DK162523B - Triazole compounds - Google Patents

Description

in

DK 162523 B

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

The triazole compounds have the general formula (I) 5 wherein R 2 is C 5 H 5 and R * is methyl, ethyl, t-butyl, cyclopropyl or cyclohexyl, or R 2 is 4-F-C 5 H 4 and R * is ethyl, n-butyl, t- butyl or n-hexyl, or R 2 is 4-C 1 -C 6 H 4 and R 1 is methyl or cyclopropyl, or R 2 is 2,4-diClC 3 H 3 and R 1 is methyl, or R 2 is 4-OCH 3 -C 8 H 4 and R * is t-butyl , cyclopropyl or cyclohexyl.

From DK Patent Application No. 4836/80 a number of compounds of the formula I shown are known, wherein R 1 is alkyl or cycloalkyl and R 2 is phenyl or phenyl substituted with chloro, fluoro, alkyl, CF 3, methoxy, phenyl, phenoxy or nitro . However, none of the compounds of the present invention can be considered known prior to August 29, 1980.

25

The compounds known from OK Patent Application No. 4836/80 as well as the compounds of the invention have a surprisingly useful effect for controlling fungi in plants.

In addition, a representative of the compounds of the invention, Compound No. 31, has shown a useful regulatory effect on the growth of plants, e.g. for shortening stems or stems in grain crops.

The compounds of the invention 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.

2

DK 162523 B

The compounds of the invention are shown in Table I.

Table I

5 | Compound No. I Ri R2 ~ I Melting point (° C1 31 i-Bu C6H5 ~ 94-95 131 Me C6H5 oil 132 Me P-CI-C5H4- 88-90 133 Me 2,4-diCl-CgHo- 77-81 139 Et c6h5 "96-97 142 Et pF-C6H4- 94 10 167 c3h5 'c6h5 ~ 91-92 176 C3H5- p-MeO-C6H4- 101-102 178 n-Bu pF-CgH4 ~ 93-95 198 t> - Bu pF-CgH4 ~ 92-93 204 t-Bu p-MeO-CgH4- 48 228 n-He PF-CgH4- 97-99 235 c6h11 C6H5- 110-111 236 ^ 6 ^ 11 P-Cl-CgH4-45 15 244_CgHn p-MeO-CgH4 -_ 92-94_ n-He = n-hexyl C3H5 = cyclopropyl c6h11 = cyclohexyl.

20

The compounds of the general formula (i) can be prepared by reacting a compound of the general formula (II) or (III): 25 n / ° \ in H, CH - C - RX X - CH - c k2 2 & (Η) (III) wherein R 1 and R 2 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 form one of its alkali metal salts in a suitable solvent. The compound of general formula (II) or (III) is suitably reacted at 20-100 ° C with the sodium salt of 1,2,4-triazole (the salt can be prepared by adding either 3

DK 162523 B

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 formed solid from a suitable solvent.

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

•ISLAND ISLAND

II 1 II. island

X-CH2-C-R X ~ ch2-C-R

(IVa) (IVb) wherein R 1, R 2 and X have the meanings defined above, down respectively a Grignard compound of the general formula (Va) or (Vb) in Y-Mg-R2 y-ug-r1 (Va ) (Vb) wherein R 1 and R 2 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 1 is alkyl or cycloalkyl, e.g. reaction, the compound of formula (II) generally dominates in the mixture. On the other hand, when R 1 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 by methods set forth in the literature.

35 4

DK 162523 B

The compounds of general formula (II) wherein R2 is 4-F-C6H4, 4-C1-CgH4, 2,4-diClCgH3 or 4-OCH3 ~ CgH4 can also be prepared by reacting the appropriate benzophenone compound of the general formula ( IV) 5

R1-CO-R2 wherein R1 and R2 have the meanings defined above, with dimethyloxosulfonium methylide (Corey and Chaykovsky JACS, 1965, 10 87, 1353-1364) or dimethylsulfonium methylide (Corey and Chay kovsky, JACS, 1962, 84, 3782) using methods cited in the literature.

The benzophenone compounds of general formula (VI) may 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. al urai niumchl or id.

