CA2013648A1 - Azolylethane derivatives and fungicides and growth regulators containing them - Google Patents
Azolylethane derivatives and fungicides and growth regulators containing themInfo
- Publication number
- CA2013648A1 CA2013648A1 CA002013648A CA2013648A CA2013648A1 CA 2013648 A1 CA2013648 A1 CA 2013648A1 CA 002013648 A CA002013648 A CA 002013648A CA 2013648 A CA2013648 A CA 2013648A CA 2013648 A1 CA2013648 A1 CA 2013648A1
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- Prior art keywords
- alkyl
- phenoxy
- alkoxy
- amino
- unsubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: Azolylethane derivatives of the general formula I
Description
~ L3~
~.Z. 0050/407g7 Aæolylethane derivatives and fun~ici.de~ and growth regulators contalnin~ them The present invention relates to novel azole com-pounds, processes for their preparation, and fungicides and growth regulators containing these compounds.
It is known that triazolylethane derivati~e~, eg.
1-(1,2,4-triaæol-1-yl)-1-phenylthio 2-methyl-2 phenyl-propaneorl-tl,2,4-triazol-1-yl)-1-(4~chlorophenylthio)-2-mathyl-2-phenylpropane, can be used as fung:icides (Eurspean Patent 91,219). Their fungicidal action is unsatis~actory.
I~ is also known that triazolylalkoxybenzyl derivative~ ran be u~ed as fungicides ~DE-26 40 823).
We have found that azolylethane derivatives of the general formula I
~Xh o N=f ~
A~CH2)n--3 where A and B are each C~-C~-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C~-cycloalkyl or Cs-C3~cyclo-alkenyl, where these radicals may ba mono8ub~k.ituted totrisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalk~l, each o 1 ~o 4 carbon atoma, D is Cl-C4-alkoxy, amlno whlch i~ unsub~tituted or ~ub-~ u~ed by C1-C3-alkyl o.r Cl-C3-~Cyl, un~ub~,itu~ed ox C
Cb-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where khese radical may be mono-substituted ~o tri~ubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer of from 1 to 5 csr 0, and X i~ CH or N, and their plant-~olerated acid addition salt~ or metal complexe~, except for the compound~ in which A is unsub-stituted phenyl, B i~ alkyl, D is alkoxy, X is N and n is O, have a ~etter fungicidal action than the known azole ~ 1 q3 ~
- 2 - O.Z. 0050/40797 compound~.
The compounds of th~ formula I contain asymmetric carbon atoms and can therefore occur as enantiomerq and dias~ereomers. In the case of the novel compounds, the mixtures of diastereomers can be separated in a conven-tional manner, for example on the basis of ~heir dif--fexent solubilitie~ or hy colum~ chromatography, and can be isolated in pure form. The racemates of the novel compounds can be resolved by known methods, for example by salt formation with an optically active acid, separa-tion of the diastereomeric salts a~d liberation of the enantiomers by means of a base. Both the individual enantiomers or diastereomers and mixtures thereof can be used as fungicidal and growth-regulating acti~e ingredients.
A and B are identical or different and are each, for example, Cl-C4-alkyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl r l-naphthyl, 2-naphthyl, p-biphenyl, phenyl, 2--chlorophenyl, 2-fluorophenyl, ~-bromophenyl, 3-chloro-phenyl, 3-bromophenyl, 3-fluorophenyl, 4-1uorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dlchlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophen~l, 2,6-dichlorophenyl, 2-chloro-6~fluorophenyl, 2-methoxyphenyl, 3-methoxy phenyl, ~-me~hoxyph0nyl, 2,4-dimethoxyphenyl, 4~ethyl-phenyl, 4-l~opropylphonyl, ~-1;ert-butylphenyl, 4;text~
butoxyphenyl,~-chloro-4-fluorophenyl,2-chloro-6-methyl-phenyl, 3,4-dLmathoxyphenyl, 3-pheno~yphenyl, 4-phenoxy-phenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 2-aminophenyl, 2~trifluoromethylphenyl, 3-trifluoromethylphenyl, 4~trifluoxome~hylphenyl~ tetra-hydropyranyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-cyclohexenyl or 3-cyclohexenyl.
n i~ O, 1, 2, 3, 4 or S.
Acid additio~ ~alts are, for examplet the hydro-ohlorides, bromides, sulfates, nitrates, phaspha~es, oxalates or dodecylbenzenes~lfonate~. The activity of - 3 ~ 0.~. 0050/~0797 the alts i~ due to the cation, so that the anion i~ in general unimportant. The novel active ingredient salts are prepared by reacting the azolylethane derivatives (I) with the acid~.
S Metal complexes of the active ingredients I or their salts can be formed with copper, zinc, tin, man-ganese, iron, cobalt or nickel by reacting the azolyl-etharle derivatives with corresponding metal salts Compounds of the formula I can be prepared by reacting a compound of the formula II
f= N Hal II
A~(CH2)n-B
where A, ~ and X have the abovementioned me nings and Hal is chlorina or bromine, with a compound of the formula D-H.
