DK157364B - Triazol Compounds - Google Patents

Abstract

Triazol compounds of the formula:<IMAGE>In which r<1> is alkyl, cycloalkyl, or possibly substituted phenyl, and R<2> is possibly substituted phenyl or possibly substituted benzyl and there acid addition salt and metal complexes produced for example through conversion of compounds (II) or (III).<IMAGE>In which X is halogen, with 1,2,4-triazol or an alkali metal thereof. Compounds I have fungicidal effects and effects on regulation of plant growth.

Description

DK 157364 B

The invention relates to novel triazole compounds useful as fungicides and plant growth regulators.

6B patent specification 1,529,818 discloses certain 1,2,4-triazole-1 compounds which can be used for the preparation of antifungal agents for the control of fungal diseases in plants. The present invention, in relation to this, constitutes a selection invention, the compounds of this invention having unexpectedly more potent effects and, surprisingly, being effective against a greater number of diseases (see Example 9 below).

The triazole compounds of the invention have the alloene formula (I):

OH

I, N-N-C H o-C-R1 ^ i.

wherein R 1 is C 1-4 alkyl or C 3-6 cycloalkyl and R 2 is benzyl optionally substituted with halogen, C 1-4 alkyl, C 1-4 alkoxy, CF 3, nitro, phenyl or phenoxy; or R1 is phenyl optionally substituted with halogen, C1-5 alkyl, O4 -4-alkoxy, CF3, nitro or phenoxy, and R2 is phenyl or benzyl optionally substituted with fluorine, bromine, iodine, C1-5-25 alkyl, C 1-4 alkoxy, CF 3, nitro or phenoxy, or acid addition salts thereof, with the proviso that the compounds of formula (I) wherein R 1 is chlorosubstituted phenyl and R 2 is phenyl are excluded.

30

The compounds of the invention may contain chiral centers. Such compounds are commonly obtained in the form of racial mixtures. However, these and other mixtures can be separated into the individual isomers by methods known in the art.

The alkyl group may be a straight or branched group of 1-4 carbon atoms. Examples thereof are methyl, ethyl, propyl (n- or iso-propyl) and butyl (n-, sec-, iso- or t-butyl).

35 2

DK 157364 B

Exemplary suitable substituents for the phenyl and for the phenyl portion of the benzyl are halogen (e.g., fluoro, chloro or bromo), C1-5 alkyl [e.g. methyl, ethyl, propyl (n- or isopropyl) and butyl (n-, sec-, iso- or t-butyl)], C 1-4 alkoxy (e.g.

5 methoxy and ethoxy). The alkyl portion of the benzyl may itself be substituted by e.g. an alkyl group (e.g., methyl or ethyl). The phenyl and benzyl are preferably unsubstituted or substituted by 1, 2 or 3 ring substituents as defined above. The benzyl and phenyl preferably have a single ring substituent in the ortho or para position. Examples of these groups are phenyl, benzyl, α-methylbenzyl, o-, m- or p-fluorophenyl, 2,4- or 2,6-difluorophenyl, o-, m- or p-bromophenyl, o-, m- or p-methoxyphenyl, 2,4-dimethoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-nitrophenyl, o-, 15 m- or p-methylphenyl, 2,4-dimethylphenyl, o-, m- or p-butylphenyl, o-, m- or p-trifluoromethylphenyl, 2-fluoro-4-methoxyphenyl, 2-methoxy-4-fluorophenyl 1, 2-methoxy-4-fluorophenyl, o-, m- or p-phenoxyphenyl and the corresponding ring-substituted benzyl and α-methylbenzyl groups.

20

The salts may be salts with inorganic or organic acids, e.g. hydrochloric acid, nitric acid, sulfuric acid, acetic acid, p-toluenesulfonic acid and oxalic acid.

Examples of the compounds of the invention are shown in Table I.

30 35 3

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+ Compounds 8 and 18 were obtained soin polymorphic compounds, and this explains their different melting points.

5

The compounds of general formula (I) can be prepared by reacting a compound of general formula (II) or (III):

χ ÇH

10 CHO-C — R X — CHO — c — R

K2 k2 (II) (III) 1 2 wherein R and R have the meanings defined above and X 15 is a halogen atom (preferably a chlorine or bromine atom) with 1,2,4-triazole either in the presence of an acid binding agent or in the form of one of its alkali metal salts in a suitable solvent. The compound of general formula (II) or (III) is conveniently reacted at 20-100 ° C with the sodium salt of 1,2,4-triazole (the salt can be prepared by adding either sodium hydride or sodium methoxide to 1.2 (4-triazole) in a suitable solvent such as acetonitrile, methanol, ethanol or dimethylformamide. The product can be isolated by pouring the reaction mixture into water and recrystallizing the solid formed from a suitable solvent.

The compounds of general formulas (II) and (III) can be prepared by reacting a compound of general formula 30 (IVa) or IVb):

X-CH 2-c-R X-CH-C-R

(IVa) (IVb) 1 2 35 wherein R, R and X have the meanings defined above, with a Grignard compound of general formula (Va) or (Vb) respectively: Y-Mg-R2 Y-Mg-R1 ( Va) (Vb) 11

DK 157364 B

12 wherein R and R have the meanings defined above and Y is a halogen (preferably chlorine, bromine or iodine) in a suitable solvent, such as diethyl ether or tetrahydrofuran.

A mixture of the compounds of general formulas (II) and (III) is generally obtained. When a compound of the general formula (IVa) wherein R "is alkyl or cycloalkyl, e.g.

