CA1168248A - Triazolylpropenol derivatives, a process for their preparation and their use as plant growth regulators and fungicides - Google Patents

Abstract

A B S T R A C T O F T H E D I S C L O S U R E

Novel triazolylpropenol derivatives of the general formula (I)

Description

1 1682~8 The present invention relates to certain new triazolyl-propenol derivatives, to a process for their production and to their use as plant growth regulators and fungicides.
It has already been disclosed that 4,4-dimethyl-1-phenyl-

2-triazolyl-1-penten-3-ols have a good fungicidal activity (see DE-OS (German Published Specification) 2,838,847). However, the action of these compounds is not always completely satisfactory, especially when low amounts and concentrations are applied. The plant growth-regulating action of these azole derivatives is likewise not always completely satisfactory.
The present invention now provides, as new compounds, the triazolylpropenol derivatives of the general formula ~ OH (I) Rn in which R represents a halogen atom, an alkyl, halo-alkyl, halo-alkoxy, alkoxy, alkylthio, halo alkylthio, alkylamino, dialkylamino, nitro, cyano, hydroxyl or alkylcarbonyloxy radical, or represents a phenyl, phenoxy radical or benzyloxy radical which is optionally monosubstituted or disubstituted by identical or different substitu~nts selected from fluorine, chlorine and methyl, n is 0, 1, 2, 3, 4 or 5, and X represents a cycloalkyl radical which can be monosub-: stituted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, 1 ~824~

chlorophenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene or represents a grouping of the formula -CRlR2-y where!in Rl and R2 are identical or different and represent alkyl radicals and Y represents an alkyl radical with more than 1 carbon atom, or an alkoxycarbonyl radical, or represents a phenyl radical which is optionally substituted by Rn;
and non-phytotoxic acid addition salts and metal salt complexes thereof wherein the metal is selected from those in main groups II to IV and in sub-groups I, II and IV to VIII of the periodic table.
The compound~ of the formula (I) according to the invention occur in the geometric isomers E (trans) and Z (cis).
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 (derived from "zusammen" (together)) configuration, and if they are on opposite sides, the compound has the E (derived from "entgegen" (opposite)) configuration.
Since an asymmetric carbon atom is also present, the compounds of the formula (I) can occur in two optical isomer forms.
The present invention relates both to the individual isomers and to the isomer mixtures.
According to the present invention ~here is further provided a process for the production of a compound of the , 1 1~8248 invention, characterised in that a triazolylpropenone derivative of the general formula ~ - CH = C - CO - X (II) Rn ~ N
N

in which R, X and n have the abovementioned meaning, is reduced, and the compound of the formula (I) thus obtained is then converted, if desired, into an acid addition ~, -2a-salt or ~etal salt co~plex thereof.
Finally, it has been found that the new tnazolyl-propenol derivatives of the formula (I) and acid addition salts and metal salt complexes thereof have powerful plant growth-regulating and powerful fungicidal properties.
Surprisingly, the co~.pounds of the present invention, exhibit a better growth-regulating and fungicidal action than the 4,4-dimethyl-1-phenyl-2-triaYolyl-l-penten-3-olS, which are known from the state of the -art and are closely lC related compounds chemically and from the point of view of their action. The active compounds according to the invention thus represent an enrichment of the art.
Preferred triazolylpropenol derivatives according to the present invention are those in which R represents a fluorine, chlorine or bromine atom; a straight-chain or branched alkyl, alkoxy or alkylthio radical with in each case 1 to 4 carbon atoms; a halogenoalkyl, halogenoalkoxy or halogenoalkylthio radical with in each case 1 or 2 carbon atoms and up to 5 identical or different halogen atoms (such as, preferably, fluorine and chlorine atoms); an alkylamino or dialkylamino radical with in each case 1 or 2 carbon atoms in each alkyl part; or a nitro, cyano or hydroxyl radical, an alkylcarbonyloxy radical with 1 to 4 carbon atoms in the alkyl part; an optionally substituted phenyl, phenoxy or benzyloxy radical (preferred substituents which may be mentioned being: fluorine, chlorine, bromine and alkyl with 1 or 2 carbon atoms), n is 0, 1, 2 or 3, X represents an optionally substituted cycloalkyl radical with 3 to 7 carbon atoms (preferred substituents which may be mentioned being: alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, halogenoalkyl with 1 to 4 carbon atoms and up to 5 identical or dif4erent halogen atoms (halogen atoms which may be mentioned being fluorine, chlorine and bromine atoms), halogenoalkenyl with 2 to 4 carbon atoms and up to 5 dentical or different halogen . .

Le A 20 458 -1 1~824~

atoms (halogen atoms which may be mentioned being fluorine, chlorine and bromine atoms), halogen, alkoxy with 1 to 4 carbon ato~s and a two-membered to five-membered methylene bridge, optionally substituted phenyl or benzyl (preferred substituents which may be mentioned being fluorine, chlorine and bromine atoms); or represents a grouping of the general formula -CR1R2-Y, in which R1 and R2 are identical or different and represent a straight-chain or branched alkyl radical with 1 to 4 carbon atoms, and Y represents a straight-chain or branched aikyl radical with more than 1 carbon atom, an aIkoxycarbonyl radical with 1 to 4 car~on atoms in the aIkyl part or a phenyl radical which is optionally substituted by Rn (in which R and n have the immediately a~ove-mentioned meanings).
Particularly preferred compounds of the present invention are those in which R repres~nts. a fluorine or 15 .chlorine atom or a methyl, isopropyl, tert.-butyl, methoxy, methylthio, isopropoxy, trifluoromethyl, difluorochloro-methyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluoromethoxy, trifluoromethyl-thio, 1,1,2-trifluoro-2-chloro-ethoxy and -ethylthio, dimethylamino, nitro, cyano, hydroxyl, acetoxy or tert.-butyl-carbonyloxy radical, or represents a phenyl, phenoxy or benzyloxy radical which is optionally monosubstituted or disubstituted by identical or different substituents selected from fluorine, chlorine and methyl, n is 0, 1, 2 or

3; X represents a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radical, which can be monosub-stituted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, tri~luoromethyl, di-chlorovinyl, dibromovinyl, methoxy, chlorophenyl, chloro-benzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene, or represents a grouping of the general formula -CR1R2-Y in which R1 and R2 are identical or different and represent a methyl, ethyl, isopropyl, n-propyl or tert.-butyl radical, and Y represents an ethyl, isopropyl, n-propyl, isobutyl or tert.-butyl radical, a methoxy-, ethoxy-, :Le A 20 458 1 1682~

isopropox~J-, isobutoxy- or tert.-buto~y-carbonyl radical or a phenyl which is optionally substituted by Rn (in which R and n have the im~ediately abo~ementioned meanlrgs).
The following ccmpounds of the general formula ~T) may be mentioned specifically, in addition to the compounds mentioned in the Preparative Examples:
Table 1 OH
~ CH = C - CH - X
Rn ~ N ~ (I) N ~
~n X
.

