FI67379C - SAOSOM FUNGISIDER ANVAENDBARA MORFOLINDERIVAT - Google Patents

Description

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Μ | 3Γ £ m ^ 1) UTLÄGG NINGSSKRI FT 673 7 9 ^ '(51) Kv.ltu / lm.Ct.3 C 07 D 295/02, 265/30, A 01 N 43/84 FINLAND — FINLAND φ) * «« ** · —λμ * ·· βι * ι * 781117 (22) ItakwnbHM — AiMMniHcrfa, 12.04.78 <FI) (23) AHnipUvt — GlMgHaOdaf 12.04.78 (41) Interpreters (ulkhafcsJ - Bllvh affaMJIg 13.10.79

Patent and Registration Office (44) Date of issue and date of issue. -

Patent and ocean registration Anadkan utiagd odi ud ^ kriftw pubUcarad 30.11.84 (32) (33) (31) * rt *** l · οιβΐΐΜ «ι · —e * fW prtork * (71) BASF Aktiengesel1schaft, D-6700 Ludwigshafen , Federal Republic of Germany - Förbundsrepubliken Tyskland (DE) (72) Walter H immele, Walldorf, Ernst-Heinrich Pommer, Limburgerhof,

Norbert Goetz, Worms, Federal Republic of Germany-Förbundsrepubliken

Tyskland (DE) (74) Oy Koi ster Ab (54) Morpholine derivatives useful as fungicides -Sasom fungisider användbara morpholine derivatives The present invention relates to novel valuable morpholine derivatives and their salts and molecular and additive compounds having good fungicidal activity.

It is known that N-tridecyl-2,5-dimethylmorpholine and its salts and its molecular and addition compounds are used as fungicides (DE patents 11 64 152 and 11 73 722 and DE application 24 61 513).

It has been found that morpholine derivatives of the formula R3 R1 * ΓΗ3 / i Λ? H3 Λ

CH -c - </ \ yCH -CH-CH -NO

Mr 3 R2r4 2 67379 12 3 4 wherein R, R, R and R are hydrogen, methyl or ethyl, and their salts and molecular and addition compounds have a good fungicidal effect which is far superior to that of known morpholine derivatives.

Salts are, for example, salts with inorganic or organic acids, e.g. chlorides, fluorides, bromides, iodides, sulphates, nitrates, phosphates, acetates, propionates or fumarates, molecular or addition compounds are formed, for example, with surfactant acids, e.g. dodecylbenzene benzene.

In the case of 2,6-dimethyl derivatives, the new compounds can be isolated as cis and trans isomers. They are prepared, for example, by reacting 2,6-dimethylmorpholine with 3-p-tert-butylphenyl-2-methylpropanal in the presence of a diluent, e.g. formic acid, at temperatures of 50-110 ° C.

The following examples illustrate the preparation of the new compounds.

Example 1 Synthesis of N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -cis-2,6-dimethylmorpholine 2,6-Dimethylmorpholine obtained by cyclization with sulfuric acid catalyzed by diisopropanolamine is separated into cis- and trans-forms by fractional distillation in a distillation column packed with stainless steel wire coils. About 75% (w / w) of 2,6-dimethylmorpholine is in the cis form, the rest in the trans form. Separation of the isomers by fractional distillation is accomplished in a column with about 40 separation bases. the cis form distills as a 99% product at 80-81 ° C at 100 torr. The trans form of 2,6-dimethylmorpholine can be obtained under the same conditions as more than 95% product at a distillation temperature of 88-89 ° at 100 torr.

575 g of 98% formic acid are first placed in a stirrer equipped with a reflux condenser, a thermometer and a dropping funnel. 345 g of 99% 2,6-cis-dimethylmorpholine are then added dropwise, with stirring and cooling. The mixture is then slowly heated to 70 ° C in a water bath. Within 4 hours, 612 g of 3-p-tert-butylphenyl-2-methylpropanal are added dropwise to the reaction mixture, maintaining the temperature at about 67379 at 100 ° C. During condensation, strong CO2 formation occurs. After completion of the reaction, the temperature of the mixture is maintained at 100 ° C for a further 2 hours with stirring.

The excess formic acid is then distilled off in vacuo. More complete separation of formic acid takes place in a water-vacuum at 100 ° C.

