IL51230A

1-phenoxy-1-(1,2,4-triazolyl)-3,3-dimethylbutan-2-ol ester their preparation and fungicidal compositions containing them

Abstract

This record has no abstract on file.

IL51230A, drawing sheet 1 — Sheet 1 of 71

Term

No projected expiry on record.

2 claims: 1 independent, 1 dependent

1
Acylated triazolyl-0 ׳ N-acetale of the general formula 0 - CH I Az 0 - CO - R CH - C(CH, ) 3 (I), in which R represents alkyl, halogenoalkyl, phenoxyalkyl, alkylamino, or optionally halo-substituted phenylamino, X represents halogen, alkyl, cycloalkyl, CF^, nitro, optionally halo-substituted phenyl, phenylalkyl optionally substituted in the alkyl portion by alkoxycarbonyl, ׳ n represents 0, 1, 2 or 3, and Az represents the 1,2,4-triazolyl-l or the 1,2,4triazolyl-4 radical, and their physiologically tolerated salts and metal complexes.

598 paragraphs in 26 sections, as filed

The present invention relates to certain new acylated triazolyl-0,N-acetals and their salts and metal complexes, to a process for their preparation and. to their use as fungicides.

It has already been disclosed that triazolyl-0,N־acetals, especially 1-phenoxy-1-[1,2,4-triazolyl-(1)]-3,3-dimethylbutan2-ols which are substituted in the phenyl part, possess good fungicidal properties (see German Offenlegungsschrift (German Published Specification) 2,324,010 which corresponds to Israel Patent Specification No. 44793). However, their activity is not always entirely satisfactory, especially when low amounts and low concentrations are used. Furthermore, their toleration by plants, and their toleration by seed when used as a seed dressing, is not always satisfactory.

The present invention now provides, as new compounds, the acylated triazolyl-0,N־acetals of the general formula

- CO - R

I

CH - C(CH3 )3 (I) in which

R represents alkyl, halogenoalkyl, phenoxyalkyl, alkylamino, or optionally halo-substituted phenylamino,

X represents halogen, alkyl, cycloalkyl, CF3 , nitro, optionally halo-substituted phenyl, phenylalkyl optionally substituted in the alkyl portion by alkoxycarbonyl, . ־־. .

n represents 0, 1, 2 or 3, and ־>

51230/3 ( Γ

Az represents the 1,2,4-triazolyl-1 or the 1,2,4triazolyl-4 radical, :

I and their physiologically tolerated salts and metal complexes. ί

The compounds of the present invention exhibit powerful 5 fungicidal properties.

Preferably, R represents straight-chain or branched~alkyl with 1 to 8 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkylamino with 1 to 4 carbon atoms in the alkyl part, or phenylamino which may optionally be substituted by halogen; χ represents halogen, nitro, straight-chain or branched alkyl with up to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, CF3, phenyl which may optionally carry one or more halo substituents or phenylalkyl with 1 or 2 carbon atoms in the alkyl part; and n represents 02 ,1 ׳ or 3. ן t

- l

I

fcn-thg phenyl part; and n represents 0, 1, 2 ur J־.

The compounds of the formula (I) possess two asymmetrical carbon atoms; they can therefore exist in the erythro-form and in the threo-form. In both cases they are predominantly in the ׳ form of racemates.

The present invention also provides a process for the preparation of an acylated triazolyl-0,N-acetal of the formula (I), in which a triazolyl derivative of the general formula

- CH I Az

OH 1

CH - C(CH3 )5 (II), in which , X, Az and n have the above-mentioned meanings, (a) is reacted with an acid halide of the general formula J Hal-CO-R (III), in which \ R has the above-mentioned meaning and

Hal represents halogen, especially chlorine or bromine, ih the presence of a solvent, and the hydrohalide so formed is converted into the free base, if required, or (b) is reacted with an acid anhydride of the general formula ' R-CO-O-CO-R (IV), in which

R has the above-mentioned meaning, in the presence of a solvent and optionally in the presence of a catalyst, or (0) is reacted with a ketene of the general formula

O=C=CH-R* (V), le A 16 038 in which

R' represents hydrogen, alkyl, alkenyl, alkynyl or halogenomethyl, in the presence of a solvent and optionally in the presence ל of a catalyst, or (d) is reacted with an isocyanate of the general formula

O=C=N-R (VI), in which R represents alkyl or optionally substituted'7 phenyl, 10 in the presence of a solvent and optionally in the presence of a catalyst, and,if required, the acylated triazolyl-O,Nacetal obtained in any of the process variants (a) - (d) is converted into a physiologically tolerated salt or metal complex thereof.

The acylated triazolyl-0,N־acetals of the formula (I) can be converted into their salts by reaction with acids, or into their metal complexes by reaction with metal salts.

Surprisingly, the acylated triazolyl-0,K-acetals according to the invention exhibit a substantially greater fungicidal 20 activity, especially against species of rust and mildew, than the triazolyl-0,N-acetals known from the state of the art, which are the most closely related active compounds. Furthermore, they are distinguished by better toleration by plants. The active compounds according to the invention thus represent 25 an enrichment of the art.

If 1-(4-chlorophenoxy)-1-[1,2,4-triazolyl-(1)]-3,3dimethyl—butan—2—01 and acetyl chloride are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation:

Le A 16 83Θ

OH

+ CHS־CO-C1

13)ג ----------------

Νχ.

