SE441527B - FUNGICIDICALLY EFFECTIVE MORPHOLINE DERIVATIVES - Google Patents

Description

7804074-8 2 transform. About 75% (weight percent) of the 2,6-dimethylmorpholine is in cis form, the remainder in trans form. The separation of the isomers by fractional distillation is successful in a column with about 40 separation steps. The Cis form changes as a 99% product at 80 - 8100 under a pressure of 13.3 kPa. The transform of 2,6-dimethylmorpholine can be obtained under the same conditions in the transition temperature range 88-89 ° C / 13.3 kPa as over 95% of product.

In a stirrer equipped with a reflux condenser, thermometer and dropping funnel, 575 g of 98% formic acid are introduced. While stirring and cooling, 345 g of 99% 2,6-cis-dimethylmorpholine are then added dropwise. Then the mixture is slowly heated on a water bath to 70 ° C. Over a period of 4 hours, the reaction mixture is added dropwise at about 10,000 with 612 g of 3-p-t-butylphenyl-2-methylpropanal.

During strong carbon dioxide evolution, the condensation is completed.

After completion of the reaction, the mixture is kept under stirring at 10,000 for another 2 hours. Thereafter, the excess formic acid is distilled off under reduced pressure. A far-reaching separation of the formic acid takes place in vacuo from a water suction at 100 ° C. The base is released from the formate by dropwise addition of 500 g of 40% sodium hydroxide solution. Suitably the sodium hydroxide solution is added at 80 - 100 ° C to promote the mixing of the amine phase formed with the alkali phase. To lower the viscosity, add 200 g of toluene. After separating the lye phase, the organic phase is washed twice with 250 g of water each time. For further purification, the amine is distilled fractionally at 26.6 Pa in a 5-bottom distillation column.

In addition to a small amount of pre-droplets (to 14300 / 26.6 Pa; 50 g), 865 g of N- (3-t-butylphenyl-2-methyl-1-propyl) -2,6-cis-dimethylmorpholine are obtained. This passes at 26.6 Pa between 143 and 14600. According to gas chromatographic analysis, the amine has a content of more than 98% pure substance. Calculated on the aldehyde, a yield of 8H, 5% was obtained.

For transfer to the hydrochloride, 30 g of the pure product are dissolved in 50 g of ethanol, which is saturated with hydrogen chloride at 7804074'3 "3_W_.m room temperature. After cooling, 23 g of the hydrochloride melting at 220 DEG C. are obtained in very pure form.

Example 2 In 70 g of 98% formic acid, 29 g of 2,6-trans-dimethylmorpholine are introduced under ice-cooling. With stirring, 41 g of 3-p-t-butylphenyl-2-methylpropanal are then added. The reaction mixture is heated to 100 ° C for 6 hours. At the beginning of the reaction, a very strong carbon dioxide evolution appears, which after about 1 hour decreases significantly. The further work-up is carried out in the same manner as described in Example 1. At 660 Pa, N- (3-pt-butylphenyl-2-methyl-1-propyl) -2,1-B-trans-dimethylmorpholine passes at 168 - 169 ° C. Yield 52 g = 86%, calculated on the aldehyde. 11 g of the amine are dissolved in 20 g of glacial acetic acid, which is saturated with dry hydrochloric acid. Upon separation, the hydrochloride crystallizes out. Melting point 165 ° C.

Other compounds of the invention are obtained in a corresponding manner.

As examples of compounds according to the invention the following can be mentioned.