The reaction is carried out in the presence or absence of a solvent or diluent~ with or without the addition of an inorganic or organic base and of a reac-tion accelerator, at from 10 to lSO~C. The preferr~d solvent~ and diluents include ketones, such as ace~one, methyl ethyl ke~one or cyclohexanone, ni.triles, such as acetonitrile or propionitrile, alcohols, such as meth anol, ethanol, isopropanol, n-butanol or glycol, ~sters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, ~uch a~ tetrahydro~uran, diethyl e-ther, dimeth~
oxyethano, dioxan~ or dii~opropyl other, ~mide~, such as dimathylormamide or N-methylpyrrolidono, as well as dimekhyl ~ulfoxide, ~ulfolane or mixture~ thereo~.
Suitable ~a~es which may also be used as acid acceptor~ in the reaction are, for example, alkali metal hydxoxide~, such as lithium hydroxide, sodium hydroxide ox potassium hydroxide, alkali metal carbonatesJ such as sodium carbonate, pota~sium carbonate or cesium car-bonate, alkali metal hydrides~ such as lithium hydride, ~odium hydride ~nd potassium hydride, alkali metal ~ ~ ~ O.Z. 0050/40797 amide~, such a~ sodium amide and potassium amido, ag well as trLphenylmethyllithium, triphenylmethylsodium, tri-phenylmethylpotassium, naphthalenelithium, naphthalene~
sodium, naphthalenepotassium, pyridine or 4-dimethyl-aminopyridine. However, other conventional bases may also be used.
Preferred reaction accelerators are metal halide~, such as sodium iodide or pota~sium iodid~, quaternary ammonium qalts, such as tetrabutylammonium chloride, bromide, iodide or hydrogen sulfate or benzyl-triethylammonium chloride or bromide, or crown ethers, such as 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclohexano-18-crown-6.
The reaction is carried out in general at from 20 to 150C under atmospheric ox superatmospheric pres~,ure, continuously or batchwise.
The starking compound~ II can be prepared by reacting a compound of the formula III
CHO
III
A~ ( C H z ) n~0 where A, B and n have the abovementioned meanings/ with a compound of ~he ~ormula IV
,x ~N IV
where X ha~ the abovem~ntioned meaning3~ in the pre~ence o~ a thionyl halide~
The reaction is carried out i~ the pxe~ence or ab~ence of a solvent ox diluent at from -30 to 80C. The preferred ~olvent~ or diluents include nitrile~, such a~
acetonitrile or propionitrile, ethers, such as tetra-hydrofuran, diethyl ether, dLmetho~yethane, dioxane or dii~opropyl ether, and in particular hydrocarbons and chloroh~drocarbon~, ~uch a~ pentane, hexane, methylene chloride, chlorofoLm, carbon tetrachloride, dichloro-ethane or ~ixture~ thereof.
-- 5 ~ O.Z. 005~/~0797 The compounds III can b~ prepared by ~ene~ally known methocls of aldehyde synthesis (Houben-Weyl-M~ller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart 1983, Vol. E).
The Examples which follow illustrate the prepara-tisn of the active ingredie~t~.
1. Preparation of the starting materials Method 1 1-(1,2,4-Triazol-l-yl)-l-chloro-2 (2,4-dichlorophenyl)-butane 132.8 g of thionyl chloride are added to a solution of 307.9 g of triazsle in 500 ml of methylene chloride at 0C. After the end of the addition, the mix-ture is s~irred at room temperature (20C) for 30 minutes and 116~3 g of 2-t2,4-dichlorophenyl)-butanal are then added. The reaction mixture is stirred for 15 hours at room temperature, after which 40Q ml of water are added to the solution and the organic phase i3 separated off.
The remaining aqueous phase is extracted twice by shaking with methylene chloride and the collectsd organic phases are washed twice with saturated sodium bicarbonate solution. The or~anic phase isolated i8 then dried over sodium sulfatQ and evaporated down, 158.2 g of 1-(1,2,4 triazol-1-yl)-1 chloro-2-(2,4-dichlorophenyl)-butane being obtained.
2. Preparatlon o~ the end product3 1-~1,2,4-Triazol-l~yl)-l-methoxy-2-(2,4-dichlorophenyl)-butana 9.4 ~ of sodium methylate and 0.2 g of potas~ium iodide are added to a solution o~ 26.6 g of 1-(1,2,4-triazol 1-yl~ chloro-2-(2,4-dichlorophenyl)-butane in 200 ml of methanel. The reaction ~ixture is refluxed for 48 hours, after which 100 ml of water are added to the solution and the mixture i8 extracted several tLmes with methyl tert-butyl ether. Tha organic phase isolated is washed twice with water, then dri~d over 90dium sulfate . ~ .
~:L3~
- 6 - O.Z. 0~50/40797 and evaporated down and the remaining residue is purified by chromatography over silica gel (9 : 1 ethyl acetate/n-hexane). 6.2 g (24%) of 1-(1,2,4-triazol~1-yl)-1-methoxy 2-(2,4-dichlorophenyl)-butane are obtained as a 1 : 1 diastereomer mixture ~compound No. 1).
