DK164667B - N-SUBSTITUTED 2,6-TRANSDIMETHYLMORPHOLINE DERIVATIVE AND FUNGICIDE CONTAINING SUCH A DERIVATIVE - 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

in

DK 164667 B

This invention relates to novel N-substituted 2,6-dimethylmorpholine derivatives and fungicides containing them.

It is known to use N-substituted 2,6-dimethylmorpholines, especially tridecyl-2,6-dimethylmorpholine (Tride-morph) as fungicides, which is disclosed in DE disclosure no. 1164152. Other N-substituted 2.6 -dime-thylmorpholines are known from DE Publication no.

10 1198125, 1173722 and 1214471.

These known 2,6-dimethylmorpholine derivatives consist of mixtures of 2,6-cis and 2,6-trans isomers and have quite a good fungicidal effect. However, plant compatibility of these substances is poor and the use of these substances often results in significant leaf damage to the treated plant.

Another fungicide sold under the trade name Fen-20 propiomorph is disclosed in DE Publication No. 2656747. In this fungicide, a cis-2,6-dimethylmorpholine derivative is used, namely the compound 4- [3- [4- (1,1-dimethyl) phenyl] -2-methyl] propyl-2,6 (cis) -dimethylmorpholin. This is thus preferred over the trans derivative. Therefore, it was assumed that for other derivatives, the cis derivative would in each case be the more valuable of the two isomers.

It has now surprisingly been found that N-substituted 2.6-30 dimethylmorpholine derivatives which are trans-isomers exhibit a much better plant compatibility than the corresponding cis-isomers and mixtures of trans / cis-isomers. The fungicidal effect is essentially independent of whether the compound is trans- or cis-isomeric or a mixture thereof.

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The compounds of the invention, which are of the nature specified in the preamble of claim 1, are characterized by the characterizing part of claim 1.

5 R means e.g. n-nonyl, n-decyl, n-tridecyl, n-dodecyl, nC ^ I ^, g-n-C 15 H 31 n-C 20 H 41, 1,5,9-trimethyldecyl, 3,7,11-trimethyldodecyl, 3-ethyl 1,3,7-trimethyl-octyl, 2-methyl-tridecyl, 3,5,5-trimethyl-hexyl, 4-ethyl-1-methyloctyl, 1,4-diethyl-octyl, 2-hexyl-hexyl, 1- methyl-dodecyl, 2-methyldodecyl, 2-ethyl-5-cyclohexyl-pentyl, cyclododecylmethyl, 4-ethyl-1-isobutyl-octyl, cyclooctyl, cyclononyl, cyclododecyl, N-oxides are e.g. Nn-tri-decyl-2,6-trans-dimethylmorpholine N-oxide, N-cyclododecyl-2,6-trans-dimethylmorpholine-N-oxide, a mixture consisting of N-alkyl-2,6-trans-dimethylmorpholine -N-oxides, whereby the alkyl group contains 11 to 14 carbon atoms.

Acid addition salts are e.g. salts with hydrochloric acid, HBr, H 2 SO 4, H 2 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 groups R may contain asymmetric carbon atoms. Thus, the active substances of formula I may be in the form of various enantiomers or diastereomers. The pure enantiomers and diastereomers as well as mixtures thereof are included in this invention.

The preparation of the trans compounds can be carried out as follows: 1. Separation of the cis / trans mixtures by thin layer chromatography (n-hexane / acetone 9: 1 - silica gel).

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3 2. Distillative separation of the cis / trans mixtures.

3. Reaction of 2,6-trans-dimethylmorpholine with a compound of formula RX wherein R is as defined 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 formula RX or reaction with ROH or the corresponding ketones or aldehydes and reduction.

Regulation 1 15

Preparation of iso-tridecyl chloride (A)

To 322 g of SOC 4 was added 450 g of iso-tridecanol (iso-tridecanol here denotes a commercial mixture of various homologous C 1 -C 2 alcohols containing 60-70% tridecyl alcohol). The mixture was stirred overnight, heated 2 h to 140 ° C, distilled the crude product and obtained 433 g of colorless oil bp. 84 to 86 ° C / 0.3 bar.

