DD235020A1 - MACRO AND / OR MICRONOUS MATERIALS CONTAINING DUENGER SYMBIONTICIDE COMBINATIONS - Google Patents

Abstract

The invention relates to macro-and / or nitronae-containing Duenger symbiotic combinations for plant nutrition and simultaneous control of harmful arthropods. In addition to the known nutrients as well as conventional auxiliaries and carriers, they contain as additional active ingredient substituted 2-aminobenzimidazoles or their metal complex compounds.

Description

Field of application of the invention

The invention relates to macro-and / or micronutrients containing fertilizer Symbiontizid combinations for plant nutrition and simultaneous control of harmful arthropods.

Characteristic of the known technical solutions

For decades it has been customary to kill phytophagous arthropods and hygiene pests by chemical compounds or to inhibit their development in such a way that their population density is below the damage threshold. Depending on the type of preparations used, these are feeding, contact or respiratory poisons, repellents or insect growth regulators.

Through the works of Erhardt (Z. Morph. Ökol. Tiere 56,1-20,1966); Mittler (J. Insect. Physiol., 17,1333-1347, 1977); Khan '(Indian, J. Entomol., 39, 8, 11, 1977); Frank (Z. Morph. Ökol. Animals 44, 329-366, 1956); Goetsch (Patent No. 174497, Austria, 1952) is known that insects are killed by the use of antibiotics or N-substituted compounds such as pyridine, pyrimidine, quinoline and acridine, or inhibited in their development.

As is known, it is possible to control the growth processes in plants in a controlled manner, or to either shorten or prolong or induce or completely suppress certain phases of plant development. For this purpose, chemical substances of different structure, which possess biocidal properties, have already been discovered and described. Such substances are, for example, chlorocholine chloride (US Pat. No. 3230069), DE-AS 1238052), maleic hydrazide (US Pat. No. 2,805,926) and succinic acid dimethylhydrazide (US Pat. No. 3,240,799). The regulation of native growth and development of the plants may be the result of the chemical action on the physiological process or on the morphology of the plants or a combined action. The different effects depend on the time of application, the stage of development of the seed or plant and the concentration. This results in a wide variety of applications. For example, the processes of germination can be selectively promoted or inhibited. Furthermore, in addition to the general morphological changes of the plant to control the length and thickness growth and to influence the vegetative and generative bud formation, the flowering process and sex determination. With such artificial regulators, the nutrient transport and metabolism physiological processes can be controlled, which are reflected inter alia in the chemical composition of the ingredients.

Object of the invention

The aim of the invention is to develop macro- and / or micronutrients containing fertilizer Symbiontizid combinations for plant nutrition and simultaneous control of harmful arthropods.

Explanation of the essence of the invention

This object is achieved in that the macro- and / or micronutrients fertilizer Symbiontizid combinations in addition to the known nutrients and conventional auxiliaries and carriers as additional active ingredient at least one substituted 2-aminobenzimidazole of the general formula

-H-C-R

I,

in the

R ^{1 is} an alkyl group having 1 to 4 C atoms, a methoxy group or an optionally one or two times by methyl

substituted amino group and R ² and R ³ , which may be identical or different, represent hydrogen or methoxycarbonyl and wherein instead of R ² and R ³ to R ³ , adjacent N atom of Aminobenzimidazoiringes and the adjacent to R ² N atom can form a hexahydro-1,3,5-triazine ring via a bis (methylene) benzylamino group, provided that R ^{1 is} methoxy or at least one metal complex compound of the general formula

(Yp - Me) X _q

II

in the

Y is a compound of general formula I,

Me a metal cation of the metals Ca, Co, Zn, Mg, Mn, Ni or Fe,

X mono- or polyvalent inorganic or organic anions, preferably halide, nitrate, sulfate, thiocyanate or acetate,

p is the numbers 1 to 8 and q is the numbers 1 to 6.

The agents according to the invention can be used in the form of solutions, emulsions, suspensions, pastes or granules, which are prepared in a manner known per se by mixing or milling processes. In addition, it is possible to bind the agents according to the invention to organic or inorganic support materials and to introduce or adjust the solids thus produced in the form of rods or other bodies into the substrate, which may optionally also be ground.

It can be used in terrestrial or hydroponic culture and on artificial substrates. The symbiotic active component may be added to the liquid or solid macro and / or micronutrients prior to application, combined with these or applied separately.

