DE1810581C3 - N-acyl-p-dialkylamino-phenylhydrazones, process for their preparation and their use for combating phytopathogenic fungi - Google Patents

Description

in which X stands for methylcarbonyl and cyano, Y stands for methyl and alkoxy with 1 to 2 carbon atoms, R ₁ and R ₂ either individually stand for methyl or together stand for an alkylene bridge with 4 to 5 carbon atoms, A stands for oxygen and B for alkyl with up to 8, door alkenyl, alkoxy and haloalkyl with up to 5 carbon atoms each, for phenyl and door phenoxy.

2. Process for the preparation of N-acyl-p-dialkylamino-phenylhydrazones, characterized in that one

a) the alkali salts of p-dialkylaminophenylhydrazones the formula

N-

// X

-N = C

C-Y

(Π)

M®

It has already become known that 1,2-di- and 1,2,3-tricarbonyl - ρ - dialkylamino - phenylhydrazones have good effectiveness against phytopathogenic fungi, such as Phytophtora species (see British patent specification 9 20 739).

The invention relates to the new N-acylp-dialkylamino-phenylhydrazones the general formula

in which R ₁ , R ₂ , X and Y have the meaning given in claim 1 and M stands for a sodium or potassium cation, optionally in inert organic solvents, with derivatives of acid chlorides of the formula

N- <f V-N-N = C

AWAY

C-Y

Il

in which X stands for methylcarbonyl and cyano, Y door methyl and alkoxy with 1 to 2 carbon

atoms, R ₁ and R ₂ either individually stand for methyl or together stand for an alkylene bridge with 4 to 5 carbon atoms, A stands for oxygen and B for alkyl with up to 8, for alkenyl, alkoxy and haloalkyl with up to 5 carbon atoms each,

stands for phenyl and for phenoxy, which are strong fungitoxic Possess properties.

The invention also relates to a process for the preparation of the aforementioned N-acyl compounds of formula (I), which is characterized in that

³⁰ that one

a) the alkali salts of p-dialkylaminophenylhydrazones of formula (II)

N-

// X

N-N = C

C-Y

Il ο

B-C-Cl

(HI)

in which A and B have the meaning given above, converts or

b) p-Dialkylamino-phenylhydrazones of the general formula

// V

N-N = C

(IV)

C-Y

in which R ₁ , R ₂ , X and Y have the meaning given above, is reacted with acid chlorides of the formula (III) in an inert organic solvent in the presence of an acid binder.

3. Use of the N-acyl-p-dialkylamino-phenylhydrazones according to claim 1 for combating phytopathogenic fungi.

in which R ₁ , R ₂ , X and Y have the meanings given above and M stands for a sodium or potassium cation, optionally in inert organic solvents, with derivatives of acid chlorides of the formula

B-C-Cl

(HI)

in which A and B have the meaning given above, converts or

b) ρ - dialkylamino - phenylhydrazones of the general formula

VN- N = c '
H

(IV)

C-Y

Il ο

in which R ₁ , R ₂ , X and Y have the meaning given above, in an inert organic solution

mittel in the presence of an acid binder with iäurechloriden of the formula (III).

Finally, the invention also relates to the use of the compounds of formula 1 for Combating phytopathogenic fungi.

The acyl derivatives according to the invention have a stronger fungicidal activity and a broader spectrum of activity Effectiveness on than the previously known non-acylated hydrazones. In addition, have the invention Compounds have a systemic, fungicidal mode of action.

In the case of the non-acylated hydrazones, the very strong ones interfere with practical use as fungicides Colourfulness.

In contrast, the acyl derivatives according to the invention are colorless to light yellow. The acyl derivatives are also notable in contrast to the previously known hydrazones, due to a significantly lower toxicity to warm-blooded animals off (see Table 1).

The sodium salt of diacetyl-carbonyl-4-dimethylamino-phenyl-hydrazone is used and isobutyl chloroformate as starting materials, so results The following equation applies to the course of the reaction according to process a):

CH ₃

N-

N-N = C

CH ₃

COCH,

COCH ₃

O CH ₃

Il /

Na "+ Cl-COCH ₂ -CH

CH ₃

CH ₃

N-

// X

COCH ₃

N-N = C + NaCl

CH ₃

COCH ₃
CH (CH ₃ ) ₂

(V)

The reaction according to process b) takes place in an analogous manner.