EXAMPLE 1

Preparation of N-iso-tridecyl-2,6-trans-dimethylmorpholine (active substance # 1) 30 g of A and 48 g of 2,6-trans-dimethylmorpholine were heated for 8 hours to 150 ° C. The crude product was dissolved in Cl 2 C and washed with dilute aqueous NaOH and then several times with water. Dry over Na 2 SO 4, concentrated, distilled and obtained 16 g of colorless oil, bp. 122 ° C / 0.2 mbar.

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EXAMPLE 2

Preparation of N-cyclododecyl-2,6-trans-dimethylmorpholine (active substance # 23) 5 130 g of cyclododecanone, 138 g of 2,6-trans-dimethylmorpholine and 1 g of p-toluene sulfonic acid were heated to reflux for 15 hours. at the water separator. The crude product thus obtained was washed after cooling with water, dried over 10 MgSO 4, concentrated and distilled. After unreacted precursors, 64 g (140 to 145 ° C / 0.3 mbar) of yellow oil distilled = N-cyclododecenyl-2,6-trans-dimethyl-morpholine (5).

The resulting enamine (B) was dissolved in vinegar ester and hydrated after the addition of 5 g of Pd / C contact (10 wt% Pd) at 60 to 70 ° C / 100 bar. Then they concentrated and distilled. 45 g of colorless oil were obtained, b.p. 136 to 138 ° C / 0.2 mbar.

Similarly, the following compounds characterized by physical data were prepared: CH,

A

r * CH3 30 35

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5

Example No._R_kp. ° C / mbar 1 isotridecyl 122 ° / 0.2 2 n-nonyl 5 3 n-decyl 4 n-tridecyl 132-133 ° C / 0.3 5 n-dodecyl 6 n-C15H31 7 N-C20H41 10 8 1, 5,3-trimethyldecyl 9 3,7-11-trimethyldodecyl 10 3-ethyl-1,3,7-trimethyloctyl 11 2-methyltridecyl 12 3,5,5-trimethylhexyl 13 4 4-ethyl-1-methyl-octyl 14 1 4-Diethyl-octyl 15 2-hexyl-hexyl 16 1-Methyldodecyl 17 2-Methyldodecyl 20 18 2-Ethyl-5-cyclohexyl-pentyl 19 cyclododecylmethyl 20 4-ethyl-1-isobutyl-octyl 21 cyclooctyl 22 cyclononyl 23 cyclododecyl 136-138 ° / 0.2

The new compounds and their salts, metal complexes and oxides are characterized by excellent activity against a wide range of plant pathogenic fungi, especially 30 from the class comprising ascomycetes and basidiomycytes. They are partially systemically active and can be used as leaf and soil fungicides. In addition, they can be used for material protection.

35 Of particular interest are the fungicidal compounds for controlling many different fungi on different crops or their seeds, especially wheat, rye, barley, oats,

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6 rice, corn, cotton, soy, coffee, bananas, sugar cane, fruit and ornamental plants in the garden, as well as vegetables such as cucumbers, beans and pumpkins.

5 The new compounds are particularly suitable for the control of the following plant diseases:

Erysiphe graminis (real mildew) in cereals,

Erysiphe cichoriacearum (true mildew) by pumpkin, 10 Podosphaera leucotricha by apples,

Unicinula necator by wine,

Erysiphe polygony by beans,

Spaerotheca pannosa by roses,

Puccinia Species by Barley, 15 Mycosphaerella musicola by Bananas,

Corticium salmonicolor at Hevea,

Ganoderma pseudoferreum at Hevea and Exobasidium vexans at tea.

The compounds are used in the way of spraying or pollinating the plants or treating the seeds of the plants with the active substances. The application takes place before or after the infection of the plants or seeds with the fungi.

