JPH0152390B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compounds represented by the following formula, acid addition salts and metal salt complexes thereof. The present invention is based on the formula [Wherein, Z is an unsubstituted phenyl group or a substituted phenyl group having up to three substituents selected from the group consisting of halogen and (C ₁ -C ₄ )alkyl, and R ² is (C ₁ - _C12 )alkyl or ( _C2 - _C4 )alkenyl, m is 0, and Q
is 1-(1,2,4-triazole) or 4-
(1,2,4-triazole) group], and acid addition salts and metal salt complexes thereof. Also disclosed herein in connection with the present invention are methods for their preparation and use as highly active broad-spectrum fungicides. Typical Z groups in the above formula () representing the compound of the present invention are phenyl, 4-chlorophenyl,
2,4-dibromophenyl, 3,5-difluorophenyl, 2,4,6-trichlorophenyl,
2,3,5-tribromophenyl, 3,4-dichlorophenyl, 2-chloro-4-iodophenyl, 3,5,6-trimethylphenyl, and the like. The term "alkyl" as used herein in the definition of ^R2 means both pendant and straight chain alkyl groups having 1 to 12, preferably 1 to 5 carbon atoms. Typical alkyl groups included in this term defined in the present invention are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, isopentyl, hexyl, heptyl, isooctyl, Nonyl, decyl, isodecyl, undecyl, dodecyl, etc. Acids that can be used to form acid addition salts in the present invention include hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, hydroiodic acid, hydrofluoric acid, perchloric acid,
p-Toluenesulfonic acid, methanesulfonic acid, acetic acid, citric acid, tartaric acid, malic acid, maleic acid,
Contains oxalic acid, fumaric acid, phthalic acid, etc. Another specific example of the present invention is a metal salt complex represented by the following formula. In the formula, Z, R ² , Q, and m are as defined in the above formula (), and M is a cation selected from A, B, B, B, B, and group of the periodic table. , and X is an anion corresponding to this, and is selected so that the sum of the charges of the cation M and the anion X is zero. Representative cations encompassed by the present invention include magnesium, manganese, copper, nickel, zinc, iron, cobalt, calcium, tin, cadmium, mercury,
These include chromium, lead, barium, etc. Representative anions encompassed by this invention are chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, perchlorate, nitrate, nitrite, phosphate, carbonate, bicarbonate. , acetate, citrate,
Oxalate, tartrate, malate, maleate, fumarate, p-toluenesulfonate, methanesulfonate, (mono) or (di)(C ₁ -
C ₁₄ ) alkyl-dithiocarbamate, (C ₁ −
_C4 ) alkylene-bis-dithiocarbamate, etc. More preferred embodiments of the invention provide for compounds, salts and complexes of formulas () and () in which Z is up to 3 (preferably up to 2) substitutions selected from the group consisting of chlorine, bromine and methyl. is a phenyl appropriately substituted with a group; R ² is (C ₁ −
_C12 ) is alkyl or allyl. Representative compounds encompassed by the present invention include the following compounds and their acid addition salts and metal salt complexes. 1-[β-cyano-β-(2,4-dibromophenyl)hexyl]1,2,4-triazole 1-[β-cyano-β-(2,4,5-trimethylphenyl)tetradecyl]1 ,2,4-triazole 4-[β-cyano-β-(3-iodophenyl)
decyl]1,2,4-triazole 1-[β-cyano-β-(2,6-dichlorophenyl)pentyl]1,2,4-triazole 4-[β-cyano-β-(3,5- diethylphenyl)buten-2-yl]1,2,4-triazole 4-[β-cyano-β-(4-iodophenyl)
undecyl]1,2,4-triazole 1-[β-cyano-β-(4-tolyl)hexyl]1,2,4-triazole 4-[β-cyano-β-(3,4-dichlorophenyl) octyl]1,2,4-triazole 1-[β-cyano-β-(2,3-difluorophenyl)propyl]1,2,4-triazole 4-[β-cyano-β-(2,5- diethylphenyl)tetradecyl]1,2,4-triazole 1 and 4-aralkyl-1,2,4 of the present invention
-Triazoles can be prepared using standard general synthetic routes. 1-aralkyl-1,2,4- of the present invention
A preferred method for producing triazoles is shown below. In this reaction sequence, Z, R ² , Q and m are as defined in formula (); Y is a halide, alkanesulfonate, arylsulfonate, etc., and 1-(1,2,4-triazole) (i.e. The metal salt in Q) is preferably a sodium or potassium salt. This reaction can be carried out without a solvent or with a suitable solvent (e.g. benzene, toluene, xylene, glyme,
The reaction can also be carried out in N,N-dimethylformamide, dimethyl sulfoxide, etc.), and the reaction temperature is about 0°C to about 150°C. When the starting material of formula () is reacted with the free base of 1H-1,2,4-triazole instead of its metal salt, the 1-substituted and 4-substituted 1 , 2,4-triazole is obtained. The two triazoles can be separated using conventional chemical separation techniques (e.g. extraction,
It can be easily separated by chromatography, crystallization, etc.). A preferred method for producing the 4-aralkyl-triazole of the present invention is shown below. In this reaction series, Z, R ² and m are defined by the formula (), and R ³ and R ⁴ are each independently hydrogen atom, halogen atom, (C ₁ -
_C4 ) is an alkyl group, nitro group or cyano group. This reaction is carried out in a suitable inert solvent (e.g., benzene, toluene, xylene, etc.) at a temperature of about 0°C to about 150°C with a suitable catalyst (e.g., p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, etc.). etc.) in the presence or absence of In this production method, either of the reactants [i.e., formula () or ()]
can be used in excess, and the method of addition is not strict. Starting materials of formula () can be prepared by standard synthetic methods. An example of such a manufacturing method is George A. Miller.