10, the compound of formula (II) generally dominates in the mixture. On the other hand, when R 1 is optionally substituted phenyl, the compound of general formula (III) generally dominates in the mixture.

The compounds of general formulas (IV) and (V) can be prepared by methods set forth in the literature.

1 2

The compounds of the general formula (II) wherein R and R, which may be the same or different, are substituted phenyl, may also be prepared by reacting the appropriate benzopheone compound of the general formula (VI)

1 2 R -CO-R

In which R and R have the meanings defined above, with dimethyloxosulfonium methylide (Corey and Chaykovsky JACS, 1965, 87, 1353-1364) or dimethylsulfonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782) using the methods cited in the literature .

The benzophenone compounds of general formula (VI) can be prepared using the Friedel-Crafts reaction by reacting a substituted benzoyl chloride with the appropriately substituted benzene in the presence of a Lewis acid, e.g. aluminum chloride.

35 1

The compounds of general formula (II) wherein each R is alkyl, cycloalkyl or optionally substituted phenyl, and 2R is optionally substituted phenyl or optionally substituted benzyl, can also be prepared by reacting an

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droxyselenide compound of general formula (VII) R1

CH0— See— CH0-C-OH

5 3 2 | i2 (VII) 1 2 wherein R and R have the meanings defined above, with methyl iodide in potassium-t-butoxide according to the method of Van Ende,

Dumont and Krief, Angew. Chem. Int. Ed., 1975, 14, 700.

The β-hydroxy selenide compound can be prepared by treating the diselenide with the appropriate ketone in the presence of butyllithium.

15

The compounds of general formula (III) wherein R 1 is alkyl 2 or cycloalkyl and R is optionally substituted benzyl (especially benzyl ring substituted by alkoxy) may also be prepared by reacting a compound of general formula (VIII)

OH

f 1

ArSCH0-C-R

2 I

R 2 (VIII) 1 2 wherein R and R have the meanings defined above and Ar is aryl (e.g., phenyl), with an alkylating agent to prepare the corresponding sulfonium salt, which is then reacted with 1.2 , 4-triazole in the form of an alkali metal salt (e.g., sodium or potassium salt). The compound of the general formula (VIII) can be prepared by methods known in the literature.

The salts of the compounds of general formula (I) can be prepared from the latter in known manner.

The compounds of general formula (I) are generally prepared by the above reactions in the form of racemic mixtures. The cleavage of these mixtures into the constituent enantiomers can be carried out by known methods. Examples of these methods are (1) formation of the di-13

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stereoisomeric salts or esters of the compound of the general formula (I) with an optically active acid (e.g. camphor sulfonic acid), separation of the isomeric salts or esters and conversion of the separated isomeric salts or esters to the enantiomers of the compound of the general formula (I) (2) forming the diastereoisomeric carbamates of the compound of the general formula (I) by reacting a haloformate (e.g., chloroformate) of the latter with an optically active amine ( eg.

(Α-methylbenzÿlamine), separation of the isomeric carbamates and conversion of the separated isomeric carbamates to the enantiomers of the compound of general formula (I); (3) forming the hemiphthate of the compound of general formula (I), reacting the hemiphthate with an optically active amine (e.g.

(Α-methylbenzylamine) to form a site of the hemiphthate, separating the isomeric salts and converting the separated salts to the enantiomers of the compound of the general formula (I) j or (4) cleavage of the mixtures in use. of enantioselective crystallization technique (Leigh, Chemistry 20 and Industry, 1970, pages 1016-1017 and ibid, 1977, page 36).

The separation of the diastereoisomeric salts, esters and carbamates can be achieved by e.g. crystallization technique or by high pressure liquid chromatography (HPLC). The enantiomers may alternatively be prepared directly from the compound of the general formula (II) by stereospecific reduction, e.g. by biochemical reduction (using, for example, yeast or Aspergillus niger) or by hydrogenation using chiral catalysts (e.g., a Wilkinson catalyst) or by reduction with borohydride / amino acid complexes.

30

The compounds and salts are active fungicides, especially against the diseases:

Piricularia oryzae on rice, 35 Puccinia recondita, Puccinia striiformis and other varieties of wheat, Puccinia hordei, Puccinia striiformis and other varieties of barley and varieties of other host plants e.g. caffeine, apples, vegetables and ornamental plants, 14

DK 157364 B

Plasmopara viticola on wine,

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew on various hosts such as 5 Sphaerotheca fuliginea on cucumber,

Podosphaera elucotricha on apples and Uncinula necator on wine, Helminthosporium spp. and Rhynchosporium spp. in cereals, Cercospora arachidicola on groundnuts and other Cercospora forms in e.g. sugar beet, bananas and soybeans, 10 Botrytis cinerea (grass mold) on tomatoes, sunbeds, wine and other hosts,

Phytophthora infestans (potato mold) on tomatoes,

Venturia inaequalis (scab) on apples.

13 Some of the compounds have also shown a broad spectrum activity against fungi in vitro. They are effective against various diseases after coughing on fruit (eg Penicillium digatatatum and italicum on oranges and Gloeosporium musarum on bananas). In addition, some of the compounds are effective as 20 dressings against: Fusarium spp., Septoria spp., Tilletia spp. (Ie wheat stink fire, which is a seed-borne disease on wheat), Ustilago spp., Helminthosporium spp. in cereals, Rhizoc-tonia solani in cotton and Corticium sasakii in rice.

25 The compounds may move mid-point seeking in the plant tissue. In addition, the compounds may be volatile enough to be active in the vapor phase against fungi on the plant.

