GB1568350A

GB1568350A - Azolyl-alkane-carboxylic acid derivatives and their use as fungicides

Info

Publication number: GB1568350A
Application number: GB17482/78A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1977-05-07
Filing date: 1978-05-03
Publication date: 1980-05-29
Also published as: CH638793A5; DE2720654A1; IL54637A0; FR2389617A1; IT7823102A0; IL54637A; JPS53137959A; DK197978A; FR2389617B1; BE866718A; BR7802840A; NL7804859A; IT1094614B

Abstract

The new azolylalkanecarboxylic acid esters and amides of the formula I <IMAGE> in which Az represents an optionally substituted azolyl radical, R<1> represents optionally substituted phenyl or alkyl, R<2> represents hydrogen, optionally substituted phenyl or alkyl, R<3> represents the groups -OR<4> or -NR<5>R<6>, where R<4> represents alkyl, cycloalkyl or optionally substituted phenyl, and R<5> and R<6> are identical or different and represent hydrogen or alkyl or together represent an alkylene bridge which may optionally contain oxygen as a further heteroatom, and salts thereof have strong fungicidal properties and are suitable for use as crop protection agents for the control of fungi. These active substances are obtained by reacting alpha -haloalkanecarboxylic acid esters and amides with azoles in the presence of a diluent and an acid-binding agent.

Description

(54) NOVEL AZOLYL-ALKANECARBOXYLIC ACID DERIVATIVES AND THEIR USE AS FUNGICIDES (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate, organised under the laws of Germany, of Leverkusen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to certain azolyl-alkanecarboxylic acid derivatives, to a process for their preparation and to their use as fungicides.

It has already been disclosed that certain phenoxy-imidazolyl- or -triazolyl-O,Nacetals, especially those substituted in the phenoxy part, possess a good fungicidal activity (see German Offenlegungsschriften (German Published Specifications) No.

2,32S,156, No. 2,201,063 and No. 2,455,955. However, their action is not always completely satisfactory, especially if low amounts and concentrations are used.

In addition, it has already been disclosed that zinc ethylene-I,2-bis-dithiocarb- amidate is a good agent for combating fungal plant diseases (see Phytopathology 33, 1113 (T1968)). However, its use as a seed dressing is possible only to a limited extent, since it is less active if low amounts and concentrations are used.

The present invention now provides the azolyl-alkanecarboxylic acid derivatives of the general formula

in which Az represents an optionally substituted azolyl radical, R1 represents optionally substituted phenyl or alkyl, R2 represents hydrogen, optionally substituted phenyl or alkyl and Rd represents the grouping WR4 or -NR5R, wherein R' represents alkyl, cycloalkyl or optionally substituted phenyl and R5 and R6, which may be identical or different, each represent hydrogen or alkyl, or R5 and R6 together represent an alkylene bridge which can optionally contain oxygen as a further hetero-atom, and their salts.

The compounds of the present invention have powerful fungicidal properties.

Preferably, R1 represents phenyl which optionally carries one or more substituents selected independently from halogen, nitro, cyano, alkoxycarbonyl with 1 to 3 carbon atoms and phenyl and phenoxy, the two last-mentioned radicals being optionally substituted by halogen, or represents alkyl with 1 to 4 carbon atoms, R2 represents hydrogen or phenyl which is optionally monosubstituted or polysubstituted by halogen, or represents straight-chain or branched alkyl with 1 to 6 carbon atoms, R3 represents an OR4 grouping, in which R4 represents straight-chain or branched alkyl with 1 to 6 carbon atoms, cycloalkyl with 5 to 7 carbon atoms or phenyl which optionally carries one or more substituents selected independently from halogen, nitro, cyano, alkoxycarbonyl with 1 to 3 carbon atoms and phenyl and phenoxy, the two last-mentioned radicals being optionally substituted by halogen, or R3 represents an NR5R6 grouping, in which R5 and R6, which may be identical or different, each represent hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, or R5 and R6 together complete a 5-membered or 6-membered ring, which can optionally contain oxygen as a further hetero-atom (pyrrolidine, piperidine and morpholine being mentioned as examples), and Az represents a pyrazol-l-yl, imidazol-l-yl, 1,2,4-triazol- 1 -yl, 1,2,3-triazol-1-yl, 1 ,3,4-triazol-1 -yl, indazol-l-yl, benzimidazol-l-yl or benztriazol-l-yl radical which is optionally substituted by methyl or ethyl.

The invention also provides for the preparation of an azolyl-alkanecarboxylic acid derivative of the formula (I) in which (a) an a-halogeno-alkanecarboxylic acid derivative of the general formula

in which R1, R2 and R3 have the meanings stated above and Hal represents halogen, especially bromine or chlorine, is reacted with an azole of the general formula Az-H (III) in which Az has the meaning stated above, in the presence of a diluent and an acid-binding agent, or (b), provided a compound of the formula (I) in which RS represents the -NR5R6 grouping is to be obtained, an azolyl-alkanecarboxylic acid alkyl ester of the formula (I) is reacted with an amine of the general formula

in which R5 and R" have the meanings stated above, optionally in the presence of a diluent.

