JPH0437828B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a triazole compound useful as a fungicide, a method for producing the compound, a fungicide and plant growth regulating composition containing the compound, a method for preventing fungal infection of plants using the same, and a method for using the same. The present invention relates to a method for regulating plant growth. European Patent Publication No. 52424 (European Patent Application No. 813048352) Formula: [In the formula, R ¹ is -CH=CH-X, -C≡C-X or -
_CH2 - _CH2 -X, where X is H, alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, or an optionally substituted aryl, aralkyl, aryloxy, alkyl, or heterocyclic group; ^R2 is alkyl, cycloalkyl (e.g. cyclopropyl, cyclopentyl, or cyclohexyl) or an optionally substituted aryl group; Z is Cl or CN or OR ³ where R ³ is H,
triazole and imidazole compounds, and acid addition salts and metal complex salts thereof, where Y is =N- or =CH-, are disclosed. The inventors have now discovered that a narrow range of compounds within the broad general group described above have a fairly high degree of fungicidal activity. Therefore, according to the invention, the following formula (): [In the formula, R ¹ is -CH=CH-X or -C≡C-X (wherein X is hydrogen or a straight-chain alkyl group having 1 to 5 carbon atoms); R ² is a halofenyl group Z is OR ³ (wherein R ³ is H, alkyl, alkenyl or alkynyl group), and acid addition salts and metal complex salts thereof are provided. The compounds of the invention may contain geometrically shaped isomers. Such compounds are generally obtained in the form of isomeric mixtures. However, these and other mixtures can be separated into the individual isomers by methods known in the art. When X is an alkyl group, it is a straight-chain alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl and amyl groups. In other respects, i.e. for R ³ considered reasonable, the alkyl group can be a straight-chain or branched alkyl group having 1 to 6, e.g. 1 to 4 carbon atoms; examples include methyl, ethyl , Prople (n
- or iso-propyl) and butyl groups (n-,
sec-, iso or t-butyl). When R ² is a halophenyl group, examples of halogens suitable as substituents on the phenyl ring are fluorine, chlorine or bromine. That is, R ² is 2-, 3- or 4-
Chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2-, 3- or 4-fluorophenyl, 2,4-difluorophenyl, 2-, 3- or 4-bromophenyl, 2-chloro-4 -fluorophenyl or 2-chloro-6-fluorophenyl groups. Preferably ^R2 is a 4-chlorophenyl or 2,4-dichlorophenyl group. Therefore, according to another aspect, the present invention relates to the general formula () [where X is H or a C ₁₄ alkyl ^group ;
is 4-chlorophenyl or 2,4-dichlorophenyl; Z is ^OR3 (wherein ^R3 is H). In yet another preferred aspect, the present invention provides a compound of the general formula (), wherein R ² is a 2-, 4- or 2,4-dichlorophenyl or difluorophenyl group. Preferred compounds have the formula: as well as Said salts may be with inorganic or organic acids, such as with hydrochloric acid, nitric acid, sulfuric acid, acetic acid, 4-toluenesulfonic acid or oxalic acid. Suitably, the metal complex salt is a complex salt containing copper, zinc, manganese or iron as the metal. The metal complex salt has the following formula: [In the formula, R ¹ and R ² , Z and Y are as described above,
M is a metal, A is an anion (e.g. chloride, bromide, iodine, nitrate, sulfate or phosphate), and n is 2 or 4.
, y is 0 or an integer from 1 to 12, and m is an integer corresponding to the valence. Examples of compounds of the invention are shown in the table below. These compounds correspond to the following formulas:

TABLE The compounds mentioned in the above table are new and therefore form part of the invention as such. The compound of the present invention represented by the general formula () is represented by the following formula ()
or ():

【formula】

[Formula] [In the formula, R ¹ , R ² and Z are as described above, and Hal
is a halogen atom (preferably a chlorine or bromine atom)
1 in the form of an alkali metal salt in the presence of an acid binder or in a convenient solvent.
It can be produced by reacting with 2,4-triazole. Compounds of the general formula () or () may be dissolved in 1,2,4 in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide.
- The sodium salt of the triazole (this salt can be prepared by adding either sodium hydride or sodium methoxide to the 1,2,4-triazole) is suitably reacted at 20 DEG to 100 DEG C. The product may be isolated by pouring the reaction mixture into water and crystallizing the resulting solid from a convenient solvent. The ethers of the present invention (R ³ =alkyl, etc.) are formed from hydroxy compounds by reacting the hydroxy compound with a suitable halide in the presence of a suitable base. Compounds of the general formula (), in which R ¹ and R ² are each as described above, are novel and useful intermediates, which compounds have the following formula (): R ¹ −<O−R ² () in which R ¹ and R ² are as previously described), dimethylsulfonium methylide (JACS, 1962, 84 ,
3782) or dimethyloxosulfonium methylide (JACS, 1965, 87 , 1353~
(page 1364). The following formula (): α, β of (in the formula, R ² and X are as described above)
-Unsaturated ketones may be formed by condensing a suitable ketone with an aldehyde in the presence of a suitable acid or base catalyst. Said compound () can also be formed by a Witzig reaction between an aldehyde of the following structural formula () and a phosphorane of the following structural formula ():

[Formula] X-C H P (Ph) ₃ () X-CH ₂ P (Ph) ₃ () (in the formula, R ² and The above phosphorane () is derived from the phosphonium salt of the above formula () by treatment with a strong base such as n-butyllithium in a suitable solvent such as ether or tetrahydrofuran by standard methods in the literature. The aforementioned aldehydes () can be formed by methods described in the literature. The above formulas () and () (where Z is OH)
Compounds of general formula (a) can also be prepared in a convenient solvent such as diethyl ether or tetrahydrofuran.
