DD209957A5 - PESTICIDES - Google Patents

Abstract

The invention relates to pesticides containing new substituted azolylallyl ketones and carbinols as active ingredients. The novel compounds of the formula I in which R 1, R 2, R 3, X and Y have the meaning given in the description are suitable for use as crop protection agents and can be used to combat such fungi with particular success which cause real mildew disease.

Description

The present invention relates to crop protection agents containing novel substituted Azolylallylketone and carbinols as active ingredients.

Characteristic of the known technical solutions

It is already known that certain 1-Allyltriazol-Qerivate such as l-cyclohexylidene-4, 4-dimethyl-2- _(l, 2,4-triazol-l-yl) -3-pentanone, l- ( Cyclohexen-4-ylidene) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -3-pentanone or -pentanol "1-chloro-4- (1,2,4- triazol-l-yl) -2,2,5-trimethyl-5-octen-3-one or 4- (l, 2,4-T _r iazol-l-yl) -2,2,6-trimethyl-5 -hepten-3-ol, have good fungicidal and plant growth-regulating properties (cf. DE-OS 2,905,981). However, the action of these compounds is not always fully satisfactory, especially at low application rates and concentrations.

Object of the invention

Surprisingly, the compounds according to the invention have a better fungicidal and plant growth-regulating action than the abovementioned 1-allyltriazole derivatives known from the prior art, which are chemically and biologically close-knit compounds. The erfindungsgeraäßen agents thus represent an enrichment of the art.

CCD 403 3 * 1-1

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Explanation of the essence of the invention

There were new substituted azolylallyl ketones and carbi nole of the general formula

R ¹

R ³ --X - CH - CH = C, _,

in which

R is hydrogen, alkyl, alkenyl, alkynyl, optionally substituted phenyl, optionally substituted cycloalkyl or optionally substituted cycloalkylalkyl,

R is hydrogen, alkyl, alkenyl, alkynyl, optionally substituted phenyl, optionally substituted cycloalkyl or optionally substituted cycloalkylalkyl,

1 2

R and R together with the carbon atom to which they are attached represent optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted 3-cycloalkyl or optionally substituted bicycloalkenyl,

R is optionally substituted cycloalkyl of 3 to 5 carbon atoms, substituted cyclohexyl or the moiety

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CH

R ^{4 is} - (CH -) - C -, where

d. Π t

OH ₃

R is optionally substituted phenyl, alkenyl,

5 alkynyl, cyano or the grouping -Z-R, where

R is alkyl, haloalkyl, optionally substituted phenyl or optionally substituted phenylalkyl and

Z is O, S, SO or SO ₂ ,

η stands for the numbers O to 2,

X is the CO or CH (GH) group and

Y represents a nitrogen atom or the CH group,

and their acid addition salts and metal salt complexes.

The erfindungsgeraäßen compounds of formula (I) are optionally in the geometric isomers E (trans) and Z (ice) before. In the E, Z nomenclature, the substituents on the double bond are classified according to the decreasing priority according to the Cahn-Ingold-Prelog rule. If the preferred substituents are on the same side of the double bond, the configuration Z (derived from together) is present; if they are on opposite sides, the configuration E (derived from opposite) is present.

In addition, the erfindungsgeraäßen compounds have the

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Formula (I) for X = CH (OH) two asymmetric carbon atoms; they can then be present in the two geometric isomers (threo and erythro form), which can be obtained in different proportions. In both cases they are present as optical isomers.

It has furthermore been found that the substituted azolylallyl ketones and carbinols of the formula (I) and their acid addition salts and metal salt complexes are obtained when substituted azolylvinyl ketones of the formula

,1

R-

R ³ - CO - C β CH - CH

in which

12 3

R , R , R and Y are as defined above,

in the presence of a diluent and optionally in the presence of a catalyst bzis, heated in the presence of alumina and optionally the Azolylallyl invention obtained according to the invention of the formula

R ¹

R ³ - CO-CH - CH = C ^ (Ia)

N-

in which

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12 3

R, R , R and Y are as defined above,

reduced in the usual way; and

optionally subsequently added to the compounds of formula (I) thus obtained, an acid or a metal salt.

Finally, it has been found that the novel substituted azolylallyl ketones and carbinols of the formula (I) and their acid addition salts and metal salt complexes have strong fungicidal and strong plant growth-regulating properties.

In addition, the new substituted azolylallyl ketones and carbinols of the formula (I) are interesting intermediates for the preparation of other crop protection agents. In the case of the keto derivatives, the keto group can be reduced to a --CH (OH) - group or a --CR (OH) - group. Furthermore, by appropriate reactions functional derivatives of the keto group can be obtained, such as. Oximes and oxime ethers, hydrazones and ketals. The carbinol derivatives can be converted to the hydroxy group in the usual way in the corresponding ethers. Furthermore, acyl or carbamoyl derivatives of the compounds of the formula (I) can be obtained by reaction with z, B. acyl halides or carbamoyl chlorides in a manner known in principle.