Furthermore, an azolyl-alkanecarboxylic acid derivative (I) obtained according to the present invention can be converted into a quatemary salt by reaction with an acid.

Surprisingly, the active compounds according to the present invention exhibit a considerably higher fungicidal activity than the phenoxy-imidazolyl- and -triazolyl O,N-acetals which are known from the state of the art and which are closely related substances chemically and from the point of view of the action, and also than the known zinc ethylene-1,2-bis-dithiocarbamidate which is a standard formulation with a similar spectrum of action. The active compounds according to the invention thus represent an enrichment of the art.

If bromo-(4-chlorophenoxy)-acetic acid tert.-butyl ester and 1,2,4-triazole are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation:

If (4-chlorophenoxy)-(1,2,4-triazol-1-yl)-acetic acid ethyl ester and ammonia are used as starting materials in process variant (b), the course of the reaction can be represented by the following equation:

Examples of starting materials of the formula (II) are: bromo-phenoxy-acetic acid ethyl ester, bromo-(4-chlorophenoxy)-acetic acid ethyl ester, chloro-(4-chlorophenoxy)-acetic acid ethyl ester, bromo-(4-chlorophenoxy)-acetic acid methyl ester, bromo-(4-chlorophenoxy)-acetic acid propyl ester, bromo-(4-chlorophenoxy)-acetic add isopropyl ester, bromo-(4-chlorophenoxy)-acetic acid tert.-butyl ester, bromo-(4 chIorophenoxy) -acetic acid sec.-butyl-ester, bromo-(4-chlorophenoxy)-acetic acid butyl ester, bromo-(4-chlorophenoxy)-acetic acid phenyl ester, bromo-(4-chlorophenoxy)acetic acid 4-chlorophenyl ester, bromo-(4-chlorophenoxy)-acetic acid cyclohexyl ester, bromo-(4-chlorophenoxy) -acetic acid dimethylamide, bromo-'( 4-chlorophenoxy) - acid morpholide, bromo-(4-chlorophenoxy)-phenyl-acetic acid ethyl ester, bromo-(4chlorophenoxy)-(4-chlorophenyl)-acetic acid ethyl ester, bromo-(4-chlorophenoxy) (2,4-dichlorophenyl)- acetic acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-propionic acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-butyric acid ethyl ester, α-bromo-α-(4- chlorophenoxy)-valeric acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-iso-valeric acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-caproic acid ethyl ester, a-bromo-a-(4- chlorophenoxy)-ss-methyl-valeric acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-γ- methyl-valeric acid ethyl ester, α-bromo-α-(4-chlorophenoxy)-ss,ss-dimethyl-butyric acid ethyl ester, bromo-(2,4-dichlorophenoxy)-acetic acid ethyl ester, bromo-(4-biphenylyloxy)-acetic acid ethyl ester, bromo-(4'-chloro-4-biphenylyloxy)-acetic acid ethyl ester, bromo-(4-phenoxyphenoxy)-acetic acid ethyl ester and bromo-(4'-chloro 4-phenoxyphenoxy)-acetic acid ethyl ester.

Some of the -halogeno-alkanecarboxylic acid derivatives to be used as starting materials are known from Chemischer Informationsdienst, 49, 257 (1973), Chem. Ber.

44, 3212 (1911) and Acta Chimica Academiae Scientiarum Hungaricae, Tomus 79 (4), 419-432 (1973). Those which have not yet been disclosed can be prepared in a simple manner by the processes described in the literature, in which, for example, the active hydrogen atom in alkane-carboxylic acid derivatives of the general formula

in which Rl, R2 and R3 have the meanings stated above, is replaced by halogen in a manner which is in itself known, such as, for example, by reaction with N-bromosuccinimide at the boil in the presence of a solvent, for example carbon tetrachloride, and in the presence of a catalyst, for example dibenzoyl peroxide.

The end products are isolated in the customary manner (see also the preparative Examples later in this text).

The alkanecarboxylic acid derivatives of the formula (V) are known or can be obtained by known methods in a simple manner in which known a-halogeno-alkanecarboxylic acid derivatives of the general formula

in which R2 and R3 have the meanings stated above and Hal is halogen, especially chlorine or bromine, are reacted with known alcohols of the general formula R1-O-H (VII) in which R1 has the meaning stated above, in the presence of a solvent, for example acetone or methyl ethyl ketone, and in the presence of an acid-binding agent, for example potassium carbonate, at the boil (see also the preparative Examples).

The azoles of the formula (III) and the amines of the formula (IV) are generally known substances of organic chemistry.

Preferred salts of the compounds of the formula (I) are, for reasons of toxicity, physiologically acceptable salts, these being, in general, salts with psysiologically acceptable acids, especially the hydrogen halide acids (for example hydrobromic acid and especially hydrochloric acid), phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, maleic acid, succinic acid, fumaric acid, salicylic acid, citric acid, sorbic acid and lactic acid) and 1,5-naphthalenedisulphonic acid. A salt is conveniently prepared by adding an acid to a compound (I) in solution.

