Fungicidal method comprising the use of benzylidenemalonodinitriles

The present invention provides a method for combatting fungi on plants, which comprises applying to the plants at least one dinitrile of the general formula

R - c ־־ c (I) r‘ in which R’ represents a hydrogen atom or a 0_χ - alkyl group and R represents a phenyl group, which may be substituted by one or more halogen atoms, alkyl, alkoxy, hydroxy, nitro, alkylamino, diC - C. alkylamino, acetamino or dibenzylamino groups or by ² Q_ the group , or in which R represents a p-diphenyl or styryl group.

The active compounds of formula I may be applied to the plants together with one or more of the follov/ing additives! a carrier, a solvent, a diluent, a dispersing agent, a wetting agent, an adhesive as well as other known pesticides or herbicidal materials.

When used in a concentration at which no phytotoxic phenomena occur, the compounds of formula I above show an outstanding effect in plant protection against harmful fungi, such as Alteraaria solani, Phytophthora infestans and Septoria apii.

The following compounds have especially good fungicidal activity;

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<img file="IL27516A_D0002.tif" />

<img file="IL27516A_D0003.tif" />

M.p.: 152-157°

<img file="IL27516A_D0004.tif" />

<img file="IL27516A_D0005.tif" />

<img file="IL27516A_D0006.tif" />

in which Y represents hydrogen, chlorine or methoxy.

....t

It is possible to manufacture directly sprayable, solutions of the compounds of the general formula (1) by:

using, for example, mineral oil fractions of high to medium’ | ־ 'I boiling range, for example, Diesel oil or kerosene, coal tar א ( oil and oils of vegetable or animal origin, as well as hydro- ן carbons for example alkylated naphthalenes or tetrahydro-:

naphthalene, optionally using xylene mixtures, cyclohexanols, : ketones and furthermore chlorinated hydrocarbons, for example trichlorethane or tetrachlorethane, trichlorethylene or;

trichlorobenzenes and tetrachlorobenzenes. It is advantagecus to use organic solvents whose boiling point lies above 100°c.

It is especially appropriate to prepare aqueous application forms from emulsion concentrates, pastes or wettable spraying powders by the addition of water. Suitable ; emulsifying or dispersing agents are non-ionic products, , for example condensation products of aliphatic alcohols, amines or carboxylic acids having a long chain hydrocarbon residue containing about 10 to 20 carbon atoms with ethylene

% ׳ oxide, for example the condensation product of octadecyl וalcohol and 25 to >0 mols of ethylene oxide, or that of!

commercial oleylamine and 15 mols of ethylene oxide or that i of dodecylmercaptan and 12 mols of ethylene oxide. .Amongst| the anionic emulsifiers which may be used, there may beί mentioned: the sodium salt of the sulphuric acid ester of' i : \ ' .

י' ’- 4 -

־ ו i ^:.

I . .i i‘ ! '1

-t-T—ו----------- .

a .

dodecyl alcohol, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleum sulphonic acid.

Cationic dispersing agents which may be used, are for βτample, quaternary ammonium compounds, for example, cetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammonium chloride.

In order to manufacture dusting and powdering materials talc, kaolin, bentonite, calcium carbonate, calcium phosphate, also charcoal, cork flour, wood flour and other materials of vegetable origin may be used as solid carrier substances. It is also advantageous to manufacture the preparations of the invention in a granulated form. The various forms of the preparations may also contain the usual additional substances which improve the distribution, adhesion, rain resistance or penetrating power. As such substances, there may be mentioned, fatty acids, resin, glue, casein or alginates.

The preparations of the invention may be used by themselves or together with customary pesticides, especially insecticides, acaricides, nematocides, bactericides, fungicides and herbicides.

The active substances of formula I may be manufactured by reacting malodinltrile with an aldehyde or ketone of the formula

R-C־O ז

R' in which R and R' have the significance initially mentioned.

The elimination of water may be accelerated by adding basic materials, for example, ammonia or primary or secondary

<img file="IL27516A_D0007.tif" />

<img file="IL27516A_D0008.tif" />

bases, for example piperidine.

It is also possible to use an acid as catalyst, for example, acetic acid.

