DK159801B - Use of triazole compounds for controlling fungi in plants - Google Patents

Description

in

DK 159801 B

This invention relates to the use of triazole compounds of Form-1:

OH

5 I

N-N-CH 2 -C-Ri I

wherein R 1 is C 1-4 alkyl or cycloalkyl and R 2 is benzyl optionally substituted with halogen, C 1-6 alkyl, C 1-4 alkoxy, CF 3, nitro, phenyl or phenoxy; or RA is phenyl optionally substituted with halogen, C 1-6 alkyl, C 1-4 alkoxy, CF 3, nitro or phenoxy, and R 2 is phenyl or benzyl optionally substituted with halogen, C 1-6 alkyl, 0-4 alkoxy, CF 3, nitro or phenoxy to control plant fungi.

From GB patent specification 1,529,818 it is known to use certain 1,2,4-triazole compounds to control fungal diseases in plants. In comparison, the present invention constitutes a selection invention in that the triazole compounds used in accordance with the present invention have an unexpectedly potent effect and are surprisingly effective against a greater number of diseases (see Example 9 below).

25

The triazole compounds of the formula shown can be used as such or in the form of an acid addition salt or a metal complex thereof.

30

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

35,

The alkyl group R1 may be a straight or branched group of 1-4 carbon atoms. Examples are methyl, ethyl, propyl (n- or iso-propyl) and butyl (η-, sec-, iso- or t-butyl).

2

DK 159801 B

Examples of suitable substituents for the phenyl and for the phenyl moiety of the benzyl are halogen (e.g., fluoro, chloro or bromo), C1-5 alkyl [e.g. methyl, ethyl, propyl (n- or isopropyl) and butyl (η-, sec-, iso- or t-butyl)], C1-6 alkoxy (e.g.

5 methoxy and ethoxy), trifluoromethyl, nitro, phenyl and phenoxy. 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-11 position. Examples of these groups are phenyl, benzyl, α-methylbenzyl, o-, m- or p-chlorophenyl, 2,4- or 2,6-dichlorophenyl, o-, m- or p-fluoromethyl, 2,4- or 2,6-difluorophenyl, o-, m- or p-bromophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2-chloro-6-fluorophenyl, o-, m- or p -methoxyphenyl, 2,4-dimethoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-nitrophenyl, 2-chloro-4-nitrophenyl, 2-chloro-5-nitrophenyl, o- , m- or p-methylphenyl, 2,4-dimethylphenyl, o-, m- or pt-butylphenyl, 2-fluoro-4-methoxyphenyl, 2-methoxy-4-fluorophenyl, 2-methoxy-4-chlorophenyl, 2- methoxy-4-fluorophenyl, o-, m- or 20-p-phenoxyphenyl, o-, m- or p-phenylphenyl (o-, m- or p-biphenylyl) and the corresponding ring-substituted benzyl groups.

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.

The metal complex is conveniently a complex comprising as metal, copper, zinc, manganese or iron. It preferably has the general formula: 3

DK 159801 B

i ° H λ

M J N — N-CH ~ -C ^ / yH ^ O

, wherein Y, R 1 and R 2 have the meanings defined above, M is a metal, A is an anion (e.g., a chloride, bromide, iodide, nitrate, sulfate or phosphate anion), n is 2 or 4, and y is 0 or an integer from 1 to 12.

Examples of the compounds inherited according to the invention are shown in Table I 15 20 25 30 35 - 4 -

DK 159801 B

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DK 159801 B

x Includes 1 mole of ethanol occluded in the crystal lattice.

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

N-Pe = n-pentyl n-He = n-hexyl = cyclopropyl = cyclopentyl CgH ^ = cyclohexyl 10

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

CHO-C-R X-CII-C-R

Wherein R and R have the meanings defined above and X 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.

DK 159301B

η

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

ISLAND ISLAND

II -i 11-2

X — CH2 — C — ΈΓ X ~ CH2 — C — R

(IVa) (IVb) 1 2 5 wherein R, R and X have the meanings defined above, with a Grignard compound of the general formula (Va) or (Vb) respectively: Y — Jig — R 2 Y — Mg — R1 (Va) (Vb) wherein R and R 4 are as 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 1 is alkyl or cycloalkyl, e.g. reaction, the compound of formula (II) generally dominates in the mixture. When, on the other hand, R R is optionally substituted phenyl, the compound of the general formula (III) generally dominates in the mixture.

