Novel halogenated 1-azolyl-butane derivatives and their use as fungicides

The present invention relates to a process for the preparation of halogenated derivatives of 1-azolylbutane of general formula I:

CHjX / cA-O- CH-A-C -Cfl_;;Y ₇ II

CH, • dl B. N 11

UJ or one ¹⁵ wherein A represents> a keto group - CH (OH) -,_: B represents a nitrogen atom or a group - £ H = * =, X represents hydrogen or halogen, Y represents halogen, Z represents halogen, phenyl and tetanyl, optionally substituted or phytooth, jar n represents 1 or 2, as ? and their physiologically compatible salts.

It is known that some derivatives of 1, 2,

4-Triazole and, in particular, 3,3-dimethyl, -l-phenoxy -1- (1,2,4-triazole -1-yl-b.utane -2- ply and butane -2-oils have good fungicidal properties {Patent, RF; G._r no. 2324010 and 2201063}. 'It is, by the way,

71574 ·:>:

'· -. · 2 U. ** known! that the imidazole derivatives, especially 3,3.-dimethyl) -1- imidazole, -î-_rilj -1- fetal oxybutnn -2- · onions and butane -2- oils substituted to the phenyl group, as well as ω - (jmldazo) -l-yl) -m-phenoxyaceptophenones. ^J .substituted, 1a phenyl and has good fungicidal properties (Patent, RFG, No. 2333354),. However, especially if. used in small quantities and in low concentrations, the efficiency of these known compounds is not always satisfactory. The present invention removes this disadvantage of the compounds from the lipid of the lipid and the pheochoxyacetophenoxyelgr: known, enlarged, at all times; the range of derivatives of these._:, realizing, .twgpar the utfnor derivatives of the general formula ^ of e.jnai Sus gr in the condensation of α-bromophenoxyKetone with the general formula II:

CH_?X

X_ /

Zn <

—O — CH— CO — C — CEL, Y

II

Br CH, <U1 in which X, Υ, Z and n take the meanings below, with azo of formula III:

LAW PRICE 71.20

<img file="RO71574A_D0001.tif" />

<img file="RO71574A_D0002.tif" />

Ν- ,.

. . Jl Β (Π1) r C · in whichUB has the above significance, the reaction taking place in acetonitrile medium at reflux and, if desired, the obtained keto-derivatives are reduced with complex hydrides in aliphatic alcohol medium by 1. 4 a- ΐθ carbon lathes at temperatures between 5 and 20 ° G, the products can be transformed into salts by reaction with acids.

The following are 21 examples of application of the process according to the invention.

Example 1

285 g (0.6 mol) of 4-chlorophenoxy-1,3,3-di.methyl -1- (1,2,4-triazole-1-yl) -butane -2-hour 28-g (0.6 mol) neutralized in accordance with Example 1 is neutralized. with an aqueous solution of sodium hydroxide. Yield 221.7 g of 4-chloro-1- (4-chlorophenoxy) 3,3-dimethyl -1- (.1,2, 4-thiazazole -1-yl) -butane -2-one (67 ,, 5% compared to the theory in relation to the amount of l-bromo-1- (4-chlorophenoxy) -3,3- dimethylbutane -2- used) as a colorless oil with the refractive index n ™ = 1,546.

example o.

CH,

OH CU,

Cl— κ θ z —O — CH— CH - C — CHjCl X HC1 1 I α-ζο ^&gt; - ο

SO, H.

CH-CO-C-CHjCl |

I! / \ / \

CHaX 1 / S1 O | O |^Z \ \/\/ /^N\

;, CH

SO, H

268.3 g {0.79 mol) of 1-hronicl-1- (4-chlorophenoxy) -3,3- dimethylbutane-2-one is dissolved in absolute 2 acetonitrile. And if⁹⁰damage to the resulting solution, 190 g (2.7 mol)

1, 2, 4-triazole, then heated for 20 h under reflux. The reaction mixture is then concentrated by distillation of the solvent under vacuum and the residue is taken up in 1000 ml of methylene chloride, washed three times with 250 ml of water, dried over sodium sulfate and concentrated again in vacuo. The remaining oil is dissolved in 1000 ml of acetone and a solution of 140 q (0.48 mol) of naphthalinsulfonic acid dissolved in 500 ml of acetone is added to the acetone solution. After 36 min, the precipitate formed is filtered through suction, ₄₅, I see. 285 g (76.6% of theory) of 4-chloro-1-(4-chloro-phenoxy) 1,5-naphthalindisulphonate - $ 3- dimethyl -1- (1,2,4-tri-azdl-l-ii) is obtained ) -button -2- melting point 245 ° C (decomposition), * 50^;- A similar result is obtained if the above synthesis is carried out at the temperature. of, 60 ° C_: with a reaction time of 96 h or at a temperature of 120 ° C and with a reaction time of 2 h. 55

Example 2.

ch₃

Cl / a \ -O-CO-C-CH-CH₂C1 1 1

....... / 'ξ CU,

II NNH

Dissolve 96.5 g (0.294 mol) 4-chloro -1 (4-chlorophenoxy) -3,3-dimethyl -1- (1,2,4-triazol -1-yl) -butane -2-one (prepared as in example. 2) in 300 ml of methanol. To this solution is added in portions at a temperature of 5 ... 10 ° C 12 g (0.3 mol) sodium borohydride. The mixture was further stirred for 15 h at room temperature, 30 ml of concentrated hydrochloric acid was added and the mixture was further stirred for 15 h at room temperature. The reaction mixture is then poured with stirring over 500 ml of saturated sodium bicarbonate solution, extracted three times with 150 ml of methylene chloride and the combined organic phases are washed twice with 100 ml of water, dried over sulfate. sodium and concentrate by distilling the solvent into the vacuum tube. The residue is dissolved in acetone, 100 ml of ethereal hydrochloric acid solution is added to the acetonic solution and concentrated to the vacuum of the water tube. The residue was taken up with ethyl acetate and crystallized at 0 ° C. 41.4 g (38¼ theoretically) of 4-chloro- (4-chlorophenoxy) -3,3- dimethyl -1- (1,2,4-triazole -1yl) -butane -2-ol hydrochloride is obtained (erythro and treo form) with. mp 157 ° C.

The same result is obtained if lithium aluminum hydride is used as reducing agent, also if the reduction reaction is carried out at a temperature of 0 ° C for 30 hours or at 20 ° C for 5 hours.

<img file="RO71574A_D0003.tif" />

Example 4

CH

Ct-Z &lt;A - / (A — O — CH — CO — C— CH_?C1 | |

CH, il

N

SO, H

I z \ / \

X 1/2 | oi O 1 \ z \ /!

SOjH

Example 6.

OH CH, / X 'I 2 O - CH- - CH-C-CHjCl

CH

II

N

Dissolve; 20.8 g of (0.05 mol) 1-bromo-4-chloro -1- [4- (4'-chlorophenyl) -phenoxy) -3,3dimethylbutane -2-. to 120 ml acetonitrile absolute, 12 g (0.175 mol) imidazole is added to the resulting solution. and heat for 40 hours at reflux. The mixture is then concentrated by distilling the solvent under vacuum and the residue is taken up with 300 ml of methylene chloride. The resulting solution is washed three times with 100 ml of water, dried over sulfate; of sodium and concentrated in vacuo, and the residue is taken up with 100 nil acetone. To the solution formed a solution of 9 g (0.038 mol) of 1,5-acetic acid naphthalindis in 50 ml of acetone is added and, after two hours, the precipitate formed under vacuum aspiration is filtered and dried. 19.6 q are obtained. (72¾ theoretically) 4-chloro- [4- (4'-chlorophenyl) - 1,5-naphthalindisulfonate. lonoxyl-3,3- dimethib-1- (imidazole -1- yl) -butane -2- melting point at 246 ° C.

Example 5

;, CH

Ț —z - CH — CO — C — CH₂C1

X_ 'X_X ij / Ν_χ CH

II

N.

It is neutralized with a solution of 4-chloro-1- [4- (4'-chlorophenyl) -phenoxy) 3,3-dimethyl -1- (imidazole -1-. ) -butane-2one, prepared according to Example 4, yielding quantitative yield of 4-chloro-1- (4- (4'-chlorophenyl) -phenoxy-1,3,3-dimethyl-1 (imidazole-1-yl) butane -2- melting point at 97 ... 99 ° C.

Suspended 18.8 g (0.04 mol) 1,5-naph-.

4-chloro -1- (4-chlorophenoxy) - talindisulfonate -,

-3,3-dimethyl -1- (imidazole -1- yl) - butane-,

2-one (prepared in Example 4, according to those described in Example 1, with a yield of 81 ¼) in 100 ml of methylene chloride, followed by the addition of 100 ml of SOr. baking soda. The organic phase, yes. separate, if. dry over, sodium sulphate and concentrate by distillation of the solvent, under vacuum, The base thus obtained is taken up with 100 ml isopropanol and the resulting solution is introduced into portions% q (0.05 mol) of sodium borohydride at³⁰ 5.5 ° C temperature. The mixture is stirred for 15 h at room temperature, then isopropanol is removed by distillation. The residue is taken up with 100 ml of methylene chloride, 100 ml of water is added and the mixture is further stirred for 15 hours at room temperature. The organic phase is separated,_f Wash twice with 50 ml of water, dry over sodium sulfate and concentrate. The remaining oily residue is boiled briefly in 100 ml of petroleum ether, thereby crystallizing. 9; 8-g (75¼ theoretically) 4-chloro -1- (4-chlorophenoxy) 3,3-dimethyl -1- (imidazole -1- yl) -butane -2ol as a mixture of isomers (erythrole and threon form ) with the melting point at 120 ..,

125 ° C.

50.

