Metal complexes of azolyl ethers, their preparation and their use as fungicides

© Start of patent term: 1975 11 15 Longest possible duration:

© Issued on: 1976 08 25 © inventor:

© dependence:

OE 331568 © Pamphlets considered to delineate the prior art:

No. 331568

The invention relates to a fungicidal agent containing at least one new metal complex of an azolyl ether as an active ingredient.

It has already been disclosed that 1,2,4-triazole derivatives, such as 1- [1,2,4-triazolyl- (1)] - 1- (4'-chlorophenoxy) -3,3-dimethyl- Butan-2-one, a good fungicidal efficacy show (see German Laid-Open Publication 2 201 063). The effect of these substances is not always very satisfactory at low application rates and concentrations, and is inadequate especially in the case of non-mildew fungi.

It was found that the new metal complexes of Azolyläthem the general formula

<img file="AT331568B_D0001.tif" />

O-CH-BR (? H₂) n

Ai. k HjO (I)

Az in which Me for a metal, in particular for a metal of I., Π. and IV. to VfH. Subgroup or 10 for a metal of H. and IV. X is halogen, nitro, cyano, optionally substituted by halogen and / or hydroxy-substituted alkyl and optionally substituted by halogen, nitro, cyano and / or methyl, aryl, cycloalkyl, amino, carboxy, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, alkylthio, haloalkyloxy , Haloalkylthio, aryloxy, arylcarbonyloxy, benzoyl, halogehbenzoyl, alkylcarbonylamino,

Dialkylamino, alkylsulfonyl, alkylsulfonyloxy, arylsulfonyl and arylsulfonyloxy; Az represents a hido15-azolyl or a 1,2,4-triazolyl (1) or a l, 2,4-triazolyl (4) radical; CO or CH (OH), R is alkyl or, optionally substituted by halogen, nitro, cyano or methyl substituted aryl,

A is an anion of an inorganic acid, in particular chloride, bromide, iodide, nitrate, sulfate or phosphate anions, a is an integer from 0 to 5, n is an integer from 0 to 1, m is integers from 1 to 4, 1 stands for integers from 1 to 6, and k stands for any number from 0 to

12 has strong fungicidal properties.

The new active ingredients can be obtained when Azolyläther the aHgemeinen formula

X.

/ Vn- (0¾)

O-CH-BR (Π)

Az in which

X, Az, B, R, a and n have the abovementioned meaning, with metal salts of the general formula

Me aj. k H₂O, (EH) in which

Me, A, 1 and k are as defined above, in the presence of solvents, such as water,

Alcohols ketones or ethers, converts.

Surprisingly, the new metal complexes of azolyl ether in the fungicidal compositions show a significantly higher fungicidal activity, especially against fungi causing fungi and foliage, than the triazole derivatives known in the art, which are the closest active ingredients.

The agents according to the invention thus represent an enrichment of the art.

If l- [l, 2,4-triazolyl- (l)] - 1- (p-chlorophenoxy) -3,3-dimethyIbutan-2-one and copper H-chloride are used as starting materials, the course of the reaction can be followed by the following Formula scheme reproduced:

No. 331568

Cl - ^ - O-CH-CO-C (CH₃)₃ I +

CuCl>

>

NCu (Cl-O-CH-CO-C (CH₃);

-Nx'N

C1₂

The active ingredients are generally defined by the formula (I). In this formula, X is preferably alkyl and cycloalkyl having in each case up to 6 carbon atoms, halogenoalkyl having up to 2 carbon atoms and up to 5 halogen atoms, in particular fluorine and chlorine atoms, hydroxymethyl, furthermore preferably phenyl, halophenyl, such as Chlorophenyl, bromophenyl, fluorophenyl and phenyl-substituted phenyl, carboxy, alkoxycarbonyl and alkylcarbonyloxy, each having up to 5 carbon atoms in total, for alkoxy, alkylthio, Haloalkoxy and haloalkylthio having in each case up to 2 carbon atoms and up to 5 halogen atoms, in particular fluorine and chlorine atoms, then preferably phenoxy, benzoyloxy, chlorophenoxy, chlorobenzoyloxy, furthermore benzoyl and chlorobenzoyl, for dialkylamino having vor10 preferably up to 4 carbon atoms in total , for alkylsulfonyl and alkylsulfonyloxy each h aving up to 2 carbon atoms and finally preferably for phenylsulfonyl and phenylsulfonyloxy,

R radical represents straight-chain or branched alkyl having 1 to 6 carbon atoms and thus represents an optionally substituted or substituted phenyl radical, with halogen, such as fluorine and chlorine, the nitro, cyano and methyl groups being mentioned as preferred substituents are. The index of the numbers 0 to 4.

