DD144148A1 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to novel carbocyclic substituted N-alkylmorpholines used to combat phytopathogenic fungi, In particular powdery mildew fungi in cereal crops, be applied can. The aim of the invention is to develop morpholine derivatives, the good fungicidal properties and the highest possible Possess plant compatibility. The task was solved so that carbocyclic substituted N-alkylmorpholines or their salts with long-chain alkanesulfonic acids as active ingredients in fungicidal agents be used. These ingredients have a very good Plant tolerance. The invented morpholine derivatives can be produced; by hydrogenation of unsaturated Mannich bases, by reduction of β-morpholine-substituted propiophenones, by hydrogenation of aromatic "substituted N-alkylmorpholines and by reaction of carbocyclically substituted amines with 2,2'-Dichlordialkyläthern.

Description

-ι-. 21 34 72

a> fungicidal agent

b); Field of application of the invention

The invention relates to new fungicidal compositions for controlling phytopathogenic fungi *, in particular powdery mildew fungi in cereal crops.

c) Characteristic of the known technical solutions

It is known that N-alkylmorpholines and their salts have fungicidal properties, for example with acetic acid (DT-PS 1 164 152, DT-PS 1 173 722, DT-PS 1 198 125). The alkyl radical on the nitrogen can be chain-shaped or cyclic and the carbon atoms of the morpholine ring can be substituted by lower alkyl groups such as methyl or ethyl "The compounds, however, have a partially unsatisfactory effect and show phytotoxic in the necessary for the fungicidal effect concentrations zen © damage to dan treated crops can cause.

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d) Object of the invention

The aim of the invention is to provide novel N-alkyl-morpholines with good utility properties ^ show the next good fungicidal properties also well tolerated by plants ¹ x '

e) nature and features of the invention

In the case of the cited known technical solutions for controlling powdery mildew fungi, in particular in cereal cultivation, phytotoxic effects can occur.

'·''''¥

The present invention is based on the idea ¹ that new substituents on the nitrogen of the morpholine give derivatives which have improved use-value properties, which are expressed in particular in a high level of plant tolerance found that new morpholine derivatives of the general formula (I)

E-CH- (CH ₂ ) _a -NO CD

wherein R = phenyl, substituted phenyl »cyclohexyl, substituted cyclohexyl, bicyclo'j2 * 2." i] -heptyl (2) or 2V2-dimethyl-bicycio [2 "2vij-heptyl (3), R ^ ₁ and S _{2 are} independent each other = hydrogen or methyl and η = 0 - 2 may be, effective active fungicidal agents

it 3 472;

represent, which have excellent plant tolerance. They thus represent a valuable enrichment of the current state of the art. The compounds according to the invention can be used as free bases or in the form of salts or addition compounds with. long-chain alkanesulfonic acids are used * The application takes place in the form of solutions, powders, suspensions or emulsions by spraying, dusting or pouring. The form of application should be based on the application in order to achieve an even distribution of the active ingredients,

"Λ. · '.' '"' ''. '' '· ·' '

J / The fungicides are suitable for controlling plant diseases ·, especially powdery mildew species as Erysiphegraminis (cereals) and Erysiphe cichoracearum (cucurbits), but are auch.anwendbar against Septoria apii (celery) or Basidiomycetes such Shizoctonia solani. They show systemic properties, especially in the control of mildews. For the successful control of fungal infections, drug concentrations of 0.01% - 0.2 % are required.

The carbocyclically substituted N-alkylmorpholines of the general formula (I) according to the invention can be prepared:

a) by hydrogenation of unsaturated Mannich bases

... (Example 3 and 5) -. ^: '"''.'.'/' ,.: .. ' ^:

b) by reduction of ß-raorpholine-substituted Propiophenbnen (Example 1)

c) by hydrogenation of aromatic-substituted N-alkylmorpholines (Example 2)

d) by reaction of amines with 2,2-dichlorodialkyl ethers. (Example 4).

The hydrogenations can be carried out at room temperature and under normal pressure. To saturate dull fatigue in the unsaturated Mannich bases

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Catalysts such as palladium on activated carbon and Rahey nickel usable. , . ' ./: /. . '; .. _; ; / ^:; .,: '. The reduction of the carbonyl group in the propiophenones to the methyl group succeeds with palladium-activated carbon, which must be carried out under esterifying conditions (glacial acetic acid / sulfuric acid), since the reaction otherwise remains at the level of the alcohols *

The hydrogenation of aromatic substituted N-Alky! Morpholine to Cyclohexylderivaten is feasible with rhodium activated carbon or platinum dioxide.

The preparation of the salts can be achieved by reacting the morpholine derivatives of general formula (I) with long-chain alkanesulfonic acids such. B. C ^ ₁ -H-.SO-H in the presence or absence of a solvent, for example water, ethyl acetate, η-hexane or acetonitrile, at

be taken (Example 6).

