PL97300B1

Metal complexes of azolyl ethers,their preparation and fungicidal compositions containing them

Abstract

1451038 Metal complexes of azolyl ethers BAYER AG 2 May 1975 [17 May 1974 18 Feb 1975] 18466/75 Heading C2C Novel metal complexes of azolyl ethers having the formula in which M is a metal, X is halogen, nitro, nitrile, optionally substituted alkyl, optionally substituted aryl, cycloalkyl, amino, carboxyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, alkylthio, halogenoalkoxy, halogenoalkylthio, aryloxy, arylcarbonyloxy, benzoyl, halogenobenzoyl, alkylcarbonylamino, dialkylamino, alkylsulphonyl, alkylsulphonyloxy, arylsulphonyl or arylsulphonyloxy, Az is an imidazolyl radical, a 1,2,4-triazolyl-(1) radical or a 1,2,4-triazolyl-(4) radical, B is CO or CH(OH), R is alkyl and optionally substituted aryl, A is an anion of an inorganic acid, a is 0 or an integer from 1 to 5, n is 0 or 1, m is 1 to 4, l is 1 to 6 and k is 0 to 12, are prepared by reacting an azolyl ether of the formula with a metal salt of the formula: MA l . kH 2 O in the presence of a solvent, suitably at a temperature of from 0‹ to 40‹ C. The novel compounds possess fungicidal properties.

PL97300B1, drawing sheet 1 — Sheet 1 of 4

Term

Term ended

Expired 15 May 1990, 36.4 years ago.

1 claim: 1 independent, 0 dependent

1
Zastrzeżenie paten towe Środek grzybobójczy, znamienny tym, że jako substancję Czynną zawiera związek metalokompleksowe eterów azolilowych o wzorze 1, w którym w Me oznacza atom metalu, X oznacza atom chlorowca, grupę nitrową, cyjanową, ewentualnie podsta36 wiony rodnik alkilowy i arylowy, cykloalkilowy, grupę- aminową, karboksylową, alkoksykarbonylową, alkilokarbonyloksylową, alkoksylową, alkilotio, chlorowcoalkrksylrwą, chlorrwcoalkilotio, aryloksylową, arylokarbonyloksylową, benzoilową, chlorowcobenzoilową, ' alkilokarbonyloaminową, dwualkiloaminową, alkilosulfenylową, alkilosulfonyloksylową, arylosulfonylową i arylosulfenyloksylową, Az -oznacza grupę imidazolilową lub l,2,4-triazolilową-(l) lub l,2,4-triazo>lilową-(4), B oznacza CO lub CH(OH), R oznacza rodnik alkilowy i ewentualnie podstawiony rodnik arylowy, A oznacza anion kwasu nieorganicznego, a oznacza liczby całkowite 0—5, n oznacza liczby całkowite 0—1, m oznacza liczby całkowite 1—4, 1 oznacza liczby całkowite 1—6 i k oznacza dowolne liczby 1—12, oraz znane nośniki i/lub substancje powierzchniowo-czynne. 97 300 Związki o wzorze 23 97 300 O-CH-B-R C? H z)n X., Me χ kH^O Wzór 3 Wzór 6 Schemat 97 300 Wzór 10 OH CH« I / 5 O-CH-CC-C-CH, (f%N CH 3 N—1 Wzór 12 97 300 97 300 Cl W.Z.Graf. Z-d Nr 2, zam. 845/78, A4, 90 Cena 45 zł

549 paragraphs in 1 section, as filed

<td>POLAND REPUBLIC CHINA</td><td>PATENT DESCRIPTION</td><td> 97300</td>

<td></td><td>Additional Patent</td><td>MKP</td>

<td>ace</td><td>to patent no. -</td><td>AON 9/22</td>

<td></td><td>Reported: 15.05.75 (P. 180399)</td><td></td>

<td></td><td>Priority: 17.05.74 Federal Republic</td><td>Int. C1.2</td>

<td>OFFICE</td><td>German</td><td>A01N 9/22</td>

<td>PATENT</td><td>The application was announced on February 14, 77</td><td></td>

<td>HALF</td><td>Patent description published: 30.12.1978</td><td></td>

Inventor> Patent holder Bayer Aktiengesellschaft Leverkusen (Federal Republic of Germany)

Fungicide l

The present invention relates to a fungicide containing as active ingredient new metal complex compounds of azoHl ethers.