U.S. Patent Application No. 642,041 (December 8, 1975) by et al.
(U.S. Patent No. 4105762) and No. 557546
No. (filed on March 12, 1975), its CIP application no.
No. 647039 (filed on January 7, 1976) (U.S. Patent No.
No. 4073921) and these applications have been assigned to the Official Assignee. The starting material of formula () is prepared by preparing the corresponding starting material of formula () in which Y is chlorine, bromine, etc., and this is prepared without a solvent or in a suitable solvent (e.g. diethyl ether, tetrahydrofuran, methanol, etc.). It can be produced by reacting with ammonia at a temperature of about -40°C to about 100°C. 1 and 4-aralkyl-1,2,4 of the invention
-Triazole addition salts can be prepared by standard techniques well known in the industry. For example, 1 of the expression ()
Or 4-aralkyl-1,2,4-triazole in a suitable solvent (e.g. diethyl ether, tetrahydrofuran, ethanol, methanol, etc.)
and treated with an equivalent or excess amount of mineral or organic acid (optionally dissolved in a suitable solvent). This mixture is then cooled or evaporated to obtain a salt, which can be used as is or recrystallized from a suitable solvent (or a mixture may be used). 1- and 4-substituted aralkyl-1 as above,
The 2,4-triazole metal salt complex is prepared by preparing a stoichiometric amount of the metal salt dissolved in a suitable solvent under stirring.
It can be produced by dropping it into a solution of 4-substituted aralkyl-1,2,4-triazole. This reaction mixture was stirred briefly and the solvent was removed under reduced pressure, resulting in 1 and 4 of formula (), respectively.
A metal salt complex of substituted aralkyl-1,2,4-triazole is obtained. Auxiliary agents used in this "in situ" formulation include agricultural detergents, emulsifiers, wetting agents, spreading agents, dispersants, fixing agents, adhesives, and the like. Solvents that can be used for these operations include any polar solvent (e.g. water, methanol, ethanol, isopropanol or ethylene glycol) and any aprotic dipolar solvent (e.g. dimethylsulfoxide, acetonitrile, dimethylformamide, nitromethane or These include acetone. The metal salt cations used in these operations include calcium, magnesium, manganese, copper, nickel,
Zinc, iron, cobalt, tin, cadmium, mercury,
It can be selected from the group consisting of chromium, lead, barium, etc. The anion corresponding to the metal salt may be any suitable anion, such as chloride, bromide, iodide, sulfate, hydrogen sulfate, phosphate, nitrate, perchlorate, carbonate, bicarbonate, hydrosulfide,
Hydroxide, acetate, oxalate, malate, citrate, etc. can be used. Any metal containing biocide can also act as a safety agent when used in place of the metal salt. Typical metals containing disinfectants that can be used in such operations are listed below. (a) Dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebisdithiocarbamate (maneb) and its coordination products with zinc ions (mancozeb). ), zinc ethylene bisdithiocarbamate (Zineb); (b)
Copper-based fungicides, such as cuprous oxide,
copper naphthenate, and Bordeaux mixtures; and (c) mixed fungicides, such as phenylmercuric acetate, N-ethylmercuric-1,2,3,
6-tetrahydro-3,6-endomethano-3,
4,5,6,7,7-hexachlorophthalamide,
Monoethanol ammonium phenyl mercuric lactate, nickel containing compounds and calcium cyanamide. Since the compound of the present invention has an asymmetric carbon atom,
Exists as a racemic mixture. The optical enantiomers of the d- and l-isomers in this racemic mixture can be determined using standard techniques known in the art (e.g., d-tartaric acid,
It can be separated by fractional crystallization with l-tartaric acid, l-quinic acid, etc., followed by making it basic and extracting the d- or l-optical enantiomer as a free base).