CH CH I 3 l \ I 3 a = cufcïïï / -y-c fi a-cs-csz- CH3 Active subst. nr 'kp. 123 ° c / o, o1 i-orr 1 E-Mš H3 'ä / SOEH 0 2 RN' Hzs fi zg smpmoa c en 3 / CH3 3 R'M> kp.1U3-1H6 ° C / 0.2 torr CH3 cis- form CH3 f »RN kp. 168-169 ° c / 5: om CH5 trans-form 11 12 13 14 16 17 18 19 f_ \ a'N \ _. / ° R-N 0. HCI “s H-" s “s nu o. Ac:“ s czxš _ a-ß (7255 r-Öâ fl s a-.vo ° z “s Clía C33 RN O * ECDC ~ CH“% 7804074-8 m.p. 220 ° C mp 155% 1as ° c / o, c2 tor-r kp. :: - s ° -: / o, os torr »kp. 12s ° c / o, oz torr kp. ~ 11o ° c / s. 0 dry mp 2o6 ° C bp 1u5 ° c / c, 3 torr 'mp 11a ° c bp '48 ° C / 0.3' dry bp u | s-1ua ° c / o, 3 - L-orr mp 229 ° c mp 17400 C33 HC ~ C00 II cis-form 78040-'74-8 The active substances according to the invention and the corresponding fungicides are particularly suitable for controlling plant diseases, eg Erysiphe graminis (true powdery mildew) on grain, Erysiphe cichoriacearum (true powdery mildew) on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Erysiphe polygoni on beans, Sphaerot- heca Microsea pannosa on roses, or vines, Mycosphaerella musi- cola on bananas, Puccinia species (rust fungi) on cereals, Uromyces appendiculatus and U. phaseoli on beans, Hemíleia vastastriX on coffee and Rhizoctonia solani. active, they are absorbed both through the roots and through the leaves and are transported in the plant tissue.

The use takes place, for example, by pouring, spraying, powdering or pickling plants or seeds with the active substances.

When using the new active substances for the treatment of plants against the fungal infections, the yields are between 0.025 and 5 kg of active substance per hectare. For surface protection of trees or fruits, the active substances can also be used in combination with plastic dispersions (0.25 to 5%, calculated on the weight of the dispersion fi. The fungicides generally contain 0.1 - 95% by weight of active substance, preferably 0.5 - 90% by weight.

The active substances can be mixed with other known fungicides. In many cases, an increase in the fungicidal spectrum of action is obtained; in a number of fungicide mixtures in a weight ratio of 1:10 to 10: 1, synergistic effects also occur, i.e. the fungicidal effect of the combination product is greater than the sum of the effects of the individual components.

Fungicides which can be combined with compounds of the invention are, for example, dithiocarbamates and derivatives thereof, e.g. zinc dimethyl dithiocarbamate, manganese ethylene disodithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate, zinc ethylene bisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N, N-ethylenebisdithiobamyl; N, N'-propylene bisdithiocarbamate), ammonia complex of zinc (N, N'-propylene bisdithiocarbamate) and N, N'-polypropylene bis (thiocarbamoyl) disulfide; heterocyclic compounds, e.g. N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester, 2-methyloxycarbonylaminohydro-2-methyloxycarbonylaminohydro -5-carboxanilido-6-methyl-1,1H-oxyatin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine, 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, e.g. dodecylguanidine acetate, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 2,5-dimethylfuran-3-carboxylic acid anilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-iodobenzoic anilide, 2- bromobenzoic anuride, 3-nitroisophthalic acid diisopropyl ester, 1- (1,2, H-triazolyl-1 ') - [1- (4'-chlorophenoxy)] - 3,3-dimethylbutan-2-one, 1- (1-imidazolyl ) -2-allyloxy-2- (2,1H-dichlorophenyl) ethane, piperazine-1,4-diyl-bis-1- (2,2,2-trichloroethyl) formamide, 2, H, 5,6- tetrachloroisophthalonitrile, 1,2-dimethyl-3,5-diphenylpyrazolinium methyl sulfate.

The active substances are used e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders, dispersants or granules, which are sprayed or sprayed in liquid or solid form, sprinkled or poured on. The form of use is completely adapted to the purpose of use; it should in any case ensure the best possible distribution of the active substance.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, mineral oil fractions of medium to high boiling point are used, e.g. kerosene or diesel oil, coal tar oils, oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example, methanol, ethanol, propanol, butanol, chloroform, carbon tetra-vao4o74-s 7 chloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, and strong polar solvents, e.g. dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone or water.

Aqueous preparations can be prepared from emulsion concentrates, pastes or wettable powders (spray powders) or oil dispersions by adding water. In preparing emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or other solvent, can be homogenized in water by means of wetting, sticking, dispersing or emulsifying agents. It is also possible to prepare concentrates of active substance, wetting agents, adhesives, dispersants or emulsifiers and, if appropriate, solvents or oils, which are suitable for dilution with water.

