10 g (72.5% of theory) of 2,3,3-trimethyl-5-(1,2,4-triazol-1-yl~-6-(4-chlorophenyl)-hexan-4-ol are obtained as colourless crystals of melting point 106-08C.
Example 3 SO3H

Cl~ 2 CIH CO C i ~ x 1/2 ~N N CH
N ~ SO3H

(Process a) 34 g (0.15 mol) of 1-(1,2,4-triazol-1-yl)-3-(dioxolan-2-yl)-3-methyl-butan-2-one in 150 ml of dimethylsulphoxide are initially introduced, 8.4 g of powdered potassium hydroxide are added at 15 C, and 36 g (0.15 mol) of 2,3-dichlorobenzyl bromide, dissolved in 30 ml of dimethylsulphoxide, are added dropwise.
The reaction mixture is stirred for a further 15 hours at 20C, and the suspension is poured onto 500 ml of water. The mixture is .~

~2S;568~
- 27a -extracted with 600 ml of methylene chloride, the organic phase is washed with twice l litre o:E water, and the solvent is distilled off. The oily residue is dissolved in 600 ml of acetone, and naphthalene-1,5-disulphonic acid in 60 ml of acetone is added.
At 0C, crystallisation occurs after 6 hours. 50 g (38.6% of theory) of l-(2,~-dichlorophenyl)-. .

~2~
.

2-(1,2,4-triazol-1-yl)-4-(dioxolan-2-yl)-4-methyl-pentan- 3-one naphthalene-1,5-disulphonate of melting point 199-201C are obtained.
Preparation of intermediate C~13 O-CH 2 - co f N~ CH3 ~ N
180.6 g (0.94 mol) of 1-chloro-3-(dioxolan- 2-yl)-3-methyl-butan-2-one, 64.9 g (0.94 mol) of 1,2,4-triazole and 142.7 g (1 mol) of potassium carbonate in 1,000 ml of methyl ethyl ketone are heated under reflux for 16 hours. The solid is fil-tered off under suction and the solvent is distilled off, the oily residue is taken up in 700 ml of methylene chloride, and the organic phase is extracted with twice ],000 ml of water. The solvent is distilled off from the organic phase. 151.3 g (7105%
of theory) of 1-(1,2,4-triazol-1-yl)-3~(dioxolan-2-yl~-3-methyl-butan-2-one are obtained as an oil with a purity of 99~ according to gas chromatography.

fH3 Cl - CH2 - C0 - C

204 g (1038 mol) of 2,2-dimethyl-4-chloro-3-keto-butanal are heatad with 93 g (1.5 mols) of ethylene glycol and 0.7 ~ 2~iS~
- 28a -g of p~toluenesulphonic acid in 400 ml of methylene chloride for 3 hours in a water separator. The organic phase is extracted with 150 ml of 5~ strength sodium hydroxide solution, and thereafter with 400 ml of water. The solvent is distilled off and the resi-due is distilled under the vacuum Erom a water jet. 211 g ~25568~

