DD281109A5 - FUNGICIDES BASED ON N-SUBSTITUTED TETRAHYDRO-1,4-OXAZINES - Google Patents

Abstract

The invention relates to fungicidal compositions based on N-substituted * and polymeric Traegermaterialien for combating phytopathogenic fungi. Compared with the low-molecular-weight active compounds, such products have an increased fungicidal activity associated with a reduction of active substance losses under practical conditions. The object is achieved according to the invention that combinations of carboxymethylcellulose and aluminum salts contain biologically active N-substituted * of the general formula I. From the combinations according to the invention, the 1,4-oxazine is released in a controlled manner. Formula I {fungicidal agents; * polymeric carrier materials; carboxymethyl cellulose; Aluminum salts; phytopathogenic fungi; Erysiphe graminis; controlled release; Practical conditions; Drug losses; environmental factors}

Description

Field of application of the invention The invention relates to fungicidal compositions based on N-substituted tetrahydro-1,4-oxazines and polymers Trägermaterialian. The underlying low molecular weight drugs and some known drug mixtures possess

a pronounced fungicidal activity. They are therefore used in many areas of agriculture and pest management as well as material and storage protection for the control of fungal diseases. The agents according to the invention are especially active against phytopathogenic fungi. Due to the special nature of their use allows their use compared to conventional formulations of corresponding fungicides, a reduction in application rate and / or Ausgabungshäullgkeit, coupled with a reduced phytotoxicity.

In addition, the fungicidal compositions of the invention allow a very effective use of the active ingredients in particular at Soil application. With fighting Piizkrankheiten securing high crop yields and a considerable economist ¹ "Icher benefits

connected.

Characteristic of the known state of the art

It is known that N-substituted tetrahydrr> -1,4-oxazines inhibit the growth of harmful fungi (König, KH, Pommer, EH, Sänne, W., Angew Chem 77 (1965) 7,327, DE-OS 1,164,152 ). In DD-PS 140412 is on the fungicidal effect. N-Aikylsubstituierten 2,5- and 2,6-Dimethylmorpholinen pointed against Erysiphe gratninis. However, the use of this compound is limited by its relatively high phytotoxicity for certain applications. In particular, in the application under field conditions, there is also the risk that these agents are lost by leaching and volatilization, by chemical, photochemical or microbial degradation and by binding to soil particles and the fungicidal 3 protection is significantly reduced. Therefore, application rates must be accepted, which exceed the actually effective fraction by a multiple and are economically and ecologically problematic.

These disadvantages can not be completely eliminated by the described synergistic fungicidal combinations containing N-substituted tetrahydro-1,4-oxazino as components (DD-PS 155481, DD-PS 157592, DD-PS 212887).

Object of the invention

The object of the invention is then to find fungicidal agent suf the basis of N-substituted tetrahydro-1,4-oxazines, which exhibit an increased biological activity compared to the active ingredient itself and enable an economically and ecologically favorable application in soil application.

Explanation of the essence of the invention

The applicability of the known fungicidal compositions based on N-substituted tetrahydro-1,4-oxazines is due to the drug losses due to before. Leaching and volatilization, as well as chemical, photochemical and microbial degradation and due to the binding to soil particles and / or insufficient fungicidal action significantly limited. This is in addition to a significant environmental impact associated with insufficient fungicidal activity. The invention is therefore based on the object to find fungicidal agents based on N-substituted tetrahydro-1,4-oxazines, which have an increased fungicidal activity and allow a reduction of drug losses due to environmental influences in soil application. According to the invention the object is achieved in that combinations of carboxymethylcellulose and aluminum salts contain biologically active N-substituted tetrahydro-1,4-oxazines of the general formula I,

where Π ¹ Ali: · /] -, cycloalkyl or

WC. ο a he a to ff or üethyl ^ i'u;

: Rail:; / Ire ο and ο

I p

ΊΊ ¹ "Π '" ii e η.

