DD215931A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

1. Claims for the contracting states : BE, CH, DE, FR, GB, IT, LI, NL, SE A 2,6-trans-dimethylmorpholine derivative of the formula see diagramm : EP0129211,P8,F2 where R is a Cycloalkyl, Cycloalkylalkyl or alkyl radical which can be substituted by one or more C1 -C7 -alkyl radicals, and the total number of carbon atoms in the substituent R is from 7 to 20, and its N-oxides and plant-tolerated addition salts with acids and metal complexes. 1. Claims for the contracting state : AT A fungicide containing a 2,6-trans-dimethylmorpholine derivative of the formula see diagramm : EP0129211,P9,F1 where R is a cycloalkyl, cycloalkylalkyl or alkyl radical which can be substituted by one or more C1 -C7 -alkyl radicals, and the total number of carbon atoms in the substituent R is from 7 to 20, and its N-oxides and plant-tolerated addition salts with acids and metal complexes.

Description

O.Z. 0050/36569

Fungicides ;

Field of application of the invention

The new fungicides can be used in agriculture as fungicides.

Characteristic of the known technical solutions

It is known to use N-substituted 2,6-dimethylmorpholines, in particular the tridecyl-Zjö-dimethylmorpholine (Tridemorph) as fungicides. (DE 1 164 152). The known active ingredients consist of mixtures of the derivatives of 2,6- cis- and 2,6- trans- dimethylmorpholine. The plant tolerance of these substances is in many cases not sufficient.

Object of the invention

The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but crops are not damaged.

Explanation of the essence of the invention

The invention has for its object to provide new chemical compounds with fungicidal activity.

It has now been found that 2,6-trans-Dimethylmorpholinderivate of the formula

CH

in which R is a cycloalkyl, cycloalkylalkyl or alkyl radical which may be substituted by one or more Cj-Cy-alkyl radicals, and the number of carbon atoms of the substituent R is 7 to 20 in total and its N-oxides and plant-tolerated acid addition salts and Metal complexes are much better plant compatible than the corresponding 2,6-cis-Dimethylmorpholinderivate. The new 2,6-Transdimethylmorpholin compounds are better plant compatible than the corresponding known cis / trans mixtures (Tridemorph). This is surprising because in the known fungicidal commercial product fenpropimorph (DE-A 2 656 747) 4- [3- [4- (1,1-dimethylethyl) phenyl] -2-methyl] -propyl-

40. -2.6 (cis) -dimethyl-morpholine, the cis-2,6-dimethylmorpholine derivative is used. It is therefore preferred over the trans derivative. One would therefore have to assume that the derivative of the cis derivative is the more valuable of the two isomers for other derivatives as well.

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R is, for example, n-nonyl, n-decyl, n-tridecyl, n-dodecyl, ⁿ " ^c 14 ^H 29» ⁿ * " ^c 15 ^H 3 l" ⁿ " ^C 2 ^H 4l>!" S 1-3 triethylene decyl, 3, 7,11-trimethyldodecyl, 3-ethyl-1, 3,7-trimethyl-octyl, 2-methyl-tridecyl, 3,5,5-trimethylhexyl, 4-ethyl-1-methyl-octyl, 1,4-diethyl octyl, 2-hexyl-hexyl, 1-methyl-dodecyl, 2-methyldodecyl, 2-ethyl-5-cyclohexyl-pentyl-cyclododecyl-methyl, 4-ethyl-1-isobutyl-octyl, cyclooctyl, cyclononyl, cyclododecyl ·

N ~ oxides are, for example, Nn-tridecyl ^ jo-trans-dimethylmorpholine-N-oxide, N-cyclododecyl-2,6-trans-dimethylmorpholine-N-oxide, a mixture consisting of N-alkyl-2,6-trans-N-oxide. dimethylmorpholine N-oxides, wherein the alkyl radical contains 11 to 14 carbons.

Acid addition salts are, for example, the salts with hydrochloric acid, HBr, H ₂ SO 4, H ₃ PO 4, acetic acid, propionic acid, oxalic acid, n-dodecylsulfonic acid, n-dodecylphenylsulfonic acid.

Metal complexes are e.g. the complexes with copper, magnesium, zinc.