The base is liberated from the formate by dropwise addition of 500 g of a 40% aqueous sodium hydroxide solution. The addition of sodium hydroxide is conveniently carried out at 80-100 ° C in order to make the resulting amine phase more miscible with the lye phase. To reduce the viscosity, 200 g of toluene are added. After separation of the lye phase, the organic phase is washed twice with 250 g portions of water. For further purification, the amine is fractionally distilled under a 0.2 torr vacuum distillation column with 5 bottoms. In addition to a small pre-distillate (up to 143 ° C under a vacuum of 0.2 torr: 50 g), 865 g of N- (3-tert-butylphenyl-2-methyl-1-propyl) -2,6-cis-dimethylmorpholine are obtained. This distills under a vacuum of 0.2 torr at 143-146 ° C. Based on gas chromatographic analysis, the amine contains more than 98% pure substance. The yield was 84.5% based on the aldehyde.

For conversion to the hydrochloride, 30 g of pure product are dissolved in 50 g of ethanol saturated with hydrogen chloride at room temperature. After cooling, 23 g of hydrochloride melting at 220 ° C are obtained in very pure form.

Example 2 Synthesis of N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -2,6-trans-dimethylmorpholine To 70 grams of 98% formic acid is added under ice-cooling 29 g of 2,6-trans-formic acid. dimethylmorpholine. 41 g of 3-p-tert-butylphenyl-2-methylpropanal are then added with stirring. The reaction mixture is heated at 100 ° C for 6 hours. At the onset of the reaction, a very strong evolution of CC> 2 occurs, which after about an hour deteriorates considerably. Further processing takes place as described in more detail in Example 1.

N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -2,6-trans-dimethylmorpholine distills under vacuum at 5 torr at 168-169 ° C.

4 67379

Yield based on aldehyde 52 g = 86%. 11 g of amine are dissolved in 20 g of ethyl acetate saturated with dry hydrogen chloride. Upon cooling, the hydrochloride crystallizes out. Sp. 165 ° C. Other compounds are obtained in a similar manner.

Examples of compounds according to the invention are the following active ingredients in which ch3 - ch3 R = CH3-C-ft-CH2-CH-CH2-CH3

Active substance No. 1 κ-ίΓΛ Kp: 123 ° C / 0.01 torr N— CH3

2 R 2 H 2 Cl 2 3 Mp: 108 ° C

CHt / -r013 3 R-N ^ Kp: 143-146 ° C / 0.2 torr cis form Ch3 ^ ch3 / \ 3 4 O Kp: 168-169 ° C / 5 torr

CH

trans format 3 ^ 3 / - \

5 * - \ 0. HCl M.p .: 220 ° C

'ch3 cis form 6 «Q • Sp: 165¾ trans formSH3 rC ch 10 /' RN o Kp: 128 ° C / 0.02 torr ct3 67379 Rl / Kp: 133 ° C / 0.05 torr \ _ / / ch3 CH0 12 Rf DEG C. [.alpha.] D @ 20 = 125 DEG C. <0.02 torr.

14 R-li Π. . HCl M.p .: 206 ° C

\ _____ j h3c 15 R-N ^ 9 Kp: 145 ° C / 0.3 torr h3c h3c ^ _

16 R-ti \. HCl M.p .: 172 ° C

h3c C2H5 x 17 ° C: 148 ° C / 0.3 torr> _ / C2H5 "/ C2H5 18 R-D> Kp: 146-148 ° C / 0.3 torr> _2 C2H5 / - ^ ch3

19 R-I ^ _0. HBr Mp: 228 ° C

^ CH, cis form 3 rCH3

_H .COO-CH mp: 174 ° C

CH HC - COOH

cis format 3 6 67379

The cowardly active ingredients of the invention and corresponding fungicides are particularly suitable for controlling plant diseases, e.g. mushroom, sphaeurotheca pannosa, rose Microsphaera querci, strawberry, Botrytis cinerea vine, Mycosphaerella musicola banana, Puccinia species (rust fungi), Uromyces appendiculata, coffee to control Hemileia vastatrix and Rhizoctonia solani. They have a systemic effect; they are absorbed both through the roots and also through the leaves and migrate to the cellular tissue of plants.

The substances are used, for example, by wetting, spraying, dusting or covering plants or seeds with active ingredients.

When new active ingredients are used to treat plants against fungal infections, the application rates are between 0.025 and 5 kg of active ingredient per hectare of surface area. To protect the surface of trees and fruits, the active ingredients can also be used in connection with artificial dispersions, in the form of dispersions of 0.25 to 5% by weight of the dispersion. Fungicides generally contain from 0.1 to 95% by weight of active ingredient, mainly from 0.5 to 90%.