The starting materials of the formula (H) are known in part. Those 1,2,4-triazoles and imidazoles derivatives of the formula (Π) in which B represents the CO group and the subscript represents 0 can be synthesized, inter alia, by reacting with haloetherketones with 1,2,4-triazoles (See, for example, German Laid-Open Publication 2 201 063 and 2,105,490). On the other hand, the Azolyl ether the formula (Π) are not yet prior art.

Thus, one obtains those 1,2,4-triazole and imidazole derivatives in which in formula (H) for n is the number l and B is the CO group, if appropriately substituted quaternary ammonium iodides with the desired azoles in the presence of Solvents or diluents at temperatures between 20 and

150 ° C converts (compare herewith the manufacturing instructions).

The usable quaternary ammonium iodides are currently not part of the state of the art. They can be prepared by methylating and quaternizing appropriately substituted amines by conventional methods. The amines themselves are known in part. You can z. B. by Mannich reaction of ether ketones with formaldehyde and amine are prepared (see

J. Am. Chem. Soc. Volume 82 [1960], pp. 1867-1872).

The corresponding triazole and imidazole derivatives in which in formula (B) B represents the CH (OH) group are obtained by reducing the respective ketone derivatives (B = CO in formula (II)) by customary methods; for example, with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent or complex hydrides optionally in the presence of a polar

Solvents (compare to this the production instructions).

Still new starting materials of the formula (Π) can be prepared in a corresponding manner, as has been generally stated above.

The metal salts still required for the preparation of the new metal complexes are generally defined by the formula (HI). Here, Me as mentioned preferably for metals of the I., IL and IV. To 40 VHI. Subgroup and metals of Π. and IV. Main group, in particular for copper, zinc, manganese, magnesium, tin, iron and nickel. Index 1 preferably represents integers from 1 to 4 and k preferably represents any numbers from 0 to 8.

The metal salts of formula (HI) are well known, readily available compounds.

No. 331568

- 4 Suitable diluents for the reaction are water and all inert organic solvents. These include, preferably, alcohols, such as methanol and ethanol, ketones, such as acetone and ethers, such as diethyl ether and dioxane.

The reaction temperatures can be varied within a substantial range. In general, one works between 0 and 40 ° C, preferably between 15 and 25 ° C.

In the preparation of the active compounds, the stoichiometric amount (depending on the degree of oxidation of the metal) of the compound of the formula (H) is advantageously used for 1 mol of the metal salt (ΠΙ). Exceeding these ratios by up to 20 mol% can be done without significant yield reduction. The workup is carried out in a manner customary for organic compounds and generally known manner.

The new active ingredients have a strong fungitoxic action in the form of the agents according to the invention. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as active ingredients in crop protection products, for controlling fungi. Fungitoxic agents in crop protection are used to control Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The active substances used in the agents according to the invention have a very broad spectrum of activity and can be used against parasitic fungi which attack aboveground plant parts or attack the plants from the ground as well as seed-transmissible pathogens.

They have a particularly good effect against parasitic fungi on aboveground plant parts such as Plasmopara species, z. B. against the causative agent of powdery mildew of the wine (Plasmopara viticola), against the causative agent of powdery mildew on apples (Podosphaera leucotricha) and apple scab (Fusicladium dendriticum), against Piricularia oryzae and Pellicularia sasakii on rice, Puccinia reeondita and Erysiphe graminis on cereals, Hemileia vastatrix of coffee, MycosphaereUa musicola on bananas, Cercospora species on peanut.

The compositions of the invention are well tolerated by plants. They have only a low warm-blooded toxicity25 and are not unpleasant to the human skin because of their low odor and their good compatibility.

The new active ingredients are converted to the preparation of the agents in the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granules, these are prepared in a known manner, for. B. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents, the use of water as diluent z. B, organic solvents are also used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. B. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons, eg Freon; as solid carriers: natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as emulsifying and / or foam-forming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, eg Alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; as a dispersant: z. As lignin, liquors and methylcellulose.