Some of the phenylhydrazones used as starting materials are known and unambiguous from the formula (IV) characterized. They are manufactured using known processes (see, for example, the British Patent 9 20 739 and Angew. Chem. 72, 984 [1960]).

The alkali salts of the p-dialkylamino-phenylhydrazones (II) are still new and are prepared from the corresponding hydrazones (IV) by one equivalent of the hydrazone with one equivalent of sodium or potassium ethylate in ethanol at 0 bis Stirred 20 ° C and concentrate the mixture and wash the precipitated salt with ether and then sharp dries.

The acid chlorides (III) used as starting materials for the reaction according to the invention are general known.

Inert organic solvents can be used as diluents for reactions a) and b) according to the invention be used. These include in particular nitriles such as acetonitrile, ketones such as acetone, Formamides such as dimethylformamide and ethers such as diethyl ether, tetrahydrofuran and dioxane.

In process b), the acid binders used are the customary acid binders, especially amines, such as Pyridine, Ν, Ν-dimethylamiline, triethylamine and inorganic Bases such as sodium hydroxide, potassium carbonate and sodium bicarbonate.

The reaction temperatures are depending on the reactivity of the acid chloride of between -30 ° C and + 30 ° C, preferably between -10 ° C and 4-20 ⁰ C.

When carrying out the reaction according to processes a) and b), it is expedient to use the Starting materials in equimolar proportions, if necessary the acidity in excess. The reaction is generally over after 4 to 30 hours. The chloride formed in the reaction, e.g. B. alkali chloride or amine hydrochloride is filtered off and The compound of the formula (I) according to the invention by concentrating the reaction solution and recrystallization won.

3c The active ingredients according to the invention have a high fungitoxic degree of effectiveness and a high degree of effectiveness Effective range and have a relatively low toxicity to warm-blooded animals, making them easy to handle and can be used in practice to combat unwanted PiIz growth. your good plant tolerance also allows use against fungal plant diseases Treatment of the standing crop or individual parts of it or of the seeds or of the Culture soil. The active ingredients are effective against parasitic fungi on above-ground parts of plants, such as Phytophthora species, Peronospora species, Podosphaera species, against tracheomycosis-causing fungi that cause the Attack plants from the ground, such as Veiticillium species, Fusarium species and Phialophora species. she but also work very well against seed-borne fungi, such as Tilletia tritici, and against soil-dwelling fungi Fungi such as Rhizoctonia, Fusarium, Pythium, Verticillium and Thielaviopsis species.

It should be emphasized that the active ingredients have a systemic effect, and indeed they will ingested both through the roots and through the leaf surface. The active ingredients are suitable as foliar fungicides, seed dressings and boss treatments.

The active compounds according to the invention can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, pastes and granulates. These are made in a known manner, z. B. by mixing the active ingredients with stretching medium, as a liquid solvent and / or solid carriers, optionally with the use of surface-active agents, that is to say emulsifiers and / or dispersants. In case of

The use of water as an extender can e.g. B. organic solvents can also be used as auxiliary solvents. Come as a liquid solvent essentially in question: aromatics, such as xylene

and benzene, chlorinated aromatics such as chlorobenzenes, paraffins such as petroleum fractions, alcohols such as methanol and butanol, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; as solid carriers: natural stone powders such as kaolins, clays, talc and chalk, and synthetic ones Ground rock, such as finely divided silica and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, ό ζ. B. alkylaryl polyglycol ethers, alkyl sulfonates and Aryl sulfonates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations as a mixture with other known ' Active ingredients are present, such as fungicides, insecticides, acaricides, nematocides, fertilizers and soil structure improvers.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferred * ° wisely between 0.5 and 90%.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates, be applied. It is used in the usual way, for. B. by spraying, spraying, misting, Spreading, dusting, pouring, dry pickling, slurry pickling, moist pickling and wet pickling.

For dressing, amounts of active ingredient of 0.01 to 10 g, preferably 0.1 to 3 g, are generally used per kilogram of seed. In soil treatment, which can be carried out over the whole area, in strips or in spots, active ingredient concentrations of 3 to 300 g of active ingredient per m ^{3 of} soil are required at the site of the expected effect, preferably 10 to 100 g per m ³ . When treating the above-ground parts of the plant, the active ingredient concentrations are between 0.001 and 3.0 percent by weight, preferably between 0.002 and 1.0.

In addition, the active ingredients also have an insecticidal and bird deterrent effect.