The compounds of general formulas (IV) and (V) can be prepared.

20 by methods cited in the literature.

1?

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 benzo-phenone compound of the general formula (VI) 25 R1-CO-R212

DK 159801 B

12 - wherein R and R have the meanings defined above, dimethyloxosulfonium methylide (Corey and Chaykovsky JACS, 1965, 87, 1353-1364) or dimethylsulfonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782) using 5 cited in the literature methods.

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.

The compounds of general formula (II) wherein each R 2 is alkyl, cycloalkyl or optionally substituted phenyl, 2 and R is optionally substituted phenyl or optionally substituted benzyl, may also be prepared by reacting a β-hydroxy selenide compound of the general formula (VII) R1

CH3-Se-CH 2 -C-OH

in 2 (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-hydroxyselenide compound can be prepared by treating the diselenide with the appropriate ketone in the presence of butyl = lithium.

The compounds of general formula (III) wherein R 1 is 2 alkyl 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) 13

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OH

i 1

ArSCH2- (j: R

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 and metal complexes of the compounds of general formula (I) can be prepared from the latter in known manner.

The complexes can e.g. is prepared by reacting the non-complexed compound with a metal salt in a suitable solvent.

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 diastereoisomeric salts or esters of the compound of 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 for the enantiomers of the compound of the general formula (I); (2) forming the diastereoisomeric carbamates of the compound of general formula (I) by reacting a haloformate 25 (e.g., chloroformate) of the latter with an optically active amine (e.g., α-methylbenzylamine), separating the isomeric carbamates and conversion of the separated isomeric carbamates to the enantiomers of the compound of general formula (I), (3) formation of the hemiphthate of the compound of general formula (I), reaction of the hemiphthate with an optical 14

DK 159801 B

active amine (e.g., α-methylbenzylamine) to form a salt of the hemiphthate, separation of the isomeric salts, and conversion of the separated salts to the enantiomers of the compound of general formula (I) j or (4) cleavage 5 of the mixtures deplete the use of enantioselective crystallization technique (Leigh, Chemistry 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. crystal licensing technique or high pressure liquid chromatography (HPLC). Alternatively, the enantiomers can 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.

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

Piricularia oryzae on rice, 20 Puccinia recondita, Puccinia striiformis and other wheat varieties, Puccinia hordei, Puccinia striiformis and other barley rust and other host plant species e.g. coffee, apples, vegetables and ornamental plants,

Plasmopara viticola on wine, 25 Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew forms on various hosts, such as Sphaerotheca fuliginea on cucumber,

Podosphaera leucotricha on apples and Uncinula necator on wine, Helminthosporium spp. and Ehynchosporium spp. on cereals, 30 Cercospora arachidicola on peanuts and other Cercospora forms on e.g. sugar beet, bananas and soybeans,

Botrytis cinerea (gray mold) on tomatoes, blackberries, wine and other hosts,

Phytophthora infestans (potato mold) on tomatoes, 35 Venturia inaequalis (scab) on apples.

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15

Some of the compounds have also shown a broad spectrum activity against fungi in vitro. They are effective against various post-harvest diseases of fruit (eg Penicillium digatatum and italicum on oranges and Gloeosporium musarum 5 on bananas). In addition, some of the compounds act as pesticides against: Fusarium spp., Septoria spp.> Tilletia spp. (i.e. wheat stink fire, which is a seed-borne disease on wheat), Ustilago spp., Helminthosporium spp. on cereals, Ehizoctonia solani on cotton and Corticium sasakii on rice.

10 The compounds can 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 15 fungal attacks on wood, hides, leather and special paint films.

The compounds may also have plant growth regulating effects.