The compounds of general formula (II) can also be prepared by reacting a β-hydroxy selenide compound of general formula (VII) R1

CH, -Se-CH - C-OH

• 2

(VIII

Wherein R 1 and R 2 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 ω-hydroxy selenide compound can be prepared by treating the diselenide with the appropriate ketone in the presence of butyllithium.

5

DK 162523 B

The compounds of general formula (I) are generally prepared by the above reactions in the form of racemic mixtures. The cleavage of these mixtures in the conventional ten teniomers can be accomplished by known methods. Examples of these methods are (1) formation of the diastereoisoric 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 general formula (I); (2) forming the diastereoisomeric carbamates of the compound of the general formula (I) by reacting a haloformate X 5 (e.g., chloroformate) of the latter with an optically active amine (e.g., α-methylbenzylamine), separating the the isomeric carbamates and conversion of the separated isomeric carbamates to the enantiomers of the compound of the general formula (I) j (3) forming the hemiphthate of the compound of the general formula (I), reacting the hemiphthate with an optically active amine (f. (for example, 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); or (4) cleavage of the mixtures using 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. crystallization technique or by 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.

6

DK 162523 B

The compounds are active fungicides, especially against the diseases:

Piricularia oryzae on rice, g

Puccinia recondita, Puccinia striiformis and other varieties of wheat, Puccinia hordei, Puccinia striiformis and other varieties of barley and varieties of other host plants eg. coffee, apples, vegetables and ornamental plants,

Plasmopara viticola on wine, 10 Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew forms on various hosts, such as Sphaerotheca fuliginea on.agurk,

Podosphaera leucotricha on apples and Uncinula necator on wine, Helminthosporium spp. and Rhynchosporium spp. on cereals, 15 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, 2 0

Venturia inaequalis (scab), on apples.

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 on bananas). In addition, some of the compounds act as dressing agents against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. wheat's siiSkhrand;:, which is a seed-borne disease of 30 wheat), Ustilago spp., Helminthosporium spp. on cereals,

Ehizoctonia solani on cotton and Corticium sasakii on rice.

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.

w O

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.

7-

DK 162523 B

The compounds may also have plant growth regulating effects.

5 The plant growth regulating effects of the compounds appear e.g. as a crippling or dwarf growth inducing 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 the supply of increased fertilizer quantities. 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 sugarcane, flowering and maturation can be affected by application of the compounds. Inhibited growth of peanuts can 20 facilitate harvesting. Growth inhibition of grasses can help in the conservation of grass rugs. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Loliura multiflorum and perennium, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca 25 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 compounds on ornamental lawns and 30 on grass discounts. They may also have an effect on the floral main emergence of e.g. grasses. The compounds can 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, roadblock, 35 knot nurture, honorary prize, thistle, scrap 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 subject to soil erosion, the presence of 8

DK 162523 B

grass cover 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 the 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 may result in increased fruit yield. In some cases, one grass species may be inhibited in growth more than other grass species. This selectivity may be useful e.g. to improve the quality of a grass blanket by preferably depressing the growth of undesirable species.

Dwarf growth can also be useful in reducing ornamental, household, garden and nursery plants (e.g.

15 poinsettia, chrysanthemum, carnation, tulip and daffodil).

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

25

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.

30

Other plant growth regulating effects caused by the compounds include changing leaf angle and promoting shoot formation in monocotyledonous plants. The former effect may be useful e.g. for changing the leaf alignment of e.g. potato crops, thereby more easily penetrating the crops and inducing an increase in photosynthesis and tuber weight. With increased shoot formation in monocotyledonous crops (eg rice), the number of 9

DK 162523 B

flowering shoots per area unit is increased, thereby increasing the total grain yield of such crops. In green defense, an increase in shoot formation could: lead to a closer 5 green weather, which can result in increased weather resistance.

The treatment of plants with the compounds May lead to leaves that develop a darker green color.

10

The compounds may inhibit or at least delay the flowering of sugar beets, 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.

1 $

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

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

The compounds can 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, as 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 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 selected for 10

DK 162523 B

use, and the identity of the plant species whose growth must be regulated. However, an application length of 0.1 to 15, preferably 0.1 to 5 kg / ha, is usually used. However, on certain plants, even application rates within these ranges within 5 ranges can produce undesirable phytotoxic effects. Routine trials may be necessary to determine the best application amount 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 regulatory purposes, but are more usually prepared for agents for such uses.

