CA1179352A - Triazolylpropenone derivatives, a process for their preparation and their use as intermediates - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Novel triazolylpropenone derivatives of the general formula

Description

~g3~

The present invention relates to certain new triazolylpropenone derivatives, to a process for their production and to their use as inter-mediates for plant growth regulators and fungicides.
It has already been disclosed th~t 4,4-dimethyl-1-phenyl-2-triazolyl-l-penten-3-ols have a good fungicidal activity ~see DE-OS ~German Published Specification) 2,838,847). ~lowever, the action of these compounds is not always c~mpletely satisfactory, especially when low amounts and concentrations are applied. The plant growth-regulating acti~on of these azole derivatives is likewise not always completely satisfactory.
The present invention now provides, as new compounds, the tria~olyl-propenone derivatives of the general formula ~ ~ CH = C - CO - X ~II) / N
R ~' N
n N -in which R represents a halogen atom, an alkyl, halo-alkyl, haloalkoxy, alkoxy, alkylthio, halo alkylthio, alkylamino, dialkylamino, nitro9 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 flu0rine, chlorine and methyl, n ls 0, 1, 2, 3, ~ or 5, and X represents a cycloalkyl radical which can be monosubstituted or polysubstituted by identical or di~ferent substituents selected erom methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, chlorophenyl, chlorobenzyl, dich-lorophenyl, dichlorobenzyl, trime~hylene and isobutylene or represents a grouping of the formula -CR R -Y, wherein Rl and R2 are identical or different and represent alkyl radicals and Y represents an alkyl radical with more than 1 carbom atom, or an alkoxycarbonyl radical, or represents a phenyl radical which is optionally substituted by Rn.
The compounds of the formula ~II) according to the invention occur in the geome~ric 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.
The present invention relates both to the individual isomers and to the isomer mixtures The new compounds of the present invention may be prepared by a process ~hich comprises reacting a triazolyl-ketone of the general formula H?C - CO - X
:1~
~ N (III) N --:

in which X has the abovementioned meaning, with an aldehyde of the general formula n ~ CH = 0 (IV) in which R and n have the abovementioned meaning, in the presence of a solvent and in the presence of a catalyst.
Preferred possible solvents for the preparation of the triazolyl-propenone derivatives of the formula (II) are inert organic solvents. These include, as preferences, alcohols (such as methanol and ethanol); ethers (such as tetrahydrofuran and dioxane), aliphatic and cycloaliphatic hydro-carbons ~such as hexane and cyclohexane); aromatic hydrocarbons (such as benæene, toluene and cumene); and halogenated aliphatic and aromatic hydro-carbons (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 particularl basic catalysts which can customarily be used, as well as buffer mixtures thereof. These ca~.alysts include, preferably, Lewis acids (such as boron triEluoride, boron trichloride, tin tetrachloride or titanium tetrachloride); organic bases (such as pyridine and piperidine); and, in particular~ piperidine acetate.
The reaction temperatures can be varied within a substantial range when carrying out this process. In general, the reaction is carried o~t at a temperature between 20 and 160C, preferably at the boiling point of the particular solvent.

935~Z:

In carrying out this processj 1 to 1.5 moles 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 inthe customary manner, such as, for example, by crystallisation or by chromatographic separation processes.
The triazolylpropenone derivatives of the formula ~II) are generally interesting intermediate products, for example, for the preparation of the compounds of the formula (I). In appropriate concentrations, they also exhibit growth-regulating and fungicidal properties.
Some of ~he 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 them are claimed in general terms t~ere-in without being mentioned therein by name. The triazolyl-ketones of the general formula ~I~N (V,~
N
in which xl represents optionally substituted cyclopropyl or optionally substituted cyclobutyl or a grouping of the general formula ~CRlR2-Yl, wherein Rl and R2 have the above-mentioned meaning and yl represents an opt:ionally substituted phenyl radical or an alkoxycarbonyl radical, and preeerably has the corresponding preferred meanings 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-CO-X (VI) in which xl has the abovementioned meaning and Hal represents a chlorine or bromine atom, with 1,2,4-triazole in the presence 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 ~V) are inert organic solvents. These include~ prefer-ably, ketones ~such as acetone and methyl ethyl keton~); nitriles ~such as acetonitrile); ethers ~such as tetrahydrofuran or dioxane); aromatic hydro-carbons ~such as benzene and toluene); formamides (such as dimethylformamide);
and halogenated hydrocarbons.
This process is carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can customarily be used, such as alkali metal carbonates ~for example sodium carbonate, potassium carbonate and sodium bicarbonate); alkali metal alcoholates (such as sodium methylate or sodium ethylate); lower tertiary alkylamines, cycloalkylamines or aralkylamines (such as triethylamine, dimethylbenzylamine or dimethylcyclohexylamine); or such as pyridine and an appropriate excess of 1,2,~-triazole.
The reaction temperatures can be varied within a substantial range in carrying out this process. In ~eneral, the reaction is carried out at a temp-erature between 0 and 120C, preferably between 20 and 100C.
In carrying out this process, 1 to 2 moles~f 1,2,~-trla2O1e and 1 to 2 ~7~352 moles of acid-binding agent are preferably employed per mole of the compounds of the formula (VI). 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 com-pound of the general formula H3C-C0-Xl (VII) in which xl has the abovementioned meaning~
in the presence 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 ~or the preparation of the triazolylpropenone derivatives of the formula (II) are generally known compounds of organic chemistry.
The compounds of the invention may be converted by reduction, e.g.
with a complex hydride or withaluminum isopropylate to the corresponding triazolylpropenone derivatives and acid addition salts and metal salt complexes thereof which have powerful plant growth-regulating and powerful fungicidal properties.
Surprisingly, such triazolylpropenone compounds exhibit a better growth-regulating and fungicidal action than the ~ dimethyl-l-phenyl-2-triazolyl-l-penten-3-olsl which are known from the state of tlle art and are closely related compounds chemically and from the point of view of their action.
Preferred triazolylpropenone derivativesof formula (II) according to the present invention are those in which R represents a fluorine, chlorine or ~1l79935~

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 op-tionally substituted phenyl, phenoxy or benzyloxy radical (preferred substi-tuents which may be mentioned being: ~luorine, 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 different 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 identical or different halogen atoms (halogen atoms which may be mentioned being fluorine, chlorine and bromine atoms), halogen, alkoxy with 1 to 4 carbon atoms and a two-membered torive-membered methylene bridge, optionally sub-tituted phenyl or benzyl ~preferred substituents which may be mentioned being fluorine, chlorine and bromine atoms); or represents a grouping of the general formula -C~lR2-Y, .in which Rl and R2 are identical or different and represent a straight-chain or branched alkyl radical with 1 to 4 carbon atoms, and Y rep-resonts a st:raight-chain or branched alkyl radical with more than 1 carbon atom~
an alkoxycarbonyl radical with 1 to 4 carbon atoms in the alkyl part or a phenyl radical which is optionally substituted by Rn (in which Rand n have the imme-diately abovementioned meanings).

~7~3S;2 Particularly preferred compounds of the present invention are those in which R represents a fluorine or chlorine atom or a methyl, isopropyl, tert.-butyl, methoxy, methylthioJ isopropoxy, trifluoromethyl, difluorochloro-methyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluorometh~xy, trifluoromethylthio, 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 sub-stituents selected from fluorine, chlorine and methyl, _ is 0~1J2 or 3, X
represents a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclohepty radical, which can be monosubstituted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorlne, chlorine, chloromethyl, trifluG~omethyl,-dichlorovinyl, dibromovinyl, methoxy, chlorphenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene, or represents a grouping of the general formula -CRlR2-Y in which Rl and R2 are identical or different and represent a methyl, ethyl, i.sopropyl, 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 which is optionally substituted by R ~in which R and n have the immediately abovementioned meanings).
The following compounds of the general formula ~II) may be mentioned specifically, in addition to the compounds mentioned in the Preparative E!xamples:

~ ~7~352 Table 1 ,~ CH = Cl - CO - X (II) R ~ ~N
n n X
- -~
4-SC~3 C~

4-C (CH3) 3 _~

~-OH

2-o?~,3,5-cl2 ~

4-()H, 3-OH

4 ~Cl C~

4-0-~ Cl C~

R X
n 4- 0-C112 _@, c~3 4-O-CH2 ~ Cl CH3 4-Cl -<

2-Cl 2,4-C1 2,4-C12 ~
4-Cl -9, Cl 4-F ~ Cl ~-Cl _~ Cl 2,4-C12 ~Cl 2-Cl, 4-CF3 ~Cl 4-Cl <~>

2-Cl 2,4-C12 ~>
2-Cl, 4-CF3 4-C 1 C~H13CC
c~l3 - lO -Rn X
C~l=CC12 4-F ~ CH3 ~ r CH=CC12 2-Cl ~ C~13 ~ CH=CC12 2,4-C12 ~ CH3 ~ CH=CC12 2-Cl, 4-CF3 ~ CH3 4-Cl ~ Cl Cl 4-F 3 ~ - CL

CH3~
2-Cl ~ Cl Cl 2,4-C12 ~ Cl ~ Cl 2-Cl, 4-CP3 C~13 ~ Cl C:L
4-Cl - O

2-Cl 2,4-C1 1:~L79352 -2-Cl, 4-CF3 4-Cl -2-Cl -Cl 2,4-C12 _~
2-Cl, 4-CF3 4-Cl 2-Cl 2,4-C12 {>
2-Cl, 4-CF3 4-F -C~CH3) 2-Cl -C(CH3) 2,4-C12 -C~CH3) 4-CF3 -C~CH3)2 -2-Cl, 4-CF3 C(C~3)2 -4-OCF3 C(CH3)2 - ~
4-Cl -C(C~13)2 _ ~ _ Cl ~-1' -C~CI-I ) ~ Cl 2,~-C12 -C(C~13)2~ Cl 4-CF3 C(C113)2- ~ _ 2-Cl, 4-CF3 -C(C~13)2_ ~ _ Cl 4-OCF3 -C(CH3)3 ~ Cl 35~
R X
n 4-Cl -C~CH3)(C2H5) 4-F -C(CH3)(C2H
2,4-C12 -C~CH3)~C2H5) 4-CF3 -C(CH3)(C2H5}
-C(CH )(C2H5) 2-Cl, 4-CF3 3 4-OCF3 -C(CH3(C2H
4-Cl ¢~C 3)2 3 4-F ( 3)2 3 2-Cl ( 3)2 3 2,4-C12 ( 3)2 3 ~ -C(CH3)2-COOCH3 4-C ~
4-OCP3 -C(CH3)2-COOcH3 -C(CH )2-COOCH3 2-Cl, 4-CP3 3 2-CP3 C(CH3)2 CC2H5 ( 3)2 2 5 4-C(CH3)2 -C(CH3)2-COOc2~l5 4-OH ( 3)2 2 5 -C(CH ) -COOC2~5 2-0}1, 3,5-C12 4-NO c(CH3)2 C 2 5 -C, (C~l ) -COOC2~15 4-0~{, 3-OC~13 3 2 ~~ -C(c~l3)2-cooC2~l5 4 ~O~ Cl C(CH3)2 COOC2H5 ~7~3~