The scope of the compounds of this invention includes both racemic mixtures and optical antipodes. The following examples are merely illustrative of methods for preparing the compounds of the invention and are not intended to limit the breadth or scope of the invention in any way. Temperatures expressed in the examples are in degrees Celsius. Example 1 4-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazole 12 g (0.036 mol) of 2-cyano-2-(2,4
-dichlorophenyl)hexyl bromide and 10
A mixture of 1H-1,2,4-triazole (0.145 mol) is heated to 185°C overnight. The reaction mixture is cooled, poured into water and extracted with ether. When the ether extracts are combined and washed with water, a white precipitate is separated from the ether layer. This precipitate was filtered and dried under reduced pressure to yield 1 g of white solid (melting point:
46-9℃). GLC and NMR analysis confirm that this material is 4-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazole. NMR ( _CDCl3 ): δ0.7−3.2 (complex multiplet, 9H),
5.0 (q, 2H), 7.2-7.8 (m, 3H), 8.15 (s,
2H). Example 2 1-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazolium nitrate and 4-[2-cyano-2-
(2,4-dichlorophenyl)hexyl]-1,
2,4-Triazolium nitrate Concentrated nitric acid is added dropwise to the ether filtrate obtained from the above experiment until the solution becomes strongly acidic. The resulting white precipitate was triturated several times with an ether/hexane mixture and then collected by filtration to yield 2 g of product (mp 110-
120℃). GLC and NMR analysis revealed that this material was 1-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazolium nitrate and 4-[2-cyano-2-
(2,4-dichlorophenyl)hexyl]-1,
Confirm that it is a mixture of 2,4-triazolium nitrate in a ratio of 2:1. NMR (DMSO): δ0.6−3.0 (m, 9H), 5.1 (q,
2H), 7.3−7.8(m, 3H), the singlet at 8.1, 8.7, and 9.2 is the result of integration 2H, 14.2(s,
1H). Example 3 1-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazolium nitrate A 2-cyano-2-(2,4-dichlorophenyl ) Hexyl bromide 1.0 mol n- in 250 ml methylene chloride
A solution containing butyl bromide and 1.0 mole of 2,4-dichlorophenyl cyanide was added to
g of tetraacetylammonium bromide to a 25% aqueous sodium hydroxide solution. The reaction mixture is vigorously stirred under reflux for 3 hours to obtain the desired product in 90% yield. to this
Purity can be determined by GLC analysis and NMR spectroscopy.
It turns out to be 90%. Then add 1.3 cyanide
molar of methylene bromide and added to a 50% aqueous ammonium hydroxide solution with either tetraethylammonium bromide or benzyltriethylammonium chloride as a catalyst.
The reaction mixture is heated to reflux (90° C.) for 3 hours until 95% of the starting material is consumed. In this reaction, approximately 5% of α-n-butyl-2,4-dichlorobenzyl cyanide always remains unreacted. B 1-[2-cyano-2-(2,4-dichlorophenyl)hexyl]-1,2,4-triazole 3.2 g (0.046 mol) of 1H-1,2,4-triazole and 1.85 g (0.046 mol) of 1H-1,2,4-triazole 2-cyano-2-(2,4-dichlorophenyl) in dimethyl sulfoxide solution (25 ml) of sodium 1,2,4-triazole obtained from sodium hydroxide (2-cyano-2-(2,4-dichlorophenyl))
Add hexyl bromide dropwise at 110°C. Stir the whole thing at 110°C for 1/2 hour. reaction mixture
Pour into 400ml of water and extract with ether.
The combined ether extracts are washed with water and dried over MgSO ₄ . The drying agent is filtered off, and concentrated nitric acid is added dropwise to the filtrate until no precipitate is formed. Filter the precipitate to confirm that it is the nitrate salt of the desired product (RH45136). NMR (DMSO): δ0.6−2.5 (complex multiplet, 9H),
5.0 (q, 2H), 7.5-7.9 (m, 3H), 8.3 (s,
1H), 8.7 (s, 1H), 14.7 (s, 1H) Example 4 When the above nitrate is returned to neutrality with a 10% ammonium hydroxide solution, a free base is obtained. NMR (CDCl ₃ ): δ0.7-2.8 (complex multiplet, 9H),
5.0 (q, 2H), 7.1-7.6 (m, 3H), 7.9 (s,
1H), 8.0(s, 1H). Example 5 1-(2-cyano-2-(4-chlorophenyl)
Propyl-1,2,4-triazole dissolved in 300 parts water in a suitable reaction vessel
Charge 10.6 parts of 1-[2-cyano-2-(4-chlorophenyl)propyl]-1,2,4-triazole nitrate and add 10% ammonium hydroxide solution until the solution is basic. The free base is then extracted twice with 200 parts of ether, the ether is washed with water, dried and evaporated to give 5.4 g of solid. Melting point 114-116℃. Example 6 1-[2-cyano-2-(4-chlorophenyl)
Propyl]-1,2,4-triazolium nitrate (a) Dissolve p-chloro-α-methylbenzyl nitrile (16.6 parts) in dry dimethyl sulfoxide and add dropwise 8.0 parts of a 50% aqueous sodium hydroxide solution. and add. Add 19.1 to this mixture under stirring.