It is already known that 1,2,4-triazole derivatives, e.g. 1- [1,2,4-triazolyl- / 1-] - 4'-chlorophenoxy / -3,3-dimethylbutanone-2 have very good activity fungicides (German Patent DOS No. 2 201 063).

The action of these substances at lower doses and concentrations is not always satisfactory and insufficient, especially for non-powdery mildew fungi.

It has been found that new metal complexes of azolyl ethers of formula 1, in which Me is a metal atom, X is a halogen atom, a nitro, cyano group, an optionally substituted alkyl, aryl, cycloalkyl, amino, carboxyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy group, alkylthio, haloalkyloxy, haloalkylthio, aryloxy, arylcarbonyloxy, benzoyl, halobenzoyl, alkylcarbonylamino, dialkylamino, alkylsulfonyl, alkylsulfonyloxy, arylsulfonyl and arylsulfonyloxy, Az is an imidazolyl or 1,2,4-thiazolyl / 1, or 1,2,4-triazolyl-4, B is CO or CH / OH /, R is an alkyl radical and an optionally substituted aryl radical , A is an anion of inorganic acid, and means integers 0-5, n means integers 0-1, m means integers 1-4, 1 means integers 1-6 and k means any numbers 0-12, have a strong fungicidal effect .

New metallocomplex compounds of the formula I are obtained by reaction of azolyl ethers 5 formula 2, in which X, Az, B, R, and n are as defined above, with metal salts of formula 3 in which Me, 1 and K are as defined above, in a solvent environment. Metallocomplex compounds of azolyl ethers with formula vect10 they have a surprisingly much better fungicidal effect, especially on fungi that cause leaf and shoot diseases than triazole derivatives known in the art, which are similar active substances.

] 5 These substances therefore enrich the state of the art.

In the case of using 1- [1,2,4-triazolyl- / 1- -] - 1 / p-chlorine ofenoxy / -3,3-dimethylbutanone-2 and copper chloride as starting compounds, the reaction is shown in the scheme given in

2o drawing.

Azolyl ethers used as starting materials are generally represented by the formula 2. In this formula, X is preferably a halogen atom, a cyano, nitro, amino group, an alkyl and cycloalkyl radical containing up to 6 carbon atoms, a haloalkyl group containing up to 2 carbon atoms and up to 5 atoms halogen, especially fluorine and chlorine, the hydromethyl group is further preferably a phenyl, halogenphenyl radical, e.g. chlorophenyl, bromophenyl, fluorophenyl, substituent 800

300 a phenyl-substituted phenyl radical, a carboxy, alkoxycarbonyl and alkoxycarbonyloxy group, having a total of up to 5 carbon atoms, an alkoxy group, an alkylthio, a haloalkoxy and a haloalkylthio with up to 2 carbon atoms; up to 5 halogen atoms, especially fluorine and chlorine, in addition phenoxy, benzoyloxy, chlorophenoxy, halobenzoyloxy, furthermore benzoyl and chlorobenzoyl, dialkylamino, preferably up to a total of 4 carbon atoms, alkylsulfonyl, alkylsulfonyloxy containing up to 2 carbon atoms and in addition phenylsulfonyl and phenylsulfonyloxy, R is preferably a straight or branched alkyl radical with 1-6 carbon atoms and a phenyl radical optionally substituted in ortho or para position, preferably halogen, e.g. fluorine, chlorine, nitro, cyano or methyl. The index a preferably denotes the numbers 0-4.

The starting materials of formula 2 are partially known. The 1,2,4-triazole and imidazole derivatives of the formula II in which B is the CO group and the index n the number 0 can be obtained, for example, by the reaction of suitably substituted halogen ether ketones with 1,2-4-triazoles or imidazoles against an acid acceptor (descriptions German Patent DOS No.

201 063 and 2 105 490).

1,2,4-riazole and imidazole derivatives of the formula II, in which n is the number 1 and B is the CO group, is obtained by reacting appropriately substituted quaternary ammonium iodides with selected azoles in an environment of solvents or diluents in temperature 20-150 ° C (manufacturing examples).

The quaternary ammonium iodides used can be obtained by methylation and quaternization in a known manner appropriately substituted 10 amines. The amines themselves are partially known.

For example, they can be prepared in a known manner by Mannich reaction of ether ketones with formaldehyde and amine J. Am. Chem. Soc. 82 (1960), 1867-1872.