(79.8% of theory~) of 1-chloro-3-(dioxolan-2-yl)-3-methyl-butan-2-one of boiling point 127-28C/14 mbar are obtained.
CH;
Cl-CH~ - C0 - C -CH0 t~3 210 9 (1.5 mols) of 1-morpholino-2-methyl-prop-1-ene are added dropwise, in the course of one hour, to 169.0 9 (1.5 mols) of chloroacetyl chloride~ dissolved in 350 ml of diethyl ether, at 5C. After ~he addi-tion is complete, the mixture is stirred for a further 10 3 hours under reflux. The solution is poured onto 100 9 of ice and brougilt to pH 5 with aqueous sodium bicar-bonate solution, and the ether phase is separated off.
The aqueous phase is extracted with 100 ml of diethyl ether, the organic phases are combined, and dried over sodium sulphate, the solvent is distilled off and the residue is distilled under the vacuum from a water jet.
136.4 9 (61~ of theory) of 4-chloro-3-keto-2,2-dimethyl-butanal of boiling point 95-98C/14 mbar are obtained.
Examples 4 and 5 20 ,ClCH CH30 _1 ~N~ CH3 Example 5: A form*
N
* A and B forms: the two pos-sible geometric isomers (Process c) 22.9 9 (0.06 mol) of 1-~2,4-dichlorophenyl)-Z-(1,2,4-triazol-1-yl)-4-(dioxolan-2-yl)-4-methyl-pentan-3-one are dissolved in 100 ml of methanol, the solution is cooled ~o 0C, and 2.95 9 (0.078 mol) of sodium borohydride are added in portions. The mixture is Le A 21 717 ~5684 stirred for a further 3 hours at room temperature, 15 ml of concentrated hydrochloric acid are added dropwise, stirring is continued for a further 3 hours and 500 ml of saturated sodium bicarbonate solution are then added.
5 The mixture is extracted with 400 ml of methylene chloride, the phases are separated, the ~organic phase is washed with twice 100 ml of water, and the solvent is distilled o-ff. The residue is taken up in 150 ml of diisopropyl ether, and the crystals are filtered off 10 under suction. 1-(Z,4-Dichlorophenyl)-2-(1,Z,4-tri-azol-1~yl)-4-(dioxolan-2-yl)-4-methyl-pentan-3-ol is obtained as the B form of melting point 178-81C, and after approx. 100 ml of diisopropyl ether have been dis-tilled off, 8.9 9 of product are obtained as the A form 15 of melting point 95~10ûC.
Example 6 Cl-~)-CH~ CH-CO-~\ CH3 N

(Process a) 30 g (0.131 mol) of 1-(imidazol-1-yl)-3-(di-oxolan-2-yl)-3-methyl-butan-2-one are dissolved in 130 20 ml of dimethylsulphoxide, 7.5 9 of powdered potassium hydroxide are added at 10C, and 21 9 of 4-chloro-benzyl chloride (0.131 mol), dissolved in 30 ml of di-methylsulphoxide, are added dropwise. After stirring has been carried out for 15 hours at 20C, the suspension 25 is poured onto 500 ml of water, the mixture is extracted with 600 ml of methylene chloride, the organic phase is extracted with 1 litre of water in each case, and the sol-vent is distilled off~ The oily residue is taken up in 300 ml of diethyl ether, the ether phase is filtered 30 and the solvent is distilled off. 14 9 (30.6~ of theory) Le A 21 717 ~:2.5~

of 1-(4 chlorophenyl)-4-(dioxolan-2-yl)-2-(imidazol-1-yl)-4-methyl-pentan-3-one of refractive i.ndex n20 = 1.5490 are obtained.
Preparation of intermediate CH2 - CO - C--~ ~

106.8 g (0.55 mol) of 1-c.hloro-3-(dioxolan-2-yl)-3-methyl-butan-2-one and 74.8 g (1.1 mols) of imidazole in 500 ml of acetonitrile are stirred for l5 hours at 65C. The solvent is distilled off, the residue is taken up in 800 ml of methylene chloride and the solution is extracted with twice 1 litre o w~ter. The methylene chloride ph~se is d.ried over sodium sul-phate, and the solvent is distilled o:~f. 71.7 g (57.7~ of theory) of l-(imidazol-l-yl)-3-(dioxolan-2-yl)-3-methyl-butan-2-one are obtained (purity according to gas chromatography 95.4%).
Example 7 Cl- ~ -CH2 - CH - CH - C
f,N ~ CH~

(Process c) ~255~8L~

- 31a -14.6 g (0.042 mol) of 4-dioxolan-2-yl)-4-methyl-1-(4-chlorophenyl)-2-(imidazol-1-yl) pentan-3-one are dissolved in 150 ml of methanol, and 2.065 g (0.055 mol~ of sodium borohydride are added in portions at 0C; after a reaction time of 3 hours at room temperature, 15 ml of hydrochloric acid (concentrated) are added dropwise, and stirring is continued for a further 3 ~ ~556~3~

hours at room temperature, and 500 ml of saturated aque-ous sodium bicarbonate solution are then added. The mixture is extracted with 400 ml of methylene chloride, the phases are separated, the organic phase is washed with twice 100 ml of water, and the solvent is distilled off. The residue is taken up in 150 ml of diisopropyl ether, and the solution is cooled to 0C. 10.8 9 (73.8 of theory) of 4-tdioxolan-Z-yl)-4-methyl-1-(4-chloro-phenyl)-2-(imidazol-1-yl)-pentan-3-ol of melting point 151~157C crystallise out cduring this procedure.
The following compounds of the general formula Il A tI) N _~1 are obtained in an analogous manner and in accordance with the process variants given:

Le A 21 717 5~i8~

Example Rl R2 A B Melting No. Point (C) or nD
_.
8 Cl ~ CH2--C(CH3)2-CH CH2 N CO 43-48 9 Cl ~ CH2-C(CH3)2 3 7 N CO 98-102 F3CO ~ -CH2-C(CH3)2-i-C3H7 N CO 1.485 11 Cl ~ H - ~ N CO 60 12 Cl ~ CH2--C(CH3)2-CH CH2 N CH(OH) 132-46 13 Cl- ~ CH2-C(C 3)2 3 7 N CH(OH) 104-11 14 F3CO- ~ CH2C(CH3)2 c3 7 N CH(OH) 1.489 CH2=CH-CH2--C(CH3j2-i C3H7 N CEI(OH) 1.497 16 CH =CH-CH CH - -C(CH ) -i-C H7 N CH(OH) 1.494 17 ~ CH2--C(CH3)2 1 C3 7 N CH(OH) 1.495 18 4 9-C(CH3)2-i-C3H7 N CH(OH) 1.485 19 Cl ~ H ~ N CH(OH) 118-20 CH3 (x HCl) ~ CH2 ~ N CH(OH) 160-66 . (x HCl~

5 ,~',, ~255~8'~

Example Rl R2 A B Melting No. 20 21 Cl ~ CH -3 ~ N CH(OH) D

22 n-c4H9-CH3 ~ N CH(OH) (56HCl) 23 ~CH - ~ N CH(OH) (25HCl) 24 Cl ~ CH2-~ N CH(OH) (65HCl) CH N CH(OH) 130 26 n-C4Hg~ i-C3H7 N CH(OH) (decomposi-27 n~C4H9 ~ N CH(OH) 144-45 28 ~ 2-C(CH3)2~ ] CH CO 69-74 29 Cl ~ CH2-C(CH3)2 ~ ~ CH CH(OH) 160-67 30 ~ Cl ~ H - ~ ~x HC ) 31 F ~ CH2--C(CH3)2-i-C3H7 N CH(OH) 127-30 , ~5~ ~L~

Example Rl R2 A B Melting No. Point (C) or nD

32Cl ~ CH2--C(CH3)2-i-C3H7 N CH(OH) 166-67 33 n~C4H9 -C(CH3)2-CH2-C(CH3)3 N CH(OH) (x HCl) 34 n~C4H9C(CH3)2 2 N CH(OH) 137-38 ~ CH2-C(cH3)2-cH=CH2 N CH(OH) (56HC8) 36CF3O ~ CH2-C(CH3)2-CH CH2 N CH(OH) (x HCl) 37 3 ~ 2C( 3):~ 2 N CH(OH) (x HCl) 38 ~ CH2-C(CH3)2-n-C3H7 N CO 1.4881 39CH3)2CHcH2cH2c(CH3)2 n C3H7 N CO viscous oil 40 n~C4H9C(CH3)2 3 7 N CO 1.4748 41 n-C4Hg-C(CH3)2-n-C3H7 N CH(OH) 1.4809 42Cl ~ CH2--C(CH3)2-n-C3H7 N CO 83 ~1 43Cl ~ CH2--C(CH3)2-n-C3H7 N CO 76 44 ~ CH2--C~CH ) -n-C3H7 N CO 1.5209 45(CH3)2CHcH2cH2 C(CH3)2 3 7 N CH(OH) 1.4789 5~