Preferred diluents which can be used for the reaction in process variant (a) are inert organic solvents, especially ketones, such as diethyl ketone and, in particular, acetone and methyl ethyl ketone; nitriles, such as propionitrile and, in particular, acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxan; benzene; formamides such as, in particular, dimethylformamide; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.

The reaction according to process variant (a) is carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can customarily be used, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine and N,N-dimethylbenzylamine, as well as pyridine and diazabicyclooctane.

It is also possible to use an appropriate excess of the azole (HI) as the acidbinding agent.

The reaction temperatures in process variant (a) can be varied within a relatively wide range. In general, the reaction is carried out at from 0 to 120"C, preferably at from 200 to 1800C.

In carrying out process variant (a), 1 to 2 moles of azole and 1 to 2 moles of acid-binding agent are preferably used per mole of the compound of the formula (II).

In order to isolate the compounds of the formula (I), the solvent is distilled off, the residue is taken up in an organic solvent and the solution is washed with water. The organic phase is dried over sodium sulphate and freed from the solvent in vacuo. The residue is purified by distillation or recrystallisation.

The azolyl-alkanecarboxylic acid alkyl esters (I) used as starting materials in process variant (b) may be prepared by process variant (a).

Preferred diluents which can be used for the reaction in process variant (b) are water and organic solvents, especially the solvents already mentioned in connection with process variant (a).

The reaction temperatures in process variant (b) can be varied within a relatively wide range. In general, the reaction is carried out at from 0 to 1000C, preferably at from 20 to 800C.

In carrying out the process (b) according to the invention, equimolar amounts of the reactants are preferably used. The compounds of the formula (I) are isolated in a generally customary manner.

The active compounds according to the invention exhibit a powerful fungitoxic action. They do not damage crop plants in the concentrations required for combating fungi. For these reasons, they are suitable for use as plant protection agents for combating fungi. Fungitoxic agents are employed in plant protection for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi which attack above-ground parts of plants or which attack the plants through the soil, as well as against seed-borne pathogens.

They display a particularly good activity against parasatic fungi on above-ground parts of plants, such as species of Erysiphe, species of Podosphaera and species of Venturia, and also against species of Pyricutana and species of Pelliculano Good actions are achieved against the pathogen of apple scab (Fusicladium dentricum), and of powdery mildew of apples (Podosphaera leucotricha), against the fungi Pyricularia oryzae and Pellicularia sasakii, and against the pathogen of powdery mildew of cereals (Erysipk graminis) as well as against other cereal diseases, such as cereal rust.

As plant protection agents, the compounds according to the invention can be used for the treatment of soil, for the treatment of seed and for the treatment of above-ground parts of plants.

The active compounds can be converted into the customary formulations, such as soMutiazs, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example; also be used as auxiliary solvents.

- As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone methyl ethyl ketene, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and diethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at zonal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such as kaolins, days, talc, chalk, quartz, attapulgite, montmorillonite or diamotaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates.

As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as abumin hydroysis products. Dispersing agents incude, for example, lignin sulphite waste liquors and methylcellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent The active compounds can be used as such, as their formulations or as the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be used in the customary manner, for example by watering, spraying, atomising, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

Especially when used as leaf fungicides, the active compound concentrations in the use forms can be varied within a fairly wide range. They are, in general, from 0.1 to 0.00001 per cent by weight, preferably from 0.05 to 0.0001 per cent.

For the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally employed.

For the treatment of soil, amounts of active compound of 1 to 1,000 g per cubic metre of soil, preferably of 10 to 200 g, are employed.

The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.

It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.

In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.

The known comparison compounds are identified as follows:

Example A.

Mycelium growth test Nutrient medium used: 20 parts by weight of agar-agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 pans by weight of disodium hydrogen phosphate 0.3 part by weight of calcium nitrate Ratio of solvent mixture to nutrient medium: 2 parts by weight of solvent mixture 100 parts by weight of agar nutrient medium Composition of the solvent mixture: 0.19 part by weight of acetone or DMF 0.01 part by weight of emulsifier (alkylaryl polyglycol ether) 1.80 parts by weight of water The amount of active compound required for the desired active compound con centration in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which had been cooled to 42 deg.C) and was then poured into Petri dishes of 9 cm diameter. Control plates to which the preparation had not been added were also set up.

When the nutrient medium had cooled and solidified, the plates were inoculated with the species of fungi stated in the table and incubated at about 21 deg.C.

Evaluation was carried out after 410 days, dependent upon the speed of growth of the fungi. When evaluation was carried out the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient medium. In the evaluation of the fungus growth, the following characteristic values were used: 1 no fungus growth up to 3 very strong inhibition of growth up to 5 medium inhibition of growth up to 7 slight inhibition of growth 9 growth equal to that of untreated control.

