CA1229615A - Substituted azolylvinyl ketones and carbinols - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A substituted azolylvinyl ketone or carbinol of the formula IA
(IA) in which R1 represents the grouping in which R3 represents the grouping -Z-R4; R4 represents alkyl which is optionally substituted by identical or different substituents; and Z represents 0, n represents 1, R2 represents alkyl, alkenyl, alkinyl, phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part, each of which is optionally substituted by identical or different substituents, wherein the substituents on the phenyl in each case being selected from halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 monoalkyl and C1-4 dialkylamino, and furthermore halogenoalkyl, halogeno-alkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, and phenyl and phenoxy which are optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; or, R2 is, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, biocycloalkyl, bicycloalkenyl, each of which is optionally substituted by identical or different substituents from the group consisting of alkyl with 1 to 4 carbon atoms and halogen; and X represents the CO or CH(OH) group and Y
represents a nitrogen atom or the CH group, or a non-phytotoxic addition product thereof with an acid or metal salt, or an addition product thereof with an acid or metal salt. The products are active in combating fungi and in regulating the growth of plants.

Description

Lo 5 The present invention is divided out of Canadian application serial number 433,750 filed on August 3rd, 1983 (the parent application) relates to new substituted azolylvinyl kittens and carbonless, several processes for their preparation and their use as fungicides and plant growth regulators.
It has already been disclosed that certain 1- vinyltri-azolyl-(halogeno)-tert.-butyl kittens and carbonless have good fungicidal properties (compare DEMOS. German Published Specification

2,906,061 published January Thea, 1981, DEMOS German Published Specification 2,938,422 published April 23, 1981, DEMOS German Published Specification 3,019,046 published November 26, 1981, and DEMOS German Published Specification published March 15, 1979, 2,838,847). However, the action of these compounds is not always completely satisfactory, especially when low amounts and concern-tractions are applied.
According to one aspect of the present invention there is provided a substituted azolylvinyl kitten or carbinol of the formula IA 1 2 R - X - C = OH - R
Nay (IA) I
in which Al represents the grouping SHEA

R (Sheehan C -SHEA

lo A 21 844-CA DIVE I - 1 -~2;296~5 in which R represents the grouping -Z-R ;
R4 represents alkyd which is optionally substituted by identical or different substituents;
Z represents 0, n represents 1, R2 represents alkyd, alkenyl, alkinyl, phenol or phenylalkyl with 1 to 4 carbon atoms in the alkyd part, each of which is optionally substituted by identical or different substituents, wherein the substituents on the phenol in each case being selected from halogen, Of 4 alkyd, Of 4 alkoxy, Of 4 alkylthio, Of 4 monoalkyl and Of 4 dialkylamino, and furthermore halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, and phenol and phonics which are optionally substituted by halogen or alkyd with 1 or 2 carbon atoms; or, R2 is, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, bicycloalkyl, bicycloaIkenyl, each of which is optionally substituted by identical or different substituents from the group consisting of alkyd with 1 to 4 carbon atoms and halogen; and X represents the CO or SHEA) group and Y represents a nitrogen atom or the OH group, or a non-phytotoxic addition product thereof with an acid or metal salt.
According to one aspect of the parent application there is provided a substituted azolylvinyl kitten or carbinol of the formula I

SLY

Al _ X - C = OH - R

N
y (I) in which R represents cycloalkyl with 3 to 5 carbon atoms which may be substituted by identical or different substituents, or substituted cyclohexyl, wherein the substituents in each case are selected from alkyd with 1 to 4 carbon atoms and halogen;
or Al may be the grouping ISSUE
R3 - (Sheehan - f SHEA

R3 represents phenol which is optionally substituted by identical or different substituents, selected from halogen, Of 4 alkyd, Of 4 alkoxy, Of 4 alkylthio, Of 4 monoalkyl and Of 4 dialkylamino, and furthermore halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, and phenol and phonics which are optionally substituted by halogen or alkyd with 1 or 2 carbon atoms, or, furthermore, R3 is alkenyl with 2 to 4 carbon atoms, alkinyl with 3 to 5 carbon atoms, cyan or the grouping -Z-R ;
R4 represents halogenoalkyl, or phenol or phenylalkyl with 1 or 2 carbon atoms in the alkyd part, each of which is optionally substituted by identical or different substituents, wherein the substituents on the phenol in each case being the - pa -I

- substituents on phenol already mentioned in the case of R3; and Z represents O, S, SO or SO, n represents a number from 0 to 2, R2 represents alkyd, alkenyl, alkinyl, phenol or phenylalkyl with 1 to 4 carbon atoms in the alkyd part, each of which is optionally substituted by identical or different substituents wherein the substituents on the phenol in each case being those substituents on phenol which have already been mentioned in the case of R3; or, R is, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, bicycloalkyl, bicycloalkenyl, each of which is optionally substituted by identical or different substituents from the group consisting of alkyd with 1 to 4 carbon atoms and halogen; but R2 does not represent optionally substituted phenol at the same time as Al represents optionally substituted cycloalkyl with 3 to 5 carbon atoms or substituted cyclohexyl or R3 represents optionally substituted phenol; and X represents the CO or SHEA) group and Y represents a nitrogen atom or the OH group, or a non-phytotoxic addition product thereof with an acid or metal salt.
The compounds of the formula (IA) according to the invention occur in the geometric isomers E (trays) and Z (is).
In the E, Z nomenclature, the substituents on the double bond are arranged in order of decreasing priority in accordance with the Cahn-Ingold-Prelog rule. If the preferred substituents are on the same side of the double bond, the compound has the Z configuration (derived from zusammen (together)), and if they - 2b -S

are on opposite sides, the compound has the E configuration (derived from entegen opposite to)).
The compounds of the formula (IA) according to the invention where X = SHEA) also have two asymmetric carbon atoms; in this case, they can exist in the form of the two geometric isomers (threw and earthier form), which can be obtained in varying proportions. In both cases, they are in the form of optical isomers.
It has furthermore been found that the substituted azolylvinyl kittens and carbonless of the formula (IA) and acid addition salts and metal salt complexes thereof - 2c -Z~6~5 are obtained by a process in which a) ketoenam;nes of the formula US