4-SCF3 -4-C(CH3) 2-OH, 3,5-Cl 4-OH, ~-OH
4 ~ C
4 ~ Cl C

4-G ~ Cl Le ~. 20-458 .
.E~ ' .... ,,.,,.,Rn.,, x . _ 4-0-CH2 ~ CH3 4-0-CH2 ~Cl CH3 4-Cl 2-Cl 2, 4-C1 2,4-Cl2 ~
4-Cl ~Cl 4-F ~lCl 2-Cl ~,Cl 2,4-Cl2 ~lC

2-Cl, 4-CF3 Cl 4-Cl _<~
4-F ~>
2-Cl 2,4-Cl2 ~>
2-Cl, 4-CF3 ~
CH=CCl2 4-Cl ~CH3 Le A 20 45 8 ....... Rn .. . .. x .. . . . .
~--CH=CCl2 4-F ~CH3 ~CH=CCl2 2-Cl \I~CH3 ~CH=CCl2 , 2, 4-Cl2 --~CH5 ~CH=CCl2 2-Cl, 4-CF3 . I~CH~

4-Cl ~1 4-F ~ Cl CH3 ~
2-Cl ~Cl Cl 2,4-C12 ~cC

2-Cl, 4-CF3 ~ Cl Cl 4-Cl O
4-F ~O
2-Cl -O
2, 4-C12 ~0 L;e A 2~ 45 8 -,,,, , Rn - - - ~
... _ .. . .
2-Cl, 4-CF3 -O
4-Cl {1 4-F -a 2-Cl -a 2, 4-C12 {~
2-Cl ~ 4-CF3 {I
4-Cl -O
4-F ~O
2-Cl {>
2 ,4-C12 -2-Cl, 4-CF3 {~
4-F -C ( CH3 )2 ~) 2-Cl -C(CH3 )2 2, 4-Cl2 -C ( CH3 )2 4-CF3 -C(CH3 )2 2-Cl, 4-CF3 -C ( CH3 )2 ~
4-OCF3 -C(CH3 )2~) 4-Cl -C(CH3 )2 ~Cl 4-F -C ( CH3 ) 2 ~)-Cl 2,4-Cl2 -C(CH3 ~2 ~Cl 4-CF3 -C ( CH3 )2 ~Cl 2-Cl, 4-CF3 -C ( CH3 ) 2 ~Cl 4-oCF3 -C ( CH3 )3 ~-Cl Le A 20 458 _ R . . ... X . .
. n. . ....... .......
... . . . .
4-Cl -C(CH3 ) (C2H~ )~
4-F -C(CH3 ) (C2Hs )~
2, 4-Cl2 -C ( CH3 ) ( Cz Hs ) ~) 4-CF3 -C(CH3 )(C2Hs )~
2-Cl, 4-CF3 -C(CH3 )(C2H5 )~
4-OCF3 -C ( CH3 ) ( C2 Hs ) 4-Cl -C(CH3 )2-COOCH3 4-F -C ( CH3 )2 -COOCH s 2-Cl -C(CH3 )2-COOCH3 2, 4-Cl2 -C ( CH3 )2 -COOCH3 4-CF3 -C ( CH3 )2 -COOCH3 ~4-OCF3 -C(CH3 )2-COOCH3 2-Cl, 4-CF3 -C ( CH3 )2 -COOCH3 2-CF3 -C (CH3 `)2 -COOC2 Hs 4-SCF3 -C(CH3 )2-COOC2H, 4-C (CH3 )2 -C (CH3 )2 -COOC2 H~
4-OH -C (CH3 )2 -COOC2 Hs 2-OH, 3, 5-C12 -C ( CH3 )2 -COOC2 Hs 4-NO~ -C(CH3 )2-COOC2Hs 4-oH, 3-OCH3 -C(CH3 )2-COOC2Hs 4~ -C (CH3 )2 -COOC2 Hs 4~Cl -C ( CH3 )2 -COOC2 Hs Le A 20 458 .

ll~s24a 4_o ~ -C(CH3 )2 -COOC2 Hs 4-0 ~ Cl -C(CH3 )2 -COOC2 H~
4-OCH2 ~ -C(CH3 )2 -4-O-CH2 ~ Cl -C(CH3 )2 -COOC2 H~
2-Cl -C(CH3 )2 -COOC2 Hs 2,4-Cl2 -C(CH3 )2-COOC2 Hs 4-F -C(CH3 )2 -C2 ~5 2-Cl -C(CH3 )2 -C2 Hs 2,4-Cl2 -C(CH3 )2 ~C2Hs 4-CF3 -C(CH3 )2 -4-oCF3 -C(CH, )2 -C2 Hs 2-Cl, 4-CF3 -C(CH3 )2 -C2H~
4-F -C(CH~ ~2 -C3H7 2-Cl -C(CH3 )2 -C~ H7 2,4-Cl2 -C(CH3 ) 2 -C3 H7 4-CF3 . -C(CH3 )a -C3H7 4-OCF3 -C(cH3 )2 -C3 H7 2-Cl, 4-CF3 -C(CH3 j2 -C3 H7 4-Cl -C(CH3 )(C2 Hs )2 4-F -C(CH3 )(C2H~ )2 2-Cl -C(CH3 )(C2 Hs )2 2,4-Cl2 -C(CH~ )(C2H~ )2 4-CF3 -C(CH3 )(C2H~ )2 4-OCF3 -C(CH3 ) (C2H~ )2 2-Cl, 4-CF3 -C(CH3 )(C2Hs )2 e A 20 458 2 4 ~

If, for example, 1-(4-chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one and sodium borohydride are used as starting substances, the course of the reaction according to the present invention ls illustrated by the following equation:

Cl ~ CH= -C0-~ ~ NaBH4 Cl ~ CH=C-CX-C
~ ~ N ~ ~ CH3 E/Z-isomer mixture E/Z-isomer mixture If, for example, l-methylcycloprop-l-yl 1-(1,2,4-triazol-l-yl)-2-(4-chlorophenyl)-ethen-1-yl ketone and aluminium isopropylate are used as starting substances, the course of the reaction according to the present invention i~ illustrated by the following equation:

Cl ~ CH=~-C ~ Al( OC3 H~ -i )3~ Cl~CH~
~11 ' ~1 E/Z-isomer mixture Z-isomer Preferred triazolylpropenone derivatives of formula (II) requred as starting substances for the reduction according to the invention are those in which X, R and n have the meanings which have already been mentioned in . connection with the description of the preferred and particularly preferred substances according to the present invention.
The triazolylpropenone derivatives of the formula (II) are novel. Ho~7ever, they can be obtained in a known manner,. by reac~ing a triazolyl-ketone of the general Le A 20 458 1 16824~

formula H2Ç - CO -. X
~ (III) in which X have the abo.ve.mentioned meaning, with an aldehyde of the general formula ~ - CH = 0 (IV) .Rn in which R and n have. the ab.oveme.ntioned meaning, in the presence of a solvent and in the presence of a catalyst.
Preferred possible solvents for the preparation of the triazolylpropenone derivati~es of the for~ula (II) are inert organic solvents. These include, as preferences.
alcohols (such as methanol and ethanol); ethers (such as tetrahydrofuran and dioxane); aliphatic and cyclo-aliphatic hydrocarbons (such as hexane and cyclohexane);
aromatic hydrocarbons (such as benzene, toluene and cumene);
and halogenated aliphatic and aromatic hydrocarbons (such as methylene chloride, carbon tetrachloride, chloroform, chlorobenzene and dichlorobenzene).
The preparation of the compounds of the formula (II) is carried out in the presence of a catalyst. It is possible to employ any of the acid and, in particular, basic catalysts which can customarily be used, as well as buffer ~ixtures thereof. These catalysts incl.ude, preferably, Lewis acids (such as boron trifluoride, boron trichloride, tin tetrachloride or titanium tetrachloride); or~anic bases ~such as pyridine and piperidine), and, in particular, piperidine acetate.