The combinations of carboxymethylcellulose and aluminum salts are obtained by simply mixing or dropping sodium carboxymethylcellulose, which is present as an aqueous swollen gel or as a solution, with or in aluminum salt solutions. The degree of substitution of the sodium carboxymethylcellulose used may be in the range of 0.5 to 1.5, wherein the use of low-substituted carboxymethyl celuloses is advantageous from an economic point of view. There are no restrictions on the quality and external form of sodium carboxymethylcellulose. In addition to pure technical products can be used with a polymer content greater than 50%. In addition, it is advantageous to use cheap Carboxymethylceilulosen as z. B. by carboxymethylation of regenerated cellulose wastes, semi-celluloses or wood pulp are available. Suitable aluminum salts are water-soluble salts, in particular aluminum sulfate with and without water of crystallization. Preferred solvent is water, but also mixtures of water with ethanol or methanol can be used. The aluminum salt solutions should have a low pH, which is preferably in the range of 2 to 4. Both the sodium carboxymethylcellulose and the aluminum salt solution may be further Hilfssioffe, such as surfactants added. Essential for the properties of the fungicidal compositions according to the invention is a specific ratio of Aluminiumioiion to carboxy groups. The content should be between 1 and 6.5, preferably 3 to 3.5 .mu.m.% Ai ³⁺ , wherein, regardless of the degree of substitution of the carboxymethylcellulose 40-70% salt-like and 60-30% are nonspecifically fixed in the polymer support. The aluminum ion content can be reduced following the preparation of the carrier both by washing processes with alcoholic mineral acids or increased by admixing further aluminum salt in solid or dissolved form and is thus adjustable to any degree. Due to the iii-wire pH of the aluminum salt solution is a part of the carboxy groups in the free acid form, which ensure an additional fixation on Coulomb interactions in addition to the Eir end of the active ingredients in the polymer network. The content of N-substituted tetrahydro-1,4-oxazines should be 10 to 30% by mass. The loading of active ingredient takes place by inclusion during the formation process of the polymer carrier. But it can also be following its preparation and optionally further modification such. B. ion exchange reactions by sorption with and without solvent. The loaded with active ingredient or possibly drug-free polymeric carrier is thermally treated, resulting in an irreversible shrinkage, which is important for the desired sustained release effect. Daloi

At the same time water is evaporated or evaporated, so that a dry product results. If necessary, carried out during drying or thereafter still a granulation or comminution of the fungicidal compositions according to known

Method. Essential for the properties of the fungicidal compositions according to the invention is an average particle diameter of

0.05-5mm, preferably from 0.2 to 2mm. The fungicidal compositions according to the invention can be converted into the customary formulations, such as granules, scattering or dusting agents, but preferably into wettable powders. They are in known

Optionally, using surface-active compounds, mixed with solid support materials or

formulated according to other known methods. The fungicidal compositions according to the invention can be used alone or together with other organic or inorganic bioactive substances for controlling harmful fungi.

The fungicidal compositions of the invention are characterized by good handleability, shelf life and reduced toxicity

due to the fixation in the polymer carrier and a thus realized retard effect. In addition, the carboxymethylcellulose matrix contributes to soil improvement as a water reservoir.

Surprisingly, it has been found that the agents according to the invention increase the mycelial growth of 11 test fungi

inhibit as the active ingredient aldimorph (main component: N-dodecyl-2,6-dimethylmorpholine, Table 2).

When applied via the soil, the agents according to the invention have at least the same or clear features on barley cultures

stronger fungicidal activity (Table 3).

