CA1185247A - Substituted 1-phenyl-2-triazolyl-pent-1-en-3-ones and process for their production - Google Patents
Substituted 1-phenyl-2-triazolyl-pent-1-en-3-ones and process for their productionInfo
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- CA1185247A CA1185247A CA000441920A CA441920A CA1185247A CA 1185247 A CA1185247 A CA 1185247A CA 000441920 A CA000441920 A CA 000441920A CA 441920 A CA441920 A CA 441920A CA 1185247 A CA1185247 A CA 1185247A
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Abstract
ABSTRACT OF THE DISCLOSURE
Substituted 1-phenyl-2-triazolyl-pent-1-en-3-ones of the formula (II)
Substituted 1-phenyl-2-triazolyl-pent-1-en-3-ones of the formula (II)
Description
This is a divislonal application of Canadian Patent Application Serial No. 391,066 filed November 27, 1981.
The present invention relates to certain new substituted l-phenyl-2-triazolyl-pent-1-en-3-ones and to a process for their production. The parent application relates to the corresponding alcohols which may be prepared by reducing the ke-tones of the present invention.
According to the present invention, it is provided, as a new compound, a substituted l-phenyl-2-triazolyl-pent-1-en-3-one Of the general formula ~ ~- CH = C - CO - C(CH3~3 (II) y~
in which X represents a halogenoalkyl~ halogenoalkoxy, halogenolkyl-thio, alkylthio, nitro, hydroxyl, dialkylamino or alkylcarbonyloxy radical, or represents a benzyloxy radical unsubstituted or substituted in the phenyl part with fluorine, chlorine,bromine or alkyl with 1 or 2 carbon atoms, Y represents a halogen atom, an alkyl, alkoxy or cyano radical or phenyl or phenoxy radical, each unsubstituted or substituted in the phenyl part with flourine, chlorine, bromine, or alkyl with l or 2 carbon atoms, _ is 1, 2 or 3~
n is 0, 1, 2, 3 or 4, and _ _ -~ n = 1 to 5.
The compounds aeeording to the present invention, of the formula (II), oeeur as the geometrieal E (trans) and 2 (cis) isomers.
In the .E, Z nomenclature, the substituents prsent on the double bond are classified aceording to the Cahn-Ingold-Prelog Rule in accordanee with deereasing priority. If the preferred substituents are on the same side - la -of the double bond, the compound is in the Z configuration (derived from the Germa~ word zusammen, that is to say together), whilst if they are on opposite sides, the compound is in the E configuration (derived from the German word entgegen, that is to say opposed).
The present invention relates both to the indlvidual isomers and to the isomer mixtures.
According ~o the present invention, i-t is further provided a process for the production of a compound of the present invention, wherein a triazolylpinacoline of the formula H2C - CO - C(CH3)3 (III) N~
N
is reacted with an aldehyde of the general formula ~ CH = O (IV) Yn in which X, Y, m and _ have the same meanings as defined above, in the presence of a solvent and in the presence of a catalyst.
The compounds of the present invention may be reduced into substituted l-phenyl-2-triazolyl-pent-1-en-3-ols, which exhibit pcwerful plant growth-regulating properties and powerful fungicidal properties.
~ ~5~
Preferred substi~uted l-phellyl-2-triazolyl-pent-1-en-3-ones o formula (II) according to the present invention are those in which X represents a halogenoalkyl, halogenoalkoxy or halogenoalkylthio radical, each with l to 2 carbon atoms and up to 5 identical or different halogen atoms ~such as, in par*icular, fluorine and chlorine atoms), an alkylthio radical with 1 to 4 carbon atoms, a nitro or hydroxyl radical, a dialkylamino radical with l to 4 carbon atoms in each alkyl part, an alkylcarbonyloxy radical with 1 to 4 carbon atoms in the alkyl part or a benzyloxy radical ].0 which is optionally substituted in the phenyl part (preferredsubstituent~s) being selected from fluorine, chlorine, bromine and alkyl with 1 or 2 carbon atoms), Y represents a fluorine, chlcrine or bromine atom, an alkyl or alkoxy radical, each with 1 to 4 carbon atoms, a cyano radical or an optionally substituted phenyl or phenoxy radical(preferred substituent(s) beihg selected from fluorine, chlorine, bromine and alkyl with 1 or 2 carbon atoms), m i5 1 or 2 and n is 0, 1, 2 or 3.
Particularly preferred compounds of the formula ~II) according to the present invention are those in which X represents a trifluoromethyl, difluorochloromethyl, fluorodichloro-methyl, trichloromethyl, 1,1,2~trifluoro-2-chloro-ethyl, trifluoromethoxy or trifluoromethylthio radical, a 1,1,2-trifluoro-2-chloro-ethoxy or -ethylthio radical, a methylthio, nitro, hydroxyl, dimethylamino, acetoxy or tert.-butylcarbonyloxy radical or a benzyloxy radical which optionally has one or two identical or different substituents selected from fluorine, chlorine and methyl, Y represents a fluorine or chlorine atom or a methyl, ethyl, isopropyl, tert.-butyl, methoxy, isopropoxy or cyano radical, or a phenyl or phenoxy radical which optionally has one or two identical or diferent substituents selected from fluorine, chlorine and methyl, _ is 1 or 2 and n iS O, 1 or 2.
The solvents which can be used for the preparation of the l-phenyl-2-triazolyl-pent-1-en-3-ones of the formula (II) are preferably inert organic solvents. These preferably include alcohols ~such as methanol and ethanol), e~hers ~such as tetrahydrofuran and dioxane), aliphatic and cycloaliphatic 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 prepaTation of the compounds of the formula ~II) is carried out in the presence of a catalyst. Any of the acidic ~nd, in particular, basic catalysts which are conventionally usable, as well as their buffer mixtures, can be employed. They preferentially include Lewis acids ~such as boron trifluoride, boron trichloride, tin tetrachloride or titanium tetrachloride), organic bases ~such as pyridine, 2,6-dimethylmorpholine and piperidine) and, in particular, piperidine acetate.
In carrying out this process, the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at a temperature between 20 and 160C, preferably at the boiling point of the particular solvent.
~ t7 In carTying out this process~ 1 to 1.5 mol of aldehyde of the formula (IV) and catalytic to 0.2 molar amounts of catalyst are employed per mol of triazolylpinacoline of the formula ~III). The products of the formula (II~ are preferably obtained as E/Z isomer mixtures. Separation into the pure isomers is possible in a conventional manner, for example by crystallisation or by chromatographic separation processes.
The l-phenyl-2-tria~olyl-pent-1-en-3-ones of the formula ~II) are generally interesting intermediate products for example for ~he preparation of the compounds according to the invention, of the formula (I). Used in appropriate concentrations, they also exhibit growth-regulating and fungicida]
properties.
The reduction of the ketones of formula ~II) according to the invention for the production of the corresponding alcohol of formula ~I) is carried out in the usual manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent, or by reaction with alurninium isopropylate in the presence of a diluent. The starting compounds of the formula (II) can be employed in the reduction as the E/Z isomer mixture or as pure isomers.
If complex hydrides are used, suitable diluents for the reaction are polar organic solvents. These include alcohols ~such as methanol, ethanol, butanol and isopropanol) and ethers ~such as diethyl ether or tetrahydrofuran).