Le A 20 ~58 The reaction temperatures can be varied within a substantia, ran~e when carrying out this process. In general, the reaction is carried out at a temperature between 20 and 160C, preferably at the boiling point of the particular solvent.
In carrying out this process, 1 to 1.5 ~loles of aldehyde of the formula (IV) and catalytic to 0.2 molar amounts of catalyst are employed per mole of triazolyl-ketone of the formula (III). The products of the formula (II) are preferentially obtained as E/Z-isomer mixtures. They can be separated into the pure isomers in the customary manner, such as, for example, by crystal-lisation or by chromatographic separation processes.
The, triazolylpropeno,ne derivatives of the formula , 15 (II) are generally interesting intermediate products, for example, for the preparation of the compounds of the formula (I) according to, the invention. In appropriate concentration~, the~J also exhibit growth-regulating and fungicidal prope,rties.
Some of the triazolyl-ketones of the formula (III) are known (see DE-OS (German Published Specification) 2,431,407 and DE-OS (German Published Specification) 2,638,470), and some of ~hem are claimed in general terms therein without being mentioned therein by name. The triazolyl-ketones of the general formula H2C -` CO - X1 (V) ~, ~J
in which x1 represents optionally substituted cyclopropyl or optionally substituted cyclobutyl or a grouping of the general formula -CR1R2-Y1, wherein R1 and R2 have the above-mentioned meaning and y1 represents an optionally substituted phenyl Le A 20 458 .
radical or an alkoxycarbonyl radical, and preferably has~the corresponding preferred meanin~s of Y, are completely new.
The triazolyl-ketones. of the formula (V) can be obtained by generally known processes, by reacting a halogenoketone of the general formula Hal-CH2-C0-Xl (VI) in which Xl has the aboveme.ntioned meaning and Hal represents a chlorine or bromine atom~
with 1,2,4-triazole in t,he pre.se.nce of a diluent and in the presence of an acid-binding agent.
Preferred possible diluents for the preparation of the triazolyl-ketones of the formula (~) are inert organic solvents. These include, preferably, ketones (such as acetone and methyl ethyl ketone); nitriles (such as acetonitrile); ethers (such as tetrahydrofuran or dioxane);
aromatic hydrocarbons (such as benzene and toluene);
20. formamides (such as dimethylformamide); and halogenated hydrocarbons.
This process i~ carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-bindings agents which can cus-tomarily be used, such as alkali metal carbonates (forexample sodium carbonate, potassium carbonate and sodium bicarbonate); al~ali metal alcoholates (such as sodium methylate or sodium ethylate); lower te,rtiary al~.yl-a~ines, cycloalkylamines or aral~ylamines (such as tri-ethylamine, dimethylbenzylamine or dimethylcyclohexylamine);or such as pyridine and an appropriate excess of 1,2,4-triazole.
The.re,acti.on temperatures. can be. varied within a ~e A 2~ 458 .

.

1 1~8248 substantial range in carry ng out this process. Ingeneral, the reaction is carried out at a temperature between 0 and 120C, preferably between 20 and 100C.
In carrying out this process, 1 to 2 ~.oles of

5 1,2,4-triazole and 1 to 2 moles of acid-binding agent are preferably employed per mole of the compounds of the formula (~I). The compounds of the formula (V) are isolated in the customary manner.
The halogenoketones of the formula (VI) are known, or they can be obtained in a generally known manner, by adding chlorine or bromine to a compound of the general formula H3C-C0-Xl (VII) in which xl has the abovementioned meaning, in the pre~ence of an inert organic solvent at room temperature; or, for example, by reacting a compound of the formula (VII) with a chlorinating agent, such as sulphuryl chloride, at 20 to 60C.
The aldehydes of the formula (IV) also required as starting substances for the preparation of the tri-azolylpropenone derivatives of the formula (II) are generally known compounds of organic chemistry.
The reduction according to the invention is carried out in the customary manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent The starting substances of the formula (II) can be employed in the form of E/Z isomer mixtures or as pure isomers.
If complex hydrides are used, possible diluents for the reaction according to the invention are polar organic solvents. These include, preferably, alcohols (such as methanol, ethanol, butanol or isopropanol), and ethers (such as diethyl ether or tetrahydrofuran). The reaction is in Le ~ 20 458 general carried out at a temperature between -10 and +30C, preferably at between -10 and~20C. For this reaction, about 1 mole of a complex hydride, such as sodium boro-hydride, calcium borohydride or lithium alanate,-are employ-ed per mole of the ketone of the formula (II). Isolationof the compounds according tG the invention is carried out in the customary manner, as is any separation of the E~Z
isomer mixtures which are always formed in the reduction with complex hydrides if E/Z-isomer mixtures are used as starting materials of the formula (II).
If aluminium isopropylate is used, preferred possible diluents for the reaction according to the invention are alcohols (such as isopropanol) or inert hydrocarbons (such as benzene). The reaction temperatures can again be varied within a substantial range; in general, the reaction is carried out at a temperature between 20 and 120C, preferably at between 50 and 100C. For carrying out the reaction, about 1 to 2 moles of aluminium isopropyl-ate are employed per mole of the corresponding ketone of the formula (II). The compounds according to the invent-ion are isolated in the customary manner.
In the reduction with aluminium iscpropylate, exclusively the Z-isomers are obtained.
The Hl-nuclear magnetic resonance of the two triazole protons is an unambiguous ch~racterislng feature of the two geometric iaomers. The difference between the shift values of these two protons in the E-forms is approximately twice the value of the difference in the corresponding Z-forms.
The following acids can be used for the preparation of physiologically acceptable acid addition salts of the compounds of the formula (I): hydrogen halide acids (such as hydrobromic acid and, preferably, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxy-carboxylic Le A 20 458 ~6824a acids (such as acetic acid, maleic acid, succinic aci`d, fumaric acid, tartaric acld, citric acid, sal.icylic acid, sorbic acid and lactic acid), and sulphonic acids (such as p-toluene-sulphonic acid and 1,5-naphthalenedisulphonic acid).
The acid addition salts of the compounds of the formula (I) can be. obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitabie inert solvent and adding the acid, for example hydrochloric ac.id, and they can be isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.
Salts. cf metals of main groups II to IV and of .s.ub-groups I and II and IV to. VIII. can preferably be used for the preparation of metal salt complexes of the compounds of the formula (I), examples of metals which may be mentioned being copper, zinc, manganese, magnesium, tin, iron and nickel.
Possible anions of the salts are, preferably, those which are derived from the following acids:
hydrogen halide acids (such as hydrochloric acid and hydrobromic acid), phosphoric acid and sulphuric acid.
The metal salt co~plexes of compounds of the formula (I) can be obtained in a simple manner by customary Frocesses, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I).
The metal salt complexes can be purified in a known manner, 30 for example by filtration, isolation and, if appropriate, by recrystallisation.

Le A 20 458 1 lS~24 The active compounds which can be used accordingto the invention engage in the metabolism o~ the plants and can therefore be employed as growth regùlators.
Experience to date of the ~.ode of action of plant growth regulators has shown that an active compound can also exert several different actions on plan~
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 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 inhibition of growth is''int'er 'a'l'ia of economic interest in the case of grasses, since it i~ thereby possible to reduce the frequency of cutting the grass in ornamental gardens, par~s and sportsgrounds, at verges, at airports or in fruit orchards. The inhibition of growth of herbaceous and woody plants at verges and in the cicinity 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 harves ng is thereby reduced or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals, which again counteracts lodging.