The following examples illustrate the invention in more detail without restricting it. Ausführungsbolsplele example 1

4 g of sodium carboxymethylcellulose with a degree of substitution of 0.9 is mixed with 40 ml of water and stirred (otwa 10 minutes) until a thick homogeneous mass is formed. To this mass, with further stirring, a solution of 1.4 g of Al ₂ (SO ₄ I ₃ χ 6H ₂ O in 70 ml of water added so that a fine-grained precipitate of Aluminiumcarboxymothykellulose is formed, which separated after a further 15 minutes stirring time using a frit and Subsequently, 2.5 g of aldimorph are thoroughly mixed into the aluminum carboxymethylcellulose and water is further evaporated by heating on a water bath (8O ⁰ C) at 13 kPa until a free-flowing product is obtained The product has an active substance content of 12 Ma .-% and is characterized by a significantly increased fungicidal activity at the same Wirksto'faufwandmenge compared to aldimorph (Tables 2 and 3).

Example 2

Analogously to Example 1, 40 g of technical sodium carboxymethylcellulose with a degree of substitution of 0.7 with 400 ml of water are mixed and homogenized by stirring. 18.5 g of Al ₂ (SO ₄ J ₃ .18H ₂ O in 350 ml of water are added to this viscous mass in such a way that a fine-grained precipitate is formed, which is separated after a further stirring time of 20 minutes and is sucked dry as far as possible by applying a water-jet vacuum 35 ml of aldimorph are thoroughly mixed in and treated on the water bath at 50 ° C. and 15 kPa until a free-flowing product has formed (about 120 minutes) .The active ingredient content is 19% by mass.

Example 3 Analogously to Example 1, solutions of 5 g of sodium carboxymethylcellulose in 100 ml of dist. Water with solutions of 5 or 10g Al ₂ (SO ₄ ), 18 H ₂ O in 50 ml dist. Water mixed and the precipitate formed separated, each with 4.3g aldimorph

loaded, added more aluminum salt as a solid and granulated on a water bath at 50 ° C for 2-3 h in a water-jet vacuum.

Al ^3t salt solution Al ³⁺ salt salt (solid)

g / 50 ml g

5 0.2 10 0.3 10 2 ^

a addition took place before the drug loading

Example 4

The aluminum carboxymethylcellulose is prepared analogously to Example 2, dried at room temperature over 240 h / 2 kPa over Cat and crushed the carrier by milling in a ball mill to a particle size of 200μιη. Subsequently, in each case 5.0 g of the material are shaken with a mixture of 5CmI 6N HCl and 200 ml of ethanol for 1.10 or 24 h, so that an A'uminiumgehalt of 2.5; 0.5 or 0Ma .-% results in the product. After washing with dist. Water and drying over CaCl ₂ , a load of 25.27 or 37 wt .-% aldimorph could be carried out by sorption without additional solvent.

Example 5

25 g of sodium carboxymethylcellulose with a degree of substitution of 0.6 are dissolved in 500 ml of water and 150 ml of aldimorph are suspended therein with vigorous stirring. The suspension is poured into a mixture of 100ml. Al ₂ (SO ₄ I ₃ χ 18H ₂ O solution, 240 ml of water and 200 ml of ethanol dripped in. Immediately an insoluble aluminum carboxymethylcellulose gel is formed After a curing time of 60 minutes, the active ingredient-containing capsules are separated by filtration, with 500 ml bidistilled water washed and dried in a desiccator over CaCl 3 at 3.5 kPa until a free-flowing product is obtained (about 100 hours). The active ingredient content is dependent on the capsule size and is at a diameter of 1.5 mm at 16.3 Ma .-% and at 0.8mm diameter at 15.4Ma .-% These products are characterized by a high mechanical stability.

Example 6 Analogously to Example 5, aqueous solutions of sodium carboxymethylcellulose, each containing 23 vol .-% aldimorph in

a mixture of 25ml sat. Al ₂ (SO ₂₎ 18H ₂ 0.60 ml of water and 50 ml of ethanol are added dropwise After a residence time of 60 minutes, the separation, washing with 500 ml of distilled water and drying over CaCl ₂ (about 100 h / 3.5 kPo) at

Room temperature.

sodium polymerized Dimensions Fungicidal agent Al ³⁺ substitutions sations- g / 100 ml aldimorph Wt .-% Degree Degree Wt .-% 430 5 2.1 0.60 440 5 24 0.8 1.05 430 10 37 0.1 1.30 45

