DE2118468A1 - Fungicides - Google Patents

Description

The present invention relates to the use of 4-dialkylaminophenylhydrazones, some of which are known, as fungicides.

It has already become known that dithiocarbamic acid derivatives can be used to control phytopathogenic fungi can (see U.S. Patent 2,317,765). In particular the zinc salt has achieved worldwide importance. Nevertheless, the effect is not always satisfactory at low application rates. It is also known that 4-dialkylaminophenyl = hydrazones of 1,2,3-tricarbonyl compounds a good one Have effectiveness against phytopathogenic fungi (cf. German Auslegeschrift 1 133 178 and German Offenlegungsschrift 1 810 581). However, the latter compounds have a spectrum of activity that is too narrow for practice.

It has been found that the partially known 4-dialkylaminophenylhydrazones the formula

(D

in which

R and R 'stand for alkyl with up to 4 carbon atoms and furthermore the two groups together with the connecting nitrogen

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χ '2118 ^ 68

atom stands for a heterocyclic ring

can, which enjhal-

th can. ,

R "represents hydrogen or acyl,

R "'for hydrogen, halogen, lower alkyl,

Lower alkoxy and acylamino and Ar is an optionally substituted one

aromatic residue,

have strong fungicidal properties.

Surprisingly, the 4-dialkylaminophenylhydrazones which can be used according to the invention show a considerably higher fungicidal effect Action with a broader spectrum of action than the compounds known from the "prior art. The compounds according to the invention Usable 4-dialkylamino-phenylhydrazones thus represent an enrichment of the technology.

In the formula (I), R and R ¹ preferably represent methyl and ethyl, further preferably together with the connecting nitrogen atom for the pyrrolidino, morpholino, piperazino, N-methylpiperazino and piperidino group; R "preferably represents hydrogen and acetyl; R ¹ " preferably represents hydrogen, chlorine, methoxy and methyl; Ar preferably represents phenyl or naphthyl, which can optionally be substituted by halogen, hydroxy, nitro, methyl, methoxy, methyl = ^ mercapto and / or the group HO-SO ₂ -.

Of the substances that can be used according to the invention, benzaldehyde-4-dimethylaminophenylhydrazone is already known as a compound (Journal for Practical Chemistry T39, 151 (1934)), but the fungicidal effect of the compound is unknown.

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The other substances that can be used according to the invention are new, but they can be obtained in a manner known in principle be by 4-dialkylaminophenylhydrazines with aromatic aldehydes in aqueous solution or in organic Reacts solvents in the neutral to acetic acid range.

Arylhydrazines suitable for the reaction are, for example called; 4-diethylamino-phenylhydrazine, 4- (methylethylamino) -phenylhydrazine, 4-pyrrolidino-phenylhydrazine, 4-morpholino-phenylhydrazine, 4- (N-methyl-piperazino) ■ -phenylhydrazine, 4-piperidino-phenylhydrazine, 4-dimethylamino-3-chlorophenylhydrazine, 4-D ± methylamino-3-methyl-phenylhydrazine, 4-dimethylamino-2-methyl-phenylhydrazine, 4-dimethylamino-3-methoxyphenylhydrazine and 4-dimethylamino-3-acetaminophenyl hydrazine.

The above-mentioned hydrazine derivatives can be prepared in a generally known manner (cf. Journal für Praxis Chemie 139, 151 (1934)).

Examples of aromatic aldehydes which are suitable for the preparation of the active compounds according to the invention are: 2-, 3- and 4-chloro-benzaldehyde, 2,4- and 2,6-dichlorobenzaldehyde, 4-bromobenzaldehyde, 2-4 , 5-trichlorobenzaldehyde, 3- and 4-nitro-benzaldehyde, 2-chloro-5-nitro-benzyldehyde ₁ 5-chloro-2-nitro-benzaldehyde, 2-, 3- and 4-hydroxy-benzaldehyde, 4- Methoxy- and 4-methylmercapto-benzaldehyde, 3,5-dichloro-2-hydroxy-benzaldehyde _f 3 »5-diiodo-2-hydroxy-benzaldehyde, 4-dimethylaminobenzaldehyde, 2-hydroxy-1-naphthaldehyde, benzaldehyde-2 —Sulphonic acid, 4-chloro-benzaldehyde-2-sulphonic acid and terephthalic dialdehyde.