י ¾0-00-0

CH-C(CH3 )j

If 1-(4-chlorophenoxy)-1-[1,2,4-triazolyl-(1)]-3,3dimethyl-butan-2-01 and acetic anhydride are used as starting materials in process variant (b), the course of the reaction can be represented by the following equation!.

OH c1-^^-0-ch-ch-c(0H3 )3 +(0¾00)¾0^ .Μ,

O-CO-CH3

Cl-^^-0-CH-CH-C(CH3 )3

If 1-(2,4-dichlorophenoxy)-1-[1,2,4-triazolyl-(1)]-3,3dimethyl-butan-2-01 and 4-chlorophenylisocyanate are used as starting materials in process variant (d), the course of the 10 reaction can be represented by the following equation:

/-<C1 °H +CX-A־N=C=0 Cl-^J^-0-pH-CH-C(CH3 )ג----------->

XC1 O-CO-NH-^-Cl Cl-^-O-CH-CH-C(CHj )3 /IK״ ίί 1N nLJj

Le A 16 838 - 6 Reactions of triazolyl derivatives of the formula (II) with a ketene of the formula (V), according to process variant (c), can be formulated analogously.

The starting materials of the formula (II) are generally known (see German Offenlegungsschrift (German Published Specification) 2,324,010), Starting materials of the formula (II) that have not previously been described in the literature can be obtained in accordance with the processes already described, by, for example, reducing the corresponding ketone derinatives with aluminium isopropylate or with complex hydrides in the presence of a solvent.

The acid halides of the formula (III) are known or can be prepared in accordance with customary processes such as, for example, by reaction of carboxylic acids or their alkali metal salts with acid halides of phosphorus or sulphur. These methods are known from the general textbooks of organic chemistry.

The acid anhydrides of the formula (IV) are known or can be prepared in accordance with known processes such as, for example, by the action of acid chlorides on the alkali metal salts of the carboxylic acids. These processes are generally known.

The formula (V) provides a general definition of the ketenes required as starting materials in process variant (c). Here, R’ preferably represents hydrogen, alkyl with 1 to 7, especially 1 to 5, carbon atoms, alkenyl or alkynyl each with up to J carbon atoms, or halogenomethyl with 1 to 3 halogen atoms, especially fluorine and chlorine. The ketenes which can be used for the reaction are also known or can be prepared in accordance with known processes such as, for example, by

Le A 16 838 thermolysis of ketones or by dehydration of carboxylic acids (see Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry) volume 7/4, Georg Thieme Verlag).

The formula (VI) provides a general definition of the isocyanates required as starting materials in process variant (d). In this formula, R preferably represents alkyl with 1 to 4, especially 1 or 2, carbon atoms, or optionally sub- stituted phenyl, with halogen, nitro and cyano being the preferred substituents'.

Possible salts of the compounds of the formula (I) are salts with physiologically tolerated acids, especially the hydrogen halide acids such as hydrobromic acid and, especially, hydrochloric acid; phosphoric acid; nitric acid; monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid; and 1,5-naphthalene-disulphonic acid.

The salts of the compounds of the formula (I) can be obtained in a simple manner in accordance with customary methods of forming salts, for example by dissolving the base in ether, for example diethyl ether, and adding the acid, for example nitric acid, and can.be isolated in a known manner, for example by filtering off, and be purified if required.

Possible complexes of the compounds of the formula (1) are complexes with metal salts. In this context, metals of main groups (II) to (IV) and of sub-groups (!), (II) and (IV) to (VIII) should be mentioned, especially^copper, zinc, manganese, magnesium, tin, iron and nickel. Possible salts are salts with physiologically tolerated acids, especially

Le A 16 838 the hydrogen halide acids, such as hydrochloric acid and hydrobromic acid, as well as phosphoric acid, nitric acid and sulphuric acid.

The metal complexes of the compounds of the formula (I) can be obtained in a simple manner in accordance with customary processes, such as, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding it to the base. The complexes can be isolated in a known manner, for example by filtering off, and can, if required, be purified by recrystallisation.

Preferred solvents for the reaction according to process variant (a) are inert organic solvents, especially ketones, such as diethyl ketone and, especially, acetone and methyl ethyl ketone; nitriles, such as propionitrile and, especially, acetonitrile; ethers, such as tetrahydrofuran or dioxan; esters, such as ethyl acetate; aromatic hydrocarbons, such as benzene or toluene; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.

In carrying out process variant (a) the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 100°C, preferably between 20° and 85°C. If a solvent is present, the reaction is advantageously carried out at the boiling point of the particular solvent.

In carrying out process variant (a), equimolar quantities of the starting materials are preferably used. The compounds of the formula (I) are obtained in the form of their hydrohalides and can be isolated as such, by precipitating them by adding an organic solvent, for example hexane, filtering them off and, if required, purifying them by recrystallisation. !De A 16 8J8 - 9 -

V

The compounds of the formula (I) can also be isolated in the form of the free base, by adding aqueous sodium bicarbonate solution to the reaction mixture and isolating the base in accordance with customary methods.

Preferred diluents for the reaction according to process variant (b) are inert organic solvents, especially the solvents listed in connection with process variant (a); however, the acid anhydride of the formula (IV) used in each particular case may also be employed as the solvent.

Preferred catalysts which can be used in process variant (b) are customary acid and basic catalysts such as, for example, sulphuric acid, hydrogen chloride, hydrogen bromide, boron trifluoride, zinc chloride, sodium acetate, sodium benzoate, sodium carbonate, calcium oxide and magnesium oxide.

