Process for preparing triazolyl-o,n-acetals

© Beginning of patent period: 1976 05 15

Longest possible duration:

© Issued on: 1977 01 25 (72) Inventor:

© dependence:

© Pamphlets considered to delineate the prior art:

OE 334 686

No. 334686

The invention relates to a fungicidal agent, which is characterized in that it contains as active ingredient at least one new triazolyl-O, N-acetal of the general formula

R² OH x ^{1 1} a

Ri_O CCR⁴ , (I)

II

Az R³ in which R¹ 5 is alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl, furthermore aryl and aralkyl, where the latter two radicals are optionally substituted in the aryl part by halogen, alkyl, alkoxy, haloalkyl, haloalkylthio, carbalkoxy, phenyl or nitro, R², R³ and R⁴ for hydrogen and for those under R¹ mentioned radicals, but where R³ and R⁴ can not simultaneously be hydrogen, and A is 1,2,4-triazolyl- (1) -, 1,2,4-triazolyl- (4) - and 1,2,3-triazoyl "(l) - Rest, wherein said radicals are optionally substituted by halogen or alkyl, in addition to extenders and or 10 or surfactants and / or carriers and optionally contains other active ingredients. It has already become known that trityl imidazoles and -1,2,4-triazoles, such as triphenylimidazole and

Triphenyl-l, 2,4-triazole, a good fungicidal activity have (see US Patent No. 3,321,366 and Belgian Patent No. 738095). However, their effect is not always quite satisfactory, especially at low application rates and concentrations. Furthermore, it is known that zinc-ethyl-l, 2-bis15 -dithiocarbamidat a good fungicidal activity against Pbycomyceten, eg against Phytophthora infestans, the causative agent of the late blight of potatoes and the brown rot of tomatoes, as well as against various soil-borne fungi. However, its effectiveness in use as a seed dressing is not always entirely satisfactory.

It has been found that the triazolyl-O, N-acetals and their salts used in the fungicidal agent have strong fungicidal properties.

Surprisingly, the active compounds used according to the invention show a considerably higher fungicidal activity than the compounds known from the prior art triphenylimidazole, triphenyl-1,2,4-triazole and zinc ethyl-l, 2-bis-dithiocarbamidate. The agents according to the invention thus represent an enrichment of the art.

The compounds of the general formula (I) have two asymmetric carbon atoms, they may therefore be in the erythro as in the threo form; in both cases they are predominantly racemates.

The compounds of the general formula (I) used in the agent according to the invention are obtained when triazole derivatives of the general formula

R² ORI-OCCR⁴

I

Az (Π) in which R¹, R², R⁴ and Az have the meaning given above, either

a) with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent, or

b) with aluminum isopropylate in the presence of a solvent, or

c) with complex hydrides optionally in the presence of a polar solvent, or

d) with formamidine sulfinic acid and alkali hydroxide, optionally in the presence of a polar solvent, reduced; or if you are

e) the triazole derivatives of the formula (H) with organometallic compounds of the general formula

Me R³ , (HI) in which R³ has the meaning given above and Me is an alkali metal or the radical

X -Mg, where X is chlorine, bromine and iodine, is reacted in the presence of an inert solvent.

If one uses 1-phenoxy-l- [l, 2,4-triazolyl- (l ') J -3,3-dimethylbutan-2-one and hydrogen as Aus45 gangsstoffe, the reaction sequence can be represented by the following formula scheme (process variant a):

No. 334686 / " ¹¹

O-CH-CC (CH ^_S

H »/ cat.

OH zN " ^SN o - O-CH-C - C (CH 2)_:IH, < ^XN

N ·

Ν ·

If 1-phenoxy-1 - [1,2,4-triazolyl- (1 ')] -3,3-dimethylbutan-2-one and aluminum isopropylate are used as starting materials, the course of the reaction can be represented by the following formula scheme (process variant b ):

CH,: c - O - Al / 3 o - O - CH - CC (CHg)₃

CH xNs

-N

CH ³x^k

O-Al / 3 o -O-CH-CH-C (CH 3>₃

NN + (H

H₂0

OH

Al (OH) O-O-CH-CH-C (CHg)₃ .NS,

N

If 1-phenoxy-1- [1,2,4-triazolyl- (1 ')] -3,3-dimethylbutan-2-one and sodium borohydride are used as starting materials, the course of the reaction can be represented by the following formula scheme (process variant c):

- |, ₊ NaBH₄⁴ €>

-O-CH-C -C (CH ^_S

Bra "© © '

