NZ197789A

NZ197789A - Certain 1-phenyl-3-substituted-2-(1,2,4-triazol-1-yl)prop-1-en-3-ols and fungicidal and plant-growth regulant compositions

Info

Publication number: NZ197789A
Application number: NZ197789A
Authority: NZ
Inventors: E Regel; K H Buechel; K Luerssen; P-E Frohberger; V Paul
Original assignee: Bayer Ag
Priority date: 1980-07-25
Filing date: 1981-07-22
Publication date: 1986-10-08
Also published as: AR230273A1; EP0044993A2; GR75282B; DE3170703D1; KR860000503B1; TR21553A; ES8206493A1; EP0044993A3; CA1168248A; EP0123971A2; OA06866A; DK329181A; EP0044993B1; KR830006242A; BR8104795A; IL63383A0; ES504256A0; AU7338081A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 1 97789 % 1977 3 9 Priority Date(s): Complete Specification Filed: .7;.?/ ^ Class: CpJ.1 Publication Date: P.O. Journal, No: c'8 0Ct'i986 }"zzi" N.Z. No. NEW ZEALAND Patents Act, 1953 COMPLETE SPECIFICATION TRIAZOLYLPROPENOL DERIVATIVES, A PROCESS FOR THEIR PREPARATION AND THEIR USE AS PLANT GROWTH REGULATORS AND FUNGICIDES We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement (Followed by lA.-* - 1A - 1977 The present invention relates to certain new triazolylpropenol derivatives, to a process for their production and to their use as plant growth regulators and fungicides. It has already been disclosed that 4,4-dimethyl-l-phenyl-2-triazolyl-l-penten-3-ols have a good fungicidal activity (see G.B. Patent Specification 2,004,276). However, the action of these compounds is not always completely satisfactory, especially when low amounts and concentrations are applied. The plant growth regulation action of these azole derivatives is likewise not always completely satisfactory. The present invention now provides a triazolylpropenol compound selected from the group consisting of OH 9h3 (1) 9 OH CH3 (2) C - CH - C - C,H7 i i 3 / (3) (5) CP. -0- CI CH = C - I If N N 'J OH CH n I \ ^ CH (6) ch3o-~{/\ pH CH^ CH - C - L J- CH ^Nn, II ^ (7) c,-Q- CI CH = C - I /N\ fi * N IJ OH I CH f3 C -/ CH C2H5 ./>• v \9 dEC^9S4 (8) CI CI CH = C - I /Nv ^ M N I OH CH, I x J CH (9) Cl cl"t> OH CH. — CH = C - CH N and (11) /CH3 i1 ■— CH = C - CH OH CH3 / N\ !1_J and physiologically acceptable acid addition salts and metal salt complexes thereof. 7 *a9decwm <0 The above compounds according to the invention occur in the geometric isomers E (trans) and Z (cis). In the E/Z nomenclature, the substituents on the double bond are arranged in order of decreasing priority in accordance with the Cahn-Ingold-Prelog rule. If the preferred substituents are on the same side of the double bond, the compound has the Z (derived from "zusammen" (together)) configuration, and if they are on opposite sides, the compound has the E (derived from "entgegen" (opposite)) configuration. Since an asymmetric carbon atom is also present, the above compounds can occur in two optical isomer forms. The present invention relates both to the individual isomers and to the isomer mixtures. An individual isomer of the above compounds may be referred to herein by using the symbol (E) or (Z) after the compound or its number, e.g. (1)(Z). According to the present invention there is further provided a process for the production of a compound of the invention, characterised in that the corresponding triazolylpropenone derivative is reduced, and the compound according to the invention thus obtained is then converted, if desired, into an acid addition salt or metal salt complex thereof. Finally, it has been found that the new triazolylpropenol derivatives of the present invention and acid addition salts and metal salt complexes thereof have powerful plant growth-regulating and powerful fungicidal properties. Surprisingly, the compounds of the present invention, exhibit a better growth-regulating and fungicidal action than the v *. : L • t9DEC\9&V 197789 4,4-dimethyl-l-phenyl-2-triazolyl-l-penten-3-ols, which are known from the state of the art and are closely related compounds chemically and from the point of view of their action. The active compounds according to the invention thus represent an enrichment of the art. If, for example, 1-methylcycloprop-l-yl 1-(1,2,4-triazol-l-yl ) -2- ( 2-chlorophenyl ) -e then-l-yl ketone and aluminium isopropylate are used as starting substances, the course of the reaction according to the present invention is illustrated by the following equation: p1 ch3 ci ch3 <^-CH=C-C0<3 i)^ o o E/Z-isomer mixture Z-isomer The corresponding triazolylpropenone derivatives are novel. However, they can be obtained in a known manner, as disclosed in co-pending Divisional Application I the disclosure of which t. is incorporated by reference. The reduction according to the invention is carried out in the customary manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent. The starting substances can be employed in the form of E/Z isomer mixtures or as pure isomers. I, ' ; , / / / 