In carrying out process variant (b), the reaction temperatures can be varied within a fairly wide range. In general,_ the reaction is carried out at between 0° and 150°C and preferably between 80° and 120°C.

In carrying out process variant (b), equimolar quantities of the reactants are preferably used. However, for simplicity, the acid anhydride of the formula (IV) can also be used as the solvent, in which case an appropriate excess becomes necessary. The compounds of the formula (I) may be isolated in the usual manner.

Preferred diluents which can be used for the reaction according to process variant (c) are inert organic solvents, especially the solvents listed in connection with process variant (a).

In carrying out process variant (c), the reaction

Le A 16 858 - 10 temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between -10° and 70°C and preferably between 0° and 40°0.

Preferred diluents which can be used for the reaction according to process variant (d) are inert organic solvents, especially the solvents listed in connection with process variant (a).

Catalysts which can be used preferably in process variant (d) are tertiary bases, such as triethylamine and pyridine, or organo-tin compounds, such as dibutyl-tin dilaurate.

In carrying out process variant (d), the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 100°C and preferably between 20° and 40°C.

In carrying out process variant (d), equimolar quantities of the reactants are preferably used. To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up in accordance with customary methods.

The active compounds according to the invention exhibit a powerful fungitoxic and bacteriotoxic action. They do not damage crop plants in the concentrations required to combat fungi and bacteria. For these reasons, they are suitable for use as plant protection agents for combating fungi and bacteria. 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

Le A 16 838 -11fungi which attack above-ground parts of plants or attack the plants through the soil, and also against seed-borne pathogens.

The active compounds display a particularly good activity against parasitic fungi on above-ground parts of plants, such as species of Erysiphe and species of Venturia, and also against species of Pyricularia and species of Pellicularia. Good effects are achieved against the pathogens of bean rust (Uromvces phaseoli) and against fungi which cause powdery mildew diseases, such as, for example, the pathogen of powdery mildew of cereals (Erysiphe graminis) and of powdery mildew of apple (Podosphaera leucotricha), It is to be emphasised that the active compounds according to the invention not only display a protective action but also are curatively active, that is when used after infection has taken place. Furthermore, the systemic action of the compounds should be pointed out. Thus, it proves possible to protect plants against fungal attack if the active compound is supplied to the above-ground parts of the plant through the soil and the root or through the seed.

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 compounds according to the invention are well tolerated by plants. They have only a low toxicity to warm-blooded animals and, because of their low odour and their good toleration by human skin, they are not. unpleasant to handle.

The active compounds according to the present invention can be converted into the usual formulations, such

Le A 16 838 - 12 as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or slid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foamforming 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 diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 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 ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers, such as

Le A 16 8?8 - 13 I polyoxyothy.lene-fa.tty acid entero, polyoxyethylene-fatty alcohol others, for example alkylurylpolyglycol ethers, alkyl sulphonates!, alkyl, sulphates and aryl sulphonates, as well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl celJulose.

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, in the form of their formulations or in the use forms prepared therefrom by farther 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 wide range. In general, they are between 0.1 and 0.00001 per cent by weight, and preferably between 0.05 and 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 used.

For the treatment of soil, amounts of active compound of 1 to 1,000 g per cubic metre of soil, preferably of 10 to Le A 16 838 - 14 >' f

200 g, are generally used.

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 10 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 15 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. Example A Uromyces test (bean rust)/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 active compound in the spray liquor was mixed with the stated amount of the solvent and the ’ concentrate was diluted with the stated amount of water which contained the stated additives.

Le A 16 838 - 15 The young bean plants, which were in the 2-leaved stage, were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse for 24 hours at 20-22°C and a relative atmospheric humidity of 70% in order to dry. They were then inoculated with an aqueous uredospore suspension of the causative organism of bean rust (Uromvces phaseoli) and incubated for 24 hours in a dark humidity chamber at 20-22°C and 100% relative atmospheric humidity.

The plants were then set up in a greenhouse under intensive illumination for 9 days at 20-22°C and a relative atmospheric humidity of 70-80%.

days after the inoculation, the infection of the plants was determined. The ratings were converted to per□ent infection. 0% denoted no infection and 100% denoted that the plants were completely infected.

The active compounds, active compound concentrations and results can be seen from the following table:

Table A

Uromyces test/protective

Active compound Infection in % of the infection of the untreated control at an active compound con____________centration of 0,005% _xCH3 oh

Cl־V_>0-CH-CH-C(CH3 )359

A״ y 1F n!Li (known) /7\C1 9H ),59 C1 n*Li (known)

Le A 16 838

Table A (continued)

Uromyces test/protective

Active compound

Infection in % of the infection of the untreated control at an active compound concentration of 0.005^

(known)

/-ץ p-C0-CH3C1־/?\־O־CH-CH-C(CH3 )3

(51)

Le A 16 8J8 - 17 Table A (continued) (Uronivces test/protective)

Active compound Infection in % of the infection of the untreated control at an active compound concentration of ______________________________________ 0.0051¾_________

C1

0-C0-CH3 'y-O-CH-CH-CCCHj )3 _Jj (34) p-CO-NH-(׳_O-Cl

Cl/׳_y.0-CH-CH-C(CH3 )3

Λ . (2)

O-CO-CHj

O-CH-CH-C(CHS)j (6)

O-CO-CH3 ^J^-O-CK-CK-C (CKj )3 ( 9 )

O-CO-CHj D-CH-CH-C(CH3)3

Cl21 /' (9a)

0-00-(0¾ ).-CH, O-CH-CH-C(CHj )j Λ (0י>

>—zCl O-CO-NH-CH3 C1 V?/°־ch־ch-c(cH3 )3 Cl

Νl3 '3 (19)

Le A 16 858

Example B

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 additions.