The active ingredients can be mixed with other known fungicides. In many cases, the spectrum of action of fungicides is thus extended; synergistic effects also occur in the case of mixtures of numerous fungicides with weight ratios between 1:10 and 10: 1, i.e. the fungicidal effect of the composite product is greater than the sum of the effects of the individual components. Fungicides that can be combined with the compounds of the invention include, for example: dithiocarbamates and their derivatives such as zinc dimethyldithiocarbarate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylenediamine-bis-ethylamethylamine-bis-dithiocarbamate, 6767379 zinc bis-dithiocarbamate) and N, Ν'-polyethylene-bis- (thiocarbamoyl) -disulfide ammonia complex, zinc- (N, N'-propylene-bis-dithiocarbamate), zinc- (N, N'-propylene-bis- dithiocarbamate) and N, N'-polypropylene-bis (thiocarbamoyl) disulfide ammonia complex; heterocyclic compounds such as N-trichloroethylthio-tetrahydronaphthalimide, N-trichloromethylthio-phthalimide, N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid ester, 2-methyloxycarbonylamino-benzimidazole, 2,3-dihydro-5-carboxyanilido-6-methyl-1,4-oxatin-4,4-dioxide, 2,3-dihydro-5-carboxyanilido-6-methyl-1,4- oxatin, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) - benzene, and various other fungicides such as dodecylguanidine acetate, 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-iodobenzoic acid anilide, 2-bromobenzoic acid anilide, 3-nitro-isophthalic acid diisopropyl ester, 1- (1,2,4-triazolyl-11) -N- (4'-chloro) enoxy) -3,3-dimethyl-butan-2-one, 1- (1-imidazolyl) -2-allyloxy-2- (2,4-dichlorophenyl) -ethane, piperazine-1,4-diyl-bis 1- (2,2,2-trichloroethyl) -formamide, 2,4,5,6-tetrachloroisophthalonitrile, 1,2-dimethyl-3,5-diphenylpyrazolinium methyl sulfate.

8 67379

The substances are used as directly applied solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays, granules by spraying, melting, sprinkling, sprinkling or wetting. The forms of use depend entirely on the intended use, in which case the distribution of the active compounds according to the invention must be as uniform as possible.

In the preparation of directly applicable solutions, emulsions, pastes and oil dispersions, medium-high-boiling mineral oil fractions, such as fuel oil or diesel oil, further coal tar oils, etc., as well as oils of vegetable or animal origin, cyclic aromatics, aliphatic, aliphatic, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, tetrachloromethane, cyclohexanol, cyclohexanone-dimethylrimethylene, chlorobenzene, isophorone, etc. strongly polar solvents, strongly polar solvents water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), oil dispersions by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances can be homogenized as such or dissolved in oil or solvents, with the aid of wetting, tackifying, dispersing or emulsifying agents. However, it is also possible to prepare concentrates containing the active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvents or oil which are suitable for dilution with water.

Surfactants which may be mentioned are: lignin sulphonic acid, naphthalenesulphonic acids, phenolsulphonic acids, alkali, alkaline earth metal and ammonium salts, alkyl aryl sulphonates, alkyl sulphates, alkyl sulphonates, sulphonates, dibutyl naphthalene sulphonates, alkaline acid sulphonic acid - and alkaline earth metal salts, salts of sulphated hexadecanols, heptadecanols, octadecanols, salts of sulphated fatty alcohol glycol glycol ether, condensation products of sulphonated naphthalene and naphthalene terephthalene derivatives with phenaldehyde and naphthalene derivatives octylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxy ilated castor oil # polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin, sulfite waste liquors and methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g. coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers include, for example, mineral soils such as silica gel, silicic acids, diatomaceous earths, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus kaolin, loess, clay, dolomite, diatomaceous earth, calcium and magnesium oxide, magnesium sulfate, magnesium sulfate, active ingredients, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal powders, bark, wood and nut peel powder, cellulose powder and other solids.

Various types of oils, herbicides, fungicides, nematode poisons, insecticides, bactericides, trace elements, fertilizers, antifoams or other antifoam agents (e.g. silicones), growth agents, may be added to mixtures or private active ingredients.

The following known reference substances were used in the following experiments.

