IL47294A

Metal complexes of imidazolyl and 1,2,4-triazolyl ethers, their preparation and fungicidal compositions containing them

Abstract

This record has no abstract on file.

IL47294A, drawing sheet 1 — Sheet 1 of 97

Term

No projected expiry on record.

19 claims: 11 independent, 8 dependent

1
What we claim is:10 Metal complexes of azolyl ethers of the general formula A T . k H 2 0 (!) in which M is copper, zinc, manganese, magnesium or tin, X is halogen, nitro, nitrile, amino, alkyl or cycloalkyl with in either case up to 6 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and up to 5 halogen atoms, hydroxymethyl, phenyl, halogenophenyl, phenyl-substituted phenyl, carboxy, alkoxycarbonyl or alkylcarbonyloxy with in either case a total of up to 5 carbon atoms, alkoxy or alkylthio with in either case 1 or 2 carbon atoms and up to 5 halogen atoms, phenoxy, benzoyloxy, chlorophenoxy, chlorobenzoyloxy, benzoyl, chlorobenzoyl, dialkylamino with a total of up to 6 carbon atoms, alkylcarbonyl^amino with a total of up to 4 carbon atoms, alkylsulfonyl or alkylsulfonyloxy with in either case 1 or 2 carbon atoms, phenylsulfonyl and phenylsulfonyloxy, Az is an imidazolyl radical, a 1,2,4-triazolyl-(1) radical or a 1,2,4-triazolyl-(4) radical, 47294/25) B is CO or CH(OH), R is alkyl with up to 6 carbon atoms or optionally phenyl substituted in o- or p-position with halogen, nitro, nitrile or methyl, A is chloride, bromide, iodide, nitrate, sulfate or phosphate anion, a is 0 or an integer from 1 to 4, n is 0 or 1, m is an integer from 1 to 4, 1 is an integer from 1 to 4, and k is an integer from 0 to 8. •
2
The compound of the formula (4)
3
The compound of the formula
4
The compound of the formula Zn (m 0-GH-00-C(CH 5 ) 3 (6)
5
The compound of the formula '
6
The compound of the formula
7
The compound of the formula Le A 15 649 47294/2
9
A process for the preparation of a compound according to any of claims 1 to *8, in which an azolyl ether of the general formula X a (CH ? ) (II), I 2 n Az in which X,. Az, B, R, a and n have the meanings stated in claim 1, is reacted with a metal salt of the general formula M A 1 . k H 2 0 (HI), in which M,־ A, 1 and k have the meanings stated in claim 1, in the presence of a solvent.
12
13. A process according to any of claims 9 to 12 , in which the reactants (11) and (III) are employed in stoichiometric amounts.
13
14. A process for the preparation of a compound according Le A 15 649 47294/2 to claim 1, substantially as hereinbefore described in any one of Examples 1 to 8,
15
16. A fungicidal composition containing as active ingredient a compound according to any of claims 1 to 8 and 15 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. 10
16
17. A composition according to claim 16 containing from 0.1 to 95% of the active compound, by weight.
17
18. A composition according to claim .17 containing from 0.5 to 90% of the active compound, by weight. !9. A method of combating fungi which comprises applying 15 to the fungi or a fungus habitat a compound according to any of claims 1 to 8 and 15 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 8 and 15 in admixture with a diluent or carrier. 20 20. A method according to claim 1θ in which a composition is used containing from 0,00001 to 0.1% of the active compound, by weight.
19
22. A method according to any of claims 19 to^21 in which the active compound is one of those hereinbefore mentioned in any of Examples A to 0, Le A 15 649 47294/2 23־. 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 according to any of claims 1 to 8 and 15 was applied alone or in admixture with a diluent or

Independent claims14

1,000 paragraphs in 136 sections, as filed

Metal complexes of imidazolyl and 1,2,4-triazolyl ethers, their preparation and. fungicidal compositions containing them

BAYER AKTIENGESELLSCHAFT

C. 45035

47294/jf .

The present invention relates to certain new metal complexes of azolyl ethers, to a process for their preparation and to fungicidal compositions containing them.

It has been disclosed that Ί,2,4-triazole derivatives, such as, for example,1-[1,2,4-triazolyl-(1)]-1-(41-chlorophenoxy)-3,3-dimethyl-butan-2-one, exhibit a good fungicidal activity (see German .Offenlegungsschrift (German .Published Specification) 2,201,063 which corresponds to Israel patent specification No. 41252). The effect of these compounds is not always entirely satisfactory if low amounts and low concentrations are used, and in particular is inadequate in the case of fungi other than mildews.