The agents according to the invention make it possible. Fertilize plants effectively while controlling harmful arthropods. The substituted 2-aminobenzimidazoles of the general formula I can be prepared by known methods (DE-OS 2253324, FR-PS 2234295, US-PS 3399212, Journal of Heterocyclic Chemistry 12, [1] 37-42 [1975]). The metal complex compounds of the general formula II can be easily obtained by reacting the substituted 2-aminobenzimidazoles with a metal salt.

The reaction can be advantageously carried out by mixing the substituted 2-aminobenzimidazoles with the metal salt in a suitable solvent, such as. As water, lower alcohol, acetone, dimethylformamide, nitromethane or a mixture thereof, if necessary, be carried out with heating. After completion of the reaction, the desired metal complex compound can be recovered and purified by methods known per se. The determination of the metal content of the complexes shown was carried out by complexometric titration with m / 10 Testalon III. An overview of the prepared and in the examples biologically tested active compounds of the general formula I and II are given in Tables I and II.

Table I Active substances of the general formula I.

active substance R ¹ R ² R ³ FPC = O analysis No. % N over. % N gef. 1.1 OCH ₃ H H 330-332 I / 2 CH ₃ COOCH ₃ COOCH ₃ 118-121 I / 3 C ₂ H ₅ COOCH ₃ COOCH ₃ 122-125 I / 4 (CH ₃ ) ₂ CH COOCH ₃ COOCH ₃ 142-147 I / 5 CHHCH ₂ J ₂ - COOCH ₃ COOCH ₃ 111-114 13.17 I / 6 OCH ₃ COOCH ₃ COOCH ₃ 151-155 12,80 I / 7 NH ₂ H H 360 13.68 I / 8 NHCH ₃ H H 300 14.08 I / 9 N (CH ₃ J ₂ H H 250-252 1.10 OCH ₃ -CH ₂ -N-CH ₂ - 143-146

Table II Metal complex compounds as active compounds of the general formula II

active substance Metailkomplexverbindung P me X q Fp ( ⁰ O Salary Me in% No. 2 Co Cl 2 (ber./gef.r ¹ _γ υ 2 Zn Cl 2 H / 1 1.6 2 Cu NO ₃ 2 180-183 7.92 / 7.93 H / 2 1.6 2 mg NO ₃ 2 183-185 8.71 / 8.68 H / 3 1.6 2 Ni NO ₃ 2 170-172 (Zer.) 7.92 / 7.73 H / 4 1.6 2 Cu NO ₃ 2 164-166 3.19 / 2.82 5.11 1.6 2 Cu Cl 2 ab185allm.Zers. 7.36 / 7.33 H / 6 1.1 2 Zn Cl 2 ab160allm.Zers. 11.15 / 11.13 H / 7 1.1 205 (dec.) 12.29 / 12.07 8.11 1.1 223-226 12.60 / 12.43

DY = compound of general formula I +) arithm. Means of several determinations

embodiment

The examples are intended to explain the effect of the agents according to the invention in more detail. The drug numbers correspond to the

Information from Tables I and II.

As a combination partner for the symbiotic active ingredients, a nutrient salt of the following composition was used:

15% N, 15% P ₂ O ₅ , 24% K ₂ O

Iron, manganese, boron, copper per 0.01%

Zinc, molybdenum, cobalt 0.0002% each

Calcium, magnesium each 0.2%

This nutrient salt is designated F in the following examples and tables.

example 1

Use of the invention for controlling the cereal aphid (Rhopalosiphum padi) on barley in hydroponic culture The nutrient salt mixtures according to the invention were prepared with water such that the nutrient solution 0.05 to 0.1% of the nutrient salt Fund 10 ~ ^{3 to} 2.5 · 10 ~ ^{4 of} a symbiontizid In this nutrient salt solution, winter barley of the variety Erfa was grown in hydroponic culture. The controls were dissolved in solutions of the nutrient salt F without addition of the symbionticide

effective component.

One day after the plants had been introduced into the solution, 25 juveniles of the wheat leaf louse Rhopalosiphum padi were placed per test vessel. After 7, 10 and 14 days, the number of aphids was determined and the efficiency was calculated according to Abbott.