Toxicity to warm-blooded animals of the previously known compounds according to the invention (see examples, column 11 and 12)

Active ingredients

LD ₅₀ values

(mg / kg
Mouse,
p. os)

COCH ₃

55

= N-CH

25-50

(known from GB-PS 9 20 739)

According to the invention:
Example 8
Example 10
Example 13

COCH ₁

> 1000

> 1000

> 1000
> 2000

Example A.
Phytophthora test

4.7 parts by weight acetone
0.3 parts by weight of alkyl aryl

polyglycol ether
Water 95 parts by weight

Solvent ...
Dispersant ..

The amount of active ingredient necessary for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the specified Amount of water that contains the additives mentioned.

Young tomato plants (Bonny best) with 2–6 leaves are sprayed with the spray liquid until they are dripping wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative atmospheric humidity of 70%. The tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a: made of 100% humidity and a temperature of 18-20 ⁰ C.

After 5 days, the attack on the tomato plants is a percentage of the untreated, but also inoculated Control plants determined. 0% means no infestation, -100% means that the infestation is just as high is like the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Phytophthora test

Active ingredient

Infection in% of the infestation of the untreated control with a concentration of active ingredient
tration
(in %)
of 0.025

(known)

example 1
Example 2
Example 8
Example 9
Example 12

0.3

0.5

0.9

6o example B
Plasmopara test

solvent

4.7 parts by weight of acetone

Dispersant .. 0.3 parts by weight of alkyl-aryl-

polyglycol ether
Water 95 parts by weight

Mix the one for the desired concentration of active ingredient The amount of active ingredient required in the spray liquid with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which the additives mentioned contains.

Young potted vines (variety Müller-Thurgau) with 2–6 leaves are sprayed with the liquid wedge until they are dripping wet. The plants remain in the greenhouse for 24 hours at 20 ^° C. and a relative atmospheric humidity of 70%. The vine plants are then inoculated with an aqueous spore suspension of Plasmopara viticola. The plants are placed in a humid chamber with 100% humidity and a temperature of 20-22 ° C.

After 5 days, the grapevine infestation is the percentage of the untreated but also inoculated control plants definitely. 0% means no infestation, 100% means that the infestation is exactly as high as at the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Plasmopara test

Active ingredient

Infection in% of the infestation of the untreated control in one
Active ingredient concentration
of 0.0031

(CHj) ₂ N- / 'Vn = N-CH (CO-CH ₃ I ₂ 50
(known)

Example 1 35

Example 2 Example 8 Example 9 Example 10 Example 12

20th
37
33
35
28

Example C
Phytophthora test / systemic on the leaf

Solvent ... 4.7 parts by weight acetone
Dispersant .. 0.3 parts by weight of alkyl-aryl-

polyglycol ether
Water 95 parts by weight

Mix the one for the desired active ingredient concentrate. Amount of active ingredient required in the spray liquid with the specified amount of solvent and dilutes there * K ;;; ..... :::! with the specified Amount of water which contains the additives mentioned.

3 FicdcrbläUchcn each of tomato plants are removed, placed in a humid chamber and with a spore suspension of Phylophthora in-

festans inoculated. The dishes are then stored at + 20 ° C for 6 hours. Subsequently the individual leaflets are immersed for 15 seconds in an aqueous suspension containing the desired Active ingredient concentration. The treated leaflets are returned to the humidity chamber.

After an incubation time of 48 hours at + 20 ^° C., the infestation of the leaves is determined in% of the untreated but also inoculated control.

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

Active ingredients, active ingredient concentrations and results are shown in the following table:

Phytophthora test / systemic on the leaf

Active ingredient

(CHj) ₂ N

(known)

Infection in% of the infestation of the untreated control with a concentration of active ingredient tration (in%) of 0.1

example 1
Example 2
Example 6
Example 8
Example 9
Example 12

-N ^ N-CH (CO-CHj) ₂ 67

3 15 37 3 0 26

Example D Phytophthora test / systemic

Solvent ... 4.7 parts by weight acetone

Emulsifier 0.3 part by weight of alkyl aryl

polyglycol ether water 95 parts by weight

The host necessary for the desired active ingredient concentration in the spray liquid is mixed amount of substance with the specified amount of solution!

means and dilutes the concentrate with the given amount of water, which the said Zi sets contains.