The substituted azolylallyl ketones and carbinols according to the invention are generally defined by the formula (I). In this formula are preferable

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R ^{- represents} hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms; straight-chain or branched alkenyl and alkynyl each having 2 to 7 carbon atoms; for optionally mono- or polysubstituted by identical or different substituents phenyl, preferably being mentioned as substituents: halogen, alkyl having 1 to 4 carbon atoms, alkoxy and alkylthio each having 1 to 4 carbon atoms, alkyl and dialkylamino having in each case 1 to 4 carbon atoms in each alkyl part , further haloalkyl, haloalkoxy and haloalkylthio having in each case 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine atoms, and optionally substituted by halogen and alkyl having 1 to 2 carbon atoms substituted phenyl and phenoxy; furthermore optionally monosubstituted or polysubstituted by identical or different substituents, cycloalkyl or cycloalkylalkyl having in each case 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 2 carbon atoms in the alkyl moiety, preference being given to substituents: alkyl having 1 to 4 carbon atoms and halogen;

2 1

R for the substituents already mentioned for R;

1 2

R and R together with the carbon atom to which they are attached, each optionally mono- or polysubstituted, identically or differently, by alkyl having 1 to 4 carbon atoms, substituted cycloalkyl having 3 to 12 carbon atoms, cycloalkenyl having 3 to 12 carbon atoms, bicycloalkyl having 4 to 24 carbon atoms or bicycloalkenyl having 4 to 24 carbon atoms;

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R is optionally mono- or polysubstituted, identically or differently substituted cycloalkyl having 3 to 5 carbon atoms, or substituted cyclohexyl, where as substituents in each case come into question; Alkyl of 1 to 4 carbon atoms and halogen; as well as for the grouping

CH ₃

R ⁴ - (CH ₂ ) _n -C CH ₃

R for optionally mono- or polysubstituted by identical or different substituents phenyl, wherein as substituents preferably the already mentioned in R phenyl substituents come into question; furthermore, straight-chain or branched alkenyl having 2 to 4 carbon atoms and alkynyl having 3 to 5 carbon atoms; for cyano as well as for the grouping -Z-R;

5 R is straight-chain or branched alkyl having 1 to 6 carbon atoms; Haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine atoms; and for each optionally mono- or polysubstituted by identical or different substituents phenyl and phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, wherein in each case as phenyl substituents preferably already mentioned in R phenyl substituents come into question;

X, Y, Z and the index η for those in the definition of the invention

given meanings,

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Particularly preferred are those compounds of formula (I) in which

Ι R is hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms and straight-chain or branched alkenyl and alkynyl having in each case 2 to 4 carbon atoms; furthermore represents phenyl, which is optionally monosubstituted to trisubstituted by identical or different substituents, substituents being mentioned as substituents; Fluorine, chlorine, methyl, isopropyl, tert-butyl, methoxy, methylthio, isopropoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylamino, dimethylamines and phenyl optionally substituted by fluorine, chlorine and methyl or phenoxy; in each case optionally monosubstituted to trisubstituted by identical or different methyl, ethyl, isopropyl, fluorine or chlorine, cyclopropyl, cyelobutyl, cyclopentyl, cyclohexyl, cyclopropylraethyl, cyclobutylmethyl ,. Cyclopentylmethyl or cyclohexylmethyl;

1

R is the substituent already mentioned for R;

2

R and R together with the carbon atom to which they are attached are each optionally mono- to trisubstituted by identical or different methyl, ethyl or isopropyl-substituted cycloalkyl of 3 to 7 carbon atoms, bicycloalkyl of 5 to 12 carbon atoms or bicycloalkenyl of 5 to 12 Carbon atoms;

R for optionally mono- to trisubstituted, the same or

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variously substituted cyclopropyl or cyclopentyl and monosubstituted to trisubstituted by identical or different cyclohexyl, wherein as substituents in question are each: methyl, ethyl, isopropyl, tert, butyl, chlorine or 3rom; as well as for the grouping

CH _o ) _n -

£ - Π

R ^{4 is} - (CH _o ) _n - C -,

R is optionally monosubstituted to trisubstituted by identical or different substituents, where as substituent

preferably the phenyl substituents already mentioned in R are suitable; also vinyl, propargyl, cyano, and the group -Z-R;

R ^{3 is} straight-chain or branched alkyl having 1 to 4 carbon atoms, and each optionally monosubstituted to trisubstituted by identical or different substituents phenyl and benzyl, wherein in each case as phenyl substituents preferably already mentioned in R phenyl substituents come into question;

X, Y, Z and the index η for those in the definition of the invention

given meaning.