The active compounds, the active compound concentrations and the results can be seen from the following table: TABLE A Mycelium growth test Fungi

'TYS13S O\ a\ I [ [ m c [ I m rrr I U(TU0]32)3 DloylydoZyd Q\ 'T, I I 3 Iri [ v, In [ v, t7103.zsnur Z7llalaDdS03W V) O\ IA a\ 3 3 C1 3 tunauzurzll8 0 .2 0 . tan7X0dsotllu? laH m m aE oe ~ m < n m vr m concentration . 0 .

0 suaosaxau?a N N 0 N z71OYdOID!Yd' 9 5 9 9 9 I 5 5 I 9 aazo DflD/f2311IC 9 - - 9 < 9 9 5 9 9 (D) - - - 9 - - 9 9 9 9 9 9 lunlll'3lllan (36) - - 3 3 - - 1 5 3 1 v, - (3?) 5 5 5 3 5 5 1 1 3 1 5 (28) - - 2 2 5 5 3 cz 5 > 1 1 m tunlylrCd tulos (34) - - 5 1 - - 1 1 5 1 5 uznxo?oxalos 5 oy I I 3 I 3 2 5 3 2!ullolal3S (12) - - - 3 o eE I 1 5 5 m 5 m u(n?Dsn, 5 > ; 11 ~ c < m U Example B.

Pyricularia and Pellicularia test Solvent: 11.75 parts by weight of acetone Dispersing agent: 0.75 parts by weight of alkylaryl polyglycol ether Water: 987.50 parts by weight The amount of active compound required for the desired concentration of active compound in the spray liquid was mixed with the stated amount of the solvent and of the dispersing agent and the concentrate was diluted with the stated amount of water.

Rice plants about 2-4 weeks old were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse at temperatures of 22 to 24 deg.C and a relative atmospheric humidity of about 70% until they were dry. Thereafter, the plants were inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Pyricularia oryzae and placed in a chamber at 24 to 26 deg.C and 100% relative atmospheric humidity.

Other rice plants, which had been sprayed and dried in the above-described manner, were infected with a culture of Pellicularia sasakii grown on malt agar and were set up at 28 to 30 deg.C and 100% relative atmospheric humidity.

5 to 8 days after the inoculation, the infection of all the leaves present at the time of inoculation with Pyricularia oryzae was determined as a percentage of the untreated but also inoculated control plants.

In the case of the plants infected with Pellicularia sasakii, the infection at the leaf sheaths after the same time was determined, again in relation to the untreated but infected control.

The evalution was made on a scale of from 1 to 9. 1 denoted 100% action, 3 denoted good action, 5 denoted moderate action and 9 denoted no action.

The active compounds, the concentrations of the active compounds and the results can be seen from the table which follows.

TABLE B Pyricularia (a) and Pellicularia (b) test Infection at an active compound concentration of 0.025% Active compound (a) (b) (E) 5 9 (B) 9 7 (F) 9 9 (2) 1 5 (31) - 5 (34) - 3 (37) - 5 Example C.

Shoot treatment test/powdery mildew of cereals (leaf-destructive mycosis) /protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether; 975 parts by weight of water were then added. The concentrate was diluted with water to the desired final concentration of the spray liquor.

To test for protective activity, single-leaved young barley plants of the Amsel variety were sprayed with the preparation of active compound until-dew-moist. After drying, the barley plants were dusted with spores of Erysiphe graminis var. hordei.

After 6 days' dwell time of the plants at a temperature of 21-22 deg.C and 8090% atmospheric humidity the occurrence of mildew pustules on the plants was evaluated. The degree of infection was expressed as a percentage of the infection of the untreated control plants. 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control. The active compound was the more active, the lower was the degree of mildew infection.

The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows: TABLE C Shoot treatment test /powdery mildew of cereals /protective Active compound concentration in the Infection in spray liquor in % of the Active compounds % by weight untreated control Untreated 100 (B) 0.001 100 (G) 0.001 66.3 (H) 0.01 91.3 (42) 0.01 0.0 (11) 0.01 0.0 (12) 0.01 0.0 (14) 0.01 0.0 (15) 0.01 27.5 (27) 0.001 0.0 (2) 0.001 25.0 (33) 0.001 38.8 (34) 0.001 21.3 Example D.

Shoot treatment test/cereal rust (leaf-destructive mycosis)/protective To produce a suitable preparation of active compound, 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.

To test the protective activity, one-leaved young wheat plants of the Michigan Amber variety were inoculated with a uredospore suspension of Puccinia recondita in 0.1% strength aqueous agar. After the spore suspension had dried on, the wheat plants were sprayed with the preparation of active compound until dew-moist and were placed, for incubation, in a greenhouse for 24 hours at about 20 deg.C and 100% relative atmospheric hum degree of infection as in the case of the untreated control. The active compound was the more active, the lower was the degree of rust infection.