As surfactants may be mentioned alkali, alkaline earth and ammonium salts of lignin sulfonic acid, naphthalene sulfonic acids, phenol sulfonic acids, alkylaryl sulfonates, alkyl sulphates, alkyl sulphonates, alkali and alkaline earth salts of dibutylnaphthalene sulphonic acid, lauryl ether sulphate, fatty alkali metal sulphates, fatty alkali metal salts hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene and naphthalene sulfonic acids with phenol and formaldehyde, polyoxietylenoktylfenoletrar, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkyl fenolpolyglykoletrar, tributylphenyl, alkyl arylpolyeteralkoholer, isotridecyl , fatty alcohol ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetals, sorbitol ester, lignin, sulfite liquor and methylcellulose sa.

Powders, dispersants and powders can be prepared by mixing or collecting the active substances with a solid carrier.

Granules, e.g. coated, impregnated and homogeneous granules, can be prepared by binding the agent to a solid carrier. Solid carriers are e.g. mineral soils, e.g. 7804074-8 8 silica gel, silicic acids, silicates, talc, kaolin, attapulgite, limestone, chalk, talc, bolus, lice, clay, dolomite, diatomaceous earth, potassium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and plant products such as cereal flour, bark, wood and nutshells, and cellulose powder. To the mixtures or the individual active substances can be added oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, defoamers (eg silicones), growth regulators, antidote agents and others. active associations.

In the experiments described below, the following known comparative substance Active subst. _ D? - 13H27 '& ¿CH3 CH3 CH3 8 c13s27-N o .cašcoox CH; C H -Û: C33 C H S0 H 9 13 27 \ <° 12 25 3 CH CH 3 s ”3 ca 21 3 ca; N o CH3 CH CH Å / L \ í ”\ v / LE:” \\ / "* (CH3 Ca * Lä ca 3 22 s '' ~ - 27 c fl yfíçn3 LK 7804074-'8 3 / H cH3> -0 .ø fl s c 3 '\ P 9 za cH // * \ s .3__0 ons CH3 cH3 _ ll_ 2 | + CH á 3 3 CRS ca - 3 CN 26 - CH: H3' CH 2 3 CH / í CHÖ 3 NI ¶ \ “¿* CH 29 Example 3 CH AA 3 CH 3 TO 7804074-8 CH few, 3 w 3 Leaves of potted wheat seedlings of the variety" Jubilar "are sprayed with water emulsions of 80% (weight percent) active substance and 20% emulsifier and powdered after inoculation of the spray coating with oidia (spores) of wheat flour dew (Erysiphe graminis var. tritici) The experimental plants are then set up in greenhouses at temperatures of 20 = a22 ° C and 75 ~ 80% relative humidity.After 10 days, the extent of nüöldag development is assessed. .

Active Attack on leaves after spraying with x-percentage spray liquid substance x = 0.006 0.012 0.025 0.05 1 1-2 1 Û-1 Û 2 1 0-1 Û 0 3 0 0 O Ü 4 1 0 0 Û 0 0 0 0 6 1 0 0 0 19 0 0 Û Û Û Û Û 0 0 7 3-4 3 2 1 8 H 4 2 1 9 2 1 1 Û 2 2 _ v. 0 3 2 28 4 R 3 3 Control (untreated) 4 0 = no infestation, in steps to 5 total infestations 780§074 ~ 8 11 Example HI another experiment is treated, in the manner described in example 3, leaves of grown in pots barley seedlings of the variety "Firlbeck's Union" and sprayed with spores (conidia) of barley powdery mildew (Erysiphe graminis var. hordea).