It is also possible, especially when using phenones as starting substances (forniula II, R’=alkyl), to react an alkali salt of malodinitrile with the phenone and to crotonise the resulting aldol compound in the presence of acids.

The present invention also provides new compounds having the general formula (1) wherein R* represents a hydrogen atom or a lower alkyl group and R represents a phenyl residue which is substituted by one or more lower alkyl or alkoxy groups, hydroxy groups, dialkylamino, acetamino or dibenzylamino groups or by the group , or which additionally to these substituents further carries a halogen atom, or carries at least 2 halogen atoms, or in which R represents a diphenyl, phenylethylene or cyclohex one group.

The following Examples illustrate the invention:Example 1

17«59 (0.1 mol) of 2,4-dichlorobenzaldehyde and 6.6 g (0.1 mol) of malodinitrile are dissolved in 150 cc of absolute ethanol and a few drops of piperidine are added to the solution at room temperature. After 2 hours, the resulting crystals are suction-filtered and dried. 21.4 g of 2,4dichlorobenzylidenemalodinitrile having a melting point cf 1^;' to 153°0 are obtained, which corresponds to 96¢ of the theoretical yield.

Example 2

Equimolecular amounts of propiophenone and malodinitrile are dissolved in benzene, treated with a little glacial acetic acid, and the entire mixture is boiled for 7 hours connected to a water separator. The resulting brownish oil is recrystallised from ethanol/water. The compound of the formula

C_OH,

<img file="IL27516A_D0009.tif" />

ON

CN melting at 67 to 71°C is obtained.

The malodinitriles of formula

ON

R - C = C | ^x ON

R' may furthermore be prepared in the same manner as described in the Examples.

<td rowspan="4"></td><td> R 'י</td><td> R'</td><td> [ Melting point :. °C</td>

<td></td><td> ci!», . ־. 5</td><td> 95 .to 9ל ' 1</td>

<td> Cny־׳CO־־KK.־־^^'’</td><td> ' η</td><td> 254 to 258</td>

<td> 1 ^ΰΗ5°־־θ־</td><td> Η י י,</td><td> יי 114 to'117.</td>

<td> 5 ,</td><td> “^&lt;/ב=\^ץ J</td><td> Η</td><td> 80 ־to 82</td>

<td rowspan="3"></td><td></td><td> . Η</td><td> 160 ' to 10? •1 .____________________________________________</td>

<td> CH״ \h-O- ^**2</td><td> ' Λ</td><td> 36 to 3θ</td>

<td> 01~^ΞΖ^׳״ _;</td><td> Η . '. .</td><td> 146 to148 ׳</td>

<td></td><td> 01,' . 01</td><td> &gt; . , 'Ή ׳ .. ׳</td><td> 78 to 81</td>

<td rowspan="3"> ’° * j ί ן</td><td> Br ho -^־&lt;כ Br</td><td> '.. Λ ;.</td><td> 173 to 176</td>

<td> 0^</td><td> . Η «י</td><td> 150 ' to 156 A.'</td>

<td>¹</td><td>^Η 4</td><td> 202 Do 200</td>

<td> ί j a</td><td> H¹</td><td> Melting point’ °θ</td>

<td> i ♦ ! aO—&lt;__/־</td><td> H’’ </td><td> , 5ם1 156 to</td>

<td> ' OCHj</td><td> . H</td><td> 65 to 37</td>

<td></td><td> Ή</td><td> 1 J 105 to 10o j</td>

<td> ί' H₂C— ό</td><td> H</td><td> ί 197 .to. 199 I i j 1</td>

<td> &gt; i</td><td> H</td><td> I 104 to loo i</td>

<td> ' 0־4-' 1</td><td> ' H</td><td> 129 to154 ־. ! i</td>

<td> HO—&lt;C&gt;- OCH₅</td><td> '' ^H</td><td> 152“ to 157 L</td>

<td> ch^o— OCH₅</td><td> H</td><td> ί 146 to 149 ! J ?</td>

<td> i j O־ch=ch- j</td><td> H</td><td> f no. . . _______________________. . - J</td>

