DD299515A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal agents and their use in crop protection. The underlying object is achieved according to the invention by the use of new * and * or by a mixture of these salts with their positional isomers * and * as active ingredients {pesticides; fungicides; * *}

Description

-α V / \ r ² -a

(I)

in which

A represents the groupings -OR ³ or -COOR ³ and R ¹ denotes straight-chain or branched alkyl having 8 to 16 C atoms,

R ² alkylene having 1 to 6 carbon atoms,

.0..CH ₃

R ³ - (( )) or - (( ^ V-OCH ₀ or _Ü 1 and

Ph Cl

Χ ^{θ is} the anion of an acid,

and the usual excipients and carriers.

2. Use of fungicidal agents, characterized in that they are used to combat fungal attack on plant materials and stored goods.

3. A method for controlling phytopathogenic fungi, characterized in that fungicidal composition according to claim 1 is allowed to act on fungi or their habitat.

Field of application of the invention

The present invention relates to novel N-alkyl-2,6-dimethyl-morpholinioalkyl aryl ether salts and N-alkyl-2,6-dimethylmorpholiniocarboxylic acid ester salts and their use for controlling phytopathogenic fungi.

Characteristic of the known state of the art The use of N-alkylmorpholines (DE 1164152, DD14041 2), their salts and their molecular and Addition compound (DE 1173722, DE 2461513) as active ingredients of fungicidal agents has long been known. Recently, a number of N-alkyl-2,6-dimethyl-morpholiniocarboxylic acid ester salts and N-alkyl-2,6-

Dimethyl-morpholinloalkyl-phenyl ether salts with fungicidal and plant growth-regulating effect known (EP 209763). However, especially at low application rates, their effect in certain indication areas may not always be

to satisfy.

Object of the invention Object of the invention It is to enrich the state of the art by new fungicidal agents with good performance properties. Explanation of the essence of the invention

The object of the present invention is to provide novel N-alkyl-dimethylinorpholinioalkyl-aryl ether and N-alkyldimethylmorpholiniocarboxylic acid ester salts having improved fungicidal activity in comparison with the compounds described in EP 209763.

It has now been found that novel N-alkyl-2,6-dimethylmorpholinioalkylether salts and N-alkyl-2,6-dimethylmorpholiniocarboxylic acid ester salts of the general formula I or a mixture of these salts with at least 15% by mass

their positionally isomeric N-alkyl-2,5-dimethylmorpholinioalkyl ether salts and N-alkyl-2,5-dimethylmorpholiniocarboxylic acid ester salts of general formula II,

^H 3 \ 1 ^H 3 ^C v

^RN . R ¹

ON X ^ ON '

\ -J ^N R ² - A V _ / \ ₂

H Γ ^NR * ^A

u; _(II) 3

in which

A represents the groupings-OR 'or -COOR ³ and R ¹ straight-chain or branched alkyl having 8 to 16 C atoms, R ² alkylene having 1 to 6 carbon atoms,

or - If ys_-OCH "or -U-ü and

X ^{e represents the} anion of an acid,

have a strong Fungitoxizität uod a broad spectrum of activity and as active ingredients of fungicidal agents for

Combating phytopathogenic fungi on crops and vegetable stocks. In the required Application concentration, the fungicidal compositions of the invention have a good plant tolerance. The active compounds can be in four different geometric structures as N-alkyl ^ .e-cis-dimethylmorphollnioalkylether- and N-alkyl ^ .e-cis-dimethylmorpholiniocarboxylic acid ester salt or N-alkyl ^ .e.-transdimethylmorpholinloalkyl ether and N-alkyl

2,6-trans-dimethylmorpholiniocarbonsäureester salt as well as in the analog N'Alkyl-2,6-cis- or N-alkyl-2,5-trans-isomers »succumb. In the compositions according to the invention, both the isomer mixture »as obtained in the synthesis, and the individual isomers can be used.

The compounds of the general formula I and II can be described in detail analogously to those described in EP 209763 Synthesis paths represent. The fungicidal compositions according to the invention have a strong activity against microorganisms and can

Accordingly, be used to combat fungal pathogens in agriculture and horticulture use.