The corresponding triazole and imidazole derivatives of the formula II in which B is the CH / OH group is obtained by reducing the corresponding ketone derivatives (B = CO in the formula 2) in a known manner. For example, it is reduced with hydrogen over a catalyst and optionally in a polar solvent environment or complex hydrides optionally in a polar solvent environment (preparation examples).

The new starting materials of formula II can be prepared in a manner analogous to the above.

Tables 1 and 2 give, for example, the starting compounds of formula 4 used.

Table 1

Compounds of formula 4 used as starting materials

300

<td>4-CBHB-ABOUT-</td><td> 1</td><td> 0</td><td>N</td><td>What</td><td>C (CH,),</td>

<td>4_SOandC, H6</td><td> 1</td><td> 0</td><td>N</td><td>What</td><td>C (CH,),</td>

300

<td>3-F</td><td> 1</td><td> 1</td><td>N</td><td>What</td><td>C (CHand), .</td>

<td>2-CH</td><td> 1</td><td> 1</td><td>N</td><td>What</td><td>C (CHand).</td>

<td>4-Cl-CeH5</td><td> 1</td><td> 0</td><td>CH</td><td>What</td><td>C (CHand)and</td>

<td>4-NO2</td><td> 1</td><td> 0</td><td>CH</td><td>What</td><td>C (CHand).</td>

300

<td>4-H5C2ABOUT WHAT-</td><td> 1</td><td> 0</td><td>CH</td><td>WHAT</td><td>C (CH3)</td>

300

<td>2-0-CgHg</td><td> 1</td><td> 1</td><td>CH</td><td>What</td><td>C (CHand),</td>

300

<td>4-SOeCH3</td><td> 1</td><td> 0</td><td>N</td><td>CHOH</td><td>C (CH3)3</td>

300

<td>2-NO2</td><td> 1</td><td> 1</td><td>N</td><td>CHOH</td><td>C (CHand),</td>

<td>4-SOand-CeHB</td><td> 1</td><td> 1</td><td>CH</td><td>CHOH</td><td>G (CH3)8</td>

800

Compounds of formula 5 used as starting materials

The metal salts used to make the metal complex compounds are generally represented by Formula 3.

In this formula, Me is preferably metals 1,

II and IV to V ^^ I side groups and metals of II and IV main group, especially copper, zinc, manganese, magnesium, tin, iron and nickel, A is preferably chloride, bromide, iodide, nitrate, sulfate, phosphate anion. The index is preferably integers 1-4 and R is rootsany tables Eczbs 0—8. 40

Metal salts of formula 3 are generally known and can be easily prepared.

In the reaction for the preparation of the compounds of formula I, water and all inert solvents, preferably alcohols, e.g. 45 tanol and ethanol ketones, e.g. acetone and ethers, e.g. ethyl ether and dioxane.

The reaction temperature may vary widely. In general, the reaction is carried out at a temperature of 0-40 ° C, preferably 15-25 ° C.

When carrying out the reaction per 1 mole of the metal salt of formula '5, a stoichiometric amount (depending on the degree of metal oxidation) of the compound of formula 2 is introduced. Exceeding these ratios to 20 · mol · does not significantly reduce the yield M. The final treatment is carried out in the usual manner for organic compounds.

The active substances of the agent according to the invention have strong fungicidal activity. At the concentrations used to combat fungi, they do not damage crop plants. For these reasons, they are used in plant protection products to control fungi. Fungicides in plant protection are used to control Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti. The active substances have a very broad spectrum of activity and can be used against parasitic fungi, infesting aerial parts of plants, found in soil and transmitted by seeds. They work, especially on fungi that parasitize above-ground parts of plants, e.g. Plasmopara species, e.g. Vine downy mildew (Plasmopara viticola) and apple powdery mildew (Podspohaere leucotricha) and scab (Fusiciadium dendriticum and Piricularia oryzae and Pellicularia soesakii on rice, Puccinia reconditais, Erysachlau on peanuts).

The active substances are well tolerated by plants, and are slightly toxic to warm-blooded animals, moreover, because they have a slight odor and are 'well tolerated by the skin, they do not create difficulties in manipulation.

The active substances of the formula I can be converted into conventional kits in the form of solutions, emulsions , suspensions, powders, pastes and granules. They are obtained in a known manner, e.g. by mixing active substances with diluents, i.e. liquid solvents, liquefied under pressure, gases and / or solid carriers, optionally using surface-active substances such as emulsifiers and / or dispersants, and / or foaming agents.