9 e If complex hydrides are used, possible diluents for the reaction according to the invention are polar organic solvents. These include, preferably, alcohols (such as methanol, ethanol, butanol or isopropanol), and ethers (such as diethyl ether or tetrahydrofuran). The reaction is in general carried out at a temperature between -10 and +30°C, preferably at between -10 and +20°C. For this reaction, about 1 mole of a complex hydride, such as sodium borohydride, calcium borohydride or lithium alanate, are employed per mole of the starting ketone. Isolation of the compounds according to the invention is carried out in the customary manner, as is any separation of the E/Z isomer mixtures which are always formed in the reduction with complex hydrides if E/Z-isomer mixtures are used as starting materials. If aluminium isopropylate is used, preferred possible i diluents for the reaction according to the invention are alcohols (such as isopropanol) or inert hydrocarbons (such as benzene). The reaction temperatures can again be varied within a substantial range; in general, the reaction is carried out at a temperature between 20 and 120°C, preferably at between 50 and 100°C. For carrying out the reaction, about 1 to 2 moles of aluminium isopropylate are employed per mole of the corresponding ketone. The compounds according to the invention are isolated in the customary manner. In reduction with aluminium isopropylate, exclusively the Z-isomers are obtained. / ■ / / / u 9 1 ^ 7 The H^-nuclear magnetic resonance of the two triazole protons is an unambiguous characterising feature of the two geometric isomers. The difference between the shift values of these two protons in the E-forms is approximately twice the value of the difference in the corresponding Z-forms. The following acids can be used for the preparation of physiologically acceptable acid addition salts of the compounds of the present invention: hydrogen halide acids (such as hydrobromic acid and, preferably, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxy-carboxylic acids (such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid), and sulphonic acids (such as p-toluene-sulphonic acid and 1,5-naphthalene-disulphonic acid). The acid addition salts of the compounds of the present invention can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the present invention in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent. Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII can preferably be used for the preparation of metal salt complexes of the compounds of the present 157789 8 invention, examples of metals which may be mentioned being copper, zinc, manganese, magnesium, tin, iron and nickel. Possible anions of the salts are, preferably, those which are derived from the following acids: hydrogen halide acids (such as hydrochloric acid and hydrobromic acid), phosphoric acid and sulphuric acid. The metal salt complexes of compounds of the present invention can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in an alcohol, for example ethanol, and adding the solution to the compound of the present invention. The metal salt complexes can be purified in a known manner, for example by filtration, isolation and, if annrnoriatp. hv rprrvsfal1 i RaH nn. / . ^ _ 1 57789 197789 - 9 - • The active compounds which can be used according to the invention engage in the metabolism of the plants and can therefore be employed as growth regulators. Experience to date of the mode of action of 5 plant growth regulators has shown that an active compound 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 10 of active compound applied to the plants or their environment and the way in which the compounds are applied. In every case, growth regulators are intended to influence the crop plants in the particular manner • desired. 15 Plant growth 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 20 "the grass in ornamental gardens, parks and sportsgrounds, at verges, at airports or in fruit orchards. The inhibition of growth of herbaceous and woody plants at verges and in the cicinity of pipelines or overland lines or, quite generally, in areas in which heavy 25 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 30 thereby reduced or completely eliminated. Furthermore, growth regulators can strengthen the stem of cereals, which again counteracts lodging. I-,e A ?Q =^6 v" \ £c, 'V ."rn _ i Q 7 7 ' • 9 1 -10- 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. 5 In the case of many crop plants, inhibition of the vegetative growth makes denser planting possible, so . that greater yields per area of ground can be achieved. An advantage of the smaller plants thus produced is also that the crop can be worked and harvested more easily. 10 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. 