The plant growth regulating effects of the compounds appear e.g. as a crippling or dwarf washing effect on the vegetative growth of woody and herbaceous mono- and di-cotyledonone plants. Such crippling or dwarf growth may be useful, e.g. in peanuts, grains and soybean, when reduction in stem growth can reduce the risk of plants going to bed, and may also allow 25 infusions of increased fertilizer amounts. The growth inhibition of woody species is useful in controlling the growth of bottom vegetation under high current lines, etc .. Compounds which induce growth inhibition may also be useful in modifying the stem growth of sugarcane, thereby increasing the concentration of sugar in the tube at harvest. IN

sugar cane can affect flowering and maturation through application of the compounds. Inhibited growth of peanuts can facilitate harvesting. Growth inhibition of grasses can help with 16

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for the preservation of grass rugs. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perennium, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca 5 spp. (eg Festuca rubra} and Poa spp. (eg 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 compounds on ornamental lawns and 10 on grass discounts. They may also have an effect on the main flower of eg. grasses. The compounds can also inhibit the growth of weeds found in the grass. Examples of such weed species are semi-grasses (e.g., Cyperus spp.) And dicotyledone weeds (e.g. bellis, roadbird, 15 knot herb, honorary price, thistle, debris and firebird ^.) The growth of vegetation other than crop (e.g. Weeds can be retarded and thus promoted the conservation of planting and field crops. In orchards, especially plantations that are subject to soil erosion, the presence of 20 grass cover is important. Excessive grass growth, however, requires substantial maintenance. in this case, as they can limit the washing without eradicating the plants, which would lead to soil erosion. At the same time, the level of competition for nutrients and water with the grass will be reduced and this can result in increased fruit yield. grass species become inhibited in growth more than other grass species. This selectivity can be useful, for example, to improve the quality of f a grass blanket by preferably suppressing the growth of undesirable species.

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

As indicated above, the compounds can also be used to reduce the washing of woody plants. This property can 17

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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 control unwanted vegetation in coniferous nurseries.

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

In potatoes can control the top of the field and inhibition of germination .; during storage be possible.

10 Other plant growth regulating effects caused by the bonds include changing leaf angle and promoting shoot formation ± monocotyledonous plants. The former effect may be useful e.g. for changing the blade orientation of e.g. potato crops, thereby allowing more light to enter the crops and inducing an increase in photosynthesis and tuber weight. With increased shoot formation in monocotyledonous crops (eg rice), the number of flowering shoots per area unit is increased, thereby increasing the total grain yield of such crops. In green weather 20, an increase in shoot formation could lead to a closer green weather, which can result in increased weather resistance.

The treatment of plants with the compounds can lead to leaves that develop a darker 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 sugar yield, thereby enabling an increase in planting density.

30 Similarly, in other root crops (eg turnips, cabbage, cuttlefish, parsnip, beetroot, yams and cassava), it may be possible to increase planting density.

18

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

The compounds may be useful in making the plants resistant to stress as the compounds can delay the emergence of plants grown from seeds, 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, since the treated plants will then remain below the snow cover in the cold weather. The compounds can also cause drought and cold resistance in some plants.

When the compounds are used for seed treatment in small amounts, they can have a growth-stimulating effect on plants. In carrying out the plant growth regulating method of 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 selected 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 5 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 amount of application for a particular compound for a particular purpose for which the compound is suitable.

The compounds can be used as such for fungicidal or plant growth regulating purposes, but are more usually prepared for agents for such applications. Thus, the invention also provides the use of a fungicide or plant growth regulator which comprises a compound which is an enantiomer or ester, salt or complex thereof, and a carrier or diluent.

19

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In the use of the invention to control fungal diseases in a plant, a compound which is an enantiomer or an ester, a salt or a complex thereof may be added to the plant, the seed of the plant or the site of the plant or seeds.

It is also possible to regulate the growth of a plant by adding to the plant, the seeds of the plant or the site of the plant or seeds, a compound which is a 10 enantiomer or an ester, a salt or a complex thereof, as previously defined.

The compounds can be used in a variety of ways e.g. prepared or unprepared, directly on a plant's 15 leaves for seeds 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 made to any part of the plant, shrub or tree, e.g. for the foliage, stems, 20 branches or roots, or for the soil surrounding the roots, or for seedling material and sprouts before sowing, laying and planting.

The term "plant" herein includes seedlings, shrubs and trees. The fungicidal use according to the invention further comprises 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 purpose 30 in that case.

The agents may be in the form of powders or powders comprising the active ingredient and a solid diluent or liquid.