The reaction is in general carried out at a ternperature between -10 and +30C, preferably at a temperature between -10 and 20C. For this purpose, about 1 mol of a complex hydride (such as sodium borohydride, calcium borohydride or lithium alanate) is employed per mol of the ketone of the formula ~II).
The isolation of the compound may be carried out in a conventional manner, as is any separation of the E/Z isomer mixtures which are always formed on reduction with complex hydrides if E/Z isomer mixtures are used as starting materials of the formula (II).
If aluminium isopropylate is used, preferred suitable diluents for the reduction reaction are alcohols (such as isopropanol) or inert hydro-carbons (such as benzene). The reaction temperatures can~ once again, be varied within a substantial range; in general, the reaction is carried ouk at a temperature between 20 and 120C, preferably at a temperature between 50 and 100C. To carry out the reaction, about 1 to 2 mol of aluminlum isopropylate are employed per mol of the corresponding ketone of the formula (II). The alcohols may be isolated in a conventional manner.
On reduction with aluminium isopropylate, exclusively the Z-isomers are obtained.
An unambiguous characterising feature of the two geometrical isomers is the Hl nuclear resonance of the two triazole protons. The difference in the shift values for these two protons is about twice as great in the E forms as in the corresponding Z forms.
Experience to date of the mode of action of plant growth regulators has sho~m that an active cornpound can also exert several different actions on plants. The actions of the compounds depend essentially on the point in time at which they are used, relative to the stage of development of the plant, and on the amounts of active compound applied to the plants or their environment and the way in which the compounds are applied. In every case, growth rogulators are intended to influence the crop plants in the particular manner desired.
Plant gro~llth regulating compounds can be employed, for example, to inhibit vegetative growth of the plants. Such inhibition of growth is inter alia of economic interest in the case of grasses, since it is thereby possible to reduce the frequency of cutting the grass in ornamental gardens, parks and sportsgro~mds, at verges, at airports or in fruit orchards. The inhibition of growth of herbaceous and woody plants at verges and in the vicinity of pipelines or overland lines or, quite generally, in areas in which heavy additional growth of plants is undesired, is also of importance.
The use of growth regulators to inhibit the growth in length of cereals is also important. The danger of lodging of the plants before harvesting is thereby reduced or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals, which again counteracts lodging.
Use of growth regulators for shortening and strengthening the stem enables higher amounts of fertiliser to be applied to increase the yield, without danger of the cereal lodging.
In the case of many crop plants, inhibition of the ve~etative growth maXes 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 vegetative 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 tha~ 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 cane, pineapples and citrus fruit or to increase the protein content in soya or cereals. Using growth regulators it is also possible, for example, to inhibit the degradation of desired constituents, such as, for example, sugar in sugar beet or sugar cane, before or after harvesting. It is also possible 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 regula~ors. 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 ornamental plants, also in connection with growth inhibition.
On the other hand, however, it is also possible to inhibit the growth of side shoots. There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes.
The amount of leaf on plants can be controlled, under the influence of growth regulators, so that 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 vi*iculture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators.
On the one hand, it is possible to prevent premature shedding of fruit.
Ilowever, on the other hand, shedding of fruit, or even the fall of blossom, canbe promoted up to a certain degree (thinning out) in order to interrupt the alternance. By alternance there is understood the peculiarity of some varieties of fruit to produce very different yields from yaar to year, for endogenic reasons. Finally, using growth regulators it is possible to reduce the force required to detach the fruit at harvest time so as to permit mechanical 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 is thereby 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 regulators. This provides the preconditions for being able to carry out complete mechanical or manual harvesting in only a single pass, for example in the case of tobacco, tomatoes or coffee.
Using growth regulators, it is furthermore possible to influence the latent period of seeds or buds of plants, so that the plants, such as pineapple or ornamental plants in nurseries, germinate, shoot or blossom at a time at which they normally show no readiness to do so. Retarding the shooting of buds or the germination of seeds with the aid of growth regulators can be desirable in regions where frost is a hazard, in order to avoid damage by late frosts.
Finally, the resistance of plants to frost, drought or a high salt content in ~he soil can be induced with growth regulators. Cultivation of _ 9 _ p'~ ~
plants in regions which are usually ~msuitable for this purpose thereby becomes possible.
The preferred time o-f application of the growth regulators depends on the climatic and vegetative 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 cornpounds 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.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes~ Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at ~he concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating those fungi which cause powdery mildew diseases, thus, for combating Erysiphe species, such as against the powdery mildew of barley or cereal causative organism (Erysiphe graminis); or for combating Venturia species, such as against the apple scab causative organism ~Fusicladium dendriticum).
It should be emphasised that the substances according to the invention not only display a protective action but in some cases also have a systemic action. Thus, it is possible to protect plants from fungal attack if the active compounds are fed to the above-ground parts of the plant via the soil and the root or via the seed.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as 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 liquefi.ed gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsi~ying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydro-carbons, such as chloroben~enes, 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 dim~thylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quart~, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepio]ite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdus~, 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 formulations.
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, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to ~5 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 known active compounds, such as fungicides, insecticides, acaricides and herbicides, and as mixtures with :Eertilisers and other growth regulators.
The active compounds can be used as SUC]l or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. They are used in the customary manner, for example by watering, spraying, atomising, scattering, dusting, :Eoaming, brushing and so on. It is furthermore possible to apply the active compounds by the ultra-low volume process or to inject the active compound itself into the soil. The seeds of the plants can also be treated.
When the compounds according to the invention are used as plant growth regulators, the amounts used can be varied within a substantial range.
In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, are used per hectare of soil surface.
When using the compounds according to the invention as fungicides, the amount used can again be varied within a substantial range, depending on the type of application. Thus, for example, the active compound concentrations in the use forms, especially for the treatment of parts of plants, are in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment 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. In the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably of 0.0001 -to 0.02%, at the action site are required.
The present invention also provides plant growth regulation or fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The p-resent invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereoE, a compound of the present inven~ion 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 the plants, or to a habitat thereof, a compound of the present invention alone or in the iorm of a composition containing as active ingredient a compound of the present invention in admi~ture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by 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.
The present invention ~urther 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.
The following examples illustrate the preparation of the ketones of formula (II) according to the present invention and their use as the intermediate for preparing the alcohols of formula ~I), as well as the biological properties of the alcohols.
Preparative Examples Example 1 CF3 Oll - CH = C - CH - C(CH3)3 (I) ~ N ~ Z isomer ~L~
~<
CH = C - C0 -C(CH3)3 (II-l) ~ F isomer 44.1 g (0.1365 mol) of 4,4-dimethyl-2-(1,2,'1-triazol-1-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-one, as an E/Z isomer mixture, and 27.9 g (0.1365 mol) of aluminium isopropylate were heated for 7 hours in 3S0 ml of boiling isopropanol; at the same time, isopropanol and acetone were continuously distilled off through a 30 cm Vigreux column, until acetone was no longer detectable in the distillate. The solution was then decomposed with ice/hydrochloric acid. After extraction with methylene chloride, the organic phase was dried over sodium sulphate, filtered and evaporated in vacuo.
The semi-crystalline mass which remained ~Yas chromatographed over silica gel 60 (Merck)/chloroform. The first fractions gave after evaporating off the solvent, 10.8 g (24% of *heory) of E isomer of 4,4-dimethyl-2-(1,2,4-triazol-l-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-one, of melting point 82C.