Working as in the above examples, however, using as a condensing medium acetone, methylethylketone, propionethyl, ethanol, tetrahydrofuran, dioxgn, benzene, dimethylformamide, methylene chloride, trichlorethylene, carbon tetrachloride and excess acetonitrile and / or triazole at a reaction temperature with⁶⁰ trapped between 60 and about 120 ° C, depending on the reactivity of the raw material and the reaction medium used, the following compounds of the general formula are obtained, given ⁶⁵ in table 1:

<img file="RO71574A_D0004.tif" />

ί

Table 1

Zn /^N\ BI

CH.X

I

N-C-CH₂YI

R

<td>exam- plul no.</td><td>Zn</td><td>A</td><td>X</td><td>Y</td><td>R</td><td>B</td><td>Melting point ° C</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td>S</td>

<td> 7</td><td>4— Cl</td><td>CO</td><td>H</td><td>Cl</td><td>ch_:!</td><td>N</td><td>190 (decomposition) SO, H f Z \ Z \ (Xl / 2 1 O | O |) \ Z \ z 1 SO, H</td>

<td> 8</td><td>A_A⁴~ \ Z</td><td>CO</td><td>H</td><td>Cl '</td><td>CH</td><td>N</td><td> 88—105</td>

<td> 9</td><td>2,4 -d</td><td>CO</td><td>H</td><td>Cl</td><td>CH</td><td>N</td><td> 63—64</td>

<td> 10</td><td>- 4 —- Γ \^Γθ2</td><td>co</td><td>H</td><td>BUT</td><td>CH</td><td>N</td><td> 105</td>

<td> 11</td><td></td><td>co</td><td>H</td><td>Cl</td><td>CH</td><td>N</td><td>188—91 SO.H 1 z \ z \ (X 1/2 1 O t O 1 1^xand SO, H</td>

<td> 12</td><td></td><td>CH (OH)</td><td>H</td><td>of</td><td>CH</td><td>N</td><td> 94—99</td>

<td> 13</td><td>4-Cl</td><td>CO</td><td>H</td><td>br</td><td>CH</td><td>N</td><td>127—131 fx HCl)</td>

<td> 14</td><td>4-Cl</td><td>CH (OH)</td><td>H</td><td>br</td><td>CH</td><td>N</td><td> 100—122</td>

<td> . 15</td><td>4-Cl</td><td>CO</td><td>H</td><td>Cl</td><td>CH</td><td>CH</td><td>266—67 SO, H 1 z \ z \ (Xl / 2 | Ο (Ο |) ι ^xSO, H</td>

<td> 16</td><td>4- \ O /</td><td>CO</td><td>H</td><td>Cl</td><td>CH</td><td>CH</td><td>203—205 SO, H Z \ Z \ (Xl / 2 | O | O |) \ Z \ z 1 SO, H</td>

<td> 17</td><td>4-NCB</td><td>CO</td><td>H</td><td>Cl</td><td>CH</td><td>CH</td><td>273 SO, H 1 z \ z \ (Xl / 2 IOI 0 1) \ Z \ z 1 SO, H</td>

<img file="RO71574A_D0005.tif" />

10

TabeiuJ î (continued)

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td> 13 </td><td>2,4-Cl₂</td><td>CO</td><td>H</td><td>Cl</td><td>CIT</td><td>GH</td><td>244 SO, H 1 / \ / \ (Xl / 2 1 OJOI) \ / \ Z 1 SORI</td>

<td> 19 </td><td>. 4-Cl</td><td>CO</td><td>H</td><td>br</td><td>CH_of</td><td>ch</td><td>238—240 SOsH - 1 z \ z \ (X 1/2 | OIO)), \ Z \ z 1 SORI</td>

<td> 20</td><td>4-Cl</td><td>CO</td><td>Cl</td><td>Cl</td><td>CH_S</td><td>CH</td><td>245 SOURCE 1 Z \ Z \ î (Xl / 2 | O io I.); \ Z \ Z -_s1 SORI</td>

<td> 21</td><td>4-Cl</td><td>CH (OH)</td><td>Cl</td><td>Cl</td><td>CH_of</td><td>CH</td><td> 113—119</td>

A series of methods for preparing some raw materials are given below for the examples cited above, as well as for obtaining these raw materials.

Preparation of raw material for exemption 1.

ci./ q \ \ ÎZ '

CH

I

-O-CO-C-CH-CH / '. I

br

CH

It is introduced, drop by drop,

213.5 g (1 mol) -1-bromine -4-. chlorine -3,3- dime.tilbutan -2- bona in a suspension of

125.5 g fl mol) 4-chlorophenol and 140 g (1 mol) potassium carbonate in 1000 ml boiling absolute acetone. The mixture was stirred Γ5 h at reflux, then allowed to cool, the inorganic residue was separated by filtration and washed with acetone. The filtrate is treated by distilling the solvent in vacuo. The residue was taken up with 1000 ml of methylene chloride, washed three times with 250 ml of water, dried over sodium sulphate and distilled. 210 g (80,7½ theoretical) are obtained 4-chloro -1- (4-chlorophenoxy) -3,3- dimethylbutane -2-one, with a boiling point of 125 ... 127 ° C at 0.1 mmHg.

To a solution of 210 g (0.01 mol) 4-chloro- (4-chlorophenoxy) -3,3- dimethylbutane -2-one in Τ0ΘΟ ml carbon tetrachloride is added dropwise at room temperature 10, 41 ml (0.81 mol) bromine so that the bromine is consumed continuously. Then the mixture is stirred for 30 minutes at room temperature.

After removal of the solvent by vacuum distillation, 268.3 g (98¾ theoretically) of crude l-bromo -4- chloro -1- (4-chlorophenoxy) -3,3- dimethylbutane -2-one is obtained directly from the reaction according to &lt;example 1.

Preparation of 1-bromo-4-chloro-3,3- dimethylbutane -2-

CH₃

I

BrCH-CO-C-CHjCt

CH₃

Dissolve 134.5 g (1 mol) 1-chloro -2,2-dimethylbulan-3-one in 500 ml ether. To this solution is added, drop by drop, under gentle cooling, 51 ml (1 mol) bromine with a flow rate to ensure that the bromine is consumed continuously. Then, the solution is stirred in 1000 ml of ice water, the organic phase is separated, washed with 250 ml of water, dried over sodium sulfate and distilled. Yield 169 g (80½ theoretically) l-bromine -4- chloro -3,3- dlmethylbutane-2-boiling point, at 95, 106 ° C / r3 mmHg.

.. Preparation of chlorine -2,2- dimethybutane-3-Orej

CH ₅

CH-CO-C-CH₂C1 I

CH₃

11., 6 g (0.1 mol) 2,2-dime to -1- hydroxybutane-3-one are added dropwise at 50 ° C., 60 ^ 0 (ice-cold cooling), to an amount of 20.5 g {0.1 mol), Ν, Ν-diethyl -1,. 2, 2-trichlorvinylamine. The mixture was stirred for 2 h at 60 ° C¹⁵ it is distilled under vacuum of the water tube.

8.1 g (60% of theoretical) are obtained 1chlor -2,2- dimotylbutane -3- one, with a melting point at 6O ... 62^dC / 12 mmHg.

2-1-Chloro -2,2- dimethylbutane -3- good se ²⁰obtain at a yield of 30%, heating at reflux 12 h, equimolar amounts of 2,2-dimethyl-1- hydroxybutane-3- one and triphenylphosphine in an amount of 10 hours] higher than carbon tetrachloride, after ²⁵which the solvent is removed by distillation, the residue is taken up in ether, filtered and distilled.

Preparation of 2,2-dimethyl -1- hydroxybutane-30 3-one stream, then allowed to cool. The inorganic residue was filtered and washed with acetone. The filtrate is concentrated by removing the solvent in vacuo and 50 ml diisopropyl ether is added to the residue and allowed to crystallize. 37.5 g (55% of theory) of 4-chloro- [4- (4'-chlorophenyl) -phenoxy] -3,3- dimethylbutane -2-one) are obtained, with a melting point at 67 ... 68 ° C.

Dissolve 33.7 g (0.1 mol) 4-chloro-1,4- (4'-chlorophenyl) -phenoxy) -3,3-dimethylbutane-2-one in 250 mL carbon tetrachloride. The resulting solution is added dropwise at room temperature, 5.1 mo) (0.1 mol) bromine in such a way that the bromine is consumed continuously, the mixture is further stirred for 30 min and stirred. . Remove the solvent by vacuum distillation. The crude l-bromo -4-chloro -1- [4- (4'-chlorophenyl) -phenoxy) -3,3- dimethylbutane -2-one is obtained, which is directly subjected to the reaction of Example 4.

Preparation of other raw materials

CH

Br-CH₂CO-C-CH-Br

CH

CH

% CH 3 OH-CO-CC

CH

Add, dropwise, a solution of 172 g (2 mol), methylisopropylketone in .1000 ml methanol, a solution of 66 g (2.2 mol) paraformaldehyde and 1 q potassium hydroxide in 10 ml methanol. The mixture s_e Heat for 15 hours under reflux, after which the methanol is distilled through a column at a temperature of 82 ° C (in the reaction mixture) and the residue is distilled under a vacuum of water. Obtain 152.7 g (68% of the theoretical) 2,2-dime til -1- hydroxybutane -3- one with the boiling point at 8O ... 82^ofC / mmHg.

.Preparation of the raw material from the example! 4

C!

