DE2760054C2 - - Google Patents

Description

The invention relates to crop protection agents, in particular Pesticides (pesticides).

The compound threo-1-phenyl-2-nitropropane is already present 1,3-diol diacetate as an intermediate of a chloramphenicol synthesis known. It was made by reacting cinnamyl alcohol acetate with sodium nitrite and reacting the thus obtained DL-erythro-1-phenyl-1-nitroso-2-nitro-3-acetoxypropanes prepared with sulfuric acid acetic anhydride. It is however, no effect of this compound is known (C.A. 50, 1965, page 6360).

In C.A. 60 (1964), column 10 529f (XIX) and g or the This paper is based on work by Z. Eckstein et al in "Bulletin of the Academie Polonaise des Sciences S'rie des sciences chimiques "Volume XI, No. 12, 1963, pages 687 to 693, the fungicidal activity of some 2-nitropropane di-1,3-ol derivatives of the formula

or their diacetates, where R 'is methyl or isobutyl stands, described. The fungicidal activity of these compounds is not yet satisfactory.

The invention is based on the object, pesticides, especially pesticides, with superior Crop protection, especially superior Effects against pests, create.

This task is carried out by the new plant protection product according to Claim solved.

Compared to the last discussed literature  known compounds has the invention used Compound threo-1-phenyl-2-nitropropane-1,3-diol diacetate a much more pronounced fungicidal activity, as the following Comparative Example 13 shows below.

As customary excipients, which in the erfindungsgmäßen plants may also be contained, in particular solvents, solubilizing or solubilizing agents, carriers, Diluents, dispersants, surface-active Agents, duration regulators, adhesives or adhesion promoting agents and / or stabilizers mentioned.

In general, the crop protection agents according to the invention contain the threo-1-phenyl-2-nitropropane-1,3-diol diacetate in in an amount of 0.01 to 96 wt .-%, in particular 0.5 to 90% by weight. The excipients are then in the supplement 100% required quantity.

The contained in the plant protection products according to the invention threo-1-phenyl-2-nitropropane-1,3-diol diacetate, as well  its mixtures with its erythro-isomer erythro-1-phenyl 2-nitropropane-1,3-diol diacetate has or have namely as already mentioned valuable superior plants protective effects, especially against pests.

Thus, the crop protection agents according to the invention have a strong fungicidal and acaricide effect without harmful phytotoxic effect. For certain  Insect species is also a significant antipyretic Determine effect ("antifeedent" effect); so eat For example, the locusters with the invention Plant protection products do not spray plants. Also their aphicidal action or action against aphids is considerable. Moreover, they make some of them angry Crops germinate and also affect the Dry matter accumulation stimulating. The invention Plant protection products thus increase in the tests applied doses in pre-run application individual treated plants dry matter accumulation as well as the germination readiness, while at the post-application neither positive plant growth-promoting nor negative phytotoxic effects zei gene.

The crop protection agents according to the invention were found in the experiments in combating the following fungal strains as effective:

Alternaria tenuis,
Monilia fructigena,
Fusarium graminearum,
Gladosporium herbarum,
Trichotecium roseum,
Fusarium oxisporum,
Aspergillus flavus,
Aspergillus oryzae,
Penicillium species,
Mucor mucedo,
Rhizopus nigricans,
Bothrytis cinerea,
Phytophthora infestans,
Endostigmas pirina,
Nigrospora oryzae and
Mildews.

The biological effect of the plant protection agents according to the invention was mainly on the following crops examined:

Wheat,
Corn,
Millet,
Mustard,
Sunflower,
Potato,
Pea,
Grapes and
Apple.