Le A 20 458 1 16824~

Use of gro~th regulators for shortening and strengthening the stem enables higher amounts of fertiliser to be applied to increase the yield, without danger of the cereal lodging.
In the case of many crop plarts, inhibition of the vegetative growth makes denser planting possible, so that greater yields per area of ground can be achieved.
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 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. This is of great utility if it is the Yegetative parts of the plants which are harvested. Promoting the 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 composition 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 beet, sugar can, 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 can, before or after harvestin~.

Le A 20 458 . ~ =

1 1~824~

It is also possible favourably 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 influenced. Sterility of the pollen 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 ornamertal plants, also in connection with growth inhibition. On the other hand, however, it is also possible to inhibit the growth of side shoGts. There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes-. The 2mount of leaf on plants can be controlled,under the influence of growth regulators, so that defoliation 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 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.
3 The shedding of fruit can also be cor.trolled with growth regulators. On the one hand, it is poss-ible to prevent premature shedding of fruit. However, Le ~ 20 458 1 16824~

on the ot~er hand, shedding of fruit, or even the fall of blossom, can be promoted up to a certain degree (thinnir.g out) in order to interrupt the al~ernance.
By alternance there is understood ~he peculiarity of some varieties of fruit to produce very different yields from year to year, for endogenic reason~. Finally, using growth regulators it is possible to reduce the force required to detach the fruit at harvest tlme so as to permit mechanical harvesting or facilitate manual harvesting.
Using growth regulators, it is furthermore possible to achieve an acceleration or retardation of ripening of the harvest product, before or after harvesting, This is of particular advantage, since it isthereby possible to achieve optimum adaptation to market requirements. Furthermore, growth regulators can at times improve the coloration of fruit. In addition, concentrating the ripening within a certain period of time is also achievable with the aid of growth regùlators. This provides the preconditions for beir.g able to carry out completely mechanical cr manual harvesting in only a single pass, for example in the case of tobacco, tomatoes or coffee.
Using plant regulators, it is furtermore possible to influence the latent period of seeds or buds of plants, so that the plants,for example pineapple or ornamental plants in nurseries, germinate, shoot or blossom at a time when 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 ir.
regions where frost is 2 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 regicns .

Le A 20 458 . _ 1 16824~

which are usuàlly unsùitable for this purpose thereb`y becomes possible.
The preferred time of application of the growth regulators depends on the climatic and vegetatlve circumstances.
The foregoing description should not be taken as implying that each of the compounds can exhibit all of the described effects on plants. The effect exhibited by a compound in any particular set of circumstances must be determined empirically.
The active compounds according to the invention also 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 protection agents.
~ungicidal agents in plants protection are employed for combating P~asmod'iopho'romyc'e't'es,''Oo'myc'e't'es, Chy-tridiom~;cetes,' Z'y~om'y'c'etes,''A's'c'om'y'cet'es,' B'as'i'~iomycetes and ~'e'u't'e'r'o'm'y'c'e't'es.
The good toleration, by plants, of the active compounds, at the concentratior.s 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 good success for combating those fungi which cause powdery mildew diseases, thus, for combating ~rysiphe species, for example against the powdery mildew of barley or cereal causative organism (Erysiphe'' ram'inis), or for combating Podosphaera species, for example against the powdery mildew of apple causative organis~. (Podosphaera leucotricha).
The substances according to the invention also exhibit a broad fungicidal in vitro spectrum.

Le 'A''2'0''~'58 The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, ~oa~.s, pastes, gr~nules, aerosols, very ~ine capsules in poly~.eric substances and in coating compositions for seed, zs well as ULV formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluer.ts or carriers, optionally wit~ the use of surface-active agents, that is to say emulsifying agents and~or dispersing agents and/or ~oam-forming agents. In the case of the use of water as an extender, organic solvents car, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xyler.e, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
By lique~ied gaseous diluents or carriers are meant liquids which would be gasecus at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, 3o nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz-attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As ~olid carriers for Eranules . .

Le A ~0 458 1 1~82~9 there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals~ and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and~or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formula~ions.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, marganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations as a mixture with other active compounds, such as fungicides, insecticides, 3 acaricides and herbicides, as well as in the form of a mixture with fertilisers and other growth regulators.
The' active compounds can be used as such or in the form of their formulations or the use forms prepared there-from, such as ready-to-use solutions, emulsifiable concen-Le A 20 45~

1 16~24~

trates, emulsions, foams~ suspensions, wettable powd`ers,pastes, soluble powders, dusting agents and granules.
They are used in the customary manner, for example by watering, spraying, atomisin~, scattering, dusting, foaming, coating and the like. Furthermore, it is possible to apply the active compounds in accordance with the ultra-icw volume process or to inject the active compound preparation or the active compound itself into the soil. It ls also possible to treat the seeds of plants.
When the compounds according to the invention are used as plant growth regulators, the amounts applied can be varied with a substantial range. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, are used per hectare of soil surface.
The amount applied can also be varied within a substantial range, depending on the method of application, when the substance~ according to the invention are used as fungicides. Thus, especially in the treatment of parts of plants, the active compound concentrations in the use forms can ~e in general be between 1 and 0.0001% by weight, preferably between 0.5 and 0.001~ by weight. In thetreatment of seed, amounts of active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are generally required. For the treatment of soil, ~ctive compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the place of action.
The present invention also provides plart growth regulation and fungicidal compositions containing 2S
active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluer.t or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

Le A 20 458 .

The present invention also provides a method of co~bating fungi which comprises applying to the fungi, ~r to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of regulating the growth of plants which comprises applying to t~.e plants, or to a habitat thereof, a compound of lO the present invention alone or in the form of a com- -position containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
~ he present invention further provides crops protected from damage by fungi by being grown in areas in which i~ediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
The present invention further provides plants, the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
Preparative Examples Examples 1 and 2 Cl ~ CH = C - CH - C
~ N ~ CH3 Le A 20 458 1 16824~

~xample (1) = Z-isomer Fxample (2) = E-isomer 16 g (0.045 mole) of 1-(4-chloropheryl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one as the E/Z-iscmer mixture were dissolved in 200 ml of isopropanol, and 0.85 g (0.0225 mole) of sodium boronate were added in portions. The mixture was stirred at room temperature for 15 hGurs and then poured onto water. The organic layer was extracted wi~h ether and the combined ether extracts were dried over sodium sulphate. After evapora-ting off the ether, 14.7 g (92% of theory) of 1-(4-chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol were obtained as the E/Z-isomer mixture.
The pure isomers were isolated by Craig distribution ~counter current distribution), the Z-isomer having a melting point of 136~ and the E-isomer having a melting point of 140C.
P'repara't'i'on'of'th'e''s't'ar't'i'n'g'mate'~i'al ~II 1) ~ CH = C - C - ~

E/Z-isomer mixture 4C g (0.175 mole) of 3-methyl-3-phenyl-1-(1,2,4-triazol-l-yl)-butan-2-one and 24.5 g (0.175 mole) of 4-chlorobenzaldehyde in 150 ml of toluene were heated under reflux with 5.25 g of glacial acetic acid and 1.75 ml of piperidine for 15 hours, and the water of reaction was separated off azeotropically. The toluene solution was washed with water, dried over sodium sulphate and evaporated in vacuo. 48.6 g (79% of theory) of 1-(4-chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-Le A 20 458 ll6s2~a penten-3-one were obtained as the E/Z-isomer mixture with a refractive index n20 of 1.6023.

