DK151015B - MORPHOLINE DERIVATIVES WITH FUNGICIDE EFFECT - Google Patents

Description

151015

The invention relates to a morpholine derivative having a fungicidal effect.

It is known from German Patent Nos. 1,164,152 and 1,173,722 that N-alkyl substituted morpholines and their salts or molecular or addition compounds of these morpholines have a good fungicidal effect. In both of the cited patents, mixtures of isomeric N-alkyl morpholines are described, for example, e.g. with isomeric tridecyl groups at the nitrogen atom. In the case of these known fungicides, they are either uniform stearyl or lauryl compounds exhibiting insufficient fungicidal activity or exhibiting good fungicidal activity, which in turn consists of difficult to reproduce isomer mixtures which are technically have less interest.

It has now been found that a morpholine level, which is peculiar to that specified in the characterizing part of the claim, exhibits good fungicidal activity, at the same time appearing as a single chemical compound.

R is a chemically prominent alkyl or alkoxyalkyl group having 12 to 15 carbon atoms and containing at least two or more branches, of the kind characteristic of terpene compounds. Compounds in which R is a perhydrated terpene residue are preferred.

The N-alkyl and N-alkoxyalkylmorpholines of the invention can be used as fungicides in the form of their free bases or as salts with inorganic acids, e.g. hydrogen halide id acids (hydrochloric acid, hydrogen bromide), sulfuric acid, nitric acid and phosphoric acids, or with organic acids, e.g. formic acid, acetic acid, butyric acid, acrylic acid, oxalic acid, adipic acid, lactic acid, tartaric acid, citric acid, trichloroacetic acid, stearic acid, oleic acid, diisopropyldithiophosphoric acid, dodecylbenzenesulfonic acid or dodecanesulfonic acid.

The preparation of N-alkyl and N-alkoxyalkylmorpholines according to the invention can be carried out according to known methods, e.g. by cyclization of dialkanolamines (N-substituted bis-2-hydroxyalkylamines) with dehydrating agents such as concentrated sulfuric acid, phosphoric acid, hydrogen halide acids, boron phosphate, aluminum phosphate or alumina (Houben-Weyl, "The Method of Organic Chemistry" 6/4, pp. 510-546) or by direct reaction of terpenal aldehydes or terpene ketones with the corresponding morpholine compounds under hydrating conditions.

When R in the morpholine derivative of the invention is tridecyl, the tridecyl group exhibits branches characteristic of terpene compounds; these tridecyl groups can be introduced into the morpholine derivatives of the invention by synthetic means by using as starting materials terpenes, e.g. the terpenal aldehydes or ketones citral, methyl citral, farnesal, geranylace tone, tetrahydrogeranyl acetone, pseudojonone, methoxypseudojonone or farnesyl acetone. It exists as a chemically uniform substance. Therefore, the new compound is distinctly different from the known compounds. The new active substances are suitable for the control of diseases caused by fungi in cultural plants, especially real mildew fungi, but also other harmful fungi. Eg. the following fungi can be combated: Erysiph-e graminis in cereals, Erysiphe cichoracearum in pumpkin species, Erysiphe polygony in beans, Microsphaera querci in oak and vines, Mycosphearella musicola in bananas, Corticium salmonicolor and Ganoderma. pseudoferreum by rubber trees.

The fungicidal agents are systemically active. They are absorbed both at the roots and above the leaves and transported into the plant tissue.

The use of the agent is carried out e.g. by spraying, powdering or pouring on the plants to be protected from fungal infection.

The agents may be used in the usual manner by the addition of solid extenders to powders or during the addition of dispersants, wetting and / or adhesives to solid or liquid compositions for the preparation of spray liquids. Further, e.g. processing into solutions and emulsions is possible, whereby, according to the aerosol method, these can be sprayed when using the usual solvents.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, medium-high boiling mineral oil fractions such as petroleum or diesel oil, as well as vegetable oil, as well as vegetable or animal origin oils, aliphatic, cycloaliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, in addition methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbon, cyclohexanol, cyclohexanone, chlorobenzene, isophorone and highly polar solvents such as e.g. water, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone under consideration.

Aqueous dispensing forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), 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 in water by wetting, adhesive, dispersing or emulsifying agents, but also from the active substance, wetting, adhesives, dispersants or emulsifiers, and optionally solvents or oils are prepared concentrates which are suitable for dilution with water.

The agents contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90 °. For surface protection of trees or fruits, the active substances can also be used in conjunction with plastic dispersions having a concentration of between 0.25 and 5 vægt (wt) in proportion to the weight of the dispersion. The amounts used are between 0.25 and 5 kg of active substance / ha flat.

151015 4

The active substances can be mixed with other fungicides. In many cases, this results in an enlargement of the fungicidal spectrum of action; in a number of these fungicidal mixtures synergistic effects also occur, ie. the fungicidal activity of the combination product is greater than the added fungicidal activity of the individual components.

The admixture of these agents to the fungicides of the invention can be made in a weight ratio of 1:10 to 10: 1.

They may also be added immediately before use (tank mix).

5 151015

The following are examples of the new morpholine derivatives: core. displacement

Compound Kp [DC] / rnm Hg of the protons in the morpholine ring> _ (<S values in ppm) _ CH3 CH3 / CH3 5) 164/2

CH M

3 ch3 ch3 6 f3 XlK0 „3 0 110 / 0.02

Cii-2 \ _ / 3 ^ -ch3? H3 jCH3 - ^ CH3 oily 4.42 (2H, m); CH 3 H S 3.69 (2H, d); 2.39 (2H, 6); 7 cH,

) ~ 0 \ ^ S

CH, Pv. B

4 / s} —o CH 3 CH, 0 CH, CH, CH, yr 3 s 3 njL3 ii H 3 0 130 / 0.03 CH3 ^ H3 οηγ ^^ γ ^ γ ch3 9 CH3 CH3 115 / 0.1 CH ° CH3 6 151015 chem. displacement

Compound Kp [° C] / fnWi Hg of the protons in the morpholine ring> _ (^ - values in ppm) 10 CH, CH, CH, T CH, 101 / 0.01

XX

CH, CH, 3 3 11 CH3 ^ CH3 CH3 CH3 in 96 / 0.01

Xx CR3 v CH3 - CH3 CH3 CH3 H \ ® ^ oily 4 * 26 (2H, m); -XxA 3.17 (2Η, ά) δ CH CK, δ 2.57 (2H, t); 12 / "Λ • εΐ2Η25 · \ 2 / · 803 ih3 r c" 3 CH,] th oily 4.00 (2H, m); 3.20 (2H, m) j

ch3 ch3 2> li0 (2H »m ^ 'S

13 - C12H25 \ O / -S03 7 151015 core. displacement

Compound Kp [° C] / mm Hg of the protons in the morpholine ring.

_ & L values in ppm) + '1¾ CHj CH3 CH3 161 / 1.5 ^ CH3 17 ch3 ch3 ch o 101 / 0.01 CH ^ \ —f 18 PH3 f3 f3_ o 115 / 0.1 CH, \ —— </ XCH, 3 19 fH3 fs .fi - / "3 0 158/2 N— / ch3 20 CH3 CH3 CH3 / CK3 111 / 0.05 CH ^ CH3CH3 21 CH3 CH3 c.H3? ^. CH3 A ^ vvv ^ nM) 102 / 0.01 CH3 W \ 1 CH3 CH.

3 e 151015 for Precision Kp C c] / mm Hg chem. displacement of the protons in the - morpholine ring% (<f - be di in ppm) * '22 CH, CH, CH, I 3 j; I 2 J_ ^ oh, «V0. * 3 3: 23 CH3 CH3 CH3 9H3 N o 110 / 0.01 υ 3 <^ ch3 2H · CH3 CH5 0H3 ^^ ch ^ A ^ sA / ^ AnQ) 120/0, 01 25 CH, CH, CH, »3 j 3 i 3 _ Λ / ν ^ ν ^ Αίο 118 / 0.1 ch3 CH, 3 26 CH- CH, CH, CH, j 3 j 3 j 3 ^ _ ^ 3 rHA ^ svAsXV ^ iJp 110 / 0.05 CH3 27 CH3 CH3 CH3CH ^ CH3 • | T ~ 0 113 / 0.05

CH3. M

CH3 ch3 9 compound Kp [° θ] / nnt H chem. displacement of the y protons .1 morpholine ring y ((^ values in ppm) + 'CH, .CH, CH, CH ,.

.3.3.3 / 3 4.17- (2H, m); CH, oily (25H, d);

3 tL rtTT

28 J 2.60 (2H, t); c12h25 ^ 5> s ° 3 θ CH, CH, CH, 1 3 3, © 3 ^ oily 4.31 (2H, m); CK 'i "3.30 (2H, d); 29 3 H J 2." (2H, t); ch 3 - (CH 2) 10 - CH 2

"-L

CH3 CH3 CH3? H3 1 - I. J / / — CH, Q Q> oily 2.40 (4H, m) / Ί ~ ch CH 3 C 12 H 25 ^ 2 '' SO 3 CH, CH, CH, 4.27 (2H, m) jl 1 1® > \ 4.05 (1H, t); 0 oily 3.40 (2H, t); CH, / 3.07 (1H, t); 31 Un3 J 2, J 2 (1H, t). 0O> so39 151015 forbindelseο compound Kp [° c] / mm.Hg chem. Displacement of the protons in the morpholine ring% (δ values in ppm) * 'CH, CH, CH, CH, .3, 3, 3 / 3 Γ ~ 4.40 (2H, m) '/ y 3 3.90 (1H, o); 3 H / oily 3.30 (1H, d>, CH 3 J 3.15 (1H, m)); 32 2.50 (1H, t) ° 12Η25-®-303θ CH, CH, CH, CH, I i Λ H'32 m * m); \) oily 3.40 (2H, m) j CK3 / ^^ qh 2.60 (2H, m) ch3 3

33 s- \ J

C 12 H 25 <3 - SO 3® CH, CH, CH, 1 H 2 I 3 3 CH 3 3.98 (2H, m) δ 3.37 {2H, d) in CH 3 H 2.68 (2H, t?) 34 c12H25- <O> SO3e CH, CH, ΟΗ ,, ττ CH, 4.42 (1H, m); i 3 i 3 i 3CH, / 3 »-, Λ ^ νΧ ^ Λ,) 2 ^ el. oily *. ° 8 <".>" 35 CH3 / Nw C1 3'29 (1H, m); HCH3 CH3 3 * 08 11 151015 chem. displacement ^ D [° C] / mm Hg of the protons i

Compound "morpholine ring> __ (<f values in ppm) - 4.48? H5 CjH5 T3fL3 Clθ 3.30 (1H, d); 'oily3 * 07 (1H * d)! 36 ^ -' CH 2 e 2 , 50 (2H, fc) CH_.

^ _ 4.09 ίΗ3 ° | H3 fa3 CH,. .0® 3.17 (1H, d); HCl oleea®ti® 2.89 (1H, d); 37 3 W-CH-3 2.40 (1H, d) j L 2.22 tH, t) 3 * “1 4.00 (1H, m) j CH, CH, CH, i 3 i 3 i 3 / ; h θ 2.8H (1H, d); CH / ° 2.61 (1H, d); 3 HV "f-CH3 oily g> 10 (1H, d); 38 CH3 J 1.93 (1H, t) 1 H-NMR spectra were recorded in CDCl3 at 220 MHz with tetramethylsilane as the internal standard (t = Note · In addition to the value, the intensity and multiplicity of the signal in question are given in parentheses.

The new compounds are, in fungicide, exactly as active as the known N-alkyl morpholine derivatives. The particular advantage of the new compounds lies in the fact that they are uniform, while in the corresponding known morpholine derivatives isomer mixtures are available.

The active substances of the invention are compounds of unambiguous constitution, on the basis of which clearly defined degradation products are produced in use, which always exhibit the same composition. A further advantage of the substances according to the invention is that sub-structures of the new compounds appear as natural building blocks and that therefore no disadvantages can be expected due to environmental impact of these new products. Thus, it has surprisingly been found that with chemically single-morphine compounds appearing as side chains essentially exhibiting a terpenic, one can obtain as good fungicidal activity as with the mixture of known isomeric morpholines.

For the following experiments, as known active substances, tridemorph (isomeric mixture of N-tridecyl-2,6-dimethylmorpholine) and N-n-dodecyl-2,6-dimethylmorpholine is used.

EXAMPLE 1

Leaves of barley-propelled barley seedlings are sprayed with aqueous emulsions (containing 80% by weight of active substance and 20% by weight of the emulsifier in the dry matter) and after the initial drying the spray coating was sprayed with oidia (spores) of barley mildew (Erysiphe graminis var.hordi). . The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 75 to 80 ° C relative humidity. After 10 days, the extent of the development of mildew fungi is assessed.

13 151015

Active substance No. Activity against Erysiphe graminis at barley. Leaf attack after spraying with. .% active substance suspensions or emulsions _0,025_0.012_ 0.006_ n-dodecyl-2,6-dimethylmorpholine 122 tridemorph OB 0 1-2 5 0 1 - + 14 0 1 - + 18 OB 0-1 1 22 1 1-2 3 23 OB 1 1-2 25 1 1-2 2 26 OB 1 1-2 28 0 2 2 29 0 2 2 31 0 0-1 2 32 OB 1 1-2

Control (untreated) _4_ + = not examined B = minor leaf damage 0 = no attack escalated to 5 total attacks EXAMPLE 2

Impact against wheat mildew

Leaves of wheat carbons driven by "Caribo" varieties are sprayed with 0.02 to 0.025 wt.% Aqueous spray liquids containing 80% active substance and 20% lignin sulfonate, calculated as dry matter, so that drip occurs. After drying the spray coating, the plants are sprinkled with oidia (spores) of wheat mildew (Erysiphe graminis var. Tritici). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and 65 to 70% relative humidity. After 10 days, the extent of the development of mildew fungus is assessed.

14 151015

Active substance No. Application concentration% 0.05 0.025 0.012 0.006

Tridemorph 0 / 2H 0 / 2H 0 / 1H 3 tridemorph salt with dodecylbenzenesilphonic acid 0 0 0 1 4-lauryl-2,6-dimethyl morpholine 223 31 0/10 0 1 32 0 0 0 1 control 4

Leaf damage / 1 single necrosis / 1H single necrosis / 2H slight leaf damage and light positions 0 no attack, escalated to 5 total attack EXAMPLE 3 20 parts by weight of the compound 5 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of sodium of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica. A fine distribution of the mixture in 20,000 parts by weight of water results in a spray liquid containing 0.1% by weight of the active substance.

EXAMPLE 4 3 parts by weight of compound 6 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.

EXAMPLE 5 30 parts by weight of Compound 7 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 part. In this way, a composition of the active substance with good adhesiveness is obtained.

EXAMPLE 6 40 parts by weight of the active substance 8 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Without dilution with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of active substance is obtained.

EXAMPLE 7 20 parts of the active substance 9 are thoroughly mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolic sulfonic acid urea-form aldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

Example 8 500 parts of tetrahydrogeranyl acetone are dissolved in 1000 parts of methanol and filled with 50 parts of methanol moist Raney-Nickel in a 3 liter autoclave. Then 340 parts of ammonia are compressed. It is then heated to 90 ° C and a pressure of 100 bar is set by pressing hydrogen. At refill, the amount of hydrogen used is supplemented until the end of the hydrogen uptake.

For work up, the reaction product is filtered and the filtrate distilled.

480 parts (= 95.5¾ of the theoretical amount) are obtained 6.10 dimethyl-2-amino-undecane, Kpg = 65 ° C. 1 part of 6,10-dimethyl-2-amino-undecane and 4 parts of water are heated in a 2 liter stirring autoclave to 140 ° C. Now 520 parts of propylene oxide are pressed in portions. Then, continue heating for another 10 hours at 140 ° C and then work up. The distillative work-up leads to 575 parts (= 91¾ of the theoretical amount) N, N-di-2-hydroxy-prop-1-yl) -N- (6,10-dimethyl-undec-2-yl) -amine, Kpg g 2 = 168 to 170 ° C.

To 530 parts of N, N-di- (2-hydroxy-prop-1-yl) -N- (6,10-dimethyl-undec-2-yl) -amine, 410 parts of concentrated sulfuric acid are allowed to stir, and The mixture is then kept for 5 hours at 13 ° C.

Then the portion is slowly added to 1400 parts of 25 wt% baking soda, which is allowed to settle and then separate the organic phase. This is worked up distillatively to give 470 parts (= 93¾ of the theoretical amount) of N- (6 ', 10'-dimethyl-undec-2'-yl) - 2,6-dimethylmorpholine, Kp ^ = 158 ° C.

Example 9 44 parts Farnesal and 23 parts 2,6-dimethylmorpholine are dissolved in 70 parts tetrahydrofuran and filled with 6 parts tetrahydrofuran-moist Raney nickel in a 250 ml shaking autoclave. It is then heated up to 195 ° C and hydrogen is compressed to 200 bar. Until the end of hydrogen uptake, the pressure of 200 bar is maintained after filling hydrogen.

The reaction product is then filtered and the filtrate is worked up distillatively. There are thus obtained 57 parts (= 87.5¾ of the theoretical amount) of N- (31,71,11'-trimethyl-dodec-11-yl) -2,6-dimethylmorpholine, Kp. = 161 ° C.

J - '^

Claims (1)

Morpholine derivative having a fungicidal effect, characterized in that it has the formula RN 0 8 X5 wherein R is a chemically prominent alkyl or alkoxyalkyl group having 12 to 15 carbon atoms and containing at least two or more branches of the kind having is characteristic of terpene compounds and wherein X ^, X ^, X ^, X ^> X ^ j Χη and Xg represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms and its salt.