or (b): (In the formula, R ¹ , R ² and hal are as described above.) A compound of the following formula (a) or (b): R ¹ M (a) R ² M (b)
[wherein R ¹ and R ² are as described above, M is a metal, preferably lithium but may be sodium or magnesium (when M is magnesium, the organometallic compound is effectively R ¹ Mghal or R ² Mghal)]. This reaction can be performed only with the compound () or only with the compound () or with the compound ()
can give a mixture of and (). Preferably, the organometallic compound (a) is reacted with the compound (b) at low temperature. Compounds of the above general formulas () and () may be formed by methods described in the literature. For example, the acetylene alcohol of the present invention can be formed by either of the following two reaction schemes 1 and 2. Reaction scheme 1 An α-haloketone of formula (b) shown below (wherein R ² is as described above) is reacted with an α-haloketone of formula () (wherein R 2 is as described above) in an inert atmosphere at low temperature. The product is worked up by reacting with a metal salt of acetylene and quenching with a proton donor. Reaction Scheme 2 An acetylene ketone of formula () below is reacted with a sulfur ylide of formula () below and the resulting epoxide is reacted with a suitable azolyl salt. Salts and metal complex salts of compounds of general formula () can be produced from the compounds in a known manner. For example, the complex salt can be formed by reacting the uncomplexed compound with a metal salt in a suitable solvent. Olefinic azolyl alcohols in which R ¹ is CH=CH-X and R ² is as previously described can be prepared using hydrogen or It may be formed by reduction of acetylenic azolyl alcohol (XII) using a metal hydride reagent, particularly lithium aluminum hydride, in a suitable solvent such as ether or tetrahydrofuran. Reaction scheme 3 The inventive compound of formula () is produced by reacting the acetylenic azolyl alcohol of formula (XII) with a metal hydride reagent. The compounds, salts and metal complexes of the invention are effective fungicides, particularly against the following diseases: Piricularia oryzae of rice, Puccinia recondita of wheat ，
(Puccinia striiformis) and other rusts, barley rust (Puccinia hordei), (Puccinia
striiformis) and other rusts and other host plants,
For example, rust on coffee, apples, vegetables and ornamental plants, powdery mildew on barley and wheat (Erysiphe
graminis) and other powdery mildew diseases of various host plants, such as Sphaerotheca fuliginea on gourds (e.g. Sphaerotheca fuliginea), Podosphaera leucotricha on apples and Uncinula necator on grapes, Helminthosporium (Helminthosporium spp.)
Rhynchosporium spp. and Pseudocercosporella herpotrichoids Cercospora arachidicola of peanuts and other Cercospora diseases such as sugar beets, bananas and soybeans Tomatoes, strawberries, grapes and Botrytis cinerea on other host plants Botrytis cinerea on apples Venturia inaequalis. Some of the compounds of the invention also showed broad spectrum activity against molds in vitro. These compounds have activity against various post-harvest diseases of fruit, such as Penicillium digitatum and Penicillium italicum on oranges and Gloeosporium musarum on bananas. Furthermore, some of the compounds of the present invention may be used to treat cereal rot Fusarium spp.
spp, Tilletia spp (i.e. wheat smut, seed-borne disease), Uatilago spp,
Helminthosporium spp, and Pseudscereo
It is effective as a seed dressing agent against rhizoctonia solani of cotton and Corticium sasakii of rice. The compounds of the present invention can move apically in plant tissues from below in an apical direction. Furthermore, the compounds of the present invention may be sufficiently volatile to be effective in the gas phase against fungi on plants. The compounds of this invention may also be useful as industrial (vs. agricultural) fungicides, such as in the prevention of mold attack of wood, hides, leather, and especially paint films. The compounds of the invention are also useful in the treatment of candidiasis and human dermatophyte infections. The compounds of the invention and their derivatives as described above also have plant growth regulating activity. The plant growth regulating effect of the compounds of the invention is demonstrated, for example, as an inhibitory or dwarfing effect on the growth of the developing parts of woody plants and herbaceous monocotyledonous and dicotyledonous plants. Such control or dwarfism is useful for groundnuts, cereals such as wheat and barley, oilseed rape, field legumes, sunflowers, potatoes and soybeans, where reduction in stem height reduces the risk of lodging. This may be accompanied by other beneficial effects such as stem strengthening, thickening and shortening, internodal shortening, increased protruding root formation and more upright stem and leaf orientation. , fertilizers may also be applied in increased amounts. Suppressing the growth of woody plants is useful for controlling undergrowth of power lines and the like. Compounds that induce inhibition or inhibition are also useful in altering stalk growth in sugarcane, thereby increasing the sugar concentration in sugarcane at harvest; It can be regulated by application. Stunting of groundnuts can aid harvest. Slowing the growth of grasses can help maintain lawns. Examples of suitable grasses are St. Augustine's grass (Stenotaphrum secundatum), Cynosurus cristatus.
cristatus), Lolium multiflorum (Lolium
muitiflorum) and perennial tare (Lolium)
perenne), Agrostis tenuis (Agrostis
tenuis), Bamiyuda grass (Cynodon dactylon),
Dactylis glomereta (Dactylis)
glomerata), Festuca species (eg Festuca rubra) and Poa species (eg Poa pratense). The compound of the present invention is
The growth of grasses can be inhibited without significant phytotoxic effects and without detrimentally affecting the appearance (especially color) of the grasses; this makes the compounds suitable for use in ornamental lawns and meadows. This makes it attractive to use on edges. Said compounds may also have an influence on the flowering of flower heads in grasses, for example. The compounds of the present invention may also inhibit the growth of weeds present in grasses; examples of such weeds include Cyperus species (e.g. Cyperus) and dicotyledonous weeds (e.g. daisies, plantains, willows, stag beetles, Thistle, scampo and wildflower). The growth of non-crop plants (eg weeds or overgrowth) can be retarded, thus aiding in the maintenance of farm and field crops.