Ο -Bh Na

V 1 -O-CH-CH-CiCHg)

Χ^ΝχΝ

N^XCH - O., O - CH ^ • CH - CH \ / & ®

0-BO-CH; Na I^x^C<^CH3>_S 'N .N_s

N

N + 2 HO

OH

NaBO "O-O-CH-CH-C (CHg)₃^XN

N-4 No. 334686

If l-phenoxy-l- [l, 2,4-triazolyl- (l ')] -3,3-dimethylbutan-2-one and formamidinesulfinic acid are used as starting materials, the Reakticnsablauf can be represented by the following formula scheme (process variant d ):

o -O-CH-C - CiCH ^ g> ISK

N-¹¹

H₂N® = C-SO₂ ® / 2 OH ® NH

- N - C - NH 2 li "2

- SO o

2e

OH o - O-CH-CH-CiCH 2, N.

• N

If 1-phenoxy-1- (1,2,4-triazolyl- (1 ')! -3,3-dimethylbutan-2-one and methylmagnesium iodide are used as starting materials, the course of the reaction can be represented by the following formula scheme (process e );

O - CH - C - C (CH ^_S

N "N>

"N + HO 2

MgBr (OH)

CHjMgBr

OMgBr / O-CH-CH \ = / II CH .Nx

NOH * o -O-CH-C-C (CH ^_G

CH "

-N ^C<^CIX

In the formula (H), R stands¹ preferably a straight-chain or branched alkyl radical having 1 to 8, in particular 1 to 4, carbon atoms, a straight-chain or branched alkenyl radical having 2 to 6, in particular 3 to 6, carbon atoms, a straight-chain or branched alkynyl radical having 2 to 6, in particular 3 to 6, carbon atoms, furthermore for cycloalkyl and cycloalkenyl with in each case 5 to 7, in particular 5 or 6, carbon atoms, in addition, an optionally substituted aryl or aralkyl radical having 6 or 10 carbon atoms in the aryl and 1 or 2 carbon atoms in the alkyl moiety. As substituents on the aryl radical, preference may be given to: Halogen, in particular fluorine, chlorine or bromine, straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms, alkoxy having 1 to 4, in particular 1 or 2, carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 Halogenato20 men, in particular fluorine and chlorine, halogenoalkylthio with 1 or 2 Köhlens toffatomen and 3 to 5 halogen atoms, in particular fluorine and chlorine, for example chlorodifluoromethylthio, carbalkoxy having 1 to 4 carbon atoms in the alkoxy part, o- or p-substituted phenyl and the nitro group.

R² is preferably hydrogen, straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms, straight-chain or branched alkenyl having 2 to 6, in particular 2 to 4, 25 carbon atoms, straight-chain or branched alkynyl having 2 to 6, in particular 3 to 5, carbon atoms, furthermore cycloalkyl or cycloalkenyl having in each case 5 to 7, in particular 5 or 6, carbon atoms, in addition, an optionally substituted aryl or aralkyl radical having 6 or 10 carbon atoms in the aryl and 1 or 2 Köhlens toffatomen in the alkyl moiety. As substituents on the aryl radical kom5

No. 334,686 preferably halogen: in particular fluorine, chlorine or bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 or 2 carbon atoms and 2 to 5 halogen atoms, in particular fluorine or chlorine.

R⁴ in formula (II) preferably represents a straight-chain or branched alkyl radical having 1 to 8, 5, in particular 1 to 4, carbon atoms, a straight-chain or branched alkenyl radical having 2 to 6, in particular 3 to 6, carbon atoms, a straight-chain or branched alkynyl radical having 2 to 6, in particular 3 to 6, carbon atoms, furthermore for cycloalkyl and cycloalkenyl having 5 to 7, in particular 5 or 6, carbon atoms, in addition, an optionally substituted aryl or aralkyl radical having 6 or 10 carbon atoms in the aryl and 1 or 2 carbon atoms in the alkyl moiety. As substituents on the aryl radical, preference may be given to: Halogen, in particular fluorine, chlorine or bromine, straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms, alkoxy having 1 to 4, in particular 1 or 2, carbon atoms, haloalkyl having 1 or 2 carbon and 1 to 5 halogen atoms in particular fluorine and chlorine, halogenoalkylthio having 1 or 2 carbon atoms and 3 to 5 halogen atoms, in particular fluorine and chlorine, for example chlorodifluoromethylthio, carbalkoxy having 1 to 4 carbon atoms in the alkoxy part, o- or p-substituted phenyl and the nitro group.