The next fractions gave, after evaporating off the solvent, 12.8 g (2~% of theory) of Z isomer of 4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-ol, of melting point l36C.
, 3~ t~ 7 Preparation of the starting product ~a compound of formula ~II)) _ Cll = C - C0 - C~CH3)3 ~ 2) N ~
~ E/Z isomer mixture 25.2 g ~0.15 mol) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 26.1 g (0.15 mol) of 2-trifluorobenzaldehyde in 350 ml of toluene were heated under reflux with 9 g of acetic acid and 3.6 ml of dimethylmorpholine for 20 hours, the water of reaction being removed azeotropically. The toluene solution was washed with water, dried over sodium sulphate, filtered and evaporated in vacuo. 44.9 g (93% of theory) of 4,4-dimethyl-2-(1,2,4--triazol-l-yl)-l-(2-trifluoromethylphenyl)-pent-1-en-3-one were obtained as an E/Z isomer mixture, of a refractive index n~ = 1.5113.
Example_2 r~~_~ CF3 CH = C - CH - C(CH3~3 (2) M
~ E isomer A solution of 0.85 g (0.0242 mol) of sodium boranate in 20 ml of water was added drop~ise to 10.7 g ~0.0345 mol) of the E isomer of 4,4-dimethyl-
The present invention relates to certain new substituted l-phenyl-2-triazolyl-pent-1-en-3-ones and to a process for their production. The parent application relates to the corresponding alcohols which may be prepared by reducing the ke-tones of the present invention.
According to the present invention, it is provided, as a new compound, a substituted l-phenyl-2-triazolyl-pent-1-en-3-one Of the general formula ~ ~- CH = C - CO - C(CH3~3 (II) y~
in which X represents a halogenoalkyl~ halogenoalkoxy, halogenolkyl-thio, alkylthio, nitro, hydroxyl, dialkylamino or alkylcarbonyloxy radical, or represents a benzyloxy radical unsubstituted or substituted in the phenyl part with fluorine, chlorine,bromine or alkyl with 1 or 2 carbon atoms, Y represents a halogen atom, an alkyl, alkoxy or cyano radical or phenyl or phenoxy radical, each unsubstituted or substituted in the phenyl part with flourine, chlorine, bromine, or alkyl with l or 2 carbon atoms, _ is 1, 2 or 3~
n is 0, 1, 2, 3 or 4, and _ _ -~ n = 1 to 5.
The compounds aeeording to the present invention, of the formula (II), oeeur as the geometrieal E (trans) and 2 (cis) isomers.
In the .E, Z nomenclature, the substituents prsent on the double bond are classified aceording to the Cahn-Ingold-Prelog Rule in accordanee with deereasing priority. If the preferred substituents are on the same side - la -of the double bond, the compound is in the Z configuration (derived from the Germa~ word zusammen, that is to say together), whilst if they are on opposite sides, the compound is in the E configuration (derived from the German word entgegen, that is to say opposed).
The present invention relates both to the indlvidual isomers and to the isomer mixtures.
According ~o the present invention, i-t is further provided a process for the production of a compound of the present invention, wherein a triazolylpinacoline of the formula H2C - CO - C(CH3)3 (III) N~
N
is reacted with an aldehyde of the general formula ~ CH = O (IV) Yn in which X, Y, m and _ have the same meanings as defined above, in the presence of a solvent and in the presence of a catalyst.
The compounds of the present invention may be reduced into substituted l-phenyl-2-triazolyl-pent-1-en-3-ols, which exhibit pcwerful plant growth-regulating properties and powerful fungicidal properties.
~ ~5~
Preferred substi~uted l-phellyl-2-triazolyl-pent-1-en-3-ones o formula (II) according to the present invention are those in which X represents a halogenoalkyl, halogenoalkoxy or halogenoalkylthio radical, each with l to 2 carbon atoms and up to 5 identical or different halogen atoms ~such as, in par*icular, fluorine and chlorine atoms), an alkylthio radical with 1 to 4 carbon atoms, a nitro or hydroxyl radical, a dialkylamino radical with l to 4 carbon atoms in each alkyl part, an alkylcarbonyloxy radical with 1 to 4 carbon atoms in the alkyl part or a benzyloxy radical ].0 which is optionally substituted in the phenyl part (preferredsubstituent~s) being selected from fluorine, chlorine, bromine and alkyl with 1 or 2 carbon atoms), Y represents a fluorine, chlcrine or bromine atom, an alkyl or alkoxy radical, each with 1 to 4 carbon atoms, a cyano radical or an optionally substituted phenyl or phenoxy radical(preferred substituent(s) beihg selected from fluorine, chlorine, bromine and alkyl with 1 or 2 carbon atoms), m i5 1 or 2 and n is 0, 1, 2 or 3.
Particularly preferred compounds of the formula ~II) according to the present invention are those in which X represents a trifluoromethyl, difluorochloromethyl, fluorodichloro-methyl, trichloromethyl, 1,1,2~trifluoro-2-chloro-ethyl, trifluoromethoxy or trifluoromethylthio radical, a 1,1,2-trifluoro-2-chloro-ethoxy or -ethylthio radical, a methylthio, nitro, hydroxyl, dimethylamino, acetoxy or tert.-butylcarbonyloxy radical or a benzyloxy radical which optionally has one or two identical or different substituents selected from fluorine, chlorine and methyl, Y represents a fluorine or chlorine atom or a methyl, ethyl, isopropyl, tert.-butyl, methoxy, isopropoxy or cyano radical, or a phenyl or phenoxy radical which optionally has one or two identical or diferent substituents selected from fluorine, chlorine and methyl, _ is 1 or 2 and n iS O, 1 or 2.
The solvents which can be used for the preparation of the l-phenyl-2-triazolyl-pent-1-en-3-ones of the formula (II) are preferably inert organic solvents. These preferably include alcohols ~such as methanol and ethanol), e~hers ~such as tetrahydrofuran and dioxane), aliphatic and cycloaliphatic 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 prepaTation of the compounds of the formula ~II) is carried out in the presence of a catalyst. Any of the acidic ~nd, in particular, basic catalysts which are conventionally usable, as well as their buffer mixtures, can be employed. They preferentially include Lewis acids ~such as boron trifluoride, boron trichloride, tin tetrachloride or titanium tetrachloride), organic bases ~such as pyridine, 2,6-dimethylmorpholine and piperidine) and, in particular, piperidine acetate.
In carrying out this process, the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at a temperature between 20 and 160C, preferably at the boiling point of the particular solvent.
~ t7 In carTying out this process~ 1 to 1.5 mol of aldehyde of the formula (IV) and catalytic to 0.2 molar amounts of catalyst are employed per mol of triazolylpinacoline of the formula ~III). The products of the formula (II~ are preferably obtained as E/Z isomer mixtures. Separation into the pure isomers is possible in a conventional manner, for example by crystallisation or by chromatographic separation processes.
The l-phenyl-2-tria~olyl-pent-1-en-3-ones of the formula ~II) are generally interesting intermediate products for example for ~he preparation of the compounds according to the invention, of the formula (I). Used in appropriate concentrations, they also exhibit growth-regulating and fungicida]
properties.
