CS249138B2 - Fungicide - 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

The present invention relates to a fungicidin composition which contains N-isotridecyl-2,6-trans-dimethylmorpholine as active ingredient and which is used for the control of deep-root diseases.

It is already known to use N-substituted 2,6-dimethylmorpholines as fungicides, in particular tridecyl-2,6-dimethylmorpholine (Tridemorph) (cf. DE 1164 152). Known active substances consist of mixtures of 2,6-cis- and 2,6-trans-dimethylmorpholine derivatives. However, the compatibility of these substances with plants is not sufficient in many cases.

It has now been found that N-isotridecyl-2,6-trans-dimethylmorpholine of formula (I)

R-O

A c

O) in which

R is an isotridecyl group, is tolerated by plants substantially better than the corresponding 2,6-cis-dimethylmorpholine derivative.

The novel 2,6-trans-dimethylmorpholine derivative is better tolerated by plants with the corresponding known cis / trans mixture (Tridemorph). This finding is surprising since, for the known fungicidally active product, conventional on the mandrel and referred to as Fenpropimorph (cf. DE-A 2 656 747) {4- (3- (4- / 1,1-dimethylethyl) (phenyl) 2-methyl] propyl-2,6- (cis) -dimethylmorpholine} is used as a derivative of cis-2,6-dimethylmorpholine, so it must have been assumed that for other derivatives the cis derivative is always more effective and therefore more valuable of both isomers.

Accordingly, it is an object of the present invention to provide a fungicidal composition comprising N-iso-tridecyl-2,6-trans-dimethylmorpholine as the active ingredient.

Due to the presence of asymmetric carbon atoms in R, the active compound of the formula I is present in the form of various enantiomers or diastereoisomers. Pure enantiomers and diastereomers as well as mixtures thereof are therefore within the scope of the active ingredients of the present invention.

In principle, the production of trans derivatives is possible as follows:

1. Separate the cis / trans mixtures by thin layer chromatography (silica gel, solvent system: n-hexane / acetone 9: 1).

2. Distillation of cis / trans mixtures.

3. Reaction of 2,6-trans-dimethylmorpholine with a compound of formula

R - X wherein

R is an isotridecyl group and

X represents a halogen atom, preferably a chlorine atom or a bromine atom.

4. Splitting 2,6-cis-dimethylmorphioline a

2,6-trans-dimethylmorpholine by distillation and subsequent reaction of 2,6-trans-dimethylmorpholine with a compound of the formula

R - X wherein

R and X are as defined above, or by reaction with a compound of formula

R = OH wherein

R is an isotridecyl group, or with the corresponding ketone or aldehyde and reduction.

The preparation of the active compound according to the invention is illustrated by the following example:

Example

Preparation of N-isotridecyl-2,6-trans-dimethylmorpholine (active substance No. 1) g of isotridecyl chloride and 48 g of 2,6-trans-dimethylmorpholine were heated at 150 ° C for 8 hours. The crude product was dissolved in methylene chloride, the methylene chloride solution was washed with dilute aqueous sodium hydroxide solution and then several times with water. The solution was dried over sodium sulfate, concentrated, and the solvent was distilled off to give 16 g of a colorless oil, bp 122 ° C / 20 Pa.

Preparation of the starting material, ie isotridecyl chloride:

To 322 g of thionyl chloride is added dropwise 250 g of isotridecanol (isotridecanol is a commercially available mixture of various C 11 -C 14 homologous alcohols containing 60 to 70% tridecyl alcohol alcohol). The reaction mixture was stirred overnight, then heated at 140 ° C for 2 hours. The crude product was distilled to give 433 g of a colorless oil.

Boiling point 84-86 ° C / 30 Pa.

N-N-isotridecyl-2,6-trans-dimethylmorpholine is characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes Ascomycetes and Basidiomycetes. This compound is partially systemically active and can be used as a leaf fungicide and as a soil fungicide. Furthermore, the active ingredient can also be used for the protection of materials against fungal diseases.

Of particular interest is this fungicidally active compound for controlling a variety of fungi on a variety of crop plants or on their seeds, in particular rye, wheat, barley, oats, rice, corn, cotton, soy, coffee, banana, sugarcane, fruit trees and ornamental plants in horticulture, as well as in the cultivation of vegetables such as cucumbers, beans and pumpkin plants.