The novel active ingredients may also be present in the formulations in admixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth promoters, plant nutrients and soil conditioners.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by weight.

The active ingredients are used in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is done in the usual way, eg by pouring, spraying,

Spraying, dusting, spreading, Trockieribeizen, wet pickling, Naßbeizen, Schlämmbeizen or encrusting.

When used as foliar fungicides, the drug concentrations in the formulations can be varied over a wider range. They are generally between 0.1 and 0.00001% by weight, preferably between 0.05 and 0.0001% by weight.

To mention is still a microbistatic and growth-regulating effect of some drugs of

No. 331568 general formula (I) containing agents.

The good fungicidal activity of the agents according to the invention is evident from the following tables.

Example 1: Plasmopara Test 5 Solvent: 4.7 parts by weight acetone

Dispersant: 0.3 parts by weight Alkyl-aryl polyglycol ether Water: 95 parts by weight Water

Mixing the necessary for the desired drug concentration in the spray liquid Wirkstaffmenge with the specified amount of the solvent and the concentrate is diluted with the specified

Amount of water containing these additives.

With the spray liquid splashed young pot fry (variety Muller-Thurgau) with 2 to 6Laübblättem to dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. Subsequently, the vine plants are inoculated with an aqueous spore suspension of Plasmopara viticola. The plants are placed in a humid chamber with a 100% humidity and at a temperature of 20 to 22 ° C.

Days after inoculation, grape infestation is determined as a percentage of untreated but also inoculated control plants.

0% means no infestation, 100% means that the infestation is just as high as in the control plants. Active ingredients, active agent concentrates and results are shown in the following table:

Table 1

Plasmopara test

<td>active substance</td><td>Infestation in% of the infestation of the untreated control at an active substance concentration of 0.0025%</td>

<td>__ z^CH3 // \ / Cl-2^_° ''^ch"^co^c_ch3 1 Vh₃¹¹ II N ¹¹(known) ci-o-ch-ch-co-c₃~ 7 1 ^ CHs Cl "- ^ N II II (known) __ /^CH3 \ Cu (Cl- / XO-CH-CO-C-CHg Cl, \ \ = / | \²1 ΌΗ3 / ,, / ^ N¹¹ II n</td><td>72 65 48</td>

No. 331568

T h e 11 e 1 (continued) Plasmopara test

<td colspan="3">active substance</td><td>Infestation in% of the infestation of the untreated control at a drug concentration of 0.0025%</td>

<td></td><td>z - /^CH3 \ Cu (ci -ZO-CH-CO-C-CH₃ ) \ ^x= / 1 ^{2 01}II ^Nii ii N - j</td><td>Cl₂</td><td>48</td>

Example 2: Podosphaera test (apple powdery mildew) / Protective

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

With the spray liquid splashed young apple seedlings, which are in the 4-6 leaf stage, 10 to the dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. They are then inoculated by probing with conidia of the powdery mildew pathogen (Podosphaera leueotricha) and in a greenhouse with a temperature of 21 to 23 ° C and a relative

Humidity of about 70% brought.

Days after inoculation, infestation of seedlings is determined as a percentage of untreated but inoculated control plants.

0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Drugs, drug concentrations and results are shown in the table below:

Table 2

Podosphaera test / protective

active substance

Infestation in% of the infestation of the untreated control at a drug concentration of 0.00062%

Cl

CH, -O-CH-CO-C ^ CH₃ , NCH₃

NN

Cu Br _ / v, \ _ /

OH CH₃

I /

CH-CH-C-CH₃

I ch₃ 'N

N (known)

Cl,

No. 331568

Table 2 (continued) Podosphaera test / Proteküv

active substance

Infestation in% of the infestation of the untreated control at an active substance concentration of 0.00062%

OH

CH,

Cu ClO-CH-CH-C-CHg

CH,

-N

Cl₂

ZnOo / CHa -O-CH-CO-C-CH3

I \

-Ν'CH, 'N

Cl₂

Example 3: Fusicladium test (apple soybean) / Protekü.v

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient necessary for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

With the spray liquid splashed young apple seedlings, which are in the 4-6 leaf stage, 10 to the dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. Subsequently, they are inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum Fuek.) And incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity.

