DK157896B - PLANT PROTECTIVE AGENT WITH FUNGICID, ACARICID AND APHICID EFFECTS AND INHIBITIVE EFFECTS ON CERTAIN INSECTS - Google Patents

Description

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The present invention relates to a novel plant protection product with fungicidal, acaricidal and aphicidal effects and inhibitory effect on the appetite of certain insects.

The present plant protection agent is characterized in that it contains as an active component one or more nitroalkanol derivatives of the formula N0

// \\ - CH - CH - CH- I

10 \ _ / I I 2

V / 0 - CO O - CO

I I

R R

wherein R is an alkyl group having 1-5 carbon atoms or optionally with one or more halogen atoms substituted phenyl group, in an amount of 96-0.01% by weight, preferably 90-0.5% by weight, optionally with known active plant protection compounds and, moreover, the necessary amount of common adjuvants for the preparation of plant protection agents.

The only compound known by the active substances is threo-1-phenyl-2-nitro-1,3-propanediol diacetate, an intermediate of a chloramphenicol synthesis produced by the reaction of β-phenylacrylic alcohol acetate (cinnamon alcohol acetate) with sodium nitrite and reaction of the resulting DL-erythro-1-phenyl-1-nitroso-2-nitro-3-acetoxy-propane with sulfuric acid acetic anhydride. No effect of this compound is known (C.A. 50, 1956, page 6360).

This method, due to its stereochemical conditions, only allows the threo product to be produced.

Due to the asymmetry center at C3C2, there are 4 isomeric modifications of the compounds of formula I which are proportional to each other by diastereomeric or optical isomerism. Thus, the two diastereomers, the threo and the erythro isomers, form a racemate which can be divided into right

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2 and left-end optical isomers. Said known compound is the threo isomer where R is a methyl group.

U.S. Patent No. 3,242,039 discloses fungicidically active compounds which are nitrosubstituted alkyl esters of aliphatic ketocarboxylic acids, i.e. unlike compounds of formula I, they do not contain any aromatic groups. Furthermore, US Patent Specification states that the known compounds are used against fungi which are harmful to horticulture, ie. they are active against completely different microorganisms than compounds of formula I, and finally they must be used at a concentration of from 30 ppm, while the compounds of formula I are active already from a concentration of 3 ppm, cf. below test results.

In addition to the nitroalkanol derivative of the formula I, depending on the particular purpose, the agent of the invention may also contain another known active ingredient for plant protection products. In addition, the agent may contain the usual adjuvants for the preparation of plant protection products. Examples thereof are solubilizing agents, carriers, diluents and / or dispersants and / or surfactants and / or substances for controlling the duration of the effect and / or substances to promote the adhesion and / or stabilizer in an amount up to 99.99%.

The active substances of formula I can be transferred to the usual 25 compositions such as solutions, emulsions, suspensions, powders, powders, soluble powders, nebulizers, foams, pastes, granules, aerosols, suspension emulsifying concentrates, seed powders, etc. Suitable forms are e.g. 50 WP (wettable powder with 50% active substances), EC (emulsifiable concentrate), Col. (colloidal suspension concentrate), microgranules, spray, etc.

These compositions are prepared in a manner known per se, e.g. by mixing the active substances with stretch agents, ie. liquid solvents, liquefied 35 gases under pressure and / or carriers, optionally using surfactants such as emulsifiers 3

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and / or dispersants and / or foaming agents.

If water is used as an excipient, organic solvents can be used as an auxiliary solvent.

As liquid solvents, e.g. These include: aromatics such as xylene, toluene or alkyl naphthalene, chlorinated aromatics such as chlorobenzene, chlorinated aliphatic hydrocarbons such as methylene chloride or ethylene chloride, aliphatic hydrocarbons such as paraffins, alicyclic hydrocarbons such as cyclohexane, alcohols such as butanol or glycol, and their ethers and esters, ketones such as acetone, methyl ethyl ketone or cyclohexanone, polar solvents such as dimethyl formamide or dimethyl sulfoxide, and water.