η-hexane or acetonitrile, at temperatures of 20-100 C

f) embodiments

Example 1 Λ "'."''.._; ^: ''. '. :;'';_.-;.';. / '.. ','

Preparation of: 1- (4-n-butylphenyl) -3- (2,6-dimethylmorpholine) ·

propane

10 g (0.029 mol) of 4-n-butyl-β- (2,6-dimethylmorpholino) propiophenone hydrochloride are dissolved in a mixture of 200 ml of glacial acetic acid and 6 ml of concentrated sulfuric acid. »It is mixed with 10 g of 5% Pd activated carbon Room temperature and atmospheric pressure hydrogenation until completion of the hydrogen uptake (about 10 hours *) hydrogenated. "The catalyst is separated off and the main amount of glacial acetic acid is distilled off in vacuo. The residue is diluted with

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Sodium hydroxide solution made alkaline "The organic phase separating off is taken up in ether, with Na 2 SO 4. dried and im

Distilled vacuum.

^Kp 3-4 \ 182 - 186 ° C Yield: 80 % d. th Sumraenformel: VSi ^K0 Molecular weight: 289.48 Example 2

Elemental analysis:

th. 84 found * 36 C 78 79 78; 24 H 10 83 10 68 N ^ ^- ,

Preparation of: 1- (4-cyclohexylcyclohexyl) -3 '' (2,6-dimethylmorpholinyl). '' propane ''. - -. / '\. '...' ':

... ^0H 3: ·

13 g (0.04 mol) of 1- (4-cyclohexylphenyl) -3- (2,6-diniethylmorpholino) propane are dissolved in 200 ml of glacial acetic acid and hydrogenated with 7 g of 10 Rh active carbon analogously to Example 1 and worked up

Yield: empirical formula: molecular weight:

208 - 210 C 80 % d. Th. C ₂₁ H ₃₉ NO

321.57

Elemental analysis!

th. 44.-. • gef. 93 C 78 22 77, 73 H 12; 35 12 ?8th N 4, 4,

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Example 3

Production of : ^,; , '' ·. , '::. : \ '. - //; ... 2,2-Dimethyl-3- [β- (2,6-dimethylmorpholino) ethyl] bicyclo

[_2.2.i | heptane

10 g (0.0408 mol) of N-2- [2,2'-dimethyl-bicyclo [2.2.i] -heptyl (3)] ethylidyl-2 _, 6-dimethylmorpholine are dissolved in 150 ml of alcohol. With ΙΟ. 10% Pd activated carbon is hydrogenated at room temperature and atmospheric pressure · After completion of the hydrogen uptake (about 8 hours) v / ird separated from the catalyst and the alcohol distilled off in vacuo. The residue is washed with dilute sodium hydroxide solution, over 1 H ₂ SO. dried and distilled in vacuo.

^Kp 5-6V yield:

Molecular Formula: Molecular Weight: 265.45

155 - 160 C 80 Jg d. Th.

Elemental analysis:

th. gef. C 76j94: 77.43 H 11.77 11.23 N 5.27 5.82

Example 4 Preparation of:

heptyl (2) methyl | -2,6-dimethylmorpholine

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25 g (0.199 mol) of 2-aminoethyl-bicyclo [2.2.ΐ] heptane and 41 g (0.239 mol) of 2,2'-Dxchlordiisopropyläther be with 0.4 mol KpCO ^ in 120 ml of cyclohexanol for about 15 hours, under Reflux heated. The mixture is then treated with water and the organic phase is washed with dilute sodium hydroxide solution and with water. It is taken up in chloroform, dried with EapSO.sub.2, and distilled under reduced pressure.

I38 - 143 ° C 85 % d; Th ·

ElementaranalyseJ

Yield:

Summary: C ^ ELr

Molecular weight: 223.37

Example 5 '. , : ·. ' .._: '. / ''

Preparation of: 2-phenyl-4- (2,6-dimethylmorpholino) -butane

th , 28 Found. ' C 75 ^; 2δ 75.89 H 11 , 27 10.92 N 6 6.56

12 g (0.048 mol) of 2-phenyl-4- (2,6-dimethylmorpholino) butybene (1) are hydrogenated and worked up in 150% alcohol with 6 g of 10% strength Pd activated carbon analogously to Example 1 and worked up.

Yield: SuKimehf ormel: Molecular weight:

143-145 C

80 % d. Th

C ₁₆ H ₂₅ NO

247.39

Elemental analysis:

th. 68 gef. C 77, 18 78.53 H ¹⁰ » 66 9.65 N   5 * 5.09

Example 6   '.' .. '' [. '' -. r ". '"...:''.' ^λ ' .- '

Production of: - V.-:

1 - (^ i-isopropylphenyl) -3 ** (2 _t 6-dimethylmorphol in o-propane

pentadecane sulfonate:

8.3 g (0.03 mol) of 1- (A-isopropylphenyl) -3- (2 _t 6-dimethyliaorpholino) -propane and ε, 9 g (0.03 mol) of pentadecane sulfonic acid are boiled for 3 hours in 50 ml of acetonitrile. After removal of the solvent left behind about 1? g of a viscous oil · The yield is practically quantitative.