Part of the methods of investigation used was that in Breeding vessels or soil cultures a corresponding amount the plant to be grown (for example, in the case of Wheat, millet, sunflower seeds, mustard or pea 100 grains) was sown and under assurance of for germination optimal conditions the percentage germination in the treated and untreated culture vessels respectively Soil cultures and also the height, the green weight  and the dry weight of the 14-day seedlings were examined. The treatment was given with a dose of 6 kg / ha of the respective active ingredient of the invention Plant protection product in Vorlaufanwendung or with the Pesticide according to the invention in post-application carried out.

When treated with a prepared according to Example 8 Mixture of threo-1-phenyl-2-nitropropane-1,3-diol diacetate with erythro-1-phenyl-2-nitropropane-1,3-diol diacetate, that ground to a particle size of 1 to 20 μ has been in pre-run application respectively with one prepared from this according to Example 9 or 10 The follow-up preparation was used in the following Table 1 summarized results (blind or Control experiment = 100%).  

Table 1

Furthermore, 0.1 to 1% strength solutions of the same, as well as 0.1% strength 2, of the plant protection compositions according to the invention containing threo-1-phenyl-2-nitropropane-1,3-diol diacetate in acetone and diluting with water were used , 3-dicyano-1,4-dithiaanthraquinone [Delan] and 0.1% N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboxylic acid imide [Difolpet] as comparison substances different types of fungi by means of the "disc procedure" treated, with a blind or control trial was run without treatment. The extent of inhibition of colony diameter was determined. The obtained activity indices are summarized in the following Table 2. Under activity index is the toxic effect on the fungus, relative to the effect in the blind or control experiment, by visual evaluation (1 = complete inhibition, 2 = partial plaque, 3 = full plaque, but other biological effect [for example morphological transformation] compared to the blank test, 4 = no difference compared to the blind test).

It is clear from Table 2 above that the Active substance threo-1-phenyl-2-nitropropane-1,3-diol diacetate of the invention Pesticides superior to the comparison substances or at least about as effective as this one.

In the following Tables 3 to 6, the results of further impact studies are compiled.

Table 6

For Table 6 above, the threo-1-phenyl-2- nitropropane-1,3-diol diacetate as such, that is in not prepared form used.

Investigations were also carried out to determine the bactericidal activity. For this purpose, the molten nutrient medium was mixed with the bacterial suspension, then poured and allowed to solidify. Holes were drilled into the solidified medium and the aqueous solutions of the substance to be investigated threo-1-phenyl-2-nitropropane-1,3-diol diacetate were pipetted into this. From the diameter of the zones of inhibition formed around these sites, the percent inhibition was based on a 0.1% aqueous solution of D-threo-1-p-nitrophenyl-2-dichloroacetamidopropane-1,3-diol [chloramphenicol]. as comparison means. The results obtained are summarized in Table 7 below.

From the above Table 7, the good effect of the invention Also produced as a bactericide.

Furthermore, field trials were carried out.

a) on maize (Fusarium infestation)

On trial plots with areas of 0.5 ha each were 3 different treatments performed before sowing, taking the prepared spray liquors into the ground were incorporated. As a crop, corn was the Variety Mv Sc 405 examined.

Treatment A:
6 l / ha of a compound containing

• a) 0.6 kg / l S-ethyldi-n-propyl thiocarbamate and
• b) 0.05 kg / l dichloroacetyldiallyl amide.
  [Eradican 6 E of the company Stauffer Chem. Co.].

Treatment B:
6 l / ha of the agent used in treatment A.
+2 l / ha of an emulsifiable concentrate preparation containing 20% by weight of threo-1-phenyl-2-nitropropane-1,3-diol diacetate {EC 20}
[Example 6 {Inventive}].

Treatment C:
6 l / ha of the agent used in treatment A.
+6 l / ha of an emulsifiable concentrate preparation containing 20% by weight of threo-1-phenyl-2-nitropropane-1,3-diol diacetate {EC 20}
[Example 6 {Inventive}].

After the treatments, the corn was sown. After 1 month Fusarium infestation was determined from 100 plants each. Also the green weight and the dry weight of the plants as well as the average crop of 100 plants each determined, the results of treatment A (without the erfndungsgemäßen agents) as 100% based were. The results are in the following Table 8 compiled.  

Table 8

The same treatments were used with another Number of remedies performed.

Treatment A ':
5 l / ha of an emulsifiable concentrate preparation containing 50% by weight of 2-ethyl-6-methylphenyl-N- (2'-methoxy-1'-methylethyl) -chloroacetamide
[Dual 50 EC].

Treatment B ':
5 l / ha of the agent used in treatment A '
+2 l / ha of an emulsifiable concentrate preparation containing 20% by weight of threo-1-phenyl-2-nitropropane-1,3-diol diacetate {EC 20}
[Example 6 {Inventive}].

Treatment C ':
5 l / ha of the agent used in treatment A '
+6 l / ha of an emulsifiable concentrate preparation containing 20% by weight of threo-1-phenyl-2-nitro-propane-1,3-diol diacetate {EC 20}
[Example 6 {Inventive}].

The results are summarized in the following Table 9 posed.

Table 9

b) grapes and apples

The emulsifiable concentrate preparation according to the invention containing 20% by weight of threo-1-phenyl-2-nitropro pan-1,3-diol diacetate {EC 20} (Example 6) was used against the  Mildew tested on wine and apples, using as reference a 50% wettable powder (50 WP) of methyl 1- (n-butylcarbamoyl) -benzimidazol-2-ylcarbamate [Fundazol the company Chinoin] was used. The experiments were carried out on small parcels. For wine (variety Veltelini) each 100 grapes were examined and it was their Infestation determined as a percentage. For the apples (variety Jonathan) was at 10 shoots of infestation of the surface evaluated. The results of these comparative experiments are in the following Table 10.  

Table 10

The above tables 8 to 10 show the superiority the agents according to the invention also in the field trials out.

The plant protection agents according to the invention can be used in Form of common preparations, such as solutions, emulsions, Suspensions, powders, wettable powders, soluble powders, Dusts, foams, pastes, granules, aerosols, Suspension or emulsion concentrates and Seed powders. Practical applications For example, wettable powders having an active ingredient content of 50%, emulsifiable concentrates, colloidal Suspension concentrates, microgranules and spray liquids or sprays.

These preparations can in a conventional manner be prepared, for example by mixing the Active ingredients with diluents, that is liquid solutions or diluents, pressurized liquefied gases and / or carriers, if appropriate using surfactants, that is Emulsifiers and / or dispersants and / or foaming agents. If water is the extender may be organic solvents as auxiliary solvents serve.

As liquid solvents, for example, the following are: Aromatic compounds, in particular aromatic hydrocarbons, such as xylenes, Toluene and alkylnaphthalenes, aromatic chlorine compounds, in particular aromatic chlorinated hydrocarbons, such as Chlorobenzenes, aliphatic chlorinated hydrocarbons, such as Methylene chloride and ethylene chloride, aliphatic hydrocarbons, such as paraffins, alicyclic hydrocarbons  substances, such as cyclohexane, alcohols, for example butanol and glycols, and their ethers and esters, ketones, such as acetone, Methyl ethyl ketone and cyclohexanone, polar solvents, such as dimethylformamide and dimethylsulfoxide, and water as well Mixtures of such.

Under liquefied gaseous extenders or Carriers are those liquids which are at Normal temperature and under atmospheric pressure are gaseous, as Aerosol propellants, for example, halocarbons and butane, propane, nitrogen and carbon dioxide, as well To understand mixtures of such.

Examples of solid carriers are natural minerals, such as kaolins, clays, talc, chalk, quartz, montmorillonite and diatomaceous earths, and ground synthetic minerals, such as fumed silica, alumina and Silicates, as well as mixtures of such. As solid carriers for granules are essentially the following in question: broken and fractionated natural rocks, for example, calcium carbonate (calcite), marble, pumice, Sepiolite and dolomite, as well as synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corncobs and tobacco stalks, and mixtures of such.