The compounds listed in the Table can be prepared similarly to Example 1.
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26 O.Z. 0050/~07~7 Generdlly speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, 20 Rhizoctonia species in cotton and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potakoes and tomatoes, 30 fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after in-fection of the plants or seeds by the fungi.
The novel compounds may e~ercise a variety of in~luences on practically40 all plant development stages, and are therefore used as growth regulators.
The diversity of action of growth regulators depends especially on ~7 O.Z. 0050/~0797 a) the type and variety of plant;
b) the time applied, with reference to the development stage of the plants and the time of the year;
c) the place and method of application (seed treatment, soil treatment, or application to foliage);
d) climatic factors, e.g., average temperature, amount of precipita-te, sunshine and duration;
e) soil conditions (including fertilization);
f) the formulation of the active ingredient; ar,d 10 g) the concentration at which the active ingredient is applied.
A description of some of the various possibilities of using the growth regulators according to the invention in agriculture and horticulture is given below.
A. vegetative plant growth can be inhibited to a considerable extent, a fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf color is darker.
Of advantage in practice is for example the reduction in grass growth on roadsides, hedyes, canal embankments and on areas such as parks, sportsgrounds, fruit orchards, lawns and airfields, thus redueing expensive and time-consuming mowing.
A further feature of economic interest is the increase in the rigor of crops which kend to lodge, such as cereals, Indian corn, sunflowers and soybeans. The shortening and strengthenin~ of the stem thus caused reduces or aliminates the danger of lodging under unFavorable weatner conclitions.
The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in cotton. It is thus pos-sible for this important crop to be harvested completely mechanically.
~5 Growth regulators may also increase or inhibit lateral branching. rhis is of interest when, for instance in tobacco plants, it is desired to inhibit the formation of lateral shoots (suckers) in favor of leaf development.
With growth regulators, it is possible for instance in winter rape to considerably increase the resistance to freeze injury. On the one hand, upward growth and the development o~ a too luxuriant (and thus particularly frost-susceptible~ leaf or plant mass are inhibited; on 28 o.z, 0050/~ 7 the other, the young rape plants are kept, in spite of favorable growth conditions, in the vegetative development stage before winter frosts begin. The danger of freeze injury is thus eliminated in plants which tend to lose prematurely their inhibition to bloom and pass into the generative phase. In other crops, too, e.g., winter cereals, it is advantageous if the plants are well tillered in the fall as a result o~ treatment with the compounds according to the invention, but enter winter with not too lush a growth. This is a preventive medsure against increased suscept;bility to freeze injury and - because of th~
relatively low leaf or plant mass - attack by various (especially fungus) diseases. The inhibition of vegetative growth also makes closer planting possible in numerous crops, which means an increase in yield, based on the area cropped.
15 B. Better yields both of plant parts and plant materials may be obtained with the novel agents. It is thus for instance possible to induce increased formation of buds, blossom, leaves, fruit, seed grains, roots and tubers, to increase the sugar content of sugarbeets, sugarcane and citrus fruit, to raise the protein content of cereals and soybeans, and to stimulate the increased formation of latex in rubber trees.
The compounds of the formula I may raise the yield by influencing plant metabolism or by promoting or inhibiting vegetative and/or generative plant growth.
C. It is also possible with growth regulators to shorten or lengthen growth stages and to ~ccelerate or retard the ripening process in plant parts either before or after harvestiny.
A factor of economic interest is for example the facilitation of har-vesting made possible by a chemical, temporally concentrated loosening (abscission~ of the adherence of stalks to the branches of citrus fruit, olive trees, and other kinds of pomes, drupes and indehiscent fruit. The same mechanism, i.e., promotion of the formation of separ-ation layers between fruit or leaf and stem of the plant, is also es-sential for a readily controllable defoliation of crop plants, e.g., cotton.
~0 D. Further, transpiration in crop plants rnay be reduced with growth regulators. This is particularly important for plants yrowing in agricultural areas which are expensive to irrigate, e.g., in arid or semi-arid areas. Irrigation frequency can be reduced by using the compounds according to the invention, making for lower costs. As a ~ ~ ~ 3 ~3 29 0.~. 0050/l~07~7 result of the use of growth regulators, the water available can be better utilized, because, inter alia, - the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climatP in the stand is favorably influenced by the more compact growth.
The active ingredients according to the invention may be applied not only 10 to the seed (as a disinfectant), but also to the soil, i.e., via the roots, and to the foliage by spraying.
As a result of th~ good tolerance by crop plants, the application rate when the active ingredients are used as growth regulators may vary within 15 wide limits.
When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are general-ly required.
For fotiage and soil treatment, amounts of from 0.01 to 10, and preferably from 0.02 to 3, kg/ha are generally considered to be sufficient.
The novel substances may be converted into conventional formulations such 25 as solutions, emulsions, suspensions, dusts, powders, pastes and granul~s.