The plants then come again for 14 days in the greenhouse.

15 Days after inoculation, infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants.

0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Drugs, drug concentrations and results are shown in the table below:

Table 3

Fusicladium test / protective

<td>active substance</td><td>Infestation% of infestation of the untreated control at an active substance concentration of 0.00125 0.00062%</td>

<td>-CK3 // ^/Cl- / O-CH-CO-C-CH₃\ = / \ 1 ch₃, N_XII ^NII</td><td>14 41</td>

<td>1 year</td><td></td>

<td>ΓΊ</td><td></td>

<td>(known)</td><td></td>

No. 331568

Table 3 (continued) Fusicladium Test / Protective

<img file="AT331568B_D0002.tif" />

The manner of preparation of the active ingredients contained in the agents according to the invention is explained in more detail in the following preparation:

Production rules:

1)

Mn ClO-CH-CO-C (CH₃)₃

<img file="AT331568B_D0003.tif" />

ci₂

H₂above (0.05 mol) manganese dichloride (MnCl₂ , 4 H₂O) are dissolved in 50 ml of ethanol and added with stirring to 29.3 g (0.1 mol) of l- [l, 2,4-triazolyl- (l)] - l-ft) -chlorphenQxy) -3,3- dimethyl-butan-2-one, dissolved in 100 ml of ethanol, added dropwise. The solvent is distilled off in a water-jet vacuum. The residue is mixed with 10 200 ml of ether and stirred for 15 h at room temperature. The desired product precipitates in the form of crystals, which are filtered off. This gives 28.3 g (76% of theory) of bis [l- (l, 2,4-triazolyl- (l) -1- (p-chlorophenoxy) -3,3-dimethyl-butan-2-one] Manganese (H) chloride dihydrate from Sohmp 218 to 222 ° C.

2)

mg

Cl-O-CH-CO-C (CH₃)₃ . &lt;^ΝχΝ

Ν '

Clo. 6HoO

No. 331568

10.2 g (0.05 mol) of magnesium dichloride (MgCl₂ · 6H₂O) are dissolved in 50 ml of ethanol and added with stirring to 14.7 g (0.05 mol) of 1 ~ [1,2,4-triazolyl- (l)] - 1- (p-chlorophenoxy) -3,3- dimethyl-butan-2-one dissolved in 100 ml

Ethanol, dripped. The solvent is distilled off in a water-jet vacuum and the oily residue is treated with ml of acetone. The mixture is stirred at room temperature for 15 h and the resulting crystalline end product is filtered off. This gives 22.2 g (90% of theory) of mono- [1- (1,2,4-triazolyl- (l) -l- (p-chlorophenaxy) -3,3-dimethyl-butan-2-one] -Magnesium (H) chloride hexahydrate of mp. 128 to 132 ° C.

3)

-O-CH-CO-C (CH₃)₃

Cl₂

N, 3.07 g (0.018 mol) of copper dichloride (CuCl₂ , 2 H₂O) are dissolved in 6 ml H₂Dissolved O and with stirring to 11.1g (0.033 mol) of l- (imidazolyl) -1- (p-bromophenoxy) -3,3-dimethyl-butan-2one, dissolved in 100 ml of ethanol ge10 drops. The precipitated Turktfaifoenen crystals are filtered off and washed with ether. This gives 12 g (99% of theory) of bis [l- (imidazolyl) -1- (p-bromophenaxy) -3,3-dimethyl-butan-2-one] - copper (!) Chloride of mp. 107-109 ° C.

4)

CuCl \ =: /

NO-CH-CO-C (CH₃)₃

<img file="AT331568B_D0004.tif" />

4.4 g (0.025 mol) of copper dichloride (CuCl ₂ «2 H₂O) are dissolved in 6 ml of water and added with stirring to 14.7 g (0.05 mol) of 1- [l, 2,4-triazolyl- (l)] -1- (p-chlorophenoxy) -3,3- dimethyl-butan-2-one, dissolved and added dropwise in 100 ml of ethanol. After stirring for one hour at room temperature, the turquoise crystals are filtered off. This gives 16 g (89% of theory) of bis [l- (l, 2,4-triazolyl- (l) -l- (p-ehlo: ^ henaxy) ~ 3,3-dimethyl-butan-2-one ] Copper (H) chloride of mp 103-104 ° C,

