CS195345B2 - Fungicide - Google Patents

Description

The present invention provides novel morpholine derivatives, salts thereof, fungicidal compositions containing the compounds as active ingredients, and a method for controlling fungi using the above compounds.

It is known from German Patent Nos. 1164 152 and 1 173 722 that the N-alkyl-substituted morpholines and their salts, or the molecular or addition compounds of these morpholines, have a good fungicidal effect. Both of the above-mentioned patents disclose, inter alia, mixtures of isomeric N-alkyl morpholines containing, for example, isomeric tridecyl residues on a nitrogen atom.

It has now been found that a morpholine derivative of general formula I-s · fv '•' / T ^s (I) wherein

R represents a chemically uniform C 9 -C 20 alkyl or alkoxyalkyl radical branched at two to four places and X 1, X 2, 2з, X 4, X 5, X 7, X 7 and X 8 represent hydrogen atoms or C 1 -C 2 alkyl groups , and salts thereof, exhibit certain functional activity.

Preferably R is a C12-C15 alkyl or alkoxyalkyl radical branched at two to four places. Preferred are those compounds wherein R represents a perhydrogenated terpene residue.

N-alkyl and N-alkoxyalkylmorfoliny present invention can be used as fungicides in the form of free bases or as salts with inorganic acids, for example with the _HA: logenovodíkovými acids as hydrochloric acid, or br-omOvo · '(iíkb'vou, acid sulfuric, nitric or phosphoric acid, of which ganic acid, for example formic acid, acetic acid, butyric acid, oxalic acid, adipic acid, lactic acid, lime, citric acid, trichloroacetic acid, stearic acid, oleic acid, diisopropyldithiophosphonic acid diphosphonic acid, dicosulfonic acid or dicosulfonic acid;

The preparation of the N-alkyl and N-alkoxyalkylmorpholines according to the invention can be carried out by methods known per se, for example by cyclization of dialkanolamines (N-substituted bis-2-hydroxyalkylamines) with dehydrating agents such as nitric acid, phosphoric acid, hydrogen halides, phosphate boron, aluminum phosphate or aluminum oxide (see Houben-Weyl, "Methodeu der organischen Chemie" 6/4, pp. 51Q-546) or by direct reaction of terpenic aldehydes or terpenic ketones with the corresponding morpholine compounds under hydrogenation conditions.

The morpholine derivatives according to the invention are branched in the tridecyl residue in a manner characteristic of terpenic compounds and can be synthesized using terpenes, e.g. . The compounds are chemically uniform. Thus, the novel compounds of the invention clearly differ from the known compounds.

The novel active compounds according to the invention are suitable for combating diseases caused by fungi on crops, in particular for controlling powdery mildew, but also for controlling other harmful fungi. For example, the following fungi can be controlled with the compounds of the invention:

powdery mildew of Erysiphe gřaminis on cereals, powdery mildew of Erysiphe cichoracearum on cucurbits, powdery mildew of Erysiphe polygoni on bean, powdery mildew of Mlcrosphaera quercl on oaks and vines, Mycospháerella musicola on bananas,

Cortlcium salmonicolor a

Ganoderma pseudoferreum on rubber trees.

The fungal compositions of the invention are systemic active. Said compositions can be taken up by both roots and leaves and transported to plant tissue.

The compositions of the invention are applied, for example, by spraying, dusting or watering the plants to be protected from fungal infection.

The active compounds according to the invention can be formulated in the customary manner by adding solid carriers to dusts or by adding dispersants, wetting agents and / or adhesives to solid or liquid preparations used for the preparation of spray suspensions. Further, the active compounds can be formulated, for example, into solutions and emulsions which can be applied in the form of aerosols using solvents conventionally used for this purpose.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable are the medium to high boiling point mineral oil fractions, such as kerosene or diesel oil, tar oils, etc., as well as vegetable or animal oils, aliphatic, Hydrocarbons, for example, running, toluene, xylene, paraffin, such as phthalene, alkyl naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, chlorobenzene, chlorobenzene. dimethylformamide, di-ethylsulfoxide, N-methyl pyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders thereof or oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized with wetting agents, adhesives, dispersing agents or emulsifiers in water. However, concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water, may also be prepared.

The compositions according to the invention contain 0.1 to 95% by weight of active ingredient, preferably 0.5 to 90% by weight. The active substances can also be used in combination with 0.25 to 5% of plastic dispersions (w / w, based on the weight of the dispersion) for the surface protection of trees or fruits. substances / ha.

The active compounds according to the invention can be mixed with other fungicides, in many cases broadening the spectrum of fungicidal activity. Some of these fungicidal compositions also exhibit a synergistic effect in that the fungicidal effect of the combination composition is greater than the sum of the efficacy of the individual components.