They can be used to combat unwanted fungi found on plants or plant parts. The fungicides

are also useful as seed dressers for the treatment of seed and plant cuttings to protect against fungal infections and can be used against occurring in the soil phytopathogenic fungi.

The agents according to the invention are particularly suitable for the prevention and cure of plant diseases, dio by fungi

caused, such. B. Erysiphe graminls (powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Erysiphe polygon!

(Bean powdery mildew), Podosphaera leucotricha (apple downy mildew), Sphaerotheca pannosa (rose mildew), Uncinula necator (vineyard powdery mildew); Rust diseases, such as those of the genera Puccinia, Uromyces or Hemileia, in particular Puccinia graminis (cereal black bread), Puccinia coronata (oat crown rust), Puccinia sorghi (corn rust), Puccinia recondita (cereal brown rust),

Uromyces fabae (bush bean rust), Hemileia vastatrix (coffee rust); Botrytis cinerea on vines and strawberries; Monilia

fructigena on apples; Plasmopara viticola on vines; Mycosphaerella musicola on bananas; Corticum salmonicolar to Hevea;

Gandoderma pseudoferreum on Hevea; Exobasidium vexans to tea; Phytophthora infestahs on potatoes and tomatoes; Alternaria solani on tomatoes. Furthermore, various of these agents also have different efficacy against phytopathogenic fungi,

such as. Ustilago avenae (avian blight), Ophiobolus graminis (cereal foot diseases), Septoria nodorum (cereal leaf and

Spelled tan), Venturia inaequalis (apple scab) and other fungal pathogens, such as Rhlzoctonia, Tilletia, Helminthosporium, Peronospora, Pythium, Alternaria, Mucor, Sclerotinia, Fusarium, Pseudocercosporella and Cladosporium. Of particular interest are the fungicidal compositions of the invention for controlling a variety of fungal diseases

various crops or their seeds, in particular wheat, rye, barley, oats, rice, maize, cotton, soya,

Coffee, bananas, sugar cane, fruit, horticultural ornamentals, vegetables such as cucumbers, beans or cucurbits. Furthermore, the agents also provide good activity against wood-discoloring and wood-destroying fungi, such. Pullaria

pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum.

Furthermore, the fungicidal compositions according to the invention show a good activity against molds, such. Penicillium, Fusarium or Aspergillus species that spoil high-moisture agricultural products or Processing products of agricultural products during storage or temporary storage cause. Such

Products to be treated include e.g. Apples, oranges, tangerines, lemons, grapefruits, peanuts, cereals and

Cereal products or legumes and meal. The compositions of the invention are also different in addition to their broad fungicidal spectrum of activity

phytopathogenic bacteria such as Xanthomonss or Erwinia species.

A part of the active compounds of the general formula I and II stands out beside the protective effect by a systemic one Effect unfolding. Thus, they are absorbed both by the root and by the leaves and in the plant tissue

or above the seed fed to the aerial parts of the plant.

The compositions of the invention are also suitable for controlling resident strains of fungal pathogens against

known fungicides, e.g. Active substances from the group of the Dicarboximld Funglzlde, such as 6-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidln (Vinclozolin); Active ingredients from the group of benzimidazole fungicides, such as i-ln-ButylcarbamoyO-benzimidazole ^ -yl-carbamic acid methyl ester (benomyl); Agents from the group of azole fungicides, such as 1- (4-chlorophenoxy-3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -butan-2-one (triadimefon)) ; Active ingredients from the

Group of aromatic hydrocarbons-containing fungicides, such as 2,5-dichloro-1,4-dimethoxy-benzene

(Chloroneb); Active substances from the group of the phenylamide fungicides, such as, for example, DL-N- (2,6-dimethylphenyl) -N- (methoxyacotyl-alanine-methyl ester (metalaxyl); active substances from the group of pyrimidine fungicides, such as, for example, Butyl-2- ^

dimethylamino-4-hydroxy-6-methylpyrimidine (dimethirimol), showing signs of resistance.