The presence of grass growing all over is important in orchards, especially in orchards that are subject to soil erosion. However, excessive grass growth requires substantial maintenance. Compounds of the invention may be useful in this situation. This is because the compounds can control the growth of plants without killing them (plant death ends in soil erosion); at the same time the degree of competition for nutrients and water by grasses is reduced and this This can result in increased fruit yield. In some cases, one type of grass can be suppressed over another; this selectivity is useful, for example, to improve the properties of a lawn by preferentially suppressing the growth of undesirable plant species. It can be. Such growth inhibition may also be useful for reducing the size of ornamental plants, houseplants, garden plants, and nursery plants, such as psyllids, chrysanthemums, carnations, tulips, and daffodils. As mentioned above, the compounds of the present invention can be used to inhibit the growth of woody plants. This property can be used to adjust the shape of hedges or to shape or reduce the need for pruning fruit trees (eg ring, pear, cherry, peach, grape, etc.). Some conifers are not significantly inhibited in growth by the compounds of the present invention, and therefore the compounds of the present invention may be useful in controlling the growth of undesirable plants in conifer nurseries. Plant growth regulating effects may manifest themselves in an increase in crop yield as described above; or in orchards or other crops, in the ability to increase fruit yield, pod yield and grain yield. For potatoes, it may be possible to control vines in the field and suppress germination in storage. Other plant growth regulatory effects produced by compounds of the invention include changes in leaf angle and changes in leaf morphology, both of which can increase light interception and utilization.
and promotion of tillering in monocots. Improved light interception has value in all major world crops such as wheat, barley, rice, corn, soybeans, sugar beets, potatoes, plantation crops, and orchard crops. The leaf angle modification effect is useful, for example, in changing the orientation of leaves in a potato crop, thereby providing light to the potatoes and causing increased photosynthesis and increased tuber weight. By increasing tillering in monocot crops (e.g. rice), the number of flowering buds per unit area can be increased, thereby increasing the total grain yield of such crops. It is. Furthermore, monocots and dicots, especially wheat,
It is possible to obtain a better gradation relationship between suppression and mitigation in both the growth and propagation stages of cereal plants such as barley, rice and maize, thereby increasing the number of flowering buds per unit area. The number of grains within the ear can be increased and the grain size distribution within the ear can be modified in a manner that increases yield. For the treatment of rice plants or crops, the compounds of the invention may be applied, for example, as fine granules or granular compositions, eg slow-release granules, to seedbeds, rice field waters and other similar cultivation sites and media. In lawns, especially those that provide amenity, increased tillering can give a denser lawn;
This can increase abrasion resilience; and can also provide increased yield and better quality of lintel, such as improved digestibility and palatability. Treatment of plants with compounds of the present invention can provide leaves with a darker green color. In dicotyledonous plants such as soybeans and cotton, there can be promotion of lateral buds. The compounds of the invention can inhibit or at least delay flowering of sugar beets (thereby increasing sugar yields) or otherwise alter the flowering pattern of a number of other crops. The compounds can also reduce sugar beet size without significantly reducing sugar yield, which can lead to increased planting densities.
Similarly, other root crops such as turnips, swede, mangold, red beet, sugar beets, yams and cassava can also be used to increase the planting density. The compounds of the present invention can be useful in restricting the growth of the developing parts of cotton plants, thereby resulting in increased cotton yields. Crop yields can be increased by improving the harvest index (ie, the yield harvested as a percentage of total dry matter produced) by changing the distribution of dry matter. This applies to all the above-mentioned root and pod crops, trees, plantation and orchard crops. Compounds of the invention may be useful in making plants resistant to external stimuli. This is because the compounds can retard germination, shorten stem height, and delay flowering in plants grown from seeds; these properties are common in regions with significant snow cover in winter. may be useful in preventing frost damage. This is because the treated plants then remain under a blanket of snow during cold weather. Additionally, the compounds may cause early blight resistance or cold damage resistance in certain plants. When applied as seed treatments at low rates, the compounds can have a growth-promoting effect on plants. In carrying out the plant growth regulating methods of the invention, the amount of compound applied to regulate plant growth will depend on a number of factors, including the particular compound chosen to be used and the amount of compound applied to regulate plant growth. Depends on the type of plant. However, generally application rates of 0.1 to 15 Kg per hectare are used, preferably 0.1 to 5 Kg per hectare. Using slow-release granules of biodegradable polymers, application rates of 1 to 10 g/ha are possible; however, lower application rates can be developed with electric spray technology. however,
For some plants, even application rates within these ranges can result in undesirable phytotoxic effects. Routine testing may be necessary to determine the best application rate for a particular compound suitable for any particular purpose. Although the compounds of the present invention can be used as such for fungicidal or plant growth regulating purposes, it is more convenient to formulate them into compositions for such uses. That is, the present invention also provides a fungicidal or plant growth regulating composition comprising the compound of general formula (1) as described above or its salt, metal complex ether or ester, and optionally a carrier or diluent. be. The present invention also provides a method for controlling fungi, which comprises applying a compound as described above, or a salt, metal complex, ether or ester thereof, to a plant, to the seeds of the plant or to the site of the seeds. The present invention also provides a compound as described above or a salt thereof,