R X
.
~ -C~cH3)2-cc2H5 4-0 - ~ Cl -C~CH3)2-COOC2H5 4-0CH2 ~ C(C 3)2 2 5 4-0-CH2 ~ Cl -C(CII ) -COOC H
2-Cl C(C 3)2 2 5 2,4-C12 -C~CH ) -COOC2H5 4-F -C(CH3)2-C2H5 2-Cl -C(CH3)2-C2H5 2,4-C12 -C(CH3)2-C2H5 4-CF3 -C(CH3)2-C2H5 4-QCF3 -C~cH3)2-c2H5 2-Cl, 4-CF3 -C(cH3)2-c2H5 4-F -C~CH3)2-C3~17 2-Cl -C~CH3)2-C3H7 2,4-C12 -C~CH3)2-C3H7 4-CF3 C( 3)2 3 7 4-OCF3 -C~CH3)2-C3H7 2-Cl, 4-CF3 -C~CH3)2-C3H7 4-Cl -C(cH3)(c2~15~2 4-1~ -C~c~13)(c2H5)2 2-Cl -c(c~l3)~c2~l5)2 2,4-C12 -C(C~13) ~C2~15)2 ~-C~3 -C(C~13)(C2ll5)2 4-OC~3 -C(cH3)(c2H5)2 2-Cl, 4-C~3 -C(C~13)(C21-15)2 ~'79352 The reduction of the triazolyl-propenones according to the invention to yield the corresponding triazolyl-propenols is shown in the following. If, for example, 1-(4-chlorophenyl)-4-methyl-4-phenyl-2-(1,2~4-triazol-l-yl)-l-penten-3-one andsodium borohydride are used as starting sub-stances, the course of the reaction is illustrated by the following equation:

Cl ~ CH= Cl-CO- ~ ~ NaBH4> Cl _ ~ CH=CI- lH-C -N N CH3 ~N I 1 3 N ~ N _ E/Z-isomer mixture E/Z-isomer mixture If, for example~ l-methylcycloprop-l-yl 1-(1,2,4-triazol-l~yl)-2-(4-`chloro-phenyl)-ethen-l-yl ketone and aluminum isopropylate are used as start-ing substances, the course of the reaction is illustrated by the following equation:

CH CH
Cl ~ CH=~-CO ~ ~ Al(OC3H7-i)3 ~ Cl ~ CH-I-C
~ ~ N N

E/Z-isomer mixt~lre Z-isomer '~'he following examples show the preparation of the triazolyl-propen-ones of fo~m~la (II) according to the ;.nvention, and their conversion to the corrcspond:ing triazolyl~propenols.
es 1 and 2 ~L~L79135~

Cl ~ - CH = C - CH - C -~ ~ CH3 N
Example (1) = Z-isomer Example (2) = E-isomer 16 g (0.045 mole) of 1-(4-chlorophenyl)-4-methyl-4-phenyl-2-(1,2,4-triazol-l-yl)-l-penten-3-one as the E/Z-isomer 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 hours and then poured onto water. The organic layer was extracted with ether and the combin~d ether extracts were dried over sodium sulphate. After evaporating 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 136C and the E-isomer having a melting point of 140C.
Preparation of the sta_ting material according to the invention O C~l Cl-- ~ C~l - Cl - C - I -([I-l) N~ N - 7 CH3 I'/Z-isomer mixture 40 g (0.175 mole) of 3-methyl-3-phenyl-1-(1,2,4-triazol-1-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 35~

piperidine for 15 hours, and the water of reaction was separated off azeo-tropically. The toluene solution was washed with water, dried over sodium sulphate and evaporated in vacuo. ~8.6 g ~79% of theory) of 1-(4-chlorophenyl) -~-methyl-4-phenyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one were obtained as the E/Z-isomer mixture with a refractive index nD of 1.6023.

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

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,~-triazole in 200 ml of acetonitrile.
The reaction mixture was heated under reflux for 18 hours and filtered when cold and the filtrate was evaporated in vacuo. The resulting oil was dissolved in chloroform and the chloroform solutionwaswashed wit~ water, dried over sodium sulphate and evaportated in vacuo. 106 g (88% of theory) of