Az is preferably the following radicals:

shark

<img file="AT334686B_D0001.tif" />

alkyl

shark

NNNHal

Alkyl'N&gt; N

Shark 'N ·'

Hiebei stands for halogen, in particular chlorine or bromine, and alkyl for the CHg group.

The triazole derivatives of the formula (II) which can be used for the preparation of the active substance are not yet known, but they are partially the subject of Austrian Patent Specification No. 320346. B. are prepared by reacting a Halogenätherketon with a 1,2,4-triazole, optionally in the presence of a solvent or diluent and an acid binder, at temperatures of preferably 80 to 120 ° C in stoichiometric proportions; Among other manufacturing processes is still the reaction of hydroxy ether with 1,2,4-triazoles in the presence of a dehydrating agent and optionally in the presence of a diluent at temperatures between preferably 140 and 200 ° C to call. Depending on the preparation process and work-up conditions, the tautomeric character of the 1,2,4-triazole is obtained accordingly

<img file="AT334686B_D0002.tif" />

H v

HN-i.

Ν 'the triazole derivatives of formula (Π) either as 1,2,4-triazolyl (4) derivatives or as 1,2,4-triazolyl (1) derivatives; Often, a mixture of both forms.

Suitable salts for compounds of the formula (I) are salts with physiologically tolerated acids. For this purpose, preferably the hydrogen halide acids, such as. As hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, mono- and bifunktio35 nelle carboxylic acids and hydroxycarboxylic acids, such as Acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic, lactic, 1,5-naphthalenedisulfuric acid.

For the reaction according to process variant a, suitable diluents are polar organic solvents. These include, preferably, alcohols such as methanol and ethanol and nitriles such as acetonitrile. The reaction is carried out in the presence of a catalyst. Preference is given to using noble metal, noble metal oxide (or noble metal hydroxide) or Raney catalysts, in particular platinum, platinum oxide and nickel. The reaction temperatures can be varied within a substantial range. In general, one works between 20 and 50 ° C, preferably at 20 and 40 ° C. The reaction may be at

No. 334686

Normal pressure, but also at elevated pressure (1 to 2 atü) durehgeführt. In the implementation according to

Variant (a) is used for 1 mole of the compound of formula (Π) about 1 mole of hydrogen and 0.1 mole of a catalyst; to isolate the compounds is filtered off from the catalyst, freed from the solvent in vacuo and the resulting products of formula (I) are purified by recrystallization. If desired, the salts of the compounds obtained are obtained by conventional methods.

Working according to variant (b), suitable diluents for the reaction are preferably alcohols, such as isopropanol, or inert hydrocarbons, such as benzene. The reaction temperatures can be varied again within a relatively wide range; in general, one works between 20 and 120 ° C, preferably at 50 to 100 ° C. To carry out the reaction, about 1 or 2 moles of aluminum isopropylate are employed per mole of the compounds of the formula (II). To isolate the compounds of the formula (I), the excess solvent is removed by distillation in vacuo and the resulting aluminum compound is decomposed with dilute sulfuric acid or sodium hydroxide solution. The further work-up is carried out in the usual way.

Working according to variant (c), come as a diluent for the reaction polar organic

Solvent in question. These include, preferably, alcohols, such as methanol, ethanol, butanol, isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at 0 to 30 ° C, preferably at 0 to 20 ° C. For this purpose, is used for 1 mole of the compounds of formula (II) about 1 mole of a complex hydride, such as sodium borohydride or lithium alanate, a. To isolate the compounds of the formula (I), the residue is taken up in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent. The further work-up is carried out in the usual way.

Suitable diluents for the reaction according to variant (d) are polar organic solvents, preferably alcohols, such as methanol and ethanol, but also water. The reaction temperatures can also be varied within a substantial range; one works at temperatures between 20 and 100 ° C, preferably at 50 to 100 ° C. For carrying out the reaction, about 1 to 3 mol of formamidine sulfinic acid and 2 to 3 mol of alkali metal hydroxide are used per mole of the compounds of the formula (II). To isolate the end products, the reaction mixture is freed from the solvent and the residue extracted with water and organic solvents, worked up in the usual manner and purified; optionally, the salt is prepared.

In the reaction according to variant (e), compounds of the general formula (I) are obtained in which R³ does not stand for hydrogen. In contrast to this, the reactions according to a to d are reduction reactions; the compounds of the formula (I) obtained here are secondary alcohols in which R³ each represents only hydrogen.