They can also be useful as industrial (as opposed to agricultural) fungicides, ie. for the prevention of fungal attacks on wood, hides, leather and especially paint films.

The compounds may also have plant growth regulating effects.

35

The plant growth regulating effects of the compounds appear e.g. as a carcinogenic or dwarf growth inducing effect on the vegetative growth of woody and herbaceous mono- and di-cotyledonone plants. Such a mess or 15

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dwarf growth can be useful, e.g. in peanuts, cereals and soybeans, when reduction in stem growth can reduce the risk of the plants renting and may also allow the supply of increased fertilizer quantities. The growth inhibition of migratory species is useful in controlling the growth of bottom vegetation under high current lines, etc .. Compounds which soin induce growth inhibition may also be useful in modifying the stem growth of sugarcane, thereby increasing the concentration of sugar in the rudder by host. In sugarcane, flowering and maturation can be affected by the delivery of the compounds. Inhibited growth of peanuts can facilitate coughing. Growth inhibition of grasses can help in the preservation of grass taps. Examples of suitable grasses are Stenotaphrum secunda-15 inch (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perennium, Agrostis tenuis, Cynodon dactylon (Bermu dawn), Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. poa pratense). The compounds can inhibit grass growth without giving significant phytotoxic effects and without adversely affecting the appearance of the grass (especially the color). This makes it attractive to use such connections on ornamental lawns and on grass discounts.

They can also have an effect on the floral head eg. grasses. The compounds may also inhibit the growth of weeds found in the grass. Examples of such weed species are semi-grasses (eg Cyperus spp.) And dicotyledone weeds (eg bellis, roadside, knobble, credit, thistle, debris and fire beaker). The growth of vegetation other than crops (eg weeds or cover vegetation) can be retarded, thus promoting the conservation of planting and field crops.

In orchards, especially plantations that are subject to soil erosion, the presence of grass cover is important. Excessive grass growth, however, requires substantial maintenance. The compounds of the invention may be useful in this case as they can limit growth without eradicating plants which would lead to soil erosion. At the same time, the level of competition for food and water with the grass will be reduced, and this can result in increased fruit yield.

16

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In some cases, a grass species may be more inhibited than other grass species. This selectivity may be useful e.g. to improve the quality of a grass blanket by preferably suppressing the growth of undesirable species.

Dwarf growth can also be useful in diminishing ornamental, household, oat and nursery plants (eg poinsettia, chrysanthemum, carnation, tulip and daffodil).

10

As indicated above, the compounds can also be used to reduce the growth of sluggish plants. This property can be used to control the growth of live fences or to shape fruit trees (eg apples). Some conifers' growth is not significantly inhibited by the compounds, so the compounds can be used to combat unwanted vegetation in coniferous nurseries.

The plant growth regulating effect may (as indicated above) appear in an increase in crop yield.

In potatoes, control of the top of the field and inhibition of germination during storage may be possible.

Other plant growth regulating effects caused by the bonds include altering leaf angle and promoting shoot formation in monocotyledonous plants. The aforementioned effect may be useful e.g. for changing the blade orientation of • e.g. potato crops, thereby more easily penetrating 30 candles into the crops and inducing an increase in photosynthesis and tuber growth. With increased shoot formation in monocotyledonous crops (-F = EKS = RIS), the number of flowering shoots per area is increased, thereby increasing the total grain yield of such crops. In overcast weather, an increase in shoot formation could lead to a closer overcast, which can result in increased weather resistance.

The treatment of plants with the compounds can lead to leaves,

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17 which develops a more dark green color.

The compounds may inhibit or at least delay the flowering of sugar beet, thereby increasing the sugar yield.

They can also reduce the size of sugar beet without significantly reducing the sugar yield, thereby making it possible to increase the planting density. Similarly, in other root crops (eg turnips, cold beet, · beetroot, parsnip, 10 root beets, yams and cassava), it may be possible to increase plant density.

The compounds may be useful for limiting the vegetative growth of cotton, thereby leading to an increase in the cotton wool yield.

The compounds can be useful in making the plants resistant to influences as the compounds can delay the emergence of plants grown from seed, shorten the stem height and delay flowering. These properties can be useful in preventing frost damage in countries where there is a significant snow cover in winter, as the treated plants will remain under the snow cover in the cold weather. Additionally, the compounds can cause drought and cold resistance in some plants.

When the compounds are used for seed treatment in small quantities, they can have a growth stimulating effect on plants. In carrying out the plant growth regulating method according to the invention, the amount of compound to be used to regulate the growth of plants will depend on a number of factors e.g. the particular compound chosen for use and the identity of the plant species whose growth must be regulated.

However, an application rate of 0.1 to 15, preferably 0.1 to 35 kg / ha, is usually used. However, in some plants even application rates within these ranges can produce undesirable phytotoxic effects. Routine trials may be necessary to determine the best appli- 18

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amount of cation for a particular compound for a particular purpose for which the compound is suitable.

The compounds may be used as such for fungicidal or plant growth regulating purposes, but are more usually prepared for agents for such uses. Such a fungicide or plant growth regulator comprises a compound which is a triazole compound of the invention or an ester, a site or a complex thereof, and a carrier or diluent.

The compounds can be used in a method for controlling fungal diseases in a plant, comprising the addition of a compound according to the invention or an ester, site or complex thereof to the plant, the plant's seed or the site of the plant 15 or the seeds. .

The compounds can also be used in a method of regulating the growth of a plant, the method comprising: adding to the plant, the seeds of the plant or the site of the plant or seeds, a compound according to the invention or an ester, a site or a complex thereof.