The reduction of the ketones of formula ~II) according to the invention for the production of the corresponding alcohol of formula ~I) is carried out in the usual manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent, or by reaction with alurninium isopropylate in the presence of a diluent. The starting compounds of the formula (II) can be employed in the reduction as the E/Z isomer mixture or as pure isomers.
If complex hydrides are used, suitable diluents for the reaction are polar organic solvents. These include alcohols ~such as methanol, ethanol, butanol and isopropanol) and ethers ~such as diethyl ether or tetrahydrofuran).
The reaction is in general carried out at a ternperature between -10 and +30C, preferably at a temperature between -10 and 20C. For this purpose, about 1 mol of a complex hydride (such as sodium borohydride, calcium borohydride or lithium alanate) is employed per mol of the ketone of the formula ~II).
The isolation of the compound may be carried out in a conventional manner, as is any separation of the E/Z isomer mixtures which are always formed on reduction with complex hydrides if E/Z isomer mixtures are used as starting materials of the formula (II).
If aluminium isopropylate is used, preferred suitable diluents for the reduction reaction are alcohols (such as isopropanol) or inert hydro-carbons (such as benzene). The reaction temperatures can~ once again, be varied within a substantial range; in general, the reaction is carried ouk at a temperature between 20 and 120C, preferably at a temperature between 50 and 100C. To carry out the reaction, about 1 to 2 mol of aluminlum isopropylate are employed per mol of the corresponding ketone of the formula (II). The alcohols may be isolated in a conventional manner.
On reduction with aluminium isopropylate, exclusively the Z-isomers are obtained.
An unambiguous characterising feature of the two geometrical isomers is the Hl nuclear resonance of the two triazole protons. The difference in the shift values for these two protons is about twice as great in the E forms as in the corresponding Z forms.
Experience to date of the mode of action of plant growth regulators has sho~m that an active cornpound can also exert several different actions on plants. The actions of the compounds depend essentially on the point in time at which they are used, relative to the stage of development of the plant, and on the amounts of active compound applied to the plants or their environment and the way in which the compounds are applied. In every case, growth rogulators are intended to influence the crop plants in the particular manner desired.
Plant gro~llth regulating compounds can be employed, for example, to inhibit vegetative growth of the plants. Such inhibition of growth is inter alia of economic interest in the case of grasses, since it is thereby possible to reduce the frequency of cutting the grass in ornamental gardens, parks and sportsgro~mds, at verges, at airports or in fruit orchards. The inhibition of growth of herbaceous and woody plants at verges and in the vicinity of pipelines or overland lines or, quite generally, in areas in which heavy additional growth of plants is undesired, is also of importance.
The use of growth regulators to inhibit the growth in length of cereals is also important. The danger of lodging of the plants before harvesting is thereby reduced or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals, which again counteracts lodging.
Use of growth regulators for shortening and strengthening the stem enables higher amounts of fertiliser to be applied to increase the yield, without danger of the cereal lodging.
In the case of many crop plants, inhibition of the ve~etative growth maXes 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 vegetative 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 tha~ 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 cane, pineapples and citrus fruit or to increase the protein content in soya or cereals. Using growth regulators it is also possible, for example, to inhibit the degradation of desired constituents, such as, for example, sugar in sugar beet or sugar cane, before or after harvesting. It is also possible 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 regula~ors. 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 ornamental plants, also in connection with growth inhibition.
On the other hand, however, it is also possible to inhibit the growth of side shoots. There is great interest in this action, for example, in the cultivation of tobacco or in the planting of tomatoes.
The amount of leaf on plants can be controlled, under the influence of growth regulators, so that 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 vi*iculture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted.
The shedding of fruit can also be controlled with growth regulators.
On the one hand, it is possible to prevent premature shedding of fruit.
Ilowever, on the other hand, shedding of fruit, or even the fall of blossom, canbe promoted up to a certain degree (thinning out) in order to interrupt the alternance. By alternance there is understood the peculiarity of some varieties of fruit to produce very different yields from yaar to year, for endogenic reasons. Finally, using growth regulators it is possible to reduce the force required to detach the fruit at harvest time so as to permit mechanical 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 is thereby 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 regulators. This provides the preconditions for being able to carry out complete mechanical or manual harvesting in only a single pass, for example in the case of tobacco, tomatoes or coffee.
Using growth regulators, it is furthermore possible to influence the latent period of seeds or buds of plants, so that the plants, such as pineapple or ornamental plants in nurseries, germinate, shoot or blossom at a time at which they normally show no readiness to do so. Retarding the shooting of buds or the germination of seeds with the aid of growth regulators can be desirable in regions where frost is a hazard, in order to avoid damage by late frosts.
Finally, the resistance of plants to frost, drought or a high salt content in ~he soil can be induced with growth regulators. Cultivation of _ 9 _ p'~ ~
plants in regions which are usually ~msuitable for this purpose thereby becomes possible.
The preferred time o-f application of the growth regulators depends on the climatic and vegetative 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 cornpounds 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.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes~ Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at ~he concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating those fungi which cause powdery mildew diseases, thus, for combating Erysiphe species, such as against the powdery mildew of barley or cereal causative organism (Erysiphe graminis); or for combating Venturia species, such as against the apple scab causative organism ~Fusicladium dendriticum).
It should be emphasised that the substances according to the invention not only display a protective action but in some cases also have a systemic action. Thus, it is possible to protect plants from fungal attack if the active compounds are fed to the above-ground parts of the plant via the soil and the root or via the seed.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as 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 liquefi.ed gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsi~ying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydro-carbons, such as chloroben~enes, 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 dim~thylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quart~, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepio]ite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdus~, 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 formulations.
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, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to ~5 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 known active compounds, such as fungicides, insecticides, acaricides and herbicides, and as mixtures with :Eertilisers and other growth regulators.
The active compounds can be used as SUC]l or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. They are used in the customary manner, for example by watering, spraying, atomising, scattering, dusting, :Eoaming, brushing and so on. It is furthermore possible to apply the active compounds by the ultra-low volume process or to inject the active compound itself into the soil. The seeds of the plants can also be treated.
When the compounds according to the invention are used as plant growth regulators, the amounts used can be varied within a substantial range.
In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, are used per hectare of soil surface.
When using the compounds according to the invention as fungicides, the amount used can again be varied within a substantial range, depending on the type of application. Thus, for example, the active compound concentrations in the use forms, especially for the treatment of parts of plants, are in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment 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. In the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably of 0.0001 -to 0.02%, at the action site are required.
The present invention also provides plant growth regulation or fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The p-resent invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereoE, a compound of the present inven~ion 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 the plants, or to a habitat thereof, a compound of the present invention alone or in the iorm of a composition containing as active ingredient a compound of the present invention in admi~ture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by 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.
The present invention ~urther 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.
The following examples illustrate the preparation of the ketones of formula (II) according to the present invention and their use as the intermediate for preparing the alcohols of formula ~I), as well as the biological properties of the alcohols.