The present invention provides, as new compounds, the metal complexes of azolyl ethers of the general formula . k H20 (I)

Az in which

M is copper, zinc, manganese, magnesium or tin,

X is halogen, nitro, nitrile, amino, alkyl or cycloalkyl with in either case up to 6 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and up to 5 halogen atoms, hydroxymethyl, phenyl, halogenophenyl, phenyl-substituted phenyl, carboxy, alkoxycarbonyl or alkylcarbonyloxy with in either case a total of up to 5 carbon atoms, alkoxy or alkylthio with in either case 1 or 2 carbon atoms and up to 5 halogen atoms, phenoxy, benzoyloxy, chlorophenoxy, chlorobenzoyloxy, benzoyl, chlorobenzoyl, dialkylamino

with a total of up to 6 carbon atoms, alkylcarbonyl amino with a total of up. to 4 carbon atoms, alkylsulfonyl or alkylsulfonyloxy with in either case 1 or 2 carbon atoms, phenylsulfonyl and phenylsulfonyloxy,

Az is an imidazolyl radical, a 1,2,4-triazolyl-(D radical or a 1,2,4-triazolyl-(4) radical, t

B is CO or CH(OH) ,

R is alkyl with up to 6 carbon atoms or optionally phenyl substituted in o- or p-position with halogen, nitro, nitrile or methyl,

A is chloride, bromide, iodide, nitrate, sulfate or i phosphate anion, a is 0 or an integer from 1 to 4, n is 0 or 1, m is an integer from 1 to 4, is an integer from 1 to 4, and k is an integer from 0 to 8.

The compounds of the formula (I) exhibit powerful fungicidal properties.

The invention also provides a process for the preparation of a metal complex of the formula (1) in which an azolyl ether of the general formula

Az in which

X, Az, B, R, a and n have the above-mentioned meanings, is reacted with a metal salt of the general formula

47294/2 ‘

ΗΑχ . k H20 (HI), in which

M, A, 1 and k have the above-mentioned meanings, in the presence of a solvent.

Surprisingly, the metal complexes of azolyl ethers, according to the invention, exhibit a substantially greater fungicidal activity, especially against fungi responsible for leaf diseases and shoot diseases, than the triazolyl derivatives known from the state of the art which are the most closely related active compounds. The compounds according to the invention thus represent an enrichment of the art.

If 1-[1,2,4-triazolyl-(1)]-1-(]3-chlorophenoxy)-5,3dimethyl-butan-2-one and copper(ll) chloride are used as starting materials, the course of the reaction can be represented by the following equation:

47294/2/'

Some ofthe starting materials of׳the formula (11) are known. Those 1,2,4-triazole and imidazole derivatives of the formula (II), in which B represents the CO group and the index n represents 0, can inter alia be obtained by reaction of appropriately substituted halogenoether ketones with 1,2,4triazoles or imidazoles in the presence of an acid-binding agent and if appropriate in the presence of a diluent (see, on this topic, German Offenlegungsschriften (German Published Specifications) 2,201,063 and 2,105,490 which correspond, to Israel patent specification Nos. 41252 and 38687, respectively)J Other azolyl ethers of the formula (II) form the subject of German Patent Specification No. 23 486 63 and Israel patent specification Nos. 45769, 45770, 45133 and 44793.

Thus, those 1,2,4-triazole and imidazole derivatives of the formula (II) in which n is 1 and B is the CO group, are obtained by reacting correspondingly substituted quaternary ammonium iodides with the desired azoles in the presence of solvents or diluents at temperatures between 20° and 15θ°0 (see the preparative Examples herein).

The quaternary ammonium iodides !which can be used also currently do not yet form part of the state of the art. They can be prepared by methylating, and quaternising correspondingly substituted amines in accordance with customary methods. The amines themselves are in some cases known. They can be prepared according to customary methods, for example by Mannich reactions of ether ketones with formaldehyde and amine (see J. Am. Chem. Soc. 82 (i960), 1867-1872).

The corresponding triazole and imidazole derivatives, of the formula (II), in which B represents the CH(OH)- group, are obtained if the particular ketone derivatives (wherein B is CO in formula (11)) are reduced according to customary methods, for example with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent, or with complex, hydrides, optionally in the presence of a polar solvent (see the preparative Examples herein).

Starting materials of the formula (II) which are still new can be prepared analogously to the general description given above.

The following may be mentioned (see Tables 1 and 2) as examples of the starting materials of the formula (II) which can be used in accordance with the invention:

Table 1: Starting materials, which can be used according to the invention, of the general formula

X (CH,) (Ha)

2׳n

Le A 15 649 a η Y B R

Le A 15 649 a η

Y B R

4-CK3

4-CH(CH5)2

2-OH,, 4-01

4-CF3

2-01

0ו

2,4-01

CH^O-CO-

2,4,6-01

4-1 1 0

4-S02H5

4-S02-^^

4-CN

Le A 15 649 a η Y B R

4-0-50^0¾

4-00¾

4-0-00-0¾

4-0-00-^7^

4-NH-COCH^

4-00¾

3-N02 .

3-ON

3-Br

3-F

3-00¾

3-0¾

3־N(0H5)2

3-0-00-0¾ 3-0-00-A

2-N02

2-ON

2-0-00-0¾

2-0¾ 2-O-CO-A

2-F

Le A 15 649 - 9 a η Y B R

4-01 1 1 N

4-0¾ . 1 1 N

2-0¾, 4-01 2 1N

2,5-Cl 2 1N

2,4-01 2 1N

2.3- 0¾ 2 1N

3.4- 0¾ 2 1N

2.4- 0¾ 2 1N

4-N02 1 1N

2,4—01

4-80^0¾

4-S02-^i?