The compounds can be used in a variety of ways e.g. prepared or unprepared, directly on the leaves of a plant for seed or other medium in which the plants are grown or to be planted, or they can be sprayed, powdered or applied as a cream or paste or they can be applied as a vapor. The application can be done to anyone! of the plant, the bush or tree, e.g. to the stem, stems, branches or roots, or to the soil surrounding the roots, or to seed material and sprouts for sowing, laying and planting.

The term "plant" herein includes seedlings, shrubs and trees.

35 19

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The treatment can be a preventive, protective, prophylactic and eradicating treatment.

The compounds are preferably used for agricultural and horticultural purposes in the form of an agent. The type of agent used in a particular case will depend on the particular form in the particular case.

The agents may take the form of powder or powder comprising the active ingredient and a solid diluent or solid carrier, e.g. fillers, such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, Fuller soil, gypsum, Hewitt's soil, diatomaceous earth and kaolin. Such grains may be preformed grains which are suitable for application to the soil without further treatment. These grains can be prepared either by impregnating pills of filler with the active ingredient or by pelleting a mixture of the active ingredient and a powdered filler. Seeds for seed dressing can e.g. include a middle part (e.g., a mineral oil) which promotes the adhesion of the agent to the seeds. Alternatively, the active ingredient may be used for agitation purposes using an organic solvent (e.g., N-methylpyrrolidone or dimethylformamide).

25

The agents may also take the form of dispersible powders or grains comprising a wetting agent which facilitates dispersion in liquids of powder or grains which may also contain fillers and suspending agents.

30

The aqueous dispersions or emulsions can be prepared by dissolving the active ingredient (s) in an organic solvent optionally containing wetting, dispersing or emulsifying agents, and then adding the mixture to water which may also contain wetting agent (s). dispersants or emulsifiers. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol diacetone alcohol, toluene, kerosene,

DK 157364 B

methyl naphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (eg 2-ethoxyethanol and 2-butoxyethanol).

5

The agents to be used in such spraying agents can also take the form of aerosol preparations, the preparation being kept in a container under pressure in the presence of a propellant, e.g. fluorine trichloromethane or dichlorodifluoromethane.

10

The compounds may be admixed in a state with a pyrotechnic mixture to form an agent suitable for forming in a confined space a rye containing the compounds.

Alternatively, the compounds may be used in microencapsulated form.

By including suitable additives e.g. additives which improve the distribution, adhesion and resistance to rain on treated surfaces, the various agents may be made more suitable for different applications.

The compounds can be used as mixtures with fertilizers (eg nitrogen, potassium or phosphorus-containing fertilizers). The agents which comprise exclusively fertilizer grains containing the compound, e.g. is coated with the compound, is preferred. Such grains contain suitably up to 25 wt. Of the compound. The invention therefore also provides a fertilizer product which comprises a compound as previously defined.

The agents may also take the form of liquid preparations for use as dipping agents or spraying agents, which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants, e.g. wetting agents, dispersing agents, emulsifiers or suspending agents.

These agents may be cationic, anionic or nonionic agents. Suitable cationic agents are quaternary ammonium compounds, e.g. cetvltrimethvlammoniumbromid.

21

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Suitable anionic agents are soaps, salts of aliphatic mono esters of sulfuric acid (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butyl naphthalenesulfonate and mixture of sodium diisopropyl and triisopropyl naphthalene sulfonates).

Suitable nonionic agents are the condensation products of 10 ethylene oxide with fatty alcohols, such as oleyl or cetyl alcohol or with alkyl phenols, such as octyl or monylphenyl and octylcresol. Other non-ionic agents are the moieties derived from long chain fatty acids and hexitol anhydrides, the condensation products of said ethyl esters with the ethylene oxide and the lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethylcellulose) and the vegetable gums (e.g., acacia and trench rubber).

The agents for use as aqueous dispersions or emulsions are usually supplied in the form of a concentrate containing a large amount of the active ingredient or ingredients, the concentrate having to be diluted with water for use. These concentrates should often be able to withstand storage for longer periods of time, and after this storage can be diluted with water to form aqueous preparations which remain homogeneous for a sufficient period of time to be applied by conventional spraying equipment. The concentrations may conveniently contain up to 95%, suitably 10-85%, e.g. 25-60 30% by weight of the active ingredient (s).

These concentrates suitably contain organic acids (e.g., alkaryl or arylsulfonic acids, such as xylene sulfonic acid or dodecylbenzenesulfonic acid), as the presence of such acids may increase the solubility of the active ingredient or active ingredients in the polar solvents commonly used in the concentrates. Suitably, the concentrates also contain a large amount of surfactant so that sufficiently stable emulsions in water can be obtained.

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22

After dilution to form aqueous compositions, such compositions may contain varying amounts of the active ingredient or ingredients depending on the intended purpose, but an aqueous composition containing 0.0005% or 0.01 may be used. % to 10% by weight of the active ingredient (s).

The agents may also contain other compounds with biological effect e.g. compounds having similar or complementary, fungicidal or plant growth regulating effect or compounds having herbicide or insecticidal activity.

The second fungicidal compound may e.g. be a compound capable of combating grain diseases (such as wheat), such as Septoria, Gibberella and Helminthosporium spp., seed and soil diseases and leaf mold, and pulverized grapes on grapes and powdery mildew and apple scab etc ..

These mixtures of fungicides may have a wider spectrum of action than the compound of general formula (I) alone.