By liquefied gaseous extenders or carriers, such liquids which are gaseous at normal temperature and under normal pressure are considered e.g. aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. As solid carriers may be used natural stone flour such as kaolin, clay soil, talc, chalk, quartz, mont-morillonite or diatomaceous earth, and synthetic stone flour such as high-dispersion silica, alumina and silicates. Preferred as solid carriers for granules are the following: finely divided and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems. As an emulsifier or foaming agent, nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfates, alkylsulfonates, arylsulfonates and protein hydrolysates. As a dispersant, e.g. lignin, sulfite waste liquor and methyl cellulose are used.

Adhesives such as carboxymethylcellulose, natural and synthetic, powdery agents can be used in the compositions.

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prepared, granular or latex-like polymers such as gum arabic, polyvinyl alcohol or polyvinyl acetate.

Furthermore, dyes such as inorganic pigments and trace nutrients such as salts of boron, iron, copper, cobalt, manganese, molybdenum and zinc can be used.

The use of the active substances according to the invention takes place in the form of the commercially available compositions and / or of the uses prepared from these compositions.

The content of active substance in the forms of use prepared can be varied within a wide range. The concentration of active substance in the forms of use can be between 0.000001 and 96% by weight, preferably between 0.01 and 10% by weight. The application takes place in a manner customary to the application.

The active substance of formula I in the composition of the invention

The preparation is prepared by adding 1-phenyl-2-nitro-1,3-propanediol of formula II

_. NO

20 / f \ I 2 1 y - CH - CH - CH2 11

OH OH

25 or its alkali metal salt is reacted with an acylating agent.

It has now been found that acyl derivatives of formula I can be prepared without difficulty and without side reactions when 1-phenyl-2-nitro-1,3-propanediol of formula II - either in threo or in erythro isomer form - or a the alkali metal salt thereof is reacted with an acylating agent under mild conditions. As the acylating agent, acid halide and / or acid anhydride is preferably used. The reaction is carried out in solvent or without the use of a solvent.

Starting from the alkali metal salt of 1-phenyl-2-nitro-1,3-propanediol, it is particularly advantageous to react alkali metal.

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the lime metal salt of propanediol of formula II, preferably its sodium salt, in a solvent, e.g. acetic acid, at approx. 40 ° C with an acid halide. In the course of this reaction, which ends in approx. 8 hours, the product obtained with good yield contains threo and erythro isomers in a ratio of 1: 1, which isomers can be separated by crystallization.

Another advantageous process variant is conducting the reaction without solvent. In this case, the pure threo or erythro diastereomer can also be converted to the corresponding threo or erythro derivative with good yield.

A further advantageous embodiment of the process is that the reaction is also carried out without a solvent with an acid anhydride as an acylating agent in the presence of a catalytic amount of a mineral acid or an acid chloride. Of course, the reaction can also be carried out with a mixture of an acid anhydride and an acid chloride.

The starting compound, the propanediol of formula II, 20, is, as already mentioned, a known and readily available compound. Starting from the sodium salt, it can be prepared in known manner (J.A.C.S. 1949, p. 2465). If used as a starting compound of the formula II threo or erythro isomer, the preparation may conveniently be made from the sodium salt (DE patent no. 1,064,937) or preferably immediately in one step from benzaldehyde and nitroethanol with alkali metal hydroxide as catalyst. .

The compounds of formula I and their mixtures have a strong fungicide and acaricidal action without harmful phytotoxic effect. Certain insect species also observe a significant "antifungal effect; thus, grasshoppers do not consume plants sprayed with the agent of the present invention. Also, the aphicidal effect of the agent of the invention is significant. In addition, the agents for some culture plants stimulate and act as well. stimulating on the solids accumulation.

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... The 6 clays according to the invention increase the preemergent used in the doses used in the experiments in individual treated plants, the dry matter accumulation as well as germination readiness and at the same time in the postemergic treatment exhibit neither positive nor negative phytotoxic effects.