4-0-S02-CH5

4-00¾

4-0-000¾

?^/־4-0-00

4-NH-COCH^ 4-00¾ 4-N02

1N

1N וN ו ו n

1N

1. 1 N

1N

I 1N

IIN

1N

CO co co co co co co co co co co co co co co co co co co co

0(0¾¾ 0(0¾¾ 0(0¾¾ 0(0¾¾

0(0¾¾ 0(0¾¾ 0(0¾¾ 0(0¾¾ 0(0¾¾ c(ch3)3

0(0¾¾

0(0¾¾ .

co co co co co co

0(0¾¾ 0(0¾¾ 0(0¾¾ 0(0¾¾

0(0¾¾ 0(0¾¾

Le A 15 649

2-00-θ 11 Ν CO C(CH3)5

2-0-/<A 1 1 N CO C(CHz)z \—f 2 2

Le A 15 649 a η Y B R

4-Br

3- C1, 4-Ν02

2-0Η5, 5-Ν02

4- ΝΗ2

4-F

4—0 (ΟΗ^) j 2,4,6-01

2- 01

3- 01

2,6-01

4-Βγ, 2-01

4-/η\

4-ί

CO CO CO 00 CO

CO 00 co 00 co co co co co co co co co co co co co

סס co co c(ch3)3 c(ch3)3 c(ch5)3 c(ch5)3 c(ch3)5

c(ch5)5 c(ch5)5 c(ch5)5

Le A 15 649 a η Y B R

4-C00H

4-S02-GH5

4-S02

4-Hc0 ׳Q-CU2 ל

4-O-SO2-CH3

4-0CF5

4-O-CO-CH3

4-0-C0T׳i?

4-NH-COCH-j

4-OGHj 3־NO2

5-CN

5-Br

3-S'

3-OCH5 3-CH3 5-N(CH5)2 3-0-C0-CH5

2-N02

2-CN

2-O-CO-CH-j

Le A 15 649

X a n

2-CH5 2-0-00-/^0

2-F

2-00-/0

4-01

2,5-01

2,4-Cl

4-Br

4-F

2-C1

3-C1

4-CH5

2-CH5, 4-C1

2.3- CH3

3.4- CH3

2,4־CH5

4־N02

4-N02, 2-C1

2-01, 5-N02

2,4,5-Cl

CH2OH

4-C1

Le A 15 649 an Y B R

4-C1

4-S02CH3 4-S02

4-CN

4-O-SO2-CH3 4-00F3 4-O-CO-CH,

4-0-C0

4-NH-C0CH,

4-0CH3

3-NO2

3-CN

5-Br

3-F

3-OCH3 3-CH3 3־N(CH3)2

5-0-cq-ch3

3-N02

2-CN

1ו י

1ו

1ד

ו1

וו

ו1

Le A 15 649

X an Y B

2-O-CO-CH5

2-CH5 2-0-C0-/7?

2-F

2-CO

5-01

4-01

4-Br

4-F

2,4-01

2,6-01

4-C(CH5)3

2-01

2,6-01,

4<D ו

וο וο

2Ο

3Ο

ΟΟ

1Ο

4-S02H5

4-502-/7^

4-CN ο

ο ο

ו ο ο

R

0(0η5)3 ο(οη5)3 ο(οη3)3 0(0η3)3 α(0Η3)3 0(0η5)5

0(0η3)5 ο(οη3)3 cj(ch3)3 c(ch3)3 c.(0h3)3 c(oh3)3 (CH,)

3 נ

0(0 H3) 3 c(ch3)3 c(0h3)3 0(0h3)3 c(ch5)5 C(OH )

3 נ

0(0h3)5 o(oh3)5 c(ch3)3 c(ch3)3 c(ch3)3 c(0h3)3

Le A 15 649

4-00

4-0-S02-OH5

4-OCF,

4-0-aO-CH,

^)-4-0-00

4-NH-COCH3

4-0CH5

3-N02

3-CN

3-Br

3-F

3-OCH5 3-CK3 5-N(0H5)2 3-0-CO-CH.j

2-NO2

2-CN

2-0-C0-CH^

2-CH5 2-0-00-/^3

2-F

2-00-(z V

4־NO2

4-O(CH5)3 4-CH3

2-C1

Le A 15 649

5-C1 ו ON _ ο ο Ν

4-C1

4-01

4-C1

4-Βγ

2-0Η5, 4-01 3,4-0Η3 2,4,5-01

4-ΟΟ-Ο-ΟΗ^

4-(ζ^ , 2,6-01

42,4,6-01

4-SO2H5

4-ΟΝ

1Ο

1ο

1ο וο וο וο

2ο

3Ο

1Ο

3Ο

2Ο

1Ο

1ο וο

3ο

1ο

Le A 15 649 a η Υ Β

4-O-SOo-CH,

צ 2

4-OC?5

4-0-C0-CH3

^״״״ * ״3-N0

3-Br

3-F

5-OCHj

5-0-00-CH5

2-N02

2-CN .