Preferred compounds according to the invention are also addition products of acids and those azolylallylketones and -carbinols of the formula (I) in which R, R, R, X and Y have the meanings which have already been mentioned as preferred for these radicals.

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Among the acids that can be added, preferably include hydrohalic acids, such as. As hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid ,, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as. As acetic acid, maleic acid, succinic acid, fumaric acid, vi / acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulfonic acids, such as. For example, p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Other preferred compounds according to the invention are addition products of salts of metals of II. To IV "main and the I. and II, and IV, to VIII. Subgroup and those azolyl-allyl-ketones and -carbinolen of the formula (I),

12 3

in which R, R ₄ R, X and Y have the meanings which have already been mentioned as preferred for these radicals.

Here, salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred such acids are in this context the hydrogen halide, such as. 8 "hydrochloric and hydrobromic acid, and phosphoric acid, nitric acid and sulfuric acid.

Specifically, in addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (I) may be mentioned (where X is the CO- or the CH (OH) -

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Group is and Y is a nitrogen atom or the CH group):

Table i

R ^ - X - CH - CH = C

CH ₂ -C (CH ₃ ) ₂ -

Cl- (O> -CH ₉ -C (.CH.) ₉ -

Cl- (O) "CH ₂ -C (CH ₃ ) ₂ -

H CH.

CH

3 3 ^H 7 "n

^C 3 ^H 7 "i

^C 4 ^H 9-n

4 9 i

CH,

^C1 - (O) -CH _p -C (CH _) _-

^C 2 ^H 5

C ₂ H ₅

CH.

^C 2 ^H 5

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-C (CH ₃ ) ₂ -

₂ -C (CH ₃ ) ₂ - -O-CH ₂ -C (I

C1- (O) -S-CH "-C (CH_) _O -

3 ^y 2

Cl- <©) -S-CH ₂ -C (CH ₃

CH.

^C 2 ^H 5

C ₂ H ₅

H'

CH.

^C 3 ^H 7 ~ ⁿ

'4 ^Π 9'

CH.

CH.

C ₂ H ₅

CH.

C ₃ H ₇ -H

C ₃ H ₇ -X

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-S-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅

^C 2 ^H 5

CH.

C ₃ H ₇ -X

-C (CH ₃ ) ₂ -

C ₄ H ₉ -H

-C (CH ₃ ) ,, - CH.

CH.

C1- (Q) -C (CH _{3). 2}

^C 2 ^H 5

CH.

^C 2 ^H 5

^C 2 ^H 5

CH.

C ₃ H ₇ -H

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R *

^C1 - \ O / " ⁰ " ^{C (CH3 )} 2 "

CH, CH.

CH.

C ₂ H ₅

C ₂ H ₅

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R ¹

! X

CH.

CH.

CH.

Oh ^cl

Cl

CH.

OCF.

CH-

ex:

H ₃ C

CH.

CH.

CH.

^H 3 ^C

H ₃ C Cl

Cl Cl

Cl

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16 R ¹

Cl Cl

CH-

Cl Cl

Cl Cl

CH-

Cl Cl

CH.

Cl Cl

CH.

Cl Cl

Cl Cl

CH.

CH-

Cl Cl

CH.

-Cl

Cl

-Cl

H ₃ C

OCF.

CH.

Cl Cl

Cl

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If, for example l- (4-chlorophenyl) -2,2-dimethyl-4- {1,2 _J 4-triazol-l-yl) -4-octan-3-one as a starting material, aluminum oxide (as a reaction component catalyst), and Methanol as a diluent, the reaction sequence can be represented by the process according to the invention by the following equation:

CH

'° ΑΙ ,, Ο, / CH ^ OH

Cl - / () V - CH ₂ - C - CO - C = ™ ^J - - - "^» ^

CH ₃

CH ₀ -C-CO - CH-CH = CH-CH

If, for example l- (4-chlorophenyl) -2,2-dimethyl-4- (l, 2 _# 4-triazol-l-yl) -5-octan-3-one as a starting material and sodium borohydride as the reducing agent, so can the Reaction process by the method according to the invention by the following equation:

CH ₃ Cl- (O) -CH-C-CO-CH-CH = CH-C _O H _C ^NaSH 4 ^

^CH 3 f

CH_OH

HC - CH - CH - CH = CH - C H CH ₃ ^ N

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The substituted Azolylvinylketone required as starting materials in carrying out the process according to the invention are generally defined by the formula (II). In this formula, R, R, R and Y preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.