R 1 _ C C / ( I I
Noah R
N
on which R1 and Y have the abovement;oned meaning and R5 and I are identical or different and repro-sent alkyd with 1 to 4 carbon atoms; or, together with the N atom to which they are bonded, repro-sent piper;d;nyl~ pyrrol;d;nyl or morpholinyl, in each case optionally Mooney in-substituted by alkyd with 1 to 4 carbon atoms, are reacted with organomagnesium compounds of the for-mute Hal - My - RZ (III) in which R2 has the abovement;oned meaning and Hal represents halogen, in the presence of a solvent and, if appropriate, in the presence of an inert gas, or b) azolyl kittens of the formula YO-YO
R1 - C0 - SHEA - N I (IV) No in which R1 and Y have the above mentioned meaning, are reacted with aldehydes of the formula 0 = OH - R2 TV
in which RZ has the above mentioned meaning, in the presence of a solvent and in the presence of a catalyst, and I if desired, the substituted azolylvinyl kittens lo A 21 844 - ~2Z~ S

according to the invention of the formula Nay (It) No R1, R2 and Y have the above mentioned meaning, obtained by processes tax and (b) are reduced in a gent orally customary manner.
If desired an acid or a metal salt can be added onto the compounds of the formula PA thus obtained.
Finally, it has been wound that the new subset-tuned azoLylvinyl kittens and carbonless of the formula IA
and acid addition salts and metal salt complexes thereof have powerful fungicidal and powerful plant growth regal-cling properties.
The new substituted azolylvinyl tones and car-boneless Go the formula TO are also interesting inter-mediates for the preparation of other plant protection agents In the case of the veto derivatives, the veto group can be reduced to a -SHEA)- group or a -CRY)-group. Furthermore, functional derivatives ox the veto group can be obtained by an appropriate reaction, such as, for example, oxides and oxide ethers, hydra zones and petals. The carbinol derivatives can be converted into the corresponding ethers on the hydroxyl group in the customary manner Furthermore, azalea or carbamoyl derive natives of the compounds of the formula IA can be ox-US twined by reaction with, for example, acylhalides orcarbamoyl chlorides in a manner which is known in print supply.
Surprisingly, the compounds according to the invention have a better fungicidal action than the 1-vinyltriazolyl-(halogeno)-tert. bottle kittens and carbine owls which are known from the prior art and are closely related compounds from a chemical and biological point lo A 21 844 of view. The compounds according to the invention also display good plant growth regulating properties. The active compounds according to the invention thus represent an enrichment of the art.
The formula It provides a general definition of the substituted azolylvinyl kittens and carbonless according to the invention. In this formula, preferably, Al represents the grouping SHEA
R (Sheehan C -SHEA
in which R3 represents the grouping -Z-R ;
R4 represents straight-chain or branched alkyd with 1 to 6 R represents straight-chain or branched alkyd with 1 to 12 carbon atoms; straight-chain or branched alkenyl or alkinyl with in each case 2 to 7 carbon atoms; phenol or phenylalkyl with 1 to 4 carbon atoms in the alkyd part, each of which is optionally monosubstituted or polysubstituted by identical or different sub-stituents, preferred possible substituents on the phenol in each case being those substituents on phenol which have already been mentioned in the case of R3; or, furthermore, cycloalkyl with

3 to 12 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyd part, cycloalkenyl with 3 to 12 carbon atoms, cycloalkenylalkyl with 3 to 7 carbon atoms in the cycloalkenyl part and 1 to 4 carbon atoms in the alkyd part, bicycloalkyl with 2 to 24 carbon atoms or ~2Z96~

bicycloalkenyl with 4 to 24 carbon atoms, each of which is option-ally monosubstituted or polysubstituted by identical or different substituents from the group comprising alkyd with 1 to 4 carbon atoms and halogen; and X, Y and Z and the index n have the meanings given in the definition of the invention.
Particularly preferred compounds of the formula IA are those in which Al represents the grouping SHEA
( on SHEA
in which R represents the grouping -Z-R4;
R4 represents straight-chain or branched alkyd with 1 to 4 carbon atoms, R2 represents straight-chain or branched alkyd with 1 to 8 carbon atoms or straight-chain or branched alkenyl or alkinyl with in each case 2 to 4 carbon atoms; or, furthermore, phenol or phenylalkyl with 1 or 2 carbon atoms in the alkyd part, each of which is optionally monosubstituted or dip or tri-substituted by identical or different substituents, preferred possible substitu-ens on the phenol being the substituents on phenol which have already been mentioned in the case of R3; or, furthermore, cycle-propel, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptyl-methyl, cycloalkenyl with 3 to 7 carbon atoms, cycloalkenylmethyl with 3 to 7 carbon atoms in the cycloalkenyl part, bicycloalkyl with 5 to 12 carbon atoms or bicycloalkenyl with 5 to 12 carbon atoms, each of wish is optionally monosubstituted or dip or in-substituted by identical or different substituents from the group comprising methyl, ethyl, isopropyl, fluorine and chlorine;
and X, Y and Z and the index n have the meaning given in the definition of the invention.
Preferred compounds according to the invention also in-elude addition products of acids and those azolylvinyl kittens and carbonless of the formula IA in which Al, R2, X and Y have the meanings which have already been mentioned as preferred for these radicals.
, us no r which can be added on include SLUICE

hydrogen halide acids, such as, for example, hydrochloric acid and hydrobrom;c acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, sup fork acid, monofunctional and bifunctional carboxylic 5 acids and hydroxycarboxylic acids, such as, for example, acetic acid, malefic acid, succinic acid, fumar;c acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for ox-ample, p-toluenesulphonic acid and 1,5-naphthalenedi-10 sulphonic acid.
Other preferred compounds according to the invent lion are addition products of salts of metals of man groups II to IV and of sub-groups I and II and IVY to VIII
and those azolylvinyl kittens and carbonless of the for-15 mute IA in which R1, R2, X and Y have the meanings already given as preferred for these radicals.
In this context, salts of copper, zinc, mangan-I eye, magnesium, tin, iron and nickel are pqrt1cularly Jo to D n eye - 1 prowar. Possible anions of these salts are those 20 which are derived from acids which lead to physiologic-ally acceptable addition products. In this connection, particularly preferred acids of this type are the hydra-gun halide acids, such as, for example, hydrochloric acids and hydrobrom;c acid, and furthermore phosphoric 25 acid, nitric acid and sulfuric acid.
If, for example, 1-(4-chlorophenyl)-Z,2-dimethyl-5-dimethylamino-4-t1,2,4-triazol-1-yL)-4-penten-3--one and n-propyl-magnesium bromide are used as starting sub-stances, the course of the reaction can be represented 30 by the following equation (process a):
SHEA
Of CH2-C-CO-C=CH-N(CH3)2 + 8r-Mg-C3H7-n 31~ N
N Jo SHEA
Cl~CH2-C-CO-C=CH-C3H7-n Shelley NUN
lo A Z1 844 N l!

LO

If, for example, 1-(4-chlorophenyl)-2,2-dimethyl-

4-(1,2,4-triazol-1-yl)-3-butanone and cyclohexanecarb-alluded are used as starting substances, the course of the reaction can be represented by the following equal

5 lion (process b):
SHEA
Of CH2-C-C3-cH2 OUCH >
SHEA NUN SHEA

, ., SHANNON
N l!
If, for example, 1-~4-chlorophenyl)-Z,2-dimethyl-4-(1,2,4-tr;azol-1-yl)-4-octan-3-one is used as the starting substance and sodium bordered is used as the 10 reducing agent, the course of the reaction can be repro-sensed by the following equation (process c):