3-methyl-3-phenyl-1-(1,2,4-triazol-1-yl)-butan-2-one were obtained and could be purified by chromatography on silica gel 60 (~erck)/chloroform: refractive index nD = 1.5~25.
ÇH3 c~l3 10 ml (0.122 mole) of sulphuryl chloride were added dropwise to a solution o~ L6.2 g ~0.l mole) of 3-methyl-3-phenyl-butan-2-one in 50 ml of benzene at ~0C. The mixture was kept at 60C, until the evolution of gas had ended, and was then distilled. 15.~ g t78.5% of theory) of 1-chloro-3-methyl-3-phenyl-bwtan-2-one with a boiling point of 80 to 85C/O.l mm ~Ig and a refrac-1~9352 tiva index n20 of 1.5310 were obtained.
Example_3 Cl _ ~ CH = I - CH ~ CH C 2 3 (3) N ~
E-isomer 2.88 g (9.5 mole) of the E-isomer of 1-(4-chloro-phenyl)-4,4-dimethyl=2-(1,2J4-triazol-1-yl)-1-hexen-3-one were dissolved in 20 ml of isopropanol, and 180 mg (4.75 mmoles) of sodium boronate were added. After stirring the mixture at room temperature for 15 hours, the isopropanol 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)-l~hexen-3-ol of melting point 130C were obtained.

Preparation of the starting material according to the invention Il 1 3 Cl _ ~ CH = C~ - C - IC - CH2 - CH3 ~ ~N C~13 N 11 ~/Z-lsomer mixture (II-2) and E-isomer (I~-3) 81.5 g (0.45 mole) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-pentan-2-one and 63.2 g (0.45 mole) of 4-chloro-benzaldehyde in 500 ml of toluene were heated under reflux with 12.5 ml oE acetic acid and ~.5 ml oE piperidine for 15 hours, and the water oE reactionwas removed azeotropically. The toluene solution was washed with water, dried over sodium sulphate and evaporated in ~17~3~2 vacuo. 127 g (93% of theory) of 1-(4-chlorophenyl)-4~4-dimethyl-2-(1,2,4-triazol-l-yl)-l-hexen-3-one were obtained as the E/Z-isomer mixture of boiling point 150 to 160~C/0.1 mm Hg.
After leaving the product to stand at room temperature for several days, the E-isomer of 1-(4-chlorophenyl)-4~4-dimethyl-2-(1,2,4-triazol-1-yl)-l-hexen-3-one of melting point 90C crystallised out.

(III-2) I N - CH - C0 - C - CH2CH3 106 g (0.55 mole) of 1-bromo-3,3-dimethyl-pentan-2-one were added dropwise to a mixtu~e of 62.1 g (0.9 mole) of 1,2,4-triazole, 95.4 g ~0.69 mole) of potassium carbonate and 600 ml of acetone at 55C. After st~rring the mixture for 15 hours, it was filtered and the filtrate was evaporated in vacuo. The oil which remained was purified by chromatography (silica gel 60 (Merck)/chloroform).
85.6 g (86% of theory) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-penten -2-one with a refractive index n20 of 1.4805 were ob~ained.

Br-CH -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 g (0.6 mole) of 3,3~din)ethylpentan-2-OTIO :in 300 ml of mcthyl alcohol at 0 to 5C and the reaction ~ixture was sub-sequently stirred for 15 minutes. It was poured OTltO ice, the organic phase was scparated off, washed with water, dried over sodium sulphate and filtered and the filtrate was evaporated. The crude product was distilled in vacuo.
101 g (87% of theory) of l-bromo-3,3-dimethylpentan-2-one with a boiling point of 80 to 88C/ll mm Hg and a refractive index n~ of 1.4685 were obtained.

Example 4 Cl ~ CH = IC-CH - ~ - CH2C~3 (4) ~ N~ N CH3 N ~ Z-isomer 30.35 g ~0.1 mole) of 1-~4-chlorophenyl)-4,4-dimethyl-2-~1,2,4-triazol-l-yl)-l-hexen-3-one as the E/Z-isomer mixture ~compare the prep~ration of the starting material in Example 3) were reduced with sodium boronate in a manner corresponding to that in Example 3. The resulting oil ~30.5g) was chromatographed on silica gel 60 ~Merck)/chloroform. lhe fractions of melting point 100 to 108C obtained after evaporating offthe chloroform were combined, and recrystallised twica from acetonitrile. The ~-isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-~1,2,4-~riazol-1-yl)-1-hexen-3-ol of melting point 119C was obtained.
Example 5 Cl ~ CH = ~ - CH