The anions Χ ^θ listed in the general formulas I and II of the active compounds do not relate to phytotoxic acids,

for example, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, oxalic acid, n-dodecylsulfonic acid and n-dodecylphenylsulfonic acid. However, they are not crucial for fungicidal activity.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, foams, Pastes, granules, natural and synthetic substances impregnated with active substance, encapsulation in polymeric substances and in Envelopes for seeds as well as ULV-KaIt and warm mist formulations. The preparation dlesor formulations can be done in a known manner, for. B. by mixing or grinding the active ingredients

of the general formulas I and II with customary solvents and / or carriers, if appropriate using surface-active agents, such as emulsifiers and / or dispersants.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic latex polymers such as Gummiarabicum, polyvinyl alcohol and polyvinyl acetate are used. As further additives, dyes and Trace nutrients may be included in the formulations of the active ingredients. The formulations generally contain between 1 and 95% by weight of active compound, preferably between 5 and 90% by mass. The method of controlling fungi is characterized in that the fungicidal compositions according to the invention Activate fungi or the objects to be protected against fungal attack in an effective amount. The active ingredients may be known in the formulations or in the various forms of application with others Active substances, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, growth regulators, Plant nutrients and soil conditioners are mixed and applied. In many cases you get

when mixing with fungicides, broadening of the fungicidal activity spectrum. In the case of a number of mixtures of the agents according to the invention with known fungicides, synergistic effects also occur, the fungicidal activity of the combination product being greater than that of the added effectiveness of the individual components.

The fungicidal agents may be used as such or in the form of the use forms prepared therefrom by further dilution

usually, for. By pouring, dipping, spraying, spraying, atomizing, injecting, silting, spreading, pickling or

Encrusting, to be applied. In the treatment of parts of plants, the drug concentrations in the use forms in a larger Range can be varied. They are generally between 0.001 and 1 wt .-%, preferably between 0.01 and 0.5 Ma .-%. The Levels of active ingredient depend on the specific application and are generally between 0.2 and 2 kg Active ingredient per hectare. In the seed treatment, in general, amounts of active ingredient of 0.01 to 50g per kilogram of seed, preferably

0.1 and 10g needed.

For the preservation or post-harvest treatment of agricultural or processed products

agricultural products are the required amounts of active ingredient 0.01 to 20 g per kilogram of material to be treated, preferably 0.1 to 10 g.

In the treatment of soil, active ingredient concentrations are from 0.0001 to 0.1 mass%, preferably from 0.001 to 0.05 mass%,

required at the place of action.

The following examples are intended to illustrate the invention further, but without limiting it and the effect of

prove fungicidal compositions according to the invention.

embodiments example 1

4- (N-h-dodecyl-2,8-dimethylmorpholinio) butyl-biphen-2-yl-ether bromide

28.4 g (0.1 mol) of N-n-dodecyl-2,6-dimethylmorpholine and 30.5 g (0.1 mol) of 4-bromobutyl-biphen-2-yl-ether are dissolved in 100 ml

Acetonitrile with the addition of a catalytic amount of sodium iodide for 18 hours under reflux. After cooling it will

the solvent is removed in vacuo. The residue is taken up in a little acetone and the solution is added until complete precipitation of an oily phase with η-hexane. After repeated repetition of this procedure, the

Solvent residues removed in vacuo leaving 37.1 g (0.063 mol) of a yellow-brown viscous oil (Comp # 12). Example 2 N-iso-tridecyl ^ .e dimethylmorpholinio-acetic acid-S-methylisoxazole-S-yl-ester chloride

29.8 g (0.1 mol) of N-iso-tridecyl-2,6-dimethylmorpholine and 17.6 g (0.1 mol) of chloroacetic acid 6-methylisoxa-ol-3-yl ester are added with the addition of a catalytic amount of sodium iodide heated in 100 ml of n-butanol for 24 hours under reflux. After this

Removal of the solvent in a water-jet vacuum, the residue is digested several times with η-hexane. The remaining

oily phase is freed of solvent residues in vacuo. This gives 28.9 g (0.061 mol) of a yellow-brown oil (Comp.

In an analogous manner, the following compounds of general formulas I and II can be prepared, the yellow

to represent brown viscous oils or resins. They are readily soluble in polar solvents such as alcohols, ketones, dimethylformamide and dimethyl sulfoxide and are characterized by their IR spectra.