The compounds of formula I have been shown to be effective in the control of the following fungal strains:

Altemaria tenuis Monil ia fructigena 10 Fusarium graminearum Gladosporium herbarum

Trichotecium roseum Fusarium oxisporum

Aspergillus flavus Aspergillus oryzae

Penicillium species Mucor mucedo

Rhisopus nigricans Bothrytis cinerea 15 Phytophtora infestans Endostigme pirina

The biological effect of the agents of the invention was mainly investigated on the following culture plants:

Wheat, corn, millet, mustard, sunflower, potatoes and 20 peas.

The method used consists in sowing in pots or soil cultures a quantity adapted to the size of the culture to be grown (eg when it comes to wheat, maize, millet, sunflower, mustard or peas 100 25 seeds ), and ensuring optimum conditions for germination, the germination percentage is tested in the treated and untreated pots and in addition the height, green weight and dry weight of the 14-day seedlings. The treatment is carried out at a dose of 6 kg / ha of the active substance preemergent or 30 with the medium postemergent.

Preemergence treatment with the mixture of the threo- and erythro-1-phenyl-2-nitro-1,3-propanediol diacetates prepared according to Example 9, which were milled to a grain size of 1-20 µm, or postemergent based on these active substances the preparations prepared according to example 10 or 11 give the results listed in Table I (control = 100%).

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Table I

Sprouting Height Green Weight Treatment_Plant_Percent _% _% 5 Preemergent Wheat 63 105.5 105 "Corn 108 99 107" Mill 111 110 120 "Mustard 116 104 121" Sunflower 108 98 120 10 "Pea 100 118 131

Post-grain wheat - - 130 "corn - - 125" flax - - 130 15 "peppers - - 130" tomatoes - - 120

Using a 0.1-1% solution in acetone and diluting with water of erythro-1-phenyl-2-nitro-1,3-propanediol-diacetate prepared according to that of Examples 1, 2 or 3 described method, the effect on various fungal species is investigated by the "plate method". The extent of the colony diameter inhibition is compared to the inhibition by treatment with 0.1% "Delan" (2,3-dicyano-1,4-dithiaanthraquinone) and 0.1% "Di-25" [N- (1,1,2-tetrachloroethylthio) -4-cyclohexene-1,3-dicarboximide] and in untreated control experiments. The activity indices obtained are given in Tables II and III. Activity index is understood to mean the toxic effect exerted on the fungus relative to the effect exerted on the untreated control by visual assessment (1 = complete inhibition, 2 = partial coating, 3 = complete coating, but other biological effect, e.g. transformation, versus control, 4 = no difference compared to control).

Table II

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Ervthro-diacetate * The "Difollan" pet "Concentrate fungus 0.1% 0.3% 0.5% 1.0% 0.1% 0.1% trol

Bothrytis cinerea 11113 1 4 10 Cladesporium herbarum 11113 - 4

Fusarium oxisporum 2 1114 1 4 15

Penicillium species 2 1113 - 4

Aspergillus 20 oryzae 2 1113 - 4

Alternaria tenuis 2 2 1 1 1 4 25 9

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Table III

Botrytis Fusarium Penicillium Aspergillus Treatment cinerea oxisporum_sp._oryzae_ 5 Threo - diacetate 0.1% 2 11 1 0.3% 111 1 10 0.5% 111 1 1.0% _1_1_1_1_

Threo dipropionate 0.1% 2 2 1 1 0.3% 111 1 0.5% 111 1 2Q 1.0% __1_1_1_1_

Dibenzoate 0.1% 2 2 2 1 0.3% 112 1 25 0.5% 111 1 1.0% _1_1_1_1_ "Part" 30 0.1% _1_4_3_3_

Untreated_4_4_4 _._ 4_ 35 In Tables IV-XII, the results of the other efficacy studies are presented.