Example 7

Action against the basidiomycete Khizoctonia solani The test was carried out in the mycelium growth test in vitro. The active ingredient is dissolved in concentrations of 5OO and 50 ppm, added to a liquefied agar and poured into sterile Petri dishes · After evaporation of the solvent, the agar plate is inoculated with the test fungus. After a 7-day incubation, the determination of the radial mycelium growth takes place «

active substance

Inhibition of mycelial growth in 500 ppm 50 ppm

.1

unheated. Kontrolls

100

97

90

70

85

98 92 70

10

60 Ö

Mr »of the examples listed above

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Action against Septoria apii, the causative agent of leaf spot disease of celery

The substance formulated as a spray powder with 20 % active ingredient is sprayed onto celery plants about 5 cm in size. After the spray coating has dried on, the plants are inoculated with a conidia suspension of the pathogen. In the course of the symptom development the following control success was bönitierti ^: '. , , : .. '. , · ·. · '·; .. '

active substance

Concentration of the active substance

effect

1 2

1000 ppm 1000 ppm

2000 ppm 1000 ppm

very good control success

very good fighting experience

moderate control success good control success

No. of examples

Example 9

Effect against the powdery mildew, black salsify (Erysiphe

cichoraceärum)

The fuel as a powder formulated with 20% of active substance is sprayed onto about 5 ^ra c große.Schwarzwurzelpflanzen "After drying of the spray coating, the inoculation of the plants is carried out by dusting with conidia of the pathogen * In the course of the following Symtomeatwicklung BekäHipfungserfolg was bonitierti

active substance

Concentration of the active substance

V / MPACT

2 3

800 ppm 200 ppm 800 ppm

very good control success

very good killing success

very good fight loss

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active substance

Concentration of the active substance

effect

No. of examples

20CX) ppm 2000 ppm

good control success

very good control success

Example 10

Action against powdery mildew on barley (Erysiphe graminis) Formulated as a spray powder with 20 % active ingredient or as an emulsion concentrate with 50% active ingredient substance is sprayed on approximately 10 cm large barley plants. After the spray coating has dried on, the plants are inoculated by dusting with conidia of the pathogen. New to fourteen days after the symptom development is scored · It resulted in the following Bekämpfungserfolgi

active substance

Concentration of the active substance

effect phytotoxicity very well none very well none very well none very well none very well none very well weak

1 2

100 ppm 100 ppm 500 ppm 800 ppm 5ΟΟ ppm 100 ppm

Kr. Of the examples

Example 11

Systenic effect against grain bilayers on barley (Erysiphe graminis)

The formulated as a wettable powder with 20% active substance or as Eraulsionskonzentrat with 50% of active substance _s are growing as an aqueous dispension of casting of the floor in the the barley plants used *

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By root absorption of the active ingredient passes through the water pipes in the above-ground parts of plants. These are inoculated after application of the substance by dusts with conidia of the pathogen · 9 to 14 days after the symptom development bonitiSrt · It resulted in the following Bekäsepfungserfolg; '.' .: ' -. , , -.- .. '. , ';,

Active ingredient ^T ' Concentration of ^ No. the examples effect phytotoxicity active substance Example 12 - ..i :: / ':. 500 ppm very well none 2 500 ppm very well none • 100 ppm very well none '' .- '4' ^:. 600 ppm very well none 5 100 ppm very well none Calixin 100 ppm very well weak

Effect of pentadecane sulfonates against Erysiphe graninis; Testing was carried out analogously to Example 10 and 11v.

Active substance of Example No. 6

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Active ingredient No. 7 (preparation analogous to Example 6)

CH

CH.

CH.

Very good effect was achieved at the following concentrations:

active substance

fungicidal action

systemic effect

eradicative phyto-effect toxicity

6 7

100 ppm 100 ppm

200 ppm 150 ppm

5OO ppm 5OO ppm

none

Claims (1)

2134 72 claims A fungicidal agent for controlling phytopathogenic fungi, characterized by a content of carbocyclic-substituted N-alkylraorpholines of the general formula (I), S-CH- (CHj-K wherein R = phenyl, substituted phenyl Cyclohexyl, substituted cyclohexyl
Bicyclo-j2.2V ^ -heptyl (2) or R ,. and Ep independently of one another can be = hydrogen or methyl and η = 0- * 2, in addition to the usual carriers, solvents and / or
Pormulierungshilfsmitteln · A fungicidal composition according to item 1, characterized in that they contain as active ingredient ⁵ © di salts of the substituted carbocyclic srfiadungsgemäßen N ~ Aikylinorpholins with long-chain alkane sulfonic acids * ·