The compounds can be used in a variety of ways e.g. prepared or unprepared, directly on a plant's 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. to the foliage, stems, branches or roots, or to the soil surrounding the roots, or to seed seed material and sprouts before sowing, laying and planting.

25

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

The compounds of the invention can be used in preventive, protective, prophylactic and eradicating treatment.

30

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 of the particular case.

35

The agents may be in 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

DK 162523B

11 magnesia, FulXer soil, plaster, Hewitt's soil, diatomaceous earth and kaolin. Such grains may be preformed grains suitable for application to the soil without further processing. These grains can be prepared either by impregnating pellets 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), sctm promotes the adhesion of the agent to the seeds. Alternatively, the active ingredient may be prepared for seed processing purposes using an organic solvent (e.g., N-methylpyr = rolidone or dimethylformamide).

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

The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient or active ingredients 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).

30

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

35

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.

12

DK 162523 B

Alternatively, the compounds may be used in microencapsulated form.

By including suitable additives · e.g. additives that improve the distribution, adhesion, 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 contain 15 ...

suitably up to 25% by weight of the compound.

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, dispersants, emulsifiers or suspending agents. These agents may be cationic, anionic or nonionic agents. Suitable cationic agents are quaternary ammonium compounds, e.g. cetyltrimethylaramoniumbromid.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), and salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, sodium, calcium or aramonium ligno sulfonate, butyl naphthalene sulfonate and sodium mixture = diisopropyl and triisopropyl naphthalene sulfonates).

3 5

Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol 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,

DK 162523 B

cation products of said partial esters with ethylene oxide and the lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethyl = cellulose) and the vegetable gums (e.g., acacia gum and tragacanth gum).

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 (s), 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 to be applied 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 xylene sulfonic acid or dodecylbenzenesulfonic acid), as the presence of such acids may increase the solubility of the active ingredient (s) in the polar solvents commonly used in the concentrates. . Suitably, the concentrates also contain a large amount of surfactant so that sufficiently stable emulsions can be obtained in water. After dilution to form aqueous compositions, such compositions may contain varying amounts of the active ingredient (s) depending on the intended purpose, but an aqueous composition containing 0.0005% or 0.01% to 10% by weight of the active ingredient may be used. active ingredient or active ingredients.

The compositions of the invention may also contain other compounds having a biological effect e.g. compounds having similar or complementary, fungicidal or plant growth regulating effect, or compounds having herbicide or insecticidal activity.

14

DK 162523 B

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 diseases and leaf mold and 5 powdery mildew 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 second fungicide for binding are imazalil, benomyl, carbendazim, thiophanate-methyl, captafol, captan, sulfur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethiri = mol, bupirimate, chlorthalonil, vinclozon, vinclozon, vinclozon , metalaxyl, presetyl aluminum, carboxin, oxy = carboxin, fenarimol, nuarimol, fenfuram, methfuroxane, nitrotal-isopropyl, triadimefon, thiabendazole, etridiazole, triadimenol, biloxazole, dithianone, binapacryl, quinomethine, quinomethioin, natin , dino = 20 cap, folpet, dichlorofluanide, ditalimphos, chitazine, cyclohexiride, dichlorobutrazole and dithiocarbamate, a copper compound, a mezkurif compound, 1- (2-cyano-2-methoxyiminoacetyl) -3- 'ethylurea, phenapanil propicomazole, etaconazole and fenqprqpemorph.

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

Suitable insecticides are pirimor, krone, dimethoate, meta = 30 cystox and formothion.

The other 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 cause 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 gibberel

DK 162523 B

the liners (e.g., GA ^, GA ^ or GA GA), the auxins (e.g., indole acetic acid, indole butyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminoin pyrine), 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 and quaternary ammonium and phosphonium compounds (e.g. abscisic acid, ancymidol (and its analogs, e.g. ispyrimol), 1- (4-chloro = phenyl) -4,6-diraethyl-2-oxo-1,2-dihydroxypyridine-3-carboxylic acid, hydroxybenzonitriles (f eg bromoxynil, dipenzoquate, benzoylpropethyl, 3,6-cichloropicolinic acid or thiocarbamates.