For the reaction according to variant (e), organometallic compounds of the formula (III) are required for the triazole derivatives of the formula (II). In this formula (HI) R stands³ preferably for alkyl, alkenyl and alkynyl each having up to 8, in particular up to 4 carbon atoms, furthermore preferably cycloalkyl having 5 or 6 carbon atoms, in particular cyclohexyl, furthermore preferably aryl and aralkyl having 6 to 10 carbon atoms in the aryl and 1 or 2 carbon atoms in the alkyl part. As substituents on the aryl radical may preferably be mentioned: fluorine, chlorine and alkyl and alkoxy with in each case up to 4 Koh40 lenstoffatomen. Me in formula (HI) is preferably lithium, sodium and the so-called Grignard group Mg-X, where X is chlorine, bromine and iodine. The organometallic compounds of the formula (ΠΙ) are generally known (a summary and overview of numerous publications can be found, for example, in GECoates, Organo-Metallic Compounds, 2nd Edition, Methuen and Co., London [I960]).

For the reaction according to variant (e) preferably anhydrous ethers, such as diethyl ether, dibutyl ether in question. The reaction temperatures can be varied between 0 and 80 ° C, preferably between 30 and 60 ° C. When carrying out the process according to variant (replaced to 1 mol of the compounds of formula (H) about 1 mole of the organometallic compound of formula (ΙΠ). The work-up of the mixtures obtained by organometallic reactions is carried out in a customary and generally known manner.

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

Fungi imperfecti.

The compositions 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.

No. 334686

They have a particularly good effect against parasitic fungi on aboveground plant parts, such as

Erysiphe species, Podosphaera species, Sphaerotheca species, Venturia species, also against Piricularia and

Pellicularia species. They are also highly effective against rust and fungus fungi, z. B. against the causative agent of Weizensteinbrandes. It should be emphasized that the agents of the invention not only a protective

Have an effect, but are also curatively effective, that can be used even after the infection. Furthermore, the systemic effect of the substance should be pointed out. It is thus possible to protect plants against fungal infestation by feeding the active ingredient to the above-ground parts of plants via the soil, via the planting or seed. As plant protection agents, the compositions according to the invention can be used for soil treatment, for seed treatment and for the treatment of above-ground parts of plants.

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

The active compounds used according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are in known

For example, by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. As liquid solvents are essentially in question:

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. Oil 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 extenders or carriers are meant liquids which are gaseous at normal temperature and under atmospheric 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, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; as a dispersant: z. As lignin, liquors and methylcellulose.

The active compounds used according to the invention may be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and soil conditioners.

The formulations generally contain between X and 95% by weight of active ingredient, preferably between 5 and 90%.

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, for. B. by pouring, spraying, spraying,

Dusting, spreading, dry pickling, moist pickling, wet pickling, slurry pickling 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%.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g / kg of seed, preferably 0.01 to 10 g are needed.

For soil treatment are amounts of active ingredient from 1 to 1000 g / m³ Soil, preferably 10 to 200 g, required.

Furthermore, the compositions according to the invention have good microbistatic activity.

The versatile uses are shown in the examples below.

Example 1: Erysiphe test / protective.

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 parts 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 cucumber plants with about three leaves leaves to dripping wet. The cucumber plants remain for drying in the greenhouse for 24 h. Then they become inoculations

No. 334686 with conidia of the fungus Erysiphe ciehoreacearum. The plants are then at 23 to

24 ° C and an approximately 75% relative humidity in the greenhouse set up.

After 12 days, the infestation of cucumber plants is determined in percent 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.

Active ingredients, drug concentrations and results are shown in Table 1 below:

Table 1

Erysiphe test

active substance

<img file="AT334686B_D0003.tif" />

o (known)

Infestation in% of the untreated controids at an active substance concentration of 0.00025%_8th

Cl-O-CH-CH-C ^ CH₃

I ^0H CH "

N.

V_N

CH _ ch₃ - / S - O - CH - CH - C ^ CH ³ \ = / I f \ ³i ^{0H CH}3

Cl / \ -S-O-CH-CH-C ^ '

CH "\ = /

CH "

N / \

OH

CH "

Nr.334686

Table 1 (continued)

<td>active substance</td><td>Affected in% of the infestation of the untreated control an active substance concentration of 0.00025%</td>

<td>1 Ci- / O-CH-CH-C / CH, \ = / | 1 \³1 OH 'CH, / \ O</td><td>2</td>

<td>O / H CH ------ / j / fl O-CH-CC &lt;-CH \ = / 1 1 \ 1 OH CH N N '</td><td>2</td>

Example 2: Erysiphe test / systemic.