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The new substances can be transferred to the usual formulations such as solutions, emulsions, suspensions, powders, powders, pastes and granules. The forms of use are entirely directed to the uses? in each case they must ensure a fine and regular distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active substance with solvents and / or carriers, optionally using emulsifiers and dispersants, whereby in the case of water as a diluent, other organic solvents can also be used as auxiliary solvent. As auxiliaries,

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For this purpose, substantially the following materials are considered: solvents such as aromatics (e.g., xylene, benzene), chlorinated aromatics (e.g., chlorobenzene), paraffins (e.g., petroleum fractions), alcohols, 5 (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide) and water; carriers such as natural stone flour, e.g. kaolin, clay, talc, chalk and synthetic stone flour (eg high-dispersion silicic acid, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquor and methyl cellulose.

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

Depending on the nature of the desired effect, the amounts used are between 0.1 and 3 kg of active ingredient or 20 or more per hectare. The new compounds can also be used for the protection of materials, including for the control of wood-destroying fungi such as coniophora puteana and polystictus versicolor. The active substances are also suitable for treating fruits against mold attack. In addition, they can be used for wound treatments against fungal infections associated with plastic dispersions. The new active substances can also be used as fungicidal active ingredients in oily wood preservatives to protect wood from wood discoloration fungi. The use proceeds in the manner of treating the wood with these agents, e.g. by impregnation or ironing.

The agents or preparations based on these ready-to-use preparations, such as solutions, emulsions, suspensions, powders, powders, pastes or granules, are used in a known manner, e.g. by spraying, misting, spraying, spraying, pickling or pouring.

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8 ning.

Examples of such compositions are: 5 I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone to obtain a solution suitable for use in the form of very small drops.

II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of addition. the ring product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water, an aqueous dispersion is obtained.

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 preparation product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water, an aqueous dispersion is obtained.

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 30 210 to 280 ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water, an aqueous dispersion is obtained.

35 V. 20 parts by weight of the compound of Example 2 are well mixed with 3 parts by weight of the sodium salt of diisobutyl-naphthalene-alpha-sulfonic acid, 17 parts by weight of sodium

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9 is the salt of an equation sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By splitting the mixture into water, a spray liquid is obtained.

5 VI. 3 parts by weight of compound 4 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a powder containing 3% by weight of the active substance is obtained.

VII. 30 parts by weight of the compound of Example 2 are thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesiveness is obtained.

VIII 40 parts by weight of the compound of Example 1 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfone-20-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.

Twenty-20 parts of the compound of Example 4 are thoroughly mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether. 2 parts sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The novel agents may also be present in these applications together with other active substances such as e.g. herbicides, insecticides, growth regulators and fungicides, or they can be mixed with fertilizers and applied. By mixing with fungicides, there is thus in many cases a flattening of the fungicidal spectrum of action.

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The following list of fungicides with which the compounds of the invention can be combined should explain, but not limit, the combination possibilities.

Fungicides with which the new compounds can be combined are, for example: sulfur, dithiocarbamates and their derivatives such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese-ethylene-bis-dithiocarbamate, manganese-z ink-ethylenediaminebis dithiocarbamate or zinc ethylene bis-dithiocarbamate, tetramethylthiuram disulfides, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate) and N, N * -polyethylene bis (thiocarbamoyl) -disulfide, N'-propylene bis-dithiocarbamate), ammonia complex of zinc (N, Ν'-propylene bis-dithiocarbamate) and N, Ν'-propylene bis (thiocarbamoyl) disulfide; nitro derivatives such as dinitro (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclics, such as N-trichloromethylthio-tetrahydrophthalimide, N- (1,1,2,2-tetrachlorethylthio) -tetrahydrophthalimide, N-trichloromethylthiophthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6 - (o-chloroanilino) -s-triazine, O-diethyl-phthalimidophosphonothioate, 5-amino-1- (bis (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy -3-Trichloromethyl-1,2,4-thiadiazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1- (butylcarbamoyl) ) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole,