The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows: TABLE D Shoot treatment test=cereal rust/protective Active compound concentration in the Infection in spray liquor in qc of the Active compounds Sc by weight untreated control Untreated 100 (J) 0.0'5 100 (F) 0.025 82.5 (D) 0.025 86.3 0.01 100 (K) 0.025 82.5 0.01 100 (L) 0.025 100 0.01 100 (29) 0.025 16.3 (31) 0.025 33.8 (36) 0.025 25.0 (27) 0.025 33.8 (7) 0.025 16.3 0.01 33.8 Example E.

Fusicladium test (apple) /protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.

Young apple seedlings in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20 degrees C and at a relative atmospheric humidity of 70%. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum) and incubated for 18 hours in a humidity chamber at 18-20 degrees C and at a relative atmospheric humidity of 100%.

The plants were then brought into a greenhouse again for 14 days.

15 days after inoculation, the infection of the seedlings was determined. The assessment data were converted to percent infection. 0% meant no infection; 100% meant that the plants were totally infected.

The active compounds, the concentrations of the active compounds and the results can be seen from the following table: TABLE E Fusicladium test (apple) /protective Infection in % at an active Active compound compound concentration of 0.01% (E) 72 (M) 43 (11) 30 (12) 19 (15) 20 (27) 16 (34) 4 (36) 22 (37) 14 Example F.

Podosphaera test (apple) /protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.

Young apple seedlings in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20 deg.C and at a relative atmospheric humidity of 70%. They were then inoculated by dusting the conidia of the apple powdery mildew causative organism (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21-23 deg.C and at a relative atmospheric humidity of about 70%.

10 days after the inoculation, the infection of the seedlings was determined. The assessment data were converted to % infection. 0% meant no infection; 100% meant that the plants were completely infected.

The active compounds, the concentrations of the active compounds and the results can be seen from the following table: TABLE F Podosphaera test (apple) ,'protective Infection in sic at an active compound concentration of Active compound 0.00062% 0.0005% (N) 45 (K) 32 (L) 79 (11) 5 (17) 30 Preparative Examples Example 1.

Process variant (a): 321.6 g (1 mol) of bromo-(4-chlorophenoxy) -acetic acid tert.-butyl ester in 1,000 ml of acetone were added to 69 g (1 mol) of 1,2,4-triazole and 111.3 g (1.1 mol) of triethylamine in 2.5 litres of acetone at oac (cooling with ice). The mixture was subsequently stirred for 1 hour at room temperature and filtered and the filtrate was concentrated in vacuo. The residue was taken up in chloroform and the chloroform solution was washed with water, dried over sodium sulphate and concentrated in vacuo.

The residue was subjected to fractional recrystallisation from cyclohexane. 213 g (69% of theory) of 4-chlorophenoxy) 1,2,4-triazol-1-yl) -acetic acid tert.-butyl ester were obtained as colourless crystals of melting point 930C.

Example 2.

Process variant (a): 321.6 g (I mol) of bromo-(4-chlorophenoxy)-acetic acid tert.-butyl ester in 1,000 ml of acetone were added to 68.1 g (1 mol) of imidazole and 111.3 g (1.1 mol) of triethylamine in 2.5 litres of acetone at 0 C (cooling with ice). The mixture was subsequently stirred for 1 hour at room temperature and filtered and the filtrate was concentrated in vacuo. The residue was taken up in chloroform and the chloroform solution was washed with water, dried over sodium sulphate and concentrated in vacuo.

The residue thereby obtained was subjected to fractional recrystallisation from cyclohexane. 213.4 g (68.9% of theory) of (4-chlorophenoxy)-imidazol-1-yl-acetic acid tert.butyl ester were obtained as colourless crystals of melting point 67"C.

Example 3.

Process variant (a) 99.9 g (0.6 mol) of ethoxy-chloro-acetic acid ethyl ester were heated under reflux with 145 g (2.1 mol) of 1,2,4-triazole in 1.5 litres of acetonitrile for 15 hours.

The mixture was allowed to cool and was filtered and the filtrate was concentrated in vacuo. The residue was taken up in 1,000 ml of water and extracted by shaking three times with 200 ml of methylene chloride each time. The combined organic phases were washed with water, dried over sodium sulphate and concentrated in vacuo. The residue was distilled. 86.5 g (74% of theory) of ethoxy-(1,2,4-triazol-1-yl)-acetic acid ethyl ester of melting point 92--98"C/0.08 mm Hg were obtained.

Example 4.

Salt formation: 199 g (1 mol) of ethoxy-( 1,2,4-triazol-1-yl)-acetic acid ethyl ester obtained according to Example 3 were taken up in ethyl acetate and converted with ethereal hydrochloric acid into the hydrochloride, which crystallised out after standing for a relatively long time in ether. After recrystallising from ethyl acetate, 199.2 g (85% of theory) of ethoxy- ( l,2,4-triazol-1-yl)-acetic acid ethyl ester hydrochloride were obtained as colourless crystals of melting point 102--105"C.

Example 5.