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

days after the inoculation, the infection of the seedlings was determined. The ratings were converted to percent 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:

Le A 16 Θ3Θ

Table B

Podosphaera test (apple)/protective

Active compound Infection in % at an active compound concentration of _____________________________0.00031%

(known)

9-co-ch2-ch(ch3)2

Cl 0-CH-CH-C(CH3)נ

Λ 06)

Example 0-1

Shoot treatment test/powdery mildew of cereal/protective (leaf-destructive mycosis)

Le A 16 838 - 20 v

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 emulsifier 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 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°0 and 80-90% 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:

Le A 16 838

Table 0-1

<td colspan="3"> .Shoot treatment test/powdery mildew of cereal/protective</td>

<td> Active compounds</td><td> Active compound concentration in the spray liquor in $ by weight</td><td> Infection in /0 of the untreated control</td>

<td> untreated . OH</td><td> a</td><td> 100.0</td>

<td> I Q4־Cy0-CH-CH-C(CHj)5 0־ (known) _,C1 OH</td><td> 0.001</td><td> 60.0</td>

<td> //'Vo-CH-CH-CtCHj), ft KJ (known)</td><td> 0.001</td><td> 82.5</td>

p-CO-CH, α־^ο־οκ.αι.(!(α1,)50,001 0,0 ® Table C-1 (continued)

Shoot treatment test/powdery mildew of cereal/protective e£e 9τ

Active compounds

Active compound con- Infection in centration in the $ of the unspray liquor in $ by treated weight control

CHj\ O-CO-CHj

Cl-M0-CH-CH-C(CH,), c¥ A (u)

0.001 3.8

M U

I

0.001 50.0

-A O-CO-NH-CH,

H-O-M-CtCH,), (23)

Am iJ .

0.001 50.0

CHj O-CO-lffl-CH,

-O-CH-CH-C(CH,), (44)

0.001

41.3

Table 0-1 (continued)

Shoot treatment test/powdery mildew of cereal/protective

Active compounds Active compound con- Infection in $ centration in the of the untreated spray liquor in $ by control _____________________________ weight______________________________ ciu O-CO-NH-CHj

C1-H-O-CH־CH־C(CH3)5 0.001 25.0

A O xHCl (24)

(2?)

9τ

J* Table 01־ (continued)

Shoot treatment test/powdery mildew of cereal/protective

Active compounds Active compound con- Infection in centration in the of the unspray liquor in $ treated by weight control

<td>n f-CO-CHiCl d-^-O-CH-CH-CfCHj),</td><td> 0.001</td><td> 11.3</td>

(D s£e 9τ

Table C-1 (continued)

Shoot treatment test/powdery mildew of cereal/protective

Active compounds Active compound con- Infection in $ centration in the of the unspray liquor in Ί> by treated weight___________control Γ ΛΗ, O-CO-CHj

C1-M-O-CH-CH־C(CHj)j 0.0005 25.0 ׳ijf (52)

I

וס

I

0-00-0¾

0-CH-CH-C(CHj),

0.0005

25.0 (53) '

0-00-0¾

Gi-^^O-CH-CH-CtCHj);

(54)

0.0005

25.0 (D . Table C-1 (continued) e£Q 9τ

Shoot treatment test/powdery mildew of cereal/protective

<td rowspan="2"> Active compounds</td><td colspan="2"> Active compound con- Infection in centration in the $ of the unspray liquor in $ treated</td>

<td> by weight</td><td> control</td>

<td> 0-co-nhMci 01^./O-CH-CH-CiCHjV (2)</td><td> 0.001</td><td> 6.5</td>

Example 0-2

Shoot treatment, test/powdery mildew of cereals/curative (leaf-destructive mycosis)

To produce a suitable preparation of active compound, 5 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 emulsifier and then 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray 10 liquor.

To test for curative activity the procedure followed was analogous, but in the converse sequence, to that for testing for protective activity. The treatment of the single- . leaved young barley plants with the preparation of active 15 compound was carried out 48 hours after the inoculation, when the infection was already manifest.

After 6 days' dwell time, of the plants at a temperature of 21-22°C and 80-90% atmospheric humidity the occurrence of mildew pustules on the plants was evaluated. The degree of 20 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:

Le A 16 838 b Table 0-2 ο

> Shoot treatment test/powdery mildew of cereals/curative p

Active compounds Active compound concen- Infection in ® tration in the spray /0 of the un00 ___________________________ liquor in $ by weight treated control βδ

untreated

OH (known) '3

0.0025 r(e1 H0-ch5 α^־°-ΟΗ<Η-0(0Η3)3(5)

0.0025

100.0

25.0

0.0

0-CO-CHj

0.0025

0.0

Example

Powdery mildew of barley ־test (Ervsiphe graminis var. Hordei)/ systemic (fungal disease of cereal shoots)

The active compounds were used as pulverulent seed treatment agents. They were prepared by extending the particular active compound with a mixture of equal parts by weight of talc and kieselguhr to give a finely pulverulent mixture of the desired concentration of active compound.