5)

<img file="AT331568B_D0005.tif" />

OH

I • O-CH-CH-C (CH₃)₃

Cl,, N_X

N20 4.4 g (0.025 mol) of copper dichloride (CuCl₂ , 2 H₂O) are dissolved in 20 ml of water and with stirring to g (0.05 mol) l- [l, 2,4-triazolyl (l)] - l- (p-bromo-phenoxy) -3,3-dimethyl Butan-2-ol, dissolved in 300 ml of ethanol, added dropwise. Concentrate the solution to half the volume and add 100 ml of water. It separates a green oil. The aqueous phase is decanted off and the organic phase is stirred with 80 ml of diisopropyl ether for 30 min. The green crystals are then sucked off. This gives 5.5 g (27% of

Theory) tetra- [1- (l, 2,4-triazolyl- (l) -l- (p-bromophenoxy) -3,3-dimethyl-butan-2-ol] copper (II) chloride of mp up to 95 ° C.

Preparation of the starting compound:

Br-0 ° OH

CH-CH-C (CH₃)₃ &lt;ⁿ^ n

N-¹¹

676 g (2 moles) of 1- [l, 2,4-triazolyi (l)] - 1- (p-bromophenaxy) -3,3-dimethyl-butan-2-one are dissolved in 31 moles of ethanol. For this purpose, 80 g (2 mol) of sodium borohydride are added at 0 to 10 ° C with stirring and ice cooling in portions of 5 g and 2 hbei 5 to 10 ° C, then 12 h at room temperature, stirred. 10

No. 331568 is cooled to 10 ° C and at 10 to 20 ° C, 300 g (3 mol) of concentrated aqueous hydrochloric acid are added. After six hours of stirring at room temperature, the suspension obtained with 3.8 1

Water containing 400 g (4.8 mol) of sodium bicarbonate, diluted. The resulting precipitate is filtered off. This gives 546.5 g (85% of theory) of 1- [1,2,4-triazolyl- (l)] -1- (p-bromophenoxy) -3,3-di5-methyl-butan-2-ol of mp 115 to 118 ° C.

6)

Zn \ __y ~ Ο-θ, Η-θΟ-Ο (CH₃3

<img file="AT331568B_D0006.tif" />

Cl₂

3.4 g (0.025 mol) ZnCl₂ are dissolved in 20 ml of ethanol and added with stirring to 16.8 g (0.05 mol) of 1- [l, 2,4-triazolyl- (l)] - l- (p-phenylphenoxy) -3,3-dimethyl- Butan-2-one, dissolved in 300 ml of ethanol, added dropwise. After stirring for 30 min at room temperature, the resulting precipitate is filtered off with suction and washed with a little ethanol 10. This gives 15 g (74% of theory) of bis [l, 2,4-triazolyl- (l) -1- (p-phenylphenoxy) -3,3-dimethyl-butane "2-one] zinc (n) chloride of mp 182 ° C.

7)

O-CH-CO-C (CH₃)₃ z

ci / N.

N ·

10.4 g (0.04 mol) of tin tetrachloride (SnCl₄) are added with stirring 24.6 g (0.075 mol) of 1- [1,2,4-triazolyl- (l)] -1- (2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one , dissolved in 200 ml of ethanol, added dropwise. Subsequently, the solvent is distilled off in a water-jet vacuum. To the residue, 50 ml of n-petane are added and allowed to stand at 0 ° C for four days. The colorless crystals deposited are then filtered off and washed with 20 ml of diisopropyl ether. This gives 29.9 g (87% of theory) of bis-il- (l, 2,4-triazolyl- (1) -1- (1,2,4-dichlorophenoxy) -3,3-dimethyl-butane-2 -on] -Zion (IV) chloride of mp 216-218 ° C.

8th)

sn _c, / / ​​\ / / /

CI

O-CH-CO-C (CH₃)₃ ch₂ , r^N^ N

6.5 g (0.025 mol) tin tetrachloride (SnCl4) are added with stirring to 17.1 g (0.05 mol) of 1- [l, 2,4-triazolyl- (1)] - 2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-one, dissolved in 100 ml of ethanol, added dropwise. It is stirred for 2 h at room temperature. The precipitated colorless crystals are filtered off and washed with 20 ml Diisopropyläther. This gives 23 g (97% of theory) of bis [l- (l, 2,4-triazolyl- (l) -2- (2,4-dichlorophenoxy) -4,4-dimethylpentan-3-one] - Tin (IV) chloride of mp. 235-236 ° C.