(III-l) ~ N - CH2 - C0 - ~ ~

103 g (0.525 mole) of 1-chloro-3-methyl-3-phenyl-butan-2-one were added dropwise to a suspension of 33.4 g (0.6 mole) of sodium methylate and 41.4 g (0.6 mole) of 1,2,4-triazole in 200 ml of acetonitrile.
me reaction mixture was heated under reflux for 18 hours and filtered when cold and the filtrate was evaporated ln vacuo. The resulting oil was dissolved in chloroform and the chloroform solution was washed with water, dried over sodium sulphate and evaporated in Vacuo. 106 g ~88% of theory) of 3-methyl-3-phenyl-1-(1,2,4-triazol-l-yl)-butan 2-one were obtained and could be purified by chromatography on silica gel 60 (Merck)/
chloroform: refractive index n20 = 1.5425.

Cl - CHz - C0 - C

lO ml (0.122 mole) of sulphuryl chloride were added dropwise to a solution of 16.2 g (0.1 mole) of 3-methyl-3-phenyl-butan-2-one in 50 ml of benzene at 40C. The mixture was kept at 60C, until the evolution of gas had ended, and was then distilled. 15.4 g (78.5% of theory) of l-chloro-3-methyl-3-phenyl-butan-2-one with a boiling point of 80 tG 85C/0.1 mm Hg and a refractive index n20 of 1.5310 were obtained.

Le A 20 458 llss2~a Example 3 OH CH
Cl ~ CH - C - CH - ~ - CH2 -CH

E-isomer 2.88 g (9.5 mole) of the E-isomer of 1-(4-chloro-phenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-one were dissolved in 20 ml of isopropanol, and 180 ~g ~4.75 mmoles) ~f sodium boronate were added. After stirring the mixture at room temperature for 15 hours, the iso-propanol was distilled off in vacuo and the residue was decomposed with water and glacial acetic acid. The organic phase was separated off and dissolved in methylene chloride and the methylene chloride solution was washed with water, dried over sodium sulphate and evaporated.
The resulting oil was stirred with diisopropyl ether and the crystals formed were filtered off and dried. 700 mg (24~ of theory) of the E-isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-ol of melting point 130C were obtained.
Preparation of the starting material Cl ~ CH = IC - e c cH2 CH3 ~ N ~ CH3 E/Z-isomer mixture (II-2) and E-isomer (II-3) 81.5 g (0.45 mole) of 3,3-dimethyl-1-(1,2,4-triazol-l-yl)-pentan-2-one and 63.2 g (0.45 mole) of 4-chloro-benzaldehyde in 500 ml of toluene wer~ heated under reflux Le A 20 458 . .

~ 1682~

with 12.5 ml of acetic acid and 4.5 ml of piperidine for 15 hours, and the water of reaction was removed azeotro~
pically. The toluene solution was washed wlth water, dried over sodium sulphate and evaporated ~n vacuo.
127 g (93% of theory) of 1-(4-chlorophenyl)-4~4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-one were obtained as the E/Z-isomer mixture of boiling point 150 to 160C/0.1 mm Hg.
After leaving the product to stand at room tem-perature for several days, the E-isomer of l-(~-chloro-phenyl)-4~4-dimethyl-2-(l~2~4-triazol-l-yl)-l-hexen-3-one of melting point 90C crystallised out.
N -~ ~3 (III-2) ~ ~ - C~2 - C0 - Cl - CH2CH3 106 g (0.55 mole) of 1-bromo-3,3-dimethyl-pentan-2-one were added dropwise to a mixture of 62.1 g (0.9 mole) Of 1,2,4-triazole, 95.4 g (0.69 mole) of pctassium carbonate and 600 ml of acetone at 55C. After stirring the mixture for 15 hours, it was filtered and the filtrate was evaporated in vacuo. The oil which remained was purified by chromatography (siiica gel 60 (Merck)/chloroform).
85.6 g (86% of theory) of ~,3-dimethyl-1-(1,2,4-triazol-l-yl)-penten-2-one with a refractive index n20 of 1.4805 were obtained.

Br-cH2-co-c-cH2cH3 A solution of 30.6 g (0.6 mole) of bromine in 120 ml of chloroform was added dropwise to a solution of 69 ~ (0.6 mole) of 3,3-dimethylpentan-2-one in 300 ml of methyl alcohol at 0 to 5 C and the reaction mixture was subsequently stirred fcr 15 rninutes. It was poured ontc Le A 20 458 1 16824~

ice, the organic phase was separated off, washed with water, dried over sodium sulphate and filtered arLd the fiitrate was evaporated. The crude product was distilled in vacuo. lOl g (87% of theory) of l-bromo-3,3-di-methylpentan-2-one with 2 boiling point of 80 to 88C/ll mm ~ and a refractive index n20 of 1.4685 were obtained.
Ex~mple 4 ~H l H3 Cl ~ CH = ~ - CH - C - CH2 CH3 (4) ~ N CH3 N ~ Z-isomer 30.35 g (G.l mole) of l-(4-chlorophenyl)-4,4-di-methyl-2-(1,2,4-triazol-l-yl)-l-hexen-3-one as the E/Z-isomer mixture (compare the preparation of the starting material in Example 3) were reduced with sodium boronate in a manner corresponding to that in Example 3. The re~ulting oil (30.5 g) was chromatographed on silica ~el 60 (Merck)/chlorofo~. The fractions of melting point 100 to 108C obtained after evaporating off the chloroform were combined, and recrystallised twice from acetonitrile. The Z-isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-friazol-l-yl)-1-hexen-3-ol of m~ting point 119C was obtained.
Exampl _5 r~H CH3 Cl ~ CH = C - CH ~ ( 5) ~N~N
N U E-isomer 3.5 g (12.2 mmoles) of the E-isomer of 1-(4-chloro-phenyl)-3-(1-methyicycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-one and 0.91 g (8.2 mmoles) of calcium chloride were dissolved in lC0 ml of isopropanol, and a solution of 0.32 g (~.5 mmoles) of sodium boronate in Le A 20 458 1 ~6824~

~0 ml of water was added dropwise a~ -5C. ~fter 90 minutes, 10 ml of acetone were added d~opwise ard the reaction mixture was evaporated''in vacuo. The residue ~las dissGl~led in methylene chloride and the solution was washed wi~h water. The organic phase was dried over sodium sulphate and filtered and the filtrate W2S evapor-ated _ 'vacuo. After purification of the residue by column chromatography, 1.7 g (48% of theory) of the E-isomer of l-(4-chlorophenyl)-3-(1-methylcycloprop-1-yl)-2~ 2,4-triazol-1-yl)-1-propen-3-ol of melting ~oint 110C were obtained.
Preparati-on of the''s't'ar'ting'm'aterial (II-4) Cl- ~ - CH = C - C0 `N
- I E-isomer This compound was obtained as described in following Example 6.
Example 6 .