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

Example 1.

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

25

Step 1. The Grignard reagent formed from isobutyl bromide (0.1 mol, 13.7 g) in sodium dry diethyl ether (50 mil and magnesium shavings (0.11 g atoms, 2.6 g) was added dropwise to a solution of phenacyl chloride (0 , 05 mol, 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 aqueous ammonium chloride solution (200 ral). 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 was stylized at reduced pressure to give 2-methyl-4-phenyl-5-chloropentan-4-ol (70%), bp 86-88 ° C / 0.01 mm Hg.

16

DK 162523 B

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 5 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. 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.

Example 2.

15

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

20

The plants were grown in John Innes Potting Compost (# 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

A C

by ball milling with aqueous Dispersol · T or as a solution in acetone or acetone / ethanol 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 of 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 obtain a final concentration of 0.05%, was added when the spray preparations 35 were 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. And 17

DK 162523 B

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 determination ranged from 4 to 14 days, depending on the disease and the environment.

Disease control was recorded using the following 10 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.

The results are shown in Table II.

20 25 30 35

DK 162523 B

18 - - j

<M

h a ~ i D D h 1d <cn <d <m ^

Eh a XI ί Z W »

H <- S

> S «I — ϋ - 1 <C ^ i

Bl hl Ό O O s ω h "> 0 m cNjmm '»' ί ^ O Q u

You w O

PS 03 -n BU · - U <

PS

ril --—— i CQ j H C - E-ι a -u pypqg 'd' 0 O CN -d1 'd' Γ0 j

E- <Z O O M 4J

mu— j __ r

<I

PS

0 cn os 3 E-i <- 03 E-t -P m co ro OM | ° o.io o o o. ,, o o o X Z -P 03 H - m H _____—------

H

<

H PS C

0) <h3

Λ Pi O

(C O U -

^ CO H · Η O OOOO o o 0 O rO o, —l Or-J

<H> h3> - m <

H

PS B <<h3 ISJ -

D X tfl i I I I I I I

U PS -H CM I I I I 1 I I I I I I I 1 I

H o P PS -

H

Pi _________ a cn 03 H Pi 12 ^ co S> 'i' i ^ sp ro 'd1 XC Λ PS PS - au _______ ^ <<& HH SQ 0) u O Φ ^ - «sp'd' ^ 'S · -d- 1d- 'd-' S- UU>

Da jz

Pi ps - ______ c • H <0 "Sh · η h cn m σι cn t" ^ SSrdCNnorn ^ O fl) p n nnnn \ o, ^ h ^ ^ ^ ^ «fe-5 fl η η η h. H, N (NM; nn - - 19)

DK 162523 B

Example 3

This example illustrates the plant growth regulating properties of the compounds. Compound No. 31 was 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 on vegetative growth therein using the following scale: 1 * 0-30% inhibition 2 = 31-75% inhibition 3 = 75% inhibition.

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

20

DK 162523 B

-P

(0 u S ro O E * tn • ro ro

cD S

Cn t — f m ω Ό (U E- <> æ <u ω -p

• H (O

i — I P

> i 0) P s o o

(0r-C

Q tP

C C O

i — i O I — i Η Ό> 1

H> i-P

C U

r-C O (D

0) U Π3 Λ__

(D

E-t ω

• H

• P CO CD -H O 3 P C CP 0)

<-P

CD

ISLAND

P

P

0) X o X r-C 3 ω Ό i— ^ 3

g O

O OQ

m ro • ro <0 o CO ro •

P

1 3 3 H d)

Λ CD

P i — I i — I O CD ro Ό

Claims (1)

R2 is 4-F-C6H4 and R1 is ethyl, n-butyl, t-butyl or n-hexyl, or R is 4-C1-C6H4 and R1 is methyl or cyclopropyl, or R2 is 2'4-diclc6H3 and R1 is methyl, or R is 4-OCH 3 -C 6 H 4 and r 1 is t-butyl, cyclopropyl or cyclohexyl. 25 30 35