CH, / or W οΛ —O -CH— COC — CH₂C (Br. CH, in a suspension of 41 g (0.2 mol) 4- (4'-chlorophenyl) -phenol and 28 g (0.2 mol) potassium carbonate in 300 ml boiling absolute acetone is introduced 42 7 g (0.2 Mole) 1-bromo-4-chloro-3,3-dimethyl -2-one. The resulting mixture was stirred for 15 hours at r65

34.8 g (0.3 mol) 2,2-dimethyl are added dropwise. -1- hydride&gt; xibutan-3one to 47.6 g (0.25 mol) of toluenesulfochloride and then at a temperature between 0 and 5 ° C, 40 ml (0.5 mol) pyridine. The mixture was allowed to stir for 15 hours at room temperature, then poured over 200 q ice and 70 ml concentrated hydrochloric acid. The organic phase was separated, dried over sodium sulfate and concentrated, distancing the solvent under vacuum of the water fallopian tube. To the residue is added 200 ml of petroleum ether, obtaining a precipitate, representing 48 g (71% theoretically) of 2,2-dimethyl-3- ketobutoxy-ptoluenesulfonic acid ester, with a melting point of 49 ... 52 ° C. ;

g (0.1 ml) of the ptoluensulphonic acid ester prepared above is ^JDissolve in 100 ml methylethyl ketone and together with 52 g (0.6 mol) lithium bromide are heated for 48 hours at reflux. The mixture was filtered by vacuum suction, the solvent was distilled off under normal pressure, the residue was dissolved in methylene chloride and washed four times with 100 ml of water. The organic phase is dried over sodium sulfate and concentrated in a vacuum of water. We obtain 15 g (84% of theoretical) 1-bromo2,2-dimethylbutane -3-one, which, as in

<img file="RO71574A_D0006.tif" />

in the case of l-chloro -2,2- dimethylbutane -3- onel, it is passed through the reaction with bromine in 1,4-dibrom -3,3- dimethylbutyl -2-one.

CHsCi

I

BrCHs-CO-C-CH₃C1 i

CH

N \_W/ basic —HBr

According to those described above, 2,2-bis-hydroxymethylbutane -2-one is first attenuated by the formation of methylethyl ketone, after which 2,2-bis-hydroxymethylbutane -3one, reacts with two equivalents of Ν, Ν-diethyl -1, 2, 2-triclorvinilamină. 2,2-bis-chloromethylbulan -3-one is obtained, which then reacts with bromine, finally giving 1-brom -3,3- b / s-chloro-ethylbutton -2-one.

As can be seen from the above examples, the compounds of formula I, wherein A represents the CH (OH) group, contain two asymmetric carbon atoms and, therefore, may be present in both geometrically isomeric forms (the erythro form and the form treo). These forms result in different quantitative ratios. In both cases, these compounds are present as optical isomers.

The reaction mechanism is presented as a sche- ³⁰matized in the following sequence of reactions, for the use of raw materials l-bromo -4-chloro -1- (4-chlorophenoxy) -3,3- idymethylbutane -2-one and 1. 35

2, 4-triazole.

CH

I — O — Cf f—CO—C—CH—.CI II _zÎ \ CH,

II II The bromophenoxyetones used as raw materials are defined by the general formula II A:

CH_ZX z ™ \ I

CO&gt; -O-CH- A -C-CH₂Y

X_Z,, “/^N\ ^R '(ΠΑ)

II B N__II

CH

Cl- / o ^ - .O — CH CO — C - CHjCl + 1 1

br

I

CH, base \_Nz I

H

CH, (

—O — CH — CO — C— CH&gt; C1 I

CH, z^N\

If 1bromo-4-chloro-1- (4-c phenoxy) -3,3- dimethylbutane -2-one and imidazole are used as starting materials, the reaction can be illustrated by the following scheme:

OH,

Z \ I

Cl &lt;o&gt; O —CH — CO — C — CH, Cip t

br

CH, in this formula, R may preferably represent 1 to 4 alkyl carbon atoms, especially methyl and ethyl; R may also represent a phenyl group, optionally substituted by halogen, in particular with chlorine, fluorine or bromine and C 1-6 alkyl having 1 or 2 carbon atoms, X may preferably represent hydrogen, 1 to 4 alkyls. carbon atoms, especially methyl and may also preferably represent halogen, especially chlorine or bromine, Z may preferably represent - halogen, especially fluorine, chlorine, bromine and -iod, a linear alkyl group or ' branched with 1 to 4 carbon atoms, cellulose having 5 to V carbon atoms, in particular cyclohexyl, 7 | it may also preferably represent halogenalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, ie fluorine or chlorine atoms, for example, the triflubmethyl group. At the same time, Z can Teprezerite alkoxy and alkylthio, being with 1 or -2 carbon atoms, alkoxycarbonyl · 1 to 5 carbon atoms, and preferably amino, cyan and nitro. In addition, Z may also preferably represent phenyl or phenoxy¹, if substituted, the substituent being preferably halogen, in particular fluorine, chlorine, bromine and iodine, as well as amino, cyano, nitro or alkyl having 1 or 2 carbon atoms; Lastly, Z may more preferably represent phenylalkyl with 1 or 2 carbon atoms in the alkyl side, optionally substituted, the substituents being on the alkyl chain, preferably alkylcarbonyl having a total of up to 3 carbon atoms and in the benzene ring. , preferably halogen, nitro and cyan. Fig. N repre-

<img file="RO71574A_D0007.tif" />

-SS

<img file="RO71574A_D0008.tif" />

7157-1 targets an integer between 0 and 3, and A has the definition given by the object of the invention.

The starting materials of formula II mentioned as examples are: 1-bromides -1- (3-chlorophenoxy) -3,3- dimethylbutan2-one, 1-bromine -4-. chloro-3,3-dimethyl -1 (4-fluorophenoxy} -butane -2-one, l-bromo-4-chloro-3,3- dimethyl -1- (4-iodophenoxy) - butane -2-one, l-bromine -1- (4-bromophenoxy) 4-chloro-3,3-dimethylbutane -2-one, 1-bromo-4-chloro-3,3-dimethyl -1- (2,4-trichlorophenoxy) buane ~ 2-one , 1-bromo-4-chloro-3,3-di4netyl-1- (2-methylphenoxy) -butane -2-one, 1-bromo-4-chloro-3,3-dimethyl -1- (4-methylphenoxy) ) -butane -2-one, 1-bromo-4-chloro3,3-dimethyl -1- (3,4-dimethylphenoxy) - butane -2-one, 1-bromo-4-chloro -1- (4-chloro-2-methylphenoxy) -3,3- dimethylbutane -2-one, ₂₀1-bromo-4-chloro -1- (4-chloro 3,5-climethyl-nooxy) -3,3- dimethylbutane 2-one, 1-brorn4-chloro-3,3-dimethyl -1- (2-methyl - 5- Nitrophenoxy) - butane -2- one, 1-bromo-4-chloro -1- (2-cyclohexylphenoxy) -3,3- dime- ₂₅tilbutan -2- one. 1-bromo-4-chloro -1- (4Cyclohexylphenoxy) -3,3- dimethylbutane -2g, 1-bromo -4-chloro -3,3-dimethyl -1- (4.methoxyphenoxy) -butane -2-one, 1- Bromo-4-chloro-3,3- dimethyl -1- (3-trifluoromethyl)_3Qnoxi) - butane -2-one, 1-bromo-4-chloro-3,3-dimethyl -1- (4-methylthiophenoxy) - butane -2-one. 1-bromo-4-chloro-3,3-dimethyl -1- (4-methoxycarbonylphenoxl) -butane -2-one, 1-bromo-4-. chloro-3,3-dime- "til -1- (2-pheniphenoxy) - butane -2-one, 1-bromo-4- chloro -1- (2-chloro-4-phenylphenoxy) 3,3-dime tilbutan -2-one , 1-bromo-4-chloro-1- [4- (4'-chlorophenoxy) -phenoxy] -3,3- dimethyl -2-one, 1-bromo -1- [4- (4'-chlorobenzyl) -₄₀

3,3- dimethylbutane -2-one, 1-bromo-4-chloro-1- (4-phenylacetyloxymethyl) -phenoxy] -3,3- dimethylbutane -2-one, l-bromo-4-chloro -1- (4-cyanophenoxy) ^ 3,3 - dimethylbutane-2-one,, (4-aminophenoxyx} -1- bromo -4- 45 chloro-3,3-dimethylbutane -2-1-one, 1- (4-chlorophen.xi) -1,4-dibromo- 3,3- dimethylbutane-2, 1- bromine: -4- clpr, -d-_?(4-Chlorophenoxy) 3,3-diethylbutane -2-one, 1-bromo-4-chloro-3-chloromethyl -1- (4-chlorophenoxy) -3-methylbu- ⁵⁰tan -2-one, 1-bromo-4-chloro-3-chloromethyl-1- (4-chlorophenoxy) -3- (4-chlorophenyl) -butane -2one.

Bromphenoxy-ketones of formula II u- ⁵⁵used as raw materials, according to the invention, are not yet known, they can be prepared by known methods, for example, by the reaction of some of the compounds of formula IV:

UV)

Ifi where Z has the meanings mentioned above with a bromethon of formula V:

Br— Cil_? CO-C-CH₂Y (V)

In which R, X and N have the above meanings, after which the remaining active hydrogen atom is replaced as known with bromine (see also the preparation examples).

Phenols of formula IV are compounds, generally known in organic chemistry.

Brometones of the general formula V are also compounds generally known from organic chemistry. They can be prepared by known and generally used methods (see also the preparation examples).

Azoles used as raw materials are defined by formula III. In this formula, B has the meanings defined by the object of the invention. As a result, formula III defines 1, 2, 4-triazole and imidazole.

As salts of the compounds of formula I, salts with acids, physiologically compatible, are taken into account. Of these acids are preferably cited as halogenic acids, for example hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, carboxylic and hydroxycarboxylic acids, mono and bifunctional, such as acetic acid, succinic acid, fumaric acid, tartaric acid, salicylic acid, citric acid, sorbic acid, lactic acid and 1,5-naphthalindlsulfonic acid.

For the reaction according to the invention, inert organic solvents can be considered as diluents. These include, preferably, ketones, such as dielyl ketone, in particular acetone and methylethyl ketone, nitriles, such as propionitrile and, in particular, acetonitrile; alcohols, such as methanol or isopropanol; ethers, such as tetrahydrofuran or dioxane; benzene; formamides such as dimethylformamide and halogenated hydrocarbons.

In applying the process according to the invention, for one mole of the compounds of formula II, preferably 2 mole triazole and 1 to 2 mole acid acceptors are used. To isolate the compounds of formula I the solvent is removed by distillation, the residue is taken up in an organic solvent and washed with water. The organic phase is dried over sodium sulfate and the solvent is removed in vacuo. The residue is purified by distillation, respectively by recrystallization.