In addition, the second fungicide may have a synergistic effect on the fungicidal effect of the compound of general formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim, thiophanate methyl, captafol, captan, sulfur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethirimol, bupirimate, vincilonil, vincloronilonil presetyl-aluminum, carboxin, oxycarboxin, fenarimol, nuarimol, phenfuma, methfuroxane, nitrotal-isopropyl, triadimefone, thiaben-dazole, etridiazole, triadimenol, biloxazole, dithianone, bina-pacryl, quinomethionate, guazitinate, guazitinate, guazitine , dinocap, folpet, dichlorofluanide, ditalimphos, chitazine, cycloheximide, dichlorobutrazole and dithiocarbamate, a copper compound, a mercury compound, 1- (2-cyano-2-methoxy-aminoacetyl) -3-ethylurea, propanil, ofurace etaconazole and phenopropemorph.

The compounds of the general formula (I) can be mixed with soil, peat or other media to protect plants from seedlings, strawberries or foliar fungi.

23

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Suitable insecticides are pirimor, krone, dimethoate, meta-cystox and formothion.

The other plant growth regulating compound may be a compound which controls weeds or seedling formation, enhances the level or life of the plant growth regulator, the effect of the compounds of the general formula (I), selectively combating the growth of the less desirable plants (f. eg grasses) or cause the compound of the general formula (I) to act faster or slower as a plant growth regulator. Some of these other agents will be herbicides. Examples of suitable agents are the gibberellins (e.g., GA4, GA4, or GA7), the auxins (e.g., indole acetic acid, indole acetic acid, naphthoxyacetic acid, or naphthenylacetic acid), the cytokinins (e.g., kinetin, diphenylurea, benzene). - imidazole, benzyladenine or benzylaminopyridine), phenoxyacetic acids (eg 2,4-D or MCPA), pyridyloxyphenoxy propionic acids, substituted benzoic acids (eg triiodobenzoic acid), morphactins (eg chlorofluoroecol), maleic acid hydrazide , glyphosate, glyphosin, long chain fatty alcohols and acids, di-kegulac, fluoroidamide, mefluoidide, substituted quaternary ammonium and phosphonium compounds (e.g. , asulam, abscisic acid, ancymidol (and its analogs, e.g., isopyrimol), 1 (4-chloro-phenyl) -4,6-dimethyl-2-oxo-1,2-dihydroxypyridine-3-carboxylic acid, hydroxybenzonitriles (e.g., bromooxynyl, dipenzoquate, benzoylpropethyl, 3,6-cichloropicolinic acid or the like) clay thio carbamter.

3 5

The following examples illustrate the invention. The temperatures o "are set at ι C.

24

DK 157364 B

Example 1.

1- (1,2,4-Triazol-1-yl) -2,3-diphenylpropan-2-ol Benzyl chloride (0.2 mol) was dissolved in tar diethyl ether (200 ml) and dripped to magnesium pans (0.22 g atoms). After reacting the entire amount of magnesium, the solution was refluxed for 1 hour and cooled to room temperature. Phenacyl chloride (0.1 mole) in tar diethyl ether (100 ml) was added dropwise in the lobe of 1 hour with such rapidity that a slight reflux was maintained. The solution was then refluxed for 2 hours and cooled to room temperature. The mixture was poured into ice and the complex decomposed with ammonium chloride solution. The ethereal solution was washed several times with water (2 x 200 ml), tarred (Na 2 SO 4), and the solvent removed in vacuo. There was thus obtained a colorless oil, namely the crude chlorohydrin dissolved in dimethylformamide (80 ml) and a solution of sodium triazole [prepared from sodium (0.1 g atom) in ethanol (40 ml) and 1 , 2,4-triazole (0.1 mol)] added dropwise at room temperature. After stirring at room temperature for 2 hours, the solution was heated to 50 ° C for 3 hours. The solvent was removed in vacuo and the residue poured into water to obtain a crystalline solid which was recrystallized from ethanol / petroleum.

25 O

ether to give the title compound, m.p. 124.5 ° C.

Example 2.

1- (1,2,4-Triazol-1-yl) -2-phenyl-3-p-fluorophenylpropan-2-ol.

30 p-fluorobenzyl chloride (0.1 mole) in tar diethyl ether (100 ml) was added dropwise to magnesium slurry (0.11 g atom) and the solution stirred vigorously until reflux occurred.

After reacting the entire amount of magnesium, the solution was refluxed for an additional 1 hour and then cooled to room temperature. Phenacyl chloride (0.05 mole) in tar diethyl ether (50 ml) was added dropwise to the solution in the lobe of 1

DK 157364 B

hour at such a rate that weak reflux was maintained. The mixture was refluxed for 2 hours and cooled to room temperature and poured into ice / ammonium chloride solution to decompose the complex. The ethereal solution was washed several times with water (2 x 200 ml), dried (3032304) and the solvent removed in vacuo to give the crude chloride hydrate as a colorless oil. The latter was dissolved in dimethylformamide (40 ml) and a solution of sodium triazole [prepared from sodium 10 (0.05 g atomic acid) in methanol (20 ml) and 1,2,4-triazole (0.05 mol)] was added dropwise at room temperature. After stirring at room temperature for 2 hours, the solution was heated to 50 ° C for 3 hours. The solvent was removed in vacuo and the mixture poured into water to obtain a crystalline solid which was recrystallized from petroleum ether / chloroform to give the title compound, mp 116-118 ° C.

Example 3

δ> 1,1-diphenyl-2- (1,2,4-triazol-1-yl) -ethan-1-ol (Compound 17).