15 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 20 promotion of generative growth, since more assimilates are formed, so that more fruit, or larger fruit, is obtained. Increases in yield can in some cases be achieved by affecting the plant metabolism, without noticeable changes in vegetative growth. A change in the composition 25 of plants, which in turn can lead to a better quality of the harvested products, can furthermore be achieved with growth regulators. Thus it is possible, for example, to increase the content of sugar in sugar beet, sugar can, pineapples and citrus fruit or to increase the protein 30 content in soya or cereals. Using growth regulators it is also possible, for example to inhibit the degradation of desired constituents, such as, for example, sugar in sugar beet or sugar can, before or after harvesting. a 20 ^58 i* 1 C/%* 197789 " - 11 - 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. 5 Parthenocarpous fruit can be formed under the influence of growth regulators. Furthermore, the gender of the flowers can be influenced. Sterility of the pollen can also be produced, which is of great importance in the breeding and preparation of hybrid 10 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 15 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 20 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 25 the mechanical harvesting of cotton, but is also of interest for facilitating harvesting in other crops, such as, for example, in viticulture. Defoliation of the plants can also be carried out to lower the transpiration of plants before they are transplanted. 30 fhe shedding of fruit can also be controlled with growth regulators. On the one hand, it is possible to prevent premature shedding of fruit. However, 1 i j.t - 12 - . on the other hand, shedding of fruit, or even the fall of blossom, can be promoted up to a certain degree (thinning cut) in order to interrupt the alternance. By alternance there is understood the peculiarity of some 5 varieties of fruit to produce very different yields from year to year, for endogenic reasons. Finally, using growth regulators it is possible to reduce the force required to detach the fruit at harvest time so as to permit mechanical harvesting or facilitate manual 10 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 15 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 20 regulators. This provides the preconditions for being able to carry out completely mechanical or manual harvesting in only a.single pass, for example in the case of tobacco, tomatoes or coffee. Using plant regulators, it is furtermore possible 25 to influence the latent period of seeds or buds of plants, so that the plants, for example pineapple or ornamental plants in nurseries, germinate, shoot or blossom at a time when they normally show no readiness to do so. Retarding the shooting of buds or the germination of seeds 30 with the aid of growth regulators can be desirable in "regions where frost is a hazard, in order to avoid damage by late frosts. Finally, the resistance of plants to frost, drought or a high salt content in the soil can be induced 35 with growth regulators. Cultivation of plants in regions q ~C; ' '* !»0, lfr A ?0 4^8 \ n '""fin -'197/19 .which are usually unsuitable for this purpose thereby becomes possible. The preferred time of application of the growth regulators depends on the climatic and vegetative 5 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 10 determined empirically. The active compounds according to the invention also exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms. The active compounds are suitable for use 15 as plant protection agents. Fungicidal agents in plants protection are employed for combating Plasmo di oph oroiriy cet esOomy cetesa Chy-tridiomycetes Zygomy cetes, As cornycetesBasidiomycetes and Deuteromy cete s. 20 The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil. 25 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, for example against the powdery mildew of barley or cereal 30 causative organism (Erysiphe' graminis), or for combating Podosphaera species, for example against the powdery mildew of apple causative organism (Podosphaera leucotricha). The substances according to the invention also exhibit a broad fungicidal in vitro spectrum. 2335E5S (fvBECm] 1 9 7 7' CV - 14 - 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 5 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 liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active 10 agents, that is to say emulsifying 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. 15 ; there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane 20 or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, 25 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, 30 nitrogen and carbon dioxide. As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz-attapulgite, montmorillonite or diatomaceous earth, and grcund synthetic minerals, such as highly-dispersed silicic 35 acid, alumina and silicates. As solid carriers for granules As liquid diluents or carriers, especially solvents, Le A 20 fcgg 1977 9 ? 