SE

The reduction step can be illustrated as below.

Using as raw materials 4-chloro -1- (4-chlorophenoxy) -3,3- dimethyl -1- (2,4-triazolyl) -butane -2-one and sodium boride, the reaction can be illustrated by the following scheme, ·

CH

I

Cl — ζ O) —O —CH —CO — C — CH₂With NaBHj \ _Z &lt;t /^N\

II N

Ν II ch,

OH CH, / - \ I 1 '► C (- &lt;O&gt; - O — CH — CH — C — CH₂CI \ __ Z I 'I z^N\

II N Ν II

CH

If 4chlor -1- (4-chlorophenoxy) -3,3- dimethyl -1- (imidazole -1- yl) -butane -2-one and sodium borohydride are used as starting materials, the reaction can be illustrated by the following scheme :

CH, ci-o 2 -O —CH — CO — C — CHj — Cl

Z \

N

N ||

I

CH

NaBH, '►Cl · / q \' \ ÎZ

OH CH, '

1

-A-CH-C-C-CH₂C1 z^N\

CH

To reduce the ketone to. Alcohol, according to the invention, can be considered as polar organic solvent diluents, among them preferably alcohols, such as methanol, butanol, isopropanol and ethers, such as diethyl ether and tetrahydrofuran. It is generally worked between 0 and 30 ° C, preferably between 0 and 20 ° C. For about 1 mol of the compound of formula I about 1 mol of a complex hydride, such as sodium boride or lithium aluminum hydride, is used. For the isolation of compounds of formula I the residue is taken up with dilute hydrochloric acid, then alkalized and extracted with an organic solvent. Next, the extract is usually processed.

From the point of view of biological activity, the compounds, according to the invention, exhibit a strong fungitoxic - as well as a bacteriotoxic - action. These substances do not harm the crop plants in the concentrations necessary to control fungi and bacteria,⁵ therefore, the new active substances are suitable to be used as thousands of spears for plant protection in order to combat these agents. in works dedicated to plant protection, means¹⁰ fungitoxic are used for combining Plasmodiophortnicetes Oomycete species_And Chytridyomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. ^L5 In addition, the active substances prepared according to the invention have a wide range of action and can be used against parasitic fungi and fungi, _2Q attacking or against the upper parts of plants¹ which attacks the plants, from the soil, as well as against pathogens that transfer through seeds. . .

₂₅ A particularly good efficiency is the compounds of formula I against parasitic fungi and fungi, such as those of the species Erysiphe, Podosphacra 'and Venturia, as well as against₃₀ the pathogenic genius that causes apple flour (Podosphaera leucotrichaj, apple bubble (Fusicladium dendriticum), cucumber flour (Erysiphe cânchoracearum) and bean rust '(Uromyces phaseoli) and also against the Pyricular fungus of Oriceae and Peaculeae. high efficiency and against cereal diseases, cereal flour and rust. It should be emphasized that the active substances prepared according to the invention carry not only a protective efficiency but also act as a curative, ie after the plants have been infected. In part, these substances also act systemically. Thus, plants⁴⁵ they can be protected against fungal attack and, if the active substance is administered to the upper parts, passing through the soil and roots or through_s0 fertilizers.

As plant protection agents, the substances prepared according to the invention can be used for the treatment of soil, seed or for treating the upper parts of plants.

As shown, active substances of formula I are well supported by plants and exhibit only low toxicity to warm-blooded animals. Due to their very weak odor and the fact that they do not attack human skin, their handling is very easy.

The processing of the active substances, prepared according to the invention, can be repaired⁶⁵ lysis in the form of usual compositions, that is

<img file="RO71574A_D0009.tif" />

.19 solutions ,, emulsions, .suspensions, powders, pastes .41 .granules, which are prepared by the usual processes, for example, by mixing the active substance with diluents, ie fused solvents, or liquefied gases. find- ⁵.ie, - under "pressure; and / or .with vehicles soJi-zÂj-.utiHznd, -eventual,, and -social substances, root.-emulsifiers and / or dispersants and / or.spumants.'- if used - water diluent case, it can be used¹⁰

-like-auxiliary solvents, for example -sol.ventixsTgantoi. And solvents. liquids. -se: «rat • Jua.consideration, mainly: aromatic hydrocarbons, such as benzene toluene and -xylene, saualchiiitoftalineto; hydrocarbs-¹⁵.iearomaticeclorurates. and chlorinated aliphatic hydrocarbons, such as benzene. chlorinated, .chlorethylene: or · methylene chloride, aromatic hydrocarbons, ca. cyclohexane sad .. paraffins,&gt; e.g., ²⁰.Lwliere_; alcohols, eahutanohil sauglico.1 ul, and ethers and esters thereof, Getons such as acetone, methyl ethyl ketone, meilisobutyl ketone or cyclohexanone, polar polar solvents, such as dimethylformamide and ²⁵ dimethylsulfide oxide _;and water, - by .diluted diluents found under .pressure are understood to mean liquids, .which under pressure .and normal temperature _see. find in a. phase, for example, the moving gases i, ³⁰aerosols, such as dichlordifluoromethane or tri.clorlluoromethane ·, as solid carriers may be considered rock flour. natural, such as clay, caoliruil, talc, chalk, quartz, tarpulgulite, montmoriltonite and³⁵diatomite, · flour - of synthetic rocks, · as dispersed cayenne sili.and aluminum oxide and silicates, as emulsifiers, nonionogenic and antonic emulsifiers, such as esters of polyoxyphenic acid, fatty alcohol ethers, ⁴⁰polyoxyethylene herein, for example, alkylarylpolygltoethyl ether; alkylsulfonates, alkylsulfates, arylsulfonates and hydrobenzyl albuminins, .ca dispersants, for example: lignin, sulphyl lysines and meylcellulose.⁴⁵ 'Active substances,. Prepared according to the invention,' may be presented, 'in compositions.and. in combination with other known active substances, for example, with fungicides, _5Qinsecticides, acaricides, nematocides, herbs, .substances, .bird protectors, growth enhancers, fertilizers._:and.materialo for improving the soil structure. ⁵⁰ 'Compositions generally contain between 0.5 and'&gt; 95%, preferably between 0.5 and 90¼ active substance.

'The active substances can be used as a- ³⁰.tare, in the form of compositions or may be administered with preparations of the foregoing ί by dilution, as solutions for the preparation, emulsions, suspensions, powders, -65 pastes and granules, which are applied by the usual methods, for example, by pouring, splashing, spraying, spreading, -sampling.switching, wet brining, brining with emulsion or by inlay.

When used as a fungicidal substance on the leaves, the concentrations of the active substance may vary in application forms between Iarqi limits, in general, between 0.1 and 0.00001 o / o, preferably between 0.05 and 0.0001o / a weight.

In the case of seed treatment, quantities of between 0.001 and 50 g of active substance are generally used, preferably between 0.01 and 10 g of active substance / kg of seed.

For soil treatment, 1 to 1000 g of active substance is needed, preferably between 10 and 200 g / im³ ground. The active substances, prepared according to the invention, also have effects of regulating the growth of plants, if they_ are used in appropriate quantities.

The multilateral possibilities for use result from the following tests.

Test A.

Design test'Padosphaera / mar - Solvent: 4.7 parts by weight acetone - Emulsifier: 0.3 parts by weight alkylpolyglycolic ether.

- Water 95 parts by weight.

The amount of active substance necessary to obtain the desired concentration of active substance in the spray liquid is mixed with the given amount of solvent and the concentrate thus obtained is diluted with the given amount of water containing the said auxiliary substances.

With the solution obtained s_G sprinkle until dripping moisture young apple seedlings, found in the development stage with 4 to 6 leaves. Plants are stored 24 h, in the greenhouse at -20 ° C - and at a relative humidity of air: 70¼. Then, the plants are inoculated by dust with Podosphaera conidia¹ leucotricha and · transferred to a greenhouse with a temperature of -21 .., 23^aDue to the relative humidity of the air of about ^ 70¼.

LarlO days after inoculation, the attack on the seedlings is determined. The values ​​obtained are recalculated in percentage of attack. 0¼ means the plant is not attacked, 190¼ means that the plants - are completely attacked.,

- The active substances, their concentrations and the obtained results are included in the table. 2,

<img file="RO71574A_D0010.tif" />

22

Table 2

The Podosphaera (apple) design test

<td colspan="2" rowspan="2">Active substance</td><td colspan="3">AttackLîp% with, a, active substance concentration of:</td>

<td colspan="2"> 0.01</td><td> 0,0025</td>

<td colspan="2">) CH + C - X 0 \ -O-GH-CH-C {CH_;,)3 ^Z 1 I</td><td></td><td></td><td></td>

<td>OH 11 '£</td><td></td><td> 100</td><td></td><td> —</td>

<td>{known) </td><td></td><td></td><td></td><td></td>

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

<td colspan="2">Cl — ΧΆ – Χ fA — O — CH — CO — C — CH₂C1 so, h</td><td></td><td></td><td></td>

<td rowspan="2">CH 11 times</td><td>Z \ Z \</td><td> __„</td><td></td><td> 79</td>

<td>χ i / u! o ι o |</td><td></td><td></td><td></td>

<td>(4) li-N</td><td>Y^xzsoshi</td><td></td><td></td><td></td>

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

<td>/ O-CH— CO — C — CHjCl \ / \ / | |</td><td>50, H 1</td><td></td><td></td><td></td>

<td>CH</td><td>z \ z \ χ i / aio ι o |</td><td> —</td><td></td><td> 55</td>

<td> (161. -11_</td><td>\ / \ Z and</td><td></td><td></td><td></td>

<td></td><td>SO, H</td><td></td><td></td><td></td>

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

<td colspan="2">Cl-ζ o CH ^ O — CH₂C1</td><td></td><td></td><td></td>

<td> 1 1</td><td> 1</td><td> _____</td><td></td><td rowspan="2"> 75</td>

<td>, N_X OH⁽⁶⁾ i-</td><td>CR,</td><td></td><td></td>

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

<td>Cl ZJ '</td><td></td><td></td><td></td><td></td>

<td>CI— / 0 \ —Q — CH — C — C — CH₂BUT \ / II</td><td>SO, H 1</td><td></td><td></td><td></td>

<td>N CH- »</td><td>z \ z \</td><td></td><td></td><td> 2</td>

<td>Z \ χ</td><td>1/2 1 O 1 O 1</td><td></td><td></td><td></td>

<td>II ^lf</td><td>\ Z \ z</td><td></td><td></td><td></td>

<td>(18)! 1 - N</td><td>1 SOjH</td><td></td><td></td><td></td>

Test B.