Step 1. Bromobenzene (0.2 mole, 31.4 g) of sodium ter diethyl ether (200 ml) was added dropwise to magnesium (0.22 g of 25 atom, 5.3 g). After reacting the entire amount of magnesium, phenacyl chloride (0.1 mol, 15.5 g) in diethyl ether (100 ml) was added dropwise and the solution was stirred at room temperature for 1 hour. The reaction mixture was poured into saturated ammonium chloride solution, washed with water (3 x 150 ml) and terre 30 (Na 2 SO 4). Removal of the ether gave a pale yellow oil which solidified on standing. Recrystallization from petroleum ether (60-80 ° C) gave 1,1-diphenyl-2-chloroethan-1-ol (60%) as a white crystalline solid, mp 56-57 ° C.

Step 2. 1,2,4-triazole (0.03 mol, 2.07 g) was added portionwise to a suspension of sodium hydride (0.03 mol, 0.72 g) in DMF (30 ml) and the solution stir until the effervescence 35 26

DK 157364 B

ceased. 1,1-diphenyl-2-chloroethan-1-ol (0.015 mole, 2.94 g) in dimethylformamide (DMF, 10 ml) was added dropwise and the solution heated to 100 ° C for 6 hours. The reaction mixture was poured into water and a white solid was crystallized out. This was filtered off, washed with water, dried and recrystallized from ethanol to give the title compound as a white crystalline substance, mp 128-129 ° C.

Example 4

1- (1,2,4-trazol-1-yl) -2-o-chlorophenyl-2-p-fluorophenylethan-2-ol (Compound 45).

A solution of dimethyloxosulfonium methylide was prepared-15

slightly under nitrogen of sodium hydride (0.03 mol) and powdered trimethyloxosulfonium iodide (0.03 mol) in ter dimethyl sulfoxide (DMSO, 30 ml). A solution of o-chlorophenyl-p-fluoro-phenyl ketone (0.025 mol) in DMSO (10 ml) was added dropwise at room temperature. The solution was then heated to 50 ° C

20 for 1 1/2 hours, cooled to room temperature and poured into water. The solution was extracted with diethyl ether (100 ml), washed with water (3 x 100 ml) and dried over anhydrous sodium sulfate. Removal of the solvent gave 1-o-chlorophenyl-1- p-fluorophenylethylene oxide (90%) as a colorless liquid.

25 1,2,4-triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in DMF (40 ml) and the solution stirred at room temperature until the effervescence ceased. 1-o-chlorophenyl-1-p-fluorophenylethylene oxide (0.02 mol) in DMF (10 ml) was added dropwise and the solution stirred at 80 ° C for 4 hours. The solution was poured into water and probed with petroleum ether to give a crystalline solid which was filtered off and dried. Recrystallization from petroleum ether (60-80 ° C) / methylene chloride gave the title compound (70%) as a white crystalline solid, mp 115-116 ° C.

27

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Example 5

2,2-dimethyl-3- (o-xnethoxybenzyl) -3- (1,2,4-triazol-1-yl) -butam-3-ol (compound 130).

5

Step 1: Potassium t-butoxide (19 g) was dissolved in dimethyl sulfide oxide (200 ml, dried by distillation from calcium hydride and sodium amide) and pincolone (15 g freshly distilled from calcium hydride) was added under argon to give a crude solution. o-Methoxyphenyl iodide (10 g) was then added and a brown color developed rapidly. The solution was stirred for 1 1/2 hours before being poured into water (1 liter) and the mixture was acidified with 2M hydrochloric acid and extracted with diethyl ether. Evaporation of the dried (MgSO 4) ethereal solution gave a gui liquid (11.8 g), bp 88-93 ° C / 0.9 mm.

The distillate solidified to form 2,2-dimethyl-4- (o-methoxyphenyl) butan-3-one (6 g).

Step 2: Thioanisole (3.3 g) was added to diazobicyclooctane

P Q

(3.5 g) in dry tetrahydrofuran (THF) under argon and the colorless solution was cooled in an ice / salt bath. 1.6M-Butyllithium solution (20 ml) in hexane was then added over 10 minutes at 0-2 ° C. After stirring the yellow solution for 15 minutes, a solid precipitated. The mixture was stirred for an additional 45 minutes in the ice bath and allowed to stand at room temperature. The mixture was then cooled in an ice bath and a solution of the product (5 g) from step 1 of ter THF (25 ml) was added at 0-5 ° C. Upon completion of the addition, the resulting yellow solution was allowed to stand overnight and then poured into water, acidified with 2M hydrochloric acid and extracted with diethyl ether. The ethereal solution was carefully washed with water, dried (MgSO4) and evaporated to give a gui liquid (8.8 g) which solidified on standing.

Recrystallization from petroleum ether (60-80 ° C) gave 2,2-dimethyl-3-hydroxy-3- (o-methoxybenzyl) -4-thiophenylbutane (3.1 g), mp 74-75 ° C.

28

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Step 31 The product (2.5 g) from step 2 was added to a stirred suspension of trimethyloxonium tetrafluoroborate (1.3 g) in methylene chloride (25 ml). After approx. A clear solution was reached for 1 hour. The solvent was then removed on a rotary evaporator to form a lyso-range gum which was dissolved in dry DMP (10 ml) and the solution was added to a solution of 1,2,4-triazole sodium salt (1.2 g) in DMP (15 ml). [The solution was prepared by washing sodium hydride with ter diethyl ether, suspending it in dry DMF and adding the triazole]. The reaction mixture was then stirred at 120 ° C for 2 1/2 hours. The reaction mixture was then cooled rapidly by pouring into water (100 ml) and the emulsion was extracted with diethyl ether (3 x 50 ml).