The application forms depend entirely on the purposes for which they ar~!
intended; they should at all events ensure a fine and uniform d~stributlon of the active ingredient. rhe formulations are produced in known manner, for example by extending the activo ingredient with solvents and/or 30 carriers, with or without the use of emulsifiers and dispersdnts; if water is used as solvent, it ~s also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., meth-35 anol, butanol), amines (e.g., ethanolamine, dimethylformamide~, and water;carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers and other surfactants, such as nonionic and anionic emulsifiers ~e.g., polyoxyethylene fatty alcohol ethers, alkyl 40 sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.
. . '' ' , :
O.Z. 005~ 0797 The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. I is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for 10 application in the form of very fine drops.
II. 20 parts by weight of compound no. 27 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and l mole of oleic acid-N-15 monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles o~ ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
20 III. 20 parts by weight of compound no. 42 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 44 is dissolved in a mixture con-sisting of 25 parts by weiyht of cyçlohexanol, 65 parks by weiyht of a mineral oil fraction having a boiliny point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 30 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 35 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
40 VI. 3 parts by weight of compound no. 27 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
20~3~
31 O.Z. 005~ 0797 VII. 30 parts by weight of compound no. 42 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained 5 having good adherence.
VIII. 40 parts by weight of compound no. 44 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to 10 give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts by weight of compound no. 1 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by 15 weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
20 In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in an increase in the fungicidal spectrum.
Use examples For comparison purpos0s, the compounds 1 ~1,2,4-triazol-1-yl)-1-phenyl-thio-2-methyl-2-phenylpropane (A) and 1-(1,2,4-triazol-1-yl)-1-(4-chloro-30 phenylthio)-2-methyl-2-pherlylpropane (B) disclosed in EP 91,219 were used.
Use Example 1 Action on Pyricularia oryzae ~protective~
Leaves of pot-grown rice sesdlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions consisting (dry basis~ of 80% of active ingredient and 20% of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were then set 40 up in climatic cabinets at from 22 to 24C and a relative humidity of 95 to 99YO. The e~tent of fungus spread was assessed after 6 days.
The results show that active ingredients 1, 27, 42, 44, 228 and 232, applied as 0.05wt% spray liquors, have a better fungicidal action (90%) than prior art active ingredients A and B (30%).
:. ' '' : ' ' . . .
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32 0,Z. 0050/l~0797 Use Example 2 Action on Pyrenophora teres 5 Barley seedlings of the "Igri" variety were sprayed to runoff at the two-leaf stage with aqueous suspensions consisting (dry basis) of 80% of active ingredient and 20~o of emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora teres, and set up for 48 hours in a high-humidity climatic cabinet at 18C. The 10 plants were then cultivated for a further 5 days in the greenhouse at 20 to 22C and a relative humidity of 70C. The extent of fungus spread was then assessed.
The results show that active ingredients 1, 27, 49, 134, 226 and 228, 15 applied as 0.05% spray liquors, have a better fungicidal action (90%) than prior art active ingredients A and B (lWo).
~.Z. 0050/407g7 Aæolylethane derivatives and fun~ici.de~ and growth regulators contalnin~ them The present invention relates to novel azole com-pounds, processes for their preparation, and fungicides and growth regulators containing these compounds.
It is known that triazolylethane derivati~e~, eg.
1-(1,2,4-triaæol-1-yl)-1-phenylthio 2-methyl-2 phenyl-propaneorl-tl,2,4-triazol-1-yl)-1-(4~chlorophenylthio)-2-mathyl-2-phenylpropane, can be used as fung:icides (Eurspean Patent 91,219). Their fungicidal action is unsatis~actory.
I~ is also known that triazolylalkoxybenzyl derivative~ ran be u~ed as fungicides ~DE-26 40 823).
We have found that azolylethane derivatives of the general formula I
~Xh o N=f ~
A~CH2)n--3 where A and B are each C~-C~-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C~-cycloalkyl or Cs-C3~cyclo-alkenyl, where these radicals may ba mono8ub~k.ituted totrisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalk~l, each o 1 ~o 4 carbon atoma, D is Cl-C4-alkoxy, amlno whlch i~ unsub~tituted or ~ub-~ u~ed by C1-C3-alkyl o.r Cl-C3-~Cyl, un~ub~,itu~ed ox C
Cb-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where khese radical may be mono-substituted ~o tri~ubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer of from 1 to 5 csr 0, and X i~ CH or N, and their plant-~olerated acid addition salt~ or metal complexe~, except for the compound~ in which A is unsub-stituted phenyl, B i~ alkyl, D is alkoxy, X is N and n is O, have a ~etter fungicidal action than the known azole ~ 1 q3 ~
- 2 - O.Z. 0050/40797 compound~.
The compounds of th~ formula I contain asymmetric carbon atoms and can therefore occur as enantiomerq and dias~ereomers. In the case of the novel compounds, the mixtures of diastereomers can be separated in a conven-tional manner, for example on the basis of ~heir dif--fexent solubilitie~ or hy colum~ chromatography, and can be isolated in pure form. The racemates of the novel compounds can be resolved by known methods, for example by salt formation with an optically active acid, separa-tion of the diastereomeric salts a~d liberation of the enantiomers by means of a base. Both the individual enantiomers or diastereomers and mixtures thereof can be used as fungicidal and growth-regulating acti~e ingredients.