Preparation of the starting compound.

CI- / \ -O-CH-CO-C (CH ₃) ₃ \ = / \

CH,

CI, Ns' N

N-¹¹

22.6 g (0.0464 mol) of [2- (2,4-dichlorophenaxy) -4,4-dimethylpentan-3-one-yl] -diäthylmethylammoniumjodid are dissolved in 250 ml of anhydrous acetonitrile and thereto portionwise 10.4 g ( 0.15 mol) of 1,2,4-triazole

No.331568. After refluxing for 24 hours, the solvent is distilled off under reduced pressure. The oily residue is taken up in 500 ml of methylene chloride and twice with 600 ml

Extracted water. The organic phase is separated, dried over sodium sulfate and in vacuo from

Solvent freed. The oily residue is triturated with diisopropyl ether and then fixed. It is filtered off, washed well with diisopropyl ether and dried. This gives 10.3 g (64.2% of theory) of 1- [l, 2,4-triazolyl- (I)] - 2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentane-3- on of the Mp. 75 to 77 ° C.

The diethylmethylammonium iodide of the formula required for the above precursor

CI- ^ -O-CH-CO-C (CH₃)₃\ CH, ^C1 I Λ

N®

J®

<img file="AT331568B_D0007.tif" />

is made as follows:

234.2 g (0.9 mol) of 2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-one, 110 g (1 mol) of diethylammonium chloride and 45 g (1.5 mol) of paraformaldehyde are dissolved in Dissolved 300 ml of anhydrous ethanol. To this is added 2 ml of concentrated hydrochloric acid and the reaction mixture is refluxed for 2 h. After addition of a further 30 g (1 mol) of paraformaldehyde, the mixture is heated under reflux for a further 2 hours and then allowed to stand at room temperature overnight. The batch is poured into 1.21 of water and extracted with 1.5 liters of ether. The aqueous phase is adjusted to pjj 8 with ammonia solution and extracted again with 11 ether. The combined ether phases are dried over sodium sulfate and freed from the solvent in vacuo. The resulting yellow oil - 177 g (52.2% of theory) of [2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-one-yl] -diäthyl-ammonium chloride - does not crystallize and therefore further reacted as crude product.

38.1 g (0.1 mol) of [2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentane-3-one-yl] -diäthyl-ammonium chloride are dissolved in 200 ml of anhydrous tetrahydrofuran and 20.2 g (0.2 mol) of triethylamine was added dropwise at room temperature. After stirring for 15 minutes at room temperature, the precipitated triethylammonium chloride is filtered off and the solvent is distilled off in vacuo. This gives 30.9 g (90% of theory) of [2- (2,4-dichlorophenoxy) -4,4-dimethylpentan-3-one-yl] -diethylamine as a yellow oil which is immediately washed in 300 ml of water-free Acetonitrile dissolved (0.09 molar approach) is. For this purpose, 21.3 g (0.15 mol) of methyl iodide are added dropwise at room temperature and with stirring. The reaction mixture is stirred at room temperature for 1 h and under reflux for 30 min, after which the solvent is distilled off under reduced pressure. The oily residue is taken up in 200 ml of a mixture of ethyl acetate and methyl ethyl ketone (1: 1) and heated to boiling. This produces a crystalline residue, which is filtered off and washed with ether. This gives 22.8 g (51.6% of theory) of [2- (2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-one-yl] -diethylmethylammonium iodide of mp. 114 to 118 ° C.