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a solid support, e.g. fillers such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, Fuller soil, plaster, Hewitt's soil, diatomaceous earth and kaolin. Such grains may be preformed grains which are suitable for application to the soil without further processing. 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. Seed dressing agents may e.g. include an agent (e.g., a mineral oil) which promotes the adhesion of the agent to the seeds. Alternatively, the active ingredient can be prepared for seed processing purposes using an organic solvent (e.g., N-methylpyr = rolidone or dimethylformamide).

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

The aqueous dispersions or emulsions may 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, dispersing, or emulsifiers. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methyl naphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (eg 2-ethoxyethanol).

The agents to be used as spraying agents may also take the form of aerosol preparations, the preparation being held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

21

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

Alternatively, the compounds may be used in microencapsulated form.

By including suitable additives e.g. additives which improve the distribution, adhesiveness and resistance to rain on treated surfaces, the various agents can 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 solely fertilizer grains containing the compound, e.g. is coated with the compound, is preferred. Such grains suitably contain up to 25% by weight of the compound.

The agents may also have liquid compositions 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. cetyltrimethylammoniumbromide.

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 ligno = 22

DK 159801 B

sulfonate, butyl naphthalene sulfonate and a mixture of sodium = diisopropyl and triisopropyl naphthalenesulfonates).

Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol = 5 or with alkyl phenols such as octyl or nonylphenol and octylcresol. Other nonionic agents are the moieties derived from long chain fatty acids and hexitol anhydrides, the condensation products of said ethylene oxide moieties and the lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethyl = cellulose) and the vegetable gums (e.g., acacia and tragacanth).

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 before use. These concentrates should often be able to withstand storage for extended periods of time and, after this storage, be diluted with water to form aqueous compositions which remain homogeneous for a sufficient period of time for application by conventional spraying equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, e.g. 25-60% by weight of the active ingredient (s). These concentrates suitably contain organic acids (e.g., alkaryl or arylsulfonic acids such as xylenesulfonic acid or dodecylbenzenesulfonic acid), as the presence of such acids may increase the solubility: of the active ingredient (s) in the polar solvents which often used in the concentrates. Suitably, the concentrates also contain a large amount of surfactant so that sufficiently stable emulsions in water can be obtained. After dilution to form aqueous compositions, such compositions may contain varying amounts of the active ingredient (s) depending on the intended purpose, but may be used.

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an aqueous composition containing 0.0005% or 0.01% to 10% by weight of the active ingredient (s).

The agents may also contain other biological action compounds 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 controlling grain diseases (eg wheat) such as Septoria, Gibberella and Helmintho sporium spp., seed and soil borne diseases and leaf mold and powdery mildew on grapes and powdery mildew and scab on apple etc ..

These mixtures of fungicides may have a wider spectrum of action than the compound of the 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 second fungicidal compound are imazalil, benomyl, carbendazim, thiophanate-methyl, captafol, captan, sulfur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethiri = mol, bupirimate, chlorthalonil, vinclozoline, vinclozoline, vinclozoline metalaxyl, presetyl aluminum, carboxin, oxy = carboxin, fenarimol, nuarimol, fenfuram, methfuroxane, nitrotal-isopropyl, triadimefon, thiabendazole, etridiazole, triadimenol, biloxazole, dithianone, binapacryl, quinomethine, quinomethioin, natin , dino = cap, folpet, dichlorofluanide, ditalimphos, chitazine, cycloheximide, dichlorobutrazole and dithiocarbamate, a copper compound, a mercury compound, 1- (2-cyano-2-relay oxyirninoacetyl) -3-ethylurea, phenapanil ofurace, propiconazole, etaconazole and phenoproperrorph.

The compounds of the general formula (I) may be mixed with soil, peat or other media to protect plants from seed trees, soil borne. or leaf fungal diseases.

24

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Suitable insecticides are pirimor, krone, dimethoate, meta = systox and formothion.