A and B are identical or different and are each, for example, Cl-C4-alkyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl r l-naphthyl, 2-naphthyl, p-biphenyl, phenyl, 2--chlorophenyl, 2-fluorophenyl, ~-bromophenyl, 3-chloro-phenyl, 3-bromophenyl, 3-fluorophenyl, 4-1uorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dlchlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophen~l, 2,6-dichlorophenyl, 2-chloro-6~fluorophenyl, 2-methoxyphenyl, 3-methoxy phenyl, ~-me~hoxyph0nyl, 2,4-dimethoxyphenyl, 4~ethyl-phenyl, 4-l~opropylphonyl, ~-1;ert-butylphenyl, 4;text~
butoxyphenyl,~-chloro-4-fluorophenyl,2-chloro-6-methyl-phenyl, 3,4-dLmathoxyphenyl, 3-pheno~yphenyl, 4-phenoxy-phenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 2-aminophenyl, 2~trifluoromethylphenyl, 3-trifluoromethylphenyl, 4~trifluoxome~hylphenyl~ tetra-hydropyranyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-cyclohexenyl or 3-cyclohexenyl.
n i~ O, 1, 2, 3, 4 or S.
Acid additio~ ~alts are, for examplet the hydro-ohlorides, bromides, sulfates, nitrates, phaspha~es, oxalates or dodecylbenzenes~lfonate~. The activity of - 3 ~ 0.~. 0050/~0797 the alts i~ due to the cation, so that the anion i~ in general unimportant. The novel active ingredient salts are prepared by reacting the azolylethane derivatives (I) with the acid~.
S Metal complexes of the active ingredients I or their salts can be formed with copper, zinc, tin, man-ganese, iron, cobalt or nickel by reacting the azolyl-etharle derivatives with corresponding metal salts Compounds of the formula I can be prepared by reacting a compound of the formula II
f= N Hal II
A~(CH2)n-B
where A, ~ and X have the abovementioned me nings and Hal is chlorina or bromine, with a compound of the formula D-H.
The reaction is carried out in the presence or absence of a solvent or diluent~ with or without the addition of an inorganic or organic base and of a reac-tion accelerator, at from 10 to lSO~C. The preferr~d solvent~ and diluents include ketones, such as ace~one, methyl ethyl ke~one or cyclohexanone, ni.triles, such as acetonitrile or propionitrile, alcohols, such as meth anol, ethanol, isopropanol, n-butanol or glycol, ~sters, such as ethyl acetate, methyl acetate or butyl acetate, ethers, ~uch a~ tetrahydro~uran, diethyl e-ther, dimeth~
oxyethano, dioxan~ or dii~opropyl other, ~mide~, such as dimathylormamide or N-methylpyrrolidono, as well as dimekhyl ~ulfoxide, ~ulfolane or mixture~ thereo~.
Suitable ~a~es which may also be used as acid acceptor~ in the reaction are, for example, alkali metal hydxoxide~, such as lithium hydroxide, sodium hydroxide ox potassium hydroxide, alkali metal carbonatesJ such as sodium carbonate, pota~sium carbonate or cesium car-bonate, alkali metal hydrides~ such as lithium hydride, ~odium hydride ~nd potassium hydride, alkali metal ~ ~ ~ O.Z. 0050/40797 amide~, such a~ sodium amide and potassium amido, ag well as trLphenylmethyllithium, triphenylmethylsodium, tri-phenylmethylpotassium, naphthalenelithium, naphthalene~
sodium, naphthalenepotassium, pyridine or 4-dimethyl-aminopyridine. However, other conventional bases may also be used.
Preferred reaction accelerators are metal halide~, such as sodium iodide or pota~sium iodid~, quaternary ammonium qalts, such as tetrabutylammonium chloride, bromide, iodide or hydrogen sulfate or benzyl-triethylammonium chloride or bromide, or crown ethers, such as 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclohexano-18-crown-6.
The reaction is carried out in general at from 20 to 150C under atmospheric ox superatmospheric pres~,ure, continuously or batchwise.
The starking compound~ II can be prepared by reacting a compound of the formula III
CHO
III
A~ ( C H z ) n~0 where A, B and n have the abovementioned meanings/ with a compound of ~he ~ormula IV
,x ~N IV
where X ha~ the abovem~ntioned meaning3~ in the pre~ence o~ a thionyl halide~
The reaction is carried out i~ the pxe~ence or ab~ence of a solvent ox diluent at from -30 to 80C. The preferred ~olvent~ or diluents include nitrile~, such a~
acetonitrile or propionitrile, ethers, such as tetra-hydrofuran, diethyl ether, dLmetho~yethane, dioxane or dii~opropyl ether, and in particular hydrocarbons and chloroh~drocarbon~, ~uch a~ pentane, hexane, methylene chloride, chlorofoLm, carbon tetrachloride, dichloro-ethane or ~ixture~ thereof.