Young Tomalcnpflanzcn (Bonny best) potted in units are poured with the spray liquid 3 - 5 leaves three times at an interval of 24 hours in such a way that only the soil in the to is completely soaked. After 24 hours after the last watering, the plants are washed with a wä igen zoosporangia suspension of the phyt fungus

(15 phthora infestans are incubated. The plants are placed in a humid chamber with a 10 ()% air flow:

and a temperature of 18-20 ° C After 5 days, the attack on the tomato plant

709 652

determined in% 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, active ingredient concentrations and results are shown in the following table:

Phytophthora test / systemic

Active ingredient

Infestation in% '° of the infestation of the untreated control at an active ingredient concentration of 120 ppm

Active ingredient
Example 5

Example 6
Example 8
Example 9
Example 11

Example 12

(known)

example 1
Example 8
Example 9

100

39 38

53

Example E.

Soil treatment product test / Pythium ultimum

To produce an appropriate preparation of the active ingredient, the active ingredient is stretched with talc to 5% and then with quartz sand to 0.5% active ingredient content.

The active ingredient preparation is mixed evenly with naturally infected compost soil, which at Experience has shown that the sowing of field peas leads to high losses among the seedlings due to Pythium ultimum leads. The soil is filled into pots and sown with 5 χ 10 seeds of the pea pea. The pots will placed in the greenhouse at 15 - 18 ° C and normal kept moist.

3 weeks after sowing, the number of healthy plants is determined as a percentage of those laid out Seeds. 0% means that no healthy plant has grown, 100% means that from all of them Seeds healthy plants have emerged.

Active ingredients, active ingredient concentrations in the soil and results are shown in the following Table.

Soil treatment product test / Pythium ultimum

WirksWilf Wirkstollkon / .. On/ in mg / liter lirdc I'fU Untreated 0 example 1 100 82 25th 66 5 62 Example 2 100 54 Example 3 100 76 25th 54 5 46

Example 13
Example 15
Example 16

Example 17
Example 18

Example 7
Example 10

Example 22
Example 14

10

Wiikstoffkonz.
in mti liter of soil

100

25th

100

25th

100

25th

100

25th
100

25th

100

25th

100

25th

100

25th

100

25th

100

25th

100

25th

100

25th

100

25th

100

100

25th

Example F

Number of healthy plants in%

88 86 44 76 54 84 62 84 62 76 62 58 86 48 34

74 40 66 54 78 74 32 86 54 38 82 62 46 64 52 46 36 44 62 60 30

Seed pesticide test / wheat stone brandy (seed-borne mycosis)

To produce a suitable dry pickling agent, the active ingredient is stretched with a Gc mix equal parts by weight of talc and kieselguhr to a finely powdered mixture with the ge desired active ingredient concentration.

Wheat seed is contaminated with 5 g of Chlamy dosporen from Tilletia caries per kg of seed. to Dressing, the seed with the dressing agent is shaken in a sealed glass bottle. The Saatgu is placed on damp clay under a top layer

ho a layer of gauze and 2 cm moderately moist compost soil for 10 days in the refrigerator at 10 ⁰ C optimal! Exposed germination conditions for the spores.

The germination of the spores on the wheat kernels is then determined microscopically, ie

6s are each occupied with around 100,000 spores. Dc The less spores are set, the more effective the active ingredient. The active ingredient is all the more effective, j fewer spores are germinated.

Active ingredients, active ingredient concentrations in the dressing agent, amount of dressing agent applied and percentage of germs in the spores can be seen from the following table:

Seed dressing test / wheat stone brandy

Active ingredients WirkstolT- Pickling agent 1 Spurs concentration expense- germination in the pickling agent amount in g / kg in % in % Seeds Unheated 10 example 1 30th 1 0.000 Example 2 30th 1 0.05 Example 5 30th 1 0.000 10 1 0.005 3 1 0.05 Example 6 30th 1 0.005 Example 8 30th 1 0.05 Example 11 30th 1 0.005 10 1 0.005 3 1 0.05 Example 12 30th 1 0.005 10 1 0.05 Example 16 30th 1 0.05 Example 17 30th 1 0.05 Example 21 30th 1 0.05 example