The new N-isotridecyl-2,6-rans-dimethylmorpholine is particularly suitable for combating the following plant diseases:

powdery mildew (Erysiphe gramrnis) on cereals,

Erysiphe cichoracearum on pumpkin plants, apple powdery mildew (Podosphaera ieucotrichai on apple trees, vine mildew (Unciinula necator) on vine, Erysiphe pplygoni on bean, Sphaeroteca pannosa on roses, various types of rust on cereals (Puosphinaella musicola) of rubber trees, Ganoderma pseudoferreum on rubber trees and

Exobasidium vexans on tea tree.

N-isotridecyl-2,6-rans-dimethylmorpholine is applied by spraying or dusting the plants with the active ingredient or by treating the seeds of the active ingredient with said active ingredient. The application is carried out before or after infection of the plants or seeds by the fungus.

N-isotridecyl-2,6-trans-dimethylmorpholine can be converted to conventional compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use forms depend entirely on the intended use. These dosage forms are in any case intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active compound with solvents and / or carriers, optionally using emulsifiers and dispersants, and other organic solvents can also be used as co-solvents when water is used as a diluent. Basically suitable excipients for this purpose are: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as natural stone meal, for example kaolin, clays, talc, chalk and synthetic stone meal (for example, highly dispersed silicic acid, silicas); emulsifiers such as non-ionic and anicic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers) (alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal composition according to the invention generally contains between 0.1 and 95% by weight of N-isotridecyl-2,6-transdimethylmorpholine, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the application rate is between 0.1 and 3 kg of active substance or more per ha. The novel compound can also be used to protect the material, inter alia, to combat wood decaying fungi such as Coniophora puteama and Polysticus versicolor. The active ingredient according to the invention is also suitable for the treatment of fruits against fungal infestation. Furthermore, said compound can be used in combination with dispersions of plastics to treat injured sites against fungal infections. The new active substance can also be used as a fungicidally active component of the rail-based means for protecting wood against fungi which cause wood coloring. The application is carried out, for example, by treating the wood with these means, for example by impregnating with a net coating.

These compositions or ready-to-use preparations such as solutions, emulsions, suspensions, powders, dusts, pastes or granules are used in a known manner, for example by spraying, misting, dusting, sprinkling, pickling or pouring.

Examples of such preparations are:

Example I parts by weight of the active ingredient No. 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone-to give a solution which is suitable for application in the form of minimal drops.

Example II parts by weight of the active substance No. 1 are dissolved in a mixture consisting of - 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. The mixture was poured into water and finely divided to give an aqueous dispersion.

Example III parts of active ingredient No. 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutainol, 20 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. The resulting solution is poured into water and a fine dispersion gives an aqueous dispersion.

Example IV parts by weight of the active substance No. 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 to 280 ° C and 10 parts by weight of an adduct of 40 mOl ethylene oxide . Pouring the solution into water and finely distributing it gives an aqueous dispersion.

Example V parts by weight of compound no. 1 is mixed with 3 parts by weight of the sodium salt diisobuty.lnaftalensulfonové ^acidic: NY, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel, and · triturated hammer NLA mill. By finely distributing the mixture in water, a suspension suitable for spraying is obtained.

Example VI parts by weight of active substance no. · Mix thoroughly with 97 parts by weight of finely dispersed. kaolin. Hereby. in this way, a dust containing 3% by weight of the active ingredient is obtained.

Example VII parts by weight of active ingredient No. 1 are intimately mixed with a mixture of 92 parts by weight of silica gel powder and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this manner. an effective formulation with good adhesion is obtained.

Example VIII parts by weight of active ingredient No. 1 are intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with water gives an aqueous dispersion.

Example IX parts of active ingredient No. 1 are intimately mixed with 2 parts of dodecylbenzenesulfonic acid, 8 parts of polyglycol diether of fatty alcohol, 2 parts of sodium salt of phenol sulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil (parts by weight). A stable oil dispersion is obtained.

The novel fungicidal composition can also be present in these dosage forms together with other active ingredients, for example with herbicides, insecticides, growth regulators and fungicides, or also with fertilizers and then applied together. When mixed with fungicides, in many cases the fungicidin spectrum is broadened.

The following list of fungicidines, which may be combined with the N-isotridecyl-2,6-thiransimethylmorpholine of the present invention, is intended to illustrate the nature of such combinations, but is not intended to be limiting.