A method for regulating plant growth is provided, which consists in applying a metal complex salt, ether or ester to the plant, to the seeds of the plant or to the site of the plant or the seeds. The compounds, salts, metal complexes, ethers and esters of the invention can be applied in a number of ways, for example directly to the leaves of plants in formulated or unformulated form, , spraying or dispersing the compounds, salts, metal complexes, ethers and esters, with or without application to the seeds or to the plants, trees or other medium in which they are growing or to be planted. or can be applied as a cream or paste preparation;
Alternatively, the compounds, salts, metal complexes, ethers and esters can be applied as vapors or as slow-release granules. It can be applied to any part of the plant, tree or tree, for example to the leaves, stems, branches or roots, or to the soil surrounding the roots;
Alternatively, it can be applied to the seeds before they are sown; or it can be applied to the soil generally, to the water of rice fields, or to hydroponic systems. The compounds of the invention can also be injected into plants or trees and can also be sprayed onto plants using electric spray technology. As used herein, the term "plant" includes seedlings, candies and trees. Further, the fungicidal method of the present invention includes preventive treatment, preventive protection treatment, preventive treatment, and eradication and eradication treatment. The compounds of the invention are preferably used for agricultural and horticultural purposes in the form of compositions. The type of composition used in any case will depend on the particular purpose encountered. The composition of the invention comprises an active ingredient and a solid diluent or carrier, such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum,
Hewitt earth, diatomaceous earth
It can be in powder or granule form, including fillers such as earth) and china clay. Such granules may be preformed granules suitable for application to soil without subsequent treatment. These granules may be formed by impregnating pellets of filler with the active ingredient or by pelletizing a mixture of active ingredient and powdered filler. Compositions for seed dressings can, for example, include agents (such as mineral oil) that help the composition adhere to the seeds; alternatively, organic solvents (such as N
-methylpyrrolidone or dimethylformamide)
can be used to formulate active ingredients for seed dressing purposes. The compositions of the present invention can also be in the form of dispersible powders, granules or particles containing wetting agents to facilitate dispersion of the powder or particles in a liquid. Such powders or particles may also contain fillers and suspending agents. One or more active ingredients are dissolved in an organic solvent optionally containing one or more wetting agents, dispersing agents or emulsifiers, and the mixture thus obtained is then dissolved in one or more wetting agents, dispersing agents or emulsifying agents as well. Aqueous dispersions or emulsions can be prepared by adding to water, which may contain wetting agents, dispersing agents, or emulsifying agents. Suitable organic solvents include ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers such as 2-ethoxyethanol and 2-ethoxyethanol. butoxyethanol). The compositions of the invention to be used as spray liquids can also be in the form of an aerosol, in which the preparation is placed in a container under pressure in the presence of a propellant, for example fluorotrichloromethane or dichlorodifluoromethane. The compounds of this invention can be mixed in dry form with a fire process mixture to form a composition suitable for generating smoke containing the active ingredient compound in a confined space. Alternatively, the compounds of the invention can be used in microencapsulated form. The compounds can also be formulated into biodegradable polymeric compositions to provide slow, controlled release of the active substance. By including suitable additives, such as those to improve the dispersion, adhesion and rain resistance of the treated surfaces, different compositions can be better adapted to various applications. The compounds of the invention can be used in mixtures with fertilizers (eg nitrogen-containing, potassium-containing or phosphorus-containing fertilizers). Formulated with the compound of the present invention,
For example, a composition consisting only of fine fertilizer particles coated with the compound is preferred. Suitably such granules contain up to 25% by weight of active ingredient compound.
Therefore, the present invention also provides a fertilizer composition containing the compound of general formula (1) or a salt or metal complex thereof. The compositions of the invention can also be in the form of solutions for use as dipping or spray solutions, which generally include
is an aqueous dispersion or emulsion containing the active ingredient in the presence of one or more surface-active agents such as wetting agents, dispersing agents, emulsifying agents or suspending agents; or a spray of a type suitable for use in electric spraying techniques. It is a composition. The above agents may be cationic, anionic or non-ionic. Suitable cationic agents are quaternary ammonium compounds such as cetyltrimethylammonium bromide. 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 lignosulfonate, calcium or ammonium, butylnaphthalene sulfonate, and a mixture of the sodium salts of diisopropyl- and triisopropyl-naphthalene sulfonic acids). Suitable nonionic agents are the condensation products of fatty alcohols such as oleyl alcohol or cetyl alcohol with ethylene oxide or the condensation products of ethylene oxide with alkylphenols such as octylphenol or nonylphenol and octyl cresol. Other non-ionic agents are partial esters derived from long chain fatty acids and hexitol anhydride, condensation products of ethylene oxide and said partial esters, and lecithin. Suitable suspending agents are hydrocolloids such as polyvinylpyrrolidone and sodium carboxymethylcellulose, and vegetable gums such as acacia and tragacanth. The composition used as an aqueous dispersion or emulsion may contain 1
It is generally supplied in the form of a concentrated liquid containing a high proportion of one or more active ingredients. The concentrate is diluted with water before use. These concentrates often withstand storage for long periods of time, and after such storage are aqueous solutions that remain homogeneous long enough to allow dilution with water to apply them by conventional electric spray equipment. A liquid formulation can be formed. Concentrates may conveniently contain up to 95% by weight of one or more active ingredients, suitably from 10 to 85%,
For example, it may contain 25-60% by weight of active ingredient. These concentrates suitably contain an organic acid (for example an alkaryl or aryl sulfonic acid such as xylene sulfonic acid or dodecylbenzenesulfonic acid). This is because the presence of such organic acids makes them soluble in the polar solvents often used for the concentrated liquid.