Tabeile III Effect of the combinations according to the invention on Rhopalosiphum padi

broth

percentage composition of the inventive (in%) nutrient solution days after administration

F active ingredient No. / 6 7 10

14

control 0.1 - broth 1 0.1 0.0005 broth 2 0.1 0.001 control 0.05 - broth 3 0.05 0.00025 broth 4 0.05 0.0005

0 = (97) ⁺ 0 = (243Γ 0 = (1083) 96 100 100 100 100 100 0 = (127) ⁺ 0 = <183Γ 0 = (648) ⁺ 76 91 99 93 98 , 100

() ⁺ = Number of aphids

Example 2

Use of tank mixes according to the invention for controlling the cereal aphid (Rhopalosiphum padi) on barley

hydroponics

The compositions according to the invention were dissolved in water in such a way that the nutrient solution contained 0.02% of the nutrient salt and various low levels of the symbioticidal agent (10 ^-3 to 10 ⁵ %). In such prepared solutions winter and spring barley of different varieties were grown in hydroponic culture. One day after the plants were put into hydroponics, 25 pups of Rhopalosiphum padi were placed. 7.10 and 14 days after the start of the experiment, the colonization density of the aphids was determined and the efficiency was calculated according to Abbott.

Table IV Effect of the agents according to the invention against Rhopalosiphum padi on various types of barley

active substance concentration 0 Nutrient salt F Efficiency (%) 10 0 = (898) ⁺ 14 No. (%) 0.0001 Conc. (%) 7 Days n. Of the application 40 0.0005 65 a) spring barley, Sort of trump 0.001 0 = (68) ⁺ 100 0 = (3480) ⁺ control 0 0.0001 0.02 10 21 1.7 0.00001 0.0005 0.02 35 0 = (24) ⁺ 58 0.0001 0.001 0.02 100 52 100 0.001 0 0.02 95 b) spring barley, Variety Lada 0.0001 0 = (24) ⁺ 99 0 = (728) ⁺ control 0 0.0005 0.02 46 15 1.10 0.0001 0.001 0.02 87 0 = (124) ⁺ 98 0.0005 0.0001 0.02 100 0 100 0.001 0.0005 0.02 84 c) winter barley, variety Erfa 0.001 0 = {16) ⁺ 100 0 = (377) ⁺ control 0.0001 0.02 0 0 5 I / 7 0.0005 0.02 68 96 85 0.001 0.02 86 99 94 0.02 43 0 = (95) ⁺ 21 I / 10 0.02 81 84 98th 0.02 79 100 98 0.02 0 = (45J ⁺ 100 0 = (88O) ⁺ control 0.02 39 62 89 1.1 0.02 100 100 100 0.02 100 100 100 0.02 29 2 87 I / 6 0.02 91 100 100 0.02 100 100 100 0.02 60 49 I / 5 0.02 100 100 0.02 100 100 0.02

) ⁺ Number of aphids

Example 3

Use of the agents according to the invention against the black bean aphid (Aphis fabae) on field beans in hydroponic culture The nutrient salt mixtures according to the invention were prepared with water such that the nutrient solution 0.05% or 0.1% of the nutrient salt F and 10 ^-3 to 2.5 10 ~ ⁴ % example of the active ingredient I / 6 contains. In this nutrient solution, field beans of the Fribo variety were grown in hydroponic culture and the controls were placed in pure nutrient saline solutions of the appropriate concentrations. Immediately after starting the experiment, 10 adult aphids were set up per test vessel and repeated (4 repetitions). 10 days later the population density of the aphids was determined and the efficiency was calculated according to Abbott.

Table V Effect of the agents according to the invention against Aphis fabae

broth

percentage composition of the inventive (in%) efficiency 10 days after application

F drug no. I / 6

control 0.1 - broth 1 0.1 0.0005 broth 2 0.1 0.001 control 0.05 - broth 3 0.05 0.00025 broth 4 0.05 0.0005

100 100

0 = (1553) ⁺ 100 100

() ⁺ Number of aphids

Example 4

Use of inventive tank mixes against the black bean aphid (Aphis fabae) on field bean in hydroponic culture

The compositions of the invention were dissolved in water so that the nutrient solution in each case 0.02% of the dietary salt F and

various low levels of symbiotic active agents (10 " ³ to 10 - *%). In this nutrient solution were added

Field beans of the Fribo variety grown in hydroponic culture. The controls were in pure nutrient solutions of the corresponding

Concentrations. On the plants used had within 4 days from 5 adults an aphid population

The settlement density of the aphids was determined 7 days after application and the efficiency was calculated according to Abbott.