When using water as the diluent, organic solvents serving as auxiliary solvents can be used, for example. Essentially, aromatic compounds, e.g. xylene, toluene, benzene, can be used as liquid solvents

300 or 'alkylnaphthalenes, chlorinated aromas, chlorinated or aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins e.g. petroleum fractions, alcohol, · such as butanol or glycol and its ethers and esters, ketones, · such as acetone, methyl ethyl ketone, methyl isobutyi ketone or cyclohexanone, high polarity solvents such as dimethylformamide and dimethyl sulfoxide, and water, with liquefied gas Diluents or carriers are liquids that are gases at normal temperature and pressure, e.g. aerosol gases such as halogenated hydrocarbons, e.g. freon; as solid carriers, natural mineral flours such as kaolins, alumina, talc, chalk, quartz attapulgite, montmorillonite or diatomaceous earth and synthetic inorganic flours are used, e.g. highly refined silicic acid, alumina and silicates; non-forming and anionic emulsifiers are used as emulsifiers and / or foaming agents, e.g. polyethylene and fatty acid ethers, polyethylene oxide and fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and arylsulfonates, and protein hydrolysates, e.g. lignin, sulfite lyes and methyl cellulose are used as dispersants.

Kits of active substances may contain admixtures of other known active substances, e.g. fungicides, insecticides, ocaricides, namatocides, herbicides, repelling birds foraging, growth substances, plant nutrients and substances'. improving soil structure. The kits generally contain 0.1 to 95% by weight of active ingredients, preferably 0.5 to 90% by weight.

Substances . active agents can be used in the form of kits or formulations prepared from them by dilution, e.g. ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Application takes place. in a known manner, e.g. by watering, nebulization, dusting, spreading in the form of dry mortar, wet mortar, semi-wet suspension and incrustation. When used as leaf fungicides, the concentration of active substances can vary widely. It is generally 0.1-0), 00001, preferably 0.05 - 0.00001% by weight.

Some compounds of the formula I still have microbostatic and plant growth regulating effects. The good fungicidal action of the active substances of the agent according to the invention is confirmed by the following examples.

Example 1. Testing Plasmopora. Solvent: 4.7 parts by weight of acetone. Dispersant: 0.3 parts by weight of alkyl aryl polyglycol ether. Water: 95 parts by weight.

In order to obtain a spray liquid with the desired concentration of active substance, the required amount of active substance is mixed with the given amount of solvent, after which the concentrate is diluted with the given amount of water containing the said additives. ............... - ..... ...........

The resulting spray liquid is sprayed on the young shoots of pot vine (species Miiller-Thurgou) with 2-6 assimilation leaves. The plants are left for 24 hours in a greenhouse at 20 ° C with a relative humidity of 70%. Then vine shoots are inoculated with a spore suspension of Plasmopara vitocola. Plants are inserted into a humid chamber with 100% air humidity and a temperature of -20-22 ° C. Five days after inoculation, the infestation of the vine is measured in% to infestation of the inoculated but untreated control plants.

Table 3 _ lists the active substances, active substance concentrations and results.

Table 3 .....

Plasmopar testing

<td>The active substance</td><td>% Paralysis to infection of untreated control plants at active substance concentration - 0; 0025%</td>

<td>Compound _ of formula 6 (known) .....</td><td> 72</td>

<td>Compound of formula 7</td><td></td>

<td>(known)</td><td> 65</td>

<td>Compound of formula 8</td><td> 48</td>

<td>Compound of formula 9</td><td> 48</td>

Example II Testing Podosphaera (powdery mildew) (preventive effect). Solvent: 4.7 parts by weight of acetone, dispersant. 0.3 part by weight of alkylaryl polyglycol ether, water: 95 parts by weight.

In order to obtain a spray liquid with the desired active substance concentration, the required amount of active substance is mixed with the given amount of solvent, and then the concentrate is diluted with the given amount of water containing the said additives. Apple seedlings are sprayed at the 4-6 leaf stage of development with liquid until sprayed. The plants are left in the greenhouse for 24 hours at a temperature of 20 ° C 'and a relative humidity of 70%.