Preparative Examples Example 1 CF3 Oll - CH = C - CH - C(CH3)3 (I) ~ N ~ Z isomer ~L~
~<
CH = C - C0 -C(CH3)3 (II-l) ~ F isomer 44.1 g (0.1365 mol) of 4,4-dimethyl-2-(1,2,'1-triazol-1-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-one, as an E/Z isomer mixture, and 27.9 g (0.1365 mol) of aluminium isopropylate were heated for 7 hours in 3S0 ml of boiling isopropanol; at the same time, isopropanol and acetone were continuously distilled off through a 30 cm Vigreux column, until acetone was no longer detectable in the distillate. The solution was then decomposed with ice/hydrochloric acid. After extraction with methylene chloride, the organic phase was dried over sodium sulphate, filtered and evaporated in vacuo.
The semi-crystalline mass which remained ~Yas chromatographed over silica gel 60 (Merck)/chloroform. The first fractions gave after evaporating off the solvent, 10.8 g (24% of *heory) of E isomer of 4,4-dimethyl-2-(1,2,4-triazol-l-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-one, of melting point 82C.
The next fractions gave, after evaporating off the solvent, 12.8 g (2~% of theory) of Z isomer of 4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-ol, of melting point l36C.
, 3~ t~ 7 Preparation of the starting product ~a compound of formula ~II)) _ Cll = C - C0 - C~CH3)3 ~ 2) N ~
~ E/Z isomer mixture 25.2 g ~0.15 mol) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 26.1 g (0.15 mol) of 2-trifluorobenzaldehyde in 350 ml of toluene were heated under reflux with 9 g of acetic acid and 3.6 ml of dimethylmorpholine for 20 hours, the water of reaction being removed azeotropically. The toluene solution was washed with water, dried over sodium sulphate, filtered and evaporated in vacuo. 44.9 g (93% of theory) of 4,4-dimethyl-2-(1,2,4--triazol-l-yl)-l-(2-trifluoromethylphenyl)-pent-1-en-3-one were obtained as an E/Z isomer mixture, of a refractive index n~ = 1.5113.
Example_2 r~~_~ CF3 CH = C - CH - C(CH3~3 (2) M
~ E isomer A solution of 0.85 g (0.0242 mol) of sodium boranate in 20 ml of water was added drop~ise to 10.7 g ~0.0345 mol) of the E isomer of 4,4-dimethyl-
2-~1,2,4-triazol-1-yl)-1-(2-trifluoromethylphenyl)-pent-1-en-3-one (compare Example 1) and 2.45 g ~0.0233 mol) of calcium chloride in 150 ml of isopropanol at 5C.
After 18 hours, 20 ml of acetone were added dropwise. After evapora~ing off the solvent, the residue which remained was stirred into water and the mixture was extracted with methylene chloride. The organic phase was s~
separated off, dried over sodium sulphatel filtered and evaporated in vacuo.
The crystal]ine mass was stlrred with diisopropyl ether and filtered off.
7.2 g (66.7% of theory) of the E isomer of 4,4-dimethyl-2-~1,2,4-triazol-1-yl)-1-(2-trifluoromethylphenyl)-~ent-1-en-3-ol, of melting point 165C, were obtained.
Example 3 F3C ~ H = C - CH - C~CH3)3 (3) ~ N ~
A solution of 5.05 g ~Q.13 mol~ of sodium boranate in 100 ml of water was added dropwise to 61.5 g ~0.19 mol) of 4,4-dimethyl-2-~1,2,4-triazol-1-yl)-1-~4-trifluoromethylphenyl)-pent-1-en-3-one, in the form of the E/Z
isomer mixture, and 14.1 g ~0.1275 mol) of calcium chloride in 400 ml of isopropanol at -5C. After 15 hours, 60 ml of acetone were added dropwise.
After ev~porating off the solvent, the residue which remained was stirred into water and the mixture was extracted with ethyl acetate. The solution was dried over sodium sulphate, filtered and evaporated in vacuo. 60.3 g ~97% of theory) of 4,4-dimethyl-2-~1,2,4-triazol-1-yl~1~4-trifluoromethyl-phenyl)-pent-l-en-3-ol were obtained as the E/~ isomer mixture, of melting point 54-55C.
The following compounds of the general formula ~I) were obtained analogously:
Table 1 _ _ X OH
~ - ~1 = C - Cll- C~CH3)3 ~I) ~1 Ex-NOmp,le Xm n Melting point ( C) or refractive index ~nD ) _ 4 4-OH _ 168 (E/Z mixture) 4-OH 3-OCH3 135 (E/Z mixture) 6 2-0ll 3,s-C12 158 (E/Z mixture) 7 4-N(CH3)2 ~ 140 (E/Z mixture) 8 4-0-CH2- ~ - 109 (E/Z mixture) 9 4-NO2 - 126 (Z isomer) 4-NO2 - 188 (E isomer) 11 4-CF3 2-C1 142 (Z isomer) 12 4-CF3 2-C1 134 (E isomer) 13 4-OCF3 - 113 (Z isomer) 14 4-OCF3 - 108 (E isomer) 4-SCF3 - 95 (Z isomer) 16 4-SCF3 - Oil (E isomer) 17 4-CF3 - 128 (Z isomer) 18 4-CF3 ~ 130 (E isomer) 19 4-CF3 3-C1 130 (Z isomer) 4-CF3 3-cl 141 (E isomer) 21 4-OCF3 3-C1 110 (Z isomer) 22 4-OCF3 3-C1 91 (E isomer) 23 3-No2 4-C1 150 (Z isomer) 24 3-No2 4-Cl Resin (E isomer)
After 18 hours, 20 ml of acetone were added dropwise. After evapora~ing off the solvent, the residue which remained was stirred into water and the mixture was extracted with methylene chloride. The organic phase was s~
separated off, dried over sodium sulphatel filtered and evaporated in vacuo.
The crystal]ine mass was stlrred with diisopropyl ether and filtered off.
7.2 g (66.7% of theory) of the E isomer of 4,4-dimethyl-2-~1,2,4-triazol-1-yl)-1-(2-trifluoromethylphenyl)-~ent-1-en-3-ol, of melting point 165C, were obtained.
Example 3 F3C ~ H = C - CH - C~CH3)3 (3) ~ N ~
A solution of 5.05 g ~Q.13 mol~ of sodium boranate in 100 ml of water was added dropwise to 61.5 g ~0.19 mol) of 4,4-dimethyl-2-~1,2,4-triazol-1-yl)-1-~4-trifluoromethylphenyl)-pent-1-en-3-one, in the form of the E/Z
isomer mixture, and 14.1 g ~0.1275 mol) of calcium chloride in 400 ml of isopropanol at -5C. After 15 hours, 60 ml of acetone were added dropwise.
After ev~porating off the solvent, the residue which remained was stirred into water and the mixture was extracted with ethyl acetate. The solution was dried over sodium sulphate, filtered and evaporated in vacuo. 60.3 g ~97% of theory) of 4,4-dimethyl-2-~1,2,4-triazol-1-yl~1~4-trifluoromethyl-phenyl)-pent-l-en-3-ol were obtained as the E/~ isomer mixture, of melting point 54-55C.