The substituted azolylvinyl ketones of the formula (II) are not yet known. However, they are the subject of a separate, parallel patent application and are obtained by

b) ketoenamines of the formula

R ³ - CO - C = CH - N '(IH)

^X R ⁷

in which

R and Y are as defined above and

R and R are the same or different and are alkyl of 1 to 4 carbon atoms; or to which they are together with the N-atom _# bonded, are optionally monosubstituted to trisubstituted by alkyl having 1 to 4 carbon atoms substituted piperidinyl, pyrrolidinyl, morpholinyl, in each case,

with magnesium-organic compounds of the formula

R ¹ Hal Mg-CH ^

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in which

1 2 R and R have the abovementioned meaning

and Hal is halogen,

in the presence of an inert organic solvent, such as ether, and optionally in the presence of an inert gas, such as nitrogen, at temperatures between -20 and 120 ⁰ C converts (see also DE-OS 3 000 643) and the preparation examples); or

b) Azolyl ketones of the formula

R ³ _CO - CH ₂ --N j (V)

in which

R and Y are as defined above,

with aldehydes of the formula

O = CH - CH "^ (V I)

in which

1 2 R and R have the abovementioned meaning,

in the usual manner in the presence of an inert organic solvent, such as toluene and in the presence

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a catalyst, such as piperidine acetate, at temperatures between 20 and 160 ⁰ C.

The ketoenatnines of the formula (III) are not yet known. However, they are the subject of a separate, parallel patent application and are obtained by Azolylketone the formula

R ³ - CO - CH ₂ -N _- J (V)

in which

R and Y have the abovementioned meaning, with amide acetals or aminal esters of the formulas

R ⁸ O

, .R

CH-N (VIIa)

R ⁸ O - CH.

NR ⁵ R ⁷

NR ⁶ R ⁷

in which

R and R have the abovementioned meaning and

8 R is alkyl of from 1 to 4 carbon atoms,

in a manner known per se in the presence of an inert organic solvent, such as a

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aromatic hydrocarbon and in particular an excess of amide acetal or, Arainalesters of formula (VIIa) or, (VIIb) is reacted at boiling heat (see also Chem. Ber IQI ₁ 41-50 (1963); D. Org. Chem. 43, 4248-50 (1978) and the preparation examples),

The azolyl ketones of the formula (V) are 'widely known (compare in this respect DE-OS 2 431 407 ~ ~ Le A 15 735__7, DE-OS 2 906 061 /' Le A 19 393J7, DE-OS 3,028,330 / ~ Le A 20 458J7, DE-OS 3 048 266 / ~~ Le A 20 763_ /, as well as the German patent applications P 3 145 857 of 19. 11. 1981 / "Le A 21 383_7 and P 3 145 858 of 19. 11. 1981 / "Le A 21 400_7, or they can be prepared by conventional methods by reacting the corresponding halogen ketones in the presence of an acid binder with 1 _# 2,4-triazole or imidazole.

The amide acetals or, respectively, the araal esters of the formulas (VII a) and (VII b) are generally known compounds of organic chemistry (compare, for example, Chem. Ber. IQI ₁ 41-50 (1968) and O. Org. Chem , 4248-50 (1978)); or they can be obtained according to the methods specified there.

The organomagnesium compounds of the formula (IV) are generally known compounds of organic chemistry, as are the aldehydes of the formula (VI).

Suitable diluents for the process according to the invention for preparing the azolylallyl ketones of the formula (Ia) under the reaction conditions are inert organic solvents. These include, preferably, ketones, such as acetone and methyl ethyl ketone; Alcohols, such as methanol,

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Ethanol or isopropanol; aliphatic and aromatic hydrocarbons, such as benzene, toluene or xylene; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene.

The process according to the invention for preparing the azolylallyl ketones of the formula (Ia) is optionally carried out in the presence of a base as catalyst. These preferably include organic nitrogen bases, such as morpholine, pyridine, triethylamine and Ν, Ν-diraethylbenzylamine.

The reaction temperatures can be varied within a substantial range in the process according to the invention for preparing the azolylallyl ketones of the formula (Ia). In general, one works at temperatures between 3ü and 150 C, preferably between 50 and 120 C.

The process according to the invention for the preparation of the azolyl-allyl ketones of the formula (Ia) is carried out either purely thermally by heating the compounds of the formula (II) or in the presence of basic catalysts, based on 1 mol of the compounds of the formula (II) O ₁ l to 1 mol of base is used, or in the presence of alumina. The isolation of the compounds of the invention takes place in all cases in the usual manner.

The reduction according to the invention for the preparation of azolylallyl-carbinols of the formula (I) is carried out in the usual manner, for. Example by reacting azolyl-allyl-ketones of the formula (Ia) with complex hydrides, optionally in Gegen-

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a diluent, or by reacting azolyl-allyl-ketones of the formula (Ia) with aluminum isopropylate in the presence of a Verdünnungsmitteis.

When working with complex hydrides, suitable diluents for this reaction according to the invention are polar organic solvents. These include, preferably, alcohols, such as methanol, ethanol, butanol, isopropanol and ethers, such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at 0 to 30 C, preferably at 0 to 20 ⁰ C. For this purpose, for 1 mole of the ketone of formula (Ia) about 1 reaction equivalent of a complex hydride »such as sodium borohydride or lithium alanate, to isolate the reduced compounds of formula (I), the residue is taken up in dilute hydrochloric acid, then made alkaline and with extracted an organic solvent. The further work-up is carried out in the usual way.

When working with aluminum isopropylate, suitable diluents for this reaction according to the invention are preferably alcohols, such as isopropanol, or inert hydrocarbons, such as benzene. The reaction temperatures can in turn be varied within a substantial range; In general, one operates between 20 and 120 ⁰ C _1, preferably at 50 to 100 C, to carry out the reaction is used for 1 mol of the ketone of the formula (Ia) about 1 to 2 moles of aluminum isopropoxide. To isolate the reduced compounds of the formula (I), the excess solvent is removed by distillation in vacuo and the

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standing aluminum compound with dilute sulfuric acid or sodium hydroxide decomposes. The further processing takes place in the usual way «

For the preparation of acid addition salts of the azolyl-allyl ketones and -carbinols of the formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of the formula (I) can be prepared in a simple manner by customary salt formation methods, ζ * B, by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, ζ. For example, hydrochloric acid, are obtained and in a known manner, for. B. by filtration, isolated and optionally purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of azolyl-allyl ketones and -carbinols of the formula (I) are preferably salts of those anions and cations into consideration, which have already been mentioned as preferred in connection with the description of erfindungsgeraäSSen metal salt complexes.

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, such. 3. by dissolving the metal salt in alcohol, ζ. Ethanol, and adding to the compound of formula (I).

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Metal salt complexes can be purified in a known manner, for example by filtration, isolation and optionally by recrystallization.

The active compounds which can be used according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

For the mode of action of plant growth regulators applies according to previous experience that an active substance can also exert several different effects on plants. The effects of the substances depend essentially on the time of application, based on the stage of development of the plant and on the amounts of active substance applied to the plants or their surroundings and on the mode of application. In any case, growth regulators are intended to influence crops in some desired manner.

Plant growth regulators can be used, for example, to inhibit the vegetative growth of plants. Such growth inhibition is of economic interest to grasses, among other things, as this can increase the frequency of grass cuttings in ornamental gardens, parks and sports facilities, on roadsides, at airports or in orchards be reduced. Of importance is also the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overhead lines or in general in areas where a strong growth of the plants is undesirable.

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Also important is the use of growth regulators to inhibit grain elongation. This reduces or completely eliminates the risk of plants being "stooped" before harvesting. In addition, growth regulators in crops can cause a stalk reinforcement, which also counteracts storage. The use of growth regulators for stalk shortening and stalk augmentation makes it possible to apply higher quantities of fertilizer in order to increase the yield without the risk of the grain being stored.

An inhibition of vegetative growth allows for many crops a denser planting, so that Hehrerträge based on the floor area can be achieved. An advantage of the smaller plants thus obtained is that the culture can be more easily processed and harvested.

An inhibition of the vegetative growth of the plants can also lead to increased yields, that the nutrients and assimilates benefit the flower and fruit formation to a greater extent than the vegetative plant parts.

With growth regulators can often achieve a promotion of vegetative growth. This is of great benefit when harvesting the vegetative plant parts. Promoting vegetative growth can, however, simultaneously promote generative growth by producing more assimilates to produce more or greater fruits »

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In some cases, increases in yield can be achieved by interfering with the plant metabolism, without causing any changes in vegetative growth. Furthermore, with growth regulators, a change in the composition of aer plants can be achieved, which in turn can lead to an improvement in the quality of the harvested products. For example, it is possible to increase the sugar content in sugar beets, sugar cane, pineapple and citrus fruits, or to increase the protein content in soya or cereals. It is also possible, for example, the degradation of desirable ingredients such. B, to inhibit sugar in sugar beet or cane, with growth regulators before or after harvest. In addition, the production or the discharge of secondary plant ingredients can be positively influenced. An example is the stimulation of latex flow in gum trees.

Under the influence of growth regulators, parthenocarp fruits may develop. Furthermore, the sex of the flowers can be influenced. Also, a sterility of the pollen can be produced, which has a great importance in the breeding and production of hybrid seed.

Through the use of growth regulators, the branching of the plants can be controlled. On the one hand, the development of side shoots can be promoted by breaking the apicoid dominance, which can be very desirable, especially in ornamental plant cultivation, also in connection with growth inhibition. On the other hand, it is also possible to inhibit the growth of the side shoots. For this effect, z, B, there is great interest in tobacco growing or in planting to-

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formats.