This is because the solubility of one or more active ingredients can be increased. It is also suitable for the concentrate to contain a high proportion of surfactants, so that a sufficiently stable emulsion in water is obtained. After dilution to form an aqueous solvent, such solutions may contain varying amounts of one or more active ingredients depending on the intended purpose, but from 0.0005% or 0.01% to 10% by weight. Aqueous solutions containing one or more active ingredients may be used. The compositions of the invention may also contain one or more other compounds with biological activity, such as compounds with similar or complementary fungicidal or plant growth activity or plant growth regulating activity, herbicidal activity or insecticidal activity. It can also contain active compounds. Said other fungicidal compounds are, for example, Septoria,
It is a compound capable of controlling diseases of grain ears (e.g. wheat) such as Gibberella and Helmlnthosporium spp, seed and soil-borne diseases of grapes, downy mildew and powdery mildew, and powdery mildew and scab of apples. can. Mixtures of these fungicides may have a broader range of activity than the compounds of general formula (1) alone; furthermore, the other fungicides may have a synergistic effect on the fungicidal activity of the compounds of general formula (1). may have. Examples of said other fungicidal compounds are imazalil, benomyl, carbendazim, thiophenate-methyl, captafol, captan, sulfur, trifoline, dodemorph, tridemorph, pyrazophos, furaxyl, ethyrimol, technazene,
dimethylimole, bupolymate, chlorothalonil, vinclozolin, procymidone, iprodione, metalaxyl, forcetyl-aluminum,
Carboxin, oxycarboxin, fenarimol, nuarimol, fuenflam, metofloxane, nitrotal-isopropyl, triadimefone, thiabendazole, ethulidiazole,
Triadimenol, Viloxazole, Dithianone, Binapacryl, Chinomethionate, Guazatine, Dodine, Fuentin Acetate, Fuentin Hydroxide, Dinocap, Folpet,
Diclofluamide, ditarimphos, chitadine, cycloheximide, diclobuturazole, dithiocarbamate, copper compounds, mercury compounds, 1-(2-
Cyano-2-methoxyiminoacetyl)-3-ethyl urea, fenapanil, ofrace, propiconazole, etaconazole and fenepropemorph. The compounds of general formula (1) may be mixed with soil, peat or other root media to protect plants from seed-borne, soil-borne or foliar fungal diseases. Suitable insecticides are pyrimole, clonetone, dimethoate, metacystochus and formothion. Said other plant growth regulating compounds regulate the formation of weeds or seed heads, improve the degree of plant growth regulating activity or shelf life of the compound of general formula (1), and improve the control of less desirable plants (e.g. grasses). or to cause the compound of general formula (1) to act more rapidly or more slowly as a plant growth regulator. Some of these other plant growth regulators are herbicides. Examples of suitable plant growth regulating compounds which can be used synergistically in combination with the compounds of the invention are gibberellins (eg GA ₃ , GA ₄ or GA ₇ ), auxins (eg indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid). ), cytokinin (e.g. kinetin, diphenylurea, benzimidazole,
benzyladenine or benzylaminopurine),
Phenoxyacetic acid (e.g. 2,4-D or
MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactin (e.g. chlorfluorechol), maleic hydrazide, glyphosate,
glyphosine, long chain fatty alcohols and fatty acids,
Dikegratsk, fluoridamide, mefluidide,
Substituted quaternary ammonium and phosphonium compounds (e.g. chlormequat, ^* chlorphonium or mepiquat chloride), ethephon, carbetamide,
Methyl-3,6-dichloroanisate, daminodito ^* , aslam, abscisic acid,
Isopyrimole, 1-(4-chlorophenyl)-
4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitrile (eg bromoxynil), difenzocort, benzoylpropethyl, 3,6-dichloropicolinic acid and technazene. Synergism is most likely to occur when used with the above compounds, particularly those marked with an asterisk (*), which are quaternary ammonium compounds. The use of a compound of general formula (1) in combination with gibberellin can be useful when it is desired to reduce the plant growth regulating effect of the compound (e.g. when the compound is intended to be used as a fungicide). case). If said compounds are to be applied to the soil surrounding the plants or to the roots of the plants, the plant growth regulating effect of said compounds can also be optionally enhanced by the use of certain phenoxybenzoic acids and their derivatives. can decrease. The invention is illustrated by the following examples, where temperatures are given in °C. Example 1 This example uses the following chemical structure: The production of a compound having the following will be explained. A small amount of 1,2,4-triazole (1.89 g) is added to a stirred suspension of sodium hydride (1.32 g, 50% dispersion in oil) in dry dimethylformamide (DMF) (75 ml). Add one by one. After the reaction was complete, 4.0 g of chlorohydrin (prepared as described below) in dry DMF (10 ml) was added in small portions to the stirred solution and then incubated for 3-4 hours.
Heat to 80-90°C (at which time all raw materials have been destroyed by gas-liquid chromatography (GLC)). The mixture was cooled, poured into water and diluted with ether for 3 hours.
Extract times. The ethereal extract is washed with water, dried over magnesium sulphate and evaporated. This produces rubber and crystallizes it into cream powder (2.5g)mp83
Bring to ~5°C. NMR (CDCl ₃ ) δ0.90 (t, 3H) 1.46 (Sextet,
2H), 2.13 (t, 2H), 4.72 (d, 1H), 4.88 (d,
1H), 5.90 (bs, OH), 7.22 (dd, 1H), 7.46
(d, 1H), 7.75 (d, 1H), 7.84 (s, 1H),
8.20 (s, 1H). 1R (Nujiol) 3200, 2230 (weak) cm ^-1 The following formula used in the above reaction: The chlorohydrin is prepared as follows. n-Butyllithium (dissolved in hexane)
18.75 ml of a 1.6M solution) at −78°C under argon.
- Add dropwise to a stirred cooled solution of pentene (3.0 ml dissolved in 20 ml dry DMF). After the addition is complete, the clear solution is stirred at -78°C for 15 minutes. 2,2′,− in dry tetrahydrofuran (THF) (20 ml) while maintaining the temperature below −68 °C.