7 r O y / ^ w ./ - 15 - there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such 5 as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as I polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, 10 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 15 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 20 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 ge-neral contain from 0.1 to 25 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight. The active compounds according to the invention can be present in the formulations as a mixture with other active compounds, such as fungicides, insecticides, 30 acaricides and herbicides, as well as in the form of a mixture with fertilisers and other growth regulators. The' active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiab.le concen- j.y a % « 19 DEc J 984 w. " ' 197789,S7?£9 - 16 - . trates, emuleions, foams, suspensions, we't table powders, pastes, soluble powders, dusting agents and granules. They are used in the customary manner, for example by watering, spraying, atomising, scattering, dusting, 5 foaming, coating and the like. Furthermore, it is possible to apply the active compounds in accordance with the ultra-lew volume process or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of 10 plants. When the compounds according to the invention are used as plant growth regulators, the amounts applied can be varied with a substantial range. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, are used per hectare 15 of soil surface. The amount applied can also be varied within a substantial range, depending on the method of application, when the substances according to the invention are used as fungicides. Thus, especially in the treatment of 20 parts of plants, the active compound concentrations in the use forms can be in general be between 1 and 0.0001% by weight, preferably between 0.5 and 0.00155 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, 25 are generally required. For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02$, are required at the place of action. The present invention also provides plant growth 30 regulation and fungicidal compositions 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. T,e ft ?0 I 57769 17 The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with an agriculturally acceptable 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 form of a composition containing as active ingredient a compound of the present invention in admixture with an agriculturally acceptable 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 an agriculturally acceptable diluent or carrier. The present invention further provides plants, the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with an agriculturally acceptable diluent or carrier. It will be seen that the usual method of providing a harvested crop may be improved by the present invention. "I977C? - 18 - 1 ■ Preparative Examples ExamPle 1 <j>H CHS ch = c- ch-£- chj-ch, rT"^ CH> (1> n !1 E-isomer 2.88 g (9.5 mole) of. the E-isomer of l-(4-chloro-pheny1)-4,4-dimethyl-2-(l,2,4-triazol-l-yI)-l-hexen-3-one 5 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 10 organic phase was separated off and dissolved in methylene chloride ana 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 15 (24$ of theory) of the E-isomer of 1-(4-chlorophenyl)- 4,4-dimethyl-2-(l,2,4-triazol-l-yl)-l-hexen-3-ol of melting point 130 C were obtained. Preparation of the starting material 0 ch3 ch = ^- ij-c - chj-ch; (TNsn n ii ch3 E/Z-isomer mixture and E-isomer 20 81.5 g (0.45 mole) of 3,3-dimethyl-l-(l,2,4-triazol- l-yl)-pentan-2-one and 63.2 g (0.45 mole) of 4-chlcro-benzaldehy.de in 500 ml of toluene were heated under reflux Lv A ?'Q 1*56 v U - - ft *j: t- . - J " 197789 1 - 19 - wit>h 12.5 nil of acetic acid and 4.5 ml of piperidine for 15 hours, and the water of reaction was removed azeotrc-pically. • The toluene solution was washed with water, dried over sodium sulphate and evaporated in. vac uo. 5 127 g (93? of theory) of l-(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 l-(4-chloro-10 phenyl)-4,4-dimethyl-2-(l,2,4-triazol-l-yl)-l-hexen-3-one of melting point 90°C crystallised out. (pi3 - ch2 - co - c - ch2ch3 ch3 106 g (0.55 mole) of l-bromo-3,3-dimethyl-pentan- 2-one were added dropwise to a mixture of 62.1 g (0.9 mole) 15 of 1,2,4-triazole, 95.4 g (0.69 mole) of potassium carbonate and 600 ml of acetone at 55°C. After stirring the mixture for 15 hours, it was filtered and the filtrate was evaporated in vacuo. The oil which remained was purified by chromatography (silica gel 60 (Merck)/chloroform). 