Process variant (a), with salt formation: 328 g (1 mol) of bromo-(2,4-dichlorophenoxy)-acetic acid ethyl ester in 500 ml of anhydrous tetrahydrofuran were added to 69 g (1 mol) of 1,2,4-triazole and 111.3 g (1 mol) of triethylamine in 1.5 litres of anhydrous tetrahydrofuran at 0.C (cooling with ice). The mixture was subsequently stirred at room temperature for 1 hour and was filtered and the filtrate was concentrated in vacuo. The residue was taken up in carbon tetrachloride and the carbon tetrachloride solution was washed with water, dried over sodium sulphate and evaporated in vacuo. The oily residue was taken up in 50 ml of acetone and an excess of ethereal hydrochloric acid was added, the hydrochloride precipitating out after the mixture had stood for several days.

239.9 g (68% of theory) of 2,4-dichloroptenoxy-(1,2,4-triazol-1-yl)-acetic acid ethyl ester hydrochloride were obtained in the form of white crystals of melting point 1010C.

Example 6.

Process variant (b): 32.3 g (0.1 mol) of (2,4-dichlorophenoxy)-( 1,2,4-triazol-l-yl)-acetic acid ethyl ester hydrochloride (Example 5) were stirred with 100 ml of concentrated aqueous ammonia solution at room temperature for 24 hours. The aqueous phase was then decanted off from the oil which had precipitated and the product, which after trituration was crystalline, was recrystallised from methanol. 16.6 g (58% of theory) of (2,4-dichlorophenoxy)-( 1,2,4-triazol-l-yl)-acetic acid amide of melting point 149 152"C were obtained.

The following compounds in Table 1 were obtained analogously to the abovementioned Examples.

T a b l e 1

X oa o g cm C - CO - R3 (I) Exaniple 1 U Ln 0 No. R R3 Az or refractive index 7 Q, (-I H > , aD ci pz 115 rl 8 ClCl H o-Q)Q 1,2,4-Triazol-1-yl 115 SrS, AhhXSrSIX I 1 (1111111 9 , rl H r1 1,2,4-Triazol-1-yl 78(xHCl) 0 0 0 0000000 N N N NNNNNNN (d cP al nlrdddcdcdcrl N r( rl d rl ri r( rl r( e a o > h o o h 8 o > ) 1 1111(111 -5 -;r -j f f 11 C11 * 1,2,4-Triazol-1-yl 12 Cl-Cl -OCH3 1,2,4-Triazol-1-yl iio(xHCi) u n n t 13 nx U O &commat;.. o o cJo cJ o -OC(CH3)3 1,2,4-Triazol-1-yl 0 0 0 0 0 I 1 (1)11111 15 C1- -OCH3 1,2,4-Triazol-1-yl 110 ~1= N=, m U Q Q Q Q " O l H H rl H H H H H H H 0 F 0 o Example Melting point ( C) No. R R R Az or refractive index

as " ~ u 18 C1- CU OC(CH3)3 1,2,4-Triazoi-l-yi 101 19 o u u re -OC(CH3)3 1,2,4-Triazol-1-yl 123 SrhSrS, I(II1 rlr(rlrl 00000 h,,,, h ts h o t I H -O r OONNNN )111)0 NNQQ QN aaa r r r r (d a i I 12 H H d rls8 H H H H n C1- n OCaHs Imidazol-1-y1 95 n 25 Cl H 6 -0C2H5 V U o o, o, o. z Imidazol-l-y1 97 CxHC1) v H u n H x 28 ≈ CH3 | H | 117 (xHCl) Q 99 Q 9 > o N es F Example Melting point ( C) No. R R R Az or refractive index

29 Cl- )1 -OC(CH3)5 Iidazol-l-yl 149 D 30 Cl H 2Metnyl-imidazol n2 :lq53l4 ,Z'Z\rr\Ln 31 n dz O X O a rl rl N Cl-1 N -0C2H5 2-Methyl-imidazol- nD:l.584l alkyl 33 rt rl O > % O O O O O 97 N d N . N N Imidazol-l-yl N N N N N D H Cl- H H NH H H H H H Imidazol-l-yl H 1 36 c1Cl n -OC(CH3)3 Imidazol-l-yl n20.:l.5655 Cn R iII En 3:n Cn ,n ?" O Cl- C > O O O O O O O O O 0( 11111111 U H H c) v v v v v c) Imidazol-l-yl 119 a o H N n 4 an tD b Ch Example Melting point ( C) No. R R R Az or refractive index

40 Cl1 C1 -OC(cH3)3 Imidazol-l-yl 120 41 Cl -Ci -Oc(CH3)3 IJnidazo1-iy1 126 42 Ci1 v N oa 0 0 o I N H r1 O O Ei N N Z st i H H n V 8 V V U V O O O I V H o0H eJ V V 40 N NOTE: NDS = 1,5-Naphthalenedisulphonic acid Preparation of starting materials Example a The compound of the formula

(b.pt. 75-81 /12 mm Hg) was prepared as described in Chem. Ber. 44, 3213 (1911).