Add 4'-trichloroacetophenone (5.0 g) dropwise. The reaction was monitored by GLC during the addition;
Acetophenone addition is stopped when acetophenone is no longer consumed. After stirring for an additional 30 minutes, the reaction is poured into water and extracted with ether. The ether extract is washed with water, dried and evaporated to give a yellow liquid (5.5 g). This compound was confirmed to be pure by NMB and GLC. NMR (CDCl ₃ ) δ1.0 (t, 3H), 1.55 (sextet,
2H) 2.24 (t, 2H), 3.56 (s, OH), 3.95 (d,
2H), 4.19 (d, 2H), 7.30 (dd, 1H), 7.40
(d, 1H) 7.89 (d, 1H) IR (liquid film) 3300 (strong), 2230 (weak) cm ^-1 Example 2 This example is based on the following formula: The production of compound No. 4 in the table having the following will be explained. Lithium aluminum hydride (51 mg) is added portionwise to a stirred solution of pentynyltriazole (prepared in Example 1) in dry ether (20 ml). After the addition is complete, the mixture is heated to reflux and monitored by GLC. After a total of 56 hours of reflux and addition of another 100 mg of LiAlH ₄ all the raw material was consumed. The reaction is cooled, poured very carefully into 100 ml of water and 15 ml of dilute hydrochloric acid, and extracted with ether. The ethereal extract is washed with water, dried and evaporated. residue
Flash chromatograph on silica gel, eluting with 98:2 methylene chloride/methanol. The product is isolated as a clear oil, which crystallizes out by rubbing with ether/petroleum fractions. The resulting white powder (200 mg) has a melting point of 94-5°C. NMR (CDCl ₃ ) δ0.86 (t, 3H), 1.38 (sextet,
2H), 2.03(q, 2H). 4.70 (d, 1H), 5.60−
6.0 (m, 1H), 6.10 (d, 1H), 7.25 (dd, 1H),
7.45 (d, 1H). 7.78 (d, 1H), 7.88 (s, 1H),
8.13 (s, 1H) Example 3 The following compound is prepared by a method similar to that described in Examples 1 and 2, having the physical properties described below. Compound No. 2 in the table NMR (CDCl ₃ ) 1.05 (t, 3H), 2.18 (q, 2H),
4.72 (d, 1H), 4.90 (d, 1H), 5.30 (s,
OH), 7.30 (dd, 1H), 7.52 (d, 1H), 7.84
(d, 1H), 7.95 (s, 1H), 8.25 (s, 1H) IR (Nudiyol) 3200, 2240 (weak) cm ^-1 mpt 129-30℃ (white solid) Compound No. 4 in the table NMR (CDCl ₃ ) 0.92 (t, 3H), 2.05 (quintet,
2H), 4.64 (d, 1H) 5.00 (s, OH), 5.06 (d, 1H), 5.60−6.04
(m, 1H), 6.02 (d, 1H), 7.14 (dd, 1H),
7.34 (d, 1H), 7.68 (d, 1H), 7.76 (s, 1H),
8.00 (s, 1H) IR (Nudiyol) 3110cm ^-1 mpt109-110℃ (Clump-like white crystals) Compound No. 15 in the table NMR (CDCl ₃ ) 0.84 (t, 3H), 1.10−1.60 (m,
4H), 2.14 (t, 2H), 4.74 (d, 1H), 4.92 (d,
1H), 5.80 (a, OH), 7.30 (dd, 1H), 7.86
(d, 1H), 7.96 (s, 1H), 8.32 (s, 1H) IR (Nudiyol) 3070, 2230 (weak) cm ^-1 mpt 83-4℃ (white crystals) Compound No. 16 in the table NMR (CDCl ₃ ) 0.87 (t, 3H), 1.05−1.50 (m,
4H), 1.90−2.20 (m, 2H), 4.62 (d, 1H),
4.70 (s, OH), 5.06 (d, 1H), 5.54−6.0 (m,
1H), 6.02 (d, 1H), 7.15 (dd, 1H), 7.6 (d,
1H), 7.68 (d, 1H), 7.80 (s, 1H) 8.0 (s,
1H) IR (Nujiol) 3070cm ^-1 mpt 58-61℃ (white powder crystal) Example 4 This example is based on the following formula: This is to explain the production of a compound having the following. Step 1 Magnesium vinyl bromide (formed from 1.6 g of magnesium turnings and 3.74 g of vinyl bromide in 35 ml of dry THF) was dissolved in 2,4-dichloro in dry ether (35 ml) under argon. Add dropwise via dropper to the stirred solution of phenacyl chloride (5.5 g). The rate of addition is adjusted to obtain a mild reflux. Thirty minutes after the addition is complete, the reaction is cooled and poured into saturated ammonium chloride. The aqueous layer is extracted twice with ether and the organic extracts are combined, dried and evaporated to give an oil (4.4 g). According to NMR analysis, the following formula: showed the presence of chlorohydrin and small amounts of raw materials. This material is used without further purification. NMR (CDCl ₃ ) 2.96 (d, 1H), 3.12 (d, 1H),
4.90-5.30 (m, 2H), 5.60-5.90 (m, 1H).
7.10−7.60 (m, 4H) IR (liquid film) 3350 (bs) Stage 2 Next stage: (Compound No. 5 in the table) Production of a compound having the following. 1,2,4-triazole (2.6 g) in dry DMF (5 ml) was prepared using sodium hydride (50% dispersion in oil, which was washed out before use) suspended in dry DMF (15 ml). 1.8 g) dropwise to the stirred suspension. The temperature increases to 40℃. After the addition is complete, the solution is stirred for 30 minutes at room temperature. drying
Step 1 reactants (4.4g) in DMF (5ml)
The chlorohydrin from was added rapidly and the mixture was heated to 50° C. for 5 hours and then left overnight at room temperature.
The mixture is poured into water and extracted three times with ether. The ether extract was washed with water, dried and evaporated to give a dark oil (4.0 g). This oil was flash chromatographed, eluting with ethyl acetate, and the desired product was isolated as a brown oil;
This is crystallized by rubbing with ether/petroleum fraction to obtain 0.55 g, mp 88-90°C. NMR (CDCl ₃ ) 4.75−5.70 (m, 5H), 3.70 (dd,
1H), 7.44 (dd, 1H), 7.60 (d, 1H), 7.95
(d, 1H), 8.08 (s, 1H), 8.28 (s, 1H) IR (Nudiyol) ν3120cm ^-1 (s) Example 5 This example describes the preparation of compound No. 6 in the table. Stage 1 Formula: Preparation of epoxide with completely dry acetylene gas is bubbled into dry THF (25 ml) at -78°C until 1 g of it is dissolved. Argon is then introduced and n-butyllithium (15.4 ml of a 1.6M solution in hexane) is then added dropwise while maintaining the temperature below -69°C. After the addition is complete, reduce the temperature to −70°C to −75°C.
2,4 in dry THF (10 ml) while maintaining
- Gradually add dichlorophenylacyl chloride (5.0 g). After the addition is complete, the mixture is stirred for 30 minutes and then warmed to room temperature overnight. The resulting brown solution is added to an aqueous ammonium chloride solution. Separate the organic layer, dry and evaporate to give a brown oil;
Distill this (90°C/0.03mm). The liquid crystallizes to a solid (2.4 g, mp 40-44°C). NMR (CDCl ₃ ) 2.62 (s, 1H), 4.70 (d, 1H),
4.96 (d, 1H), 61.6 (s, 1H), 7.32 (dd,
1H), 7.48 (d, 1H), 7.96 (d, 1H), 7.95 (s,
1H), 8.20 (s, 1H) IR (nujiol) ν3265cm ^-1 3120cm ^-1 (weak) Stage 2 The following formula: Preparation of a compound with 1,2,4-triazole (0.48 g) in DMF (5 ml) was added dropwise to sodium hydride (0.34 g of a 50% dispersion in oil) in dry DMF (15 ml). and add to form an anion. After the addition is complete, the mixture is stirred at room temperature for 30 minutes. Dry DMF (15
The epoxide (1.0 g) from the reaction of step 1 in 1.0 ml) is slowly added dropwise and the mixture is then heated to 50° C. for 4 hours. After standing overnight at room temperature, the solution is poured into water and extracted with ether. The extract was dried and evaporated to give a brown oil which was purified by flash chromatography eluting with ethyl acetate to give a brown oil which was crystallized by rubbing with ether to give a light brown powder m.