"Ή

H ₃ C

- A

, H,

- A

(D

(ID

No. R ¹ R ² A R ' X 1 i-tridecyl (CHj) ₂ OR ' biphen-2-yl br 2 i-tridecyl (CH ₂ ), OR ³ 2,5-dichloro-4-methoxyphenyl < br 3 i-tridecyl (CHj) OR ' 6-methyl-isoxazol-3-yl br 4 I-tridecyl (CH ₂ J ₃ OR ' biphen-2-yl br 5 i-tridecyl (CHj) ₃ OR ' 2,5-dichloro-4-methoxyphenyl br 6 i-tridecyl (CHj) ₃ OR ' 5-methylisoxazole-3-yl br 7 i-tridecyl (CHj) ₄ OR ' biphen-2-yl br 8th i-tridecyl (CHj) ₄ OR ' 2,5-dichloro-4-methoxyphenyl br 9 i-tridecyl (CHj) ₄ OR ³ 6-methyl-isoxazol-3-yl br 10 n-dodecyl (CH ₂ ), OR ' biphen-2-yl br 11 n-dodecyl (CH ₂ ) ₃ OR ' biphen-2-yl br 12 n-dodecyl (CHj) ₄ OR ' biphen-2-yl br 13 i-tridecyl CHj COOR ' biphen-2-yl Cl 14 i-tridecyl CH ₂ COOR ' 2,5-dichloro-4-methoxyphenyl Cl 15 i-tridecyl CH ₂ COOR ' 5-methyl-isoxazol-3-yl Cl 16 i-tridecyl CH (CH ₃ ) COOR ' biphen-2-yl br 17 n-dodecyl CH ₂ COOR ' biphen-2-yl Cl 18 n-dodecyl CH ₂ COOR ³ 2,5-dichloro-4-methoxyphenyl Cl 19 n-dodecyl CH, COOR ' 5-methylisoxazole-3-yl Cl

verb

 No.

IR spectra (capillary layer); Characteristic gangs (cm " ¹ I

2960,2920,2870,

760.660

2950,2920,2860,

2965,2930,2870,

2965,2925,2870,

2960,2960,2870,

2965,2930,2870,

2960,2860,1690,

700.665

2965,2920,2870,

690.655

2965,2920,2870,

2960,2925,2865,

2960,2925,2860,

760,700,655

1710.1 595.1 580.1 500.1470.1430.1380, 1330.1, 220.1180, 1130, 1080.1, 050, 1020, 880, 845,

1 595.1 560.1495, 1460.1, 375.1, 330.1, 210, 1120, 1130, 1080, 1045, 880, 8oo, 760, 665

1 670.1470, 1380.1, 340.1, 250.1, 220, 1180, 1115, 1085, 1030, 765, 665

1 705.1 595.1 580.1 500.1465.1435.1 380.1330.1 220.1180.1120.1080.1 025.760.700.655

1 595.1 555.1490, 1460, 1375.1, 325.1, 205, 1120, 1130, 1080, 1035, 830, 760, 655

1 670, 1465, 1385, 320, 220, 118, 1120, 1080, 1025, 760, 655

1 600.1 580.1 510.1465, 1430.1, 380.1, 330.1, 270.1, 230, 110, 80, 110, 10, 120, 050, 1025, 880, 760,

1735.1 595.1 580.1 500.1460.1430, 1370, 1220.1, 210, 1180, 1440, 1095, 1040, 825, 760,

1740, 1610, 1575, 1500, 1465, 1730, 1710, 1630, 15, 15, 1450, 1740, 171, 171, 155, 1465;

1390.1 220.1 200.1180.1100.1 075.1 040.870.800.760.665 1370.1 210.1 200.1 075.760.665 1430.1 380.1 280.1 215,1180,1150,1105,1 040,1 010,870,840,

The compounds of the general formulas I and II can, for. B. in the form of the following formulations are used:

! .. example. '

Solution concentrates: 80 parts by weight of compound 9 are mixed with 20 parts by weight of N-methyl-2-pyrrolidone. It will

obtained a solution that is suitable for use in the form of very small drops.

II. Example

Emulsifiable concentrates: 25 parts by weight of compound 7 are mixed with 2.5 parts by weight of epoxidized vegetable oil, parts by weight of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts by weight of dimethylformamide and 57.5 parts by weight of xylene. From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

III. example

Injection powder: 20 weight point of the compound 17 are mixed well with 5 weight points of the sodium salt of a lignosulfonic acid from a sulfite liquor, 1 part by weight sodium salt of di-iso-butylnaphthalene-sulfonic acid and 74 parts by weight of silica gel and ground in a corresponding mill. A spray powder is obtained which can be diluted with water to give suspensions of any desired concentration.