Table VI Effect of inventive tank mixes against Aphis fabae

Active substance Concentration% Nutrient salt F Efficiency (%)

No Conc. (%) 7 days after application

Control - 0.02 0 = (2038) ⁺

(3 repetitions)

1/1 0.0001 0.02 72

0.0005 0.02 100

0.001 0.02 100

I / 5 0.0001 0.02 50

0.0005 0.02 100

0.001 0.02 100

I / 6 0.0001 0.02 83

0.0005 0.02 100

0.001 0.02 100

(). ⁺ Number of aphids

Example 5

Use of tank mixes according to the invention against chrysanthemum aphid (Pyrethromyzus sanborni) on chrysanthemum The compositions according to the invention were dissolved in water such that the nutrient solution contained 0.02% of the nutrient salt F and various low levels of the symbioticidal agent. In this nutrient solution chrysanthemum seedlings were grown with 10 adult aphids in hydroponic culture.

The controls were placed in pure broths of the appropriate concentrations. 25 days after application, the population density was determined and the efficiency was calculated according to Abbott.

Table VII Effect of inventive tank mixtures against Pyrethromyzus sanborni

Active substance Concentration (%) Nutrient salt F Efficiency (%)

No Conc. (%) 25 days after application

Control - 0.02 0 = (135) ⁺

1/1 0.0005 0.02 100

0.001 0.02 100

I / 5 0.0005 0.02 100

0.001 0.02 97

I / 6 0.0005 0.02 100

 0.001 0.02 100

() ⁺ Number of aphids

Example 6 '

Use of the inventive compositions against the common spider mite (Tetranychus urticae) on bush beans The Nährsalzgemische invention were mixed with water so that the nutrient solution containing 0.1% of Nährsalzes F and 10 ~ ³ or 5 10 ~ ^4% of the active ingredient I / 6 , In this nutrient solution, bean plants (Phaseoius vulgaris variety Jutta) were grown in hydroponic culture. The control was placed in nutrient salt solutions of the appropriate concentration.

Twenty adult females of Tetranychus urticae were added to each plant and the number of mites (all mobile stages) was determined 14 days after application and the efficiency was calculated according to Abbott. For each test member, 3 repetitions were applied.

Table VIII Effect of the agents according to the invention against Tetranychus urticae

Nutrient solution Percentage composition of nutrient solution Efficiency (%)

12 days after application F active ingredient

L / 6

99.6 99.7

Example 7 -

Use of the agents of the invention with Spinnmiiben heavily infested dwarf beans The combinations of the invention were mixed with water so that the nutrient solution containing 0.1% of Nährsalzes F and 10 ^-3 and 5 x 10 ^"4% of the active ingredient no. I / 6. This nutrient broth was supplemented with Jutta bean varieties (Phaseolus vulgaris) heavily infested with Tetranychus urticae, and the number of live mites was determined 15 days later and Abbott's efficiency was calculated.

control 0.1 - broth 1 0.1 0.0005 broth 2 0.1 0.001 () ⁺ Number of mites

Table IX Effect of the agents according to the invention against Tetranychus urticae

control 0.1 - broth 1  · 0.1 0.0005 broth 2 0.1 0.001 () ⁺ (Number of mites

Nutrient Solution Percentage Composition of Invention Efficiency in%

appropriate nutrient solution 15 days after application

F active ingredient I / 6

0 (> 1000) ⁺ > 97 (32) ⁺ > 96 (41) ⁺

Example 3

Effect of the agents according to the invention in depot application against the black bean aphid (Aphis fabae)

field beans

With the Mittelin enriched Filterpappstreifen or Wattestopfen potted bean plants were inserted into the well-fertilized soil and pots constantly poured.

Five repetitions were used per test member.

Experiment a) Filter cardboard strip with active ingredient No. 1/5 and nutrient salt F

20 juveniles of black bean aphid were planted on the field bean plants. 12 days after application, the number of aphids per test member was determined and the efficiency was calculated according to Abbott.

Table X Effect of the agents according to the invention, applied in shaped bodies, against aphis fabae on field beans

Quantity per pot Number of aphids Efficiency (%) in g unheated. control - 344 active substance No. I / 5 0.1 27 92

Experiment b) Cotton plug with active ingredient No. I / 6 and nutrient salt F ₁ -

Ten adult aphis fabae were planted per field bean plant. After 12 days, all aphids were removed and counted and again 10 adults were put on to test the duration of action. 5 days after the 2.Aufsetz took place a 2nd count. From the results, the efficiency was calculated according to Abbott.