For the treatment of seed, barley seed was shaken with the mixture of active compound and extender in a closed glass bottle. The seed was sown at the rate of 3 x 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a greenhouse. 7 days after sowing, when the barley plants had developed their first leaf, they were dieted with fresh spores of Ervsiphe graminis var. Hordei and grown further at 21-22°C and 80-90% relative atmospheric humidity and 16 hours' exposure to light. The typical mildew pustules formed on the leaves over the course of 6 days.

The degree of infestion was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denotes 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 infeetion.

The active compounds and concentrations of active compound in the seed treatment agent, as well as the amount used of the latter, and the percentage infection with mildew can be seen from the table which follows:

Le A 16 838 - 30 Table

Powdery mildew of barley test (Erysiphe graminis yar,hordei)/systemic

Active compounds Active compound con- Amount of Infection in centration in the dressing in % of the un________________________dressing in $ by weight g/kg of seed treated control without dressing - - 100.0־

OH (CH3)3C-f\0-CH-CH 3 3 Ο I \ , K 2100.0 10 ל

A.c(ch3)3 (known)

(known)

0-C0-CH3, Cl-^0-CH-CH-C(CH3)5 25 10 0.0

Al nUj (1)

Η σ>

ΚΛ CO

Table (continued)

Powdery mildew of barley test (Erysiphe gramlnis var, hordei)/systemic

Active compounds Active compound con- Amount of Infection in centration in the dressing in $ of the un____________________________dressing in t by weight g/kg of seed treated control

0-C0-CH2

Cl-^)-O-pi-CH-C(CHj)j

I υί

טז

O-CO-CHj-CHj

Cl-^-O-CH-CH-CtCH,), (27) /K

O-CO-CHjCl

Cl^-O-CH-CH-CtCHjj

Λ nLJj

O-CO-CH,

Cl4 (4) φ

853

Table (continued)

Powdery mildew of barley test (Erysiphe graminis var.hordei)/systemic

Active compounds Active compound con- Amount of Infection in centration in the dressing $of the undressing in $ by weight used in g/kg treated of seed control

O-CO-CHj

I^-O-CH־CH-C(CH,), zL (29)

2.5

0.0 υί υϊ

O. O-CO-CHj ), (50)

2.5

25.0

0-CO-CH,

Br-Q-O-CH-CH-C(CH,), (59)

0.0

Ά O-CO-CH, C1-Q-0-CH-CH-C(CHj)j (52)

A

0.0

8£8 9־C

Table (continued) . .

Powdery mildew of barley test (Erysiphe gramiuis van hordei)/systemic

Active compounds Active compound con- Amount of Infection in centration in the dressing $ of the undressing in $ by in g/kg treated _____________________________weight_________________of seed control ;1 0-C0-CH3

Cl-^Yo-CH-CH-ClCHj), 215 2 '°.

(40)

O-CO-CHj

F-^-O-CH-CH-CtCHj), 2.5 20.0

Λ .(41)

N—1

100.0

Example Ε;

Shoot treatment test/cereal rust/protective (leaf-destructive mycosis)

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 dimethylforamide and 0.06 part by weight of alkylaryl polyglycol ether emulsifier 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°0 and 100% relative atmospheric humidity.

After 10 days' dwell time of the plants at a temperature of 20°C and 80-90% atmospheric humidity, the occurrence of rust 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 rust infection.

The active compounds, active compound concentrations in the spray liquor and degrees of infection can be seen from the table which follows:

Le A 16 838

Table Ξ

Shoot treatment test/cereal rust/protective

Active compounds untreated

Active com- Infection pound conA in % of centration the unin the spray treated liquor in % control by weight

100.0 r-x PH (CH3 ^C-^^0-CH-CH-C(CH5 )30.0275,0 ל n!__ע (known)

0.025

0.0

O-CO-CHj

01-θ-0-ΟΗ-ΟΗ-0(ΟΗ3 )3 CH־ An n1—b (12)

0.025

0.0

O-CO-NH-CHj θ-^-0-0Η-0Η-0(0Η3 )3

Λ (18) n1—ע ,Cl 0-C0-CH3 /—( 1 , X0.01

Cl-0?>0־-CH-CH-C(CH3 )3 ^C1 '(40) <i if

13.8

8.8

Example Fi

Germinating capacity test/seed treatment/wheat

To prepare a suitable dry dressing, the active compound was diluted with a mixture of equal parts by weight of talc and kiebelguhr to give a finely pulverulent mixture

of the desired concentration of active compound.

For the dressing treatment, the wheat seed was shaken with the dressing in a closed glass bottle. The seed was sown at the rate of 2 x 100 grains in seed boxes on sterile 5 quartz sand. 5 cm of sterile brick grit was used as the covering layer. The boxes were set up in a greenhouse at a temperature of +15°C and were kept at a normal moisture.

The number of plants which had emerged on the 21st day characterised the germinating capacity of the seed under 10 the influence of the preparations. If this, value was markedly lower than that of the untreated control boxes, the germinating capacity had been impaired.

Table F

Germinating capacity test/seed treatment/wheat

Active compound Amount of Number active com- of emerged pound used plants, in in mg/kg of %, on the _________________________seed______21st day without dressing - 83.0

Cl-vA-0-CH-CH-C(CH3 )350052 •5 • q |N n!*J (known)

OH Br-^\\-0-CH-CH-C(CH3 )j 50060.0

A nL-Jj (known)

y—y y-CO-CH, Cl־vCy-0-CH-CH-C(CH3 )3 50072.0

le A 16 838

Example G

Phytotoxicity test/cucumbers

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95.0 parts by weight

The amount of active compound required for the desired active compound concentration in the spray liquor was mixed with the stated amount of the solvent and the concentrate was diluted with the stated amount of water, which contained the stated additives. Young cucumber plants were sprayed with the spray liquor until dripping wet. After they had dried, the plants were set up in a greenhouse at a temperature of +20°0 and about 70$ relative atmospheric humidity.