H ₃ C

H ₃ C

N-N = C

CH ₁

COCH ₃

COCH,

107.6 g (0.4 Mo!) Of the dry sodium salt of diacetyl - carbonyl - 4 - dimethylamine - phenylhydrazone are suspended in 1 liter of acetonitrile and at 10 ° C 31.4 g (0.4 mol) of freshly distilled acetyl chloride, dissolved in 50 ml of acetonitrile, are added dropwise with stirring. The mixture is stirred at 0 to 10 ° C. for 1 hour and then for 3 hours at room temperature. From the sodium chloride is filtered off and the brown-red filtrate is concentrated in vacuo. The oily residue is in recrystallized repeatedly from heat from 300 ml of isopropanol, until any starting product that may still be present has been separated off. 70 g (60% of theory) are obtained N-acetyl-diacetylcarbonyl-4-dimethylaminophenylhydrazone as yellow needles with a melting point of 151 ° C.

Representation of the sodium salt used as the starting material

In a freshly prepared sodium ethylate solution (23 g of sodium in 1.5 liters of ethanol) are 247 g (1 mole) finely powdered diacetyl-carbonyl-4-dimethylaminophenylhydrazone entered and then stirred for 12 hours at room temperature. The unusual one Na salt is suctioned off and suspended in 1.5 liters of benzene. Then add 0.8 liters of benzene distilled off, added new benzene and distilled off again to azeotrope ethanol and water to remove. The sodium salt is suctioned off from the remaining benzene, washed with ether and im Vacuum dried.

Example 2

COCH ₃

COCH,

O OCH ₂ CH (CH ₃ J ₂

269 g (1 mol) of dry sodium salt of diacetylcarbonyl - 4 - dimethylamine - phenylhydrazone are suspended in 2 liters of acetonitrile and 150 g (1.1 mol) of isobutyl chloroformate, dissolved in 100 ml of acetonitrile, are added dropwise ^{with stirring at -20 13 C.} It is stirred for 2 hrs. At -10 to -20 ⁰ C and then for 3 hrs. At room temperature. The sodium chloride formed is filtered off and the filtrate is concentrated in vacuo. The oily, red-brown residue is taken up in 300 ml of boiling ligroin and the crystal pulp which separates out after cooling is pressed off sharply and repeatedly recrystallized from ligroin. 112 g (32% of theory) of N-carboisobutoxy-diacetyl-carbonyl-4-dimethylaminephenylhydrazone are obtained as yellow flakes with a melting point of 103 ° C. In a manner analogous to that described in Examples 1 to 2, the following compounds can be prepared according to . Formula (I) can be produced:

example
No. CH, CH, X Y Λ B. 3 CH, CH, CN OC ₂ H ₅ O OCH, 4th CH, CH, COCH, CH, O OC ₁₁ H, 5 CH., CH, CN OC, H, O OQ ₁ H ₅ 6th CH, CH, CN OC ₂ H ₅ O OCI I ₂ CH (Cl i,) ₂ 7th CH, CH, CN OC ₂ H, O ~ - / ~ \ 8th CH, CH ₃ COCH, CH, O OCH, 9 CH, CH, COCH, CH, O OC ₂ H ₅ 10 CH, CU, COCH, C \ h O \ / 1 1 COCH, cn, O CMU

Selimp. (O

190 153 114 146

1S4

143 127

197 Π0

continuation

example

12th
13th
14th
15th
16
17th
18th
19th
20th

CH, CH, CH ₃ CH ₃ CH, CH ₃ CH, CH, CH,

/ (CH ₂

13th

CH ₃ CH, CH, CH, CH, CH, CH, CH ₃ CH, CH ₂ -

COCH,

COCH,

COCH,

COCH,

COCH,

COCH,

COCH ₃

CN

CN

COCH,

CH,

CH ₃

CH,

CH,

CH,

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

CH,

O 0 0 O O 0 O 0 O

14th

C ₃ H ₇ -Ii

-CH ₂ CH ₂ CH ₂ -C!

C (CH,) = CH ₂

CH = C (CH,) ₂

CH (CH,),

C ₂ H ₅

CH,

CH ₃

C ₂ H ₅

CH,

M.p. Γ O

132

129-131

167-169

137-139

147

128-13C

155-15E

156

129

116-11!

CH,

CH,

COCH,

CH ₃

CH,

O -CH ₂ -C- (CH ₂ ), -CH, oil

CH,

Claims (1)

Patent claims: 1. N - acyl - ρ - dialkylamino - phenylhydrazones the formula R ₁ X Ν - <\ - N — N = C (I) R ₂ C CY // \ Il SUBSCRIPTION