2-0-C0-CH,

2-CH5

2-F

2-0-(0

2-CHj, 4-01

4-C1

2-01

2,4-01

0N וn

0N

0N וn

0N

10N

0N

0 .N

10N

0N

1N

OH OH

CHOH

OHOH

CHOH

CHOH c(ch5)5 u (H 3) 3 c(ch3)3 c(ch3)3 c(ch3)3 c(ch5)3 c(ch3)5 c(ch5)3 c(ch5)3 c(ch5)3 C(CH3)3 c(ch3)3 c(ch3)3 c(ch3)3 ’c(ch3)3

3(CH3)3 o(ch3)3 0(0h3)3 c(ch3)3 0(oh3)3 c(ch,) c(ch3)3 c(ch3)3 c(ch3)3 0(ch3)3 c(ch3)3 o(0h3)3 c(ch3)3

Le A 15 649

X a

Y B

R

2,5-Cl

OH OH

2,3-CH,

ג____

4- F

CHOH

2,4-Cl c(ch3)3 c(ch3)3 c(ch5)3 c(ch3)3

4-C1

4-SOrjCH,

CHOH

4-CN

4-co-r '

4-0-S0o-CH, . 5

4-OC?3

4-O-CO-CH3

4-0-00-/7¾

4-NH-00CH3

4-OCH3

3-N02

3-CN

3-Br

3-F

3-OCH3 3־CH3 3-N(CH3)2 3-o-co-ch3 3-O-CO-Z׳^

2-NO2

N

CHOH

Le A 15 649 a η Y B R

2-CN

2-0-C0-CH,

2-CH5

2-0-CO׳׳/־^

2-0-(0,

2-F

4-C1

2-01

3- 01

2,4-01

4- F

2-CH5, 4-01

ו ו

4-01 1

4-C0-^_^

4-0-S0o-GH7

4-OCF5

4-0-00-CH5

4-0-00-P

4-NH-C0CH5

ו.

c(ch3)3 c(ch5)5 0(ch3)5 C(CH,)

3 נ c(oh3)2 c(ch5)3 c(ch3)5 o(oh5)3 c(ch3)3 c(ch3)3

C(CH3)3 c(0h3)3 0(0h3)3 c(ch3)3

c(ch3)3 c(ch3)3 c(ch3)3 c(ch3)3 c(ch3)3 c(ch3)3 c(oh3)3 Q(ch3)3 0(ch3)3

Le A 15 649

X an

Table 2; Compounds, which can be used according to the invention, of the general formula

(lib)

Le A 15 649

X a η B

<td> The metal salts</td><td> of the</td><td> formula</td><td> (HI)</td><td> are generally</td>

known, easily accessible compounds.

Diluents which can be used for the reaction according to the invention are water and all inert organic solvents, especially alcohols, such as methanol and ethanol, ketones, such as acetone, and ethers, such as diethyl ether and dioxan.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 40°C, preferably between 15° and 25°C.

In carrying out the process according to the invention, the stoichiometric amount (depending on the oxidation level of the metal) of the compound of the formula (II) is employed per mole of the metal salts (III). It is possible to exceed these ratios by up to 20 mol % without significant reduction in yield. Working up is carried out in a generally known manner customary for organic compounds.

The active compounds according to the invention exhibit a powerful fungitoxic action. They do not harm crop plants

Le A 15 649

- ל2 in the concentrations required to combat 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 Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfect!.

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

They display a particularly good action against parasitary fungi on above-ground parts of plants, such as species of Plasmopara. for example against the pathogen of grape downy mildew (Plasmopara viticola), against the pathogen of powdery mildew of apple (Podosphaera leuchotricha) and of apple scab (Fusicladium dendriticum), against Piricularia oryzae and Pellicularia sasakii on rice, Puccinia recondita and Erysiphe graminis on cereals, Hemileia vastatrix on coffee, Mycosphaerella musicola on bananas and species of Cercospora on groundnuts.

The compounds according to the invention are well tolerated by plants. They only have a low toxicity to warmblooded 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 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 solid or liquefied gaseous diluents or carriers,

Le A 15 649 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 polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples

Le A 15 649 of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.

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% by weight of active compound, preferably from 0.5 to 90% by weight.

The active compounds can be used as such, in the form of 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 are used in the customary manner, for example by watering, spraying, atomising, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

When used as leaf fungicides, the active compound concentrations in the use forms can be varied within a substantial range. They are generally from 0.1 to 0.00001 per cent by weight, preferably from 0.05 to 0.0001%.

A microbistatic and growth-regulating action of some active compounds of the general formula (1) should also be mentioned.

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

Le A 15 649 fungi which comprises applying to the fungi or a fungus habitat 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 the formula (I) is illustrated in the following biotest Examples. Example A

Plasmopara Test

Solvent: 47־ parts by weight of acetone

Dispersant: 03־ 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 liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated dispersing agent.

Young potted vines (variety MWller-Thurgau) with 2-6 foliage leaves were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20°C and a relative atmospheric humidity of 70$־ The vines were subsequently inoculated, with an aqueous spore suspension of Plasmopara viticola. The plants were brought

Le A 15 649 into a moist chamber with an atmospheric humidity of 100% and a temperature of 20-22°C.