Erysiphe Protective Test [cucumbers] - Solvent; 4.7 parts by weight acetone 5 - Emulsifier: 0.3 parts by weight alkylpolyglycolic ether;

- Water: 0.5 parts by weight.

Mix the quantity of active substance necessary to obtain the desired amount of active substance in the spraying liquid with the given quantity of solvent and the concentrate thus obtained; dilutes with the given amount of water, which; contains the auxiliary substances mentioned.

With the solution, - obtained - sprinkle young cucumber plants, until dripping moisture. For drying, cucumber plants are kept for 24 hours in the greenhouse. Then, for inoculation, they are dusted with the conidia of the fungus Erysiphe cichoriacearum, after which the plants

<img file="RO71574A_D0011.tif" />

71,574 transfer to a greenhouse with a temperature of 23 ... 24 ° C and a relative air humidity of 75¼.

After 12 days the cucumber on the cucumber plants is determined. Values ​​are recalculated in attack percentages 0¼ means that the plants are not attacked, lOOVo means that the plants are completely attacked.

The active substances, their concentrations and the results obtained are shown in table 3.

Table 3

The erysiphe test (cucumbers) design

<td rowspan="2">Active substance</td><td colspan="4">Needle in% with an active substance concentration of: %</td>

<td> 0,00062</td><td> 0,0005</td><td> 0,00031</td><td> 0,00025</td>

<td>(CH JjC— / OO — CH — CH — C (CH₃)_{: Q} /^N\ OH II N N || (known)</td><td> —</td><td> —</td><td> 66</td><td> —</td>

<td>Cl \ _ ci-OO-CH-CH-C (CH ·,),^X-,^z i 1 there Z^N\ ^OHf! N N_H (known)</td><td> —</td><td> —</td><td> 29</td><td> __</td>

<td>(CH₃)₃C-O ^ -O-CH-CH-C (CH₈)₃Z \ °^HII n II N (known)</td><td> 100</td><td> —</td><td> —</td><td> — </td>

<td>"'J¹¹I know₃h Cl ^ O ^ O-CH - C ° -C- Ci + Cl Z \ Z \^_ N CH x 1/2 | O | O | Z \ ^CH'\ Z \ Z II N 1₍₁₎ N. || SO₃H</td><td> —</td><td> —</td><td> —</td><td> 10</td>

<td>CH_:, CI — T o / 6 — O — CH — CO — C — CH₂C1 Ψ³-’¹⁴X— '1 1 1 •, tV CH Z \ Z \ . , / \^{CH 1} x 1/2 1 or IO [ * '^1: ·. ^: ..... II N \ Z \ z - · - (7) 'N II 1 SO.II</td><td> —</td><td> —</td><td> —</td><td> 0</td>

Table 3 (continued)

The erysiphe test (cucumbers) design

<td rowspan="2">' Active substance</td><td colspan="4">Attack in% as an active substance concentration of: "/" </td>

<td> 0,00062</td><td> 0,0005</td><td> 0.00031</td><td> 0,00025</td>

<td>CH f eX o -o-cu-co-c- ch_qci \ _z \ _x ₍ | /^K\ CH, 8 ,, N (ai ν β</td><td> —</td><td> —</td><td> —</td><td> 22</td>

<td>CH CH-O-CO-C-CH₂C1 ^ °^3HJt L · Z \ Z \ Z \ CH, x _1/2 | 0 j O 1 II fi \ Z \ Z (4) II ν I SO, H</td><td> —</td><td> 62</td><td> —</td><td> —</td>

<td>CH / ~ \ 1 Cl— &lt;o&gt; —O — CH — CO — C — CHjCI SO, H 11 '1 / N, CH, Z \ Z \ îf ,, x 1/2 1 O | 0 | (11 ί γ ^^ζSO, H</td><td> —</td><td> 46</td><td> —</td><td> —</td>

<td>CH^Z 0 f O \ —O — CH— CO — C— CH₂C1 SO, H x_Z \ _Z | ι 1³CH, Z \ Z \ îf ,, x 1/2 IOJO | (16) II NY^{X /}SO, H</td><td> —</td><td> 62</td><td> —</td><td> —</td>

<td>CH O, N — Y&gt; CH — CO — C — CH₂C1 SO »H “Ν ΓΗ Z \ Z \ CH, x 1/2 l OIO (17) II N SO, H</td><td></td><td> 66</td><td> —</td><td> —</td>

Test C. casting mold with. the quantity given by

Erysiphe Systemic Test (cucumber) - Solvent: 4.7 parts by weight acetone;

- Emulsifier: 0.3 parts by weight of alkylpolyglycolic ether;

- Water: 95 parts by weight.

The quantity of active substance necessary to obtain the desired concentration of active substance in the solvent is mixed and the resulting concentrate is diluted, with the given amount of water, containing the said auxiliary substances.

Pour on cucumber plants sprouted in a homogeneous soil until the development stage t-2 leaves, within a week three times 10 cm³pouring liquid of given concentration 100 cm² ground.

<img file="RO71574A_D0012.tif" />

<img file="RO71574A_D0013.tif" />

2S

The plants thus treated are inoculated with the conidia of the fungus Erysiphe cichoracearum, after which the plants are placed in a greenhouse at a temperature of 23 ... 24 ° C and have a relative air humidity of 70¼. ⁵ ; After 12 days, the aisuJpra attack of cucumber plants is determined. The obtained values ​​are recalculated in the attack β / o: 0¼ means that the plants are not attacked, 100% means that the plants are completely attacked.

The active substances, their concentrations and the obtained results are included in table 4.

Table 4

Erysiphe / systemic test

<td>Active substance</td><td>The attack in% against the attack of the untreated control plants; concentration of active substance and PPm</td>

<td>(O χ o -O- CH-CH-C (Ci L), | | OH lt N N__B (known)</td><td> 100</td>

<td>BUT \ _ ci - &lt;fo \ -0-CH-CH-C (CH₃) j^X“\ ^{1 1}there /^N\ ^OHin N Ν 11 (known)</td><td> 100</td>

<td>CH Cl- &lt;o) -O - CH-CO-C-CHjCl SO, II LTI / N_x CH, Z \ / \ π jî x 1/2 IO | O | Ν Ϊ \ / \ / I¹'SO., H</td><td> 27</td>

<td>CH, z \ 1 OjN— &lt;OY O- CH CO — C — CH₂C1 Z ^ \ CH, β N N | (10)</td><td> 75</td>

<td>CH Z \ ¹&lt;O&gt; -O-CH-CO-C- -CH₂C1 so₃h ti I z^N\ CH „Z \ Z \ read N -1/210101 N it ... \ Z \ Z^fl'&gt; I, H</td><td> 6</td>

<img file="RO71574A_D0014.tif" />

Test D.

Fusicladium design test (apple) - Solvent: 4.7 parts by weight of acetone;

- Emulsifier: 0.3 parts by weight of alkylpolyglycolic ether;

- Water: 95 parts by weight,

To obtain_e the desired substance concentration in the spray liquid, the required amount of active substance is mixed with the given amount of solvent and the concentrate thus obtained is diluted with the given amount of water, which contains said auxiliary substance.

You can spray young apples found in the development stage with 4-6 leaves with this liquid until dripping moisture. The plants are stored 24 h in a greenhouse at a temperature of 20 ° C and a relative air humidity of 70¾. Then, the plants are inoculated with an aqueous solution of pathogenic conidia, which causes buba, apple (Fusicladium dentriticum) and incubated for 8 hours in a humid room with a temperature of 18, 20 ° C and a relative humidity of the air. of 100¾. after which the plants are returned to the greenhouse for 14 days.

At 15 days after inoculation, the attack on the seedlings is determined. The obtained values ​​are recalculated in% of attack. 0% means that the plants are not attacked and 100½ means that the plants are completely attacked.

The active substances, their concentration and the results obtained are shown in table 5.

T-hive 5

Fusiclachum test (mum) design

<td rowspan="2">Active substance</td><td colspan="2">Attack in% with a concentration of active substance by:</td>

<td> 0,025</td><td rowspan="2"> 0,01</td>

<td>But _z &lt;^ o —O — CH— CO — C (CH₃). | a / “\ BN N II (known)</td><td> 43</td>

<td>Cl \ _ Cl- \ o \ -O-CH-CH-C (CHj)_of\ l / \ °^HII N N || (known)</td><td> —</td><td> 62</td>

<td>CH z “\ l Cl- &lt;o) —O CH - CO-C — CH_?C1 SO, H 1 to 1 CH, Z \ Z \ II \ χΐ / Ωΐθϊθΐ N II γ⁽¹* ΞΟ, Η</td><td> —</td><td> 11</td>

<td>CH_;itCi-XO YO \ -O -CH CO - C — CH₂C1 so, h \ _Z \ _z 11 1 / \ CIR Z \ Z \ ( ^XN xi / etoioiot N fl V^{X /}^(?) SORI</td><td> —</td><td> 16</td>

<td>ch₃X o Yζ O&gt; —O — CH — CO — C — CH₂C1 \ "z \ _Z, |_ZN \ CH, II N N || (8)</td><td> —</td><td> 0</td>

<img file="RO71574A_D0015.tif" />

32

Test E. Uromyces Protective Test (tar rust) - Solvent 4.7 parts by weight acetone;

- Emulsifier: 0.3 parts by weight of alkyllarpoliglicalic ether;

- Water: 95 parts by weight, in order to obtain the desired concentration of active substance in the spray liquid, mix the required amount of active substance with the given amount of solvent and the resulting concentrate is diluted with the given amount of water, which contains said auxiliary substance.