-- 5 ~ O.Z. 005~/~0797 The compounds III can b~ prepared by ~ene~ally known methocls of aldehyde synthesis (Houben-Weyl-M~ller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart 1983, Vol. E).
The Examples which follow illustrate the prepara-tisn of the active ingredie~t~.
1. Preparation of the starting materials Method 1 1-(1,2,4-Triazol-l-yl)-l-chloro-2 (2,4-dichlorophenyl)-butane 132.8 g of thionyl chloride are added to a solution of 307.9 g of triazsle in 500 ml of methylene chloride at 0C. After the end of the addition, the mix-ture is s~irred at room temperature (20C) for 30 minutes and 116~3 g of 2-t2,4-dichlorophenyl)-butanal are then added. The reaction mixture is stirred for 15 hours at room temperature, after which 40Q ml of water are added to the solution and the organic phase i3 separated off.
The remaining aqueous phase is extracted twice by shaking with methylene chloride and the collectsd organic phases are washed twice with saturated sodium bicarbonate solution. The or~anic phase isolated i8 then dried over sodium sulfatQ and evaporated down, 158.2 g of 1-(1,2,4 triazol-1-yl)-1 chloro-2-(2,4-dichlorophenyl)-butane being obtained.
2. Preparatlon o~ the end product3 1-~1,2,4-Triazol-l~yl)-l-methoxy-2-(2,4-dichlorophenyl)-butana 9.4 ~ of sodium methylate and 0.2 g of potas~ium iodide are added to a solution o~ 26.6 g of 1-(1,2,4-triazol 1-yl~ chloro-2-(2,4-dichlorophenyl)-butane in 200 ml of methanel. The reaction ~ixture is refluxed for 48 hours, after which 100 ml of water are added to the solution and the mixture i8 extracted several tLmes with methyl tert-butyl ether. Tha organic phase isolated is washed twice with water, then dri~d over 90dium sulfate . ~ .
~:L3~
- 6 - O.Z. 0~50/40797 and evaporated down and the remaining residue is purified by chromatography over silica gel (9 : 1 ethyl acetate/n-hexane). 6.2 g (24%) of 1-(1,2,4-triazol~1-yl)-1-methoxy 2-(2,4-dichlorophenyl)-butane are obtained as a 1 : 1 diastereomer mixture ~compound No. 1).
The compounds listed in the Table can be prepared similarly to Example 1.
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26 O.Z. 0050/~07~7 Generdlly speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, 20 Rhizoctonia species in cotton and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potakoes and tomatoes, 30 fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after in-fection of the plants or seeds by the fungi.
The novel compounds may e~ercise a variety of in~luences on practically40 all plant development stages, and are therefore used as growth regulators.
The diversity of action of growth regulators depends especially on ~7 O.Z. 0050/~0797 a) the type and variety of plant;
b) the time applied, with reference to the development stage of the plants and the time of the year;
c) the place and method of application (seed treatment, soil treatment, or application to foliage);
d) climatic factors, e.g., average temperature, amount of precipita-te, sunshine and duration;
e) soil conditions (including fertilization);
f) the formulation of the active ingredient; ar,d 10 g) the concentration at which the active ingredient is applied.
A description of some of the various possibilities of using the growth regulators according to the invention in agriculture and horticulture is given below.
A. vegetative plant growth can be inhibited to a considerable extent, a fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf color is darker.
Of advantage in practice is for example the reduction in grass growth on roadsides, hedyes, canal embankments and on areas such as parks, sportsgrounds, fruit orchards, lawns and airfields, thus redueing expensive and time-consuming mowing.
A further feature of economic interest is the increase in the rigor of crops which kend to lodge, such as cereals, Indian corn, sunflowers and soybeans. The shortening and strengthenin~ of the stem thus caused reduces or aliminates the danger of lodging under unFavorable weatner conclitions.
The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in cotton. It is thus pos-sible for this important crop to be harvested completely mechanically.
~5 Growth regulators may also increase or inhibit lateral branching. rhis is of interest when, for instance in tobacco plants, it is desired to inhibit the formation of lateral shoots (suckers) in favor of leaf development.
With growth regulators, it is possible for instance in winter rape to considerably increase the resistance to freeze injury. On the one hand, upward growth and the development o~ a too luxuriant (and thus particularly frost-susceptible~ leaf or plant mass are inhibited; on 28 o.z, 0050/~ 7 the other, the young rape plants are kept, in spite of favorable growth conditions, in the vegetative development stage before winter frosts begin. The danger of freeze injury is thus eliminated in plants which tend to lose prematurely their inhibition to bloom and pass into the generative phase. In other crops, too, e.g., winter cereals, it is advantageous if the plants are well tillered in the fall as a result o~ treatment with the compounds according to the invention, but enter winter with not too lush a growth. This is a preventive medsure against increased suscept;bility to freeze injury and - because of th~
relatively low leaf or plant mass - attack by various (especially fungus) diseases. The inhibition of vegetative growth also makes closer planting possible in numerous crops, which means an increase in yield, based on the area cropped.