The emulsifying and / or foaming agents especially non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, Alkyl sulfates, alkyl sulfonates, aryl sulfonates and protein hydrolyzates, or mixtures thereof. As a dispersant, for example, lignin, sulfite liquors and methylcellulose, as well as mixtures of such.  

Examples of adhesives which in the inventive Plant protection products may be included Carboxymethylcellulose, natural and synthetic powdered, granular or latex-shaped polymers, such as gum arabic Polyvinyl alcohol or polyvinyl acetate, as well as mixtures of such.

Furthermore, in the crop protection agents according to the invention Dyes, such as inorganic pigments, and / or Trace nutrients, for example salts of boron, iron, copper, Cobalt, manganese, molybdenum and / or zinc.

The application of the active compounds of the formula I may be in the form of commercial preparations thereof and / or these Preparations prepared use forms done.  

The active ingredient content of the commercial preparations prepared application forms can vary widely. So the drug concentration of these applications 0.000001 to 100 wt .-%, preferably 0.01 to 10 wt .-%, amount. The application takes place in one of the application forms adapted usual way.

The contained in the plant protection products according to the invention threo-1-phenyl-2-nitropropane-1,3-diol diacetate be prepared in such a way that 1-phenyl-2-nitropropane 1,3-diol of the formula

or an alkali salt thereof with an acetic acid or from her deducing acylating agent is implemented under mild conditions. Provided Mixtures of the erythro and threo isomers may arise these are separated the threo isomer in the usual way.

Suitably acylating is an acetic acid halide and / or acetic anhydride used.  

The reaction may be advantageous in a solvent be performed. It can also be used without it of a solvent.

When starting from an alkali metal salt of 1-phenyl-2-nitropropane 1,3-dioles of Formula II is considered, then it is special Advantageously, the alkali metal salt, preferably sodium salt, of 1-phenyl-2-nitropropane-1,3-diole of the formula II in a solvent, for example in acetic acid, at about 40 ° C with an acetic acid halide as the acylating agent implement. Over the course of this approximately 8 hours lasting reaction the product obtained in good yield contains the threo and erythro isomers in a ratio of about 1: 1, from which crystallizes the threo isomer can be separated.

Also advantageous is the embodiment, in which the reaction is carried out without solvent. In this case, the pure threo diastereomer of 1-phenyl-2-nitropropane-1,3-diole of the formula II also in good yield to the corresponding threo-1-phenyl-2-nitro propane-1,3-diol diacetate of the formula I are reacted.

In this case, according to a specific preferred embodiment the reaction without solvent with acetic anhydride as acylating agent in the presence of a catalytic amount of a mineral acid or boron trifluoride, expedient in the form of Bortrifluoridätherates, or a carboxylic acid chloride corresponding to the carboxylic acid anhydride carried out.  

Of course, the reaction can also be done with a mixture of Acetic anhydride and an acetic acid halide, in particular Acetic acid chloride, be carried out.

The starting compounds, the 1-phenyl-2-nitropropane 1,3-diol of the formula II or their alkali metal salts are as already mentioned known and easily accessible Links. The sodium salt can be prepared in a known manner (J.A.C.S., 1949, page 2465). The threo isomer of 1-phenyl-2-nitropropane 1,3-dioles may suitably be obtained from the corresponding sodium salt (German Patent 10 64 937) or even more advantageous directly in one stage from benzaldehyde and Nitroethanol produced with an alkali metal hydroxide as a catalyst have been.

The invention will be apparent from the following examples explained in more detail.  