10 67379

Active ingredient No. / CH3 / ^ λ 7 C13H27- \ 9 'CH3 (known) ^ / CH3 8 C13H27-N o .ch3cooh \ - v

OF

CH

(known) 3 y_ / CH ._v

/ \ jl · '\\ _.SO, H

9 C13H27- \ P -C12H15 3 X ° H3 (known)

Example 3

Wheat seedlings grown in pots, of the species "Jubilar", are sprayed with aqueous emulsions made from a product containing 80% (w / w) of active ingredient and 20% emulsifier and, after spraying, dusted oyster (Orysiphe graminis var.tritici). The test plants are then placed in a greenhouse at a temperature between 20-22 ° C and a relative humidity of 75-80%. After 10 days, the amount of yeast development is determined.

11 67379

Active substance Contamination of leaves after spraying with x% _ active substance dispersion_ _x = 0.006 0.012 0.025 0.05 1 1-2 1 0-1 0 2 1 0-1 0 0 3 0 0 0 0 4 10 0 0 5 0 0 0 0 6 10 0 0 19 0000 20 0000 7 (known) 3-4 321 8 (known) 4 421 9 (known) 2 110 control (untreated) 4 0 = no contamination, scale to 5 = completely contaminated Example 4

In a further experiment, the leaves of barley seedlings of the species "Firlbecks Union" grown in pots were treated as described in Example 3 and pollinated with spores (conidia) of barley yeast (Erysiphe graminis var.hordei).

Active substance Contamination of the leaves after spraying with x% active substance dispersion_ __x = 0,006_0,12_0,025 1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 7 (known) 2 1 0-1 8 (known) 3 11 control (untreated) 4 0 = no contamination, scale to 5 = completely contaminated 12 67379

Example 5

The leaves of wheat plants grown in pots are artificially infested with spores of wheat brown rust (Puccinia recondita) and the plants are placed in a water-saturated chamber at a temperature of 20-25 ° C for 48 hours. The plants are then sprayed with aqueous spray dispersions containing a mixture of 80% of the active ingredient to be tested and 20% of sodium lignin sulphonate dissolved or emulsified in water, and the plants are placed in a greenhouse at a temperature between 20-22 ° C and a relative humidity of 75-80%. After 10 days, the rate of development of rust fungi is assessed.

Active substance Contamination of leaves after spraying with x% _ active substance dispersion_ x = 0.025 0.05 0.1 1 2-3 1-2 0 3 0 0 0 4 0 0 0 5 0 0 0 6 0 0 0 19 0 0 0 20 0 0 0 7 (known) 43 2 8 (known) 44 3 9 (known) 43 3 control (untreated) 4 0 = no contamination, scale to 5 = completely contaminated

Example 6 90 parts by weight of compound 3 are mixed with 10 parts by weight of N-methyl-β-pyrrolidone to give a solution suitable for use as small droplets.

Example 7 20 parts by weight of compound 4 are dissolved in a mixture of 80 parts by weight of xylene, 10 parts by weight of the coupling product of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of part of the addition of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and finely dissolving the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

Example 8 20 parts by weight of compound 3 are dissolved in a mixture of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of 40 moles of ethylene oxide. and 1 mole of castor oil coupling product. By pouring and finely dissolving the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

Example 9 20 parts by weight of compound 4 are dissolved in a mixture of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of between 210 and 280 ° C and 10 parts by weight of 40 moles of ethylene oxide and 1 mole of castor oil. liittymistuotetta. By pouring and finely dissolving the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

Example 10 20 parts by weight of the active compound 5 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from sulphite waste liquor and 60 parts by weight of powdered silica gel and ground finely. By dispersing the mixture finely in 20,000 parts by weight of water, a spray dispersion containing 0.1% by weight of active ingredient is obtained.

Example 11 3 parts by weight of compound 3 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a powder is obtained which contains 3% by weight of active ingredient.

Example 12 30 parts by weight of compound 4 are thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed on the surface of this silica gel. In this way, an active ingredient preparation with good adhesion is obtained.

Claims (2)

14 67379 Example 13 40 parts by weight of the active compound 3 are mixed thoroughly with 10 parts of the sodium salt of phenolsulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of active ingredient. Example 14 20 parts by weight of the active compound 4 are thoroughly mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of phenol sulfonic acid urea-formaldehyde condensate and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained. Morpholine derivatives useful as fungicides of the formula R3 R1? H3 / \ / ^ \ “Λ- / V ?, RR 1 3 4 wherein R, R, R and R are hydrogen, methyl or ethyl, and their salts, molecular and addition compounds. Compound according to Claim 1, characterized in that it is N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -cis-2,6-dimethylmorpholine.