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11 2-Thodane methylthio-benzthiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5 carboxanilodo-6-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- (1- (2,2,2-trichloro-ethyl) -formamide), 2- (thiazolyl- (4)) -benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6 -methyl-pyrimidine, bis- (p-chlorophenyl) -pyridine methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) - benzene and other substances such as dodecylguanidine acetate, 3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutaramide, hexachlorobenzene, N-dichlorofluoromethylthio-N ', n'-dimethyl-N- phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) acetamide 2-methyl-benzoic anilide, 2-iodo-benzoic anilide, 1- (3,4-dichloro) anilino) -1-formylamino-2,2,2-trichloroethane, DL-methyl-N-2,6-dimethyl-phenyl) -N-furoyl (2) -alanate, DL-N- (2,6-dimethyl) -phenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, 5-nitro-isophthalic acid di-isopropyl ester, 1- (1'-2'-41-trizolyl-1 ') -4' -chlorophenoxy) -3 3-Dimethyl-butan-2-one, 1- (1 ', 2', 4'-triazolyl-1 ') -1- (4'-chlorophenoxy) -3,3-di

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12 methylbutan-2-ol, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N -5-imidazolylurea.

The following experiment shows the biological activity against real mildew (erysiphe graminis var. Hordei) and especially the plant compatibility of the new N-substituted 2.6-10 trans-dimethylmorpholines.

Attempt

Barley seedlings (Hauters Pfålzer summer barley) were sprayed in the 15 one leaf stage with an aqueous solution of active substance at various concentrations. Twenty-four hours after treatment, artificial inoculation was performed with spores of barley mildew (Erysiphe graminis var. Hordei). The test evaluation was performed 10 days after the infection.

20

As test compounds (fungicides), N-isotridecyl 2,6-dimethylmorpholine was used partly as pure trans-isomer according to the invention and partly as pure cis-isomer and as a cis / trans-isomer mixture (tridemorph), respectively. Compounds 25 were used at four different concentrations and 24 hours after treatment with the fungicides the effect on the plants was visually assessed. The damage effect on the plants was evaluated on a scale of 1-5, with 1 corresponding to no injury and 5 corresponding to total leaf death. The table below shows the assessment. It is clearly seen that the trans isomeric form has a much greater plant compatibility than the cis isomeric form and the cis / trans mixture isomeric form, respectively. The fungicidal effect was satisfactory in all cases. There was no apparent difference in the fungicidal effect of the three test fungicides.

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Treatment concentration

Compound (%) Leaf damage (1-5)

Tridecyl-2,6-0.02 3 dimethyl-morpholine 0.01 2 5 Cis / trans-isomer 0.005 1 form (Tridemorph known 0.0025 1 from DE 1164152) N-isotridecyl-2,6-0.02 3 dimethyl-morpholine 0.01 2

Cis isomer 0.005 1 form 0.0025 1 N-isotridecyl-2.6-0.02 l dimethyl-morpholine 0.01 l

Trans-isomer 0.005 1 form (According to the invention 0.0025 1 15 sen) 20 25 30 35

Claims (5)

A N-substituted 2,6-trans-dimethyl rhorpholine derivative of the formula Λ-Γ3 RN PI, N-4 CH, 10 j wherein R is a cycloalkyl, cycloalkylalkyl or alkyl group which may be substituted by one or more C -C ^ alkyl groups and wherein the number of carbon atoms in the substituent R is in total between 7 and 20, as well as its N-oxides and plant-compatible acid addition salts and metal complexes, characterized in that the derivative is a trans isomer. 20 2. 2,6-trans-dimethylmorpholine derivative according to claim 1, characterized in that it is Nn-tridecyl-2,6-trans-dimethylmorpholine, N-cyclododecyl-2,6-trans-dimethylmorpholine or a mixture consisting of N-alkyl -2,6-trans-dimethylmorpholines, whereby the alkyl group is optionally branched and contains 11 to 14 carbon atoms. Fungicide, characterized in that it contains a compound of formula I according to claim 1. Fungicide according to claim 3, characterized in that it contains a solid or liquid carrier. Fungicide according to claim 3 or 4, characterized in that the 2,6-trans-dimethylmorpholine derivative is Nn-tri-decyl-2,6-trans-dimethylmorpholine, N-cyclododecyl-2,6-trans-dimethylmorpholine or a mixture consisting of N-alkyl-2,6-trans-dimethylmorpholine, wherein the alkyl group DK 164667 B is optionally branched and contains 11 to 14 carbon atoms. 5 10 20 25 30 35