Add part of methylene dibromide. The temperature rises from room temperature to 90°C. The mixture is stirred for 1 hour, poured into water and extracted with methylene chloride. After distilling off the methylene chloride, 20.5 parts of crude 2-cyano-2-(4-chlorophenyl)propyl bromide remain. (b) 1,2,4-triazole (5.49 parts) is dissolved in a mixture of 25 parts of toluene and 30 parts of dimethyl sulfoxide in a flask equipped with a stirrer, a separator for removal of the solvent and a dropping funnel. Add granular sodium hydroxide (3.18 parts) and heat the mixture to 135°C.
25 parts of toluene is distilled off and the water produced is removed. When the reaction mixture became clear, the temperature was lowered to 110 °C and the 2-cyano-2-(4-
A solution of 20.54 parts of (chlorophenyl)propyl bromide in dimethyl sulfoxide (25 parts) is added and the mixture is stirred at this temperature for 2.5 hours. The reaction mixture is cooled, poured into water and the water is extracted several times with methylene chloride. The combined extracts are washed with water, then concentrated aqueous sodium chloride solution, and dried over magnesium sulfate, leaving a crude oily product that carries off the methylene chloride. When this oil is dissolved in ether and treated with concentrated nitric acid,
13.8 parts of nitrate are precipitated. The melting point of this thing
163℃ (decomposition). Example 7 1-(2-cyano-2-phenylhexyl)-
1,2,4-triazole hydrochloride In a 300 ml flask equipped with a stirrer, condenser, thermometer and Dean Stark trap, 5.7 parts of granulated sodium hydroxide, 50 parts of dimethyl sulfoxide.
and 10 parts of 1,2,4-triazole. The mixture is heated to 60-90°C under stirring until the sodium hydroxide is dissolved. Add 25 parts of toluene and increase the temperature to 115-120°C. Reaction water (4
Part) was distilled off by azeotropic distillation while the above temperature was increased to 2.
Keep time. Then, the temperature is raised to 130-140°C to distill off toluene. The reactor is cooled to 115 DEG C. and 38.5 parts of 2-cyano-2-phenylhexyl bromide are added dropwise over 30 minutes. The temperature is then increased to 130-140° C. until the reaction is complete by gas chromatography. The reaction mixture was then cooled to below 100°C, 150 parts of water was added dropwise, the product was extracted from the aqueous layer twice with 100 parts of diethyl ether, the ether was washed with 50 parts of water, and the mixture was soaked in magnesium sulfate overnight. Dry on top. Evaporation to remove the ether gives 33 parts of an oil.
This is dissolved in 300 parts of ether and treated with a stream of dry hydrochloric acid until acidic. Continue stirring and cooling until solid formation stops. The solids are collected by filtration and the remaining ether is removed to give 21 parts of a product having a melting point of 155-160°C (decomposition). Example 8 1-(2-cyano-2-phenylhexyl)-
1,2,4-triazole 1-(2-cyano-2-phenylhexyl)-
1,2,4-triazole hydrochloride (16.1 parts)
Dissolve in 300 parts of water. The mixture is made basic by adding 25% sodium hydroxide solution under stirring and cooling. The aqueous solution was extracted twice with 200 parts of diethyl ether, the combined extracts were washed with 100 parts of water, dried over sodium sulfate, filtered and
Removal of the ether by evaporation yields 11.5 parts of free base. Example 9 1-[2-cyano-2-phenylhexyl]-
Zinc chloride complex of 1,2,4-triazole 6.5 g (0.0256 mol) of 1-[2-cyano-2-phenylhexyl]-1 in 120 ml of methanol,
Add 1.5 g (0.0111 mol) of zinc chloride to the 2,4-triazole and stir for 15 minutes. Removal of methanol yields 9.6 g of residue. A solid product precipitates when this material is absorbed into warm ethanol. This material is filtered off to yield 5.9 g (59%) of product, mp 175-177°C. Example 10 1-[2-cyano-2-(2,4-dichlorophenyl)decyl]-1,2,4-triazole hydrochloride (a) 1 with stirrer, addition funnel, condenser and thermometer A flask is charged with 50 parts of dichlorophenylacetonitrile, 100 parts of 1-bromooctane, and 135 parts of dimethyl sulfoxide. Add 146 parts of 50% sodium hydroxide solution through the addition funnel, keeping the temperature below 60°C. The mixture was then stirred for 3 hours and then 250 parts of water,
Then 250 parts of hexane are added and the mixture is stirred. The hexane layer is separated, washed with water, dried and concentrated to yield 69.3 parts of crude 2-(2,4-dichlorophenyl)decanenitrile. (b) The method of Example 7 is then repeated using 3.1 parts of granular sodium hydroxide, 5.3 parts of triazole, 50 parts of dimethyl sulfoxide and 25 parts of toluene. After removing the toluene, 30 parts of 2-(2,4-
Add dichlorophenyl)decanenitrile at 115°C. Heat the mixture at 115°C for 2 hours and at 130°C overnight. After cooling to below 100°C, 200 parts of water are added very slowly. The mixture was extracted twice with 100 parts of diethyl ether, and the ether content was extracted with water.