Example b.

242.7 g (1 mol) of -chlorophenoxy-acetic acid tert.-butyl ester and 178 g (1 mol) of N-bromosuccinimide were heated to the boil in 1.2 litres of carbon tetrachloride, a pinch of azo-bis-isobutyric acid nitrile being added from time to time. The mixture was heated under reflux until the succinimide formed floated on the solvent (about 2 hours). Thereafter, the mixture was cooled to 0 C and filtered and the filtrate was concentrated in vacuo. The solid residue was recrystallised from a little carbon tetrachloride. 244.4 g (76% of theory) of bromo-(4-chlorophenoxy)-acetic acid tert.butyl ester were obtained as colourless crystals of melting point 760 C.

The starting materials in Table 2 which follows were obtained analogously.

T a b 1 e 2

Melting Boiling point R point ( C) ( C/mm Hg) R R

C16 H -OC2H5 139-42/0.2 Cl H -OC2 H 81 Cl H -OC2 H5 124-7/0.1 Cldl H -OC(CH! ) viscous oil C1 CH3 -OC(CH3 ) viscous oil C1 H -0- 80 H If " 2 85 39 Cl- H -OC(CH ) 85 Cl Cl TC." H -olcn, 86 Cl1 H -04 viscous oil d 9 -OC2 H 78 Cl 4 -OCH3 viscous oil C1 t -oCH3 100 Cl oC(CH3)3 viscous oil Cll o -OC(CH3 )3 viscous oil TABLE 2-cont.

Melting Boiling point point (vac) ( C/mm Hg) R1 R2 R3

Cl oC1 -OC 85 C14 C1 -OCH, loll Cl- eFC1 ~go~,, -oc(CH3 )3 viscous oil C1 FC1 -oC(CH3) 96 Cl Cl -oC(CH3)3 viscous oil Br4F H -OC2 H5 75 oC1 H -OC,H, 126-9/0.2 C1 CH3 -OCH3 viscous oil Preparation of precursors Example c.

150.6 g (l mol) of chloroacetic acid tert.-butyl ester were added to 128.6 g (1 mol) of 4-chlorophenol and 138.2 g (1 mol) of potassium carbonate in 1,000 ml of methyl ethyl ketone at the boil. The mixture was heated under reflux for 8 hours and filtered and the filtrate was concentrated in vacuo. The residue was taken up in chloroform and the chloroform solution was washed with 1 N sodium hydroxide solution and water. The organic phase was dried over sodium sulphate and concentrated in vacuo and the residue was distilled. 74.6 g (61.5% of theory) of 4-chlorophenoxy-acetic tert.butyl ester were obtained as a colourless oil of boiling point 98-100 C/0.4 mm Hg, which later crystallised completely (melting point 420 C).

The precursors in Table 3 which follows were obtained analogously. T a b l e 3

Melting point Boiling point R R R ( C0) ( C/ mm Hg)

Clue H -OC2H 42 100-115/0.3 C1- /i\7 H -CC2 H5 49 H H -OQH5 viscous oil ClCCl N -0C(CH3)3 viscous oil C1 C1- ~ CH3 -oC(CH3)5 105-07/0.3 ClCl H -04 97 C1- )- H -oC(CH3)3 75 Clj C1gX 127 ClC1 CH3 -OCH, 146-49/12 H H -0{g 81 1 - -9Q H5 154/O.2 Cl- - -OCH3 61 sC1 Cga -OCH3 78 Cl- - -0C(CH)3 105 ClCl - -oC(CH3 ) viscous oil C1 -C1 -OCH3 120 Cl j- t-C1 -OCH3 88 Cl- t-C1 -oC(CH3)3 49 4 t-C1 -OC ( CH3 )3 74 Cl -C1 -OC(CH3)3 111 Cl- CH3 -OCH3 77-81/0.2 TABLE 3 cent.

R1 ,2 MRlting point Boiling point R R2 R3 ( C) ( C/mm Hg)

,C1 C1 Ci-1 C2H5 -OC(CH3)3 108-10/0.3 Cl 122/0.18 C1 s-C, H, -oC(CH3)3 C1- O i-C*H9 -OC(CH3)3 112-13/0.15 C1- H, -oC(CH3)3 viscous oil C1 t - Call, -OCH3 viscous oil C1- i-C3 H7 -OC*H9-n 153-55/10