The plants treated in this way are inoculated by dusting with apple conidial spores (Padosphaera leucotricha) and placed in a greenhouse at a temperature of 21-23 ° C and a relative humidity of about 70%. 10 days after inoculation, the infestation of the seedlings will be determined as a percentage of the infestation of the untreated · but also the · inoculated control plants, where 0% means no infestation and 100% that infestation is as high as that of the control plants.

VJ 300

Table 4 lists the active substances, the concentration of active substances and the results obtained.

Table 4

Podosphaera testing (preventive action)

<td>The active substance</td><td>Paralysis% to infestation of untreated control plants at active substance concentration 0.000626%</td>

<td>Compound 0 formula 6 (known)</td><td> 20</td>

<td>Compound of formula 10</td><td> 4</td>

<td>Compound of formula 11</td><td> . 0</td>

<td>Compound of formula 12</td><td> 4</td>

<td colspan="2">Example III. Fusicladium testing (scab</td>

apple) preventive action.

Solvent: 4.7 parts by weight of acetone; emulsifier: 0.3 part by weight of alkylaryl polyglycol ether; 95 parts by weight of water.

The amount of active substance needed to reach the desired concentration in the spray liquid is mixed with the amount of solvent given, after which the concentrate is diluted with the amount of water containing the additives mentioned. Young apple seedlings in the 4-6 quantitative stages of spraying are sprayed with liquid obtained for spraying.

The plants are kept in the greenhouse for 24 hours at 20 ° C and a relative humidity of 70%. An aqueous suspension of apple scab (Fusicladium dendriticum Fuck) conidial spores is then inoculated and incubated for 18 hours in a humid chamber at 18-20 ° C and a relative air humidity of 100%. Plants are placed back into the greenhouse for 14 days. After 15 days from the moment of inoculation, the degree of infestation of seedlings is determined in% of the degree of infection Table 5

Fucicladium testing (preventive action)

<td rowspan="2">The active substance</td><td colspan="2">Percentage of infestation of untreated control plants at active substance concentration</td>

<td>Compound 0 formula 6 (known)</td><td> 14</td><td> 41</td>

<td>Compound of formula 13</td><td> 0</td><td> 1</td>

<td>Compound of formula 14</td><td> 4</td><td> 4</td>

<td>Compound of formula 12</td><td> 0</td><td> 0</td>

control seedlings also inoculated but not treated, with 0% meaning no infestation and 100% means that infestation is the same as for control plants.

Table 5 lists the active substances, the concentration of active substances and the results obtained.

Example IV 10 g (0.05 mol) of manganese chloride (MnCla X 4 H2O) are dissolved in 50 ml of ethanol and 29.3 g (0.1 mol) of 1- [1,2,4-triazoillo- / 1 /] - / p-chlorophenoxy / -3,3-dimethylbutanone-2 dissolved in 100 ml of ethanol. The solvent is distilled off under reduced pressure by a water pump. The residue is treated with 100 ml of ether and stirred for 15 hours at room temperature. The desired product is isolated in the form of crystals which are collected by filtration. 28.3 g (76% of theory) of bis- [l-1,1, 2,4-tr] and GlylG- / 1 / -1- / p-chlorophenoxy-3-hydrate are obtained; dimethylbutanone-3-yl] -1manganese (II) (formula 15), melting point 210-222 ° C.

Example V. 10.2 g (0.05 mole of mangamic chloride (MgCl3 X 6 H2O) in 50 ml of ethanol are dissolved and 14.7 g (0.05 mole) dropwise added with stirring - [- 1.4, 2.4 -triazoll10 ////] - // p-chlorffenoxy / -3,3-dimethylbutanone-2 dissolved in 100 ml of ethanol The solvent is distilled off under reduced pressure by a water pump, the oily residue is treated with 50 ml of acetone. ' for 15 hours at room temperature after which the remaining crystalline end product is filtered off. 22.2 g (90 ° theoretical yield) of mono- [1-1,2,4-triazolyl / -1 / -1- / p-chlorophenoxy-3,3-dimethylbutenon-3-yl] - hexahydrate is obtained. magnesium (formula 16), melting point 128-122 ° C.

Example VI. 3.07 g · (0.018 mol) of copper chloride (CuCh X 2H2O) in 6 ml of water are dissolved and 11.1 g (0.033 mol) of 1- (indazolyl / -1- / p-bromophenoxy / -3) are added dropwise to the stirring. , 3-dimethylbutanone-2 dissolved in 100 ml of ethanol.