Wash twice with 50 parts, evaporate the ether, redissolve in 300 parts of ether and acidify with dry hydrochloric acid. Continue cooling and stirring until solids form. The solids are filtered off and dried in a vacuum oven to give 1-[2-cyano-(2,4-
9 parts of hydrochloride of dichlorophenyl)decyl]-1,2,4-triazole are produced. (melting point 125
~131°C) Example 11 1-[2-cyano-2-(2,4-dichlorophenyl)decyl]-1,2,4-triazole 5.3 g (0.07697 mol) in 50 ml DMSO
1H-1,2,4-triazole and 3.1g
To 7.0 g (0.0769 mol) of the sodium salt of 1H-1,2,4-triazole obtained from (0.759 mol) of NaOH, 30.0 g (0.0767 mol) of 2-cyano-
2-(2,4-dichlorophenyl)decyl bromide (prepared in conventional manner) is added and the reaction mixture is stirred at 130° C. for 20 hours. This mixture is then cooled and mixed with 200 ml of water. The separated organic material was extracted with 2 x 100 ml of ether, the combined extracts were washed with 2 x 50 ml of water, dried over anhydrous magnesium sulfate and concentrated to yield 24.0 g (82.5%) of the crude product. obtain. Dissolve this substance in ether,
Treat with hydrogen chloride gas until acidic with litmus paper. The precipitated solid was filtered out and 9.0g (28.2
%) hydrochloride (melting point 125-31 °C). 2.0g to 6.7g (0.0161 mol) hydrochloride in 200ml water
(0.025 mol) of 50% NaOH is added and the mixture is stirred. The organic soluble material was extracted with 2 x 200 ml of ether, the extract was washed with 2 x 50 ml of water, dried over anhydrous magnesium sulfate and concentrated.
4.9 g (80.2%) of oily product are obtained. Example 12 5-[4-cyano-4-(2,4-dichlorophenyl)-pentenyl-1]-1,2,4-triazole Into the reaction vessel described in Example 7, 50 parts of 2,4- Dichlorophenylacetonitrile is charged with 26.9 parts of 50% sodium hydroxide, 35.4 parts of allyl bromide, and 6.4 parts of tetraethylammonium bromide. The mixture was flushed with nitrogen and heated to reflux (86°C) for 1 hour with stirring. Then a second portion of sodium hydroxide solution (16
part) is added and the mixture is refluxed for an additional hour and cooled. Add 250 parts of water, then 250 parts of hexane. After thorough stirring, the hexane layer is separated, washed with water, dried over magnesium sulfate, filtered, and concentrated to yield 59.5 parts of crude 1-cyano-(2,4-dichlorophenyl)-3-butene. generate. Next, 1-cyano-1-(2,4-dichlorophenyl)-3-butene (59.5 parts) was added to 75 parts of dimethyl sulfoxide and 45.8 parts of methylene dibromide.
into the same reaction vessel. 50 under nitrogen sweep
% sodium hydroxide solution at a reaction temperature of 50℃
Add at a rate that maintains: After the addition is complete, the reaction mixture is heated at 60° C. for 3 hours. Adding water and hexane (150 parts) in the usual manner and washing, drying and distilling the hexane layer yields 42.5 parts of 5-bromo-4.
-(2,4-dichlorophenyl)-4-cyano-1
-Pentene is formed. In the same manner as in Example 7, 1H-1,2,4-triazole (8.7 parts), 5.0 parts of sodium hydroxide, 100 parts of dimethyl sulfoxide and 50 parts of toluene are reacted. Remove toluene and cool to 115 °C;
5-bromo-4-(2,4-dichlorophenyl)-
A solution of 4-cyano-1-pentene (40 parts) in dimethyl sulfoxide (10 parts) is added and the mixture is heated to 115°C for 30 minutes and then to 125°C for 1 hour. The reaction mass is cooled to below 100°C, treated with 150 parts of water, stirred, cooled, and extracted with ether. After washing, drying and concentrating the ether component in the usual manner,
27 parts of 5-[4-cyano-4-(2,4-dichlorophenyl)pentenyl-1]-triazole (crude product: melting point 84-87°C, purified product by recrystallization method:
(melting point 88-90℃) is produced. The following table and table shows the structure and elemental analysis of some of the more preferred compounds encompassed by this invention.

【table】

【table】

[Table] 1 and 4-aralkyl-1,2,4 of the present invention
- Triazoles, their optical enantiomers, acid addition salts and metal salt complexes are broadly acting fungicides and have high activity against plant pathogens. Such compounds, dimorphisms, salts and complexes may contain from about 50 to about
When applied at a rate of 2000 ppm, reticular stain disease (Helminthosporium teres) in barley, Botrytis Cinerea in faba beans, powdery mildew (Erysiphe polygoni) in kidney beans,
Downy mildew in grape seedlings (Plasmopora
viticola), rice blast disease (Piricularia
oryzae), late stem blight (Phytophthora infestans) in tomato seedlings and stem rust (Puccinia graminis f.sp. tritici) in wheat seedlings.