. SHEA
Cl~>-CH2-C-CO-C=CH-C3H~-n Noah SHEA NUN SHEA OH
N if r- I I
Cl~,~CH2--C - CH--C=CH-C3H7--n SHEA I NUN
N ill The formula (II) provides a general definition of the ketoenamines to be used as starting substances 15 for process (a) according to the invention. In this formula, R1 preferably represents those radicals which have already been mentioned as preferred for this sub-stituent on connect;on-w;th the description of the sub-stances of the formula IA according to the ;nvent;on.
20 R5, R6 and Y have the meanings Gwen on the define Tony of the invention.
The ~etoenamines of the formula (II) are not yet lo A 21 844 _ 9 ~22961~

known. However, they are obtained by reacting azolyl kittens of the formula Ye Al _ C0 - SHEA - N (IV) N

in which Al and Y have the above mentioned meaning, with aside acetals or animal esters of the formulae R70 \ / R5 OH - N (Via) R70 / \ R5 or ~MR5R6 R 0 - OH (Vim) -sir SLUICE

in which R5 and R6 have the above mentioned meaning and R7 represents al]cyl with 1 to 4 carbon atoms, in a manner which is in itself known, in the presence of an inert organic solvent, such as, for example, an aromatic hydrocarbon, and such as, in particular, an aside acutely or aminal ester of the formula (Via) or (Vim) employed in excess, at the boil (in this context, compare also Chum. Ben. 101, 41-50 (1968); J. Org. Chum. 43, 4248-50 (1978) and the preparation examples).
Most of the azolyl kittens of the formula (IV) are known (in this context, compare DEMOS (German Published Specification) 2,431,407 published January 15, 1976, DEMOS 25 (German Published Specification) 2,906,061 published January 8, 1981, DEMOS (German Published Specification) 3,028,330 published April 8, 1982, DEMOS
(German Published Specification) 3,048,266 published July 29, 1982, and DEMOS (German Published Specifications) 3,145,857.

I

[lo A 21 383] and 3,145,858 both published on May 26, 1983, [lo A 21 400]), or they can be prepared by customary methods, by reacting the corresponding halogen kittens with 1,3,4-triazole or imidazole in the presence of an acid-binding agent.
The aside acetals and aminal esters of the formulae (Via) and (Vim) are generally known compounds of organic chemistry (compare, for example, Chum. Ben. 101, 41-50 (1968) and J. Org.
Chum. 43, 4248-50 (1978)); or they can be prepared by the processes described in these references.
The formula (III) provides a general definition of the organomagnesium compounds also to be used as starting substances for process (a) according to the invention. In this formula, R2 preferably represents those radicals which have already been men-toned as preferred for these substituents in connection with the description of the substances of the formula IA according to the invention. Hal preferably represents chlorine or bromide.
The organomagnesium compounds of the formula (III) are generally known compounds of organic chemistry.
The formula (IV) provides a general definition of the azolyl kittens to be used as starting substances for process (b) according to the invention. In this formula, Al and Y preferably represent those radicals which have already been mentioned as pro-furred for these substituents in connection with the description of the substances of the formula IA according to the invention.
The formula (V) provides a general definition of the aldehydes also to be used as starting substances for process (b) ~2~96~S

according to the invention. In this formula, R preferably no-presents those radicals which have already been mentioned as preferred for this substituent in connection with the description of the substances of the formula IA according to the invention.

- aye -I

The aldehydes of the formula TV) are generally known compounds of organic chemistry.
The azolylvinyl kittens to be used as starting substance; for process (c) according to the invention 5 are substances according to the invention.
Preferred possible solvents for the reaction according to the invention in process pa) are inert organic solvents, in the pure form or as mixtures. These include, preferably, ethers, such as deathly ether, 10 methyl ethyl ether, tetrahydrofuran or Dixon, aliphatic and aromatic hydrocarbons, such as, in particular bent zone, Tulane or zillion, and hexamethylphosphoric acid trimmed.
The reaction temperatures can be varied within 15 a substantial range in carrying out process (a) accord-in to the invention. In general, the reaction is car-rued out between -50 and ~150C, preferably between -20 and ~120C.
The reaction according to the invention in pro-20 cuss (a) can be carried out in the presence of an inert gas, such as, for example, nitrogen or helium.
In carrying out process (a) according to the invention, 1 to 1.5 mows of organomagnesium compounds of the formula (III) are preferably employed per mow of 25 ketoenamine of the formula IT The compounds of the formula IA are isolated in the customary manner.
Preferred possible solvents for process (b) according to the invention are inert organic solvents.
These include, preferably, alcohols, such as methanol 30 and ethanol; ethers, such as tetrahydrofuran and Dixon;
aliphatic and cycloaliphatic hydrocarbons such as hex-aye and cyclohexane; aromatic hydrocarbons, such as bent zone, Tulane and cumin; and halogenated aliphatic and aromatic hydrocarbons, such as ethylene chloride, car-35 bun tetrachloride, chloroform, chlorobenzene and dip chlorobenzene.
lo A 21 844 - 13 -:3L2Z96~

Process (b) according to the invention is carried out in the presence of a catalyst It is possible to use all the acid and, on particular, basic catalysts, and buffer mixtures thereof, which can usually be used.
Preferred catalysts include Lewis acids, such as, for example, boron trifluoride, boron trichloride, tin twitter-chloride or titanium tetrachloride; organic bases, such as pardon and piperidine; and, in particular, piper-iodine acetate.
The reaction temperatures can be varied within a substantial range in carrying out process (b) accord-in to the invention. In general, the reaction is car-fled out between ZOO and Luke, preferably at the boil-in point of the particular solvent.
In carrying out process (b) according to the invention, 1 to 1.5 mows of alluded of the formula (V) and catalytic to 0.2 molar amounts of catalyst are em-plowed per mow of triazole-ketone of the formula (IV).
The compounds of the formula IA are isolated in the 20 customary manner.
The reduction according to the invention in pro-cuss (c) is carried out in the customary manner, for example by reaction with complex hydrides, if appropriate in the presence of a delineate, or by reaction with alumina 25 I'm isopropyl ate in the presence of a delineate.
If complex hydrides are used, possible diluentsfor this reaction according to the invention are polar organic solvents. These include, preferably, alcohols, such as methanol, ethanol, buttonhole or isopropanol, and 30 ethers, such as deathly ether or tetrahydrofuran. The reaction is in general carried out at O to 30C, pro-fireball at O to ZOC. For this reaction, about 1 react lion equivalent of a complex hydrides such as sodium bordered or lithium alienate, is employed per mow of 35 the kitten of the formula (It). To isolate the reduced compounds of the formula IA, the residue is taken up in lo A 21 844 ~2Z96~