Precipitating turquoise crystals are filtered off and washed with ether. 12 g (99% of theory) of bis- [l- / imidazolyl-l- / p-bromophenoxy / -3,3-dimethylbut2-n-3-yl]-copper chloride (formula 17) with a melting point of 107 - 109 ° is obtained. C.

Example VII. 4.4 g (0.025 mol) of copper chloride (CuCh X 2H2O) are dissolved in 6 ml of water, and 14.7 g (0.05 mol) of 1- [1,2,4-thiazolyl- / 1 -] - // p-chlorolffenoxy-3,3-dimethylbutanone-2 dissolved in 100 ml of ethanol. After stirring for 1 hour at room temperature, the turquoise crystals are filtered off. 16 g (89 °% of theory) of bis- [1- / 1,2,4-triaz-1-yl- / -1 / -1- / p-chlorophenoxy / -3.3 & lt; 2 & gt; e are obtained.<Copper tobutanone-2-yl] of formula 8 with a melting point of 103-104 ° C.

Example VIII. 4.4 g (0.025 mol) of copper chloride (CuCl2 X 2H2O) are dissolved in 20 ml of water and 17 g (0.05 mol) of 1- [1,2,4-triazolyl / l] is added dropwise with stirring. l // p-bromophenxks / -3,3-dimethylbutanone dissolved in 300 ml ethanol.

«7800

The solution is concentrated to half volume and 100 ml of water are added. Green oil separates. The aqueous phase is decanted and the organic phase is stirred in 80 ml diisopropyl ether for 30 minutes. The green crystals are filtered off. 5.5 g (27% of theory) of tetra- [l / 1,2,4-triazolyl / l / -1- / p-bromophenoxy / -3,3-dimethylbutanol-2-yl] copper are obtained. (formula 10), melting point 92 - 95 ° C.

Preparation of starting compound. 676 g (2 moles) of 1- [1,2,4-triajo) lilo- / -1 /] -1 / p-bromophenoxy / -3,3-dimethylbutanone-2 are dissolved in 3 liters of methanol. To this is added in portions of 5 g at a temperature of 0 - 10 ° C, while stirring and cooling. ice, a total of 80 g (2 moles) of sodium borohydride and stirred for 2 hours at 5-10 ° C, followed by 12 hours at room temperature. Then it cools down. up to 10 ° C, at 10-20 ° C. 300 g (3 moles) of concentrated aqueous hydrochloric acid are added.

After 6 hours of stirring at temperature. The resulting suspension is diluted with 3.8 liters of water containing 400 g (4.8 mol) of sodium bicarbonate. The resulting precipitate is filtered off. 546 g (85% of theory) of 1- [1,2,4-thiaziazoyl] -l] p'-bromophenoxy / -3,3-dimethylbutanol-2 (formula 18) is obtained, m.p. 115 - 118 ° C.

Example IX. 3.4 g (0.025 mol of ZnCffe in 20 ml of ethanol) are dissolved and 16.8 g (0.05 mol) of 1- [1,2,4-triazolyl / 1 / -1- (p-phenylphenoxy) is added dropwise to the solution with stirring. -3,3-d of dimethylbutanone-2 dissolved in 300 ml of ethanol. After stirring for 30 minutes at room temperature, the precipitate formed is filtered off, washed with a small amount of ethanol. 15 g (74% of the theoretical yield of bis- [1,2, 4-triazolyl- (1 / -1- (p-phenylphenoxy) -3,3-dimethylbutanon-2-yl] (formula 12), m.p. 182 ° C.

Example X. 10.4 g (0.04 mol) of tin chloride (SnCU) to 24.6 g (0.075 mol) of 1- [1,2,4- ^ 1,370 ^ 0- / 1 / ^ / are added dropwise with stirring. 2,4-dichlorophenoxy / -3,3-dimethylbutanone-2 dissolved in 200 ml of ethanol. The solvent is then distilled off under reduced pressure by a water pump. 50 ml of n-pentane are added to the residue and left for 4 days at 0ABOUTC.

Colorless crystals then precipitated. filtered and washed with 20 ml diisopropyl ether. 29.9 g (77% of theory) of bis- [1- / 1,2,4-triazolyl-1,1-1,1 / 2,4-dichlorophenoxy-3,3-dimethylbutanon-2-yl chloride is obtained. ] -tin (IV), formula 19, melting point 216-218 ° C.