Examples of fungicides that may be combined with the novel N-isotridecyl-2,6-trans-dimethylmorpholine include: sulfur, dithiocarbamates and derivatives thereof, such as zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bis-dithiocarbamate, ethylene bis- manganese dithiocarbamate ethylenediamine-bis-dithiocarbamate manganese-disintegrated tetramethylthiuram disulfides ammoniacal complex

Zinc ethylene-bis-diethiocarbamate a

N, N‘-polyethylene-bis- (thiocarbamoyl) disulfide

N, N'-propylene-bis-diíhi o ^ι carbamate zinc ammonia complex

Zinc N, N‘-propylene-bis-dithiocarbamate and N, N‘-polypropylene-bis- (thilpkaabamoyl disulfide);

nitro derivatives, such as dinitro (phenylcronate)

2-sec-butyl-4,6-dinitrophenyl-3,3-

dimethylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate heterophyllic compounds such as N-trichloroamethylthiothetrahydrophthalimide N- (1,1,2,2) tetrahydrophthalimide N-trichloromethylthiophthalimide 2-he; - (- (-)

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

O, O-Diethylphthalimidophosphonothioate 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-thiazole 5-ethoxy-Mtichloirmethyl-1,2,4-thiadiazole

2,3-Dicyclo-1,4-dithioanthquinoline 2-thio-1,3-dithio (4,5-b) quinoxaline 1- (butylcarbamoyl) methyl ester

-2-BE nzimidazoikarbamové ^l of 2 ^^ (^ i ^ .hoxyk <arbonylaminobenzimida ^ zC'l rhodanmethylthiobenzlhiazoιl 2-4- (2-ohlorrenylhyУdaao.no of 3-methyl-5-pyridin-isloixazolon Thiol-L-oxadiazole B-Hydroxycholine or its copper (I) salt

2,3-dihydro-5-carboxanilldo-6-methyl-1,4-oxathiine-4,4-di: oxide

2,3-diУydro'-5-carboxatliin-6-methyl-1,4-oaaahiih

2- (Furyl) benzimidazole piperazine-1,4-diylbis- [1- (2,2,2-trichloroethyl bromoformide)]

2- (thiazol-4-yl) [benzimidazole

S-biphenyl-d-dimethylamino-K-dihydroxy-iu

methylpyrimidine bis- (p-chlorophenyl) pyridine dimethanol

1,2-bis- (3-ethoxycarbonyl-4-thioureido) benzene

1,2-bis- (3-methoxycyclonyl-2-thioinreidol) benzene and other substances such as dodecylguamidine acetate

3- (3- (3,5-Dimethyl-2-oxycycloheyyl) -

-2-hydroxy-ethyl ¹ sxye] glutaramide hexachloirbenzen dmhl'crfluormethylthio N-N ', N'-dimethyl-N-sulfuric acid fenyldiomld

2,5-dimethylfuron-3- 2,5-dimethylfuranyl-caryoinyanilide cycloheyylamide

-Acid acid

2-Methyl-N- (ethylamino-carbonyl) -2- (methylimino) acetamide 2-methylbenzoic acid anilide and 2-iodo-benzoic acid 2-methylbenzoic acid anilide 1- (3,4-dichloroanilino) -1-fornynylamino-2,2,2-trichloroethane DL-methyl-N, N-O-dimethylphenyl-N, uroyl (2) -olaninate methyl ester DL-N- (2 ', 4', 4'-enyl) -N- (2'-methoxyloxyethyl) otonine diisopropyl ester 5- (1 ', 3') - (L ', 2', 4'-triosot-1'-yl) -4'-chlorophenoyl-3,3'-biphenyl-2-one

1- (t ⁴ 2 ', 4'-triazolil'-yl] -1- (4'-chlorophenyl _L xy) ^ 3-dimethylbuton-2-ol

N- (2, y-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyric acid

N- (n-propyl) -N- (2,4,6-trichloro-emethylethyl) -N-imidosolylurea.

The following experiment illustrates the biological activity against Erysiphe graminis vor. Hordei and, in particular, the compatibility of the novel: N-isiotridecyl-2, γ-rons-dimethylmorpholine by plants.

Example A

Young barley plants ('Hauters Pfalzer' barley) are sprayed with an aqueous solution of the active substance of varying concentrations at the stalk of one leaf. An artificial spore infestation (Erysiphe gromiirs vor. Hordei) is carried out 24 hours after spraying. Evaluation of the experiment is carried out 10 days after infection.

The test results are summarized in Table A below:

active substance

N-isotridecyte-2 ', γ-dimethylmorphiotin concentration of the active ingredient in the spray suspension (w / w) leaf damage (1 to 5)

in the form of the cis-isomer 0.02 3 0.01 2 in the form of the trons-isomer 0.02 1 (Effective Substance No. 1) 0.01 1 nridemorph 0.02 3 (mixture of cis- and trans-isoimmes) 0.01 2

Claims (1)

Functional composition, characterized in that it contains, in addition to a solid or copolymable carrier, the active ingredient N-isodecyl-2,6-tri-dimethylmorpholine.