Example 7

5g of technical sodium carboxymethyl cellulose with a degree of substitution of 0.7 are dissolved in 100% water. 5 g of Al ₂ (SO ₄ I ₃ .18H ₂ O in 50 ml of water are added to the viscous solution with vigorous stirring, and after 10 minutes the precipitate formed is separated off and excess liquid is removed in a water-jet vacuum. (4-tert-butylphenyl) -2-methyl-1-propyl | -cis-2,6-dimethyl-tetrahydro-1,4-oxazin untergemiocht thoroughly and dehydrated at 5O ⁰ C in a water jet vacuum until a free-flowing granules ( about 30 minutes.) 13.5 g of a fungicidal agent containing 28.2% of active ingredient are obtained.

Table 1 Characterization of the fungicidal compositions prepared by way of example

Ser. Aldimorph- Al ³⁺ - example No. salary salary Wt .-% Wt .-% 1 12 3.0 1 2 19 2.6 2 3 25 3.5 3 4 18 4.5 3 5 23 6.5 3 6 25 2.5 4 7 27 0.5 4 8th 37 0 4 9 15.4 to 16.3 1.8 5 10 24 2.1 6 11 37 0.8 6 12 45 0.1 6 13 " 28 0.2 7

a Active ingredient: 4- [3- (4-tert-butylphenyl) -2-methyl-1-propyl] -cis-2,6-dimethyl-tetrahydro-1,4-oxazine

Example 8 Fungicide test in vitro. The compounds became a liquefied agar medium in concentrations of 0.05, 0.005 and 0.0005% active ingredient

added and poured into sterile Petri dishes. After evaporation of the solvent, the agar plates were inoculated with the respective test fungus. After incubation in the breeding area for 3 to 30 days, depending on the test fungus, the radial mycelial growth of the felt was determined. The inhibition of mycelial growth in% is given in Table 2.

Table 2 Inhibition of mycelial growth of the agents according to the invention in comparison to dimorph Test substance Percent inhibition of mycelial growth after application of the test substance in. Jen

concentrations 0.05% 0.005% 0, ( Test fungus: Alternaria tenuis aldimorph 100 86 40 Ser. NM 100 85 55 Ser. No. 3 100 96 83 Test fungus: Fusariumnivale aldimorph 55 30 17 Ser. number 1 100 27 17 Ser. No. 3 77 40 17

Test fungus: Gaeumannomyces graminis 97 93 2 28 22 Rhizoctonia solani 82 27 73 aldimorph 97 95 78 50 98 82 96 96 100 92 Ser. number 1 98 97 77 Helminthosporium sativum 100 Sclerotinia scleroto irum 93 Lt 1.No. 3 98 Thielaviopsis basicola Fusarium culmorum 75 15 3 100 Test fungus: 100 32 100 90 98 100 35 aldimorph: 96 75 Phomabetae 3 of the mycelial coat 67 Ser. NM 97 95 0.005% 27 Ser. No. 3 100 Phytophthora cactorum Test fungus: central inhibition * 98 - aldimorph 0.05% 100 - Ser. number 1 Pythiumspec. Test fungus: 91 17 aldimorph 100 25 Ser. NM Test fungus: 5 aldimorph 25 Ser. number 1 is over Test substance Pro 0, C concentrations Test fungus: 0 Aidimorph 3 Ser. number 1 Test fungus: 0 aldimorph 17 Ser. number 1 Test fungus: 12 aldimorph 89 Ser. number 1 Test fungus: 0 aldimorph 95 Ser. number 1

Examples Systemic testing against cereal powdery mildew (Erysiphe graminis) on barley At a stature height of barley of 4cm, the insoluble compositions of the invention in the soil of Barley plants attracted experimental vessels incorporated. Through root reception and acropetal forwarding reaches the Active ingredient in the above-ground parts of plants. The plants are left 3 days after the application of the agent with conidia of Powdered mildew (Erysiphe graminis) inoculated and then at favorable for the course of the disease temperature and Humidity conditions incubated. 10 to 12 days after the application, the evaluation of the disease development and the Plant tolerance. The evaluation of the fungicidal effect or phytotoxicity is carried out by the summation of all credit score. 27/27 is the im Maximum value to be achieved with the least fungicidal effect and maximum phytotoxicity. 0/0 is the best

Result.