15 B. Better yields both of plant parts and plant materials may be obtained with the novel agents. It is thus for instance possible to induce increased formation of buds, blossom, leaves, fruit, seed grains, roots and tubers, to increase the sugar content of sugarbeets, sugarcane and citrus fruit, to raise the protein content of cereals and soybeans, and to stimulate the increased formation of latex in rubber trees.
The compounds of the formula I may raise the yield by influencing plant metabolism or by promoting or inhibiting vegetative and/or generative plant growth.
C. It is also possible with growth regulators to shorten or lengthen growth stages and to ~ccelerate or retard the ripening process in plant parts either before or after harvestiny.
A factor of economic interest is for example the facilitation of har-vesting made possible by a chemical, temporally concentrated loosening (abscission~ of the adherence of stalks to the branches of citrus fruit, olive trees, and other kinds of pomes, drupes and indehiscent fruit. The same mechanism, i.e., promotion of the formation of separ-ation layers between fruit or leaf and stem of the plant, is also es-sential for a readily controllable defoliation of crop plants, e.g., cotton.
~0 D. Further, transpiration in crop plants rnay be reduced with growth regulators. This is particularly important for plants yrowing in agricultural areas which are expensive to irrigate, e.g., in arid or semi-arid areas. Irrigation frequency can be reduced by using the compounds according to the invention, making for lower costs. As a ~ ~ ~ 3 ~3 29 0.~. 0050/l~07~7 result of the use of growth regulators, the water available can be better utilized, because, inter alia, - the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climatP in the stand is favorably influenced by the more compact growth.
The active ingredients according to the invention may be applied not only 10 to the seed (as a disinfectant), but also to the soil, i.e., via the roots, and to the foliage by spraying.
As a result of th~ good tolerance by crop plants, the application rate when the active ingredients are used as growth regulators may vary within 15 wide limits.
When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are general-ly required.
For fotiage and soil treatment, amounts of from 0.01 to 10, and preferably from 0.02 to 3, kg/ha are generally considered to be sufficient.
The novel substances may be converted into conventional formulations such 25 as solutions, emulsions, suspensions, dusts, powders, pastes and granul~s.
The application forms depend entirely on the purposes for which they ar~!
intended; they should at all events ensure a fine and uniform d~stributlon of the active ingredient. rhe formulations are produced in known manner, for example by extending the activo ingredient with solvents and/or 30 carriers, with or without the use of emulsifiers and dispersdnts; if water is used as solvent, it ~s also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., meth-35 anol, butanol), amines (e.g., ethanolamine, dimethylformamide~, and water;carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers and other surfactants, such as nonionic and anionic emulsifiers ~e.g., polyoxyethylene fatty alcohol ethers, alkyl 40 sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.
. . '' ' , :
O.Z. 005~ 0797 The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. I is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for 10 application in the form of very fine drops.
II. 20 parts by weight of compound no. 27 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and l mole of oleic acid-N-15 monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles o~ ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
20 III. 20 parts by weight of compound no. 42 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 44 is dissolved in a mixture con-sisting of 25 parts by weiyht of cyçlohexanol, 65 parks by weiyht of a mineral oil fraction having a boiliny point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 30 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 35 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
40 VI. 3 parts by weight of compound no. 27 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
20~3~
31 O.Z. 005~ 0797 VII. 30 parts by weight of compound no. 42 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained 5 having good adherence.
VIII. 40 parts by weight of compound no. 44 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to 10 give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts by weight of compound no. 1 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by 15 weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
20 In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in an increase in the fungicidal spectrum.
Use examples For comparison purpos0s, the compounds 1 ~1,2,4-triazol-1-yl)-1-phenyl-thio-2-methyl-2-phenylpropane (A) and 1-(1,2,4-triazol-1-yl)-1-(4-chloro-30 phenylthio)-2-methyl-2-pherlylpropane (B) disclosed in EP 91,219 were used.
Use Example 1 Action on Pyricularia oryzae ~protective~
Leaves of pot-grown rice sesdlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions consisting (dry basis~ of 80% of active ingredient and 20% of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were then set 40 up in climatic cabinets at from 22 to 24C and a relative humidity of 95 to 99YO. The e~tent of fungus spread was assessed after 6 days.
The results show that active ingredients 1, 27, 42, 44, 228 and 232, applied as 0.05wt% spray liquors, have a better fungicidal action (90%) than prior art active ingredients A and B (30%).
:. ' '' : ' ' . . .
, -~ ~ ~ t~
32 0,Z. 0050/l~0797 Use Example 2 Action on Pyrenophora teres 5 Barley seedlings of the "Igri" variety were sprayed to runoff at the two-leaf stage with aqueous suspensions consisting (dry basis) of 80% of active ingredient and 20~o of emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora teres, and set up for 48 hours in a high-humidity climatic cabinet at 18C. The 10 plants were then cultivated for a further 5 days in the greenhouse at 20 to 22C and a relative humidity of 70C. The extent of fungus spread was then assessed.
The results show that active ingredients 1, 27, 49, 134, 226 and 228, 15 applied as 0.05% spray liquors, have a better fungicidal action (90%) than prior art active ingredients A and B (lWo).