The second plant growth regulating compound may be a compound which controls weeds or seed head formation, improves the level or life of the plant growth regulating effect of the compounds of general formula (I), selectively combats the growth of the less desirable plants (e.g. grasses) or causing the compound of 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. GA ^, GA ^ or GA ^), the auxins (e.g., indole acetic acid, indole butyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. , benzimidazole, benzyladenine or benzylaminopyrine), phenoxyacetic acids (e.g. 2,4-D or MCPA), pyridyl = oxyphenoxypropionic acids, substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g. chlorofluorecol), maleic = acid hydrazide, glyphosate, glyphosin, long-chain fatty alcohols and acids, dikegulac, fluoroidamide, mefluoidide, substituted quaternary ammonium and phosphonium compounds (e.g., chlorine = mequat, mepiquat chloride or chlorophonium), dichloroanicate, daminocide, asulam, abscisic acid, ancymidol (and its analogs, eg isppyrimol), 1- (4-chloro = phenyl) -4,6-dimethyl-2-oxo-1,2-dihydroxypyridine-3-carboxyl = acid, hydroxybenzonitriles (e.g. bromooxynil, dipenzoquate, benzoylpropethyl, 3,6-cichloropicolinic acid or thiocarbamates.

The following examples illustrate the invention. Temperatures are given in ° C.

Example 1.

1- (l, 2/4-triazol-l-yl) -2,3-diphenylpropane-2-ol

Benzyl chloride (0.2 mole) was dissolved in dry diethyl ether (200 ml) and dripped to magnesium shavings (0.22 g atoms).

25

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After reacting the entire magnesium quantity, the solution was refluxed for 1 hour and cooled to room temperature. Phen = acyl chloride (0.1 mole) in dry diethyl ether (100 ml) was added over 1 hour at such a rate 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 aramonium chloride solution. The ethereal solution was washed several times with water (2 x 200 mL), dried (Na 2 SO 4), and the solvent removed in vacuo. There was 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 methanol (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 give a crystalline solid which was recrystallized from ethanol / petroleum ether to give the title compound, mp 124.5 ° C.

Example 2.

1- (1,2,4-triazol-l-yl) -2-phenyl-3-p-fluorphenylpropan-2-ol.

p-fluorobenzyl chloride (0.1 mole) in dry diethyl ether (100 ml) was added dropwise to magnesium chips (0, 11 g atom) and the solution stirred vigorously until reflux. After reacting the entire amount of magnesium, the solution was refluxed for a further 1 hour and then cooled to room temperature. Phenacyl chloride (0.05 mol) in dry diethyl = ether (50 ml) was added dropwise to the solution over 30 of 1 hour at such a rate that gentle reflux was maintained. The mixture was refluxed for 2 hours and cooled to room temperature and the mixture poured into ice / ammonium chloride solution to decompose the complex.

The ethereal solution was washed several times with 26

DK 159801 B

water (2 x 200 ml), dried (Na 2 SO 4) and the solvent removed in vacuo to give as a colorless oil the crude chlorohydrin. The latter was dissolved in dimethylformamide (40 ml) and a solution of sodium triazole [prepared from 5 sodium (0.05 g atoms) 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 give a crystalline solid which was recrystallized from petroleum ether / chloroform to give the title compound, mp 116-118 ° C.

Example 3

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

Step 1. Bromobenzene (0.2 mole, 31.4 g) in sodium dry diethyl = ether (200 ml) was added dropwise to magnesium (0.22 g atom, 5.3 g). After reacting the entire amount of magnesium, phenacyl chloride (0.1 mol, 15.5 g) in diethyl = 2Q 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 dried (Na 2 SO 4). Removal of the ether gave a pale yellow oil which solidified upon standing. Recrystallization from petroleum = 25 ether (60-80 °) afforded 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 stirred. until the noise ceased. 1,1-diphenyl-2-chloroethan-1-ol (0.015 mol, 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 27 crystallized

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white solid. 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.

2-methyl-4-phenyl-5- (1,2,4-triazol-1-yl) -pentan-4-ol (Compound 31).

Step 1. The Grignard reagent formed from isobutyl bromide (0.1 mol, 13.7 g) in sodium dry diethyl ether (50 ml), and magnesium chips 10 (0.11 g atoms, 2.6 g) were added dropwise to a solution of phenacyl chloride (0.05 mole, 7.7 g) in sodium dry diethyl = ether (100 ml) to maintain gentle reflux. The solution was then stirred at room temperature for 1 hour and the magnesium complex decomposed by pouring into a saturated ammonium chloride solution (200 ml). The ethereal extract was washed with water (3 x 150 ml) and dried (Na 2 SO 4). Removal of the solvent gave a colorless liquid which distilled at reduced pressure to give 2-methyl-4-phenyl-5-chloropentan-4-ol (70%), bp 86-88 ° C / 0.01 mm 20 Kg.