It is particularly effective for controlling race 15B-2). In evaluating such compounds, a pre-sterilization evaluation is performed by spraying 300 ppm of the compound onto plants from a container at a volume of 150 gallons/acre. A common method is to grow potted plants appropriately for susceptibility to fungal diseases to give a rating, then spray and dry them on a moving belt. The plants are inoculated with fungal spores and cultured until disease development to determine or assess percent control. The following test method is used to evaluate the fungicidal activity of the compounds, enantiomers, salts and complexes of the invention. Example A Barley Reticular Spot (Helminthosporium teres) Barley (var. Wong) is cut to approximately 2.5 inches in height 24 hours prior to chemical treatment. In this way, the height of the plants will be uniform and the treated plants can be inoculated quickly. Inoculation is applied by hand spraying the barley leaves until small droplets of inoculum are visible on the leaves. The inoculated plants are incubated in a humid environment of 75-80° for 24 hours and then transferred to a greenhouse of 70-75°. Treatment comparisons are made 6 to 7 days after inoculation. Irregular, typical symptoms of barley reticulate stain appear on the part that first comes into contact with water, and as the lesions spread, they rot. Certain 1 and 4-aralkyl-1,2,4-triazoles of the present invention are
Complete control of Helminthosporium teres at a dosage of 300ppm. Example B Broad bean gray mold leaf spot (Botrytis cinerea) Chemically treated broad bean (var. Vicia faba)
Trim to a height of about 45 inches in advance. This ensures uniform plant height and rapid and uniform inoculation of treated plants. Inoculation is applied by spraying the broad bean leaves with a herbicide belt sprayer.
The inoculated plants were grown in a humid environment at 75–80°C.
Incubate for hours. Treatment comparisons are performed 66-68 hours after inoculation. Typical symptoms of broad bean gray mold appear on the leaves and stems of plants in a regular circular or lanceolate shape. Certain 1 and 4-aralkyl-(1,2,4-triazoles) of the present invention exhibit greater than 70% control against Botrytis cinerea at a dosage of 300 ppm. Example C Erysiph powdery mildew (Erysiph polygoni) Erysiph powdery mildew (Erysiph polygoni)
Soak 2 plants per pot 24 hours in advance. The leaves and stems of French beans are inoculated by spraying until a uniform film of inoculum is visible on the plants. Keep the inoculated plants under greenhouse conditions. Treatment comparisons are performed 8-10 days after inoculation. The typical disease symptom of common bean powdery mildew is white mycelium (fruiting) on the leaf surface. Certain 1 and 4-aralkyl- of the invention
(1,2,4-triazole) completely controls Erysiphe polygoni at a dose of 300 ppm. Example D Grape Siebel (var. Siebel) Grape seedlings (var. Siebel
1000) is used. Plasmopora viticola is cultured on grape leaves at 65-75° for 7 days. The grape leaves are inoculated by spraying with a manual airbrush until uniform droplets of inoculum are visible on the leaves. The inoculated plants were placed in a humid environment for 65 minutes.
Incubate at −70° for 48 hours and then place in a greenhouse. Typical symptoms of grapevine disease, which are pale yellow spots of various sizes and shapes (often circular with no sharp borders), appear on the upper surface. Under humid conditions, the lower leaf surfaces become covered with significant fungal growth. Certain 1 and 4-aralkyl-(1,2,4-triazoles) of the present invention exhibit greater than 90% control against Plasmopora viticola at a dosage of 300 ppm. Example E Piricularia oryzae Cut rice (var. Nova 66) to about 5 inches in height 24 hours before chemical treatment. This ensures uniform plant height and speeds up inoculation of treated plants. The rice leaves and stems are inoculated by spraying with an airbrush until a uniform film of inoculum is visible on the leaves. The inoculated plants are incubated in a humid environment (75-80°) for 24 hours and then placed in a greenhouse environment. Treatment comparisons are made 7-8 days after inoculation. Early lesions of blast disease (small brown rotting spots) appear on the leaves. Typical lesions are spindle-shaped, 1-2 cm long, with a large rotting gray center and brown margins. Predetermined 1 of the present invention
-aralkyl-(1,2,4-triazole) is
Piricularia oryzae is completely controlled at a dose of 300ppm. Example F Tomato late blight (Phytophthora
Tomato seedlings 2.5 to 3 inches tall are fed with a water-soluble fertilizer 4 to 5 days before chemical treatment to encourage rapid succulent growth and better disease symptom development. The spore suspension is applied onto the leaves using a Devilbiss sprayer at an air pressure of 8-10 psi until microdroplets form on the underside of the leaves. Before placing the inoculated seedlings in a 70-75〓 greenhouse,
Leave in a humid environment at 60-62〓 for 40-45 hours. Treatment comparisons are made 5-6 days after inoculation. Typical late tomato blight initially appears as irregular, green-black watery spots that spread and turn brown into a hard, wavy surface. Severe infection resembles frost damage. The 1-aralkyl-(1,2,4-triazole) of the present invention is 300 ppm
Complete control of Phytophthora infestants at a dosage of . Example G Wheat stem rust (Puccinia graminis f.sp.