N
E-isomer 3.5 g ~12.2 mmoles) of the E-isomer of 1-~4-chloro~phenyl)-3-~1-methylcycloprop-l-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 100 ml of isopropanol, and a solution of 0.32 g ~8.5 mmoles) of sodil~m boronatc in 20 ml of water was addcd dropwise at -5C. Aeter 9U minutes, 10 ml o~ acetona were added dropwise and the reaction m:ixture was evaporated in vacuo. The residue was dissolved in methylene chloride and the solution was washed with water. The organic phase ~:IL7~35~

was dried over sodium sulphate and filtered and the iltrate was evaporated in vacuo. After purification of the residue by column chromatography, 1.7 g (48% oE theory) of the E-isomer of 1-(4-chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,~-traizol-1-yl)-1-propen-3-ol of melting point 110C were obtained.
Pr~paration of the starting material according to the invention (II-4~ Cl ~ CH = C - CO ~

~ F.-isomer This compound was obtained as described in following Example 6.
Ex mple 6 Cl ~ CH = C - CH ~ (6) ~N
N ¦ Z-isomer 10.0 g (3.48 mmoles) of 1-(4-chlorophenyl)-3-~1-methylcycloprop-1-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 aluminum isopropylate in 300 ml of boiling isopropanol were heated for 6 hours; during this procedure isopropanol and acetone were contin-- uously distilled off over a 30 cm Vigreux column, until acetone could no longer be d~teC~edin the distillate. The solution was then evaporated and ice/
hydrochlor:i.c acicl was adcled to the residùe. AEter extraction with ether, thecombined ~.thcr extracts were washed with water, dried over sodium sulphate and Eiltcrecl and the filtrate was evaporated. The oil which remained was chroma-tographed over silica gel 60 (Merck)/chloroform. The first fractions gave, afterevaporating o:Ef the solvent~ 3.~ g of the ~-isomer of 1-(~-chlorophenyl)-3-~L~ 7~3S~:

(l-methylcycloprop-l-yl)-2-(1,2,4-triazol-1-yl)-propen-3-ol of melting point 89C.
The next fractions gave, after evapor~ting off the solvent, 7.8 g of the Z-isomer of 1-(4-chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-l-yl)-l-propen-3-ol of melting point 124C.
Preparation of the starting material accordi~g to the invention II-s) Cl- ~ CH - ~C - CO ~

~ E/Z-isomer mixture 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-~1,2,4-triazol-1-yl)-l-propen-3-one of melting point 82C was obtained by reacting l-methyl-1-(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-methylcyclopropane were added dropwise to a suspension of 27.6 g (0.4 mole) o 1,2,4-triazole and 41.4 g (0.3 mole) of potassium carbonate in 500 ml of acetone at 60C. After heating the mixture to 60C for 15 hours, the salts were filtered off and the filtrate was evaporated in vacuo. The oil which remain~d was purified by chromatography (silica gel 60 (Merck)/chloroform).
35.7 g (90% oE theory) of l-mothyl 1-~1,2J4--triazol-1-yl-acetyl)-cyclopropane oE melting point 58C were obtained.