Table 3

Fungicidal action and phytotoxicity of the agents according to the invention in vivo when applied over the soil in comparison to aldimorph in the case of Erysiphe graminis on barley in Σ of the bonus notes.

Ser. No. effort concentration 2,000 ppm AS 8th 1 500 ppm AS fungiz. 1 000 ppm AS fungiz.Wirkg. Phytotox. 3 fungiz.Wirkg. Phytotox. 20 Wirkg. Phytotox. 19 0 19 7 14 5 aldimorph 12 9 13 0 13 0 1 6 9 11 0 20 0 3 9 16 10 9 12 3 4 11 12 11 9 0 5 21 8th 6 19 8th 7 20 8th 8th 21 17 10 19 11 19 12

Example 10 Production of a wettable powder The solid drug combinations were pre-ground, all formulation ingredients mixed and finely ground until

a particle size <40μηη is reached. As an example of the composition of a wettable powder, the following formulation can be cited:

52% Test Sample No. 1 12% Aldimorph 5% Sodium Oleoylmethyltanride

10% calcium lignosulfonate

33% amorphous silica hydrate

Claims (9)

1. fungicides middle! based on biologically active N-substituted tetrahydro-1,4-oxazines, characterized in that f.- combinations of carboxymethyl cellulose and aluminum salts contain biologically active N-substituted tetrahydro-1,4-oxazino of the general formula I ^ B ² E U R ^{1 is} alkyl, cycloalkyl or aralkyl radicals and R ^{2 is} hydrogen or methyl groups. 2. Fungicidal agent according to claim 1, characterized in that the carboxymethyl cellulose has a degree of substitution of 0.5 to 1.3 and including technical products polymer contents> 50%. 3. A fungicidal composition according to claim 1, characterized in that one uses as aluminum salts acidic salts whose aqueous solutions have a pH of 2 to 4, in particular aluminum sulfate with and without water of crystallization. 4. A fungicidal composition according to claim 1, characterized in that as biologically active tetrahydro-1,4-oxazines in particular aldimorph (main constituent 4-dodecyl-2,6-rJimethyl-tetrahydro-1,4-oxazine and 4- [3- (4- tert-butylphenyl) -2-methyl-1-propyl] -cis-2,6-dimethyl-tetrahydro-1,4-oxazine. 5. Fungicidal agent according to claim 1 to 4, characterized in that the combinations contain 1 to 6.5, preferably 3 to 3.5 Ma .-% Al ³⁺ , wherein 40 b "s70% de: aluminum ions salt-like and 60 to 30 % non-specific bound. 6. A fungicidal composition according to claim 1 to 5, characterized in that the polymer carrier contains 5 to 20% of carboxy groups in the free acid form. 7. A fungicidal composition according to claim 1 to 6, characterized in that the initial moist products in the temperature range of 2O ⁰ C to 9O ⁰ C Favor * of 2O ⁰ C to 5O ⁰ C, if appropriate, in vacuo or via appropriate desiccants dehydrated and camit irreversibly shrinking. 8. A fungicidal composition according to claim 1 to 7, characterized in that the average particle diameter 0.05 to 5 mm, preferably 0.2 to 2 mm and the content of biologically active material 5 to 50Ma .-%, preferably 10 to 30Ma. -%. 9. Fungicidal agent according to claim 1 to 8, characterized daduich that they additionally contain formulation auxiliaries and / or additives, in particular organic or inorganic bioactive substances.