The reaction of the 4-dialkylaminophenylhydrazines - preferably in the form of their dihydrochlorides - with the aromatic aldehydes can take in water and / or organic solvents

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Addition of acid-binding agents, such as sodium or potassium acetate, Sodium or potassium carbonate, sodium phosphate, triethylamine or urea take place. The aldehyde-4-di = alkylamino-phenylhydraune are in crystalline form obtain. You can, if you wish, by implementing Acylic agents such as acetic anhydride, propionyl chloride, Carbonic acid methyleoter chloride, methyl isocyanate, butyl = isocyanate, into which N-acyl derivatives are converted.

The active ingredients according to the invention have a high level of fungicidal activity Efficiency and a great disputes about the effect and have a relatively low toxicity to warm blooded animals. In addition, they are colorless or only slightly yellow in color. As a result, they are simple and without nuisance or endangering the workforce for practical control usable for unwanted fungal growth. The good tolerance to plants allows it to be used against fungal plant diseases by treating the standing cultivated plant or individual parts thereof or the seed or else of the culture soil. The compounds according to the invention are effective against parasitic fungi on parts of plants above ground, like Phytophthora species, causing tracheomycosis Fungi that attack the plants from the ground, such as Verticil = lium species, Fusarium species and Pialophora species. they seem but also against eame-transferable fungi, such as Tilletia tritici, and against soil-dwelling fungi, such as Rhizoctonia-, Fusarium, Pythium, Vertlcillium and Thielaviopsis species. It should be particularly emphasized that the active compounds according to the invention have a curative effect against attack on tomatoes as well as from potatoes with Phytophthora infestans.

The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pacts and granules. These will produced in a known manner, e.g. B. by mixing the

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BATH ORIGINAL

'Γ

- ■ ι

Active ingredients with extenders, solvents and / or solids Carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants. In the case of π ■ · use of water as a diluent organic solvents can also be used. The following are essentially coined: Aromatics such as xylene, benzene, toluene; chlorinated aromatics such as chlorobenzene, dichlorobenzenes, trichlorobenzene; Paraffins, such as petroleum fractions, paraffin oil; Alcohols such as methanol, ethanol, butanol; Ketones such as acetone, butanone, cyclohexanone; polar solvents, such as "methylformamide, N-methylpyrrolidone, Dimethyl sulfoxide and water. As solid carriers are called: Natural rock flour, such as kaolin, clay, talc, chalk; synthetic carriers, such as highly dispersed Silicic acid and silicates. The following emulsifiers can be used: Nonionic and anionic emulsifiers, such as Polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, -z. 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 present in a mixture with other known active ingredients, such as. B. other fungicides, insecticides, acaricides, Nematicides as well as fertilizers and soil structure improvement agents.

The formulations generally contain between 0.1 and 95 percent by weight active ingredient, preferably between 0.5 and 90 #.

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, Panten or granules, are used. The application

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0 9 8 ^ i- 1 1 J 1

achieht in the usual way, ζ. Β. by splashing, spraying, Fogging, scattering, dusting, pouring, dry pickling, slurry pickling, wet pickling or wet pickling.

In general, amounts of active ingredient per kilogram of seed of 0.01 g to 10 g, preferably 0.05 to 5 g, are used for dressing. to use. When treating the soil over the whole area, Can be carried out in strips or punctiform, active ingredient concentrations are at the site of the desired effect 1 to 500 g of active ingredient per m of soil are required, preferably 10 to? 00 g per m. When treating the Above-ground parts of the plant contain the active ingredient concentrations between 0.001 and 5 percent by weight, preferably between 0.002 and 1 percent by weight.

The compounds which can be used according to the invention also have a microbicidal effect. There is also an insecticidal and an acaricidal effect *

The many possible uses are based on the following Examples:

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Example A; .

Phytophthora test solvent: 4 »7 parts by weight acetone

Dispersant: 0.3 part by weight of alkylaryl polyglycol ethers Water: 95 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount Amount of the solvent and dilute the concentrate with the specified amount of water, which the said Contains additives.

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 ^{at 20 °} C. and a relative atmospheric humidity of 70 ° C. for 24 hours. The tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a 100 $ strength humidity and a temperature of 18 - 20 ⁰ C accommodated.