After 5 days, the infection of the vines was determined as a percentage of the untreated but also inoculated control plants. 0% means no infection, 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table:

Table A

Plasmopara test

Active compound Infection in % of the infection of the untreated control at an active compound concentration of 0.0025%

(known) he A 15 649

Table A (continued)

Plasmopara test

Active compound

Infection in % of the infection of the untreated control at an active compound concentration of 0.0025%

(11)

Example B

Podosphaera test (powdery mildew of apples) [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 emulsifier.

Young apple seedlings in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants reamined in a greenhouse for 24 hours at 20°C and at a

Le A 15 649 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°0 and at a relative atmospheric humidity of about 70%.

Ten days after the inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants.

0% means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following

Table:

Table B

Podosphaera test/protective

Active compound Infection in % of the infection of the untreated □ontrol at an active compound concentration of 0.00062%

Le A 15 649

47294/2 >

Table B (continued) Podosphaera test/protective

Active compound Infection in % of the infection of the untreated control at an active compound concentration of 0.00062%

Example C

Fusicladium test (apple scab) (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 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°C and at a relative atmos31a pheric humidity of 70$. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum Fuckel) and incubated for 18 hours in a.humidity chamber at 18-20°C and at a relative atmospheric humidity of 100%.

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

days after inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants.

0% means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table:

Le A 15 649

Table C

5 649

Fusicladium test/protective Active compound Infection in $ of the infection of the untreated control at an active compound concentration of _________________________________________________________________________0,0012¾¾ 0,00062¢

Table 0 (continued)

Fusicladium test/protective

649 5 1־

Active compound

Infection in $ of the infection of the untreated control at an active compound concentration of

0000125¢

0,00062^

(6)

La H e C (continued)

Fusicladium test/protective

Active compound Infection in $ of the infection of the untreated control at an active compound concentration of

--------—----._______________________OOOQ1250__________0,00002¢ _

34a

Example D

Sprout treatment test (mildew of wheat) (protective) (leaf destroying mycosis)

For the preparation of an active composition 0.25 parts by weight of active compound were dissolved in 25 parts by weight of dimethylformamide and 0.06 parts by weight of water in order to obtain the desired concentration of spray.

In order to test the protective effect, one-leaf wheat plants (Michigan Amber) were innoculated with a suspension of uredb spores of Puccinia recondita in a 0.1% aqueous agar suspension. After the spore suspension has started to dry, the wheat plants were sprayed with the spray liquid until dripping wet and the plants were placed for incubation into a greenhouse for 24 hours at about 20°C and a relative humidity of 100%.

After the plants were kept for 10 days at a temperature of 20°C arid a relative humidity of 80-90%, the infection of the plants with mildew was evaluated. The infection was determined as a percentage of the untreated control plants.

0¾ means no infection; 100% means that the infection was exactly as great as in the case of the untreated control plants.

The active compounds, the concentration of the active compounds in the spray liquid and the results can be seen from the following table: .

b Table D

Sprout treatment test (mildew of wheat) (protective)

Active compound concentration in infection in % the spray liquid of the untreated in % by weight control untreated

0.025 (known)

25.0 x2H2O

0.025

33.8

12.5

17.5 c Example E

Barley mildew test (Erysiphe graminis var. hordei ) (systemic) (fungal grain sprout disease)

The application of the active compounds is effected in powdery seed treatment agents. They are produced by extending the active compound with a mixture of equal parts of tald and diatomaceous earth׳ so as to obtain a fine powdery mixture of the desired concentration.

For the treatment of barley seeds, they are shaken together with the extended active compound in a closed glass bottle. The seeds are sown together with 3x12 grain at a depth of 2 cm in flower pots containing a mixture of one part per ־ ,/R volume of Fruhstorf unity earth and. one part per volume of quartz sand. Germination takes place under favourable conditions in the green house. Seven days after sowing, when the first leaf of the barley plhnts has developped, the plants are dusted with fresh spores of Erysphe graminis var. hordei and cultivated further at 21-22°C and 80-90% relative humidity under influence of light for 16 hours per day. Within six days typical mildew infection can be observed on the leaves of the plants.

0% means no infection, 100% means that the infection was exactly as great as in the case of the untreated controls.

The active compounds, the concentrations of the active compounds and the amount of their application as well as the percentage of mildew infection are shown in the following table:

d Table E

Barley mildew (Erysphe graminis var. Hordei) (systemic)

Active compound concentration amount of active infection of active can- carposition in in % of the pound in can- gAg seeds untreated position in % control per weight

UNTREATED

100

0 o

e Example F

Seed staining test (barley blight) (seed mycosis)

For the preparation of a dry staining agent the active compound is extended with a mixture of equal parts by weight of talc and diatomaceous earth so as to obtain a fine powdery mixture of the desired concentration.

For staining the baley seeds, which are naturally infected with barley blight (Ustilago nuda), are shaken together with the staining agent in a closed glass bottle. The seeds are sown together with 2x100 grain at a depth of 2 cm in seed boxes containing a mixture of one part per volume Fruhstorf unity earth and one part per volume quartz sand. The boxes are placed into a green house, kept at a temperature of about 18eC, kept normally humid and exposed to light for 16 hours per day. After 10 to 12 weeks the barley reaches the blossom stage and shows healthy and diseased ears, of barley.

After this time.the diseased ears of barley are determined as a percentage of the total ears formed. 0% means that all ears are infected.