20 85.6 g (86? of theory) of 3,3-dimethyl-l-(l,2,4- 20 triazol-l-yl)-penten-2-one with a refractive index n^ of 1.4805 were obtained. CH3 Br-CH2-CO-C-CH2CH3 CH, A solution of 50.6 g (0.6 mole) of bromine in 25 120 ml of chloroform was added dropwise to a solution of 69 g (0.6 mole) of J>» 3-dimethylpentan-2-one in 300 ml of methyl alcohol at 0 to 5°C and the reaction mixture was subsequently stirred for 15 minutes. It was poured onto X,p ft pn 4-^8 I I 9 7 ? C 9 197789 ice, the organic phase was separated off, washed with water, dried over sodium sulphate and filtered and the filtrate was avaporated. The crude product was distilled j_n vacuo. 101 g (87% of theory) of l-bromo-3,3-dimethylpentan-2-one with a 20 boiling point of 80 to 88°C/11 mm Hg and a refractive index nD of 1.4685 were obtained. Other starting materials may be prepared in a corresponding manner. Example 2 ch, I c — chg ch3 ( 2) ch3 Z-isomer 30.35 g (0.1 mole) of l-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-l-y1)-l-hexen-3-one as the E/Z-isomer mixture (compare the preparation of the starting material in Example 1) were reduced with sodium boronate in a manner corresponding to that in Example 1. The resulting oil (30.5 g) was chromato-graphed on silica gel 60 (Merck)/chloroform. The fractions of melting point 100 to 108°C obtained after evaporating off the chloroform were combined, and recrystallised twice from acetonitrile. The Z-isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-l-yl)-l-hexen-3-ol of melting point 119°C was obtained. CH (p - CH - SJ ? >1 • > & The prepared other compounds according to in a corresponding manner. the present invention Melting Point °C OH CH 3 CI-/' CH = C - CH - C - n-C„H., 142 (Z-Isomer) V-— / ' I ' HO (E-Isomer) i, N CH n II 3 CI // X OH CH- CH = C - CH I 148 128 (Z-Isomer) (E-Isomer) H n N OH CF-.—ft _ 1 3 \ /-CH = C - CH ^ N . (\ n l| CH. 133 (Z-Isomer) 120 (E-Isomer) CF- CI // W OH CH. CH = C - CH \ / N\ fl N 141 (Z-Isomer) 140 (E-Isomer) 1977 - 22 - ch3o- OH CH- I \ CH = C - CH _>■ N 126 (Z-Isomer) 132 (E-Isomer) N /C1 OH CH, /T\ 1 ' CI —( 7- CH = C - CH - c - C,H, /IT T . \ / i .25* 140 (Z-Isomer) ^ ii N I! CH3 CI CI n CH OH CH- 130 (Z-Isomer) 126 (E-Isomer) CI CI — CH = C - 1 ,/N\, II * N OH CH. CH 118 (Z-Isomer) 80 (E-Isomer) CF 3 OH CH — CH = C - CH -3 'N N, N. 130 (Z-Isomer) 95 (E-Isomer) and 146 (Z-Isomer) 132 (E-Isomer) The plant growth regulant and fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples. The known comparison compounds disclosed in U.K. Patent Specification 2,004,276. (B) = r\cl ?H \0/-CH=^-CH-C(CH3 ), fTNVN N U h3 co^ och3 3 OH = \0)-CH=f-CH-C(CH5 ) ii u (D) = ?H CH—C-CH-C (CHS )3 ff1^ S_J 1984 * Example A Inhibition of growth of grass (Festuca pratenals) Solvent! 30 parts by weight of dimethylformamide Emulslflert 1 part by weight of polyoxyethylene sorb1tan monolaurate v To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulslfler and the mixture was made up to the desired concentration with water. Grass (Festuca pratensis) was growrii in a greenhouse up to a height in growth of 5 cm. In this stage, the plants were sprayed with ..the preparations of active compound until dripping wet. After 3 weeks, the additional growth was measured and the inhlbitloo 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. > The active compounds, active compound concentrations and results can be. seen from the table which followsi 197789 - 25 - 1 ,9D£C|984"'J 197789 - 26 - Table A Inhibition of growth of grass (Pestuca pratensis) Active compound Concentration Inhibition of growth in % in % (control) - 0 A 0.05 0 (known) B 0.05 (known) C 0.05 (known) D 0.05 (known) (10)(E) 0.05 35 Example B 27 1 Inhibition of growth of cotton Solventi 30 parte by weight of dimethylformamide Emulslfler» 1 part by weight of polyoxyethylene sorb 1 tan To produce a euitable preparation of active compound* 1 part by weight of active compound wae nixed with the stated amount of solvent and emulslfler 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 preparation of active compound until dripping wet. After 3 weeks, the additional growth of the plants was measured and the inhibition of growth in per cent of the additional growth of the control plants was calculated. 