Cl ~ ~ (6) Z-isomer 10.0 g (3.48 mmoles) of 1-(4-chlorophenyl)-3-(1-met~.ylcycloprop-l-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-one as the E/Z-isomer mixture and 7.1 g (3.48 mmoles) of aluminium isopropylate in 300 ml of boiling isopropanol were heated for 6 hours; during this procedure isopro-panol and acetone were continuously distilled off cver a 30 cm Vigreux column, until acetone could no longer be Le A 20' 4'58 detected in the distillate. The solution was then evaporated ard ice/hydrochloric acid W2S added to the residue. After extraction with ether, the combined ether extracts were washed with water, dried over sodium sulphate and filtered and the filtrate was evaporated. The oil which remained was chromatographed over silica gel 60 (Merck)/chloroform. The first fractions ga~e, after evaporating off the solvent, 3.5 g of the E-isomer of 1-(4-chlorophenyl)-3-(1-methyicycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-propen-3-ol of melting point 89C.
The next fractions gave, after evaporating off the solvent, 7.8 g of the Z-isomer of 1-(4-chlorophenyl)-3-(l-me~hylcycloprop-l-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-ol of melting point 124C.
15' ~'~eparat10h of the startihg m'aterial (II-5) ~ CH = ~ - C0 ~

~ ~ E/Z-isomer mixture 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-one of melting point 82C
was obtained by reactin~ l-methyl-l-(1,2,4-triazol-1-yl-acetyl)-cyclopropane with 4-chlorobenzaldehyde in a manner corresponding to that in Example 3.

~III-3) ~ N - CH2 - C0 ~

42.5 g (0.24 mole) of l-bromoacetyl-l-methylcyclo-propane were added dropwise to a suspension of 27.6 g (0.4 mole) of 1,2,4-triazole and 41.4 g (0.3 mole) of potassium carbonate in 500 ml of acetone at 60C. After heating Le A 20 458 ==~= . .. .

llss2~a the mixture to 60C for i5 hours, the salts were filterèd of~ and the filtrate was evapor~ted in ~vacuo. The oil which remained was purified by chromatography (silica gel 60 (Merck)/chloroform).
35.7 g (90% of theory) of 1-methyl-1-(1,2,4-tri-azol-l-yl-acetyl)-cyclopropane of melting point 58C were obtained.

Br - CH2 - C0 ~

15 ml of bromine, dissolved in 75 ml of chloroform, were added dropwise to a solution of 29.4 g (0.3 mole) of 1-acetyl-l-methylcyclopropane in 150 ml o methyl alcohol.
The solution was stirred at 10C until it was com-pletely decolorised, and was poured onto ice and washed with water. The chloroform phase was dried over sodium sulphate and filtered, the filtrate was evaporated and the residue was distilled 44 g (82.5% of theory) of l-bromoacetyl-l-methyl-cyclopropane with a boiling point of 85 to 90C/ll mm Hg and a refractive index n20 of 1.5002 were obtained.
Example 7 Cl ~ CH = C - CH - C - COOC2H~

N ~
Z-iscmer A mixture of 63.4 g (0.1825 mole) of the Z-isomer of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-methyl-2-(1,2,4-triazol-l-yl)-l-penten-3-one, 37.6 ~ (0.1825 mcle) of alu-minium isopropylate and 350 ml of isopropanol was heatedto the boiling point, and acetone was distilled off azeo-tropically, as a mixture with isopropanol, over a Vigreux Le A 20 458 .

1 1~82 - 3~ -column. The solution was poured onto lce-cold dilute hydrochloric acid and extracted by shaking with methylene c~.loride. The or~anic phase was separated off, dried over sodium sulphate, filtered and evaporated. ' The oil which remained was stirred with petroleum ether and the resulting crystals were filtered off and rinsed with di-isopropyl ether. 22.7 g (35.6% of theory) of the Z-isomer of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-methyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol of melting point 90C
were obtained.
Preparat;o-n of the startin~ ~aterial (II-6) Cl ~ CH = IC - C0 - Cl - COOC2E~
~ N~N CH3 ~J
Z-isomer A mixture of'90 g (0.4 mole) of dimethyl-(1,2,4-triazol-l-yl-acetyl)-acetic acid ethyl ester, 56.2 g (0.4 mole) of 4-chlorobenzaldehyde, 12 g of acetic acid and 5 ml of 2,6-dimethylmorpholine in 300 ml of toluene was heated under reflux for 18 hours, and the water of reaction was separated off continuously. The cooled reaction solution was washed with water, dried over sodium sulphate and filtered and the filtrate was concentrated. 124 g (90%
of theory) of 1-(4-chlorophenyl)-4-ethoxycarbonyl-4-methyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one with a re-fractive index n20 of 1.5751 were obtained.

N ~ ICH3 (III-4) ¦ N - CH2 - C0 - C - COOC2H~

Le A 2~ 45 1 ~682~

165.9 g (0.7 mole) of bromoacetyl-dimethyl-acet`ic `
acid ethyl ester were added dropwise to a suspension of 96.7 g (1.4 moles) of 1,2,4-triazoie and l44.g g (1.05 moles) of potassium carbonate in 1,200 ml of acetone at 25 C. After stirring the mixture for 15 hours, the salts were filtered off and the filtrate was evaporated.
The oil which remained was purified over silica gel 60 (Merck). 120.7 g (76.6% of theory) of dim~thyl-(1,2~4-triazol-l-yl-acetyl)-acetic acid ethyl ester with a ref-10 ractive index nD f 1.4770 were obtained.

8r-CH -CO-C-COOC2H5 95.4 ml (1.87 moles) of bromine, dissolved in 1,000 ml of chloroform, are added dropwise to a solution of 295.5 g (1.87 moles) of acetyl-dimethyl-acetic acid ethyl ester in l,OGO ml of methyl alcohol at 0C. After stirring the mixture at room temperature for 15 hours, it was poured onto ice, the chloroform phase was separated off, washed with water, dried over sodium sulphate and evapora-ted and the residue was distilled. 780 g (88% of theory) of bromoacetyl-dimethyl-acetic ac~d ethyl ester with a boiling point of 90 to 115C/0.5 mm Hg and a refractive index nD of 1.4658 were obtained.
The following compounds of the general formula (I) were obtained in a corresponding manner:
Table 2 OH
~ CH - C - CH - X

Le A 20 458 ~ 16~24~
- 37 ~
Ex- Melting ample Rn X I point (C) No. . .. . ..... . .... ...... ... .. . ..... .
I-8 4-Cl -C(CH3 )a~C~H7 142(Z-Isomer) I-g 4-Cl -C(CH~ )~-C3H7 llO(E-Isomer) I-lO 4-F -C(CH~ )2-COOC2H5 80(Z-Isomer) -ll 2-C1,4-CF3 -C(CH3 )2 ~COOC2Hg 87(Z-Isomer) -12 4-F ~ 124(E-Isomer) I-13 4-F ~ 106(Z-Isomer) I-14 2-C1 ~ 148(Z-Isomer) I-15 2-Cl ~ 128(E-Isomer) 2,4-Cl2 ~ 148(Z-Isomer) I-17 2 ,4-C12 ~ .126(E-Isomer) I- ~8 4-CF3 ~ 133(Z-Isomer) I- 19 4-CF3 ~ 120(E-Isomer) I-202-Cl,4-CF3 ~ 141(Z-Isomer) I-212-C1 ,4-CF3 ~ 140(h-Isomer) I-22 4-oCF3 ~ 104(Z-Isomer) I-23 4-OCF3 ~ 94 (E-Isomer) I- 24 4-OCH~ ~ 126(Z-Isomer) I- 25 4-OCH3 ~ 1 132(E-Isomer) Le A 20 458 11682~