The following compounds of the general formula ~I) were obtained analogously:
Table 1 _ _ X OH
~ - ~1 = C - Cll- C~CH3)3 ~I) ~1 Ex-NOmp,le Xm n Melting point ( C) or refractive index ~nD ) _ 4 4-OH _ 168 (E/Z mixture) 4-OH 3-OCH3 135 (E/Z mixture) 6 2-0ll 3,s-C12 158 (E/Z mixture) 7 4-N(CH3)2 ~ 140 (E/Z mixture) 8 4-0-CH2- ~ - 109 (E/Z mixture) 9 4-NO2 - 126 (Z isomer) 4-NO2 - 188 (E isomer) 11 4-CF3 2-C1 142 (Z isomer) 12 4-CF3 2-C1 134 (E isomer) 13 4-OCF3 - 113 (Z isomer) 14 4-OCF3 - 108 (E isomer) 4-SCF3 - 95 (Z isomer) 16 4-SCF3 - Oil (E isomer) 17 4-CF3 - 128 (Z isomer) 18 4-CF3 ~ 130 (E isomer) 19 4-CF3 3-C1 130 (Z isomer) 4-CF3 3-cl 141 (E isomer) 21 4-OCF3 3-C1 110 (Z isomer) 22 4-OCF3 3-C1 91 (E isomer) 23 3-No2 4-C1 150 (Z isomer) 24 3-No2 4-Cl Resin (E isomer)
3-CF3 - 120 (Z isomer) 26 3-CF3 - 1.5080 (E isomer) 27 4 CH3Coo_ _ 130 (E isomer) The following starting compo~nds of the formula (II) were obtained analogously to Example 1 and analogously to the process descri.bed in the text:
Table 2 m\
~ CH = C - CO - C(CH3)3 ~II) y N
n ~
Ex- X Y Melting point (C) or ample m n refractive index (n20) .
II-3 4-OH _ 186 (E isomer) II-4 4-N02 - 125 ~E isomer) II-5 4~0H 3-OCH3 134 (E/Z mixture) II-6 2-OH 3,5-C12 210 (E/Z mixture) II-7 4~N(CH3)2 - 112 (E/Z mixture) II-8 4-0-CH2 ~ - 120 (E/Z mixture) II-9 4-CF3 - 119 (E isomer) II-10 4-CP3 2-C1 1.5134 (E/Z mixture) II-ll 4-0-CF3 - 98 (E isomer) II-12 4-OCF3 - 1.514-5 (E/Z mixture) II-13 4-~F3 3-C1 1.5236 (E/Z mixture) II-14 4-OCF3 3-C1 1.5195 (E/Z mixture) II-15 3-CF3 - 1.5220 (E/Z mixture) II-16 3-CF3 - 1.5168 (E isomer~
II-17 4 CH3COo_ _ 95 (E isomer)
Table 2 m\
~ CH = C - CO - C(CH3)3 ~II) y N
n ~
Ex- X Y Melting point (C) or ample m n refractive index (n20) .
II-3 4-OH _ 186 (E isomer) II-4 4-N02 - 125 ~E isomer) II-5 4~0H 3-OCH3 134 (E/Z mixture) II-6 2-OH 3,5-C12 210 (E/Z mixture) II-7 4~N(CH3)2 - 112 (E/Z mixture) II-8 4-0-CH2 ~ - 120 (E/Z mixture) II-9 4-CF3 - 119 (E isomer) II-10 4-CP3 2-C1 1.5134 (E/Z mixture) II-ll 4-0-CF3 - 98 (E isomer) II-12 4-OCF3 - 1.514-5 (E/Z mixture) II-13 4-~F3 3-C1 1.5236 (E/Z mixture) II-14 4-OCF3 3-C1 1.5195 (E/Z mixture) II-15 3-CF3 - 1.5220 (E/Z mixture) II-16 3-CF3 - 1.5168 (E isomer~
II-17 4 CH3COo_ _ 95 (E isomer)
4~7 The plant growth regulant and fungicidal activity of the compounds of this invention is illustrated by the 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.
The known comparison compounds are identified as follows:-(A) = ~ CH=C-CH-C(C113)3 N
OH
IB) = F ~ CH = C - CH - C~CH3)3 N~
~C) = Cl ~ CH = C- CH - C(C~13)3 Exa~ple A
Inhibition of growth of grass ~Festuca pratensis) Solvent: 3Q parts by weight of dimethylformamide Emulsifier: l part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active compound1 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.
Grass (Festuca pratensis) was grown in a greenhouse up to a height in growth of 5 cm. In this stage, -the plants were sprayed with the preparations of acti~e compowld until dripping wet. A-fter 3 weeks, the additional growth was measured and tlle 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 compounds (12), (18), (10) 9 (1~) and (3~
exhibited a better inhibition of growth than the compounds (A), (B) and (C) known from the prior art.
lQ Example B
Inhibition of growth of barley 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 was mixed with the stated amount of solvent and emulsifier and *he mixture was made up to the desired concentration with water.
Barley plants were grown in a greenhouse to the 2-leaf stage.
In this stage, the plants were sprayed with the preparation of active compound until dripping wet. After 3 weeks, the additional growth was measured on all plants 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 compound (18) exhibited a better inhibition of growth *han the compounds (A), (B) and (C) known from the prior art.
E xamp 1 e C
Inhibition oE growth of cotton Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolaurate.
To produce a suitable preparation of active compound, 1 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 growth of the plants was measured and the inhihition 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 compounds (9), ~14), (11), (6), ~10), (18), ~17), (15) and (12) exhibited a better inhibition of growth than the compounds (A), (E) and (C) known from the prior art.
Example D
Inhibition of growth of soya beans Solvent: 10 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of polyGxyethylene sorbitane monolaurate.
l'o 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 mixture was made up to the desired concentration with water.
~ 3~"7 Young soya bean plants, in the stage in which the first secondary leaves had unfolded, l~ere 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. 100% meant that growth had stopped and 0~ denoted a g:rowth corres-ponding to that of the untreated con*rol plants.
In this test, active compounds (3), ~9), ~14), ~11), ~10), ~18), ~17), ~15) and ~12) exhibited a better inhibition of growth than the compound ~A) known from the prior art.
Example E
Inhibition of growth of sugar beet 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 was mixed with the stated amounts of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Sugar beet plants were grown in a greenhouse until formation of the cotyledons was complete. In this stage, the plants were sprayed with the preparations of active compound until dripping wet. After 1~ days, the additional growth of the plants was measured and the inhibition of growth in per cent of thc additional growth of the control plants was calculated. 0%
inhibition of growth denoted a growth which corresponded to that of the control plants. 100% inhibition of growth meant that growth had stopped.
In this test, active compounds ~3), ~9), ~14), ~11), (10), ~18), ~17), ~15) and ~12) exhibited a better inhibition of growth than the compounds ~A) and ~B) known from the prior art.
Example ~
~ormation of ethylene 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 was mixed with the statcd 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 ~ean leaves. These were introduced into vessels which could be closed air-tight, together with 1 ml of the preparation of active compound or control solution.
After 24 hours the ethylene which had collected 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 of the controls.
The figures of merit had the following meanings:
O denoted evolution of ethylene as in the case of the control + denoted slightly increased evolution of ethylene ++ deno*ed greatly increased evolution of ethylene ~++ denoted very greatly increased evolution o ethylene.
In this test, active compounds (3) and (9) caused more formation of ethylene than the compounds (A) and (B) known from the prior art.
Example G Stimulation of photosynthesis After treatment of soya bean plants with the active compounds (13), ~11) and ~14), a stimulation of photosynthesis compared to control plants was found. In contrast, treatment with the known compound ~A) did not produce this effect.