The aliphatic or cycloaliphatic radicals R may contain asymmetric carbons. The active compounds of the formula I can thus be present in the form of various enantiomers or diastereomers. The pure enantiomers and diastereomers as well as their mixtures are encompassed by this invention.

The preparation of the trans compounds is possible as follows:

1. Separation of cis ~ / trans Gemisehe by thin layer chromatography (η-hexane / acetone 9 ί 1 - silica gel).

2. Distillative separation of the cis / trans mixtures

3. Reaction of 2,6-trans-dimethylmorpholine with a compound of the formula RX in which R has the meanings given in claim 1 and X is a halogen atom (preferably chlorine or bromine).

; ; , - '. ..,. ' .. '..' /

4. Separation of 2,6-cis-dimethylmorpholine and 2,6-trans-dimethylmorpholine by distillation and subsequent reaction of 2,6-trans-dimethylmorpholine with a compound of the formula RX or reaction with ROH or the corresponding ketones or aldehydes and reduction ,

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Regulation 1

Preparation of iso-tridecyl chloride (A) "

To 322 g SOCIt was added 450 g iso-tridecanol (with isotridecanol we mean a commercial mixture of various homologous C ^ ₁ -C ^ -alcohols containing 60 to 70% tridecyl alcohol) added dropwise. The mixture was stirred overnight, heated for 2 hours at 140 ^e C, the crude product was distilled and obtained 433 g of colorless oil, bp. 84 to 86'C / 0.3 bar.

embodiments example 1

Preparation of N ~ iso-tridecyl-2,6-trans-dimethylmorpholine (active ingredient No. 1)

3OgA and 48 g of 2,6-trans-dimethylmorpholine were heated to 150 * for 8 h. The crude product was dissolved in CH 2 Cl 2, washed with dilute aqueous NaOH and then washed several times with water. It was dried over Na2SO4, concentrated, and distilled to obtain 16 g of colorless oil, bp. 122 ° C / O, 2 mbar.

Example 2

Preparation of N-cyclododecyl-2,6-trans-dimethylmorpholine (active ingredient No. 23),

130 g of cyclododecanone, 138 g of 2,6-trans-dimethylmorpholine and 1 g of p-toluenesulfonic acid were heated to reflux for 15 h in a water separator. The crude product thus obtained was washed with water after cooling, dried over MgSO 4, concentrated and distilled. After unreacted precursors 64 g (140 to 145 ^e C / O, 3 mbar) distilled yellowish oil »N-cyclododecenyl-2,6-trans-dimethylmorpholine (B).

The resulting enamine (B) was dissolved in ethyl acetate and hydrogenated after addition of 5 g of Pd / C contact (10 wt.% Pd) at 60 to 70 ^e C / 100 bar. Then you narrowed and distilled. This gave 45 g of colorless oil, bp. 136 to 138 ^e C / 0.2 mbar.

Correspondingly, the following compounds labeled with physical data were prepared:

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MLB

Example no. R! 3dp. C / mbar [ 136 - 138VO, 2 10 1 isotridecyl 122 ^e / O, 2 2 n-nonyl 3 n-decyl 15 4 n ~ tridecyl 132 - 133V0.3 5 n-dodecyl 6 HC ₁₅ H ₃₁ , · '.' 7 ⁿ ~ ^c 20 ^H 41 8th 1,5,3-trimethyldecyl \ 20 9 3,7,11-trimethyldodecyl 10 3-ethyl-l, 3,7-trimethyloctyl 11 2-methyltridecyl 12 3,5,5-trimethylhexyl 13 4-ethyl-l-methyl-octyl 25 14 1,4-diethyl-octyl 15 2-hexyl-hexyl 16 1-methyldodecyl 17 2-methyldodecyl 18 2-ethyl-5-cyclohexyl-pentyl 30 19 Cyclododecyl-methyl 20 4-ethyl-l-isobutyl-octyl 21 cyclooctyl 22 cyclononyl 23 cyclododecyl

The new compounds and their salts, metal complex compounds and oxides are distinguished by their outstanding effectiveness against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. They are sometimes systemically effective and can be used as foliar and soil fungicides. Furthermore, they can also be used in liaterialschutz.