The ethereal solution was washed thoroughly with water, dried (MgSO4) and evaporated to give a pale yellow liquid. The mixture was subjected to column chromatography on silica, eluting with diethyl ether to give a colorless liquid which solidified by probing with diethyl ether. Recrystallization from petroleum ether (60-80 ° C) gave the title compound (0.5 g, 23%), mp 113-116 ° C.

Example 6

2- (1,2,4-Triazol-1-yl) -1-cyclopentyl-1- (2,4-dichlorophenyl) ethanol (Compound No. 313)

Cyclohexene oxide (19.6 g, 0.2 mole) in sodium dried ether (45 ml) was added dropwise to the Grignard reagent formed from 2,4-dichlorodiodo benzene (54.6 g, 0.2 mole) and magnesium pans (5.0 g, 0.2 g atoms) in sodium-dried ether (100 ml) with cooling to 0-10 ° C. After complete addition, the solution was warmed to room temperature. Toluene (100 ml) was added and the ether removed at 70 ° C. The solution was stirred at 70-80 ° C for 2 hours, cooled to room temperature and acidified with 2N H 2 SO 4 (300 mL). The ether layer was washed with 2N H2SO4 (2 x 200 mL), water (2 x 250 mL) and dried over anhydrous sodium sulfate. Removal of the solvent gave a 29

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mercurial oil which upon purification (flash chromatography on silica eluted with hexane: touue = 1: 1) gave cyclopenty1-2,4-dichlorophenylmethanol (24.5 g) as an orange oil.

Cyclopentyl-2,4-dichlorophenylmethanol (8.5 g, 0.035 mol) was stirred in acetic acid (85 ml) and a solution of chromium trioxide (10.6 g, 0.1 mol) in water (40 ml). was added dropwise at room temperature. After complete addition, the reaction mixture was heated to 50 ° C for 2 hours, cooled to 10 room temperature, poured into water (100 ml) and extracted with ether (2 x 200 ml). The ether extracts were washed with 2N NaOH (2 x 200 mL) and water (2 x 200 mL) and dried over anhydrous sodium sulfate. Removal of the solvent gave a pure liquid which on purification (flash chromatography on silica eluted with hexane: toluene = 7: 3) gave cyclopentyl-2,4-dichlorophenyl ketone (5.1 g).

Sodium hydride (0.48 g, 0.02 mol) was suspended in tort DMSO (20 ml) and heated to 70 ° C for 2 hours under nitrogen.

After cooling to 0 ° C, tort THF (20 ml) was added followed by trimethylsulfonium iodide (4.08 g, 0.02 mol) in tort DMS0 (20 ml) and the solution was stirred at 0 ° C for 2 minutes.

Cyclopentyl-2,4-dichlorophenyl ketone (2.43 g, 0.01 mol) in tort DMSO (10 ml) and tort THF (10 ml) was added to this mixture at 0 ° C and the solution was allowed to be warmed to room temperature over the course of 2 hours. The reaction mixture was then poured into water (200 ml) and extracted with ether (3 x 150 ml). The ether extracts were washed with water (5 x 200 ml) and dried over anhydrous sodium sulfate, and the solvent was removed to give 1-cyclopentyl-1- (2,4-dichlorophenyl) ethylene oxide (2.57 g) gui oil.

A solution of 1-cyclopentyl-1- (2,4-dichlorophenyl) ethylene oxide (2.57 g, 0.01 mole) in tort DMF (2 ml) was added to a stirred solution of sodium triazole [from 1 , 2,4-triazole (1.38 g, 0.02 mol) and sodium hydride (0.48 g, 0.02 mol)] in tort DMF (20 ml) at room temperature. The reaction mixture was heated to 90 ° C for 5 hours and then allowed to 30

DK 157364 B

/ decolour, where it was poured into water and extracted with diethyl ether. The ether extracts were washed with water and then concentrated over anhydrous sodium sulfate and concentrated under reduced pressure to give a white solid which was purified (flash chromatography on silica eluted with ethyl acetate-petrol = 1: 1) to give the title compound (1, 1 g), m.p. 157eC.

Example 7

10

The compounds were tested against a wide range of foliar fungal diseases in plants. The following technique was used.

The plants were grown in John Innes Potting Compost (no. 1 or 2) in mini pots with a diameter of 4 cm. A layer of fine sand was placed in the bottom of the pots containing the dicotyledonous plants to facilitate the uptake of the test compound by the roots. The test compounds were prepared either by 20 ball milling with aqueous Dispersol T or as a solution in acetone or acetone / ethanol, diluted to the required concentration immediately for use. For leaf diseases, suspensions (100 ppm) of active ingredient were sprayed onto the soil. An exception to this was the tests on Botrytis cinerea,

2 S

Plasmopara viticola and Venturia inaequalis. The spray preparations were applied to maximum retention and the roots soaked to a final concentration of 40 ppm a./tor. Tween 20, to achieve a final concentration of 0.05%, was added when the spray preparations were used for cereal varieties.

For most of the forests, the compound was added to the soil (roots) and promised (by spraying) one or two days, for the plant was inoculated with the diseases. An exception was the test on Erysiphe graminis, where the plants were inoculated 24 hours before treatment. After inoculation was

DK 157364 B

The 31 animals were placed in an appropriate milieu to allow the infraction to occur and then incubate until the disease was ready for determination. The period between inoculation and determination ranged from 4 to 14 days, depending on the disease and the environment.