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10

Table IV

Sprøjteopløsn. Sample concentration orga- Mortality

Connection% nism% D ~ "

Erythio-1-phenyl-0.02 0.02 Tetranyl-4.6 nitro-1,3-propaned-0.2-chloro-76.0-oldiacetate (50 WP) 2.0 ticae 100.0 10 Threo and erythio 0.02 13.5 2-Nitro-1-3-propyl 0.2 88.8 Pandiol diacetate 2.0 97.3 (50 WP) "Diazinori" - 0.2 100.0 " Fenkapton "**)

Threo and erythro 2.0 Megaurea 88.0 1-Phenyl-2-nitro-2.0 vicae 70.0 20/3 Propane-diol diacetate "Dimetoate" (dimethyl S- (N-methyl) -25 carbamylmethyl) - dithiophosphate 2.0 100.0 after 24h 48h 30%

Compound according to 0.01 Acyrtho-90 Ex. 4, 1-20 μια 0.1 siphon 95 100 1.0 (Aphids) 100 100 35 "Methylparathione" (0,0-dimethyl-O- [p-nitrophenyl] - 0.5-Diethyl-O-2-isopropyl-4-methyl-6-pyrimidyl-thio phosphate 45 **) S- (2,5-Dichlorophenylthiomethyl) -0.0 -diethyldithiophosphate 11

Table V

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Sprøjteopløsn. Sample concentration of organ- Antifodium- Compound _% _ nism_ effect

Threo- and erythro-0.1 indian unchanged l-phenyl-2-nitro-0.3 unchanged 1,3-propanedioldi-0.0 grass-consumed 10 acetate mare

Table VI 15

Spray theopl. Inhibition of concentrate germ

Compound,% Sample Organ_ 0.1% 1.0% Threo-1, 0.1 and 1.0 Alternaria tenuis partial total phenyl-2-Fusarium graminearum "" nitro-1,3-Trichotecium roseum "" propanediol-Aspergillus flavus "diacetate Penicillium species" 25 (50 WP) Rhizopus cinerea none partial

Phytophtora infestans partial total Endostigme pirina "”

Monilia fructigena none "30 12

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Table VII Spray Tea Solution.

concentration Infection rate 5 Compound _% _ Specimen _% _

Threo-1- 0.05 Potato Leaves Infected 5.0 Phenyl-2- 0.1 Cated with Phytophtora 0.0 Nitro-1.3-1.0 Infestance 0.0 10 Propanedial Diacetate (50 WP) "Zineb" 0.3 20.0 (zinc-ethylene bis-thiocarbamate) (80 WP)

Untreated - 100.0 Threo-1- 0.1 Phytophtora, artificial 0.0 phenyl-2 infection on potato-nitro-1,3-fault cutter propanedial diacetate 25 (5? WP) .................................................. .....

Threo-l-0.0Ϊ Potato leaves infected with 26 phenyl-2,1,1 with Fusarium 0 nitro-1,3 '1,0 0 30 propanedial diacetate (50 WP) "Zineb" (zinc 0.1 40 35 ethylene) -bis- thiocarbamate (80 WP), q Untreated - 50

Connection according to 0.1 Potato Leaves Infected 5 Ex 4 (50 WP) with Phytophtora infestans "Orthocid" (N-0.2 0 45 [trichloromethylthio] -4-cyclohexene-1,2-dicafboximide)

Untreated - 60 50

Connection according to Phytophtora, artificial in- 0. 4 0.1 section on potato cut - _ter___ 55 Note to Table VII:

Effect of "Zineb" (zinc ethylene bis-thiocarbamate) (80 WP) in 0.2% 1s solution is considered 100%.

Table VIII

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13

Sprøjteopl. Inhibition of spo- Effect

Connection concentrates. % _% _ 5%,% Specimen 0.1% 1.0% 0.1% 1.0%

Connect 0.1 and Alternaria tenu's total total 111 333 distribution 1.0 according to. Fusarium graminea- 10 ex. 4 compartments "" 300 833 (50 WP) Trichotecium roseum "" 90 300

Aspergillus flavus 150 466

Penicillium species "11 112 275

Bothrytis cinerea "" 166 316 15 Rhizopus nigricans partial "0 170

Mucor mucedo "" 0 266

Table IX

Compound Inhibition in% at concentrations (ppm) of active substance of 25

Svampeart_1_3_5_10_20_50

Threo-diacetate

Nigrospora oryzae (N.o.) 13.6 100.0 100.0 100.0 100.0 100.0

Helminthosporium sativum (H.s.) _ 44.0 100.0 100.0 100.0 100.0 100.0 35 Threo-diacetate N.o. 9.6 - 91.3 93.1 100.0 100.0 H.s._0.0 66.8 100.0 100.0 100.0 100.0

According to Ex. 4 40 N.o. 0.0 - 32.1 100.0 100.0 100.0 Hs._8.1 - 34.2 95.3 100.0 100.0

According to Ex. 7 N.o. 11.5 34 72 - 100.0 45 H.s._5_ 15 68 - 100.0 "Zineb" (80 WP) N.o._3.3 - 12.7 18.6 - 71.2 50 In this experiment, the compounds of formula I have been tested pure.