dilute hydrochloric acid and the mixture is then rendered alkaline and extracted with an organic solvent. Further working up is effected in the customary manner.
If aluminum isopropyl ate is used, preferred possible delineates for this reaction according to the invention are alcohols, such as isopropanol, or inert hydrocarbons, such as Bunsen. The reaction temperatures can again be varied within a substantial range; in general, the reaction is carried out at between 20 and 120C, preferably at 50 to 100C. For carrying out the reaction, about 1 to 2 mows of aluminum isopropyl-ate are employed per mow of the kitten of the formula tip). To isolate the reduced compounds of the formula IA, the excess solvent is removed by distillation in vacua and the aluminum compound formed is dissociated with dilute sulfuric acid or sodium hydroxide solution.
Further working up is effected in the customary manner.
Those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention are preferably used for the preparation of acid addition salts of the azolylvinyl kittens and carbonless of the formula IA-The acid addition salts of the compounds of the formula IA can be obtained in a simple manner by custom-cry salt formation methods, for example by dissolving compound of the formula IA on a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and, if necessary, purified by washing with an inert organic solvent.
Salts of those anions and cations which have already been mentioned-as preferred in connection with the description of the metal salt complexes according to the invention are preferably used for the preparation of metal salt complexes of azolylvinyl kittens and carbonless of the formula IA.
lo A 21 aye Sue The metal salt complexes of the compounds of the formula KIWI can be obtained in a simple manner by gust-ovary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding 5 the solution to the compound of the formula IA. Metal salt complexes can be isolated in a known manner, for example by filtration, and if necessary purified by no-crystallization.
The active compounds according to the invention 1û exhibit a powerful m;crob;c;dal action and can be em-plowed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fung;c;dal agents in plant protection are em-15 plowed for combating Plasmod;ophoromycetes, Oomycetes,Chytr;d;omycetes, Zygomycetes, Ascomycetes, Posed-Maoists and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly Z5 good success for combating cereal diseases; thus, for example, against the powdery mildew of barley causative organism tErysiphe grimness), the brown rust on wheat causative organism (Pucc;nia recondite), the spot blotch disk ease of cereals causative organism (Cochliobolus sativus), the brown spot disease on wheat causative organism tLep-to-Shari nodorum) or the leaf spot disease on barley causative organism (Pyrenophora meres); and furthermore for combating Venturi species, such as against the apple scab causative organism (Venturi inkwells), and rice diseases, such as Pyricularia and Pellicularia~
The active compounds which can be used according lo A Z1 844 :~2~6:~S

to the invention engage on 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 5 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 environment and 10 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.
15 Such inhibition of growth is inter aria of economic interest in the case of grasses, since it is thereby possible to reduce the frequency of cutting the grass in ornamental gardens, parks and sports grounds, at verges, at airports or in fruit orchards. The inhibition of 20 growth of herbaceous and woody plants at verges and in the vicinity of pipelines or overland lines or, quite generally, in areas in which heavy additional growth of plants is undesired, us also of importance.
The use of growth regulators to inhibit the 25 growth in length of cereals is also important The danger of lodging of the plants before harvesting is thereby no-duped or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals which again counteracts lodging. Use of growth regulators for 30 shortening and strengthening the stem enables higher amounts of fertilizer to be applied to increase the yield, without danger of the cereal lodging.
In the case of many crop plants, inhibition of the vegetative growth makes denser planting possible, so 35 that greater yields per area of ground can be achieved.
An advantage of the smaller plants thus produced is also lo A 21 844 ~Z~96~1S

that the crop can be worked and harvested more easily.
Inhibition of the vegetative growth of plants can also lead to increases on yield, since the nutrients and assimilates benefit blossoming and fruit formation to a greater extent than they benefit the vegetative parts of plants.
Promotion of vegetative growth can also frequently be achieved with growth regulators. Thus us of great utility if it is the vegetative parts of the plants which are harvested. Promoting the vegetative growth can, however, also simultaneously lead to a promotion of goner-ate 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 compost-lion 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, ZOO to increase the content of sugar in sugar beet, sugar cane, pineapples and citrus fruit or to increase the pro-loin content in soya or cereals. Using growth regulators it us also possible, for example, to inhibit the degrade anion of desired constituents, such as, for example, 25 sugar in sugar beet or sugar cane, before or after her-vesting. It us also possible favorably to influence the production or the efflux of secondary plant constituents.
The stimulation of latex flux on rubber trees may be men-toned as an example.
Parthenocarpous fruit can be formed under the influence of growth regulators. Furthermore, the gender of the flowers can be influenced. Sterility of the pot-ion can also be produced, which is of great importance on the breeding and preparation of hybrid seed.
ranching of plants can be controlled by using growth regulators. On the one hand, by breaking the lo A 21 84~

~L22961S

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 duffel-lion of the plants at a desired point in time is achieved Such defoliation is of great importance in the mechanical harvesting of cotton, but is also of interest for facile stating harvesting in other crops, such as, for example, in viticulture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators. On the one hand, it us possible to prevent premature shedding of fruit. However, on the other hand, shedding of fruit, or even the fall of boos-some can be promoted up to a certain degree (thinning out) in order to interrupt the alternance. my al~ernance there is understood the peculiarity of some varieties of fruit to produce very different yields from year to 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 harvest-in or facilitate manual harvesting.
Using growth regulators, it is furthermore posy sidle to achieve an acceleration or retardation of ripen-in of the harvest product, before or after harvesting.
This is of particular advantage, since it is thereby possible to achieve optimum adaptation to market require-mints. Furthermore, growth regulators can at times imp prove the coloration of fruit. In addition, concentrate in the ripening within a certain period of time is also lo A 21 ~44 3~Z~

achievable with the aid of growth regulators. This pro-vises the preconditions for being able to carry out come plate mechanical or manual harvesting in only a single pass, for example in the case of tobacco, tomatoes or 5 coffee.
Using growth regulators, it us furthermore pus sable to influence the latent period of seeds or buds of plants, so that the plants, such as, for example, pine-apple or ornamental plants on nurseries, germinate, shoot 10 or blossom at a time at which they normally show no readiness to do so. Retarding the shooting of buds or the germination of seeds with the aid of growth 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 purpose thereby becomes possible.
The active compounds can be converted to the cuss tumor formulations, such as solutions, emulsions, sup-pensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as ULV formulations.
These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or disk 30 pursing 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: aroma alias, such as zillion, Tulane or alkyd naphthalenes, 35 chlorinated aromatics or chlorinated aliphatic hydra-carbons, such as chlorobenzenes, chLoroethylenes or lo A 21 844 - - -~296~LS

ethylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil free-lions, alcohols such as buttonhole or glycol as well as their ethers and esters, kittens, such as acetone, methyl ethyl kitten, methyl isobutyl kitten or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphox;de, as well as water. my liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pros-sure, for example aerosol propellant, such as halogenatedhydrocarbons as well as butane, propane nitrogen and carbon dioxide. As solid carriers there are suitable:
for example, ground natural minerals, such as kaolin, clays, talc, chalk quartz, attapulgite, montmorillon;te or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and sift-gates. As solid carriers for granules there are suit-able: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, 20 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 Emil-s;fy;ng and/or foam-form;ng agents there are suitable:
for example, non-;on;c and anionic emulsifiers, such as 25 polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl-sulphates, arylsulphonates as well as albumin hydrolysat;on products. As dispersing agents there are suitable: for example, lignin-sulphite 30 waste liquors and methyl cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or lattices, such as gum Arabic polyvinyl Alcoa hot and polyvinyl acetate, can be used in the formula 35 anions.
It is possible to use colorants such as inorganically A 21 844 - 21 _ ~L~2~16~5 pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic distaffs, such as alizarin distaffs, ago distaffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of Ron, man-5 Gaines, 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 according to the invention 10 can be present in the formulations as a mixture with other known active compounds, such as fungicides, insect Saudis, acaricides and herbicides, and also as mixtures with fertilizers and other growth regulators.
The active compounds can be used as such, in the I Norm of their formulations or as the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes soluble powders, dusting agents and granules. They are used in the customary manner, for 20 example by watering, spraying, atomizing, scattering, dusting, foaming, coating and the like. Furthermore, it is possible to apply the active compounds on accord-ante with the ultra-low volume process or to inject the active compound preparation or the active compound itself 25 into the soil. It is also possible to treat the seeds of plants.
When the compounds according to the invention are used as plant growth regulators, the amount applied can be varied within a substantial range. In general, 0 01 30 to 50 kg, preferably 0.05 to 10 kg, are used per Hector of soil surface.
When the substances according to the invention are used as plant growth regulators, they are applied within a preferred period of time, the exact definition 35 of which depends on the climatic and vegetative circus-stances.
lo A 21 844 gas When the substances according to the invention are used as fungicides, the amount applied can also be varied Winnie a substantial range, depending on the net-use of the application. Thus, in the treatment of parts 5 of plants, the concentrations of active compound in the use forms are generally between 1 and 0~0001 % by weight, preferably between OHS and 0.001 by weight. In the treatment of seed, amounts of active compound of 0.001 to 50 9 per kg of seed, preferably 0.01 to 10 9, are gent 10 orally required. In the treatment of soil, active come pound concentrations of 0.00001 to 0.1 % by weight, pro-fireball of 0.0001 to 0.2 are required at the place of action.
The preparation and use of the substances according to the invention and owe substances according to the invention of the parent application are illustrated by the examples which folly.
Preparation examples Example 1 Of Ho - C - C0 - C = OH- C3H7 -n C~3 NUN
N _ process a 49.9 g (0.15 molt of 1-(4-chlorophenyl)-2,Z-di-methyl-5-dimethylamino-4-(1,2,4-triazo~-1-yl)-4-peenter-3-one are dissolved in 750 ml of ether, and a solution of 33.9 9 (0.23 molt of n-propyl-magnesium bromide in 100 ml of ether is added drops at -20C. The react lion mixture us subsequently stirred for 1.5 hours during which it warms to room temperature. The reaction mixture is adjusted to a pi value of 7 to 8 with dilute hydra-caloric acid. The organic phase is then separated off, washed with water, dried over sodium sulfite and concern-treated. The residue is purified by column chromatography lo A Z1 844 .

silica gel; ethyl acetate/cyclohexane = 3:1). 30.1 9 t60.5 % of theory) of 1-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-octen-3-one of refractive index n2~0 1.5429 are obtained.
S Preparation of the starting material _ Jo Of H 3 Of -Chihuahuas - C - C0 - Of = OH - N(CH3)~
SHEA NUN
No 50 9 (0.18 Mel) of 1-(4-chlorophenyl)-2,2-di-methyl-4-(1,2,4-triazol-1-yl)-3-butanone are heated under reflex with 23.6 9 (0.138 molt of d;methylformamide d;-methylacetal for 8 hours. To isolate the end product the reaction mixture is concentrated in vacua. 56.5 9 (94.4 of theory) of 1-(4 chlorophenyl)-2,2-d;methyl-5-dimethylam;no-4-~1,2,4-triazol-1-yl)-4-penten-3--one of refractive index n20 1.5797 are obtained.
OH

C l OH 2 - C - CO - OH 2 - SHEA N

37 9 (0.13 molt of 4-bromo-1-(4-chlorophenyl)-2,2-d;methyl-3-butanone, 13.3 9 (0.019 molt of 1,2,4-truly and 53.8 9 (0.39 molt of potassium carbonate are heated under reflex in 300 ml of acetone for 8 hours.
The mixture is allowed to cool, the inorganic residue is filtered off with suction and the filtrate is concern-treated. The residue is taken up in chloroform and the mixture is washed with water, dried over sodium sulfite and concentrated. The residue is stirred with deathly ether, filtered off with suction and dried at 50C in vacua. 18.8 9 (52 of theory) of 1-(4-chlorophenyl)-2~2-dimethyl-4-(1~2~4-triazol-1-yl)-3-butanone of melting lo A 21 844 ~296 S

point 127C are obtained.
SHEA
Of -SHEA - C - C0 - SHEA - or SHEA

98.8 9 (owe molt of bromide are added drops to 130 9 (0.62 molt of 1-(4-chlorophenyl)-2,2-dimethyl-3-butanone in 1000 ml of chloroform at room temperature.
The reaction mixture is subsequently stirred for 1 hour and is then concentrated. 174.7 9 (97.3 I of theory) of 4-bromo-1-(4-chloroph-enyl)-2~2-dimethyl-3-butanonno of refractive index n2D0 1.5570 are obtained.
Example 2 Of SHEA C OH - C = OH - C3H7-n c~3 No N l (Process c) 7 9 (0.021 molt of 1-(4-chlorophenyl)-2,2-di-methyl-4-(1,2,4-triazol-1-yl)-4-octen-3-one (Example 1) are dissolved in 100 m! of methanol, and a solution of 0.21 9 Tao molt of sodium bordered in 5 ml of ice-water is added drops at -10C. The reaction mixture is subsequently stirred at 0C for 1.5 hours and is then adjusted to a pi value of 6 to 7 with dilute hydra-Z0 caloric acid. The reaction mixture is concentrated by distilling off the solvent in vacua. The residue is taken up in chloroform and the mixture is washed with water, dried over sodium sulfite and concentrated.

6.5 9 ~92.9 of theory) of 1-(4-chlorophenyl)-2,2-di-25 methy;-4-(1,2,4-triazol-1-yl)-4-octen~3~ol of refractive index nD20 1.5383 are obtained.

lo A 21 844 ~22961S

Example 3 c~3 C1- @ I -C- C0 - C = OH -N
N Z - Form 8.2 9 (0.03 molt of 1-t4-chlorophenyl)-2,2-di-methyl-4-t1,2,4-triazol-1-yl)-3-butanone, 3.4 9 ~0.03 S molt of cyclohexanecarbaldehYde~ 1.1 g (0.018 molt of acetic acid and 0.8 9 (0.009 molt of piperid;ne are do solved on 60 ml of Tony and the solution us heated under reflex for 8 hours, using a water separator. The cooled reaction solution is washed with water, the orgy arc phase is extracted with sodium bisulphite solution precipitate which has separated out is filtered off with suction and the Tulane phase is washed with sodium bicarbonate solution. After drying over sodium sulphater the solvent is stripped off on a rotary evaporator and the oily residue (11.0 g) is chromatographed on a column, over silica gel using petroleum ether/glacial acetic acid (2:1). The first fractions were combined and the solvent mixture was stripped off on a rotary evaporator.
3.0 9 (26.9 of theory) of 1-(4-chlorophenyl)-20 5-cyclohexyl-2~.2-dimethyl-4-(1,2,4-tria~ol-1-yl)--4-pen-ten-3-one forum) are obtained as a light-coloured oil.
Z0 MHz-NMR, CDCl3 (I, Pam): 1.12 (s, OH); 1.20 (m, OH);
1.70 em, SO); 2.90 (s, OH);, 6.35 id, OH); 7.05 (d, OH);

7.23 (d, OH); 8.00 (s, OH) and 8.07 (s, OH) The fulling compounds of the general formula (I) or (IA) Al _ X -- C - OH - R2 No ( IA) N ¦¦
are obtained in a corresponding manner by the processes described.
lo A 21 844 SLUICE