Claims

WHAT WE CLAIM IS:1. Azolyl-alkanecarboxylic acid derivatives of the general formula

in which Az represents an optionally substituted azolyl radical, R1 represents optionally substituted phenyl or alkyl, R2 represents hydrogen, optionally substituted phenyl or alkyl and R8 represents the grouping -OR4 or -NR5R , wherein R4 represents alkyl, cycloalkyl or optionally substituted phenyl and R5 and R6, which may be identical or different, each represent hydrogen or alkyl, or R5 and R8 together represent an alkylene bridge which can optionally contain oxygen as a further hetero-atom.
2. Compounds according to claim, in which R1 represents phenyl which optionally carries one or more substituents selected independently from halogen, nitro, cyano, allcoxycarbonyl with 1 to 3 carbon atoms and phenyl and phenoxy, the two lastmentioned radicals being optionally substituted by halogen, or represents alkyl with 1 to 4 carbon atoms, R2 represents hydrogen or phenyl which is optionally monosubstituted or polysubstituted by halogen, or represents straight-chain or branched alkyl with 1 to 6 carbon atoms, Rs represents an OR4 grouping, in which R4 represents straight-chain or branched alkyl with 1 to 6 carbon atoms, cycloalkyl with 5 to 7 carbon atoms or phenyl which optionally carries one or more substituents selected independently from halogen, nitro, cyano, all:oxycarbonyl with 1 to 3 carbon atoms and phenyl and phenoxy, the two last-mentioned radicals being optionally substituted by halogen, or Rs represents an -NR5R6 grouping, in which R5 and R6, which may be identical or different, each represent hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, or R5 and R6 together complete a 5-membered or 6-membered ring, which can optionally contain oxygen as a further hetero-atom, and Az represents a pyrazol-l-yl, imidazol-l-yl, 1,2,4-triazol-l-yl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl, imidazol-l-yl, benzimidazol-l-yl or benztriazol-l-yl radical which is optionally substituted by methyl or ethyl.
3. Compounds according to claim 1 in the form of salts.
4. Compounds according to claim 3, in which the salts are formed with physiologically acceptable acids.
5. The compound according to claim 1 or 3 that is disclosed in any one of Examples 1 to 42.
6. A process for the preparation of an azolyl-alkanecarboxylic acid derivative according to claim 1, in which (a) an a-halogeno-alkanecarboxylic acid derivative of the general formula

in which R1, R2 and R5 have the meanings stated in claim 1, and Hal represents halogen, is reacted with an azole of the general formula Az-H (III) in which Az has the meaning stated in claim 1, in the presence of a diluent and an acid-binding agent, or (b), provided a compound of the formula (I) in which R3 represents the -NR5R6 grouping is to be obtained, an azolyl-alkanecarboxylic acid alkyl ester of the formula (I) is reacted with an amine of the general formula

in which R5 and R' have the meanings stated in claim 1, optionally in the presence of a diluent.
7. A process according to claim 6(a), in which Hal represents chlorine or bromine.
8. A process according to claim 6(a) or 7, in which the reaction is effected in the presence, as an acid-binding agent, of an alkali metal carbonate, a lower tertiary alkylamine, a cycloalkylamine, an aralkylamine or an excess of the azole (III).
9. A process according to claim 6(a), 7 or 8, in which the reaction is effected at from 00 two 1200C.
10. A process according to claim 9, in which the reaction is effected at from 200 to 1800C.
11. A process according to any of claims 6(a) and 7 to 10, in which 1 to 2 moles of the azole (III) and 1 to 2 moles of the acid-binding agent are employed per mole of the compound (II).
12. A process according to any of claims 6(a) and 7 to 11, in which the compounds of the formulae (II) and (III) are each hereinbefore specifically mentioned.
13. A process according to claim 6(b), in which the reaction is effected at from 0 to 1000C.
14. A process according to claim 13, in which the reaction is effected at from 200 to 800C.
15. A process according to claim 6(b), 13 or 14, in which equimolar amounts of the reactants are employed.
16. A process according to any of claims 6 to 15, in which the reaction is effected in an inert organic solvent.
17. A process for the preparation of a compound according to claim 3, in which an acid is added to a compound of the formula (I) in solution.
18. A process for the preparation of a compound according to claim 1 or 3, substantially as described in any one of Examples 1 to 6.
19. Compounds according to claim 1 or 3 whenever prepared by a process according to any of claims 6 to 18.
20. A fungicidal composition containing as active ingredient a compound according to any of claims 1 to 5 and 19 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surfaceactive agent.
21. A composition according to claim 20 containing from 0.1 to 95% of the active compound, by weight.
22. A method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound according to any of claims 1 to 5 and 19 alone or in the form of a composition containing as active ingredient a compound according to any of claims I to 5 and 19, in admixture with a diluent or carrier.
23. A method according to claim 22 in which a composition is used containing from 0.00001 to 0.1% of the active compound, by weight.
24. A method according to claim 23 in which a composition is used containing from 0.0001 to 0.05% of the active compound, by weight.
25. A method according to claim 22, in which the active compound is applied to soil in an amount of 1 to 1000 g per cubic metre of soil.
26. A method according to claim 25, in which the active compound is applied in an amount of 10 to 200 g per cubic metre of soil.
27. A method according to claim 22, in which the active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.
28. A method according to claim 27, in which the active compound is applied in an amount of O.O1 to 10 g per kg of seed
29. Crops protected from damage by fungi, by being grown in areas in which immediately prior to and/or or during the time of the growing a compound according to any of claims 1 to 5 and 19 was applied alone or in admixture with a diluent or carrier.