In addition, to study growth inhibition, WP formulations have been added to suitable nutrient media in amounts which have given a concentration in the nutrient medium 14

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of active substance respectively. 0, 100, 500 and 2,000 ppm. The nutrient media is inoculated with the test organisms and growth inhibition is indicated by the control as base (= 0). The results are shown in Table X.

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16

Bactericidal efficacy studies.

The molten nutrient medium is mixed with bacterial suspension, poured into bowls and allowed to solidify. Holes are drilled in the solidified nutrient media and pipetted into these by the substances to be examined. Based on the diameter of the inhibition zones formed around these sites, inhibitions are determined in% based on the control. The results are shown in Table XI.

Table XI

10

Bacteria Percent inhibition 100 ppm 1000 ppm 2000 ppm 15 threo-erythro-threo-erythro-threo-erythro-diacetate diacetate diacetate

Escherichia 20 coli 30.7 11.5 46.1 23.0 53.8 30.7 S taphylococcus aureus 44.4 0.0 100 16.6 111.1 33.3 Mycobacterium peregrinus 43.3 0, 0 66.6 26.6 80.0 26.6

Bacillus subtilus 26.9 11.5 50.0 23.0 61.5 30.7 30

Serratia marcesceus 0.0 0.0 21.7 0.0 34.7 0.0

Xanthomonas pelargonii 17.3 - 43.4 - 60.8

As a control, a chloramphenicol solution having a concentration of 1000 ppm was used.

40

Field trials of maize (Fusarium attack).

45 On test parcels with a size of 0.5 ha, three treatments are applied before sowing, with the produced spray liquids being incorporated into the soil. As a cultural plant is tested 17

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corn of the variety etc. Sc 405.

Treatment A); 6 liters / ha "Eradican 6E" (manufacturer Stauffer Chem. Co.; active ingredient per liter 0.6 kg of s-ethyl dipropyl-thiocarbanate + 0.05 kg of dichloroacetyl diallylamide).

Treatment B1; 6 liters / ha "Eradican 6E" + 2 liters / ha 20 EC (20% emulsion concentrate) according to Example 11.

Treatment C 2: As B) but at 6 liters / ha 20 EC.

After the three treatments, the corn was sown. After 1 month of 10 months, the attack is determined by Fusarium on 100 plants. Also the weight in the green state ("green weight") and the dry state weight ("dry weight") of the plants as well as the average harvest per year. 100 plants have been determined.

The result is shown below, with the results of treatment 15 A) (without compound of formula I) being set to 100%.

Fusarium- Green- Dry- Average. Treatment attack weight weight harvest * 20 A) 22% 100% 100% 100% B) 6% 112% 108% 107% 25 C) 4% 115% 110% 109% * intended for the same water content.

Treatments A), B) and C) were repeated with the difference that 5 liters / ha of "Dual" 50 EC ("Dual" = 2-ethyl-6-methylpheny 1 -N- (2 - with thoxy-1-methylethyl 1) -chloroacetamide) instead of 6 liters / ha "Eradican 6 E". The results have been as follows;

Fusarium 35 Treatment attack Green weight Dry weight A) 27% 100% 100% B) 7% 110% 107% 40 C) 2% 118% 116%

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18 bl On grapes and apples.

The agent of Example 11 is tested against mildew on wine and apples. The experiments take place on small parcels. The wine 5 (black: Veltelini) is searched for every 100 grapes and the attack is measured in%. At the Apples (Black: Jonathan), the attack is assessed on the surface for every 10 shots. The results of this comparison experiment are shown in Table XII.