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, Particularly interesting are the fungicidal compounds for combating a variety of fungi on various crops or their seeds, especially wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, bananas, sugarcane, fruit and ornamentals in horticulture, as well Vegetables - such as cucumbers, beans and cucurbits - ·

The new compounds are particularly suitable for controlling the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoriacearum (true Methltau) on cucurbits, Podosphaera leucotricha on apples, Uncinula necator on vines,

Erysiphe polygoni on beans, Sphaerotheca pannosa on roses,

Puccinia species on cereals, Mycosphaerella musicola on bananas, Corticium salmonicolor on Hevea, Ganoderma pseudoferreum on Hevea and Exobasidium vexans on tea.

^ The compounds are applied by spraying or dusting the plants with the active substances or by treating the seeds of the plants with the active substances. The application takes place before or after the infection of the plants * or seeds by the mushrooms.

The new substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The forms of application depend entirely on the purposes of use; they should in any case ensure a fine and even distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or excipients, if appropriate using emulsifiers and dispersants, it being possible to use other organic solvents as auxiliary solvents in the case of the use of water as diluent. Suitable auxiliaries are essentially: solvents such as aromatics (e.g., xylene, benzene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., petroleum fractions), alcohols (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide), and water; Carriers such as ground natural minerals, e.g. Kaolins, clays, talc, chalk and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers,

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Alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite-blue and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and .90% by weight of active ingredient.

The application rates are depending on the nature of the desired effect between 0.1 and 3 kg of active ingredient or more per ha. The new compounds can also u.a. used to combat wood-destroying fungi, such as Coniophora puteana and Polystictus versicolor. The active substances are also suitable for the treatment of fruits against mold infestation. Furthermore, they can be used in conjunction with plastic dispersions for wound treatment against fungal infections. The new active substances can also be used as fungicidally active components of oily HoIz preservatives to protect wood against wood-discolouring fungi. The application is carried out by treating the wood with these agents, for example soaking or painting.

The compositions or the ready-to-use preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are: 25

I. 90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone and obtains a solution which is suitable for use in the form of very small drops.

"v '··."'. '

II. 20 parts by weight of the compound of Example 2 are in a

Mixture dissolved, consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecyl '' 'benzenesulfonic acid and 5 weight parts of the adduct of 40 moles of ethylene oxide to 1 Mole of castor oil. By pouring and finely distributing the solution in water to obtain an aqueous dispersion.

III. 20 parts by weight of compound 4 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and finely distributing the solution in water nan receives an aqueous dispersion.

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IV. 20 parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 * C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water to obtain an aqueous dispersion.

V. 20 parts by weight of the compound of Example 2 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in water, a spray mixture is obtained.

VI. 3 parts by weight of compound 4 are intimately mixed with 97 parts by weight of finely divided kaolin. This gives a dust containing 3 wt.% Of the active ingredient.

VII. 30 parts by weight of the compound of Example 2 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which has been sprayed onto the surface of this silica gel. This gives a preparation of the active substance with good adhesion.

VIII. 40 parts by weight of the compound of Example 1 are intimately mixed with 10 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with water gives a dilute aqueous dispersion.

IX. 20 parts of the compound of Example 4 are intimately mixed with 2 parts Calci.urasalz of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. This gives a stable oily dispersion.

The novel agents may also be present in these forms of application together with other active ingredients, such as e.g. Herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers and applied. In the case of mixing with fungicides, in many cases an enlargement of the fungi-cidal spectrum of activity is obtained.

O.Z. 0050/36569

The following list of fungicides with which the compounds according to the invention can be combined is intended to illustrate, but not limit, the possible combinations.

    · -. *

Fungicides _s that can be combined with the novel compounds, for example:

Sulfur;

Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, manganese-zinc-ethylenediamihbis-dithiocarbamate or zinc ethylenebisdithiocarbamate,

Tetramethylthiuram disulfide, ..... '

Asmoniac complex of zinc-CNjN-ethylene-bis-dithiocarbamate) and Ν, Ν'-polyethylene-bis- (thiocarbamoyl) -disulfide, zinc-CNjN'-propylene-bis-dithiocarbamate);

Ammonia complex of zinc-CNjN'-propylene-bis-dithiocarbamate) and N, N'-propylene-bis (thiocarbamoyl) disulfide;

Nitro derivatives, such as ⁷ .

Dinitro- (l ~ methylheptyl) -phenylcrotonat,

Z-sec-butyl ^ jo-dinitrophenyl-SjS dimethacrylate,

Z-sec '.- butyl AJOE-dinitrophenyl isopropyl carbonate; _

heterocyclic substances, such as

N-trichloromethylthiotetrahydrophthalimide, N- (l lj ^ _s ^ .a-tetrachloroethylthio tetrahydrophthaliniid, N-trichloromethylthio phthalimide,

^ Heptadecyl-Z-imidazolin-acetät,

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

0,0-Diethyi-phthalimidophosphonothioate, 5-amino-1- (bis (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole, S-ethoxy-S-trichloromethyl-1, 2,4- thiadiazole,

2,3-dicyano-l, 4-dithioanthrachinon,

2-Thiö-l, 3-dithio (4,5-b) quinoxaline,

methyl (1- (butylcarbamoyl) -2-benzimidazolecarbamate, ^ -methoxycarbonylaminobenzimidazole,

2-Thodänmethylthio-benzothiazole,

4- (2-chlorophenylhydrazobenzo) -3-methyl-5-isoxazolone, pyridine-2-thiol-oxide,

8-hydroxyquinoline or its copper salt,

2, S-dihydro-S-carboxanedio-o-methyl-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2- Furyl) -benzimidazole, piperazine-1,4-diyl-bis (1H, (2,2,2-trichloroethyl) -formamide),.

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2- (thiazolyl (4)) - benzimidazole,

S-butyl-dimethyl-amino-hydroxy-O-methyl-pyrimidine, bis (p-chlorophenyl) -pyridinemethanol,

l, 2-bis (3-ethoxycarbonyl-2-thioureido) benzene, l, 2-bis (3-methoxycarboyl-2-thioureido) benzene

'"

and other substances, such as.

dodecylguanidine acetate,

3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutaramide _> hexachlorobenzene,

N-dichlorofluoromethylthio ^ N'jN'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide,

2,5-dimethyl-furan-S-carboxylic acid cyclohexylamide, 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) -acetamide, 2-methylbenzoic acid anilide,

2-iodo-benzoic acid anilide,

l- (3,4-dichloroanilino) -l-formylamino-2,2,2-trichloroethane,

DL-methyl-N-2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethylphenyl) -N - :( 2 ^l -methoxyacetyl) -alanine methyl ester, di-isopropyl 5-nitro-isophthalate,

1- (1 ', 2', 4'-triazolyl-1 ^f ) -4 ^f -chlorophenoxy) -3,3-dimethylbutan-2-one, 1- (Γ, 2 ', 4'-triazolyl-1') -l- (4-chlorophenoxy) -3,3-dimethylbutan-2-ol, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, N- (n -propyl) - N- (2,4,6-trichlorphenoxyethyl) -N ^l -imidazolylharnstoff.

The following experiment shows the biological activity against powdery mildew (Erysiphe graminis v. Hordei) and in particular the plant compatibility of the new N-substituted 2,6-trans-dimethylmorpholines. 30

attempt

Barley seedlings (Hauters Palatinate spring barley) were sprayed in the single-leaf stage with aqueous solution of different concentrations. 24 hours after the treatment, the artificial inoculation was carried out with spores of barley powdery mildew (Erysiphe graminis var. Hordei). The experimental evaluation was made 10 days after the infection.

The result of the experiment shows that active compound 1 when used as 0.0025; 0.005; 0.01 and 0.02% (wt.%) Spray liquor produces lower leaf damage (1) than the compound N-isotridecyl-2,6-cis-dimethylmorpholine (2) and the compound tridemorph.

Claims (1)

- 10 - O.Z. 0050/36569 Claim for invention Fungicidal agent, characterized by a content of a solid or liquid carrier and a 2,6-trans-dimethylraorpholine derivative of the formula CH ₃ in which R represents a cycloalkyl, cycloalkylalkyl or alkyl radical which may be substituted by one or more C 1 -C 6 -alkyl radicals and the number of carbon atoms of the substituent Rines is from 7 to 20 or its N-oxides or its plant-tolerated acid addition salts or metal complexes , ,