Example 1 Wettable powder preparation

It became threo-1-phenyl-2-nitropropane-1,3-diol diacetate or a mixture of threo-1-phenyl-2-nitropropane-1,3-diol diacetate with erythro-1-phenyl-2-nitropropane-1,3-diol diacetate in a jet or micronizing mill at least 80% to a particle size of 1 to 20 μ zukleinert. The millbase was with 1 to 5 wt .-% of a neutral or non-basic wetting agent and with 20 to 60% by weight of a solid inert binder such as kaolin or bentonite, homogenized. The thus obtained wettable Powder contained about 60 to 82% by weight of active ingredient.

example 2 Wettable powder preparation

The procedure was as described in Example 1, with the difference that in the course of the  Grinding and homogenizing except the inert binder also a stability-enhancing acidic buffer substance, for example, potassium or sodium dihydrogen phosphate, lactic acid or tartaric acid, in an amount of 10 to 20% by weight was added. The wettable powder preparation thus obtained contained about 54 to 76% by weight of active ingredient.

example 3 Sprühpräparat

It was threo-1-phenyl-2-nitropropane-1,3-diol diacetate in benzene or in a benzene homologue (such as toluene or a xylene) to one 0.1 to 1% solution dissolved. The solution was 1 to 3% wetting agent and 1% of a liability-increasing auxiliary substance added. The mixture was mixed with a propellant gas (for example a chlorofluorohydrocarbon [Freon], Propane / butane gas or carbon dioxide) in aerosol bottles, whose nozzle is a fine drizzle or Spray sent out.

example 4 Emulsifiable concentrate

At least one threo-1-phenyl-2-nitropropane-1,3-diol diacetate was added 80% ground to a particle size of 1 to 20 μ, then it became with the same weight of an inert organic solvent mixed and still in the course of homogenization supplemented with 5 to 7% of a wetting agent. The thus obtained emulsifiable concentrate contained about 47 to 48 wt .-% active ingredient and could with the solvent used arbitrarily be diluted.  

example 5 microgranules

It was threo-1-phenyl-2-nitropropane-1,3-diol diacetate in chloroform or dissolved in another chlorinated hydrocarbon, wherein a solution was prepared whose concentration was to be applied Homogenizer corresponded. This solution was in a "wet" way of working Homogenizer, for example, a coating pan, on a solid carrier (for example perlite or coke powder) applied with a particle size of 0.1 to 1 mm and the Active ingredient content was adjusted to 10 to 30 wt .-%.

example 6 Emulsifiable concentrate

1 part by weight of threo-1-phenyl-2-nitro-1,3- Propandioldiacetat with 2 parts by weight of a 5% solution of acetic acid in xylene and with 0.28 parts by weight a non-basic wetting agent homogenized. The mixture was xylene (or isophorone or cyclohexane) diluted to an active ingredient content of 20 wt .-%.  

Compare recordable 7

This example shows that in the inventive Pesticide used threo-1-phenyl-2-nitro Propan-1,3-diol diacetate a more pronounced fungicidal activity has as the from C. A. 60 (1964), column 10 529f (XIX) and g known 2-nitropropandi-1,3-ol derivatives of formula given above, in which R 'is methyl or Isobutyl stands.

The fungicidal action of the test compounds over the Mushroom Helminthosporium sativum was cultivated using the in Pest. Sci. 13, 557-562 (1982) determined. The results obtained are as follows Table summarized.

test compound Total inhibitory concentration (%) on agar medium against Helminthosporium sativum Compound A | 0,001% Compound B 0.1% Compound C 0.05% Connection A = Compound according to the present invention Compound B = Compound (I) described in said reference, d. H. R 'represents the methyl group Compound C = Compound (IV) described in said reference, d. H. R 'represents the isobutyl group.

From the experimental results summarized in Table 11 above shows that the inventively used Compound threo-1-phenyl-2-nitropropane-1,3-diol diacetate fungicidal activity of the two comparative compounds A and B exceeds 2 or 1½ orders of magnitude.

Claims (1)

Plant protection agent based on a 2-nitropropane-1,3-diol derivative, characterized in that it comprises threo-1-phenyl-2-nitropropane-1,3-diol diacetate of the formula contains.