Table XII

Percent attack

Treatment Mildew on wine Mildew on apples 15 Untreated 36 43 "Fundazole" *) 10 kg / ha - 38 20 threo-1-phenyl-2 nitro-1,3-propane-diol diacetate 2 kg / ha 0 25 0, 4 kg / ha 0 0 0.04 kg / ha 4 0.29 *) "Fundazole": Manufacturer: Chinoin Active substance: Methyl 1- (butylcarbamoyl) benzimidazol-2-yl carbamate (50 WP)

The invention will be further elucidated in the following by way of examples.

Example 1

Preparation of erythro-1-phenyl-2-nitro-1,3-propanediol diacetate 158 g of 1-phenyl-2-nitro-1,3-propanediol sodium salt are mixed with stirring at a temperature below 20 ° C over 25 minutes. in 700 ml of acetic acid. Then add to

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19 the mixture over 35 minutes at a temperature not exceeding 20 ° C, 304 ml of acetyl chloride dropwise. The reaction mixture is stirred for 14 hours at 40 ° C, after which the separated sodium chloride is removed by filtration. To the filtrate is added 600 ml of petroleum ether. The mixture is stirred for 2 hours under cooling in ice water, whereupon a crystalline precipitate is filtered off.

Yield: 55 g corresponding to 25.6%.

Melting point: 81 - 82 ° C.

The crystal fractions recovered by repeated evaporation of the mother liquor consist of a mixture of diacetates of threo and erythro modifications.

Yield: 110.2 g corresponding to 51%.

Melting point: 55 - 61 ° C.

15 The substances thus obtained can be used together or separately for plant protection.

Example 2 Preparation of erythro-1-phenyl-2-nitro-1,3-propanediol diacetate 4.9 g of erythro-1-phenyl-2-nitro-1,3-propanediol is dissolved in 14.7 ml of glacial acetic acid, and 7.85 ml of acetyl chloride are added to the solution at room temperature. The mixture is kept at 40 ° C for 6 hours, then left at room temperature overnight. A lot of petroleum ether is added to the solution and it is left in the refrigerator for 4 hours. The separated crystalline product is filtered and washed with petroleum ether.

Yield: 3.08 g corresponding to 44%.

Melting point 819 ° C.

35 20

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Example 3

Preparation of erythro-1-phenyl-2-nitro-1,3-proanediol diacetate 5 8.0 g of erythro-1-phenyl-2-nitro-1,3-proanediol is dissolved in 11.2 ml of acetic anhydride and the solution is added slowly drop 11.2 ml of acetyl chloride at a temperature not to exceed 40 ° C. The mixture is kept for an additional 8 hours at 40 ° C, then it is poured onto 30 g of ice while stirring, and slowly diacetate is excreted. This is kept for 2 hours at 0 ° C. 11.75 g of crude product is recovered, which is recrystallized from 66 ml of ethanol. The filtered crystals are washed with petroleum ether.

Yield: 4.7 g corresponding to 41%.

Melting point 79 - 80 ° C.

Example 4 Preparation of threo-1-phenyl-2-nitro-1,3-propanediol-dibenzoate 19.7 g of threo-1-phenyl-2-nitro-1,3-propanediol is slowly mixed with 28 g with stirring. (24.1 ml) of benzoyl chloride 25 in such a way that the temperature does not exceed 20 ° C, then the temperature is raised to 85 - 90 ° C and the mixture is kept at this temperature for 7-8 hours, then left overnight. Then the dibenzoate is precipitated with diethyl ether. After filtration, the product is washed acid-free with petroleum ether.

Yield of crude dibenzoate: 19.6 g, corresponding to 48.5%. Recrystallized from ethanol / tetrahydrofuran: 15.8 g corresponding to 80.5%.

Melting point: 130.5 - 132 ° C.

35 21

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Example 5

Preparation of threo-1-phenyl-2-nitro-1,3-proopanediol di-palmitate 5

A mixture of 10 g of threo-1-phenyl-2-nitro-1,3-propanediol and 55.8 g of palmitoyl chloride is stirred for 8 hours at 80 ° C. After cooling, the reaction mixture is mixed with petroleum ether, after briefly the separated crude product 10 is filtered off and washed with petroleum ether. Once recrystallized from ethanol, the yield is 9.95 g, corresponding to 29.3%. Melting point: 51-53 ° C.