Example 1 R2 Melting point No. R X Y (C.) or n20 clue 4 SHUCKS CO N -C7H15-n viscous oil SHUCKS CO N -Kiwi 36-39 6 Of- -OCH2-C(CH3)2- CO N -C7H15-n viscous oil 7 OcH2-c(cH3) - CO N -SHEA 96

8 SHUCKS CO N 2 1.5703 Of

9 SHUCKS CO N -SHEA Jo vi s cows of 1 Of- -OCH2-C(CH3) - CO N -C4Hg-n viscous oil 11 Of- SHUCKS CO N Of 124 12 Of- OCH2-C(CH3)2- CO N -Shekel viscous oil clue Of 13 Of- OCH2-C(CH3)2- CO N-CH2-~-Cl 110 14 Of- SHUCKS CO NCH2 120 Of- O-CH2-C(CH3)2- CO N-CH2- 116 16 Of- SHUCKS CO N-C(CH3)3 1.5401 ~296~1L5 Example 1 2 Melting point No. R X y R (C) or no 17 Of- SHUCKS CO N -C4Hg-n 1.5419 18 Of- SHUCKS CO N -C4Hg-n viscous oil 19 Of- SHUCKS CO N SHEA 136-28 Of- SHUCKS CO N CH(CH3)C2H5 viscous oil 21 Of- OCH2-C(CH3)2- CO N -Kiwi viscous oil 22 Of- SHUCKS CO N -C2H5 viscous oil Of Of 23 SHEA C(CH3)2- CO N -SHEA- Of viscous oil 24 Of- SHUCKS CO N -C3H7-n 1.5679 Of- SHUCKS CO N -C2H5 1.5662 26 Of- SHUCKS CO N -SHEA 1.5749 27 H2-C(CH3)2- CO N - (Z-Form) 29 H2-C(CH3)2- CO N - (E-Form) Of- SHUCKS CO N - viscous oil 31 Of- SHUCKS CO N - viscous oil ;

96~

Example 1 R2 Melting point No. R X Y (C) or n20 --. D
32 Of- SHUCKS CO N - viscous oil (Z-Form) 33 Of- SHUCKS CO N - viscous oil 34 Of- SHUCKS CO N - viscous oil 35 Of- SHUCKS CO viscous oil (E-Form) 36 Of- OKAY CO N -CH(CH3)C2H5 1.5372 37 Of- OKAY CO N C3H7 n 1.5421 38 Of- -C(CH3)2- CO N -C2H5 viscous oil Of 39 OUCH C(CH3)2 SHEA) N -C3H -i viscous oil SHUCKS SHEA) N -C4Hg-n viscous oil Of I
41 OCH2-C(CH3)2- SHEA) N -SHEA- Of viscous oil clue 42 Of- SHEA C(CH3)2- SHEA) N -C H -I 1.5333 Of 43 Of- O-CH2-C(CH3)2- SHEA) N -C2H5 30`

44 Of- o OH C(CH I SHEA) N -CH(CH3)C2H5 Of- -CH2-C(cH3)2CO N -Kiwi 30 Of 46 Of- CH2-C(CH3)2-CH(OH) N -SHEA- 54-56 -;

Example 1 R2 Melting point -No. R X Y (C) or nD
. . _ 47 Of- SHUCKS SHEA) N SHEA 120-24 Of Of 48 Of- OCH2-C(CH3)2- SHEA) N -SHEA- Of viscous oil 49 Of- OCH2-C(CH3)2 SHEA) N Chin viscous oil 2 5 OUCH C(CH3)2 SHEA) N -SHEA viscous oil 51 CH3-OCH2-C(CH3)2 SHEA) N -SHEA viscous oil 52 C2H5-ocH2-c(cH3)2 SHEA) N -Kiwi 1,4790 53 CH3-OCH2-C(CH3)2 SHEA) N -Kiwi 1,4867 54 Of OCH2-C(CH3)2- SHEA) N -C4Hg-n viscous oil 55 Of- Shucks SHEA) N Of viscous oil 56 Of- OCH2-C(CH3)2- SHEA N 2 C1 viscous oil 57 Of- SHUCKS SHEA) N -C3H7-n 1,5690 58 Of- Shucks SHEA) N -SHEA 1,5638 59 Of- SHUCKS SHEA) N -C2H5 1,5544 shucks SHEA) N - Of (Forum) 61 SHUCKS SHEA) N - F 139 'I.

I

Example R2 Melting point No. X Y (C) or nD
-62 Of- OCH2-C(CH3)2 SHEA) N - Of 96(Z-Form) 63 Of- OCH2-C(CH3)2- SHEA) N - Of 176(E-Form) 64 C2H5-OCH2-c(cH3)2 SHEA) N - Of 130(E-Form) C2H5-CH2-C(CH3)2 SHEA) N - Of 124 Of 66 CH3-OCH2-C(CH3)2 SHEA) N - Of 134(Z-Form) 67 CH3-OCH2-C(CH3)2 SHEA) N - Of 116(E-Form) Of 68 Of- OCH2-C(CH3)2- CX~OH) N - viscous oil (Z-Form) 69 Of- OCH2-C(CH3)2- SHEA) N - amorphous SHUCKS SHEA) N - viscous oil 71 SHUCKS SHEA) N - (Z-Form) 72 Of- OKAY SHEA) N -C2H5 viscous oil 73 Of- OKAY SHEA) N -c3H7-n viscous oil 74 Of- -C(CH3)2- SHEA) N CH(CH3)C2H5 viscous oil CH2=CH-C(CH3)2- SHEA) N - Of 128 I, .

~2;2~

Example welting point No. R X Y R2 (C) or nD

76 Cluck (SHEA- SHEA) N - Of 136(Z-Form) 77 NC-C(CH3)2- SHEA) N - F 220(E-Form) 78 NC-C(CH3)2- SHEA) N - Of 194(E-Form) 79 CH2=CH~C(CH3)2 Of 128(Z-Form) 80 CH2=CH-C(CH3)2 SHEA) N - Of 128(Z-Form) 81 Of- SHUCKS CO OH -SHEA viscous oil 82 Of- SHUCKS CO OH C3H7 i viscous oil 83 Of- SHUCKS CO OH C3H7 n viscous oil 84 Of- -C(CH3)2- CO OH -C2H5 -1.5595 Of 85 Of- OCH2-C(CH3)2- CO OH -C(CH3)2- 1.5463 86 Of- OCH2-C(CH3)2- CO OH -SHEA 1.5637 87 Of- O-CH2-C(CH3)2- CO OH -fH-CH3 1.5420 Of C2H5 88 Of- OCH2-C(CH3)2- CO 7 15 n 1.5367 89 Of- OCH2-C(CH3)2- CO OH C3H7 i 1.5511 90 Of- SHUCKS CO OH -oh SHEA 30 .