The active compounds, the concentrations of the active compounds and the number of infected ears are shown in the following table:

־f Table F

Seed staining test (barley blight)

Active compound active compound amount of number of concentration in staining infected ears staining agent agent in in % of total in % by weight g/kg seeds ears untreated

6.5

5.6

g ־

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

Example 1 .

10g (0.05 mole) of manganese dichloride (MnClg 0 4 1^0) were dissolved in 50 ml of ethanol and the solution was added dropwise, whilst stirring, to 29.3 g (0.1 mole) of 1-(1,2,4triazolyl-(1)]-1-(2-chlorophenoxy)-3,5־diinethyl-butan-2-one, dissolved in 100 ml of ethanol. The solvent was distilled off in a waterpump vacuum. 200 ml of ether were added to the residue and the mixture was stirred for 15 hours at room temperature. The desired product separated out in the form of crystals, which were filtered off. 28.3 g (7b% of theory) of bis-[1,2,4-triazolyl-(1 )-1-(j)-chlorophenoxy )-3,5-dimethyl15 butan-2-one]manganese (II) chloride dihydrate of melting point 218-222°C were obtained־ Example 2

Le A 15 649

10.2 g (0.05 mole) of magnesium dichloride (Mg012 . b Η2θ) were dissolved in 50 ml of ethanol and the solution was added dropwise, whilst stirring, to H. 7 g (0.05 mole) of 1[1,2,4-triazolyl-(1 ) ]-1-(jB-chlorophenoxy)-3,3-dimethyl5 butan-2-one, dissolved in 100 ml of ethanol. The solvent was distilled off in a waterpump vacuum and 50 ml of acetone were added to the oily residue. The mixture was stirred for 15 hours at room temperature and the crystalline product which resulted was filtered off. 22.2 g (90% of theory) of mone(1-(1,2,4-triazolyl-(1 )-1-(j5-chlorophenoxy)-3,3-dimethylbutan-2-one]magnesium (II) chloride hexahydrate of melting point 128-132°C were obtained.

Example 3

(3)

3.07 g (0.018 mole) of copper dichloride (0uCl2 . 2 Η,,Ο) were dissolved in 6 ml of HgO and the solution was added dropwise, whilst stirring, to 11.1 g (0.033 mole) of 1(imidazolyl)-l-(2-bromophenoxy)-3,3-dimethyl-butan-2-one, dissolved in 100 ml of ethanol. The turquoise-coloured crystals which thereupon precipitated were filtered off and washed with ether. 12 g (99% of theory) of bis-[1-(imidazolyl)1 -(£-bromphenoxy)-3,3-dimethyl-butan-2-one]copper(II) chloride of melting point 1O7-1O9°C were obtained.

Le A 15 649

Example 4

4«4 g (0025־ mole) of copper dichloride (CuCl2 . 2 H20) were dissolved in 6 ml of water and the solution was added dropwise, whilst stirring, to 14. 7 g (0.05 mole) of 1-(1,2,45 triazolyl-(1)]-1-(£-chlorophenoxy)-3,3-dimethyl-butan-2-one, dissolved in 100 ml of ethanol. After stirring for one hour at room temperature, the turquoise-coloured crystals were filtered off. 16 g (89% of theory) of bis-[1-(1,2,4triazolyl-(1)-1-( j)-chlorophenoxy)-3,3-dime thyl-butan-2-one] copper (11) chloride of melting point 103-104°0 were obtained.

Example 5

4.4 g (0.025 mole) of copper dichloride (CuCl2 , 2 1^0) were dissolved in 20 ml of water and the solution was added dropwise, whilst stirring, to 17 g (005־ mole) of 1-(1,2,4triazolyl-(1)]-1-(2-bromophenoxy)-3,3-dimethyl-butan-2-ol, dissolved in 300 ml of ethanol. The solution was concentrated to half its volume and 100 ml of water were added. A green oil separated out. The aqueous phase was decanted off and the organic phase was stirred for 30 minutes with 80 ml of diisoLe A 15 649

4/ propyl ether. The resultant green crystals were then filtered off. 5-5 g (27% of theory) of tetra-/T-(1,2,4triazolyl-( 1.)-1-(2-bromophenoxy)-3,5-dimethyl-butan-2-ol] copper(II) chloride of melting point 92-95°C were obtained.

Preparation of the starting compound:

OH

O-CH-CH-C(CH^)

676 g (2 moles) of 1-(1,2,4-triazolyl-(1)]-!-(p-bromophenoxy)-J, J-dimethyl-bu.tan-2-one were dissolved in 5 1 of methanol־ A total of 80 g (2 moles) of sodium borohydride was added thereto, 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°0 and JOO g (J moles) of concentrated aqueous hydrochloric acid were added at 10 to 20°C. After stirring for six hours at room temperature, the resulting suspension was diluted with J.8 1 of water which contained 400 g (4.8 moles) of sodium bicarbonate. The precipitate thereby produced was filtered off. 546.5 g (85% of theory) of 1-(1,2,4-triazolyl-(1) ]1־-(j3-bromophenoxy)-5,3dimethyl-butan-2-i01 of melting point 115-118°C were obtained. Example 6

Le A 15 649

5.4 g (0.025 mole) of ZnCl2 were dissolved in 20 ml of ethanol and the solution was added dropwise, whilst stirring, to 16. 8 g (0.05 mole) of 1-[1 ,2,4-triazolyl-(1) ]-1-(])-phenyl phenoxy)-33׳-dimethyl-butan-2-one, dissolved in 300 ml of ethanol. After stirring for 30 minutes at room temperature, the resulting precipitate was filtered off and rinsed with a little ethanol. 15 g (74% of theory) of bis-[1,2,4-triazolyl (1)-1 -(2-phenylphenoxy)-3,3-dimethyl-butan-2-one]zinc(ll) chloride of melting point 182°C were obtained.