Analogously to the rules 1 to 8 can be - in each case starting from suitable compounds (Π) and (HI) produce the following compounds of the general formula.

me

CH-BR (CH₂)_n / m

Ai

N12

No. 331568

<td>melting</td><td>ü O_, ll</td><td>© b- TH</td><td>185</td><td>142 - 143</td><td>109 - 111</td><td>117 - 120</td><td>© © rh © rh</td><td>136</td><td>183 - 185</td><td>105-107</td><td>206-209</td><td>192</td><td>125 - 128</td><td>130 - 132</td><td>141 - 143</td>

<td colspan="2">ι-l</td><td>eq</td><td>cq</td><td>cq</td><td>eq</td><td>cq</td><td>eq</td><td>eq</td><td>eq</td><td>cq</td><td>cq</td><td>eq</td><td>cq</td><td>eq</td><td>cq</td>

<td></td><td></td><td></td><td>i!</td><td>ι-l</td><td>i-i</td><td>F-4</td><td>1- &lt;</td><td>ι-ί</td><td>1-4</td><td>^ -4</td><td>^ 4</td><td>fH</td><td></td><td></td><td>1-4</td>

<td>&lt;!</td><td></td><td>ü</td><td>υ</td><td>ü</td><td>Ü</td><td>Ü</td><td>Ü</td><td>Ü</td><td>υ</td><td>O</td><td>O</td><td>ü</td><td>ü</td><td>ü</td><td>O</td>

<td colspan="2">9</td><td>cq</td><td>cq</td><td>cq</td><td>cq</td><td>cq</td><td>cq</td><td>"μ</td><td>"μ</td><td>cq</td><td>eq</td><td>cq</td><td>eq</td><td>eq</td><td>cq</td>

<td></td><td></td><td>CQ</td><td>"</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>eQ</td><td>JQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td>

<td></td><td></td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td>

<td rowspan="2">rt</td><td></td><td>rt</td><td>K</td><td>w</td><td>w</td><td>rt</td><td>rt</td><td>w</td><td>w</td><td>K</td><td>w</td><td>w</td><td>"</td><td>w</td><td>"</td>

<td></td><td>CJ</td><td>a</td><td>p.</td><td>p.</td><td>a</td><td>p.</td><td>p.</td><td>p.</td><td>a</td><td>p.</td><td>p.</td><td>a</td><td>a</td><td>a</td>

<td></td><td></td><td>O</td><td>Ό</td><td>ό</td><td>ü</td><td>ü</td><td>b</td><td>b</td><td>O</td><td>ü</td><td>ü</td><td>O</td><td>ü</td><td>O</td><td>O</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rt</td><td>rt</td><td>rt</td><td>w</td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">w</td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td>O</td><td>u</td><td>O</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>K</td><td>rt</td><td>w</td><td>K</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td>

<td></td><td></td><td>O</td><td>U</td><td>O</td><td>O</td><td>O</td><td>ü</td><td>O</td><td>υ</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>ü</td>

<td colspan="2">i *</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td><td>rt</td>

<td colspan="2">3</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>©</td><td>O</td><td>©</td><td>rh</td><td>©</td>

<td colspan="2">σί</td><td>rh</td><td>rh</td><td>eq</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>cq</td><td>rh</td><td>©</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>1 II</td><td></td><td></td><td></td><td>1 11</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td>CM</td><td>rh</td><td></td><td></td><td></td><td></td><td>CM</td><td></td><td></td><td></td><td>rh</td><td></td><td></td>

<td>X</td><td></td><td>ifc</td><td>O</td><td>O 1</td><td>fc fp</td><td>1 II |</td><td>ifc</td><td>i-l ü</td><td>O %</td><td>V 1</td><td>3</td><td>ü</td><td>O J</td><td>pq</td><td></td>

<td></td><td></td><td>4 &lt;</td><td>'ψ</td><td>cq *</td><td></td><td></td><td></td><td></td><td>'Tf *</td><td>'ψ</td><td></td><td></td><td>cq *</td><td>χμ</td><td></td>

<td>Φ</td><td></td><td>s</td><td></td><td>8th</td><td>3</td><td>d</td><td></td><td>8th</td><td></td><td>s</td><td>ö</td><td>3</td><td>3</td><td>3</td><td>3</td>

<td>§</td><td></td><td>ü</td><td>O</td><td>O</td><td>O</td><td>ü</td><td>ü</td><td>ü</td><td>O</td><td>O</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td>

<td>s</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CQ</td><td>fc</td><td>05</td><td>O</td><td>rh</td><td>cq</td><td>CO</td><td></td><td>©</td><td>©</td><td>b-</td><td>©</td><td>©</td><td>©</td><td>rh</td><td>eq</td>

<td>fc</td><td></td><td></td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>rh</td><td>cq</td><td>cq</td><td>cq</td>

<td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

No. 331568

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No. 331568