100% inhibition of growth meant that growth had stopped and 0 % denoted a growth corresponding to that of the control plants. monolaurate The active compounds, active compound concentrations and results can be seen from the table which followsi - 28 - 1 197789 Table B Inhibition of growth of cotton Active compound Concentration in % Inhibition of growth in % (control) - 0 A 0.05 5 (Known) B 0.05 (known) ** C 0.05 (known) D 0.05 Cknown (.1) CE) 0.05 35 (.1) CZ) 0.05 50 (9) CZ) 0.05 50 (.8) (E) 0.05 70 ** (10) CE) 0.05 1.00 ) = dark green leaf colour j 17 JAN 1985 197789 '197789 Example C Inhibition of growth of soya beans Solvents 10 parts by weight of nt • fAn 0£ Emulslfleri 2 parts by weight of polyoxyethylene sorbitan 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 emulslfler and the mixture was made up to the desired concentration with water. Young soy bean plants, in the stage in which the first secondary leaves had unfolded, were sprayed with the preparations of active compound until dripping wet. After 2 weeks, the iadditional 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 growth corresponding to that of the untreated control plants. » The active compounds, active compound concentrations and jf results can be seen from the tabl0~which follow : Table C Inhibition of growth of soya beans Active compound Concentration Inhibition of growth in % in % (control) - 0 B 0.05 10 (known) C 0.05 0 (known) D 0.05 0 (known) CI) CE) 0.05 40 ** (.9) (Z) 0.05 50 C8) (R) 0.05 75 ** = dark green leaf colour „ . . 1 97789 -31 - 19778 " Example 2) Inhibition of growth of sugar beet Solvents 30 parts by weight of dimethylformamide Eifiulsifier's 1 part by weight of polyolxyethylene sorbitan 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 emulslfler 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 14 days, the additional growth of the plants was measured and the inhibition of growth in per cent of the additional growth of the control plants was calculated. 0% inhibition of growth denoted a growth which corres ponded to that of the control plants. 100% inhibition of growth meant that growth had stopped. > The active compounds, active compound concentrations and results can be seen from the table which followss - 32 - 1 197789 Table D Inhibition of growth of sugar beet Active compound Concentration in % Inhibition of growth in % (control C (knov^n) D (known) (1)(E) (1)(Z) (9) (Z) (8)(E) 0.05 0.05 0.05 0.05 0.05 0.05 0 15 15 75 ** 50 60 ** * 45 ** * **) — *) dark green leaf colour thick leaves - 33 - Example E Comparison compounds: 137789 1 OH CH3 (E) = CH = C - CH || " z-Isomer N U (UK-PS 2,04 6,260; Compound No.33) CI pjt OH 3 (F) - C1 CH = C - CH [r% N H Z-Isomer (UK-PS 2,046,260; Compound No.37) K Example E Erysiphe test (barley) / protective Solvent: 100 parts by weight of dimethylformamide Emulslflerj 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulslfler, 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. horde!. The plants were placed in a greenhouse at a temperature of about 20°C 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. The active compounds# active compound concentrations and results can be seen from the table which follows. L * * 2 tl V* - 35 - 97783 Table E Erysiphe-Test (barley) / protective Active compound Active compound concentration in the spray in % by weight 1 Degree of infection in % of the untreated control (E) (F) 0.00025 0.00025 100 100 (1) (E) (2) (E) (3) (E) (4) (E) 0.00025 0.00025 0.00025 0.00025 0.0 77.3 72.5 72.5 197789 36 Example F Erysiphe test Charley}/ seed treatment The active compounds are used as dry dressings. These are prepared by extending the particular active compound with a ground mineral to give a finely pulverulent mixture, which ensures uniform distribution on the seed surface. To apply the dressing, the seed is shaken with the dressing in a closed glass flask for 3 minutes. 3 batches of 12 grains of the barley are sown 2 cm deep in standard soil. 7 days after sowing, when the young plants have unfolded their first leaf, they are dusted with spores of Erysiphe graminis f. sp. hordei. The plants are placed in a greenhouse at a temperature of about 20°G and a relative atmospheric humidity of about 80% in order to promote the development of powdery mildew pustules. Evaluation is carried out 7 days after the inoculation. The active compounds, active compound concentrations and results can be seen from the table which follows: 17jANj9ss - 37 - 197789 Table F Erysiphe test (barley)/seed treatment Active compound Amount of active compound applied in mg/kg of seed Disease infestati in % of the untre ed control CE) 1000 100 (F) 1000 75.0 (1)(E) 1000 0.0 C4)(Z) 1000 0.0 (5) CZ) 1000 25.0 C6) CE) 1000 21.3 Example G - 38 - ^ 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 compound, 1 (Z) and (E) 1 part by weight of active compound^was mixed with the stated amounts of solvent and emulsifier, and the concentrate was •i \ 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 20°C 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. The active compounds, active compound concentrations and results can be seen from the table which follows. b a A ?e g ■- X </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 9 *7 *1? 89 9 7 7 8 9 Table G Erysiphe-Test (barley)/ protective Active compound Active compound Degree of infection concentration in in % of the untreated the spray in % control by weight (C) (known) (1)(E) (1)(Z) 0.0025 0.0025 0.0025 100 0.0 5.0 19778s - 40 - 1 WHAT WE CLAIM IS:-