After 5 days, the attack on the tomato plants is determined as a percentage 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:

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Tabel

Phytophthora test

Active ingredient infestation in # of the infestation of the untreated control an active ingredient concentration of

0.0062

0.0031

S CH ₂ -NH-SS _n CH ₂ -NH-C-S '"

S (known)

Zn 63

96

Cl

Cl

V- CH = N-NH - ^ ~ V n '

ΛΙΤΤ

54

20th

66

CH " 40

74

CH = N-NH

fJTI 43

48

CH = N-NH

CH, 60

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Port setting

Tabel

Phytophthora test

Active ingredient

Infection in </ o the infestation of the untreated control "at an active ingredient concentration of

0.0062

0.0031

SO ₃ H

/ TA CH = N-NH_ / ~ V Ν '

* = / ^N CH

OH

32

13th

20th

CH = N-NH _ / ~~

, CH-

w = / ^S CH

71

OH

CH VCH = N-NH - // V / ³

N-NH

, CH-

20th

31

Cl

CH = N-NH _ / ~~ V- n '

CIL

NO,

52

75

Le A 13 580

2 0 9 8 A A / 1 1 9 9

Example B;
Phytophthora test / curative solvent: 4.7 parts by weight acetone

Dispersant: 0.3 parts by weight of alkylaryl polyglycolate. Water: 95 parts by weight

The amount of active ingredient required for the desired concentration of active ingredient in the preparation is mixed with the amount indicated Amount of the solvent and dilute the concentrate with the specified amount of water, which the said Contains additives.

Leaflets are removed from tomato plants (Bonny Best variety) and put them upside down in Petri dishes, cover and bottom with damp blotting paper are provided. The leaflets entered are sprayed with an aqueous spore suspension of Phytophthora infestans μηα incubated in a closed dish for 6 hours at 20 C. Then the leaves are immersed in the preparation preparation prepared according to the above procedure. The dive time is 15 seconds.

After another incubation of 3 days at 2O ⁰ C in a closed shell is determined attack on the treated leaflets in percentage of the infection of the untreated but also inoculated leaflets (= control). 0 fo means no infestation, 100 i <> means that the infestation is just as high as in the control.

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

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Active ingredient

Tabel

Phytoohthora test / curative

Infestation in # of the infestation in the untreated control an active ingredient concentration of $ 0.025

S CH ₂ -NH-CS _n CH, -NH-C-S ''

^C. I!

S (known)

Zn 100

NH-N = CH JT \ _ Cl 40

20th

β \ - CH = N-NH-V ^ Cl

PTT

ft V- CH = N-NH -Jf%

Cl

^ CH ₃ ^V CH, 13th

Cl

Cl

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209844/1199

Port setting

Al

Tabel

Phytoj'ithora test / curative

Active ingredient

Infection in <fo of the infestation of the untreated control at an active ingredient concentration of 0.025 jo

CH.

26th

C ¹ H

46

Λ1ΤΤ

30th

CH = N-NII

SO ₃ H

OH

-OXl-

CH

HO - // V-CH = N-NH- / V

PTT

26th

\ _ CH-N-NH- /

33

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2118 Λ ß 8

Example C; Agar plate test

Testing for fungitoxic effectiveness and the breadth of the effect ssρ ectrum3

Solvent: acetone parts by weight: 100

For the production of an appropriate preparation of active substance takes 1 part by weight of active ingredient in the specified amount of solvent.

The active ingredient preparation is added to potato dextrose agar, which has been liquefied by heating, in an amount such that the desired active ingredient concentration is obtained. After thorough shaking to evenly distribute the active ingredient, the agar is poured into Petri dishes under sterile conditions. After the mixture of substrate and active ingredient has solidified, test mushrooms are inoculated from pure cultures into discs of 5 mm diameter. The Petri dishes remain at 20 ^° C. for 3 days for incubation.

After this time, the inhibitory effect of the active ingredient on the mycelial growth is determined taking into account the untreated control determined in categories. 0 means no mycelial growth, neither on the treated substrate nor on the Inoculum; - means mycelium growth only on the inoculum, no overgrowth on the treated substrate; and + means Mycelial growth from the inoculum onto the treated substrate, similar to the overgrowth onto the untreated substrate in the Control.

Active ingredients, active ingredient concentrations, test mushrooms and the inhibitory effects achieved are shown in the following table:

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6611 / ^ 8602

UI CD O

OQOO

525 te «

O O

O O

O —O V) ΓΟ

tsi

part

I.
O

O = Cd I

02

tSJ

Cf (D

to

O O

CD

Ρα)