Active attack on leaves after spraying with x-percentage spray liquid substance x = 0.006 0.012 0.025 1 0 0 0 2 0 0 0 3 0 0 '0 H 0 0 0 0 Ü 0 0 0 0 19 Û Û Û O 0 0 7 2 1 0-1 known 8 3 1 1 Control (untreated) 40 = no infestation, in steps to 5 = total infestation Example 5 Leaves of potted plants grown in pots are artificially infected with spores of wheat brown rust (Puccinia recondita) and set up for H8 hours at 20 ~ 25oC in a chamber saturated with water vapor. The plants are then sprayed with aqueous spray liquids, which consist of an aqueous or emulsified mixture of 80% of the active substance and 20% of sodium and are set up in greenhouses at temperatures of relative humidity. After lignin sulfonate, - 22 ° c and at 75 - so% day, the extent of the development of rust fungi is assessed. 7s04o74-s 12 2 Active Attack on leaves after spraying with x-percentage spray liquid of active substance substance x = 0.025 0.05 0.1 1 2-3 1-2 0 3 0 0 0 4 0 0 0 0 0 0 0 0 0 19 0 0 0 0 0 0 '7 4 3 2' g know Q 4 3 9 4 3 3 Control (untreated) 0 = no attack, in steps to 5 = total attack Example 6 90 parts by weight of compound 3 are mixed with 10 parts by weight of N-methyl-u-pyrrolidone and obtain a solution which is suitable for use in the form of very small drops.

Example 7 parts by weight of compound 4 are dissolved in a mixture of 80 parts by weight of xylene, 10 parts by weight of storage product of 8-10 moles of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzene sulfonate and 5 parts by weight of storage product of 40 moles of ethylene oxide in 1 mole of castor oil. By pouring and atomizing the solution in 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.02% by weight of the active substance.

Example 8 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 storage product of 7 moles of ethylene oxide on 1 mole of isooctylphenol and 10 parts by weight of storage product of 40 moles of ethylene oxide in 1 mole of castor oil. By pouring and comminuting the solution in 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.02% by weight of active substance. 7so4o74-a 13 Example gel 9 parts by weight of the compound H are dissolved in a mixture of parts by weight of cyclohexanol, 65 parts by weight of mineral oil fraction with a boiling point of 210 - 28000 and 10 parts by weight of product of H0 mol of ethylene oxide in 1 mol of castor oil. By pouring and comminuting the solution in 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.02% by weight of active substance.

Example gel 10 parts by weight of the substance 5 are intimately mixed with 3 parts by weight of sodium diisobutylnaphthalene α-sulfonate, 17 parts by weight of sodium salt of lignin sulfonic acid from a sulphite liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By atomizing the mixture in 20,000 parts by weight of water, a spray liquid is obtained, which contains 0.1% by weight of active substance.

Example gel 11 3 parts by weight of compound 3 are intimately mixed with 97 parts by weight of fine-grained kaolin. In this way, a powder is obtained which contains 3% by weight of active substance.

Example gel 12 parts by weight of compound 4 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 on the surface of this silica gel. In this way, a preparation with good adhesion is obtained.

Example gel 13 40 parts by weight of the substance 3 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable water dispersion is obtained. By diluting with 100,000 parts by weight of water, a water dispersion is obtained, which contains 0.0N% by weight of active substance.

Example gel in parts of substance 4 is intimately mixed with 2 parts of calcium dodecylbenzenesulfonate, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid urea-formaldehyde condensate and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained. 7804074-8 14 Exemgel 15 Leaves of potted wheat-grown plants are artificially infected with spores of wheat-brown rust (Puccinia recondita) and set up H8 h at 20 - 25 ° C in a steam-saturated chamber.

Then the plants are sprayed with aqueous spray liquids, which contain a mixture of 80% substance to be examined, and 20% temperatures between 20 and 2200 and at 75 ~ 80% relative humidity. After 10 days, the extent of rust fungus sodium lignin sulfonate is assessed, and set up in greenhouses during development.

Active attack on the leaves after spraying with x-percentage spray liquid substance x = 0.025 0.05 0.1 3 Û 0 Ü 21 5 4 4 22 4 4 3 2 ”known L * I * L * 26 5 H 3 27 N 3 3 29 H 3 3 Control (untreated) 0 = no attack in step to 5 = total attack

Claims (2)

7804074-8 I5 PATENT REQUIREMENTS Fungicidally active morpholine derivatives of the formula R 3 R 1 ef * T * ÅA C , molecular and addition compounds. Morpholine derivative according to claim 1, which is N- (3-p-tertiarybutylphenyl-2-methyl-1-propyl) -cis-2,6-dimethylmorpholine.