The plants were repeatedly evaluated with regard to damage. The evaluation was carried out on a 1-9 rating scheme. 1 denoted no damage and 9 denoted that the plant had been totally damaged or had died. The period of observation was, as a rule, 10 days.

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

Table G Phytotoxicity test

Active compound Damage at an active compound concen________________________tration of 0,2$_____

OH

C1-c3)-O-CH-CH-C(CH3 )3 5 n1—ע (known) /—OH C1<_y-°־CH-CH-C(CH3)3 5 /K, o (known)

Le A 16 838 - 38 Table G (continued) Phytotoxicity test

Active compound

Damage at an active compound concentration of

0.2%__

(known)

O-CO-CHj

CH-C(CH3 )3 (5) (j)-CO-CHs

C1^0-CH-CH-C(CH3)3 2 ω

-.01 0-C0-CH2-CH(CH3 )2

Cl-CjA-0-CH-CH-C(CH3 )3 nL_L1 (36)

0aN

/—VC1 O-CO-NH-C_J-C1 C1־0-(?\־CH-CH-C(CH3 )3

Λ (־)

Le A 16 838

Table & (continued)

Phytotoxicity test

Active compound

Damage at an active compound concentration of 0.2%___

O-CO-CHj <^#Α0-0ηΑ-0(0Η5 ’ ώ (6)

0-00-(0¾ )2-ch3 0-ch-ch-c(ch3)3

(j)-C0-NH-CH3 0-ch-ch-c(ch3)5

Le A 16 838

Example Η

Phytophtohoia test (tomatoes) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95.0 parts by weight

The amount of the 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 addtitions.

Young tomato plants with 2 to 4 foliage leaves were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20 °C and at a relative atmospheric humidity of 70 %. The tomato plants were then inoculated with an aqueous spore suspension of Phytophtora infestans. The plants were brought into a moist chamber with an atmospheric humidity of 100 % and a temperature of 18-20°C.

After 5 days the infection of the tomato plants was determined. The assessment data were converted to per cent infection: 0 % means no infection; 100 % means that the plants were totally infected.

The active compound, the concentration of the active compound and the results can be seen from the following table:

Le A 16 8J8

Table Η

Phytophthora test (tomatoes)/protective

Active compound

Infection in % at an active compound concentration (by weight of 0.0025 %

CH,-NH-CS-S , ' )Zn

CH^NH-CS-S' (known)

O-CO־NH-CH3

O-CH-CH-C(CH,), t כ כ

N (16)

Le A 16 838

Example I

Phytophthora test (tomatoes) / curative

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95.0 parts by weight

Young tomato plants with 2 to 4 foliage of water leaves were inoculated with an aqueous spore suspension of infestans. The plants remain for hours at 20

Phytophtora.

Q-, 1

C and at a relative atmospheric humidity of

After a short drying up time the plants.were sprayed with the spray liquor, which had been prepared in the manner stated above, until they were dripping wet. The plants were then brought into a moist chamber with an atomospheric humidity of 100 % and a temperature of 18-20 °C.

After 5 days the infection of the tomato plants was determined. The assessment data were converted to per cent infection: 0 % means no infection; 100 % means.that the plants werw totally infected.

The active compound, the concentration of the active compound and the results can be seen from the following table:

Le A 16 838

V ί

Table I

Phytophthora test (tomatoes) / curative

Active compound

Infection in % at an active compoud concentration of 0.025 %

CH2-NH-CS-S. ׳ yEn

CHg-NH-CS-s/ (known)

O-CO-NH-CHj <^>-£^-O-CH-CH-C (ch3 )3

17'

The process of the present invention is illustrated by the following preparative Examples.

Le A 16 838

Example 1:

__ ο - CO - CH, C1\^/־ 0 ־ CH - CH - C(CH3 )3 ό

Preparation in accordance with process variant (a)

8.0 g (0.1 mole) of acetyl chloride were added, at room temperature, to 29.5 g (0.1 mole) of l-(4-chlorophenoxy)-l[l,2,4-triazolyl-(.l)]-3,3-dimethyl-butan-2-ol in 100 ml of ethyl acetate. The mixture was then heated for 4 hours under reflux, allowed to cool and concentrated by distilling off the solvent in vacuo. The residue was taken up in benzene and the solution was washed with aqueous sodium bicarbonate solution and dried oyer sodium sulphate. The solvent was distilled off in a waterpump vacuum and the residue was recrystallised from n-hexane. 15 g (44.5% of theory) of 2acetoxy-1-(4״ohlorophenoxy)-1-[1,2,4-triazolyl-(l)]-3,3dimethyl-butane were obtained as an isomer mixture of melting point 86-93°C.