5

The disease control was recorded using the following scale: 4 = no disease 3 = trace - 5% disease on untreated plants 2 = 6-25% disease on untreated plants 1 = 26-59% disease on untreated plants 0 = 60- 100% disease on untreated plants.

15

The results are shown in Table II.

20 25 30 35

32 DK 157364 B

CO ~

H

H

<C - H K φ K O r-i MS £

H H

--—- - C H - KO Ό o u S CL) H c CO Q T3

OH I

UK o «U -π H C ~

U K

C _______________ ~ co H C ~

B H YY (C

khg BS θ (, Γ> (ν ·) ΜΓ, ·> ηο ··) '' 3, '3 <Γθ * 3 <ρ ·> Ι-ι <ν) Γ' ·> '> ι, ηΓ' ' ) θΓ '·)' ΐ, '* ρ OH jj mu - c

K

ο co K K -.

B C 4-) K B φ

2 g ο ο O O and I HOOi — IOOOOOCNOOOOO

OH O B K JJ X S -

K H CM

H

H <3 K c

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DK 157364 B

37

Example 8.

This example illustrates the plant growth regulating properties of the compounds. The compounds were used in the form of a 4000 ppm solution in distilled water and the solution was transferred to the leaves of young seedlings of various plants. The experiments were repeated twice. At 12 or 13 days after treatment, the plants were determined for plant growth regulating effects and phytotoxic symptoms.

Table III shows the growth inhibitory effect of compounds 10 on vegetative growth by the following scale: 1 = 0-30% inhibition 2 = 31-75% inhibition 3 = 75% inhibition.

Although no number is given, the compound of all 15 was substantially ineffective as a growth inhibitor. Additional plant growth regulating properties are listed as follows: G = more dark green leaf color A = apical effect T = effect on shoot formation.

DK 157364 B

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DK 157364 B

Example 9

In this example, the effect of the following compounds of GB Patent No. 1,529,818 is compared with the compounds of the invention also set forth below.

-

CONNECT STRUCTURE

NUMBER

! 0 -; -

In OH

(Compound | f / # 1 in ta- "" "" ".CH-CH - (/ ') - Cl bell I in GB (CH

Chfg 15__ II OH _ (Compound Tr - | /? No. 3 in ta- - CH-CH- \ y bel I in GB Cl / \ / 1,529,818)

III OH

(Compound Tr | /) # 4 in ta- _ __ * CH-CH- ('N)

call I in GB / 7 ~ \ W

1.529.818) V y -CH2

IV OH

(Compound Tr____ | No. 11 in Ta- - "~~ - ^ CH-CH f y-'Cl bell I in GB // \ \ _ / 30 1,529,818) F-V y-CH2 - 35

DK 157364 B

40

CONNECT STRUCTURE

NUMBER

5 V F

(Connection

No. 13 in ta- OH

call I in GB CH2 1,529,818) I, __ I ^ ΓΛ

Tr-CH-C- (f x) -Cl

I_U W

we flew h

(Compound F

No. 6 in ta-ÇH2 f / bel I in GB Tr-CH-CH-V 'V- Cl 15 1,529,818) \ - /

WE YOU

(Compound I II

No. 5 in ta- ^ y '^ Cl OH

call I in GB CH2 I

20 1,529,818) | In fi ^ T r-C H-C H- {f y-C 1 VIII OH _ (Compound 1 u

No. 17 Tr-CH2-Ç-V

25 1 \ - /

Table I) J

XIII OH _ (Compound | // v.

No. 6 in ta- Tr-CH2 - C-CH2— ('y bel I) \ - / 35

CONNECT STRUCTURE

NUMBER

41

DK 157364 B

XIV OH _ (Compound | U # 1 in ta- T1 - CH2-C-CH2 ~~ \ /

-1 11 W

kJ

10 ---

XVIII OH

(Compound | Fig. 14 of T r-CH2-C- ('M-Cl Table I) | \ - / ch2 ·· __ùr'

XX OH

{Connection} fi

No. 45 in Tr-CH 2 -C - ('' V— F

Table I) I \ _ / 2 ° [Tl "___

XXII OH

(Compound | fi ^

No. 27 in Tr-CH 2 -e- (f y-F

Table I) \ - /

Cl

XXIII OH

(Compound | /, λ

JU No. 46 in Tr-CH2-C - // Λ_F

Table 1) J. F \ == y ___ 35

DK 157364 B

42

CONNECT STRUCTURE

NUMBER

5 XXIV OH ._ (Compound | fi \\

No. 29 in Tr-CH2-Ç - (/ F

Table I) | p ^ | \ / 10 - NB. In the above list, "Tr" means 1,2,4-1 r in the azole group, ie. N-N- 15 20 25 30 35

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Claims (2)

A triazole compound, characterized by the general formula (I) OH N-N-C H o-C-R1 15. J 1 wherein R 1 is C 1-4 alkyl or C 3-6 cycloalkyl and R 2 is benzyl optionally substituted with halogen, C 1-4 alkyl, C 1-4 alkoxy, CF 3, nitro, phenyl or phenoxy; or R * is phenyl optionally substituted with halogen, C 1-6 alkyl, O 4 -4-alkoxy, CF 3, nitro or phenoxy, and R 2 is phenyl or benzyl optionally substituted by fluoro, bromo, iodo , C1-5 alkyl, C1-4 alkoxy, CF3, nitro or phenoxy, or acid addition salts thereof, with the proviso that the compounds of formula (I) wherein R 1 is chloro-substituted phenyl and R 2 is phenyl are excluded. Compound according to claim 1, characterized by the general formula: 30 OH, N-N-CH 2 -c-Γ) -F