IV. Example Granules: 6 parts by weight of compound 6 are mixed with 0.25 parts by weight of epichlorohydrin and 6 parts by weight Acetone dissolved. Thereafter, 3.5 parts by weight of polyethylene glycol and 0.25 parts by weight of cetyl polyglycol ether are added. The

The solution thus obtained is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It will be a

Micro granules obtained, which can be used in this form. The examples which follow are intended to illustrate the fungicidal action of the agents according to the invention, but without them

limit.

Example A Wheaty mildew test (Erysiphe gramlnis / wheat) Potted-grown wheat plants of the 'Alcedo' variety are doused in the single-leaf stage with active compound preparations

sprayed from 1 part by weight of active ingredient, 100 parts by weight of acetone and 0.25 parts by weight of alkylaryl polyglycol ether

and diluted with water to the desired Wirkstoffkonzentraticn '. After the drying of the

Spritzbelages the plants are dusted with conidia (spores) of wheat powdery mildew (Erysiphe gramlnis var. Tritici). Subsequently, the test plants for a period of 2 to 3 hours at 90 to 100% relative humidity in

an incubation and then at temperatures between 20 and 22 ^carbon C and 75 to 80% relative humidity

Greenhouse set up. After 6 days, the powdery mildew of the wheat plants is determined. The efficiency of the funds is from ABBOTT

calculated.

Table A Action against Erysiphe graminis on wheat Active substance concentration: 100 mg χ 1 " ¹

Connection no. efficiency in percent N-i-tridecyl ^ .e dimethylmcrpholinlo-methyl acetate-chorid (known) (No. 5 from EP 209 763) 88 2- (N-l-tridecyl-2,6-dimethyl-morpholinio) ethyl-phenyl ester bromide (known) (No. 86 from EP 209 763) 84 5 100 7 100 9 100 15 100

Example B Botrytis test (Botrytis cinerea / field bean) (Vicia fabal leaflet spot infection method Cut leaf spring of potted bean plants (Vicia faba) of the variety "Fribo" in the four-leaf stage

are briefly immersed in active compound preparations made of 1 part by weight of active compound, 100 parts by weight of acetone and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired drug concentration

become. After the spray coating has dried on, dib leaves with a conidia suspension of Botrytis cinerea are obtained

Washing up of 12 to 16 day old fungal cultures on malt agar nutritive medium (3% malt, conidial density β χ 1 oVml)

is recovered, punctiform inoculated. The broadleaf leaflets are shells in an incubation cabin at a

Temperature of 22 ⁰ C and maintained at 90 to 100% relative humidity. After 2 days, the Botrytis infestation of field bean leaflet is determined. The infections are counted

and 'multiplied by a factor for the strength of infection (rating scale from 1 = no infestation to 5 = very severe infestation). The resulting value is given in% infection input and in relation to the untreated control of the

Efficiency calculated. Table B Action against Botrytis cinerea on field bean leaves Active substance concentration: 600mg x I ^-1

Connection no. efficiency In percent N-i-tridecyl ^ .e dimethylmorphollnio-essigsauremethylester chloride (known) (No. 5 from EP 209 763) 22 2- (N-i-tridecyl-2,6-dimethylmorpholinio) -ethyl-phenyl ester bromide (known) (No. 86 from EP 209 763) 55 4 96 5 76 6 86 7 96 9 61 12 68 13 63 15 51, 17 43

Claims (1)

1. Fungicidal agent / characterized characterized in that they as active ingredients N-alkyl 1-2,6-dimethylrnorpholinioalkylether salts and N-alkyl ^ a-dirnethylrnorpholiniocarbonsäureester salts of the general formula I or a mixture of these salts with at least 15 wt .-% of their positional isomers N-alkyl-2,5-dimethylmorpholinioalkylester salts and N-alkyl-2,5-dimethylmorpholiniocarbonsäureester salts of the general formula II ^H 3 ^C \ 1 ^H 3 ^C