Step 2. 1,2,4-triazole (0.03 mol, 2.07 g) was added portionwise to 100% sodium hydride (0.03 mol, 0.72 g) in dry DMF (30 ml) and stirred at room temperature. until the shower ceased. 2-methyl-4-phenyl-5-chloropentan-4-ol (0.01 mole, 2.1 g) in dry DMF (10 ml) was added dropwise at room temperature and the solution was then stirred at 100 ° C. for 6 hours. On cooling to room temperature, the solution was poured into water to precipitate a solid which was recrystallized from petroleum (60-80 °) / chloroform to give the title compound (60%) as a white crystalline solid, m.p. 95 ° C.

28

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Example 5

1- (1/2 / 4-triazol-r-yl) -2-o-chlorophenyl-2-p-fluorophenyl = ethan-2-ol (compound 45}.

A solution of dimethyl oxo sulfonium methylide was prepared under nitrogen of sodium hydride (0.03 mol) and powdered trimethyloxosulfonium iodide (0.03 mol) in dry dimethyl sulfoxide (DMSO; 30 ml). A solution of o-chlorophenyl-p-fluorophenyl ketone (0/025 mol) in DMSO (10 ml) was added dropwise at room temperature. The solution was then heated at 10 to 50 ° C 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-chloro = phenyl-1-p-fluorophenylethylene oxide (90%) as a colorless liquid.

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-Chloro = phenyl-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 decomposed 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.

Example 6

2/2-Dimethyl-3- (o-methoxybenzyl) -3- (1,2,4-triazol-1-yl) -butan-3-ol (Compound 130).

Step 1; Potassium t-butoxide (19 g) was dissolved in dimethyl sulfide oxide (200 ml, dried by distillation from calcium hydride and 29 g).

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sodium amide) and pinacolone (15 g, freshly distilled from calcium hydride) were added under argon to give a yellow 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 yellow liquid (11.8 g), bp 88-93 ° C / 0.9 mm. The distillate solidified to give 2.2-10 dimethyl-4- (o-methoxyphenyl) butan-3-one (6 g).

Step 2; Thioanisole (3.3 g) was added to diazobicyclooctane (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 then allowed to warm to room temperature. The mixture was then cooled in an ice bath and a solution 20 of the product (5 g) from step 1 in dry THF (25 ml) was added at 0-5 ° C. After 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 washed thoroughly with water, dried (MgSO4) and evaporated to give a yellow 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.

Step 3; The product (2.5 g) of 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 obtained for 1 hour. The solvent was then removed on a rotary evaporator to form a light orange gum dissolved in dry DMF (10 ml) and 3 °

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the solution was added to a solution of 1,2,4-triazole sodium salt (1.2 g) in DMF (15 ml). [The solution was prepared by washing sodium hydride with dry 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 dry column chromatography on silica eluting with diethyl ether to give a colorless liquid which solidified upon decomposition with diethyl ether. Recrystallization from petroleum ether (60-80 ° C) gave the title compound 15 (0.5 g, 23%), mp 113-116 ° C.

Example 7

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 4 cm in diameter. A layer of fine sand was placed in the bottom of the pots containing the dicotyledonous plants to facilitate the uptake of test compound by the roots. The test compounds were prepared either by ball milling with aqueous Dispersol T or as a solution in acetone or acetone / ethanol which was diluted to the required concentration immediately before use. For the leaf diseases, suspensions (100 ppm) of active ingredient were sprayed onto the soil. An exception to this was the tests on 30 Botrytis cinerea, Plasmopara viticola and Venturia inaequalis. The sprays were applied for maximum retention and the roots soaked to a final concentration equal to 40 ppm a.i./ dry soil. Tween 20, to achieve a final concentration of 0.05%, was added when the spray preparations 31

DK 159801 B

was used for cereals.

For most of the experiments, the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the diseases. A 5 exception was the test on Erysiphe graminis, where the plants were inoculated 24 hours prior to treatment. After inoculation, the plants were placed in an appropriate environment to allow the infection to occur and then incubated until the disease was ready for determination. The period between inoculation and assay ranged from 4 to 14 days, depending on the disease and the environment.