H-

OJ c + O Ma

a 3 0 ο π-Ir ¹ 0 co Ν I ^

H- (Jq c + · CQ c + 4 c + CD fO H- O c + Ö H ₃ H ₃ I

Corticium rolfsii

Sclerotinia sclerotioruin

Verticillium alboatrum

Thielaviopsis basicola

Phytophthora cactorum

Pusarium culmorum

H P et cf (D

HJ (D CO c +

continuation

Tabel

Agar plate test

Active ingredient

Active ingredient conc. in the
Substrate
in mg
in liter

• Η · Η ü · Η • Η ID -P «Η UH O O O U

CÖ 0 • rl tt Ö O • Η-Η

OO! Η fn CD φ HH OO

3 • Η * Η O -P • Η CO -P U J3

ω H

ϊ>

03

• Η 03

O • Η CO

> H

co ο

H CU Ή • Η Xl CtJ

EH, α

co

ft h

O

■ ρ +;>

• Η Ih (η

VNH-N = CH-V / V Cl

100

100

100

100

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Port setting

Tabel

Agar plate test

Active ingredient

CH

Active ingredient conc. in the
Substrate
in mg

in liter

100

100

100

100

• H -H U -H

• H ra

-P = H? H H

O O

cö 3

• H h Ö O • H -H

H S H • H iH O -P • H CÖ -P

ω Η

to

•H

ω ο

• Η CO t> HO

CO

0)

O C

· Η CO «J

cd U ο

si 2

Ά Ih O

-P -P hü Λ α} PM

Le A 13

- 16 -

continuation

Tabel

Agar plate test

Active ingredient

• Η · Η CD E. S. ? CQ
• Η I. CO CD E.
3 I. O
S. O -ri
• Η CD
■ Ρ Ή • Η £ 5 oat: CQ ico ' gate' arii H ο ο JL) • Η H Pl co
CD O CO KJ
ps ü O U • Η O H CO O O Active ingredient ero • Η H
• Η • Η
t> conc. in the
Substrate ο ero tic ela- Top.' in mg 00 H
ϋ You
O) • Η
si in liter CO > · EH PM

CH ν ³

V NH-N = CH- / V OH

100

100

CH

Cl

NO, 100

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Example D:

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

For the production of a suitable dry pickling agent ver-r If the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to form a finely powdered one Mixture with the desired concentration of active ingredient.

Wheat seed is contaminated with 5 g of Tilletia tritici chlamydospores per kg of seed. For dressing, the seed with the dressing agent is shaken in a sealed glass bottle. The seeds are exposed to optimal germination conditions for the spores ^{in a refrigerator at 10 °} C. for 10 days on moist loam under a covering layer of a layer of gauze and 2 cm of moderately moist compost soil.

The germination of the spores on the wheat kernels is then determined microscopically, each with around 100,000 Spurs are occupied. The fewer spores germinated, the more effective the active ingredient.

Active ingredients, active ingredient concentrations in the seed dressing, seed dressing application rates and percentage of germination of the spores can be seen from the following table:

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Tabel

Seed dressing test / Weizenstein.brand

Active ingredient

unpickled

CHp-NH-CS _n

Zn (known)

Il

N- / ⁷ V-NH-N = CH- / '

Active ingredient- dressing- spore-

Concentrated effort germination

tion in quantity in in $>

Dressing g / kg seed

in Gev? .- $

10

10

0.005

CH ₃ "

CH ₃ N

CH, ^X j

CH, N

NH-N = CH-AXw C1

NH-N = CH

Cl

Cl

Cl

> _ / V-NH-N = CH

Cl Cl

OH/

Le A 13

Cl

3 1 0.05 10 1 0.000 30th 1 0.000

30th

10
30th

10
30th

0.05

0.005

Q.005 0.000

0.000

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21 1 8 / ύ 6 8

Port setting

20th

Tabel

Saätgutbeizißj ttel test / wheat stone brandy

Active ingredient

Active ingredient- dressing- spore-

Concentrated effort germination

tion in amount in%

Dressing g / kg seed
in ^

NH-N = CH_ / V SCH

3 30

NH-N = CH- / V-NO ₂ ™ 0.005

0.005 0.000

OH/'"

CH _3x

NO,

Cl

NH-N = CH

NO,

'N - / ~ \ - NH-K = CH

SO ₃ H

30th

30th

30 0.000

0.000

0.000

3 ^s -.

OH

30th

NH-N = CH- / V OH 30 0.005

0.000

CH,
CH,

OH

30 0.005

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? 0 9 Β 4 4/1 1 Π

21 1R4R8
XA

Port setting table

Seed dressing test / wheat stone brandy

Active ingredient dressing agent spore concentration expenditure germination

Effectiveness in quantity in in fo

Dressing g / kg seed

in weight -Jq

Cl

NH-N = CH _ / ~~ \ 30 1 0.005

NO ₂ '

I..3 A. I 5 ') 80 -21-

I Ü 9 HA 4 / Π <) <)

lie rs t ellungsbei s pi e le:

-A V. NH-N = CH

The known benzaldehyde-4-dimethylamino-ph.enylhydrazone can be prepared according to the literature (Journal for practical chemistry 139, 151 (1934)). The following new compounds are obtained in a basically similar manner:

Example 1:

^0H ? \

24 g (0.17 mol) of 4-chloro-benzaldehyde are dissolved in 200 ml of methanol and 50 ml of a saturated sodium acetate solution is added and freshly prepared at 0 to 5 ⁰ C under good stirring, 40 g (0.13 mol) of 4- Dimethylaminophenylhydrazine dihydro = chloride entered. After 15 minutes, the mixture is diluted with 500 ml of water, enough aqueous ammonia solution is added dropwise until a pH of 8 is reached, the mixture is filtered and washed with water and methanol. After drying in vacuo, 37 g (0.135 mol) of 4-chlorine are obtained -benzaldehyde-4-dimeth.ylamino-ph.enyl = hydrazone as a pale yellow crystalline powder of pp. 135 C (with decomposition). The yield is 80 % of theory.

The following compounds of the general formula are obtained analogously

* ~ ^ NH-N = CH-Ar

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2 nights 9 8 A A / 11

example

No.

"Ar" stands for

Cl

Eq

Cl

Cl Cl

Cl 0 K- SCH,

NO,

0 VNO,

NO,

Cl

Cl

116 -

129 -

NO,

135 - HO (with decomposition)

approx. (with decomposition)

111 (with decomposition)

101 (with decomposition)

148-152
(with decomposition)

208
(with decomposition)

1? 2 - 140
(with decomposition)

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2 O 9 8 A A / 1 1 9

Example no.

"Ar" stands for

1t

13th

14th

173 - 175 (with decomposition)

254 - 255 (with decomposition)

184-185

157 - 165 (with decomposition)

Example 15;

NH-N = CH

35 g (0.17 mol) of benzaldehyde-2-sulfonate are dissolved in 600 ml of water, 50 ml of a saturated sodium acetate solution is added and freshly prepared at 0 to 5 ⁰ C 40 g (0.18 mol) of 4-dimethylamino phenylhydrazine dihydrochloride entered. Most of the condensation product precipitates out as a gray crystal powder. Sufficient aqueous soda solution is added dropwise until a pH of 7 is reached, then it is filtered, washed with water and dried in vacuo. 41 g (0.128 mol) of 2-sulfobenzaldehyde-4-dimethylaminophenylhydrazone are obtained as a light gray crystal

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powder, melting at 202 -. 203 ⁰ C (with decomposition). The yield is $ 75> of theory.

Example 16t

NH-N = CH _

The compound is obtained as described in Example 15. Pp. 185 ⁰ C (with decomposition).

Example 17t

NH-N = CH - // VCH = N-NH

22.5 g (0.168 mol) terephthalic dialdehyde is dissolved in 200 ml of methanol, 100 ml of saturated aqueous sodium acetate solution and 200 g of ice was added and then at ⁰ ° C 85 g (0.38 mol) of freshly prepared 4-dimethylamino phenyl = hydrazine dihydrochloride entered with thorough stirring. After 15 minutes, it is diluted with 1 liter of water, filtered, washed with water and methanol and dried in vacuo. This gives 56 g (0,14- mol) of terephthalic dialdehyde-bis (4-dimethylamino-phenylhydrazone), mp. 215 ⁰ C (with decomposition). The yield is 83 # of theory.

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Claims (5)

Patent claims: 1) Fungicidal agent, characterized by one. Content of 4-Dialkylamino-phsny Lr.ydrazones of the formula II ¹ " in which R and R 'for alkyl with up to 4 carbon atoms stand and. also the "two groups in common with the connecting nitrogen atom stand for a heterocyclic ring that can contain other heteroatoms » • R "represents hydrogen or acyl, R" ^{1 represents} hydrogen, halogen, I'jiederalkyl, Lower alkoxy and acylamino stands and Ar represents an optionally substituted aromatic radical. 2) A method of combating fungi, characterized in that 4-Malkylamino-phenylhydrazones like according to claim 1 Allows fungi or their habitat to act. 3) Use of 4-dialkylamino-phenylhydrazones according to Claim 1 for combating fungi. 4) Process for the preparation of fungicidal agents, characterized in that 4-dialkylamino-pheny! Hydrazones are used according to claim 1 mixed with extenders and / or surface-active agents. Le A 13 580 - 26 BATH ORIGINAL 209844/1199 5) 4-dialkylamino-phenylhydrazones of the formula R- \ y N-N = GH-Ar R '" in which R, R ', It "and R'" those specified in claim 1 Have meaning and Ar is substituted phenyl and optionally substituted Naphthyl stands. Le A 13 580 209844/1199