Tritici race 15B-2) Seven-day-old wheat (var. Monon) is pruned to approximately 2.5 inches 24 hours before chemical treatment to achieve a uniform height and promote uniform inoculation. Wheat stem rust is cultivated on wheat seedlings (var.Monon) for 14 days under greenhouse conditions. Wheat is inoculated by applying a suspension of stem rust spores using a DeVilbiss sprayer at 5 psi air pressure until runoff. After inoculation, the wheat is placed in a humid environment at about 68〓. Continuous darkness for 12 hours using a timer, then light for a minimum of 3 to 4 hours at 500 foot candle light intensity. The temperature in the room should not exceed 85°C. After the light period, spraying is stopped and the plants are allowed to dry slowly and placed in a greenhouse environment. Comparative treatments are carried out after plants have been grown for two weeks under greenhouse conditions. Wheat stem rust is characterized by brick-colored spores in irregularly shaped ascus clusters on the leaves and stems of wheat seedlings. Certain 1 and 4-aralkyl-(1,2,
4-triazole) at a dose of 300 ppm.
Complete control of Puccinia graminis f.sp. tritici race 15B-2. 1 and 4-aralkyl-1,2,4 of the invention
- triazoles, optical enantiomers, acid addition salts and metal salt complexes are useful as agricultural fungicides;
It can be applied to various parts (eg seeds, soil or stems). For such purposes, the compounds can be used in technical or pure prepared form, solutions or preparations. The compound is usually absorbed into a carrier or formulated to be suitable for application as a fungicide. For example, these chemicals can be formulated into wettable powders, emulsified concentrates, powders, granular formulations, aerosols or flowable emulsified concentrates. In such formulations, the compound is enriched with a liquid or solid carrier and, if desired, a suitable surfactant is added. Usually (particularly in the case of formulations for foliar spraying) it is preferred to include agricultural auxiliaries (eg wetting agents, spreading agents, dispersing agents, fixing agents, adhesives, etc.).
Such adjuvants commonly used in the industry are those described by John W.
McCutcheon, Inc. Publication, "Annual Report on Detergents and Emulsifiers". Generally, the compounds of the invention are dissolved in a given solvent (eg, acetone, methanol, ethanol, dimethylformamide, pyridine or dimethyl sulfoxide) and the solution is made up with water. The concentration of this solution can vary from about 1% to about 90%, and about 5%
to about 50% is preferred. To prepare an emulsified concentrate, the compound is dissolved in a suitable organic solvent (or mixture) with an emulsifier that allows the disinfectant to be dispersed in water. The concentration of active ingredient in the emulsified concentrate is usually between about 10% and about 90%;
For flowable emulsion concentrates it is up to about 75%. Wettable powders suitable for spraying are prepared by mixing the compound with finely divided solids (e.g. clays, inorganic silicates or carbonates and silica) and incorporating wetting agents, sticking agents and/or dispersing agents into this mixture. Can be manufactured. The concentration of active ingredient in such formulations is usually about 20% to about 98%, preferably about 40% to about 75%. To make a typical hydrating powder, 50 parts 1-
[β-(2,4-dichlorophenyl)hexyl]
1,2,4-triazole, 45 parts of precipitated hydrated silicon dioxide (sold under the trade name Hi-Sil), and 5 parts of sodium lignosulfonate are combined.
In another method of manufacturing, a kaolin type (Barden) clay is used as a substitute for Hi-Sil in the above hydrating agent;
25% Hi-Sil is replaced with synthetic sodium silicoaluminate (sold under the trade name Zeolex 7). 1- and 4-aralkyl-
1,2,4-triazole, its optical enantiomer,
The salt and complex are mixed with a finely divided inert solid (which may be of organic or inorganic origin). Materials useful for this purpose include vegetable flours, silicas, silicates, carbonates and clays. One method for conveniently producing a powder is to dilute a wettable powder with a finely ground carrier. Powder concentrates are usually prepared containing about 20% to about 80% active ingredient, which are then diluted to give a working concentration of about 1% to 10%. 1- and 4-aralkyl-1,2,4-triazoles, their optical enantiomers, salts and complexes can be prepared by conventional methods such as conventional high gallon hydraulic spraying,
Can be applied as a fungicide spray (low gallon spray, air blast spray, air spray and powder). The degree of dilution and application rate will depend on the type of equipment used, the method of application and the disease being controlled, but preferred effective amounts are from about 0.1 pounds to about 50 pounds of active ingredient per acre. As a seed protectant, the amount of poison coating the seeds is typically about 0.1 to about 20 ounces per 100 pounds of seed. This chemical is usually used as a soil fungicide.
Incorporate into the soil or apply to the surface at a rate of about 0.1 to about 50 pounds per acre. As a foliar fungicide, the toxic agent is applied to growing plants at a rate of about 0.25 to about 10 pounds per acre. Sterilizing agents that can be used in conjunction with the sterilizing agent of the present invention are listed below. (a) dithiocarbamates and their derivatives, such as: ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebisdithiocarbamate (maneb) and its coordination compounds with zinc ions (mancozeb); Zinc ethylene bisdithiocarbamate (zineb), zinc propylene bisdithiocarbamate (propineb), sodium methyldithiocarbamate (metham),
Tetramethylthiuram bisulfide (thiram), complex of zineb and polyethylene thiuram bisulfide, 3,5-dimethyl-1,
3,5-2H-tetrahydrothiadiazine-2
-thione (dazomet); and mixtures thereof and with copper salts; (b) Nitrophenol derivatives, such as: dinitro-(1-methylheptyl)phenylcrotonate (dinocap), 2-sec-butyl-4, 6-
dinitrophenyl-3,3-dimethylacrylate (binapacryl), and 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate; (c) heterocyclic structures such as: N-trichloromethylthiotetrahydrophthalimide (captan);
N-trichloromethylthiophthalimide (folpet), 2-heptadecyl-2-imidazole acetate (glyodine), 2-octylisothiazol-3-one, 2,4-dichloro-6
-(o-chloroanilino)-s-triazine, diethyl phthalimide phosphorothioate, 4-
Butyl-1,2,4-triazole, 5-amino-1-[bis(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-
1,2,4-thiadiazole, 2,3-dicyano-1,4-dithianthraquinone, 2-thio-1,3-dithio-
(4,5-b)-quinoxaline (thioquinox),
Methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate (benomyl), 2
-(4'-thiazolyl)benzimidazole (thiabendazole), 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,
Pyridine-2-thiol-1-oxide, 8-
Hydroxyquinoline sulfate and its metal salt; 2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxatine-4,4
-dioxide, 2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxatine, α-(phenyl)-α-(2,4-dichlorophenyl)-5-pyrimidinyl-methanol (triarimol), cis-N-[(1,1,2,2-
tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide, 3-[2
-(3,5-dimethyl-2-oxycyclohexyl-2-hydroxy]-cycloheximide, dehydroacetic acid, N-(1,
1,2,2-tetrachloroethylthio)-3a,
4,7,7a-tetrahydrophthalimide (captafol), 5-butyl-2-ethylamino-
4-hydroxy-6-methylpyrimidine (ethirimol), 4-cyclododecyl-2,6-
acetate of dimethylmorpholine (dodemorph),
and 6-methyl-2-oxo-1,3-dithiolo[4,5-b]-quinoxaline (quinomethionate). (d) Mixed halogenated fungicides, such as: tetrachloro-p-benzoquinone (chloranil), 2,3-dichloro-1,4-naphthoquinone (dichlone), 1,4-dichloro-
2,5-dimexybenzene (chloroneb), 3,
5,6-trichloro-o-anisic acid (tricamba), 2,4,5,6-tetrachloroisophthalonitrite (TCPN), 2,6-dichloro-4-nitroaniline (dichloran), 2
-chloro-1-nitropropane, polychloronitrobenzenes such as: pentachloronitrobenzene (PCNB) and tetrafluorodichloroacetone; (e) bactericidal antibiotics such as: griseofulvin, kasugamycin and streptomycin; (f) copper-based fungicides. For example: cuprous oxide, basic cupric chloride, basic copper carbonate, copper naphthenate, and Bordeaux mixtures; and (g) mixed fungicides, such as: diphenyl, dodecylguanidine acetate (dodine), phenylmercuric acetate. , N-ethylmercuric-1,2,
3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercuric monoethanolammonium lactate, p-dimethylaminobenzenediazosodium sulfonate, methylisothiocyanate, 1 -thiocyano-2,4
- dinitrobenzene, 1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, lime sulfur, sulfur and 1,2-
Bis(3-methoxycarbonyl-2-thiourido)benzene (thiophnatemethyl). 1 and 4-aralkyl-1,2,4 of the invention
-Triazoles, optical antipodes, acid addition salts and metal salt complexes can be used effectively in a variety of ways. These compounds have a broad spectrum of fungicidal activity and can therefore be used in grain storage. These complexes can also be used as fungicides in lawns, orchards and golf courses. 1 and 4- of the present invention
Other uses of aralkyl-1,2,4-triazoles will be readily apparent to those skilled in the agricultural and horticultural arts.

Claims (1)

[Claims] 1 formula [Wherein, Z is an unsubstituted phenyl group or a substituted phenyl group having up to three substituents selected from the group consisting of halogen and (C ₁ -C ₄ )alkyl, and R ² is (C ₁ - _C12 )alkyl or ( _C2 - _C4 )alkenyl, m is 0, and Q
is 1-(1,2,4-triazole) or 4-
(1,2,4-triazole) group], and acid addition salts and metal salt complexes thereof.