Ex- MeltingO
ample Rn Xpoint ( C) I-26 2,4-Cl -C(CH3)2-C2H5140(Z-Isomer) I-27 2,4-Cl2 -C(CH3)2- ~ -Cl152(Z-Isomer) I-28 2,4-Cl2 C(CH3)2 COOC2H5 100(Z-Isomer) I-29 2,4-Cl2 ~ 126(Z-Isomer) I-30 2,4-Cl2 -C(C~3)2- ~ -Cl158(E-Isomer) I-31 2,3-Cl2 CH130(Z-Isomer) I-32 3,4~Cl2 ~ 118(Z-Isomer) I-33 3,4-Cl2 ~ 80(E-Isomer) I-34 2,3-Cl2 ~ 126(E-Isomer) I-35 2,4-Cl2 ~ 126(E-Isomer) C~
I-36 3-CP3 CH3130(Z-Isomer) I-37 3-CF3 CH395(E-Isomer) I-38 2-CH3 ~ 146(Z-Isomer) I-39 2-CH3 ~ 132(E-Isomer) The following starting substances of the formula (II) were obtained in a manner corresponding to that in the foregoing preparative Examples: 1 to 3 and 5 to 7:

Le A 20 458 ll6s2~a Table 3 ~ - CH = ~ - C0 - X (II) Rn N ~
Ex- IMelting point (C) ample R X or refractive No. n index (n20 D
.....
II-7 4-Cl -(CH3 )2 C~ H~ 8g(E-Isomer) II-8 4-Cl -(CH3 )2-C~H7 1.5492 (E/Z-mixture) II-9 2-C1,4-CF3 . -C(CH3 )2 -COOC2H5 104(Z-Isomer) II-10 4-F ~ 74(E-Isomer) II-11 2-Cl ~ 1. 5929 (E-II- 1 2 2-Cl ~ Isomer) CH~ mixture) II-13 2, 4-Cl2 ~ 84(E-Isomer) II-14 2,4-Cl2 ~ 1.5978 (E/Z-CH3 mixture) II-15 4-CF3 ~ . 1. 5142 (E-CH3 Isomer) II-16 4-CF3 ~ 1. 5440 (E/Z-CH3 mixture) II-17 4 - OCF3 ~ 1.5334 (E-CH~ Isomer) II-18 4-oCF3 ~ 1.5362 (E/Z-CH mixture) II-19 12-Cl,4-CF3 ~ 11.5232 (E-I CH3 1Isomer) II-20 2-C1,4-CF3 ~ 1.5334 (E/Z-~ CH3 mixture) II-21 4-oCH3 ~ 92 (E-Isomer) II-22 4-oCH3 ~ 1.5g~9 (E/Z-mixture) Le A 20 458 ., 11682~

The following precursors of the .ormula (III) were ' obtained in a manner corresponding to that in the foregoing Preparative Examples l to 3, 6 and 7:
' ~able 4 :
.
N=\
¦ ~ - CH2 - CO - X
:=N~ (III~

Example Melting point (C) or refractive No. index (~20)-..... ............................. ........ D.......... .

III-5 -C(CH3)2-C3H7 1.4796 -C(CH3)2-C3H7 60C
III-7 -C(CH3)2 ~ F oil The plant growth regulant and fungicidal activity of the compounds of this invention is illustrated by the 1,0 following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found earlier in this specification.
The known comparison compounds are identified as follows: -Cl OH
(A) = Cl ~ CH=C-CH-C(CH3)3 N

Le A 20 458 1 16~32L1 Cl OH
(B) = ~ CH=C-CH-C(CH3 )3 ~ N`N
'N ~

(C) = ~ -CH-~-CH-C(CH3)3 N
N ~

OH
(D) = ~ CH=~-CH-C(CH3)3 1~
N

Example A
Inhibition of growth -of grass (~estuca pratensis) Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active compound, 1 part by weight of active compound W2S mixed with the stated amounts of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Grass (Festuca pratensis) was grown in a green-house up to a height in growth of 5 cm. In this stage, the plants were sprayed with the preparations of active compound until dripping wet. After 3 ueeks, the additional grow,th was measured and the inhibition of growth .

Le ~ 20' ~'58 _ _ 1 1 6 ~ 2 Ll ~

in per cent of the additional growth of the control plants was calcula~ed. 100% inhibition of growth ~eant that growth had stopped and 0% denoted a growth corr~sponding to that of the control plants.
In this test, active compounds (I-12) and (I-37) exhibited a better inhibition of growth than the compounds (A), (B), (C) and (D) known from the prior art.
Examp-le B
Inhibition of growth of c'otton Solvent: 30 parts by weight of dimethylfor~amide Emulsifier: l part by weight of polyoxyethylene sorbi.ta~.e monolaurate To produce a suitable preparation of active compound, l part by weight of active compound was mixed with the stated amount of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Cotton plants were grown in a greenhouse until the 5th secondary leaf had unfolded completely. In this stage, the plants were sprayed with the preparations of active compound until dripping wet. After 3 weeks, the additional ~rowth of the plants was measured and the inhibition of growth in per cent of the additional growth of the control plants was calculated. 100% inhibition of growth meant that growth had stopped and 0% denoted a growth corresponding to that of the control plants.
In this test, active c~x~nds (I-3), (I-4), (I-6), (I-32), (I-34), (I-35) and (I-37) exhibited a ~etter inhibition of growth than the co~x~nds (A), (B), (c) and (D) known from the prior art.
Example C
Inhibit-ion of growth 'of's'oya'b'e'ans Solvent:' lO parts by weight of methanol Emulsifier: 2 parts by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active com-35 pound, l part by wei.ght. of active compound was mixed ~Ji.th Le A 20 458 ll6s2~a - ~3 -the stated amounts of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Young soya bean plants, in the stage in which the first secondary leaves had unfolded, were sprayed with the preparations of active compound until dripping wet.
After 2 weeks, the additional growth was measured and the inhibition of growth in % of the additional growth of the control plants was calculated. lOQ% meant that growth had stopped and 0% denoted a growth corresponding to that of the untreated control plants.
In this test, active c~x~nds (I-3), (I-6), (I-12), (I-32), (I-34) and (I-35) exhibited a bet ~ ~ ibition of gr~h than the c~x~nds (B), (c) and (D) known from the prior art.
Examp'l'e D
Infl'uence on growth of_sugar beet Solvent: 30 parts by weight of dimethylformamide Emulsifier: l part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active compound, l part by weight of active compound was mixed with the stated amounts of solvent and emulsifier and the mixture was made up to the desired concen~ration with water.
Su~ar beet was grown in a gr~enhouse until formation of the cotyledons was complete. In this stage, the plants were sprayed with the preparation of active compound until dripping wet. After 14 days, the addition-al growth of the plants was measured and the influence on growth in per cent of the additional growth of the control plants was calculated. 0% influence on growth denoted a growth which corresponded to that of the cGntrol plants.
Negative values characterised an inhibition of growth in comparison to the control plants, whilst positive values characterised a pro~otion of growth in comparison to the Le A_20 ll58 ~ 16824~

control plants.
In this test, compounds II-3)~ (I-4), (I-6), (I-12), (I-13), (I-32), (I-34) and ~I-35) according to the invention exhibited a better in~luence on growth than the compounds (c) and (D) known from the prior art.
Exam~le E
~ormation -of ethylene Solvent: 30 parts by weight of dimethylformamide ~mulsifier: l part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active compound, l part by weight of active compound was mixed with the stated amounts of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Pieces of leaf of identical size were punched from soya been leaves. These were introduced into vessels which could be closed air-ti~ht, together with l ml of the preparation of active compound or control solution. After 24 hours the ethylene which had co~ected in the vessels was determined by customary methods of detection. The evolution of ethylene from the pieces of leaf treated with the preparations of active compound was compared with the evolution of ethylene from the controls.
0 denoted evolution of ethylene as in the case of the control + denoted slightly increased evolution of ethylene ++ denoted greatly increased evolution of ethylene +++ denoted very greatly increased evolution of ethylene In this test, active compounds (I-12) and (I-i3) caused greater formation of ethylene than the compounds (B), (C) and (D) known from the prior art.