With this liquid, young bean plants are sprayed, found in the development stage with two leaves, until dripping moisture. The plants are kept lightly in the greenhouse for 24 hours, at a temperature of 2 °, 22 ° C and a relative humidity of 70%. Then, the plants are inoculated with a suspension of uredospores of the agent that causes the bean rust (Uromlces phaseoli) and incubated for 24 hours in a damp dark room at a temperature of 20 ... 22 ° C and at a relative humidity of 100% air.

The plants are kept in the greenhouse in the cone¹⁰ hold for nine days light at a temperature of 2O ... 22 ° C and a relative humidity of 80%.

At 10 days after inoculation, the attack on the plants is determined. values¹⁵ obtained are recalculated in% of attack. 0% means that the plants are not attacked and 100% means that the plants are completely attacked.

The active substances, the a20 concentrations of these and the obtained results are included in table 6.

Table 6

Uromyces test (protective)

<td colspan="2" rowspan="2">Active substance</td><td colspan="3">The attack in% against the attack of the untreated plants with an active substance concentration</td>

<td colspan="2"> 0,005</td><td> 0,00025</td>

<td>(CH₃), C- / O ^ -O-CH-CH-C (CH₃}₃X — X | ]</td><td></td><td></td><td></td><td></td>

<td>OH II N</td><td></td><td> 71</td><td></td><td> —</td>

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

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

<td>CI-YO -O-CH-CH-C-CHjCl _s j | j</td><td></td><td></td><td></td><td></td>

<td>OH CH II i</td><td></td><td> —</td><td></td><td> 84</td>

<td> (61</td><td></td><td></td><td></td><td></td>

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

<td>YO ^ - &lt;O ^ —O — CH — CO — C — CHCl x_x \ _X 1 1</td><td>SO.H 1</td><td></td><td></td><td></td>

<td colspan="2">CH_of / \ Z \ Q | ,, x 1/2 | O | O | IN THE \/\/</td><td> —</td><td></td><td> 10</td>

<td> (16)</td><td>1 OS H</td><td></td><td></td><td></td>

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

<td>CI -'o Y or -O-CH-CO-C-CH / Ci x_x ^ -X 1 I</td><td>S'O.fl I</td><td></td><td></td><td></td>

<td>/ N. CH II 11 </td><td>/ \ / \ 1 O 1 O 1 \ / \ / j</td><td> -—</td><td></td><td> 29</td>

<td> (4)</td><td>it₃h</td><td></td><td></td><td></td>

34

Test F. Test for the protective-curative treatment of the bush / cereal stalk (Mycosis destroying leaves).

The advantageous preparation is obtained by introducing 0.25 parts by weight of the active substance into 25 parts by weight dimethylformamide and 0.06 parts by weight alkylpolyglycolic ether. To the resulting chew is added 975 parts by weight of water, and the concentrate thus obtained is diluted with water to the desired concentration for the splashing liquid. 15

For examining the projective capacity of the liquid, young barley plants are sprinkled, the Amsel sort with the active substance preparation, up to the dew moisture. After drying, the rice plants²⁰they are dusted with spores of Erysiphe graminus var, horde. In order to examine the healing efficiency, the same procedure is performed, but in reverse order. Young barley plants with a single leaf are treated with the active substance preparation 48 hours after inoculation, when the infection is already manifest.

After a six-day stay of the plants at a temperature of 21, 22 ° C and a relative humidity of 80 ... 90%. the attack of the plants with flouring pills is evaluated. The degree of attack is expressed in% of attack against the untreated control plants. 0% means that the plants are not attacked and 100% means the same degree of attack as in the untreated control plants. The active substance is the more effective the lower the attack of flour. The active substances, their concentrations and the results obtained are recorded in table 7.

Table 7

Test for the treatment of olives / cereal flour / protective / curative

<td rowspan="2">' Active substance</td><td rowspan="2">5?" ® ω 1 * 4 - + - »4-1 4-» you will β · &lt;P- to ** Ss £ «S sS« c So st ω 2 R</td><td colspan="2">Attack in% of the untreated control plants</td>

<td>protective</td><td>curative</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>untreated</td><td> —</td><td> 100,0</td><td> 100,0</td>

<td>OH⁷ a&gt; CH-O-C | | there Z^N\ °^Hl) f&gt; li NxHCl (known)</td><td> 0,01</td><td> 66,3</td><td> —</td>

<td>Cl _ / _⁷ θ '} —O — CH CO— \ _ / | \ _ / /^N\ || _Nx HC1 (known)</td><td> 0,01</td><td> —</td><td> 50,0</td>

<td>/ A O-CH-CH-C (CH₃b j 1 /^N\ OH II « II N (known)</td><td> 0,01</td><td></td><td> 17,4</td>

36

Table 7 (continued)

<td> 1'</td><td> 2</td><td> 3 '</td><td> 4</td>

<td>Cl. _Z '' ·. \ O — O — CH ·· CO —QCII,), / ~ i Cl. ·. / \. ll N ·. ν II (known) '' - -</td><td> 0,001</td><td> ( 91,3</td><td> —</td>

<td>Cl _Z Y / -o — CH — CH— C (CH,), N_ / | | :: &lt;·· || N. . ·. ' • N || . (known);</td><td> 0,001</td><td> 82.5</td><td> —</td>

<td>CH Cl- o \ - (f O -o-CH-CO-C-CI CCI SO, H \ _Z \ _Z 1 | ( CH, Z \ Z \ i | ^X|, x 1/2 | EYE | II; n V^{x /}&lt;· ”SO, H</td><td> 0,01</td><td> 0,0</td><td> 0,0</td>

<td>CH Cl-YY-o-CH-CO C-CH₂C1 so, h II 1 ' / N, CH, Z \ Z \ (\ X 1/2 | OI 0] | i Ν γ \ /⁽¹⁵⁾...... SO., 11</td><td> 0,01</td><td> 0,0</td><td> 0,0.</td>

<td>CH 0 ON —O — CH CO — C — CHICI SO, H / N_x CH, / \ Z \ , &lt;\ x 1/2 | O j OI II i &lt;¹⁶&gt; SO, H</td><td> 0,01</td><td> 0,0</td><td> 75</td>

<td> _/^C1 Y Cl- / O - -O CH- -CO -C-CHjCl ȘOj^h^x-^z 1 1 _{/ X /}'\ Z^N\ ^CH·· 'x 1/2 (o | o [ II II \ z \ z II ν ι (18) SO, H</td><td> 0,01</td><td> 21,3</td><td> —</td>

<td>CH Z \ ¹Cl- &lt;o O-CH- CH-C- CH ;, C1^x-^z III OH CH, II ll II ^N (6)</td><td> 0,01</td><td> 0,0</td><td> 0,0</td>

<img file="RO71574A_D0016.tif" />

38

Table Ί (continued)

<td colspan="2"> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>Cl- / oVo-CH-CO-C CHiCI s_ / | |</td><td></td><td></td><td></td><td></td>

<td>CH. II N N 1 | (2)</td><td></td><td> 0,001</td><td> 0,0</td><td></td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>/ O / —O — CH — CH — C —CH_PCl ^x-^z 1 1 l OH CH. II N N II (12)</td><td></td><td> 0,001</td><td> 0,0</td><td> —</td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>Cl- &lt;O&gt; —O — CH — CH — C — CH, C1 III</td><td></td><td></td><td></td><td></td>

<td>OH CH. II N N || x HCl</td><td></td><td> 0,001</td><td> 0,0</td><td> — .</td>

<td>U)</td><td></td><td></td><td></td><td></td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>Cl- / oY- / oY — O — CH — CO — C — CH₂C!</td><td>SO.H</td><td></td><td></td><td></td>

<td>, N \ CH. I N ^XN ||</td><td>Z \ Z \ O | O | \ Z \ Z</td><td> 0,001</td><td> 0,0</td><td> —</td>

<td> (7)</td><td>1 SO.H</td><td></td><td></td><td></td>

<td colspan="2">CH. / o / - / o / —O — CH — CO — C — CH₂C1 \ z \ Z i 1</td><td></td><td></td><td></td>

<td>/ N \ CH. nn N β (Δ)</td><td></td><td> 0,001</td><td> 0.0</td><td></td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>/ \ 1 Cl- &lt;o&gt; —O — CH — CO — C — CH, Br \ Z j |</td><td></td><td></td><td></td><td></td>

<td>/ N \ CH. II NX HCl N ||</td><td></td><td> 0,00025</td><td> 21,3</td><td> —</td>

<td> (13)</td><td></td><td></td><td></td><td></td>

<td>CH.</td><td></td><td></td><td></td><td></td>

<td>ci- / o / -O-CI I-cr-IC-CIIjHr -^z 1 1 1</td><td></td><td></td><td></td><td></td>

<td>_ZN \ OH CH. 8 No. N | 1</td><td></td><td> 0,00025</td><td> 0,0</td><td></td>

<td> (14)</td><td></td><td></td><td></td><td></td>

Test G, Systemic test for barley rooting (Erysiphe graminis var bordei (cereal logs disease caused by nails)

5'

The active substance is applied as a powder composition for the treatment of seeds. The composition of a mixture in the form of a fine powder with the desired concentration of active substance, is prepared by di-¹⁰taking the respective active substance with a mixture consisting of equal parts of talc and tallow. .

The rice seed for treatment is stirred with the active substance diluted in one ¹⁵closed container. The seeds are seeded with 3 X 12 grains in flower blocks at a depth of 2 cm in a mixture of homogeneous soil, Fruhstorf and quartz sand diluted in equal volume. Germination and sunrise takes place under favorable greenhouse conditions. At 7 days after sowing, when the barley plants have developed their first strawberry, they sprinkle on fresh spores of Erysiphe graminis var. barley and is still grown at 2i ... 22^aAnd at a relative humidity of 80 90% air, receiving light for 16 hours a day. Within 6 days, typical oidium pustules are formed on the leaves.