_ 24 -Example 11 Erysiphe test (barley)/protective/
Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compo~md, l 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 Erysiphe 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 clearly superior activity compared with the compound (A) known from the prior art was shown, for example, by the compounds ~3), ~9), ~10), (11), ~12), ~14), ~15) and (18).
r~xample I
Powdery mildew of barley test ~Erysiphe graminis var.hordei)/systemic (fungal disease of cereal shoots).
The active compounds were used as pulverulent seed treatment agents. These were produced by extending the active compound with a mixture of equal parts by weight of talc and kieselgur to give a finely pulverulent mixture of the desired concentration of active compound.
Por the treatment of seed, barley seed was shaken with the extended active compound in a closed glass bottle. The seed was sown at the rate of 3 x 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a green-house. 7 days after sowing~ when the barley plants had unfolded their first leaf, they were dusted with fresh spores of Erysiphe graminis var. hordei and grown on at 21 to 22~C and 80 to 90% relative atmospheric humidity and 16 hours~ exposure to light. The typical mildew pustules formed on the leaves within 6 days.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control. The more active was the active compound, the lower was the degree of mildew infection.
In this test, a c~early superior activity compared with the compounds (A) and ~C) known from the prior art was shown, for example, by the compounds ~3), (9~ and ~10).
Exan~le J
Seed dressing test/stripe disease of barley ~seed-borne mycosis).
To produce a suitable dry dressing, the active compound was extended with a mixture of equal parts by weight of talc and kieselgur to give a finely powdered mixture with the desired concentration of active compound.
To apply the dressing, barley seed, which was naturally infected by Drechslera graminea (commonly described as Helminthosporium gramineum), was shaken with the dressing in a closed glass flask. The seed, on moist filter paper discs in closed Petri dishes, was exposed to a temperature of ~C
for 10 days in a refrigerator. The germination of the barley, and possibly also of the fungus spores, was thereby lnitiated. 2 batches of 50 grains of the pre-germinated barley were subsequently sown 3 cm deep in ~ruhstorfer standard soil and cultivated in a greenhouse at temperatures of about 18C in seed boxes which were exposed to light for 16 hours daily. The typical symptoms of the stripe disease developed within 3 to ~ weeks.
After this time, the number of diseased plants was determined as a percentage of the total number of emerged plants. The fewer were the plants diseased, the more effective was the active compound.
In this test, a clearly superior activity compared with the compound (A) known from the prior art was shown, for example, by the compound (3).
In these Examples, the compounds according to the present invention are each identified by the number ~given in brackets~ of the corresponding preparative Example.
The known comparison compounds are identified as follows:-(A) = ~ CH=C-CH-C(C113)3 N
OH
IB) = F ~ CH = C - CH - C~CH3)3 N~
~C) = Cl ~ CH = C- CH - C(C~13)3 Exa~ple A
Inhibition of growth of grass ~Festuca pratensis) Solvent: 3Q parts by weight of dimethylformamide Emulsifier: l part by weight of polyoxyethylene sorbitane monolaurate To produce a suitable preparation of active compound1 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.
Grass (Festuca pratensis) was grown in a greenhouse up to a height in growth of 5 cm. In this stage, -the plants were sprayed with the preparations of acti~e compowld until dripping wet. A-fter 3 weeks, the additional growth was measured and tlle 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 compounds (12), (18), (10) 9 (1~) and (3~
exhibited a better inhibition of growth than the compounds (A), (B) and (C) known from the prior art.
lQ Example B
Inhibition of growth of barley 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 was mixed with the stated amount of solvent and emulsifier and *he mixture was made up to the desired concentration with water.
Barley plants were grown in a greenhouse to the 2-leaf stage.
In this stage, the plants were sprayed with the preparation of active compound until dripping wet. After 3 weeks, the additional growth was measured on all plants 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 compound (18) exhibited a better inhibition of growth *han the compounds (A), (B) and (C) known from the prior art.
E xamp 1 e C
Inhibition oE growth of cotton Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitane monolaurate.
To produce a suitable preparation of active compound, 1 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 growth of the plants was measured and the inhihition 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 compounds (9), ~14), (11), (6), ~10), (18), ~17), (15) and (12) exhibited a better inhibition of growth than the compounds (A), (E) and (C) known from the prior art.
Example D
Inhibition of growth of soya beans Solvent: 10 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of polyGxyethylene sorbitane monolaurate.
l'o 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 mixture was made up to the desired concentration with water.
~ 3~"7 Young soya bean plants, in the stage in which the first secondary leaves had unfolded, l~ere 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. 100% meant that growth had stopped and 0~ denoted a g:rowth corres-ponding to that of the untreated con*rol plants.
In this test, active compounds (3), ~9), ~14), ~11), ~10), ~18), ~17), ~15) and ~12) exhibited a better inhibition of growth than the compound ~A) known from the prior art.
Example E
Inhibition of growth of sugar beet 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 was mixed with the stated amounts of solvent and emulsifier and the mixture was made up to the desired concentration with water.
Sugar beet plants were grown in a greenhouse until formation of the cotyledons was complete. In this stage, the plants were sprayed with the preparations of active compound until dripping wet. After 1~ days, the additional growth of the plants was measured and the inhibition of growth in per cent of thc additional growth of the control plants was calculated. 0%
inhibition of growth denoted a growth which corresponded to that of the control plants. 100% inhibition of growth meant that growth had stopped.
In this test, active compounds ~3), ~9), ~14), ~11), (10), ~18), ~17), ~15) and ~12) exhibited a better inhibition of growth than the compounds ~A) and ~B) known from the prior art.
Example ~
~ormation of ethylene 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 was mixed with the statcd 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 ~ean leaves. These were introduced into vessels which could be closed air-tight, together with 1 ml of the preparation of active compound or control solution.
After 24 hours the ethylene which had collected 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 of the controls.
The figures of merit had the following meanings:
O denoted evolution of ethylene as in the case of the control + denoted slightly increased evolution of ethylene ++ deno*ed greatly increased evolution of ethylene ~++ denoted very greatly increased evolution o ethylene.
In this test, active compounds (3) and (9) caused more formation of ethylene than the compounds (A) and (B) known from the prior art.
Example G Stimulation of photosynthesis After treatment of soya bean plants with the active compounds (13), ~11) and ~14), a stimulation of photosynthesis compared to control plants was found. In contrast, treatment with the known compound ~A) did not produce this effect.
_ 24 -Example 11 Erysiphe test (barley)/protective/
Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compo~md, l 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 Erysiphe 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 clearly superior activity compared with the compound (A) known from the prior art was shown, for example, by the compounds ~3), ~9), ~10), (11), ~12), ~14), ~15) and (18).
r~xample I
Powdery mildew of barley test ~Erysiphe graminis var.hordei)/systemic (fungal disease of cereal shoots).
The active compounds were used as pulverulent seed treatment agents. These were produced by extending the active compound with a mixture of equal parts by weight of talc and kieselgur to give a finely pulverulent mixture of the desired concentration of active compound.
Por the treatment of seed, barley seed was shaken with the extended active compound in a closed glass bottle. The seed was sown at the rate of 3 x 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a green-house. 7 days after sowing~ when the barley plants had unfolded their first leaf, they were dusted with fresh spores of Erysiphe graminis var. hordei and grown on at 21 to 22~C and 80 to 90% relative atmospheric humidity and 16 hours~ exposure to light. The typical mildew pustules formed on the leaves within 6 days.