Example 7

10.4 g (0.04 mole) of tin tetrachloride (SnCl^) were added dropwise, whilst stirring, to 246־ g (0.075 mole) of 1[1,2,4-triazolyl-(1)]-1-(2,4-dichlorophenoxy)-33׳-di«Bethylbutan-2-one, dissolved in 200 ml of ethanol. The solvent was then distilled off in a waterpump vacuum. 50 ml of n-pentane were added to the residue and the mixture was left to stand for four days at 0°C. The colourless crystals which had separated, out after this time were filtered off and rinsed with 20 ml of diisopropyl ether. 29.9 g (37% of theory) of bis-[1-(1,2,4-triazolyl-(1)-1-(1,2,4-dichlorophenoxy)-3,3dimethyl-butan-2-one]tin(!V) chloride of melting point 216-218°C were obtained.

Le A 15 649

Example 8

65־ g (0.025 mole) of tin tetrachloride (SnCfa) were added dropwise, whilst stirring, to 17.1 g (0.05 mole) of 1[1,2,4-triazolyl-(1)]-2-(2,4-dichlorophenoxy)-4,4-dimethylpentan-3-one, dissolved in 100 ml of ethanol. The mixture was stirred for a further 2 hours at room temperature. The colourless crystals which had precipitated were filtered off and rinsed with 20 ml of diisopropyl ether. 25 g (97% of theory) of bis-[1-(1,2,4-triazolyl-(1)-2-(2,4-dichlorophenoxy)-

4,4-dimethyl-pentan-3-one].tin(rv) chloride of melting point 235-236°C were obtained.

Preparation of the starting compound:

22.6 g (0,0464 mole) of [2-(2,4-dichlorophenoxy)-4,4dimethyl—pentan-3-onyl]—diethylmethylan1monium iodide were dis— solved in 250 ml of anhydrous acetonitrile and 10.4 g (0.15 mol) of 1,2,4-triazole were added in portions. After heating for 24 hours under reflux, the solvent was distilled off under reduced pressure. The oily residue was taken up in 500 ml of methylene chloride and was extracted with twice 600 ml of water. The organic phase was separated off, dried over sodium sulphate and freed from the solvent in vacuo. The oil residue

Le A 15 649 was triturated with diisopropyl ether and thereafter solid!fiedo It was filtered off, well washed with diisopropyl ether and dried. 10.3 g (64.2% of theory) of 1-(1,2,4triazolyl-(1)]-2-(2,4-dichlorophenoxy)-4,4-dimethyl-pentan3-one of melting point 75-77°C were obtained.

The [2-(2,4-dichlorophenoxy)-4,4-dimethyl-pentan-3-onyl]diethylmethylammonium iodide of the formula

O-QH-CO-O(CH5)5

TH,

C2H5 |^c2H5 required for the preparation of the above intermediate was prepared as follows:

234.2 g (0.9 mole) of 2-(2,4-dichlorophenoxy)-4,4dimethyl-pentan-3-one, 110 g (1 mole) of diethylammonium chloride and 45 g (15־ moles) of paraformaldehyde were dissolved in 300 ml of anhydrous ethanol. 2 ml of concentrated hydrochloric acid were added and the reaction mixture was heated to the boil under reflux for 2 hours. After addition of a further 30 g (1 mole) of paraformaldehyde, the mixture was again heated for 2 hours under reflux and was then left to stand overnight at room temperature. The batch was poured into 1.2 1 of water and extracted with 1.5 1 of ether. The aqueous phase was adjusted to pH 8 with ammonia solution and again extracted with 1 1 of ether. The combined ether phases were dried over sodium sulphate and freed from the solvent in vacuo. The resulting yellow oil - 177 g (52.2% of theory)

Le A 15 649 of [2-(2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-onyl ] diethylammonium chloride - did not crystallise and was therefore reacted further in the form of the crude product.