Under the influence of growth regulators of leaf on plants can be controlled so that defoliation of the plants is achieved at a desired timing. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also of interest in other crops such as z * B in viticulture to facilitate the harvest. Defoliation of the plants may also be done to reduce the transpiration of the plants before transplanting.

Likewise can be controlled with growth regulators the fruit case. On the one hand, a premature fruit drop can be prevented. On the other hand, however, the fruit fall or even the fall of the flowers can be promoted to a desired extent ("thinning") to break the alternation. Alternating means the peculiarity of some fruits to bring very different yields endogenously from Dahr to Dahr. Finally, it is possible with growth regulators to reduce the forces required to detach the fruits at the time of harvest, to facilitate mechanical harvesting or to facilitate manual harvesting.

With growth regulators can also accelerate or delay the ripeness of the crop before or after harvest reach. This is of particular advantage because it can bring about an optimal adaptation to the needs of the market. Furthermore, growth regulati-

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In some cases, they improve fruit colouration. In addition, with growth regulators, a temporal concentration of maturity can be achieved. This creates the conditions for that z. 3. In the case of tobacco, tomatoes or coffee, a complete mechanical or manual harvesting can be carried out in one operation.

Through the use of growth regulators, the seed or bud rest of the plants can be further influenced, so that the plants, such as. As pineapple or ornamental plants in nurseries, germinate, shoot or blossom at which they normally show no readiness at a time. Delaying bud sprouting or seed germination using growth regulators may be desirable in areas prone to frost to prevent damage from late frosts.

Finally, with growth regulators, a resistance of the plants to frost, dryness or high salt content of the soil can be induced. This makes it possible to cultivate plants in areas that are normally unsuitable for this purpose.

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active substances are suitable for use as pesticides.

Fungicides in crop protection are used for the

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combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, 3asidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of above-ground parts of plants,. of plant and seed, and soil,

As plant protection agents, the active compounds according to the invention can be used with particularly good success for controlling such fungi which cause true mildew diseases, such as for combating Erysiphe species, such as, against the pathogen of barley or cereal powdery mildew (Erysiphe graminis) Control of leaf spot disease in cereals (Pyrenophora teres), for combating barley barley disease (Cochliobolus sativus), for combating Venturia species such as, for example, B, against the scab acquirer (Venturia inaequalis) / or for combating rice diseases such as z * B "Pellicularia sasakii.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrapure encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents, under pressure.

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liquid gases and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, for example, organic solvents may also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, Z "B, petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. As aerosol propellant, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: z. B, ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates. Suitable solid carriers for granules are: z * 3. fractured and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. As an emulsifying and / or foam-producing

52 629 11/38 - 32 -

de means are suitable: z, B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, "z" B. alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and EivveiS hydrolyzates are suitable as dispersants: z »B. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate can be used in the formulations.

It can dyes such as inorganic pigments, eg. B, iron oxide, titania »ferrocyan blue and organic dyes such as alizarin, azo, metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

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

The active compounds according to the invention may be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and other growth regulators,

The active compounds can be used as such, in the form of their formulations or the forms of use prepared therefrom, such as

62 529 11/33

ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is carried out in a conventional manner, z, B, by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or the active ingredient preparation or the active ingredient inject yourself into the ground. It can also be the seed of the plants to be treated.

When using the compounds of the invention as plant growth regulators Aufvvandmengen can be varied within a substantial range. In general, one uses O ₇ Ol to 50 kg per hectare of soil surface, preferably 0.05 to 10 kg.

When using the substances according to the invention as plant growth regulators, the application is made in a preferred period of time, the exact delimitation of which depends on the climatic and vegetative conditions »

Even when using the substances according to the invention as fungicides, the amount of material used can be varied within a relatively wide range, depending on the type of application. Thus, the active ingredient concentrations in the treatment of plant parts in the use forms are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001 wt -.%. In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, needed. At treatment of the soil are drug concentrations of

62 629 11/38 - 34 -

0.00001 to 0.1% by weight, preferably from 0.0001 to 0.2 %, at the site of action.

The preparation and use of the substances according to the invention are illustrated by the following examples,

Herstellunqsbeispiele example 1

? ^H 3 Cl - / F) S - CU - - C - CO - CH - CH = CH - C ₀ H, -

14 g (0.042 mol) of 1- (4-chlorophenyl) -2,2-dimethyl-4-bis (1,2 _/ 4-triazol-1-yl) -4-octen-3-one and 14. g of alumina heated in 200 ml of methanol for 24 hours under reflux. The reaction mixture is allowed to cool, filtered off with suction through kieselguhr and the filtrate is concentrated. This gives quantitatively 1- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-octen-3-one of the refractive index n _Q = 1.5312,

Production of the Ausqanqsproduktes

CH.,

CH -C-CO-C = CH-CH-C-H_ CH ₃ ^ N.