<td></td><td> -°2^H5</td><td> ' 67 to 70 ξ j</td>

<td> • 0₂:;-hQ&gt;-</td><td> -ακ₅</td><td> ; סל! 154 to ך</td>

<td></td><td> «</td><td></td>

<td> R</td><td> R*</td><td> Melting point °C</td>

<td> ch-o-^A. &lt;5 \ss/</td><td> ־־H,</td><td> 60 to 62</td>

<td></td><td> —CHj</td><td> 96 to 98</td>

<td> OCHj</td><td> -ch₃</td><td> 139 to 145</td>

<td> C1“Q-</td><td> -CHj</td><td> 95 to 96</td>

<td> Br—</td><td> —CHj</td><td> 93 to 95</td>

<td> O“</td><td> -⁰¾</td><td> 92 to 94</td>

סו

Example 5 g of active substance are finely ground with 40 g of Bolus alba and 5 g of a specially precipitated silicon dioxide and 5 g of a wetting and dispersing agent.

In this way, a 500 strength spraying powder is obtained, which may be dispersed in water in any desired concentration.

Example 4

Celery plants are grown in a greenhouse, and are sprayed with spraying broths (manufactured according to Example 3) containing 0.02¢ of active substance, 2 days before infection with the fungi Septoria apii and Erysiphe. After infection, the plants are placed for 2 to 3 weeks in an incubation chamber at high atmospheric humidity and are subsequently assessed for attack, in comparison with an untreated control.

The following results are obtained.

Protective Effect

<img file="IL27516A_D0010.tif" />

<img file="IL27516A_D0011.tif" />

<img file="IL27516A_D0012.tif" />

Septoria

1)100¢

2)89¢

3)90¢

4)88¢

Erysiphe

60¢

70¢

80¢

Some of these compounds, for example, No. 3> also show a considerable effect against Altemaria sol. (95¢).

Example 5 one year old apple trees of the Jonathan variety are sprayed eleven times.during the vegetation period, at ten day intervals, with an active substance solution containing a compound .according to Example 1 ♦ The spray liquid was obtained by dispersing 0.1¢ of the active substance in /5 water. 7 1 of the aqueous suspension.were sprayed per plant. 10 days after the start of the treatment, the attack by the micro-organism Podosphaera leucotricha was determined.by checking 200 leaves from each of 5 equally strong plants.

It was found that the treated plants were largely free from attack, whilst the untreated control plants were attacked over at least 50¢ of the leaf surface.

Example 6 :

Some particularly pronounced effects of compounds of the general־ formula (1) are given below.

M.p.: 152-157° lias an broad fungicidal effect against plantpathogenic fungi: at a concentration of 0.1^/95¢ effective against Alternaria; 65¢ against Septoria; 80¢ against Eryslphe.

M.p.: 146-148°

<img file="IL27516A_D0013.tif" />

Is 100¢ effective against Septoria at a concentration of 0.02¢ active substance'.

Is 100^ effective against Septoria at a concentration of 0.1¢ active substance .

80¢ effect against Septoria apii at 0.1¢ active substance.

<img file="IL27516A_D0014.tif" />

Fungicide

Fungicide

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Fungicide

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Fungicide

<img file="IL27516A_D0017.tif" />

Fungicide

Fungicide

Fungicide

<img file="IL27516A_D0018.tif" />

Fungicide

<img file="IL27516A_D0019.tif" />

Fungicide

Fungicide

<img file="IL27516A_D0020.tif" />

Fungicide

M.p.: 183 188° ־

<img file="IL27516A_D0021.tif" />

Fungicide

<img file="IL27516A_D0022.tif" />

Fungicide

B.p. : 14O°/12 ,mm

10/2־271

<img file="IL27516A_D0023.tif" />

CN

Fungicide

GN

M.p. : 143 - 145°

Example 7

The effect of the compound according to Example 1 against leaf spot fungi, was confirmed for celery (Apium graveolens L.) using the fungus Septoria apii Chest. Celery plants were grown in the greenhouse and 2 days before infection were sprayed once with a broth containing 0.02$ active substance of the product under investigation. After infection with an aqueous suspension of spores of Septoria apii, the plants were incubated in a humidity chamber at room temperature and were subsequently assesed for attack in comparison with an untreated control (0$ effect). The effect of the compound of the invention was 100$, without phytotoxicity. ‘

The compounds listed in Example 2 showed similar, good effects.