1. A triazolylpropenol compound selected from the group consisting of (i) cl"\Zy>"CH " ? " CH ~ ? ~ °2Hs N l| OH 9H3 i i ch3 (2) CI OH CH, I I CH = c - CH - C - n*C3n7 /IK ' II N N CH. (4) CF OH l CH = C - CH N< CH. ff N_ II \ I 97789 - 41 - (5) cf- * CI oh ch. ch = c - ch I /n\ (l N H II n (6) ch3o- // \\ ch = n oh ch- c - ch % \ CI / ( °H <7> c1 x" /~ ch " ^ ~ ch ff n n- n II CH, I 3 c - c0hk I 2 5' CH. (8) CI CI ch 1 9 7 7 S 9 - 42 - 1 (9) CI cl-t> OH CH. CH = C - CH N [I (10) CF 3_ — CH = N C I 'N OH CH. - CH N and CH. (11) OH C"3 ' CH = C - CH — II N. Ns and physiologically acceptable acid addition salts and metal salt complexes thereof.

2. A process for the production of a triazolylpropenol compound according to claim 1 characterised in that a corresponding triazolylpropenone derivative is reduced and the resulting compound of claim 1 is then converted, if desired, into an acid addition salt or a metal salt complex thereof. 1 9778 43

3. A process according to claim 2 characterised in that the reduction is carried out with sodium borohydride, calcium borohydride or lithium alanate in a polar organic solvent.

4. A process according to claim 3 characterised in that the reduction is carried out at a temperature between -10 and 2 0QC.

5. A process according to claim 2 characterised in that the reduction is carried out with aluminium isopropylate in an alcohol or inert hydrocarbon as the diluent.

6. A process according to claim 5 characterised in that the reduction is carried out at a temperature between 5 0 and 100@C.

7. A process for the preparation of a compound according to claim 1, substantially as herein described or exemplified.

8. A compound according to claim 1 characterised in that it is prepared by a process according to any of claims 2 to 7.

9. A fungicidal or plant-growth-regulating composition characterised in that it contains as active ingredient a compound according to claim 1 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.

10. A composition according to claim 9 characterised in that it contains from 0.1 to 95% of the active compound, by weight.

11. A method of combating fungi, characterised in that there is applied to the fungi, or to a habitat thereof, a compound according to claim 1 alone or in the form of a composition containing as active ingredient a compound according to claim 1 in admixture with an agriculturally acceptable diluent or carrier. 17 JAN 1985 1 9 7 /' 8 9 44

12. A method of regulating the growth of plants characterised in that there is applied to the plants, or to a habitat thereof, a compound according to claim 1 alone or in the form of a composition containing as active ingredient a compound according to claim 1 in admixture with an agriculturally acceptable diluent or carrier.

13. A method according to claim 11 characterised in that a composition is used containing from 1 to 0.0001% of the active compound, by weight.

14. A method according to claim 13 characterised in that a composition is used containing from 0.5 to 0.001% of the active compound, by weight.

15. A method according to claim 12 characterised in that the active compound is applied to an area of agriculture in an amount of 0.01 to 50 kg per hectare.

16. A method according to claim 15 characterised in that the active compound is applied to an area of agriculture in an amount o"f 0.05 to 10 kg per hectare.

17. A method according to claim 11 characterised in that the active compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.

18. A method according to claim 17 characterised in that the active compound is applied to soil in an amount of 0.0001 to 0.02 per cent by weight.

19. A method according to claim 11 characterised in that the active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed. , 1 97789 197789

20. A method according to claim 19 characterised in that the active compound is applied to seed in an amount of 0.01 to 10 g per kg of seed. BAYER AKTIENGESELLSCHAPT By Their Attorneys HENRY HUGHES LIMITED H. BURTON ^ Assistant CoWnissioner of Patents </div>