Example XI. 6-5 g (0.025 mol) of tin chloride are added dropwise to '17.1 g (0.05 mol) 1- [1,2,4-thiiazoyl O ////] - 2- / 2,4-dichlorophenoxy14, 4-dimethylpentanone-3 dissolved in 100 ml ethanol. Stir for an additional 2 hours at room temperature. The precipitated colorless crystals are filtered off and washed with 20 ml of diisopropyl ether. 23 g (97% of theory) (bis - [- 1, 2,4-triazolyl-1 - 2-2.4-dichlorophenoxy / -4,4-dimethylpentanone-324 chloride are obtained

-yl] -tin (IV), formula 20, melting point 235 - 236 ° C. >

Preparation of starting compound: 22.6 g (0.0464 mol) of [2- / 2,4-dichlorophenoxy / -4,4-pentane-3-yl] -dimethylamino iodide is dissolved in 250 ml of anhydrous acetonitrile. and 10.4 g (0.15 mol) 1,2,4-triazole are added in portions. After 24 hours of heating under reflux, the solvent is distilled off under reduced pressure. The oily residue is dissolved in 500 ml of methylene chloride and extracted twice with 600 ml of water each.

The organic phase is separated, dried with sodium sulfate and freed from the solvent under reduced pressure.

The oily residue is triturated with diisopropyl ether which then solidifies. It is filtered off, washed well with diisopropyl ether and dried. 10.3 g (64.2% of theory) are obtained. 1- [4,2,4-traazoyl ///] - 2-2.4-dichlorophenoxy / -4,4-dimethylpentane> nu-3 / , model 21, melting point 75-77 ° C.

The dimethyl methyl iodide iodide of formula 22 used as an intermediate is prepared as follows: 234.2 g (0.9 mol) of 2-2.4-dichlorophenoxy [-4,4-dimethylpentanone-3,10 g (110 g) is dissolved. 1 mol) diethylammonium chloride and 45 g (1.5 mol) paraformaldehyde in 300 ml anhydrous ethanol. To this is added 2 ml of concentrated hydrochloric acid and the reaction mixture is refluxed for 2 hours. under reflux condenser. After addition of 30 g (1 mol) paraformaldehyde is heated for another 2 hours. hours under reflux and then left overnight at room temperature. The batch is poured into 1.2 liters of water and extracted with 1.5 liters of ether. The aqueous phase is adjusted to pH8 with ammonia solution and again extracted with 1 liter of ether. The combined ether phases are dried with sodium sulfate and freed from the solvent under reduced pressure. The obtained yellow oil 177 g (52.2% of theory) of [2- / 2,4-dichlorophenoxy / -4,4-dimethylpantan-3-onyl] -dimethylammonium chloride does not crystallize and is further reacted as a crude product.

38.1 g (0.1 mol) of [2 / 2,4-dichlorophenoxyA-4 '^ - ^ <^' chloride is dissolved: me '^; yl ^ and ^' ^^ n-3-onyl] -dimethylammonium chloride in 200 ml. 20.2 g (0.2 mol) of triethylamine, dropwise, at anhydrous tetrahydrofuran. The mixture is stirred at room temperature for 5 hours, then the precipitated triethylammonium chloride is filtered off and the solvent is distilled off under reduced pressure. 30.9 g (9 (0% of theory of [2- / 2,4-dichlorophenoxy / -4,4-dimethyl // penn-mon-2-yl] -dimethylamine are obtained in the form of a yellow oil, which immediately dissolves. in 300 ml of anhydrous acetonitrile (0.09 molar feed), 21.3 g (0.15 mol) of methyl iodide are added dropwise at room temperature with stirring The reaction mixture is stirred for 1 hour at room temperature and 30 minutes under a condenser and the solvent is distilled off under reduced pressure. The oily residue is dissolved 'in 200 ml of a mixture of ethyl acetate' and methyl ethyl ketone (1: 1) and

97.-800 heated to boiling. A crystalline residue is formed, which is filtered off and washed with ether.

22.8 g (51.6 · theory) of B-ethylpentan-3-methyl] -dimethylmethylamino iodide is obtained, mp 114-118 ° C.

According to examples IV - XI, the compounds listed in table 6 * are obtained

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
19742423987	–	–	–
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
PL97300B1This record	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
IL47294A	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