Obtain p129-131°C (0.52 g). NMR (CDCl ₃ ) 2.36 (s, 1H), 2.70 (d.1H),
3.36 (d, 1H), 71.0-7.50 (m, 3H) IR (liquid film) 3300cm ^-1 (strong) 2120cm ^-1 (weak) Example 6 Mix the following ingredients and stir until all ingredients are dissolved. An emulsion is formed by stirring the mixture. Compound of Example 1 10% Ethelene dichloride 40% Calcium dodecylbenzenesulfonate 5% "Lubrol" L 10% "Aromazol" H 35% Example 7 A composition in the form of particles readily dispersible in a liquid, e.g. , is prepared by grinding together the three components listed in the presence of added water and then admixing with sodium acetate. The resulting mixture is dried and passed through a British standard mesh sieve, size 44-100, to obtain the desired particle size. Compound of Example 2 50% "Dispersol" T 25% "Lubrol" APN5 1.5% Sodium Acetate 23.5% Example 8 All of the following ingredients are ground together to produce a powder composition that is easily dispersible in liquids. Compound of Example 3 45% "Dispersol" T 5% "Rizapol" NX 0.5% "Cellophas" B600 2% Sodium Acetate 47.5% Example 9 The active ingredient is dissolved in a solvent and the resulting liquid is sprayed onto the china clay granules. . The solvent is then evaporated to produce a granular composition. Compound of Example 4 5% Fine china clay 95% Example 10 A composition suitable for use as a seed dressing is prepared by mixing the following three ingredients. Compound of example 1 50% mineral oil 2% china clay 48% Example 11 A powder is prepared by mixing the active ingredient with talc. Compound of Example 2 5% Talc 95% Example 12 A dispersion (Col) composition is prepared by ball milling the ingredients listed below and then forming an aqueous suspension of the milling mixture and water. Compound of Example 3 40% "Dispersol" T 10% "Lubrol" APN5 1% Water Example 13 Dispersion by mixing the ingredients listed below with each other and then grinding the mixture until all are thoroughly mixed. A powder composition is produced. Compound of Example 4 25% "Aerosol" OT/B 2% "Dispersol" AC 5% china clay 28% Silica 40% Example 14 This example describes the preparation of a dispersible powder composition. The ingredients are mixed and the mixture is then ground in a pulverizing mill. Compound of Example 1 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% Ceramic clay 34% Example 15 The following ingredients were mixed and then ground to formulate the ingredients. to make a dispersible powder. Compound of example 2 25% "Aerosol" OT/B 2% "Dispersol" A 5% china clay 68% In Examples 6 to 15, the proportions of the given components are in % by weight. All compounds in the table are formulated in the same manner as described in Examples 6-15. Descriptions of the compositions or substances represented by the various trade names and trade names mentioned above are provided below. Lubrol L: A condensate of nonylphenol (1 mol) and ethylene oxide (13 mol) Aromazole H: A solvent mixture of alkylbenzenes Dispersol T&AC: A mixture of sodium sulfate and a condensate of formaldehyde and sodium naphthalene sulfonate Lubrol APN5 : Nonylphenol (1 mol)
and naphthalene oxide (5.5 mol) Cellophas B600: Sodium carboxymethylcellulose thickener Rizapol NX: Condensate of nonylphenol (1 mol) and ethylene oxide (8 mol) Aerosol OT/B: Dioctyl sodium sulfosuccinate Perminal BX: Sodium alkylnaphthalene sulfonate. Example 16 Compounds of the present invention are tested against diseases caused by various fungi that parasitic the leaves of plants. The technique used is as follows. Plants were grown in John Innes flower pots (No. 1 or 2) placed in small flower pots with a diameter of 4 cm. A layer of fine sand is provided at the bottom of the pot containing the dicots to facilitate uptake of the test compound by the roots of the plants. The test compound was dissolved in Dispersol T.
The test compounds were formulated by bead milling with an aqueous solution or as a solution by dissolving the test compound in acetone or acetone/ethanol and diluting it to the desired concentration immediately before use. For leaf diseases, active ingredient content
Spray the suspension at 100 ppm onto the soil. Exceptions to this are Botryis cinerea, Plasmopara viticola and Venturia
This is a test for (inalqualis). The spray solution is applied to the leaves to maximum retention, and the roots are immersed so that the final concentration of active ingredient is equivalent to approximately 40 ppm per dry soil. When applying spray liquid to grains,
Tween 20 was added to give a final concentration of 0.05%. For most tests, the test compound is applied to the soil (roots) and foliage (by spray) one or two days before inoculating the plants with the disease. An exception is the test for powdery mildew (Erysiphe graminis) on barley, in which the plants are inoculated with the disease 24 hours before treatment. After the plants were inoculated with the disease, they were placed in an appropriate environment to allow infection, and were allowed to develop the disease until the disease could be evaluated. The period from inoculation to disease evaluation was varied between 4 and 14 days depending on the type of disease and environment. The percentage of disease control was recorded using the following grading: 4 = no disease 3 = disease of cone to 5% on untreated plants 2 = disease of 6 to 25% on untreated plants 1 = untreated 26-59% disease on plants 0 = 60-100% disease on untreated plants The results obtained are shown in the table below.