The degree of infection was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control. The more active was the active compound, the lower was the degree of mildew infection.
In this test, a c~early superior activity compared with the compounds (A) and ~C) known from the prior art was shown, for example, by the compounds ~3), (9~ and ~10).
Exan~le J
Seed dressing test/stripe disease of barley ~seed-borne mycosis).
To produce a suitable dry dressing, the active compound was extended with a mixture of equal parts by weight of talc and kieselgur to give a finely powdered mixture with the desired concentration of active compound.
To apply the dressing, barley seed, which was naturally infected by Drechslera graminea (commonly described as Helminthosporium gramineum), was shaken with the dressing in a closed glass flask. The seed, on moist filter paper discs in closed Petri dishes, was exposed to a temperature of ~C
for 10 days in a refrigerator. The germination of the barley, and possibly also of the fungus spores, was thereby lnitiated. 2 batches of 50 grains of the pre-germinated barley were subsequently sown 3 cm deep in ~ruhstorfer standard soil and cultivated in a greenhouse at temperatures of about 18C in seed boxes which were exposed to light for 16 hours daily. The typical symptoms of the stripe disease developed within 3 to ~ weeks.
After this time, the number of diseased plants was determined as a percentage of the total number of emerged plants. The fewer were the plants diseased, the more effective was the active compound.
In this test, a clearly superior activity compared with the compound (A) known from the prior art was shown, for example, by the compound (3).
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 1-phenyl-2-triazolyl-pent-1-en-3-one of the formula in which X represents a halogenoalkyl, halogenoalkoxy, halogeno-alkylthio, alkylthio, nitro, hydroxyl, dialkylamino, alkylcarbony-loxy or a benzyloxy radical unsubstituted or substituted in the phenyl part with fluorine, chlorine,bromine or alkyl with 1 or 2 carbon atoms, Y represents a halogen atom or an alkyl, alkoxy, cyano or phenyl or phenoxy radical, each unsubstituted or substituted in the phenyl part with fluorine chlorine, bromine, or alkyl with 1 or 2 carbon atoms, m is 1, 2 or 3, n is 0, 1, 2, 3 or 4, and m + n = 1 to 5.
2. The compound according to claim 1, wherein Y represents a halogenoalkyl, halogenoalkoxy or halogeno-alkylthio radical, each with 1 or 2 carbon atoms and up to 5 identical or different halogen atoms, an alkylthio radical with 1 to 4 carbon atoms, a nitro or hydroxy radical, a dialkylamino radical with 1 to 4 carbon atoms in each alkyl part, an alkyl-carbonyloxy radical with 1 to 4 carbon atoms in the alkyl part or a benzyloxy radical unsubstituted or substituted in the phenyl part with fluorine, chlorine, bromine or alkyl with 1 to 2 carbon atoms, Y represents a fluorine, chlorine or bromine atom, an alkyl or alkoxy radical, each with 1 to 4 carbon atoms, a cyano radical, or phenyl or phenoxy radical, each unsubstituted or substituted in the phenyl part with fluorine, chlorine, bromine or alkyl with 1 to 2 carbon atoms, m is 1 or 2 and n is 0, 1, 2 or 3.
3. The compound according to claim 1, wherein X represents a trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluoromethoxy or trifluoromethylthio radical, a 1,1,2-trifluoro-2-chloro-ethoxy or -ethylthio radical, a methylthio, nitro, hydroxyl, dimethylamino, acetoxy or tert.- butylcarbonyloxy radical or a benzyloxy radical which is unsubstituted or substituted with one or two identical or different substituents selected from fluorine, chlorine and methyl, Y represents a fluorine or chlorine atom or a methyl, ethyl, isopropyl, tert.-butyl, methoxy, isopropoxy or cyano radical, or a phenyl or phenoxy radical which is unsubstituted or substituted by one or two identical or different substituents selected from fluorine, chlorine and methyl, m is 1 or 2 and n is 0, 1 or 2.
4. The compound according to claim 1, wherein X represents a trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino, benzyloxy, acetoxy, nitro or hydroxy radical, Y represents a chlorine atom or a methoxy radical, m is 1, and n is 0, 1 or 2.
5. The compound according to claim 1, wherein X represents 2- or 4-trifluoromethyl, 4-trifluoromethoxy, 3- or 4-nitro, 2- or 4-hydroxy or 4-trifluoromethylthio radical, Y represents a chlorine atom, m is 1, and n is O or 1.
6. A process for the production of a l-phenyl-2-triazolyl-pent-1-en-3-one as defined in claim 1, characterised in that a triazolylpinacoline of the formula (III) is reacted with an aldehyde of the general formula (IV) in which X, Y, m and n are as defined in claim 1, in the presence of a solvent and in the presence of a catalyst.
7. The process according to claim 6, wherein in the compound of formula IV, X represents a trifluoromethyl, difluoromethyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluoromethoxy or trifluoromethylthio radical, 1,1,2-trifluoro-2-chloro-ethoxy or -ethylthio radical, a methylthio, nitro, hydroxyl, dimethylamino, acetoxy or tert.-butylcarbonyloxy radical or a benzyloxy radical which is unsubstituted or substituted with one or two identical or different substituents selected from fluorine, chlorine and methyl, Y represents a fluorine or chlorine atom or a methyl, ethyl, isopropyl, tert.-butyl, methoxy, isopropoxy or cyano radical, or a phenyl or phenoxy radical which is unsubstituted or substi-tuted by one or two identical or different substituents selected from fluorine, chlorine and methyl, m is 1 or 2 and n is 0, 1 or 2.
8. The process according to claim 6, wherein in the compound of formula IV, X represents 2- or 4-trifluoromethyl, 4-trifluoromethoxy, 3- or 4-nitro, 2- or 4-hydroxy or 4-trifluoromethylthio radical, Y represents a chlorine atom, m is 1, and n is 0 or 1.
9. The process according to claim 6, 7 or 8, wherein the catalyst is a Lewis acid or pyridine, 2,6-dimethyl-morpholine, piperidine or piperidine acetate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3044802.3 | 1980-11-28 | ||
| DE19803044802 DE3044802A1 (en) | 1980-11-28 | 1980-11-28 | SUBSTITUTED 1-PHENYL-2-TRIAZOLYL-1-PENTEN-3-OLE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PLANT GROWTH REGULATORS AND FUNGICIDES |
| CA000391066A CA1169075A (en) | 1980-11-28 | 1981-11-27 | Substituted l-phenyl-2-triazolyl-pent-l-en-3-ols, a process for their preparation and their use as plant growth regulators and fungicides |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391066A Division CA1169075A (en) | 1980-11-28 | 1981-11-27 | Substituted l-phenyl-2-triazolyl-pent-l-en-3-ols, a process for their preparation and their use as plant growth regulators and fungicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185247A true CA1185247A (en) | 1985-04-09 |
Family
ID=25669494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000441920A Expired CA1185247A (en) | 1980-11-28 | 1983-11-24 | Substituted 1-phenyl-2-triazolyl-pent-1-en-3-ones and process for their production |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1185247A (en) |
-
1983
- 1983-11-24 CA CA000441920A patent/CA1185247A/en not_active Expired
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