\c~l3 Br C~l2 C

~l~9~S~

15 ml of bromine, dissolved in 75 ml of chloroform, were added dropwise to a solution of 29.4 g ~0.3 mole) of l-acetyl-l-methylcyclopropane in 150 ml of methyl alcnhol.
The solution was stirred at 10C until i~ was completely decolorised, and was poured onto ice and washed with water. The chloroform phase was dried over sodium sulphate and filtered, the filtrate was evaporated ~nd the residue was dis~illed.
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.
_xample 7 Cl- ~ CH = C - CH - C - COOC2H5 (7) 'N`'N CH3 ~ ~ Z-isomer 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-1-yl)-1-penten-3-one, 37.6 g (0.1825 mole) of aluminum isopropylate and 350 ml of isopropanol was heated to the boiling point, and acetone was distilled off azeotropically, as a mixture with isopropanol, over a Vigreux column. The solution was poured onto ice-cold dilute hydrochloric acid and extracted by shaking with methylene chlor-ide. The organic phase was separated oef, dried over sodium sulphate, filtered and evaporated. The oil which remained was stirred with petroleum ether nnd the resulting crystals were filtered off and rinsed with diisopropyl 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 oE melting point 90C were 3L~ 7~3~2 obtained.
Preparation'of the starting material according to'the invention (II-6) Cl ~ CH = C~ - C0 - I - COOC2H5 Z-isomer A mixture of 90 g (0.4 mole) of dimethyl-(1,2,4-triazol-1-yl-acetyl)-acetic acid ethyl e~ter, 56.2 g (0.4 mole) of 4-chlorobenzaldehyde, 12 g of ac0tic acid and 5 ml of 2,6-dimethylmorpholine in 300ml 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)-l-penten-3-one with a refractive index nD of 1.5751 were obtained.

N ~ ICH3 (III-4) ~ N - CH2 C0 - C - COOC2H5 165.9 g (0.7'mole) of bromoacetyl-dimethyl-acetic acid ethyl ester were added dropwise to a suspension of 96.7 g (1.4 moles) of 1,2l4-triazole and 144.9 g (1.05 moles) of potassium carbonate in 1,200 ml of acetone at 25C. After stirring the mixture for 15 hours, the salts wer~ fiJtered off and the filtrate was evaporated. The oil wllich remained was purified over silica gel 60 (~erck). 120.7 g (76.6% of theory) of dimethyl-(1,2,~-triazol-1-yl-acetyl)-acetic acid ethyl ester with a refractive index n~ of 1.4770 were obtained.

, `` 1179352 Br-CH2-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 1,000 ml of methyl alcohol at 0C.
After stirring the mixture at room tempera~ure for 15 hours, it was poured onto ice, the chloroform phase was separated off, washed with water, dried over sodium sulphate and evaporated and the residue was distilled. 780 g ~88%
of theory) of bromoacetyl-dimethyl-acetic acid ~thyl 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 ~H
CH = C - CH - X (I) ~n N l ~L~L7~35;2 Ex- Melting ample Rn Xpoint (C) ... ... ~
I-8 4-Cl -C~CH3)2-C3H7142(Z-Isomer) I-9 4-Cl -C~CH3)2-C3H7110~E-Isomer) I-10 4-F -C~CH ) -COOC H80~Z-Isomer) I-ll 2-Cl,4-CF3 -C~cH3)2-cc2 587~Z-Isomer) I-12 4-F CH ~ 124~E-Isomer) I-13 4-F ~H3 ~ I 106(Z-Isomer) I-14 2-Cl ~ 148(Z-Isomer) I-15 2-Cl ~ 128~E-Isomer) I-16 2,4-C12 ~ 148~Z-Isomer) I-17 2,4-C12 ~ 126~E-Isomer) I-18 4-CF3 ~ 133(Z-Isomer) I-19 4-CF3 C ~ 120(E-Isomer) I-20 2-Cl,4-CF3 CH ~ 141~Z-Isomer) I-21 2-Cl,4-CP3 CH 140~E-Isomer) I-22 4-OCF3 CH 104(Z-Isomer) I-23 4-OCF3 ~ 94(E-Isomer) I-24 4-OCI-13 _ ~ 126(Z-Isom~3r) 1-2g 4-OCH3 ~ 132(E-Isomer) ~L1793S2 Ex- Melting ample Rn X point ~C) No.
_ __ _ I-26 2,4-C12 -C~CH3)2-C2H5 140(Z-Isomer) I-27 2,4-C12 -C(c~l3)2 { O } C] 152~Z-Isomer) I-28 2,4-Cl-C~CH ) -COOC H5lOO(Z-Isomer) I-29 2,4-C12 C2 ~ 126~Z-Isomer) I-30 2,4-C12 -C~CH3)2 ~ Cl 158~E-Isomer) I-31 2,3-C12 3 ~ 130~Z-Isomer) I-32 3,4-ClCH3 ~ 118~Z-Isomer) I-33 3,4-C12 CH3 ~ l 80~E-Isomer) I~34 2,3-C12 CH3 ~ 126~E-Isomer) I-35 2,~-C12 C2H5 ~ 126~E-Isomer) I-36 3-CF3 3 ~ 130~Z-Isomer) I-37 3-CF3H3 ~ 95~E-Isomer) I-38 2-CH3CH3 ~ 146~Z-Isomer) :[-39 2-CH3CH ~ 132~-Isomer) ~ he following starting substances o~ the formula ~II) were obtained in a manner corresponding to that in the foregoing preparat.ive Examples: 1 to 3 and 5 to 7:

a35~:

Table 3 ~ - CH = Cl - CO - X (II) Rn N _ ~

Ex- Melting point (C) No. R~ X r refractive _ II-7 4-C1 -(CH3~2-C3H7 89(E-Isomer) II-8 4-C1 -~C~13)2-C3H7 1.5492 ~E/Z-mixture) II-9 2-C1~4-CF3 -C(CH3)2-COOC2~15 104(Z-Isomer) II-10 4-F CH ~ 74(E-Isomer) II-ll 2-C1 1.5929 (E-Isomer) II-12 2-C1 ~ 1.5843 (E/Z-mixture) II-13 2,4-Cl2 CH ~ 84(E-Isomer) II-14 2,4-C12 C~l 1.5978 ~E/Z-mixture) II-15 4-CF3 3 ~ 1.5142 ~E-Isomer) II-16 4-CF3 ~ 1.5440 (E/Z-mixture) II-17 4-OCF3 C~ ~ 1.5334 (E-Isomer) II-18 4-OCF3 C~ ~ 1.5362 (E/Z-mixture) II-19 2-C1,4-CF3 CEI~ 1.5232 ~E-Isomer) II-20 2-Cl,4-C~73 ~ 1.5334 ~E/Z-mixture) II-21 4-OCH3 C ~ 92 ~E-I~omer) II-22 4~0CH3 ~ 1.5989 ~E/Z-mixture) 3S~

The following precursors of the formula (III) were obtained in a manner corresponding to that in the foregoing Preparative Examples 1 to 3, 6 and 7:
Table 4 N
~ N ~ CH2 ~ C0 - X (III~

Example Melting point ( C) or refractive No, index (n20) ~ _, _ _ _ III-5 -C(CH3)2-C3H7 1.4796 III-6 ¦ -C(CH3)2-C~H7 60C
III-7 1 -C(CH3)2 ~ F oil

Claims (22)

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

1. Triazolylpropenone derivatives of the general formula (II) 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 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, dichlorovinyl, dibromovinyl, methoxy, chlorophenyl, chlorobenzyl, dichlorophenyl, dichlorobenzyl, trimethylene and isobutylene or represents a grouping of the formula -CR1R2-Y, wherein R1 and R2 arc indentical 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.

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 benzy-loxy 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, flourine, chlorine, chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, chlorophenyl, chlorobenzyl, dichloropllenyl, dichlorobenæyl, tri-methylene and isobutylene, or represents grouping of the general formula -CR1-R2-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. 1-(4-Chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-hexen-3-one, E/Z-isomer mixture.

18. 1-(4-Chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-l-yl)-1-hexen-3-one, E-isomer.

19. 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl) -1-propen-3-one, E-isomer.

20. 1-(4-Chlorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl) -1-propen-3-one, Z-isomer.

21. 1-(4-Fluorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol-1-yl)-1-propen-3-one.

22. 1-(4-Fluorophenyl)-3-(1-methylcycloprop-1-yl)-2-(1,2,4-triazol -1-yl)-1-propen-3-one, E-isomer.