Le A 20 458 _ 1 16824~

Example F
- Erysiphe test ~barley)/protective Solvent: 100 parts by weight of dimethylforma~ide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration-To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Er-ysiphe graminis f.sp.
hordei.
The plants were placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a si~nificantly superior activity compared with the prior art was exhibited, for example, by the compounds (I-3), (I-4~ 6) L (I-12) a~d rI

Le A 20 458 . .

Claims (43)

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

1. A triazolylpropenol compound of the formula (I) in which R represents a halogen atom, an alkyl, halo-alkyl, haloalkoxy, alkoxy, alkylthio, halo alkylthio, alkylamino, dialkylamino, nitro, cyano, hydroxyl or alkylcarbonyloxy radical, or represents a phenyl, phenoxy radical or benzyloxy radical which is optionally monosubstituted or disubstituted by identical or different substituents selected from fluorine, chlorine and methyl, n is 0, 1, 2, 3, 4 or 5, and X represents a cycloalkyl radical which can be monosubstituted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, trifluoromethyl, dichloro-vinyl, dibromovinyl, methoxy, chlorophenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene or represents a grouping of the formula -CR1R2-Y, wherein R1 and R2 are identical or different and represent alkyl radicals and Y represents an alkyl radical with more than 1 carbon atom, or an alkoxycarbonyl radical, or represents a phenyl radical which is optionally substituted by Rn;

and non-phytotoxic acid addition salts and metal salt complexes thereof wherein the metal is selected from those in main groups II to IV and in sub-groups I, II and IV to VIII of the periodic table.

2. Compound as claimed in claim 1, wherein R is a fluorine, chlorine or bromine atom.

3. Compound as claimed in claim 1, wherein R is straight-chained or branched alkyl.

4. Compound as claimed in claim 1, wherein R is alkoxy or alkylthio radical of 1 to 4 carbon atoms.

5. Compound as claimed in claim 1, wherein R is haloalkyl, haloalkoxy or haloalkylthio radical of 1 or 2 carbon atoms and up to 5 identical or different halogen atoms.

6. Compound as claimed in claim 1, wherein R is alkylamino or dialkyl-amino radical of 1 or 2 carbon atoms in each alkyl part.

7. Compound as claimed in claim 1, wherein R is nitro, cyano or hydroxyl radical.

8. Compound as claimed in claim 1, wherein R is alkylcarbonyloxy radical with 1 to 4 carbon atoms in the alkyl part.

9. Compound as claimed in claim 1, wherein R is optionally substituted phenyl, phenoxy or benzyloxy radical.

10. Compound as claimed in claim 1, wherein n is 0.

11. Compound as claimed in claim 1, wherein n is 1.

12. Compound as claimed in claim 1, wherein n is 2.

13. Compound as claimed in claim 1, wherein n is 3.

14. Compound as claimed in claim 1, wherein X is a cycloalkyl radical of 3 to 7 carbon atoms, optionally substituted as defined in claim 1.

15. Compound as claimed in claim 1, wherein R is a grouping of the formula -CR1R2-Y, wherein R1 and R2 are identical or different and represent a straight-chain or branched alkyl radical of 1 to 4 carbon atoms, and Y is a straight-chain or branched alkyl radical of more than 1 carbon atom, an alkoxy-carbonyl radical of 1 to 4 carbon atoms in the alkyl part or a phenyl radical which is optionally substituted by Rn.

16. Compound as claimed in claim 1, wherein R is a fluorine or chlorine atom or a methyl isopropyl, tert.-butyl, methylthio, isopropoxy, trifluoro-methyl, difluorochloromethyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloroethyl, trifluoromethoxy, trifluoromethylthio, 1,1,2-trifluoro-2-chloroethoxy and -ethylthio, dimethylamino, nitro, cyano, hydroxyl, acetoxy or tert.-butylcarbonyloxy radical, or represents a phenyl, phenoxy or benzyloxy radical which is optionally monosubstituted or disubstituted by identical or different substituents selected from fluorine, chlorine and methyl, n is 0, 1, 2 or 3 and X represents a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radical, which can be monosubstituted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, chlorophenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene, or represents grouping of the general formula -CR1R2-Y, in which R1 and R2 are identical or different and represent a methyl, ethyl, isopropyl, n-propyl or tert.-butyl radical and Y represents an ethyl, isopropyl, n-propyl, isobutyl or tert.-butyl radical, a methoxy-, ethoxy-, isopropoxy-, isobutoxy- or tert.-butoxy-carbonyl radical or a phenyl radical which is optionally substituted by Rn.

17. Compound as claimed in claim 1, in the form of an acid addition salt derived from a hydrogen halide acid, phosphoric acid, nitric acid, sulphuric acid, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, or a sulphonic acid.

18. Compound as claimed in claim 1, in the form of a metal salt complex in which the metal is copper, zinc, manganese, magnesium, tin, iron or nickel and the anion is derived from a hydrogen halide acid, phosphoric acid, nitric acid or sulphuric acid.

19. 1-(4-Chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-ol, E-isomer.

20. 1-(4-Chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-ol, Z-isomer.

21. 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-ol, E-isomer.

22. 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-ol, Z-isomer.

23. 1-(4-Fluorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-ol, E-isomer.

24. 1-(4-Fluorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-ol, Z-isomer.

25. A process for the production of triazolylpropenol derivatives according to claim 1, characterized in that a triazolylpropenone derivative of the general formula (II) in which R, X and n have the same meanings as in claim 1, is reduced and the result-ing compound of the formula (I) is then converted, where required, into a non-phytotoxic acid addition salt or metal salt complex thereof as defined in claim 1.

26. A method of combating fungi, which comprises applying to the fungi, or to a habitat thereof, an effective amount of a triazolylpropenol compound as claimed in claim 1.

27. A method according to claim 26 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.

28. A method according to claim 27, wherein a composition is used contain-ing from 1 to 0.0001% of the active compound, by weight.

29. A method according to claim 27, wherein a composition is used contain-ing from 0.5 to 0.001% of the active compound, by weight.

30. A method according to claim 26, wherein said compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.

31. A method according to claim 26, wherein said compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight.

32. A method as claimed in claim 26, wherein said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

33. A method as claimed in claim 26, wherein said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

34. Method of regulating plant growth, which comprises applying to the plants, or to a habitat thereof, an effective amount of a triazolylpropenol com-pound as claimed in claim 1.

35. A method according to claim 34 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.

36. A method according to claim 35, wherein said compound is applied to an area of agriculture in an amount of 0.01 to 50 kg per hectare.

37. A method according to claim 35, wherein said compound is applied to an area of agriculture in an amount of 0.05 to 10 kg per hectare.

38. A method according to claim 26 or 37 wherein said compound is the compound of claim 19.

39. A method according to claim 26 or 37 wherein said compound is the compound of claim 20.

40. A method according to claim 26 or 37 wherein said compound is the com-pound of claim 21.

41. A method according to claim 26 or 37 wherein said compound is the compound of claim 22.

42. A method according to claim 26 or 37 wherein said compound is the compound of claim 23.

43. A method according to claim 26 or 37 wherein said compound is the compound of claim 24.