38.1 g (0,1 mole) of [2-(2,4-dichlorophenoxy)-4,4dimethyl-pentan-3-onyl]-diethylammonium chloride were dissolved in 200 ml of anhydrous tetrahydrofuran and 20.2 g (0.2 mole) of triethylamine were added dropwise at room temperature. After stirring for quarter of an hour at room temperature, the triethylammonium chloride which had precipitated was filtered off and the solvent was distilled off in vacuo, 309־ g (90% of theory) of [2-(2,4-dichlorophenoxy)-

4,4-dimethyl-pentan-3-onyl]-diethylamine were obtained as a yellow oil, which was immediately dissolved in 300 ml of anhydrous acetonitrile (0.09 molar batch). 21.3 g (0.15 mole) of methyl iodide were added dropwise thereto at room temperature, whilst stirring. The reaction mixture was stirred for 1 hour at room temperature and for 30 minutes under reflux and thereafter the solvent was distilled off under reduced pressure. The oil residue was taken up in 200 ml of a mixture of ethyl acetate and methyl ethyl ketone (1:1) and the whole was heated to the boil. This produced a crystalline residue, which was filtered off and rinsed with ether. 22.8 g (51.6% of theory) of [2-(2,4-dichlorophenoxy)-4,4-dimethyl-pentan-3-onyl]-diethylmethylammonium iodide of melting point 114-118°C were obtained.

The following compounds of the general formula

Le A 15 649

were prepared by methods analogous to those described in

Examples 1 to Θ,

Le A 15 649 b

β . Example M׳I a η Y B R m A 1 Melting point

No. (M

6t9׳ S U

μ φ >

Example Μ ׳ I a n. Y

No.

Sn - 00 N

Sn 40 1 01־ N

Sn l-Q 1 0Ϊ flu 4-C1 1 0N

Si 27 Zn 4-011 0 I flu 40 101־ H flu 2,4-Cl 2 0CH

Sn 2,4-01 2 0CH

Zn 2,4-Cl 2. 0CH

B R m A 1 Noting point

C(OH5)5 2 Cl 4 184 - 187

CO C(CH5)5 2 Cl 4173

CO C(CE5)5 2 Cl 4 149 - 152 ¢0 2 Cl 2 146 149.

CO -φ 2 Cl 2205

CHOH φ 3 Cl 2 112-115

CO C(CH5)5 '2 Cl 2 190 - 193Z

CO C(CH3)5 2 Cl 4 90 - 110Z

CO C(CH5)5 2 Cl 2 90 - 1062

47294/2 4).

Contents136

53 members in 28 offices

This recordMember, by publication datePriority claim18 more offices are in the list below

Priority claims4

Priority claims
Document	Office	Kind	Date
2423987	Germany	A	1974-05-17
2423987	Germany	A	1974-05-17
742423987	–	–	–
DE19742423987	–	–	–

Members53

Family members, oldest first
Document	Office	Kind
IL47294A0	Israel	A0	1975-07-28
ATA371975A	Austria	A	1975-11-15
BE829124A	Belgium	A	1975-11-17
BE829191A	Belgium	A	1975-11-17
IE41065L	Ireland	L	1975-11-17
DK219175A	Denmark	A	1975-11-18
FI751429A	Finland	A	1975-11-18
FI751429A7	Finland	A7	1975-11-18
NO751571L	Norway	L	1975-11-18
SE7505596L	Sweden	L	1975-11-18
DK218575A	Denmark	A	1975-11-19
NL7505752A	Netherlands (Kingdom of the)	A	1975-11-19
NL7505751A	Netherlands (Kingdom of the)	A	1975-11-20
DE2423987A1	Germany	A1	1975-11-27
DE2424250A1	Germany	A1	1975-12-04
FR2271219A1	France	A1	1975-12-12
FR2271353A1	France	A1	1975-12-12
JPS50155574A	Japan	A	1975-12-15
JPS5116668A	Japan	A	1976-02-10
LU72483A1	Luxembourg	A1	1976-03-17
DD119123A5	German Democratic Republic (until 1990)	A5	1976-04-12
BR7503033A	Brazil	A	1976-04-13
BR7503036A	Brazil	A	1976-04-13
ZA753171B	South Africa	B	1976-04-28
ZA753172B	South Africa	B	1976-04-28
CH577489A5	Switzerland	A5	1976-07-15
AT331568B	Austria	B	1976-08-25
GB1451038A	United Kingdom	A	1976-09-29
AU8115775A	Australia	A	1976-11-18
US4005083A	United States of America	A	1977-01-25
ES437715A1	Spain	A1	1977-02-01
GB1464692A	United Kingdom	A	1977-02-16
ES437716A1	Spain	A1	1977-03-16
TR18370A	Türkiye	A	1977-05-01
PL97300B1	Poland	B1	1978-02-28
HU171714B	Hungary	B	1978-03-28
CS181178B2	Czechoslovakia (until 1993)	B2	1978-03-31
DK138180B	Denmark	B	1978-07-24
DK138180C	Denmark	C	1979-01-08
IL47294AThis record	Israel	A	1979-01-31
SU654145A3	Soviet Union (until 1991)	A3	1979-03-25
FR2271219B1	France	B1	1979-03-30
FR2271353B1	France	B1	1979-04-13
CA1053420A	Canada	A	1979-05-01
IE41065B1	Ireland	B1	1979-10-10
IT1035758B	Italy	B	1979-10-20
IT1038170B	Italy	B	1979-11-20
DE2424250B2	Germany	B2	1981-01-22
DE2424250C3	Germany	C3	1981-11-12
DE2423987C2	Germany	C2	1986-01-16
JPS6110476B2	Japan	B2	1986-03-29
NL180105B	Netherlands (Kingdom of the)	B	1986-08-01
NL180105C	Netherlands (Kingdom of the)	C	1987-01-02