Solvent; 4.7 parts by weight of acetone

Dispersant: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient required for the desired concentration of active substance in the casting 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.

Cucumber plants grown in unit-grown cucumber plants are in the 1 to 2 leaf stage within a week three times with 20 ml of the casting liquid in the stated active ingredient concentration, based on 100 cm³ Earth, poured.

The treated plants are inoculated after treatment with conidia of the fungus Erysiphe cichoracearum. Subsequently, the plants are placed at 23 to 24 ° C and a relative humidity of 70% in the greenhouse. After 12 days, the infestation of cucumber plants in% of untreated, but also inoculated control plants is determined.

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

Active ingredients, drug concentrations and results are shown in Table 2 below;

No. 334686

Table 2

Erysiphe test / systemic

<img file="AT334686B_D0004.tif" />

No. 334686

Example 3: Podosphaera test (apple powdery mildew) / protective.

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient required for the desired concentration of active compound in the spraying liquid is mixed with the stated amount. Amount of solvent and dilute the concentrate with the specified amount of water containing the additives mentioned.

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

Days after inoculation, infestation of seedlings is determined in% 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, drug concentrations and results are shown in the following Table 3:

Table 3

Podosphaera test / protective

<td rowspan="2">active substance</td><td colspan="2">Infestation in% of the infection of the untreated control at an active ingredient concentration from</td>

<td>0.00062</td><td>0.00031</td>

<td>N-_fkJ</td><td></td><td></td>

<td>oj-o (known) CH,</td><td>52</td><td>79</td>

<td>- / 3 Cl-f'S-O-CH-CH-C-CH_q\ - / Ti \ ³1 OH CH, N \ II II¹¹-N &lt;F &lt;^CH3&gt; 3</td><td>5</td><td>16</td>

<td>Cl- \ -O-CH-C-OH \ = / 1 1 1 1 H ci /ⁿ^ n &gt; 1 II nf threo form</td><td>0</td><td></td>

Nr.334686

Table 3 (continued)

<td rowspan="2"></td><td rowspan="2">active substance</td><td colspan="2">Affected in% of the infestation of the untreated control an active ingredient concentration from</td>

<td>0.00062</td><td>0.00031</td>

<td rowspan="2">"-O- l</td><td>f (^CH3&gt; 3</td><td></td><td></td>

<td>-O-CH-CH 1 i 1 OH</td><td>0</td><td></td>

<td>CI</td><td>/ 'S,</td><td></td><td></td>

<td></td><td>n-ü</td><td></td><td></td>

<td>erythro form</td><td></td><td></td><td></td>

<td rowspan="2">Br</td><td>θ &lt;^0Ηλ -O-CH-CH 1 I</td><td>0</td><td></td>

<td>Λ °^H(ΐί</td><td></td><td></td>

<td></td><td>ιϊ ¹¹</td><td></td><td></td>

<td>Γ³</td><td></td><td></td><td></td>

<td></td><td>O-CH-CH-C (CH ^_SΛ ^Ahί »</td><td>4</td><td></td>

<td></td><td>II N-¹¹</td><td></td><td></td>

Example 4: Sprout Treatment Test / Mildew / Protective (Foliar Mycosis).

To prepare a suitable preparation of active compound, 0.25 parts by weight of active compound in 25 parts by weight of dimethylformamide and 0, 06 parts by weight of emulsifier W are added and 975 parts by weight of water are added. The concentrate is diluted with water to the desired Fndkonzentration the spray mixture.

To test for protective activity, the monocled barley seedlings of the variety Amsel are sprayed with the preparation of active compound dewatered. After drying, the barley plants are dusted with spores of Erysiphe graminis var, hordei.

After 6 days residence time of the plants at a temperature of 21 to 22 ° C and a humidity of 10 80-90% is evaluated, the stocking of plants with mildew pustules. The level of infestation is expressed as a percentage of the infestation of untreated control plants. 0% means no infestation and 100% the same degree of infestation as in the untreated control. The active ingredient is the more effective, the lower the rust attack.