Claims (8)
1. Azolylethane derivatives of the general formula I
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, and their plant-tolerated acid addition salts or metal complexes, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, and their plant-tolerated acid addition salts or metal complexes, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
2. A fungicidal agent containing a carrier and a fungicidally effective amount of an azolylethane derivative of the general formula I
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
3. A process for combating fungi, wherein a fungicidally effective amount of an azolylethane derivative of the general formula I
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or Cs-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-D3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0, is allowed to act on the fungi, or the materials, areas, plants or seed threatened by fungus attack.
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or Cs-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-D3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0, is allowed to act on the fungi, or the materials, areas, plants or seed threatened by fungus attack.
4. A growth-regulating agent, containing a carrier and a growth-regulat-ory amount of an azolylethane derivative of the general formula I
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
I, where A and B are each C1-C8-alkyl, phenyl, biphenyl, naphthyl, benzyl, tetrahydropyranyl, C3-C8-cycloalkyl or C5-C8-cycloalkenyl, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, D is C1-C4-alkoxy, amino which is unsubstituted or substituted by C1-C3-alkyl or C1-C3-acyl, unsubstituted or C1-C4-alkyl-substituted mercapto, thiophenyl, aminophenyl, hetaryloxy or phenoxy, where these radicals may be mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl or haloalkyl, each of 1 to 4 carbon atoms, n is an integer from 1 to 5 or 0, and X is CH or N, or a plant-tolerated acid addition salt or metal complex thereof, except for the compounds in which A is unsubstituted phenyl, B is alkyl, D is alkoxy, X is N and n is 0.
5. A compound of the formula I as set forth in claim 1, where A is 2,4-dichlorophenyl, B is methyl, D is methoxy, n is 1 and X is N.
6. A compound of the formula I as set forth in claim 1, where A is 2,4-dichlorophenyl, B is methyl, D is methoxy, n is 2 and X is N.
7. A compound of the formula I as set forth in claim 1, where A is 2,4-dichlorophenyl, B is methyl, D is methoxy, n is 3 and X is N.
8. A compound of the formula I as set forth in claim 1, where A is 2,4-dichlorophenyl, B is methyl, D is ethoxy, n is 3 and X is N.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3914944.7 | 1989-05-06 | ||
| DE3914944A DE3914944A1 (en) | 1989-05-06 | 1989-05-06 | AZOLYLETHANE DERIVATIVES AND FUNGICIDES AND GROWTH REGULATORS CONTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2013648A1 true CA2013648A1 (en) | 1990-11-06 |
Family
ID=6380222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002013648A Abandoned CA2013648A1 (en) | 1989-05-06 | 1990-04-02 | Azolylethane derivatives and fungicides and growth regulators containing them |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0397005A3 (en) |
| JP (1) | JPH02306967A (en) |
| KR (1) | KR900018050A (en) |
| AU (1) | AU616843B2 (en) |
| CA (1) | CA2013648A1 (en) |
| DE (1) | DE3914944A1 (en) |
| IL (1) | IL93981A (en) |
| NZ (1) | NZ233565A (en) |
| ZA (1) | ZA903390B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4009594A1 (en) * | 1990-03-26 | 1991-10-02 | Basf Ag | FUNGICIDAL AZOLYLETHANE DERIVATIVES |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ181916A (en) * | 1975-09-10 | 1979-01-11 | Ici Ltd | 1-substituted-1,2,4-triazoles and fungicidal compositions |
| EP0091219B1 (en) * | 1982-04-01 | 1987-10-21 | Schering Agrochemicals Limited | Heterocyclic fungicidal and growth regulant compounds, and compositions containing them |
-
1989
- 1989-05-06 DE DE3914944A patent/DE3914944A1/en not_active Withdrawn
-
1990
- 1990-04-02 CA CA002013648A patent/CA2013648A1/en not_active Abandoned
- 1990-04-02 IL IL9398190A patent/IL93981A/en not_active IP Right Cessation
- 1990-04-30 EP EP19900108210 patent/EP0397005A3/en not_active Withdrawn
- 1990-05-02 JP JP2115319A patent/JPH02306967A/en active Pending
- 1990-05-04 AU AU54677/90A patent/AU616843B2/en not_active Ceased
- 1990-05-04 KR KR1019900006405A patent/KR900018050A/en not_active Application Discontinuation
- 1990-05-04 NZ NZ233565A patent/NZ233565A/en unknown
- 1990-05-04 ZA ZA903390A patent/ZA903390B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3914944A1 (en) | 1990-11-08 |
| JPH02306967A (en) | 1990-12-20 |
| EP0397005A2 (en) | 1990-11-14 |
| IL93981A0 (en) | 1991-01-31 |
| EP0397005A3 (en) | 1991-12-18 |
| AU5467790A (en) | 1990-11-08 |
| AU616843B2 (en) | 1991-11-07 |
| IL93981A (en) | 1994-04-12 |
| NZ233565A (en) | 1991-04-26 |
| ZA903390B (en) | 1992-01-29 |
| KR900018050A (en) | 1990-12-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |