DE2858296C2 - Phenalkyl substd. 1,2,4-triazole derivs. - Google Patents

Abstract

2-Phenyl-2-cyano-2-substd.- ethyl-(1,2,4-triazole) derivs. of formula (I) and their enantiomorphs and their acid-addn. salts and metal complexes are new (n is 0-4; X is halogen, NO2, trihalomethyl, CN, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C alkylsulphinyl or 1-4C alkylsulphonyl; R is 1-12C alkyl, 5-7C cycloalkyl, 2-4C alkenyl, 5-6C cycloalkenyl, 3-4C alkynyl or Ph, PhCH2 or phenethyl each opt. substd. by 1 or 2 halogen; and Q is unsubstd. 1- or 4-(1,2,4-triazolyl)). Cpds. (I) are broad-spectrum systemic fungicides effective against phytopathogenic fungi. Applied to crops etc. at 0.1-50 lbs/acre or to seeds as a protectant at 0.1-20 oz/100 lbs.

Description

The invention relates to new substituted 1,2,4-triazoles and acid addition salts and metal salt complexes thereof. Furthermore The present invention relates to a fungicidal agent, that contains these connections.

From R. Wegler, chemistry of crop protection and pest Control agents, 1977, are 1,2,4-triazoles with fungicides Effectiveness known. Through the invention new compounds of the formula

provided in which
Z is phenyl or naphthyl, each optionally substituted with up to three, preferably up to two, substituents selected from halogen, nitro, trihalomethyl, cyano, (C₇-C₁₄) aralkyl, (C₁-C₄) alkyl, (C₁-C₄ ) Alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, each of the latter four groups optionally being substituted by up to two substituents is selected from halogen, nitro, trifluoromethyl, cyano, methyl, methoxy, methylthio, methylsulfinyl and methylsulfonyl,
R¹ is one of groups (5) to (7) as defined below in connection with R²; R²

• (1) hydrogen,
• (2) (C₁-C₁₂) alkyl,
• (3) (C₃-C₈) cycloalkyl,
• (4) (C₂-C₈) alkenyl,
• (5) (C₅-C₈) cycloalkenyl,
• (6) (C₂-C₈) alkynyl,
• (7) phenyl or naphthyl, optionally substituted as stated in connection with Z,
• (8) phenyl- (C₁-C₄) alkyl or naphthyl- (C₁-C₄) -al kyl, optionally substituted in the aryl as stated in conjunction with Z,

means
with the proviso that R¹ is not 2-halophenyl, 4-halophenyl, 2,4-dihalophenyl or 4-methylphenyl when R² is H,
Q 1- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl) is, optionally substituted with up to two substituents, selected from halogen, (C₁-C₄) alkyl, nitro and Cyano,
m is 0 or 1,
n is 1 or 2,
or
an acid addition salt which is compatible with agricultural purposes or a metal complex of a compound of the formula I which is compatible with agricultural purposes

Typical examples of substituted phenyl or naphthyl are 4-chlorophenyl, 2,4-di bromophenyl, 3,5-difluorophenyl, 2,4,6-trichlorophenyl, 2,3,5-tri bromophenyl, 3,4-dichlorophenyl, 2-chloro-4-iodophenyl, 3-chloro-4-ni trophenyl, 2,4-dinitrophenyl, 4-phenoxyphenyl, 2-phenylthio phenyl, 3-phenylsulfinylphenyl, 4-phenylsulfonylphenyl, 4-chlorophenoxyphenyl, 2,4-dibromophenoxyphenyl, 3,5-difluoro phenylthiophenyl, 4-chloro-2-methylphenylsulfinylphenyl, 3,4-di iodophenylthiophenyl, 4-trifluoromethyl-2-chlorophenylsulfonyl phenyl, 2-cyano-4-methoxyphenylsulfinylphenyl, 4-methylthio phenoxyphenyl, 2-methylsulfinylphenylsulfinylphenyl, 4-methyl sulfonyl-3-chlorophenoxyphenyl, 3,5,6-trimethylphenyl, 2-Ni tro-4-methoxyphenyl, 2-chloronaphthyl, 2-nitronaphthyl, 2,4-dimethoxyphenyl, 4-trifluoromethylphenyl, 2-nitro-4- trifluoromethylphenyl, 3,5-dimethylthiophenyl, 2-cyano-5-methyl phenyl, 2,4-dimethylsulfinylphenyl, 2,4-dimethylsulfonylphenyl, 2,4-dodonaphthyl, 2-iodo-4-benzylphenyl,  3,4,5-trimethylphenyl and 2-iodo-4-methylphenyl. Typical examples of substituted phenyl- (C₁-C₄) alkyl or Naphthyl- (C₁-C₄) alkyl are 2,4-dichlorobenzyl, 2,4-dibromobenzyl, 2,5- Dinitrobenzyl, 2,4,6-trichlorobenzyl, 3,5-dimethoxyphenethyl, 2,5-di methylthiophenylpropyl, 2,4-dodophenyl-2-methylpropyl, 3,4-dimethylsulfinylbenzyl, 2,3-dimethylsulfonylphenylethyl, 2,4,5-trimethylphenylbutyl, 2,4-dicyanonaphthylmethyl, 2-Ni tronaphthylpropyl, 2,4-dibromonaphthylbutyl, 1-nitronaphthylethyl and 2-nitronaphthylethyl.

The term "alkyl" used includes both branched to understand as well as straight-chain alkyl groups.

Typical alkyl groups which are suitable according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-He xyl, n-heptyl, isooctyl, n-nonyl, n-decyl, isodecyl, n-unde cyl and n-dodecyl.

Q is unsubstituted 1- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl), then these two groups can bis to contain two substituents consisting of halogen, (C₁-C₄) -Al kyl, nitro or cyano are selected.

The acids used to produce the acid of the invention addition salts can be used, for example as from hydrochloric acid, hydrobromic acid, sal nitric acid, sulfuric acid, phosphoric acid, hydrogen iodide right, hydrofluoric acid, perchloric acid, p-toluenesulfone acid, methanesulfonic acid, acetic acid, citric acid, wine acid, malic acid, maleic acid, oxalic acid, fumaric acid or Phthalic acid.

The metal salt complexes according to the invention correspond in typi the formula

wherein Z, R¹, R², Q, m and n are those related to the Formula (I) have the meaning given and M is a cation is from groups IIA, IB, IIB, VIB, VIIB and VIII of the Periodic Table of the Elements is selected while X is a counter anion selected in such a way that the sum of the valence charges of the cation M and the anion X Results in zero.

Typical cations are magnesium, manganese, copper, nickel, Zinc, iron, cobalt, calcium, tin, cadmium, mercury, Chromium, lead or barium.

Typical anions are chloride, bromide, iodide, fluoride, sulfate, Bisulfate, perchlorate, nitrate, nitrite, phosphate, carbonate, Bicarbonate, acetate, citrate, oxalate, tartrate, malate, maleate, Fumarate, p-toluenesulfonate, methanesulfonate, (mono) - or (di) - (C₁-C₄) alkyldithiocarbamate and (C₁-C₄) alkylene-bis-di thiocarbamate.  

Typical connections are as follows:
4- [β- (4-cyanophenyl) -β-phenylpropyl] -1,2,4-triazole,
4- [β-) 4-benzylphenyl) -4-chlorophenethyl] -1,2,4-triazole,
and the acid addition salts and metal salt complexes thereof which are compatible with agricultural purposes.

The substituted 1,2,4-triazoles according to the present invention can be made using standard synthetic methods, especially those methods that are themselves used to manufacture of analog connections are known.

A preferred method of making connections According to the present invention:

In this sequence of reactions Z, R¹, R², Q, m and n have the meaning given in the formula (I), Y can be a halide, Be alkanesulfonate or arylsulfonate, while the metal salt is preferably a sodium or potassium salt. The reaction  can be carried out in the presence of a suitable solvent leads, such as benzene, toluene, xylene, glyme, N, N-dimethyl formamide or dimethyl sulfoxide. The reaction temperatures can be 0 to 150 ° C.

If the starting material of formula (III) with the free 1H-1,2,4-triazole base instead of its metal salt usually implemented at temperatures of 50 to 180 ° C, then a mixture of 1-substituted and 4-substi tuiert 1,2,4-triazoles obtained. Leave these triazoles easy to separate using conventional chemical separation methods NEN, for example by extraction, chromatography or Crystallization.

Another preferred method of making the substi tuated triazoles according to the present invention are as follows:

In this reaction sequence, Z, R¹, R², m and n have the Zu in connection with the formula (I), while R³ and R⁴ are hydrogen, halogen, (C₁-C₄) alkyl, nitro or Mean cyano. This reaction is usually done in one inert solvents such as benzene, toluene or xylene, carried out. The reaction is usually carried out at 0 to 150 ° C, optionally in the presence of a suitable catalyst, such as p-toluenesulfonic acid, benzenesulfonic acid or methanesulfone acid, executed. Any reactant can be used in this manufacturing process  method are used in an excess, whereby Art the addition is not critical.

The starting materials of formula (III) can be Establish standard synthesis method. Examples of such Manufacturing methods can be found in BE-PS 838 928 or in the corresponding DE-OS 26 04 047.

The starting materials of formula (IV) can be obtained from Her provision of the corresponding starting materials of the formula (III), in which Y represents chlorine or bromine, and reaction with ammonia, optionally in the presence of a suitable Solvents such as diethyl ether, tetrahydrofuran or Me thanol, at temperatures usually between -40 and Fluctuate 100 ° C, are produced.

The addition salts of the substituted 1,2,4-triazoles according to The present invention can according to known standard methods which are manufactured. For example, a connection of formula (I) in a suitable solvent, such as diethyl ether, tetrahydrofuran, ethanol or methanol, dissolved and with an equivalent amount or an excess amount a mineral or organic acid, the given if it can be dissolved in a suitable solvent, be treated. The mixture is then either cooled or evaporated to give the salt which either used as such or from a suitable solution tel or from a combination of suitable solvents is recrystallized.

The metal salt complexes of the compounds of formula (I) can be prepared by dropwise stirring a stoichiometric amount of a metal salt (dissolved in a suitable solvent) to a solution of a verbin of formula (I), dissolved in a suitable solution medium, is added. The reaction mixture can briefly ge are stirred, the solvent being reduced Pressure is removed to give the desired metal salt.  

The metal salt complexes can also by mixing stoichiometric amounts or excess amounts of the metal salt and a compound of formula (I) in the desired th amount of solvent, which suitable auxiliary contains, immediately before spraying onto plants Fighting mushrooms are made. Tools that to carry out these "in situ manufacturing methods" ver can be used from detergents, emulsifiers agents, wetting agents, spreading agents, dispersants agents, tackifying agents, adhesives or others Adjuvants exist that are used in agriculture will.

Solvent used for such in situ methods can be, for example, any polar solution medium, such as water, methanol, ethanol, iso propanol or ethylene glycol, or any aprotic dipo lare solvents, for example dimethyl sulfoxide, aceto nitrile, dimethylformamide, nitromethane or acetone.

Metal-containing fungicides can also be considered safe de means, d. H. to reduce phytotoxicity, instead of le non-fungicidal metal salts can be used. Typical Metal-containing fungicides used for these in situ methods The following can be used: a) Dithiocarbamates and also derivatives, such as iron (III) dimethyldithiocarbamate (Ferbam), Zinc dimethyl dithiocarbamate (ziram), manganese ethylene bisdithiocar bamat (Maneb) and its coordination product with zinc ion (Mancozeb), zinc ethylene bisdithiocarbamate (Zineb), b) fungizi de copper-based, such as copper (I) oxide, copper naphthenate and Boredeaux mixture, and c) various fungicides, such as phenyl mercury acetate, N-ethyl mercury ber-1,2,3-6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlor phthalimide, phenylmercury monoethanol ammonium lactate, nickel ent holding compounds and calcium cyanamide.  

The compounds of the invention, with the exception of Ver bond in which R¹ and R² each represent hydrogen, have an asymmetric carbon atom and exist hence in the form of racemic mixtures. The d and l enantio Morphing in these racemic mixtures can be done according to Stan Standard methods are separated, for example by fracture nier crystallization with d-tartaric acid, l-tartaric acid or l-quinic acid, followed by an alkaline and a Extraction of the free enantiomorphic d- or l-base follows.

The following working examples 1 to 5 show manufacturing methods of compounds of the invention in which R¹ has a meaning other than cyano. In these examples and the following examples relate to Temperature information in ° C.

The compounds prepared according to Examples 1 to 5 as well as other analogous compounds which are produced according to the invention have been put together in Table I below quantified. Analysis values follow in Table II.  

The substituted 1,2,4-triazoles, acid according to the invention addition salts and metal salt complexes are broad-spectrum fun gicides that differ in a high degree of activity which have phytopathogenic fungi. These connections, Salts and complexes are particularly effective in applied Control amounts of about 50 to about 2000 ppm of barley spot disease (Helminthosporium teres) Barley plants, gray mold (Botrytis cinerea) on Faba beans, powdered mildew (Erysiphe polygoni) on beans plants, plum powdery mildew (Plasmopora viticola) on wine Grape seedlings, rice brandy (Piricularia oryzae) on rice plants, late tomato blight (Phytophthora infestans) on tomato seedlings and wheat stem rust (Puccinia gra minis f. sp. tritici race 15B-2) on wheat seedlings.

A preliminary study is carried out to investigate these connections to determine the fungicidal activity using of the compounds in a carrier in a concentration of 300 ppm carried out, the plants until draining be sprayed (approximately 570 l / 4050 m² (150 gallons / acre).

The method generally used is one potted plants in a growth state in which the Plants are susceptible to fungal disease, on a moving belt with the fungicidal agents to spray and then let them dry. The Plants are then loaded with the appropriate fungal spores vaccinates which can be developed until the sick has occurred. The percentage of combat will then determined.

Typical compounds, acid addition salts and metal salt complexes according to the present invention make a 70 up to 90% fungal control when using the above be written method while maintaining a concentration of 300 ppm of (1) Helminthosporium teres on barley plant zen (var. Wong), (2) botrytis cinerea on broad-leaved  Bean plants (var. Vicia faba), (3) Erysiphe polygoni Bean plants (var. Drawf Hort), (4) Plasmopora viticola on grape seedlings (var. Siebel 1000), (5) Piricularia oryzae on rice plants (var. Nova 66), (6) Phytophthora in festans on tomato plants (var. Rutgers) and (7) Puccinia graminis (f. sp. tritici race ISB-2) on wheat plants.

The compounds of formula I and their acid addition salts and metal salt complexes are widely used as a broad spectrum fungicides used, for example in the storage of Cereals and as fungicides on lawns, in fruit plantations, Vegetable beds and on golf courses.

When used as fungicides, the Invention active ingredients usually to combat phytopatho genes fungi on growing plants, plant seeds or plants zen growth sites, such as the soil, in one fungicidally effective amount applied.

The substituted 1,2,4-triazoles, acid addition salts as well Metal salt complexes according to the present invention can be as agricultural fungicides in various places bring, for example on seeds, the ground or on Leaves, especially if it is an edible benefit plant acts. For such purposes, the connections in the manufactured technical or pure form in form of solutions or formulations. The Ver Bonds are usually mixed with one for country economic diluents or Carriers used to make them for subsequent distribution to make them suitable as fungicides. For example, the fungicidal active ingredients specified above with a carrier or Diluents in the form of dusts, granules, aerosols, emulsifiable concentrates, wettable powders or flow capable emulsion concentrates are formulated, the The last three formulations are usually an interface share ves agent included. Furthermore, there is no wording set of liquid or solid carrier and, if appropriate, suitable  Neter surfactants possible. More details suitable methods for producing For mulations as well as other pesticides related with the fungicidal active ingredients according to the present invention come into question, reference is made to DE-OS 26 04 047.

Be on two subclasses of the compound of the invention especially pointed out.

The first subclass are compounds of formula (I) (as well the metal salt complexes and acid addition salts thereof), wherein Z represents phenyl or naphthyl, optionally substituted in the aryl group with (C₁-C₄) alkyl, (C₁-C₄) alkoxy, halogen or nitro, stands, the group

(C₃-C₄) alkyl and Q is unsubstituted 4- (1,2,4-tria zolyl). Connections of this first subclass when used as plant fungicides properties compared to other similar ver bonds, but R¹ and R² are each hydrogen stand.

The second subclass of the compounds of formula (I) (a finally the acid addition salts and metal complexes thereof) are those where the group

represents an alkyl group having more than 4 carbon atoms contains, for example 6 to 14 carbon atoms.

Claims (3)

1. Compound of the formula wherein
Z is phenyl or naphthyl, each optionally substituted with up to three substituents, selected from halogen, nitro, trihalomethyl, cyano, (C₇-C₁₄) aralkyl, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, each of the latter four groups optionally being substituted with up to two substituents, selected from Halogen, nitro, trifluoromethyl, cyano, methyl, methoxy, methylthio, methylsulfiniyl and methylsulfonyl,
R¹ is one of groups (5) to (7) as defined below in connection with R²; R²

• (1) hydrogen,
• (2) (C₁-C₁₂) alkyl,
• (3) (C₃-C₈) cycloalkyl,
• (4) (C₂-C₈) alkenyl,
• (5) (C₅-C₈) cycloalkenyl,
• (6) (C₂-C₈) alkynyl,
• (7) phenyl or naphthyl, optionally substituted as indicated in connection with Z,
• (8) phenyl- (C₁-C₄) -alkyl or naphthyl- (C₁-C₄) -alkyl, optionally substituted in the aryl as indicated in connection with Z, means

with the proviso that R¹ is not 2-halophenyl, 4-halophenyl, 2,4-dihalophenyl or 4-methylphenyl when R² is H,
Q 1- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl) is, optionally substituted with up to two substituents, selected from halogen, (C₁-C₄) alkyl, nitro and Cyano,
m is 0 or 1,
n is 1 or 2,
or an agriculturally acceptable acid addition salt or agriculturally acceptable metal complex of a compound of formula (I). 2. Fungicidal agent, characterized in that it is as Active ingredient a compound according to claim 1 and for compatible with agricultural purposes tel or a compatible for agricultural purposes chen carrier contains.