For these combinations, the following compounds have been used as particularly suitable active substances:

dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, lithium ethylene-bis-dithiocarbamate, ethylenediamine-bis-dithiocarbamate, zinc-ethylenedi-bis-dithiocarbamate tetramethyldithiocarbamate;

3,5-dimethyl-l? 3 _{I-5-2H-2-.tetťůhydrothíadlazin} thlon,

Zinc N, N'-propylene-1,2-bis-dlthlokarbamate, zinc ammoniacal complex, Zn-N'-propylene-bi§-dlthiocarbartate and

N, N'-polypropylene-bls- (thiocarbamoyl) disulfide;

nitrophenol derivatives such as dinitr- (1-methylheptyl) phenylcronate,

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

2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

hetercyclic compounds such as

N-trichloromethylthio-tetrahydrophthalimide,

N-Trichloromethylthio-phthalimide

N- (1,1,2,2-tetrachloroethylthlo) -tetrahydrophthalimide,

N, N-Dimethyl-N-phenyl- (N-fluorodichloromethylthlo) sulfonamide,

N-methyl-N-phenyl- (N'-fluorochloromethylthto] -N'-methylsulfonamide,

2-4-β-di-2-imidazoline,

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

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-dithlaanthraquinone,

2-thiol-1,3-dith10- [4,5-b] quinoxaline, 1-butylcarbamoyl-2-benzimidazolecarbamic acid methyl ester,

2-methoxycarbonylaminobenzimidazole.

1- (5-cyanpentylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester,

2-thloocyanatomethylthiobenzthlazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thlol-1-oxide,

8-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide; 2,3-dihydro-5-cavboxanilido-6-methyl-1,4-oxathiin,

5,5-dimethyl-3- [3,5-dichlorophenyl] -2,4-dihydro-1,3-oxazolidine,

2- (1,2-furyl) benzimidazole, piperazine-1,4-diylbis- [1- (2,2,2-trichloroethyl) -formamide,

2- [4-thiazolyl] beiisimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) pyridine methanol,

1,2-bis- (3-ethoxycarbonyl-2-thiour eido) benzene,

1,2-bis- (3-methoxycarbonyl-2-thioureido) behzen, and various fungicides such as dodecylguanidine acetate,

3- [2- (3,5-Dimethyl-2-hydroxy-cyclohexyl) -2-hydroxy-ethyl] -glutariinide or 2,5-dimethylfuran-3-carboxylic acid, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2- 3-nitroisophthalic acid diisopropyl ester, hexachlorobenzene,

2,3-dichloro-1,4-naphthoquinone,

1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene diazonium sulphonate,

2-chloro-1-nitropropane, polychloronitrobenzenes,

1-Phenylthiosemicarbazide, Bordeaux, compounds containing nickel and sulfur.

The above-mentioned compositions can be admixed with the fungicides according to the invention in a weight ratio of 1: 10 to 1C: 1. These substances can also be added, if necessary, just before use (Tankmix).

Examples of novel morpholine derivatives include the compounds summarized below;

number · VZlOlrfeC boiling point chemical merge- (° C / Pa) sun protons niny in the morpholino circle (values of δ of in ppm] ^x)

92/60

118/200 oily 3.97 (2H, m);

3.55 (2 H, d);

2.72 (2H, t) _;

154/267

С Ну

164/267

110 / 2,7 number · · - compound formula boiling point (° C / Pa) chemical shift of protons in morpholine ring (δ values in ppm) ^x)

oily

4.42 (2 H, m);

3.69 (2 H, d);

2.9 (2H, 6j);

130/4

115 / 13.3

101 / 1.3

96 / 1.3 oily

4.26 (2 H, m);

3.17 (2 H, d);

2.57 (2 H, t);

compound number

VZOriQC boiling point (° C / Pa) chemical shift of protons in the morpholino ring (values 6 у ppm] ^x)

Oilejevitá

4.00 (2 H, m);

3.20 (2H, t);

2.40 (2H, t);

161/200

196/133

oily

4.55 (2H, т);

3.56 (1H, d);

3.47 (1H, d);

2.57 (1H, t);

2.53 (1H, t);

CHy

101 / 1.3

number · vizcar ^ euc · boiling point chemical merge- (° C / Pa) sun protons niny in the morpholine ring (values <5 in ppm) ^x 1

115 / 13.3

158/267

111 / 6.7

102 / 1,3

143/53

110 / 1,3

120 / 1,3

118 / 13,3 Compound number in the Mottteer boiling point chemical after (° C / Pa) sun protons in the morpholine ring (δ values, in ppm) ^x)

110 / 6.7

113 / 6.7

oily 4.17 (2H, m);

3.25 (2 H, d);

2.60 (2 H, t);

CH3 - (CH3) 10 - CH2 --SO3. . 4.31 (2 H, m);

3.30 (2 H, d);

2.48 (2 H, t);

^CH i oily 2.40 (4H, m)

4.27 (2 H, m);

4.05 (1H, t);

3.40 (2 H, t);

3.07 (1H, t);

2.72 (1H, t)

^c ii ⁱ £ / 9) ~ ^S0 ?

oily

4.32 (1H, m);

3.40 (2 H, m);

2.60 (2 H, m)

oily 3.98 (2H, m);

3.37 (2 H, d);

2.68 (2 H, t)

oily 4.42 (1H, m);

4.08 (1H, m); ·

3.29 (1H, M);

3,08 · (ΙΗ, ΙίΙ-35 number, relative to the compound boiling point (° C / Pa) chemical shift of protons in morpholine ring [S values in ppmj ^x >

oily

4.48 '(1H, m &lt; + &gt;;

3.30 (1H, d);

3.07 (1H, d);

2.50 (2H, t)

4.09 (1H, m);

3.17 (1H, d);

2.89 (1H, d);

2.40 (1H, d);

2.22 (1H, i

Θ

CHýCOO

4.00 (1H, mj;

2.82 (1H, d);

2.61 (1H, d);

2.10 (1H, d);

1.98 (1H, J)

Legend:

^{The X,} NM'R spectra (H ¹ ) were measured in deuterochloroform at 220 MHz using tetramethylsilane as an internal standard (δ = 0 ppm>). = triplet, m = 'multiplet'

The novel compounds of the invention are as effective as the known N-alkylmorpholine derivatives. A particular advantage of the novel compounds is that they are uniform, whereas the corresponding known morpholine derivatives are mixtures of isomers.

The active compounds according to the invention are compounds of definite constitution and, when used, produce degradation products of the same composition. A further advantage of the compounds according to the invention is that the partial structural fragments of these novel compounds occur as the basic building blocks of natural substances, so that no disadvantages in terms of undesirable environmental pollution can be expected with these new substances. Surprisingly, it has been found that chemically uniform morpholine derivatives having a predominantly terpenic residue as a side chain exhibit as good fungicidal activity as mixtures of known isomeric morpholines.

In the tests described below, Tridemorph (a mixture of isomeric N-tridecyl-2,6-dimethylmorpholine and N-n-dodecyl-2,6-dimethylmorpholine) is used as a known comparator.

Example 1

Leaves of barley seedlings, cultivated9

They are sprayed with aqueous emulsions of the test compounds (containing 80% by weight of active ingredient and 20% by weight of emulsifier in the dry matter) and, after the spray coating has dried, is sprayed with spores of Erysiphe graminis var. hordei. The test plants are further stored in a greenhouse at a temperature between 20-25 ° C and 75-80% relative humidity. After 10 days, the extent of powdery mildew occurrence is determined.

3 <5

The active substances, the active substance concentrations and the results obtained are summarized in the following table, in which the active substances are indicated by numbers corresponding to the numbers in the above list, the + sign indicating that the test has not been performed. using a scale of 0 to 5, where 0 means no attack and 5 complete attack.

Table

Activity against Erysiphe graminis var. hordei after spraying with aqueous suspensions or emulsions

active substance 0,025 efficiency at concentration (in%) of the active substance in the spray 0.012 0.006 n-dodecyl-2,6-di- 1 2 2 methylmorpholine Tridemorph OB 0 1 to 2 5 0 1 _ + 14 0 1 16 0 0. - + 18 OB 0 to 1 1 22nd 1 1 to 2 .. 3 23 OB 1 1 to 2 25 1 1 to 2 2 26 OB 1 1 to 2 28 0 2 2 29 0 2 2 31 0 0 to 1 2 32 OB 1 1 to 2 inspection (untreated) 4

'Example 1 a d 2

Effectiveness against powdery mildew

The leaves of germinated wheat plants ('Cartbo') are sprayed with 0.02 to 0.025% (w / w) aqueous sprayings containing 80% active ingredient and 20% lignin sulphonate in the dry state. After the spray coating has dried, the plants are dusted with spores of powdery mildew of Erysiphe graminis var. and further stored in a greenhouse at 20-22 ° C and 65-70% relative humidity. After 10 days, the extent of powdery mildew is found.

The active substances, active substance concentrations and results obtained are summarized in the following table. Efficacy is expressed using a scale of 0 to 5, where 0 means no attack and 5 represents complete attack, and where leaf damage is expressed using the following symbols:

indicates individual necrosis,

1H indicates individual necrosis and lightening and

2H indicates slight leaf damage and lightening

Table

Activity against powdery mildew Erysiphe graminis var. tritici active ingredient efficiency at concentration (%) of active ingredient in spray / 0.05 0.025 0.012 0.006

tridemorph 0 / 2H 0 / 2H 0 / 1H 3 tridemorph salt with dodecylbenzenesulfonic acid 0 0 0 1 31 0/1 0 0 1 32 0 0 0 1 control 4

EXAMPLE 1 ad 3 parts by weight of Compound 1 is mixed with 10 parts by weight of 'N-methyl-.alpha.-pyrrolidone, to give a solution which is Mhloldlný to alp | L! I! K | a (C i V ^е fiorrně 'the best droplets.

Attaches weight parts. of compound 2 is 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 per 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of addition 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 5 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide per mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor. ' oils. By pouring and 'finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight (¼) of the active ingredient. .

Example '.

parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 DEG-280 DEG C. and 10 parts by weight of an editorial product of 40 moles ethylene oxide per mole castor oil. By pouring and finely distributing 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 7 parts by weight of active compound 5 are mixed well with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulfonic acid sodium salt from waste sulphite lyes and 60 parts by weight of powdered silica gel and ground in a hammer mill. . By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example.

3 parts by weight of compound 6 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way it is obtained. dust containing 3% by weight of active ingredient.

Example 9 parts by weight of compound 7 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 the silica gel. In this way, an effective formulation with good adhesion is obtained.

EXAMPLE 10 parts by weight of the active compound 8 are thoroughly mixed with W parts of the phenol sulfonic acid, urea and formaldehyde condensation product. 2 parts silica gel and 48 parts water to give a stable aqueous dispersion. By diluting the dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

Example 11 parts of the active ingredient 9 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid. 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenolsulfonic acid, urea and formaldehyde, and 68 parts of paraffinic mineral oil fraction to obtain a stable oily dispersion.

Example 12

500 parts of tetrahydrogeranylacetone are dissolved in 1000 parts of methanol and the solution, together with 50 parts of Raney-nickel wetted with methanol, is introduced into a 3 liter 'autoclave'. 340 parts of ammonia are pressed into the autoclave, the 'autoclave' is heated to 90 ° C and pressurized with hydrogen to a pressure of 10 MPa. The amount of hydrogen consumed is replenished until the hydrogen uptake is completed.

The reaction mixture was filtered and the filtrate was distilled. 480 parts (ca. 95.5 percent of theory) of 6,10-dimethyl-2-aminoundecane are obtained with a boiling point of 65 ° / 6.7 Pa.

400 parts of 6,10-dimethyl-2-aminoundecane and 4 parts of water are heated to 140 ° C in a 2 liter stirring autoclave and 520 parts of propylene oxide are pressed in portions into the autoclave. The reaction mixture was heated at 140 ° C for 10 hours and then worked up. Distillation yielded 575 parts (about 91% of theory) of N, N-di (2-hydroxy-1-propyl) -N- (6,10-dimethyl-2-undecyl) amine, b.p. 168-170 degrees Celsius. / 1.3 Pa.

19-5345

To 530 parts of N, N-di (2-hydroxy-1-propyl) -N- (6,10-dimethyl-2-undecyl) amine was added 410 parts of concentrated sulfuric acid with stirring and the mixture was heated at 130 ° C for 5 hours. .

The reaction mixture is then slowly added to 1400 parts of 25% (w / w) sodium hydroxide solution and after settling, the organic phase is separated and distilled. 470 parts (about 93% of theory) of N- (6 &apos;, 10 &apos; -dimethyl-2 &apos;-undecyl) -2,6-dimethylmorpholine having a boiling point of 158 [deg.] C./269 mbar are obtained.

EXAMPLE 13 parts of farnesal and 23 parts of 2,6-dimethyl morpholine are dissolved in 70 parts of tetrahydrofuran and the solution, together with 6 parts of Raney-nickel moistened with tetrahydrofuran, is placed in a 250 ml shaking autoclave. The autoclave was heated to 195 ° C and pressurized to 20 MPa with hydrogen. Until the hydrogen uptake is complete, the pressure in the autoclave is maintained at 20 MPa by further hydrogen addition.

The reaction mixture was filtered and the filtrate was distilled. 57 parts (about 87.5 percent of theory) of N- (3 ', 7', 11'-trimethyl-r-dodecyl) -2,6-dimethylmorpholine having a boiling point of 161 ° C / 200 Pa are obtained.

Claims (1)

A fungicidal composition comprising a solid or liquid carrier and, as active ingredient, a morpholine derivative of the formula I in which: R represents a chemically uniform alkyl or alkoxyalkyl radical of 9 to 20 carbon atoms, branched at two to four, X 1, X 2, X 2, X 1, X 5, X 6, X 7 and X 7 are hydrogen or C 1 -C 2 alkyl, or a salt thereof.