62 529 11/38 - 35 -

49.9 g (0.15 mol) of 1- {4-chlorophenyl) -2-dimethyl-S-dimethylamino-4- (1,2,4-triazol-1-yl) -4-penten-3-one are dissolved in 750 ml of ether and treated dropwise at -20 ⁰ C with a solution of 33.9 g (0.23 mol) of n-propylmagnesium bromide in 100 ml of ether. The mixture is stirred for 1.5 hours, with the reaction mixture warmed to room temperature. With dilute hydrochloric acid, the reaction mixture is adjusted to a pH of 7 to 8. Thereafter, the organic phase is separated, washed with water, dried over sodium sulfate and concentrated. The residue is purified by column chromatography (silica gel, ethyl acetate / cyclohexane = 3: 1). This gives 30.1 g (60.5 % of theory) of 1- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) 4-octen-3-one from

20

Refractive index n ~ = 1.5429,

L - C - CO - C = CH - N (CH.,)

50 g (0.18 mol) of L - (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -3-butanone are mixed with 23.6 g (0.138 mol ) Dimethylformamide dimethyl acetal heated under reflux for 8 hours. To isolate the final product, the reaction mixture is concentrated in vacuo. 56.5 g (94.4 % of theory) of 1- (4-chlorophenyl) -2,2-dimethyl-5-dimethylamino-4- (1,2,4-triazol-1-yl) are obtained. 4-penten-3-one of the refractive index n ^ ° = 1.5797.

62 629 11/38

Cl

ChL · -C-CO-CH ^ -N

37 g (0.13 mol) of 4-bromo-1- (4-chlorophenyl) -2,2-dimethyl-3-butanone, 13.3 g (0.19 mol) of 1,2,4-triazole and 53, 8 g (0.39 mol) of potassium carbonate are refluxed in 300 ml of acetone for 8 hours. It is allowed to cool, filtered off from the inorganic residue and the filtrate is concentrated. The residue is taken up in chloroform, washed with water, dried over sodium sulfate and concentrated. The residue is stirred with diethyl ether, filtered off with suction and dried at 50 C in vacuo. This gives 18.8 g (52 % of theory) of 1- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -3-butanone of melting point 127 ^° C. ,

? ^H 3

CH ₀ - C - CO - CH ₀ -Br

^CH 3

130 g (0.62 mol) of 1- (4-chlorophenyl) -2,2-dimethyl-3-butanone in 1000 ml of chloroform are treated dropwise at room temperature with 98.8 g (0.62 mol) of bromine. The reaction mixture is allowed to stir for 1 hour and then concentrated. Wan receives 174.7 g (97.3 % of theory) of 4-8rom-l- (4-chlorophenyl) -

20 2,2-dimethyl-3-butanone of refractive index n _Q = 1.5570,

62 629 11/38

Example 2

CH, OH

ι -J t

CH - C - CH - CH - CH = CH - C ₀ H,

C. ι t_

CH_ .N 3 /

11.3 g (0.034 mol) of 1- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-octan-3-one (Example 1) are dissolved in Dissolved 100 ml of methanol and treated at -10 C dropwise with a solution of 0.38 g (O ₁ moles) of sodium borohydride in 5 ml of ice water. The mixture is stirred for 1.5 hours at ^{0 0} C and then the reaction mixture with dilute hydrochloric acid to a pH of 6 to 7, the reaction mixture is concentrated by distilling off the solvent in vacuo * The residue is taken up in methylene chloride, washed with water , dried over sodium sulfate and concentrated. 10.7 g (95 % of theory) of 1- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazolelyl) -5-octen-3-ol of the refractive index are obtained n ^ = 1.5340 »

In appropriate manner and according to the procedures indicated, the following compounds of formula (I) are obtained:

Table 2

- χ - CH - CH = C

(I)

Example, no.

r:> 3

Melting point ( ⁰ C) or

3 Cl- / Q) -OCH ₂ -C (CH ₃ J. ₂ ^V ~ ^/ Cl

CO N

4 Cl - / Q - O - CH - C (CH) - CH (OH) CH

^C 2 ^H 5

^C 6 ^H 13

Tough oil

1.5352

5 Cl

-SCH ₂ -C (CH ₃ J ₂ - CO

6 Cl ~ ^ Q ^ -O-C (CH ₃ ) ₂ .

, CH-

CO CO

CO N

H H

^C 2 ^H 5

^C 2 ^H 5

1.5558

1.5366

1.4938 viscous oil

Table 2 (continued)

Example no.

R ² ) Melting point ( ⁰ C) or n ) Tough oil ^C 2 ^H 5 Tough oil C ₂ H ₅ 30 H 1.5631 C ₂ H ₅ 1.5438 ⁰ ^ ₉ " ¹ 1.5300 1.4936 ^C 6 ^H 13 tough oil 1.5254

10 Cl- / O 11 Cl-

14

15 16

.OCH ₂ -C (CH ₃ ) -

CH.