Table XI Effect of the agents according to the invention, applied in moldings, against Aphis fabae

1st evaluation - 8 days after application

Amount per pot ing Number of aphids Efficiency (%) unheated. Control drug No. 1/6 0.1 1219 16 98.7 2. evaluation -8 days + 5 days after application = 5 days after replacement Amount per pot ing Number of aphids Efficiency (%) unheated. Control drug no. I / 6 0.1 723 130 82

Example 9

Mortality of black bean aphid (Aphis fabae Scop.) On field bean (Vicia faba) - studies on parts of plants

Plant parts of Vicia faba were treated with the metal complex compounds of the general formula II according to the invention in various concentrations based on the content of active ingredient No. I / 6 in comparison.

Subsequently, the colonization of each plant part with 20 larvae (L ₁ ) of Aphisfabae. 7 days after application, the number of aphids per test member (5 repetitions) was determined and the efficiency was calculated according to Abbott.

Table XII Effect of metal complex compounds against Aphis fabae on Vicia faba compared to substituted ones aminobenzimidazoles

Active substance Concentration (%) Nutrient salt F Efficiency Nn. Conc. (%) (%)

unheated.

Control 0.02 0 (62) ⁺

I / 6 0.0041 0.02 100

0.00082 0.02 100

0.00041 0.02 62

0.000082 0.02 10

11/1 0.0041 0.02 100

0.00082 0.02 100

0.00041 0.02 97

0.000082 0.02 16

II / 2 0.0041 0.02 100

, 0.00082 0.02 100

0.00041 0.02 99

0.000082 0.02 71

I / 6 0.00385 0.02 100

0.00077 0.02 100

0.000385 0.02 100

0.000077 '0.02 11

II / 3 0.00385 0.02 100

0.00077 0.02 100 '

0.000385 0.02 100

0.000077 0.02 45

() ⁺ Number of aphids

»* Example 10

Use of the agents of the invention for combating cereal aphid (Rhopalosiphum padi) on barley in hydroponic culture Winter barley of the variety Erfa was treated with the metal complex compound H / 7 and for comparison with the substance 1/1 in various concentrations.

The application took place via the root. All plants, including those of the control, were adjusted in solutions of nutrient salt F. One day after the treatment, 25 juveniles of Rhoctalosiphum padi cereal aphid were placed per test vessel. After 10 days, the number of Ahabids was determined and the Wirkunasarari narh Ahhntt determined

Table XIII Effect of inventive complex compounds against Rhopalosiphum padi on winter barley compared to the active ingredient

Active substance Concentration (%) Nutrient salt F Efficiency

No. Conc. (%) (%)

Control - 0.02 0 (151) "

1/1 0.0037 0.02 97

0.00185 0.02 100

0.00093 0.02 49

0.00046 0.02 9

II / 7 0.0037 0.02 100

0.00185 0.02 90

0.00093 0.02 42

0.00046 0.02 37

() ⁺ Number of aphids

Claims (2)

Invention claim: Fertilizer Symbiontizid combinations containing macro- and / or micronutrients for plant nutrition and simultaneous control of harmful arthropods, characterized in that they at least one substituted as an additional active ingredient in addition to the known nutrients and conventional excipients and carriers 2-aminobenzimidazole of the general formula in the R 'is an alkyl group having 1 to 4 C atoms, a methoxy group or an optionally one or two times by methyl substituted amino group means and
R ² and R ³ , which may be the same or different. Represent hydrogen or methoxycarbonyl and in which, instead of R ² and R ^3, the N-atom of the aminobenzimidazole ring adjacent to R ³ and the nitrogen atom adjacent to R ² have a hexahydro-1,3,5-bis via a bis (methylene) benzylamino group. can form triazine ring, provided that R ^{1 is} methoxy or at least one metal complex compound of the general formula (Yp - Me) X _q (II), in the Y is a compound of general formula I. Me a metal cation of the metals Ca, Co, Zn, Mg, Mn, Ni or Fe X mono- or polyvalent inorganic or organic anions, preferably halide, nitrate, sulfate, thiocyanate or acetate, ρ the numbers 1 to 8 and
q is the numbers 1 to 6,
contain.