Example Rl R2 A B Melting No. Point (C) _ . _ _ 46 Cl ~ CH2- -C(CH3)2-n-C3H7 N CHIOH) 106 47 ~ CH2- -C(CH3)2-n-C3H7 N CH(OH) 1.4941 48 ~ CH2- -C(CH3)2-n-C3H7 N CH(OH) 1.5240 49 Cl ~ CH2~ -C(CH3)2-n-C3H7 N CH(OH) 90-92 n-C6H13 -C(CH3)2~i-C3H7 N CH(OH) (50HCl) 51 Cl ~ CH2- -C(CH3)2-CH2-C(CH3)3 N CH(OH) 105-08 52 Cl ~ CH2 ~ N CH(OH) (63HC41) 53 CF3O ~ CH2- ~ N CH(OH) 148-50 (x HCl) 54 CF3- ~ CH - 3 ~ N CH(OH) (x2HCl) Cl ~ CEI2- -C(CH3)2-CH(OCH3)2 N CO 1.5275 56 Cl- ~ CH2- -C(CH3)2 CH(OCH3)2 N CO 85-87 57 Cl ~ CB2- -C(CH3)2-CH(OCH3)2 N CH(OH) 1.5330 SB ~ Cl- ~ C~2 -C~CH3~2-CB~OC33)2 N CH~OB) ¦106-110 ~55~

Example Rl R2 A B Melting No. Point (C) or nD
_ 59 Cl ~ CH2--C(CH3)2-CHO NCH(OH) 141-44 Cl ~ CH2- -C(CH3)2-CH(OCH3)2 CH CH(OH) 154-60 61 Cl- ~ CH2- -C(CH3)2-CH(OCH3)2 CH CH(OH) 132-34 62 Cl ~ CH2- -C(CH3)2-CH=NOCH3 N CH(OH) (x HCl) 63 ~ -CH2-~ i C3 7 NCH(OH) 74-76 64 n-C4Hg- ~ NCH(OH) 72-75 ~ CH2--C(CH3)2-CH=CH2 NCH(OH) (44HCl) 66 ~ CH2--C(CH3)2-CH=C~I2 NCH(OH) (31HCl) 67 ~ CH2--C(CH3~2-CH=CH2 NCH(OH) (14HCl) - 38 - ~ %S S~ ~

Use _amples The compounds indicated below are employed as comparative substances in the examples which follow:

(A) Cl ~ CH2-CH-CO-C(CH3)3 N

~B)~ CH2-CH CO f CH2 ~ ~ N 3 N X HCl (C)Cl--~CH2-CH-CH-C-CH2F

~ N~N CH3 r_~Cl ClH3 (D)Cl ~ -CH -fH-CO-C-CH2F
~ ,N 3 N- ~

I I
(E)n_c4Hg fH_cH_cl_cH2F

N ~ C 3 ~ OH CH3 (F)CH2-CH-CH-C-CH2F

~ ~ CH3 N

- 38a - 12S56~

fH3 (G~ n-C4Hg-CH-CO-C-CH2F
~ N~N CH3 11~
N

(H) Cl ~ -CH2-CH-CO-C-CH2Cl ~ N 3 N

~2~5~

Example A
Sphaerotheca test (cucumber) t protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable pre~aration of active com-pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca ful igi nea.
The plants are then placed in a greenhouse at 23 to 24C and at a relative atmospheric humidity of about 75~.
Evaluation is carried out 1û days af~er the inoculation.
In this test~ a clearly superior activity com-pared with the pr;or art is shown, for example, by the compounds according to the following preparation examples:
2 and 13.

Le A 21 717 :~:255~8~
~ 40 -Example B
Erysiphe test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl poly-glycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the s~ated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-tration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.
The plants are placed in a greenhouse at a tem-perature of about 20C and a relative atmospheric hum-idity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation is carr;ed out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples:
25 11, 19, 8, 1, ~, 2, 13, 12, 21, 2Z, 23 and 24.

Le A 21 717 , ,.

~255684 Example C
-Cochliobolus sativus test (barleyj / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mi~ed w;th the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired con-centration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain in an incuba-tion cabinet for 48 hours at 20C and 100% relative atmospheric humidity.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80%.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds according to the following preparation examples:
2, 12, 21, 22, 23 and Z4.