A pure stereoisomer of melting point 153-154°C could be isolated by recrystallisation from ethyl acetate. Preparation in accordance with process variant (b)

591 g (2 moles) of l-(4-chlorophenoxy)-1-[1,2,4-triazolyl(l)]-3,3-dimethyl-butan-2-01 in 1.2 1 of acetic anhydride were heated with 10 g of sodium acetate for 16 hours at 100°C. The solution was then cooled and stirred into 5 1 ofioe water, whilst keeping the temperature at 20° to 25°C. Asneary, crystalline mass precipitated, which was taken up in 2.5 1 of methylene chloride. The solution was washed with water and sodium bicarbonate solution, dried over sodium sulphate and concentrated in vacuo by distilling off the solvent.

Le A 16 83Θ - 45 674 g (100% of theory) of 2-acetoxy-l-(4-chlorophenoxy)-1[l,2,4-triazolyl-(l)]-3,3-dimethyl-butane were obtained as an isomer mixture of melting point 88-95°0.

On recrystallisation from 500 ml of ethyl acetate, a pure stereoisomer of melting point 149-153°C could be isolated. Preparation of the starting material

OH

Cl/'A- 0 - CH - CH - C(CH3)3 \בב/ I

587 g (2 moles) of l-(4-chlorophenoxy)-l-[l,2,4triazolyl-(l)]-3,3-dimethyl-butan-2-one were dissolved in 3 1 of methanol. A total of 80 g (2 moles) of sodium borohydride was added in portions of 5 g at 0° to 10°C, whilst stirring and cooling with ice, and the mixture was stirred for 2 hours at 5° to 10°C and then for 12 hours at room temperature. It was then cooled to 10°C and 300 g (3 moles) of concentrated aqueous hydrochloric acid were added at 10° to 20°C. After stirring for six hours, at room temperature, the suspension obtained was diluted with 3.8 1 of water which contained 400 g (4.8 moles) of sodium bicarbonate. The precipitate thereby produced was filtered off. 502 g (85% of theory) of l-(4-chlorophenoxy)-[1,2,4-triazoly1-(1)]-3,3dimethyl-butan-2-01 of melting point 112-117°C were obtained. Example 2:

- CO - NH -θ-Cl

- CH - CH - C(CH3)3

Preparation in accordance with.process variant (c)

A solution of 3.1g (0.02 mole) of 4-chlorophenylLe A 16 838 - 46 r

4isocyanate in 50 ml of ether and 3 drops of triethylamine was added to 6.6 g (0.02 mole) of l-(2,4-dichlorophenoxy)• l-[l,2,4-triazolyl-(l)]-J,3-dimethyl-butan-2-01 in 30 ml of ethyl acetate and 50 ml of absolute ether. The mixture 5 was left to stand for 48 hours at room temperature, the . solvents were distilled off in vacuo and the residue was recrystallised from petroleum ether/ether .(1:1). 4.8 g (50>t of theory) of 2-(4-chlorophenylcarbamoyl)-1-(2,4dichlorophenoxy)-1-[1,2,4-triazolyl-(1)]-3,3-dimethyl10 butane were obtained as an isomer mixture of melting point 183-184°C.

Example 3:

Salt formation S03 H

4.9 לי g (0.014 mole) of 1-(2-phenyIphenoxy)-1-[1,2,4triazolyl-(l)]-3,3-dimethyl-butan-2-01 in 30 ml of acetic anhydride were heated with 0.1 g of sodium acetate for 15 hours at 100°C. Thereafter, the mixture was allowed to cool and was stirred into 300 ml of water and extracted by shaking with 200 ml of chloroform. The chloroform solution was washed with four times 50 ml of water and once with 100 ml of saturated sodium bicarbonate solution, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo. 50 ml of acetone, in which 1.44 g of naphthalene-l,5-disulphonic acid were dissolved, were added to the residue, whereupon the salt precipitated in a crystalline form. 3.1 g (42% of theory) of 2-acetoxy-l-(2-phenylphenoxy)-l-[l,2,4-triazolyl-(l)]Le A 16 838 47 ־ -

3.3- dimethyl-butane naphthalene-l,5-disulphonate were obtained as a stereoisomer of melting point 213°C.

Example 4:

- co - ch3 CH-C(CH3)3012 (4) 2

Complex formation

8.8 g (0.03 mole) of l-(3-chlorophenoxy)-l-[l,2,4triazolyl-(l)]-3,3-dimethyl-butan-2-01 in 45 ml of acetic anhydride were stirred with 0.1 g of sodium acetate for 15 hours at 100°C. When the solution had cooled it was added to 450 ml of water and the mixture Was stirred for 15 hours at room temperature and extracted with three times 100 ml of methylene chloride. The combined organic phases were washed with 100 ml tf water and 100 ml of saturated sodium bicarbonate solution, dried over sodium sulphate and concen* trated by distilling off the solvent in vacuo. The residue was dissolved in 50 ml of ethanol. 2.4 g (0.014 mole) of copper dichloride in 7 ml of water were added. The mixture was concentrated in a waterpump vacuum, 100 ml of ethyl acetate were added to the residue and the crystalline precipitate formed was filtered off. 8.1 g (67% of theory) of bis- [2-acetoxy-l- (3-chlorophenoxy) -1- [1,2,4-triazolyl- (1)}-

3.3- dimethyl-butane]-copper(II) chloride were obtained as an isomer mixture of melting point 181-183°C.

The following compounds we obtained by methods analogous to those of the above Examples.