Example 6 15

Preparation of threo-1-phenyl-2-nitro-1. 3-propanediol-diphenyl nvlacetat

A mixture of 4.0 g of threo-1-phenyl-2-nitro-1,3-propanediol and 9.4 g of phenylacetyl chloride is stirred for 5 hours at 70 ° C and then for 10 hours at 85 ° C. After cooling, the reaction mixture is cleaved with ice and left overnight. The product, which is separated in the form of a thick oil, is separated from the aqueous portion, dissolved in 15 ml of diethyl ether, dried with magnesium sulfate and filtered. The resulting solution is added with 25 ml of petroleum ether and filtered after a few days. the separated crystalline product (5.6 g) is taken off and peeled with 15 ml of ethanol and left in the refrigerator. The next day, the mixture is filtered and washed with cold ethanol. The crude product thus obtained is recrystallized from 12.5 ml of ethanol and the filtered product is washed with cold ethanol and petroleum ether.

Yield: 4.1 g, corresponding to 46.6%.

Melting point: 63 - 64 ° C.

35 22

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Example 7

Preparation of threo-1-phenyl-2-nitro-1,3-propanediol di-p-chlorobenzoate 5

A mixture of 1.95 g of threo-1-phenyl-2-nitro-1,3-propanediol and 5.35 g of p-chlorobenzoyl chloride is stirred for 14 hours at 85 - 90 ° C. Ice is added to the cooled reaction mixture which is left overnight and then filtered and washed with water and petroleum ether. The crude product thus obtained is crystallized from 62 ml of ethanol.

Yield: 1.08 g, corresponding to 23.4%.

Melting point: 107 - 109 ° C.

Example 8

Preparation of WP preparation

The compound of formula I is ground in a micronization mill to at least 80% with a grain size of 1-20 µm. The goods are homogenized with 1-5% by weight neutral or non-basic wetting agent and with 20-60% by weight solid inert binder such as kaolin or bentonite. The WP preparation thus prepared, i.e. moist powder, contains approx. 82-60% by weight of active substance (82 WP-60 WP).

Example 9

Preparation of WP Preparation 30

As described in Example 8, there is the difference that during the grinding and homogenization, in addition to the inactive binder, a further stability-enhancing acidic buffer substance, e.g. potassium or sodium dihydrophosphate, lactic acid or tartaric acid in an amount of 10-20% by weight.

Example 10 23

DK 157896 B

Preparation of a Spray Composition 5 A compound of formula I is dissolved in benzene or in a benzene homologue (toluene, xylene), to a 0.1% solution. The solution is added 1-3% wetting agent and 1% adjuvant to improve the adhesion. The mixture is filled with a propellant, e.g. Freon, propane / butane gas, carbon dioxide, on 10 aerosol bottles whose nozzle ensures a fine spray.

Example 11

Preparation of an EC preparation 15

A compound of formula I is milled for at least 80% to a grain size of 1-20 μια, then mixed with the same weight of an inert organic solvent and added during the homogenization an additional 5-7% wetting agent. The emulsifiable concentrate thus obtained contains approx. 47-48% active substance and can be diluted as desired with the solvents used.

Example 12 25

Preparation of a microaranulate

One. compound of formula I is dissolved in chloroform or another chlorinated hydrocarbon, preparing a solution whose concentration matches the homogenizer to be used. This solution is charged to a homogenizer operating by wet method, e.g. a coating boiler, on a solid support having a grain size of 0.1-1 mm, e.g. perlite, coking powder and the content of the active substance are adjusted to 10-30%.

Claims (1)

Wherein R is an alkyl group having 1-5 carbon atoms or an optionally substituted phenyl group having one or more halogen atoms, in an amount of 96-0.01% by weight, preferably 90-0.5% by weight, optionally with known active plant protection compounds, and moreover the required amount of 20 common adjuvants for the preparation of plant protection products.