-SLY

Example 1 Remelting point No. R X Y (C) or n20 91 Of- OCH2-C(CH3)2- CO OH -C3H7-n viscous oil OUCH C(CH3)2 CO OH -fH~CH3 viscous oil 93 Of- OCH2-C(CH3)2- CO OH -C2H5 53~57 94 Of- OCH2-C(CH3)2- CO OH -C4Hg-n viscous oil 95 Of- SHUCKS CO OH -Kiwi viscous oil 96 Of- OCH2-C(cH3)2 SHEA) OH -C3H7-n 33 97 Of- SHUCKS SHEA) OH -CH-CH3 30 98 Of- SHUCKS SHEA) OH -Kiwi 31 99 Of- SHUCKS SHEA) OH -C3H7-n viscous oil 100 Of- OKAY SHEA) OH -C2H5 viscous oil 101 Of- O-cH2-c(cH3)2- SHEA) OH -C(CH3)3 viscous oil 102 Of O-cH2-c(cH3)2- SHEA) OH -CH~CH3)C2H5 viscous oil Ç1 103 Of- 2 C(CH3)2- SHEA) OH -OH 80 Of 104 Of- OCH2-C(CH3)2- SHEA) N -Kiwi viscous oil 105 C1- OCH2-C(CH3)2- SHEA) Chicano viscous oil - aye -s Example 1 R2 Melting point No. R X Y (C) or nD
SHEA
106 SHEA CO N -CH2CH2-~H 1,4996 107 SHEA SHEA) N Ho viscous oil E- and Z-form: the two possible geometric isomers Use examples:
-The compounds shown below are used as comparison substances in the fungicide examples which follow:

(A) (CH3)3c-cO-f=cH-c(cH3)3 No N

(B) (cH3)2c-co-c=cH
I

(C) (CH3)3C-CO-f=CH-No - 32b -~Z296:1S

(D) (CH3)3C-CO-CI=CH clue NUN
N

(En (CH3)3C-CO-lc=cH-cH(cH3)2 I NUN
OH Of.
(F) (CH3)3C-CH-C-CH Of it SHEA OH
tug) FCH2-C - CH-C=CH-C7H15 SHEA NUN
SHEA OH
thy ClCH2-C - SHUCKS G
SHEA NUN
. . I!

lo A 21 844 -SLY

Example A
Venturi test apple protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether 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 concentrate is diluted with water to the desired concentrator 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 inoculated with an aqueous Canada suspension of the apple scab causative organism (Venturi inkwells) and then remain in an incubation cabin at 20C and 100~ relative atmospheric humidity for 1 day.
-The plants are then placed in a greenhouse at OKAY and a relative atmospheric humidity of Abbott%.
Evaluation is carried out 1Z days after the inoculation.
In this test, a clearly superior activity compared with the prior art us shown, for example by the compounds according to the following preparation examples: 54, 57, 2, 59, 33, 3, 70, 71 and 77.
.

lo A 21 844 - I -6~5 Example Erysiphe test barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyp glycol ether To produce a suitable preparation of active come 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 concern-trat;on.
To jest for protective activity, young plants are sprayed with the preparation of active compound until dimmest. After the spray coating has dried on, the plants are dusted with spores of Erysiphe grimness fop horde.
The plants are placed in a greenhouse at a them-portray of about 20C and a relative atmospheric hum-idiot of about 80%, in order to promote the development of powdery mildew pustules.
Z0 Evaluation is carried out 7 days after the inoculation.
In this test a clearly superior activity come pared with the prior art is shown, for example, by the compounds according to the following preparation examples:
25 18, 11, 10, 17, 16, 7, 6, 21, 70, 38, 37, 36, 1, 27, 28, 29, 33, 3, 34, 85, 89, 87, 90, 95, 93, 91, 83, 82, 46, 49, 4Z, 39, 73, 59, 101, 105, 104, 102, 96, 99, 98, 97 and 100.

lo A 21 8~4 6~5 Example C
Puccini test (wheat) / 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 come pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the con-cent rate is diluted with water to the desired concentration.
To test for protective activity, young plants are inoculated with a spore suspension of Puccini recondite in a 0.1% strength aqueous ajar solution. After the spore suspension has dried on, the plants are sprayed with the preparation of active compound until dew-moist. The plants remain in an incubation cabin at 20C and 100 relative atmospheric humidity for 24 hours.
The plants are placed in a greenhouse at a tempera-lure of about Z0C and a relative atmospheric humidity of about 80% on order to promote the development of rust Z0 pustules.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity come pared with the prior art is shown, for example, by the Z5 compounds according to the following preparation examples:
14, 55, 54, 43, 45, 57, 2, 58 and 64.

lo A 21 844 9~15 Example D
Cochl;obolus sativus test (barley) / protective Solvent: 100 parts by weight of dimethylformam;de Emulsifier: û.25 parts by weight of alkylaryl polyp glycol ether To produce a suitable preparation of active come pound, 1 part by weight of active compound us mixed with the stated amounts of solvent and emulsifier, and the concentrate us diluted with water to the desired con-centrat;on.
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 Canada suspension of Cochliobolus sativus~ The plants remain in an incubi-ton cabin for 48 hours at 20C and 100X relative atmospheric humidity.
The plants are placed on a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80X.
Evaluation us carried out 7 days after the ;noculat;on.
In thus test, a clearly superior activity come pared with the prior art us shown, for example, by the compounds according to the following preparation examples:
24, 57, 2, 58, 59, 93, 82 and 96.

lo A 21 844 ~2Z9~

Example E
Influence on growth of sugar beet Solvent: 30 parts by weight of dimethylformam;de Emulsifier: 1 part by weight of polyoxyethylene S sorbitane monolaurate To produce a suitable preparation of active come pound, 1 part by weight of active compound us mixed with the stated amounts of solvent and emulsifier and the mix-lure is made up to the desired concentration Thea water.
Sugar beet us grown in a greenhouse until format ton of the cotyledons us complete. In thus stage, the plants are sprayed with the preparation of active come pound until dropping 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 con-trot plants us calculated. I influence on growth denotes a growth which corresponds to that of the con-trot plants. Negative values characterize an inhibition of growth on comparison to the control plants, whilst positive values characterize a promotion of growth in comparison to the control plants.
In this test, active compounds 49, 104, 39, 96r I 98, 97, 73, 74, 24, 57, I 58, 59~ I 60, 75 and 79 according to the invention exhibit a powerful influence on growth.

lo A 21 844 Z2~6.~15 Example f Inhibition of growth of cotton Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active come pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mix-lure is made up to the desired concentration with water.
Cotton plants are grown on a greenhouse until the Thea 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, active compounds 19, 9, 104, 39, 98, 21, 74, 2, 59, So, 75 and 78 according to the invention exhibit a powerful inhibition of growth.

lo A 21_844 ~2Z9615 Example G
Stimulation of the fixation of C02 on soya beans Solvent: 30 parts by weight of d;methylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active come pound 1 part by weight of active compound us mixed with the stated amounts of solvent and emulsifier and the mix-lure 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 jet. In the further course of the experiment, the fixation of Cozy in the plants us determined by customary methods. The values are compared with those of the control plants, which have not been treated with the active compounds.
. .