Le A 16 838 μ

» Ο-CO-Η ** Μ-O-CH-ffl-CtCHjJj (I),

<td rowspan="2"> υί 0)</td><td rowspan="2"> Example Ho.</td><td rowspan="2"> X η.</td><td rowspan="2"> R</td><td rowspan="2"> Position in which 'the l,2jMriazolyl radical Az is bonded</td><td colspan="2"> Melting point (°C)</td>

<td> Isomer mixture</td><td> pure stereoisomer</td>

M Position in which Melting point (°C) ® Example X R the 1,2,4-triazol- Isomer pure stereoNo. 11 yl radical Az is bonded mixture isomer q£q 9כד

J-CHj,4־Cl CH3 0) W

858

I

וע

I

<td rowspan="2"> Example No.</td><td rowspan="2"> X n</td><td rowspan="2"> R</td><td rowspan="2"> Position in which the 1,2,4-triazolyl radical Az is bonded</td><td colspan="2"> Melting point (°C)</td>

<td> Isomer mixture</td><td> pure stereoisomer</td>

<td> ׳25</td><td> 3>4-(CH־),</td><td> CHj</td><td> (1)</td><td></td><td> 182-84 Mcuci) £ 4</td>

e£9 9τ υι

I

<td rowspan="2"> Example No,</td><td rowspan="2"> A</td><td rowspan="2"> R</td><td rowspan="2"> Position in which the 1,2,4-triazolyl radical Az is bonded</td><td colspan="2"> Melting point (°C)</td>

<td> Isomer mixture</td><td> pure stereoisomer</td>

כר9

I

וט

<td> Example No.</td><td> X n</td><td> R</td><td colspan="3"> Position in which Melting point (°C) the 1,2,4-triazol- T yl radical Az is 1?0?61י bonded mture stere0־ isomer</td>

Table 11 (continued)

<td> tn co bi co</td><td> Compound No.</td><td></td><td> R</td><td> Position in which the 1,2,4-triazolyl radical Az is bonded ־ ־</td><td> Melting point (°C) Isomer mixture pure stereoisomer</td>

Table 11 (continued)

I

Compound ϊ D n .. .

., n « Position in.which the Meltins mint i°rl No. 1,2,4-triazolyl radical _ ™g point ( C)

Az is bonded Isomer mixture pure stereo____________ ison1er

_____________________________________________________________________ ׳ 55' 3־CF, CH,

-כ ׳

Table 11 (continued)

Compound Xn

No.

Position in.which the Melting point (°C) 1,2,4-triazolyl radical T . .

Az is bonded Isomer mixture pure stereo״ isomer

<td> 73</td><td> *0</td><td> -NH־C4H9-t</td><td> (1)</td><td> 120 (decpmp.) (Formal</td>

Contents26

38 members in 29 offices

This recordMember, by publication datePriority claim19 more offices are in the list below

Priority claims4

Priority claims
Document	Office	Kind	Date
2600799	Germany	A	1976-01-10
2600799	Germany	A	1976-01-10
26007998	–	–	–
DE19762600799	–	–	–

Members38

Family members, oldest first
Document	Office	Kind
PT66046A	Portugal	A	1977-02-01
IL51230A0	Israel	A0	1977-03-31
BE850239A	Belgium	A	1977-07-11
DK5877A	Denmark	A	1977-07-11
FI770045A	Finland	A	1977-07-11
FI770045A7	Finland	A7	1977-07-11
SE7700065L	Sweden	L	1977-07-11
NL7700143A	Netherlands (Kingdom of the)	A	1977-07-12
DE2600799A1	Germany	A1	1977-07-14
JPS5287170A	Japan	A	1977-07-20
FR2337719A1	France	A1	1977-08-05
BR7700076A	Brazil	A	1977-09-06
ZA77101B	South Africa	B	1977-11-30
TR18945A	Türkiye	A	1977-12-20
DD129395A5	German Democratic Republic (until 1990)	A5	1978-01-18
GB1505241A	United Kingdom	A	1978-03-30
PT66046B	Portugal	B	1978-06-22
AU2109477A	Australia	A	1978-07-13
SU621302A3	Soviet Union (until 1991)	A3	1978-08-25
PL101196B1	Poland	B1	1978-12-30
ATA7877A	Austria	A	1979-01-15
GR62062B	Greece	B	1979-02-19
NZ183028A	New Zealand	A	1979-03-16
US4145428A	United States of America	A	1979-03-20
EG12330A	Egypt	A	1979-03-31
AU502450B2	Australia	B2	1979-07-26
AT351863B	Austria	B	1979-08-27
CS195322B2	Czechoslovakia (until 1993)	B2	1980-01-31
IL51230AThis record	Israel	A	1980-02-29
CA1077943A	Canada	A	1980-05-20
PH14133A	Philippines	A	1981-03-03
HU176915B	Hungary	B	1981-06-28
CH629078A5	Switzerland	A5	1982-04-15
FI61699B	Finland	B	1982-05-31
FR2337719B1	France	B1	1982-07-09
FI61699C	Finland	C	1982-09-10
IT1077110B	Italy	B	1985-05-04
JPS6224425B2	Japan	B2	1987-05-28

1-phenoxy-1-(1,2,4-triazolyl)-3,3-dimethylbutan-2-ol ester their preparation and fungicidal compositions containing them

Abstract

Term

- CO - R

I

I

OH 1

OH

O-CO-CH3

V

C1

M U

I

-A O-CO-NH-CH,

-O-CH-CH-C(CH,), (44)

I

I

O-CO-CH,

0-CO-CH,

A

OH

N (16)

Q-, 1

OH

I

I

I

I

I

Priority claims4

Members38

Numbers

Titles

Classification