Table: Example 17 This example illustrates the plant growth regulating properties of compounds of the invention. The test compound is applied as a total spray of emulsion diluted to give the concentrations indicated in the table. Plants are grown in 7.62 cm pots filled with peat and sprayed at the two-leaf stage. The plant growth regulating effect is evaluated 13 or 19 days after application of the test compound. Growth inhibition rate is recorded on a scale of 1 to 3: 1 = 0 to 30% inhibition rate 2 = 31 to 75% inhibition rate 3 = 75% or more inhibition rate No number 1 to 3 means no effect represents. The associated plant growth regulating properties are shown as follows: G = darker green color of the leaves A = tip growth action T = tillering action The results are shown in the table. If the numbers don't show,
The test compound is substantially inert as an inhibitor.

[Table] Symbols of test plant species in the table Note AT Agrostis tenuis (Agrostis tenuis)
tenuis) CC sinothrus cristatus
(Cynosurus cristatus) DA Dactylis Glomereta (Dactylis
glomerata) LT Lettuce (Lactuca sativa) SB Sugar beet (Beta vulgaris) TO Tomato (Lycopersicum esculentum) SY Soybean (Glycine max) CT Cotton (Gossypium hirsutum) MZ Corn (Zea mays) WW Winter wheat (Triticum aestivum) BR Barley (Hordeum vulgare) Example 18 Compounds of the invention are tested against a range of foliar diseases of plants. The technique used is as follows. For all tests, plants were placed in small pots with a diameter of 4 cm (No. 1).
or 2) grown inside. A layer of fine sand is provided at the bottom of the pot containing the dicots to facilitate uptake of the test compound by the roots of the plants. The test compound was formulated by milling in a bead mill with an aqueous Dispersol T solution, or the test compound was formulated as a solution by dissolving the test compound in acetone or acetone/ethanol and diluting it to the desired concentration immediately before use. . For all diseases, solutions and suspensions are applied to the roots of the plant by spraying on the leaves to maximum retention capacity or via the soil ("systemic penetration test"). When the spray solution is applied to cereals. Tween 20 was added to give a final concentration of 0.05%. Foliar applications included eradication eradication applications ("erad"), in which the test compound was applied 1 day after inoculation, and inoculation of plants with the disease. This is a prophylactic application (“prot”) in which the test drug is applied one or two days before the application. Inoculation of the disease is carried out by spraying a spore suspension onto the leaves of the test plants. The plants were then placed in an appropriate environment, infected, and allowed to develop until the disease could be evaluated. The period from inoculation to disease evaluation was varied between 4 and 14 days depending on the type of disease and environment. The percentage of disease control was recorded using the following grading: 4 = no disease 3 = 5% disease on untreated plants 2 = 6-25% disease on untreated plants 1 = untreated 26-59% disease on seeds 0 = 60-100% disease on untreated plants The results shown in the table below show that Cercospora arachidicola on peanuts, Podosphaera leucotricha on apples, Podosphaera leucotricha on apples For Venturia inaequalis and Uncinula necator, the lowest concentration (ppm) at which the test chemical can cause 5% or more disease damage (i.e., the dosage range at which control plants progress from grade 3 to grade 2). It is. In tests for barley powdery mildew (Erysiphegraminis) and wheat rust (Puccinia recondita), the results were as follows: range). Preliminary protection ("port"), eradication eradication ("erad") and systemic penetration ("syst") results are given in the table. In this table the indicated formation, for example: 0.01 - 0.05 means that the concentration in ppm is 0.01ppm in the particular case in question.
It should be noted that the value is between 0.5ppm and 0.5ppm. The symbol "<" represents "less than" or "lower than" a given specific density value, and ">" means "greater than" or "higher than" a given specific density value. Compounds Nos. 1 to 6 of the table of the invention (listed first in the table) are compound Nos. 1 to 55 of the table of European Patent Publication No. 52424 (European Patent Application No. 813048352) and
The results in the table demonstrate that it is significantly more active than 57 (listed after the table). Said compound No.
1-6 are not only more active against specific diseases, but their overall distribution of preventive protection, eradicative eradication and systemic properties over the target range makes the compounds more active as broad-spectrum agricultural fungicides. to make it more useful.

【table】

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Claims (1)

[Claims] Primary formula (): [In the formula, R ¹ is -CH=CH-X or -C≡C-X (wherein X is hydrogen or a straight-chain alkyl group);
R ² is a halophenyl group, Z is OR ³ (wherein R ³ is H, alkyl, alkenyl or alkynyl group)] and stereoisomers thereof; and acid addition salts and metal complex salts thereof . 2 R ² is 2-, 3- or 4-chlorophenyl,
2,4- or 2,6-dichlorophenyl, 2-,
3- or 4-fluorophenyl, 2,4-difluorophenyl, 2-, 3- or 4-bromophenyl, 2-chloro-4-fluorophenyl, 2-chloro-6-fluoro-phenyl or 2-, The compound according to claim 1, which is a 3- or 4-methoxyphenyl group. 3 X is H or C _1-5 alkyl group; R ² is 4
-chlorophenyl or 2,4-dichlorophenyl group, and Z is ^OR3 (provided that ^R3 is H). Quaternary formula: as well as The compound according to any one of claims 1 to 3, which is a compound having the following. 5 A compound of the following formula () or (): [Formula] [Formula] (wherein R ¹ , R ² and Z have the following meanings, and X is a halogen atom) in the presence of an acid binding agent of the following formula (), characterized in that it is reacted with 1,2,4-triazole or in the form of one of its alkali metal salts in a convenient solvent: [In the formula, R ¹ is -CH=CH-X or -C≡C-X (wherein X is hydrogen or a straight-chain alkyl group);
R ² is a halophenyl group, and Z is OR ³ (wherein R ³ is H, alkyl, alkenyl or alkynyl group). Sixth formula (): [In the formula, R ¹ is -CH=CH-X or -C≡C-X (wherein X is hydrogen or a straight-chain alkyl group);
R ² is a halophenyl group, Z is OR ³ (wherein R ³ is H, alkyl, alkenyl or alkynyl group)] or a salt, metal complex salt, ether or ester thereof and optionally A fungicidal or plant growth regulating composition comprising a carrier or a diluent.