Active ingredients, active compound concentrations in the spray mixture and infestation levels are shown in the following Table 4:

No. 334686

Table 4

Sprout Treatment Test / Cereal Mildew / Protective

<td>drugs</td><td>Concentration of active ingredient in the spray liquor in wt.%</td><td>Affected in% of the untreated control</td>

<td rowspan="2">untreated ch₂NH-cs-s ^ | zn CHj-NH-CS-S ^</td><td>-</td><td>100</td>

<td>0.3 0.1</td><td>64.0 80.5</td>

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

<td rowspan="2">- / "s CI- / V-O-CH-CH-C &lt;-CH, \ = / 1 \ ³i ^{0H CIi}3^{N /} Λι II</td><td>0.01</td><td>0.0</td>

<td>0, 001</td><td>0.0</td>

<td>-N</td><td></td><td></td>

<td rowspan="2">ch₃ON- / S - O - CH - CH - C - CH,² \ = / II \ ³i OH CH₃N '\ II</td><td>0.01</td><td>6.3</td>

<td>0.001</td><td>10.8</td>

<td>'1 N</td><td></td><td></td>

<td rowspan="2">/ /^Η3 CI- / V- 0 - CH - CH - C ^ - CH \ = / | 1 \³1 i °^{H CH}3 CI N^x11</td><td>0.01</td><td>0.0</td>

<td>0.001</td><td>0.0</td>

<td>II¹¹-N</td><td></td><td></td>

<td>erythro form</td><td></td><td></td>

<td rowspan="2">^CH. y 3 CI- / O - CH - CH - Cr - CH \ = / | 1 \ 1 i ^{0H CH}3 CI II</td><td>0.01</td><td>0.0</td>

<td>0.001</td><td>0.0</td>

<td>'-N</td><td></td><td></td>

<td>threo form</td><td></td><td></td>

<td>ch₃= = 1 in CH,</td><td>0.01 0.001</td><td>0.0 0.0</td>

<td>1!-_N</td><td></td><td></td>

No. 334686

Table 4 (continued)

<td colspan="2">drugs</td><td>Active substance concentration in the spray mixture in wt.%</td><td>Infestation in% of untreated control</td>

<td>^CH3</td><td>CH</td><td></td><td></td>

<td></td><td>- \ / ³y-O-CH-CH-Cr-CH,</td><td>0.01</td><td>0.0</td>

<td>'/ ' =</td><td>= / 1 1 \</td><td>0.001</td><td>23.8</td>

<td>CH /</td><td>1 OH ΌΗ N. ³^NII</td><td></td><td></td>

<td></td><td>II¹¹-N</td><td></td><td></td>

<td></td><td>CH,</td><td></td><td></td>

<td>Br / V</td><td>/ -O - ​​CH - CH - C &lt;- CH,</td><td>0.01</td><td>0.0</td>

<td>\ = /</td><td>1 1</td><td>0, 001</td><td>0.0</td>

<td></td><td>1 OH OH₃^N \ II</td><td></td><td></td>

<td></td><td>II¹¹-N</td><td></td><td></td>

<td>CI l</td><td>CH,</td><td></td><td></td>

<td>^a(-&gt; -</td><td>/ -O - ​​CH - CH - CH © CH,</td><td>0.01</td><td>0.0</td>

<td></td><td>II \ ³</td><td>0, 001</td><td>6.3</td>

<td>l</td><td rowspan="2">'OH CH₃</td><td></td><td></td>

<td rowspan="2">CI</td><td rowspan="2"></td><td rowspan="2"></td>

<td>II H</td>

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

Example 5: Barley powdery mildew test (Erysiphe graminis var. Hordei) / systemic (fungal cereal disease).

The application of the active ingredients is carried out as a powdered seed treatment agent. They are prepared by stretching the respective active ingredient with a mixture of equal parts by weight of talc and

Diatomaceous earth to a finely powdered mixture with the desired drug concentration.

For seed treatment shake barley seed with the stretched active ingredient in a sealed glass bottle. The seeds are sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of 1 part by volume Fruhstorfer unit earth and 1 vol. Part quartz sand. The germination and the casserole are done under favorable conditions in the greenhouse. 7 days after sowing, when the barley plants have unfolded their first leaf, they are spiked with fresh spores of Erysiphe graminis var. Hordei and further cultivated at 21 to 22 ° C and 80 to 90% relative humidity and 16 hours exposure. Within 6 days the typical mildew pustules develop on the leaves.

The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. Thus, 0% indicates no infestation and 100% the same degree of infestation as with the untreated control. The lower the powdery mildew case, the more effective the active ingredient.