In this test, active compounds 23, 7, 6, Z1 and 36 according to the invention exhibit good stimulation of the fixation of C02.

ye A Z1 844 sly Example H
Inhibition of growth of soya beans _ Solvent: 30 parts by weight of d;methylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolayer To produce a suitable preparation of active come pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mix-lure 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 stage, the plants are sprayed with the preparations of active compound until dripping wet After 3 weeks, the additional growth of all the plants is measured and the inhibition of growth in per cent of the additional growth of the control plants us calculated. Lowe inhibition of growth means that growth has stopped and 0% denotes a growth corresponding to that of the control plants In this test, active compounds 98, 62, 67, 75, 78 and 79 according to the invention exhibit powerful inhibit lion of growth.

lo A Z1 844

Claims (3)

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

1. A substituted azolylvinyl ketone or carbinol of the formula IA
(IA) in which R1 represents the grouping in which R3 represents the grouping -Z-R4;
R4 represents alkyl and Z represents O, n represents 1, R2 represents alkyl, alkenyl, alkinyl, phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part, each of which is optionally substituted by identical or different substituents, wherein the substituents on the phenyl in each case being selected from halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 monoalkyl and C1-4 dialkylamino, and furthermore halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, and phenyl and phenoxy which are optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; or, R2 is, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, biocycloalkyl, bicycloalkenyl, each of which is optionally substituted by identical or different substituents from the group consisting of alkyl with 1 to 4 carbon atoms and halogen; and X represents the CO or CH(OH) group and Y represents a nitrogen atom or the CH group, or a non-phyto-toxic addition product thereof with an acid selected from a hydrogen halide acid, phosphoric acid, nitric acid, sulphuric acid, a monofunctional or a bifunctional carboxylic acid or hydroxycarboxylic acid, or a sulphonic acid or a copper, zinc, manganese, tin, iron or nickel metal salt.
2. A compound of formula IA as defined in claim 1 wherein R1 represents the grouping in which R3 represents the grouping-Z-R4;
R4 represents straight-chain or branched alkyl with 1 to 6 carbon atoms;
R2 represents straight-chain or branched alkyl with l to 12 carbon atoms; straight-chain or branched alkenyl ox alkinyl with in each case 2 to 7 carbon atoms; phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part, each of which is optionally monosubstituted or polysubstituted by identical or different substituents, substituents on the phenyl in each case being those substituents on phenyl which have already been mentioned in the case of R2; or, furthermore, cycloalkyl with 3 to 12 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, cycloalkenyl with 3 to 12 carbon atoms, cycloalkenylalkyl with 3 to 7 carbon atoms in the cycloalkenyl part and 1 to 4 carbon atoms in the alkyl part, bicycloalkyl with 2 to 24 carbon atoms or bicycloalkenyl with 4 to 24 carbon atoms, each of which is optionally monosubstituted or polysubstituted by identical or different substituents from the group consisting of alkyl with 1 to 4 carbon atoms and halogen.
3. A compound according to Claim 1, in which R1 represents the grouping in which R3 represents the group -Z-R4;
R4 represents straight-chain or branched alkyl with 1 to 4 carbon atoms, R2 represents straight-chain or branched alkyl with 1 to 8 carbon atoms or straight-chain or branched alkenyl or alkinyl within each case 2 to 4 carbon atoms; or, furthermore, phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part, each of which is optionally monosubstituted or di- or tri-substituted by identical or different substituents, substituents on the phenyl being the substituents on phenyl which have already been mentioned in the case of R2; or, furthermore, cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclo-pentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cycloalkenyl with 3 to 7 carbon atoms, cycloalkenylmethyl with 3 to 7 carbon atoms in the cycloalkenyl part, bicycloalkyl with 5 to 12 carbon atoms, or bicycloalkenyl with 5 to 12 carbon atoms, each of which is optionally monosubstituted or di- or tri-substituted by iden-tical or different substituents from the group consisting of methyl, ethyl, isopropyl, fluorine and chlorine.

4. A method of combating fungi or regulating the growth of plants which comprises applying to such fungi or to a habitat thereof, or to such plants or to a location in which such plants are to be grown, a fungicidally effective or plant growth regu-lating effective amount of a compound according to Claim 1.

5. A method of combating fungi which comprises applying to a fungus or a fungus habitat a fungicidally effective amount of a compound according to Claim 1.
6. A method according to Claim 5 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.

7,. A method according to Claim 6 wherein the active ingre-dient concentration in said composition is between 0.0001% and 1%
by weight.

8. A method according to Claim 6 wherein the active ingre-dient concentration in said composition is between 0.001% and 0.5%
by weight.
9. A method according to Claim 5, 6 or 8 wherein the com-pound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

10. A method according to Claim 5, 6 or 8 wherein the com-pound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

11. A method according to Claim 5, 6 or 8 wherein the com-pound is applied to soil in an amount to give a soil concentration of 0.00001 to 0.1% by weight at the place of action.

12. A method according to Claim 5, 6 or 8 wherein the com-pound is applied to soil in an amount to give a soil concentration of 0.0001 to 0.02% by weight at the place of action.
13. A method of regulating the growth of plants which com-prises applying to such plants or to a location in which such plants are to be grown a plant growth regulating effective amount of a compound or addition product according to Claim 1.
14. A method according to Claim 13 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.

15. A method according to Claim 13 wherein the compound is applied to an area of cultivation of plants in an amount of from 0.01 to 50 kg per ha of soil surface.

16. A method according to Claim 14 wherein the compound is applied to an area of cultivation of plants in an amount of from 0.05 to 10 kg per ha of soil surface.
17. A process for preparing a compound of formula IA as defined in claim 1 which comprises a) reacting a ketoneamine of the formula (II) . 47 in which R1 and Y have the abovementioned meaning and R5 and R6 are identical or different and represent alkyl with 1 to 4 carbon atoms; or, together with the N atom to which they are bonded, represent piperidinyl, pyrrolidinyl or morpholinyl, in each case optionally mono- to tri-substituted by alkyl with 1 to 4 carbon atoms, with an organomagnesium compound of the formula Hal - Mg - R2 (III) in which R2 has the abovementioned meaning and Hal represents halogen, in the presence of a solvent; or b) reacting an azolyl ketone of the formula (IV) in which R1 and Y have the abovementioned meaning, with an aldehyde of the formula O - CH - R2 (V) in which R2 has the abovementioned meaning, in the presence of a solvent and in the presence of a catalyst, and c) where required, the substituted azolylvinyl ketone according to the invention of the formula (Ia) ]

R1, R2 and Y have the abovementioned meaning, obtained by process (a) or (b) is reduced and where required forming a non-phytotoxic acid addition product thereof with an acid selected from a hydrogen halide acid, phosphoric acid, nitric acid, sulphur-ic acid, a monofunctional or bifunctional carboxylic acid or hydroxycarboxylic acid or a sulphonic acid or a copper, zinc, manganese, tin, iron or nickel metal salt.

18. A fungicidal or plant growth regulating composition comprising a fungically or plant growth regulating effective amount of a compound according to claim 1 as active ingredient in admixture with a solid diluent or carrier, or a liquidfied normally gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface active agent.

19. The composition according to claim 18 wherein the active ingredient concentration in said composition is between 0.1 and 95% by weight.

20. The composition according to claim 18 wherein the active ingredient concentration in said composition is between 0.5 and 90% by weight.

21. The composition according to claim 18 or 20 wherein the active ingredient in said composition is a compound according to

claim 2.

22. The composition according to claim 18 or 20 wherein the active ingredient in said composition is a compound according to

claim 3.