The degree of attack is expressed in% of attack against the untreated control plants. Thus, 0%. it means that the plant is not attacked and 100% means that the degree of attack is the same as in untreated control plants. The active substance is the more efficient the lesser the pitting attack.

Active substances, their concentrations; and the results obtained are shown in table 8.

Table 8

Barley flour test (Erysiphe graminis var hordei) / systemic

<td>Active substance'</td><td>Concentration of the active substance in brine, You weight</td><td>£ 5 to s S £ 3 e _CT.s β, Λ Δ4-. G • X t «ty VW ζπ w</td><td>&lt;d ι td c * β · ^φ-.0 / 1, ο ο nj&gt; td φ ^5ΐ® &lt;£ ε'2</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>nesaramurat</td><td> —</td><td> —</td><td> .100,0</td>

<td> _/^Uζ O ^&gt; - O — CH — CO — CțCHjh II N N_IL (known)</td><td> 10</td><td> 2</td><td> 100,0</td>

<td>(CRihC - O - O - CH - CH - C (CH_;1) OH -II N N i | (known)</td><td> 25</td><td> ' 10</td><td> 100,0</td>

<td> _/^C1/ O y - O — CH — CO — C (CH s) 1 ZK II II II N (known)</td><td> 25.</td><td> 10</td><td> 100.0</td>

<img file="RO71574A_D0017.tif" />

<img file="RO71574A_D0018.tif" />

σι 574

42

Table 8 (continued)

<td> 1</td><td> 2</td><td> 3</td><td>Λ. .</td>

<td>1 i_Γ| ../ θ^:γ: ο ·. CH-CH ~ C (CB,), ' / N. \ OH; ii_s (known)</td><td> • .. 1, '25 .</td><td>ί; 10 '</td><td>• H 48.0</td>

<td>Y Cl^ZO -O-CH-CO C -CH_ofCl \ _iZ,,_Z^ \ CH, 11 Ν r. H HI A)</td><td>HO</td><td> 12</td><td> '0,0</td>

<td>CH_A, N— / O?&gt; —O — CH — COC — CHpCl | | / N \ CH, HI N; : N II ΪΚ »</td><td> 10</td><td> 2</td><td> 10,0</td>

<td>.ch, Z'O ^ —O — CH — CO — CCH, C1 SO, H^x—^z 1 in 1_ZN_X CH, Z \ Z \ / \ 'ⁿk ° A⁹J n ii γ ^{x /}⁽¹¹⁾ SO_iH</td><td> 10</td><td> 2</td><td> 0,0</td>

<td>CH Cl-Zo '} —O — Ol — CO — C — CH₂C1 Y^H\ / ι ι I Ν ΓΗ Z \ z \ /^K\ ^CHL x 1/2 [o | or | II ii \ z \ z There we are (15) SO, H</td><td> 25</td><td> 40</td><td> 0,0</td>

<td>CH OjN-^ZO ^&gt; - O-CH-CO-C-CtljCi ^ °^{: BC}N CH Z \ 'x 1/2 | 0 | O | II II \ Z \ Z II Ν I , (17) SO, H</td><td> 25</td><td> 10</td><td> 0,0</td>

<td>CH_z \ l Cl-CO&gt; -O-CH-CH-C-C1I₂C1^x-^z III_Z^N\ OH CH, II II If N (6)</td><td> 25</td><td> 10</td><td> 0,0</td>

<img file="RO71574A_D0019.tif" />

Test H. Design test for treating logs (cereal rust (Irunze destroying Mycosa)

0.25 parts by weight of the active substance are added to 25 parts by weight dimethylformamide and 0.06 parts by weight of alkylarylpolyglycol ether and 975 parts by weight of water are added to the mixture to obtain a preparation of the active substance. The concentrate is diluted with water to the desired concentration for the spray liquid.

Protein efficiency research. It is made by inoculating the young wheat plant with a single leaf (Michigan amber lot) with an uredosuspension of Puccinia recondita in a 1¼ aqueous agar solution. After drying the spore suspension, the wheat plants are sprayed in the active substance preparation until dew moisture and transferred to a greenhouse for incubation, where. keep limes for 24 hours at about 20 ° C and at relative air humidity of 100 ¼.

The treated plants are kept in the greenhouse for 10 days at a temperature of about 20 ° C and a relative humidity &amp; air of 80 ... 90%, after which the attack of the plants with rust pustules is evaluated. The degree of attack ss expresses in% of the attack on the untreated control plants. Thus, 0% means that the plants are not attacked and 100% means that the plants have the same degree of attack as the untreated control rims. The active substance is more effective the smaller the rust attack.

The active substances, their concentrations in the spraying liquid and the degrees of attack are recorded in table 9.

- Table 9

Test for treating logs / cereal rust / design

<td>Active substance</td><td>3 .2 X &amp; E'aSS at p. t Ol a cj c It is her A 3 3 A β And omο om 4-5</td><td>The attack in% girl of the control plants untreated</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>untreated</td><td> —</td><td> 100,0</td>

<td>. (CH)_iC - &lt;^ O / -O-CH-CH-G (CH ,.)., / OH 11 No. NOT (known)</td><td> 0,025</td><td> 75,0</td>

<td>θ / —O — CH CO— C (CH.,) j / “No. Ct Χ^Λ\ II ii II ^N(known)</td><td> 0,025</td><td> 90,0</td>

<td>Cl- / o —O — CH — CH — C (CH_:,)., OH he ll them ^N(known)</td><td> 0,025</td><td> 5 0,0</td>

4ή

Table 9 (continued)

<td> 1</td><td> 2</td><td> 3</td>

<td>ch Cl- o / —O — CH — CO — C — CH₂C1 ^ °^Ηn Ah Z \ Z \ Z^N\ ^CHL Xl / 2 | A | A | II N \ Z \ Z N 11 1 (1) SO. '. H</td><td> 0.025</td><td> 0,8 :</td>

<td>CH_SCl— {O ζ O \ —O — CH — CO C - Cyl-Cl - ^x- ι ι Z \ Z \ Z^N\ ^CHL xl / 2 | A | 0 | 11 N \ Z \ Z N 11! (7) SO; lH</td><td> 0.025</td><td> 0.0</td>

<td>Cl ,,,, _Z country^HtCl— C θ \ —O — CH — CO — C — CH, Cl \ _z, j / * \ CH_:it11 No. N | 1 &lt;91</td><td> 0,025</td><td> 33,8</td>

<td>CH Ζ ~ ^ \ 1 O; N — ζ O) —0 — CH— CO— C—CH.CI 1 1 / Ν_χ CH II N N | [ (10)</td><td> 0,025</td><td> 41,3</td>

<td>CH O-CH-CO-C-CHîCl Ș °^Ah - 1 ¹ / \ Λ Z^N\ ^CHI xl / 2 | O | O | 1 N \ z \ z N fl 1 (11) SO3H</td><td> 0,025</td><td> 50,0</td>

<td>CH z ~ \ ¹Cl- &lt;0&gt; —0 — CH — CO — C — CH_?d ^x-^z 1 1 _χΝ_χ CH 11 No. N, J | (2)</td><td> 0,025</td><td> 0,0</td>

<td>CH Z \ 1 - O-CH-CH-C-CH, C1 1 1 1 OH CU, (1 N. N | 1. .. 112)</td><td> :0,025</td><td> 0,0</td>

<img file="RO71574A_D0020.tif" />

7(574

4J

Table 9 (continued)

<td> 1</td><td> 3</td><td> 3</td>

<td>CH Cl- &lt;f O^X —O — CH CH — C — CHCl III OH CII, II N N || and HC1 (3)</td><td> 0,025</td><td> 0.0</td>

<td>CH CI— &lt;fo \ —O — CH — CO — C — CH_?br I 1 CH ί || N N || * HC1 (131</td><td> 0,025</td><td> 8.8</td>

<td>CII CI-0-CH-CH-C-CH₂br^x-^z 1 1 1 yN \ OH CH, II N N || (141</td><td> 0,025</td><td> 0,0</td>

<td>CH CI— (0 OO — CH CO — C— CH / Ί SO, H_ZN \ CH, Z \ Z \ if \ xl / 2 | O | Ol II n⁽⁴¹ SO, H</td><td> 0,025</td><td> 0.0</td>

<td>CH :, CI - / O - O - CH - CO - C - CHjCl θΐ ° ^H ” ^{! 1} Z \ Z \ Z^N\ ^CH'Χ1 / 2ΙΌ1Ό1 II IY^{v /}(15) SO, H</td><td> . 0.025</td><td> . 40,0</td>

<td>_ZC1 CH, _Ζ 1 CI— / or \ —O — CH — CO — C — CH₂Cl Ș °^{: H} - ^{1 1} z \ z \ Z^N\ ^{C, f}^ x 1/2 mo) II II \ Z \ Z the N | (18) SO.Ji</td><td> 0,025</td><td> 0,0</td>

Test I. Pyricularia and Pelliculana test - Solvent: 11.75 parts by weight acetone, · - Dispersant: 6.75 parts by weight alkylpolyglycolic ether;

- Water: 987.50 parts by weight;

- ARe additions - parts by weight.

In order to obtain the desired concentration of active substance in the spray liquid, the amount of active substance required is mixed with the given amount of solvent and the amount of dispersant and the concentrate thus obtained is diluted with the given amount of water.

Sprinkle with 2 X 30 rice plants aged about 2 ... 4 weeks until

<img file="RO71574A_D0021.tif" />

<img file="RO71574A_D0022.tif" />

at dripping moisture with splashing liquid. The plants are stored until the liquid is dried in a greenhouse at a temperature of 22 ... 24 ° C and a relative air humidity of about 70%. Then, 5 parts of the plants are inoculated with a suspension of 100,000 up to 200000 / ml spore Py ricularia oryzae and placed in a room with a temperature of 24 ... 26³C and with a relative air humidity of 10 100%. The other part of the plants is infected with a culture of Peiicularia sasakii grown on malt agar and kept at a temperature of 28 ... 30 ° C and at a relative humidity of 100% air.