Active ingredients, active substance concentrations in the seed treatment agent as well as its application rate and the percentage mildew dust case are shown in Table 5 below:

No. 334686

Table 5

Barley powdery mildew test (Erysiphe graminis var. Hordei) / systemic

<td>drugs</td><td>drug concentration in mordant in weight%</td><td>Pickling agent quantity in g / kg seed</td><td>Infestation in% of untreated control</td>

<td>unstained II-^Nii ii</td><td></td><td></td><td>100</td>

<td>| (known) 0¾ -NH-CS-Sv</td><td>30</td><td>10</td><td>100</td>

<td>| \ n CHj - NH -CS -S⁷(known) CH,</td><td>30</td><td>10</td><td>100</td>

<td>__ / 3 Cl- / O-CH-CH-C (-CH, \ = / II \ ³1 OH CH N. ³II II -_N</td><td>25</td><td>10</td><td>0.0</td>

Example 7: Fusicladium test (apple scab) / protective.

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 parts 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 to 6 leaf stage, 10 to dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum Fuck.) 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 seedlings is determined in% 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, drug concentrations and results are shown in Table 6 below:

No. 334686

Table 6

<img file="AT334686B_D0005.tif" />

No. 334686

Table 6 (continued)

<td rowspan="2">active substance</td><td colspan="2">Infestation in% of the infestation of the untreated control at an active substance concentration (in%) of</td>

<td>0,025</td><td>0.00125</td>

<td>C (CHJ, ΖΛ ¹BrV-O-CH-CH \ = / I 1 i ^0H&lt; ^N¹ II N-1 '</td><td>-</td><td>12</td>

Rules for the manufacture of the active substance. Regulation 1:

_ OH _

Cl- / O - CH - CH- / X \ = / I \ = /

31.4 g (0.1 mol) of u- (4'-chlorophenoxy) -w- [1,2,4-triazolyl (l ')] acetophenone are dissolved in 300 ml of methanol. This solution is added with stirring and ice cooling in 3 g (0.08 mol) of sodium borohydride. The reaction mixture is stirred for 1 h at room temperature and then the solvent is distilled off in vacuo. The residue is taken up in dilute hydrochloric acid, briefly heated and filtered. The filtrate is then made alkaline with sodium hydroxide solution. The resulting precipitate is filtered off and taken up in Esslg10 ester. After distilling off the ethyl acetate leaves an oil that crystallizes when triturated with ligroin. Obtained after the recrystallization from ligroin / isopropanol 25 g (98% of theory) of 1- (4 '-Chlorphenoxy) -l- [l, 2,4-triazolyl- (l')] -2-phenylethanol of melting point 117 ° C.

Presentation of the preliminary product:

32.5 g (0.1 mol) of ω-ΒΓοηι-ω- (4'-chlorophenoxy) acetophenone and 30 g (0.44 mol) of 1,2,4-triazole are dissolved in 240 ml of acetonitrile 15 and 48 h heated to reflux. After distilling off the solvent, the residue is taken up in 800 ml of water. This aqueous solution is extracted several times with methylene chloride and the methylene chloride solution washed twice with 200 ml of water, then dried over sodium sulfate and the solvent was distilled off in vacuo.

The residue crystallizes out, and it can be melted from ligroin / isopropanol (2: 1) to a melting point of 98 to 100 ° C.

The required as starting material for the precursor &lt;n-bromo-w- (4 '-chloiphenoxy) acetophenone is by condensation of 4-ChlorphenoI with ω-chloroacetophenone and bromination of the resulting ω- (4' -Chlorphenoxy) acetophenone in the usual manner prepared and has a melting point of 71 ° C.

Regulation 2:

OH CH

Cl - (/ y_0 -CH-CH-C-CH \ = / II i ^CH'N

N587 g (2 moles) of L - ^ '- chlorophenoxy-1-IL.a.-triazolyl-il¹)] -3,3-dimethyl-butan-2-one are dissolved in 3 l of methanol. For this purpose, at 0 to 10 ° C with stirring and ice cooling in portions of 5 g in total 80 g

No. 334,686 (2 moles) of sodium borohydride and stirred at 5 to 10 ° C for 2 hours, then at room temperature for 12 hours. It is then cooled to 10 ° C and added at 10 to 20 ° C, 300 g (3 mol) of concentrated aqueous hydrochloric acid. After six hours of stirring at room temperature, the suspension obtained is diluted with 3.8 l of water containing 400 g (4.8 mol) of sodium bicarbonate. The resulting precipitate is filtered off. This gives 502 g (85% of theory) of 1- (4'-chlorophenoxy) -l- [l, 2,4-triazolyl (l ')] - 3,3-dimethyl-butan-2-ol of melting point 112 up to 117 ° C.