_cl

CO

CO

CH (OH) CH (OH)

CH (OH) CH (OH)

CH (OH) CH (OH)

CO

N N N N

N H

H H

CH

H H

H H H

62 629 11/33

Verwendunqsbeispiele

In the following examples, the compounds listed below are used as verieichssubstanzen:

OH »

(A) (CH), C-CH-CH-CH

Lj

/ -ν

(B) (CH) C - CO - CH - CH = / H

Lj

(C) (CH ₃ J ₃ C - CO - CH - CH = /

? ^H 3

(D) ClCH ₀ - C - CO - CH - CH

CH. H.

OH

(E) (CH ₃ J ₃ C - CH - CH - CH = C

CH.

CH. -CH-

62 629 11/38 - 41 -

Example A

Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To prepare 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 concentration,

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. When the spray coating has dried on, plants are inoculated with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain at ^20.degree. C. and 100 for 1 day; Incubation.

at 20 C and 100 % relative humidity in one

The plants are then grown in the greenhouse at 20 C and a. Relative humidity of about 70 % .

12 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. 3, the compounds according to the following preparation examples: 11.

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Example S

Erysiphe test (barley) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried, the plants are spotted with spores of Erysiphe graminis f. sp. horde! pollinated.

The plants are placed in a greenhouse at a temperature of about 20 C and a relative atmospheric humidity of about 80% set _t to the development of mildew pustules to favor,

7 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds according to the following preparation examples: 3, 11, 6, 14, 5, I ₁ 12, 2, 13, 8 and 16.

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Example C Growth inhibition in barley

Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and filled with water to the desired concentration,

Barley plants are grown in the greenhouse up to the 2-Slattstadium "At this stage, the plants are sprayed dripping wet with the WirkstoffTubereitungen. After 3 weeks, the growth in all plants is measured and the growth inhibition in percent of the growth of the control plants is calculated. It means 100 % inhibition of growth stagnation of growth and O % growth corresponding to that of the control plants.

The active compound according to the invention shows better growth inhibition in this test than the compounds (D) and (E) known from the prior art,

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Example D Growth in sugar beets

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the specified amounts of solvent and emulsifier and the mixture is filled with water to the desired concentration,

Sugar beets are grown in the greenhouse until the cotyledons have fully developed. "At this stage, the plants are sprayed to drip point with the active ingredient preparation. After 14 days, the growth of the plants is measured and the growth influence as a percentage of the growth of the control plants is calculated. 0 % growth influence means a growth corresponding to that of the control plants, negative values characterize a growth inhibition, positive a growth promotion compared to the control plants,

The active compounds 2 and 12 according to the invention show in this test a stronger growth influence than the compounds (A) and (E) known from the prior art.

Claims (6)

62 629 11/38 - 45 Claim for invention R is hydrogen, alkyl, alkenyl, alkynyl, optionally substituted phenyl, optionally substituted cycloalkyl or optionally substituted cycloalkylalkyl, R is hydrogen, alkyl, alkenyl, alkynyl, optionally substituted phenyl, optionally substituted cycloalkyl or optionally substituted cycloalkylalkyl, 2 * Fungicidal and plant growth regulating agents, characterized by a content of at least one substituted azolylallyl ketone or -carbinol of formula (I) in point 1, in addition to extenders and / or 62 629 11/38 surfactants. 2
R and R together with the carbon atom to which they are attached represent optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted bicycloalkyl or optionally substituted bicycloalkenyl, R is optionally substituted cycloalkyl with 3 62 629 11/38 to 5 carbon atoms, substituted cyclohexyl or the grouping ? ^H 3
R ^{4 is} - (CJ-U) _n - C -, wherein R is optionally substituted phenyl, alkenyl, alkynyl, cyano or the grouping -Z-R, wherein R is alkyl, haloalkyl, optionally substituted phenyl or optionally substituted phenylalkyl and Z is O ₁ S, SO or SO ₂ , η stands for the numbers O to 2, X is the CO or CH (QH) group and Y represents a nitrogen atom or the CH group, as well as their acid addition salts and metal salt complexes, in addition to extenders and / or surface-active agents. 3. Method for controlling fungi , characterized in that one substituted azolyl ketones or carbinols of the formula (I) in point 1 can act on fungi or plants or their habitat, 4. Use of substituted azolylallyl ketones or carbinols of the formula (I) in point 1, characterized in that they are used as plant protection products * 5. Use of substituted azolylallyl ketones or carbinols of the formula (I) in item 1, characterized in that they are used for controlling fungi and for regulating plant growth. 6. A process for the preparation of crop protection agents, characterized in that one mixes substituted Azolylallylketone or -carbinols of the formula (I) in item 1 with extenders and / or surface-active agents.