Disease control was recorded using the following scale: 4 = no disease 15 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.

The results are shown in Table II.

32 DK 159801 B

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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 using the following scale: 1 = 0-30% inhibition 2 = 31-75% inhibition 3 = 75% inhibition.

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

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Example 9

In the present example, the effect of the following compounds known from GB Patent No. 1,529,818 and some 5 compounds used according to the invention is compared.

CONNECT STRUCTURE

NUMBER

10--

In OH

(Compound Tr * -j // 'λ No. 1 in ta- ^ CH-CH-V') -> 01 bell I in GB iCH2) 3 \ / 1,529,818) CH3 15__ Π OH - (Compound Tr- J // \\ No. 3 in ta-CH-CH-V y bel I in GB Cl / \ - / 1,529,818) Cf \ / 20 C1 "U-CH2

III OH

(Compound Tr ---- j β # 4 in ta- "CH-CH-ybel I in GB f / ~ \ \ - / 25 1,529,818) V y-CH 2 IV OH _ (Compound Tr-j /) \\ No. 11 in ta- _ "" "^ CH-CH-y-Cl 30 1? 529,818) F- ^ ~ ^ -CH2 \ = / 35

CONNECT STRUCTURE

NUMBER

DK 159801B

45

5 V X

(Connection

No. 13 in ta- y OH

call I in GB CH2 1,529,818} I, -.

1 ΓΛ,

Tr-CH - C-V x) - Cl

VI OH

(Compound — F

No. 6 in ta-9H2 /) bell 1 in GB Tr-CH --- CH- (f ') -Cl 15 1,529,818)

VII A

(Compound! H

No. 5 in ta- Cl OH

2Q bel I in GB CH2 1,529,818) 1 Λ-Λ

Tr-CH-CH - \ _ / C1 VIII OH _ ^ (Compound | /} ^ No. 17 Tr-CH2-C- ('') 25 1 As \ - /

Table I) ί J

XIII OH

(Compound No. 7 of No. 6 in ta-Ti - CH 2 -C-CH 2 -value I) I A /

ISLAND

F

35

DK 159801 B

CONNECT STRUCTURE

NUMBER

46 5 XIV OH _ (Compound | 1) in ta-Tr-CH 2 -C-CH 2 - V ') bell I) Vs /

ISLAND

in Island--

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(Compound | fi # 14 in Tr-CH2-C- ('X \ -C1 Table I) | \ - / ch2 16__

XX OH

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Table I) \: -: / 20 I ^ C1 __Ks_

XXII OH

(Compound 1 /} ^

No. 27 in Tr-CH 2 -C- ('-F

Table I) Js, \ - /

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Cl

XXIII OH

30 (Compound 1 Γ * λ

No. 46 in Tr-CH 2 -C- ('XV.F

Table I) I \ - · /

ij F

I_I _ ^ _ In

35

DK 159801 B

CONNECT STRUCTURE

NUMBER

47 5 XXIV OH _ (Compound I J \

No. 29 in Tr-CH2-C- \ ') -F

Table I)

F

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__________________________________ _ o c>

Claims (3)

As can be seen from the foregoing, the comparative compounds of GB Patent No. 1,529,818 are generally much less active (i.e., the regulation fails at higher concentrations) against the entire disease area. Thus, it will be seen that the compounds used according to the invention are generally between 10 and 100 times more active than the comparison compounds. Claims. 10 1. The use of triazole compounds of the formula: OH N-N-CHO-C-R 1 U wherein R * is C 1-4 alkyl or cycloalkyl and R 1 is benzyl optionally substituted with halo, C 1-6 alkyl, C 1-4 alkoxy, CF 3, nitro, phenyl or phenoxy; or R * is pbenyl optionally substituted by halogen, C1-5 alkyl »C1-4 alkoxy, CF3, nitro or phenoxy, and r2 is phenyl or benzyl optionally substituted by halogen, C1-5 alkyl, C1-4 alkoxy, CF3, nitro or phenoxy to control plant fungi. Use according to claim 1 of compounds of the formula of claim 1 wherein R 1 is phenyl or chlorophenyl and R 1 is chlorophenyl. 30