Regulation 3:

OH CH

Ci- / O-CH-CC-CH "\ = / III ^s ' ^CHs ^CHin ^{3 3} "N

A solution of 31.2 g (0.22 mol) of methyl iodide in 100 ml of anhydrous ether is added dropwise to a suspension of 4.8 g (0.22 mol) of magnesium turnings in 50 ml of anhydrous ether with stirring and reflux cooling, the solvent comes to a boil. When the addition is complete, to this Grignard solution is added a solution of 29.4 g (0.1 mol) of 1- (4'-chlorophenoxy) -1- [1,2,4-triazoly- (1 ')] -3, 3-dimethyl-butan-2-one added dropwise in 100 ml of anhydrous ether and heated to boiling under reflux for 18 h. After cooling, the reaction mixture is introduced into a solution of 80 g of ammonium chloride in 600 ml of 15% water, to which 250 ml of ethyl acetate are added and carried out for 15 min. The organic phase is separated off and the aqueous phase is extracted again with ethyl acetate. Both ethyl acetate Ausschüttelungen are washed twice with 100 ml of water, dried over sodium sulfate and freed from the solvent in vacuo. The crystalline precipitate is taken up in hot petroleum ether, leaving it undissolved, and filtered hot. This gives 11 g (36% of theory) of 1- (4'-chlorophenoxy) -l- [l, 2,4-triazolyl (l ')] 20 -2,3,3-trimethyl-butan-ol of the melting point 158 to 160 ° C.

Regulation 4:

OH CH \ ¹¹

Br-O-CH-CH-C-CH₃ "I

N, 33.6 g (0.1 mol) of 1- (4'-bromophenoxy) -1- [1,2,4-triazolyl- (1 ')] -3,3-dimethylbutan-2-one are dissolved in 300 ml of ethanol and to a 8 g (0.2 mol) of sodium hydroxide in 40 ml of water containing sodium hydroxide solution 25 and then added 32.4 g (0.3 mol) of formamidinesulfinic acid. The reaction mixture is heated to boiling for 3 h under reflux, filtered and the solvent distilled off in vacuo. The oily residue is taken up in 100 ml of water and extracted twice with 100 ml of methylene chloride. The combined organic phases are washed twice with 100 ml of water, dried over sodium sulphate and freed from the solvent in vacuo. The resulting oil is boiled with petroleum ether, where it crystallizes. Filtration gives 26.5 g (79% of theory) of 1- (4'-bromophenoxy) -1- [1,2,4-triazolyl (1 ')] -3,3-dimethylbutane-2 -ol of melting point 115 to 118 ° C.

Regulation 5:

OH CH "/ 'X II (/ O-CH-CH-C-CH \ = / II

CH "

N-¹¹ (erythro and threo form)

29.5 g (0.114 mol) of 1-phenoxy-1- [l, 2,4-triazolyl- (1 ')] -3,3-dimethyl-butan-2-one are dissolved in 250 ml of Me19

No. 334,686th ethanol and added portionwise at 0 to 5 ° C with stirring and reflux cooling 5.8 g (0.15 mol) of sodium borohydride. After 12 hours of stirring at room temperature, first, as described in Example 2, with 20 ml of conc. Hydrochloric acid and 250 ml of saturated sodium bicarbonate solution worked up. The sodium bicarbonate-containing suspension is extracted twice with 150 ml of methylene chloride each time. The combined organic precipitates are washed neutral twice with 100 ml of water each time, dried and freed from solvent in vacuo. The resulting oil is boiled with hot petroleum ether. This leaves a crystalline residue (I), which is filtered hot and dried. The filtrate is freed from the solvent under reduced pressure and this residue (II) is triturated with petroleum ether and a little ether. This gives a total of 23.4 g (79% of theory) of 1-phenoxy-1- [l, 2,4-triazolyl- (1 ')] -3,3-dimethyl-butan-2-one, 10 of which are 4, 1 g (I) erythro form of melting point 132 ° C and 19.3 g (II) threo form of melting point 88 to

94 ° C.

Similarly, the following compounds of the formula

RiO - C - C - R⁴¹ L

Az R³ receive:

Nr.334686

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<td>N &lt;</td><td>- &amp; = 2 - »= £ 3 = £ 3 &gt; - &amp; = / ^ · == 'κ- κ-'</td>

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Nr.334686

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No. 334686

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No. 334686

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<td>tq &lt;</td><td>= &amp; = 5 Yes a -_B= / B =^Z</td>

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<td>CQ P5</td><td>c 1 "M Where ü 1</td>

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Nr.334686