At 5 to 8 days after inoculation, the attack is determined in% of all the leaves existing at the time of inoculation with Pyricularia orizae compared to the untreated control plants, but also inoculated. At the same time, it is determined the attack also on the leaves of the plants infected with Pîlllcularia sasakîi in comparison with the control plants, also infected, but not treated. The attack is evaluated with ratings from 1 to 9. Thus, 1 means 100% effectiveness, 3 = good effect, 5 =. moderate effect and 9 = no effect.

The active substances, their concentrations and the results obtained are shown in table 10.

Table 10 and Pellicuioria fb)

PyricuJaria's thesis)

<td rowspan="2">Active substance</td><td colspan="2">Attack In% against 'attack of untreated plants with 0 active substance concentration of 0.025¼</td>

<td>a)</td><td>b)</td>

<td>CI - (θ / 'O-CH- CH-C (CH₃h | | OH II N N__II (known)</td><td> 9</td><td> 9</td>

<td>CH CI-Y or -0-CH-CO-C-CHC1 1 1 /^N\ ^CH'· X 1/2 1 OI 0 1 (1 N \ / \ Z N II I (1) SO, H</td><td> 3</td><td></td>

<td>CH / 0 O and -O-CH-CO-C-CHjCl_χΝ_χ CH IN THE N || 13)</td><td> 3</td><td></td>

<td>CH CI— &lt;O&gt; -0 — CH — CO — C — CH₂C1 1 1_ZN \ CH, II N N || (2)</td><td> 5</td><td> 1</td>

<img file="RO71574A_D0023.tif" />

<img file="RO71574A_D0024.tif" />

K. test. Test for mycelium growthJui

The culture medium used: 2Θ parts by weight agar-agar, · 200 parts by weight potato decoction; 5 parts in potatoes counting of potatoes; 5 parts malt weight; 15 parts by weight dextrose; 5 parts in pepton qreutate; 2 parts by weight disodium phosphate; 0.3 parts by weight of calcium nitrate. The ratio between the solvent mixture and the culture medium: 2 parts by weight solvent mixture; 1ΌΌ parts by weight medium culture with agar.

Composition of solvent mixture; 0.19 parts by weight dimethylformamide or acetone; 0.01 parts by weight emulsifier (alkylpolyglycolic ether); 1.80 parts by weight - water; 2 parts by weight solvent mixture. .

Mix the quantity. .of. under the₇active sample required for the concentration of desired active substance in the culture medium with the given amount of solvent mixture. The resulting concentrate 52 thus mixes then in the proportion given above I the liquid culture medium, cooled to 42^DC and pour into Petri dishes - having a diameter of 9 cm. At the same time, control plates without active substance content are prepared.

After the culture medium has cooled and solidified, the plates are inoculated with the fungal species listed in Table 11 and incubated at about 21 ° C.

The result is evaluated after 4 to 10 days depending on the growth rate of the fungus. The evaluation is done by comparing the radial growth of their mice on ₁₅ the culture media treated with that of the control culture media. The following qualifications are used: 1 without fungal development; up to 3 growth inhibited strongly_; up to 5 moderately inhibited growth; up to 7 the increase inhi .... bată.slab; 9 the Jewish growth with the untreated witness.

The active substances, their concentrations and the results obtained are contained in Table 11.

<img file="RO71574A_D0025.tif" />

Φ

Ό ε

ο φ

φ ί »φ

Φ

Φ a

*-4

GQ φ

St

<td rowspan="15">tuj c: 3 ΐκ "</td><td>KJJDSDS Duo / nan / aj</td><td>CD</td><td>to</td><td> 03</td><td> 03</td><td> 1</td>

<td>Ojooisnui "// 3JA» ijÎTso3Ă ^ /</td><td>LQ</td><td colspan="2">· ”· | a</td><td> 03</td><td></td>

<td colspan="2">mnQuiuiOJb i uiiîiîodsoi / ju / uiiuj / j 2</td><td></td><td>tO</td><td> 03</td><td>CO</td>

<td colspan="2">stîoasajsîi / oi djoî / c / o / o / i / j * 2</td><td> 03</td><td> 03</td><td colspan="2">W) j co</td>

<td>3DZÂJ0 Diju / rtOiJAj</td><td colspan="2">ι 1</td><td>σ&gt;</td><td> 03</td><td>t</td>

<td>iii / ujfloq / a /// Winf 3pJ9A</td><td>VH</td><td>to</td><td> 03</td><td> 03</td><td>to</td>

<td>odjsz / p sf? A;? og</td><td>A</td><td> 03</td><td>Ό</td><td> 03</td><td>to</td>

<td>snunacjoÂjiu snjoqoţiqooD</td><td>A)</td><td>a&gt;</td><td colspan="2"> 03 | 03</td><td> 1</td>

<td>umuinrn uiniqjĂd</td><td> ¢0</td><td>•a</td><td> 03</td><td> 03</td><td>CN</td>

<td>IUDîOS nruojzOzrtfy</td><td></td><td>*a</td><td> 03</td><td> 03</td><td>Ό</td>

<td>wnundjjov wnipujopjjoo</td><td>&lt;D</td><td> 1</td><td> 03</td><td> 03</td><td>it·</td>

<td>OfOA / U uznfjDsnj</td><td>iO</td><td> 1</td><td> 03</td><td> 03</td><td> 1</td>

<td>u / n / orjo / apff oftiiîojops *</td><td></td><td>a&gt;</td><td>A&gt;</td><td> 03</td><td>tO</td>

<td colspan="2">u / njouz / na; ÎlÎÎÎfJDSn ^ |</td><td>a</td><td> 03</td><td> 03</td><td> 1</td>

<td>uidd 'βΛίρη nțuuisqos op ElțBJJUODUOJ</td><td>CN</td><td>a</td><td></td><td></td><td>a you</td>

<td colspan="2">Active substance</td><td> -</td><td>SC y. u Ι- ο γ- η- it Z \ 3 1 °] | \ z § A 3 u </td><td>SC u 1 X Ϊ / * “ r ~ 1 Z \ 3 [O 1 KY g A 3 o ~</td><td>« X a u A £ S ° A / = * δ- * 1 \ = 5 I ^^xi 1 \ ZO I § and j5 ί υ</td><td>tt \ O / £ \ Θζ "° CN X g SC X u — 6 - u 1 a u A /^ζη S- &lt; 1 t ΓοΊ = \ z 1 a</td>

SO., H

<img file="RO71574A_D0026.tif" />

-Λ

L ζ

Table 11 (continued)

56

<td>O.</td><td>IO</td><td> 1</td><td>IO</td><td>, τΗ</td>

<td>iO ·</td><td></td><td>τ-1</td><td></td><td> «</td>

<td></td><td>rt</td><td> -</td><td>Ό</td><td>rt</td>

<td>RT</td><td> 1</td><td>Ό</td><td> -</td><td> -</td>

<td>Ol * —1</td><td> 1</td><td> 1</td><td> 1</td><td>and</td>

<td></td><td> 1</td><td> 1</td><td>rt</td><td>rt</td>

<td>a</td><td> 1</td><td></td><td>Ό</td><td>rt</td>

<td> 05</td><td>to</td><td> 1</td><td>Ό</td><td></td>

<td>CO-</td><td>&lt;a</td><td>τ^-ί</td><td>CN</td><td>I- (</td>

<td>T + *.</td><td>Ό</td><td>Ό</td><td>rt</td><td></td>

<td>a·.</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>Ό</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>"φ</td><td>Ό</td><td>rt</td><td>Ό</td><td>rt</td>

<td>rt ·</td><td>IO</td><td> 1</td><td> 1</td><td>Ό</td>

<td>c &lt;</td><td>A</td><td></td><td></td><td></td>

<td></td><td>X ,,A X 1 X u — u A υ p^z' r z \ 1 ο 1 \ z Λ | Q 1 \ z</td><td>0 X "U XIX and — ύ — υ. 1 o. 9 · ^ - X you^—day 1 a σ 1 NZ \ and O | £ \ z 1 a</td><td>C^:ΐ £ Γ · σ. U; " XIX U-U op u-O 1 'P' SZ 1 \ = ^ o ^Λ1. z \ | o | · sr \ ZX</td><td>0 X "U" XX Π O— &lt;j —uo 8-o * and ΖΊ £ υ- ι t iZi \ Z S2 ! u</td>

<img file="RO71574A_D0027.tif" />

.57 5S

<td>&lt;X&gt; »· * R '</td><td>co,</td><td>. · · ,,. i.</td><td></td><td> «-4</td><td> •7 -</td>

<td>Ό.</td><td> - </td><td></td><td></td><td></td><td></td>

<td></td><td>&lt;A</td><td>♦ M</td><td> *—4</td><td>CO</td><td>»f</td>

<td>co</td><td> 1</td><td>"-I</td><td> -</td><td>Ό</td><td>CN</td>

<td> 2</td><td>co · -</td><td> *“4</td><td>I</td><td>Ί</td><td>WTT</td>

<td></td><td>UO</td><td>&lt;a</td><td>, Ό</td><td>CO</td><td> -</td>

<td>a -4</td><td>co</td><td></td><td></td><td>CN</td><td>+ -i</td>

<td>A</td><td>.. CN</td><td>co</td><td></td><td></td><td></td>

<td> • ·.« ·</td><td>CO</td><td> '</td><td> -</td><td>~ i</td><td></td>

<td>t * s</td><td>t-1</td><td></td><td> «-</td><td>co</td><td></td>

<td> ¢0</td><td></td><td>CN</td><td></td><td>and</td><td></td>

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The advantage presented by the present invention constitutes the realization of a process that allows the preparation of active substances with a higher fungicide efficacy than triazolyl and imidazolyl derivatives with • until now and a toxic '; you're down.