Le A 21 717 ~S~

Example D
Influence on growth of sugar beet Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 parts by weight of polyoxyethylene sorbitane mono-laurate To produce a suitable preparation of active compound, 1 part by weight oi active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.
Sugar beet is grown in a greenhouse until formation of the cotyledons is complete. in this stage, the plants are sprayed with the preparation of active compo~nd until dripping wet. After 14 days, the additional growth of the plants is measured and the influence on growth in per cent of the additional growth of the control plants is calculated. 0% influence on growth denotes a growth which corresponds to that of the control plan~s. ~egative values characterize an inhibition of growth in comparison to the control plants, whilst positive values characterize a promotion of growth in comparison to the control plants.
In this test, the active compounds 8, 12, 1, 9, 13, 21, 22, 23 and 24 have a better influence on growth than the compounds (B), (D), (E) and (F), which are known from the prior art.

~55~

Example E
Inhibition of growth of cotton Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane mono-- laurate To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.
Cotton plants are grown in a greenhouse until the 5th secondary leaf has unfolded completely. In this stage, the plants are sprayed with the preparations of active compound until dripping wet. After 3 weeks, the additional growth of the plants is measured and the inhibition of growth in per cent of the additional growth of the control is calculated. 100% inhibition of growth means that growth has stopped and 0% denotes a growth corresponding to that of the control plants.
In this test, the active compounds 8, 12, 2, 13, 21, 22, 23 and 24 effect better inhibition of growth than the compounds (B), (D), (E), (F), (G) and (H), which are known from the prior art.

~25X~

Example F
Inhibition of growth of soya beans Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane mono-laurate To produce a suitable preparation of active compound, 1 part by weight of active compound i5 mixed wi-th the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.
Soya bean plants are grown in a greenhouse until the first secondary leaf has unfolded completely. In this s-tage, the plants are sprayed with the preparations of active compound until dripping wet. After 3 weeks, the additional growth is measured on all the plants and the inhibition of growth in per cent of the additional growth of the control plants is calculated. 100%
inhibition of growth means that growth has stopped and 0% denotes a growth corresponding to that of the control plants.
In this test, the active compound 8, 12, 1, 2, 13, 21, 22, 23 and 24 effect better inhibition of growth than the com-pounds (~), (D), (E), (F) and (G), which are known from the priorart.

~5~

Exampl_ G
Stimulation of the fixation of C2 in soya beans -Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane mono-laurate To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.
Soya bean plants are grown in a greenhouse until the first secondary leaf has unfolded completely. At this stage, the plants are sprayed with the preparations of active compound until dripping wet. In the further course of the experiment, the fix-ation of C02 in the plants is determined by customary methods.
The values are compared with those of the control plants, which have not been treated with the active compounds.
Further experimental data and the results oE this exper-iment are given in the table below. The figures of merit have the following meanings:
- denotes inhibition of the fixation of CO2 0 denotes fixation of CO2 as in the case of the con-trol denotes low stimulation of the fixation of CO2 ++ denotes powerful stimulation of the fixation of CO2 ++~ denotes very powerful stimulation of the fixation of ~2 In this test, -the active compounds 20, 1 and 13 effect better stimulation of the fixation of CO2 than the compounds (C), (D), (E), (G) and (H), which are known from the prior art.

Claims (4)

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

1. An azolyl-ketone of the formula IIa, or an acid addition salt thereof, (IIa) in which A is a nitrogen atom or the CH group, and R4 is the CHO group, or a -CH=O derivative selected from the group consisting of -CH=N-OH, alkoximinomethyl with 1 to 4 carbon atoms in the alkoxy group, di-(C1-4)-alkoxymethyl, dioxolane and dioxane.

2. A compound according to claim 1 wherein R4 is CH=0, methoxyiminomethyl, dimethoxymethyl dioxolane or 1,3-dioxane radical.

3. A process for preparing a compound of formula IIa as defined in claim 1, or an acid addition salt therefor which comprises reacting 1,2,4-triazole or imidazole with a halogen-methyl ketone of formula VI

wherein R4 is as defined in claim 1 and Hal' is chlorine or bromine, and where required, forming an acid addition salt there-of.

4. A process according to claim 3 wherein R4 is CH=O, methoxyiminomethyl, dimethoxymethyl or a dioxolane or 1,3-dioxane radical.