HU208221B - Herbicidal compositions containing a 2,6-dinitro-aniline derivative and method for producing said active agent - Google Patents

Abstract

1505249 Substituted methallylamino dinitrobenzenes and processes for their preparation ELI LILLY & CO 19 March 1975 [23 March 1974] 13028/74 Heading C2C The invention comprises the 2,6-dinitroanilines of Formula I in which R represents an ethyl, propyl or allyl group which may be prepared by reacting a compound of Formula II in which X is a halogen atom with an amine of formula optionally in the presence of an acid acceptor and/or a solvent or aqueous alkaline medium. Herbicidal compositions comprise a compound of Formula I together with at least one inert diluent or carrier.

Description

BACKGROUND OF THE INVENTION The present invention relates to herbicidal compositions for controlling weeds of a solan species containing a 2,6-dinitroanil derivative, i.e. Netyl-N-methylyl-4- (trifluoromethyl) -2,6-dinitroaniline. The invention further relates to a process for the preparation of this active ingredient.

We have found that N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline of formula (I) has a selective herbicidal activity, i.e. it is phytotoxic to a wide variety of weeds, but at the same time including cotton, soybeans, green beans, etc. - does not damage. This compound can thus be used for the selective control of parasitic weeds between crop plants.

Although the compound of formula (I) is disclosed in U.S. Pat. is within the scope of the general formula of the compounds described in U.S. Pat. However, its effect is significantly better than that of its structural analogues, as will be demonstrated in the comparative efficacy experiments described below.

The herbicidal compositions according to the invention contain from 1.0 to 60% by weight of the active ingredient 2,6-dinitroaniline derivative of the formula I in an amount of 1099% by weight of an inert carrier and / or diluent and / or other excipients, preferably emulsifying agents and / or surfactants. In combination.

The compound of formula (I) may be prepared by reacting a 2,6-dinitrobenzene derivative of formula (II) wherein X is a halogen atom, preferably a chlorine atom, with an amine of formula (ΙΠ).

The reaction is preferably carried out in an organic solvent or an alkaline aqueous medium. The reaction temperature may be from 0 to 100 ° C, but in some cases

We can also work at temperatures above 100 ° C. The reaction time varies depending on the temperature, but the reaction is usually complete in about 1-24 hours.

The starting compounds of formula (II) and the compound of formula (III) are known commercially available compounds or may be prepared by methods known per se.

Suitable organic solvents for the reaction include aromatic hydrocarbons such as benzene and toluene, alcohols such as ethanol and isopropanol, and other inert organic solvents such as tetrahydrofuran and dimethylsulfoxide. In order to bind the hydrogen halide (e. G. Hydrochloric acid) liberated during the reaction, it is necessary to add an acid acceptor such as triethylamine to the organic solvent. The reaction is also readily carried out in an alkaline aqueous medium; in this case, the base is preferably sodium carbonate, but other bases such as sodium hydroxide or potassium carbonate may be used.

The reaction is generally carried out at a temperature between 0 'C and 100' C, however, at pressures greater than atmospheric, it is also possible to carry out the reaction at a temperature above 100 'C. The reaction is usually carried out at the boiling point of the mixture. In our experience, increasing the temperature does not cause either thermal decomposition or side reactions.

The reaction rate generally varies with the reaction temperature. Accordingly, the reaction rate can be greatly enhanced by using a high boiling point solvent as the reaction medium and carrying out the reaction at the boiling point of the system. After a reaction time of 1 hour, the compound of formula (I) can generally be isolated in good yield; the reaction is usually complete within 24 hours even at low temperatures.

The preparation of the active ingredient according to the invention is described in detail in the following example.

Example 1

N-ethyl-N-methallyl-4- (trifluoromethyl) -2,6-dinitroaniline

540 g (2 moles) of 4-chloro-3,5-dinitrobenzotrifluoride, 240 g (2.4 moles) of N-ethyl-N-metallylamine, 240 g (2.4 moles) of diethylamine and 3 5 L of absolute ethanol mixture is refluxed for 2 hours and then allowed to stand at room temperature for 20 hours. The reaction mixture was diluted with an equal volume of water and extracted with several portions of diethyl ether (5 L). The combined ethereal phases are washed with water, twice with dilute aqueous hydrochloric acid, and again with water. The aqueous layers were washed with diethyl ether and the ether layer washed with water. The combined ethereal phases were dried over magnesium sulfate and filtered. The filtrate was evaporated to dryness in vacuo. The residue was recrystallized twice from 150 ml of light petroleum (b.p. 60-71 ° C). 209 g of yellow crystals are obtained, m.p. 54-57 ° C. The product was found to be N-ethyl-N-methyl-4- (trifluoromethyl) 2,6-dinitroaniline by NMR. Microanalysis results from formula C ₁₃ H _I4 F ₃ N ₃ O ₄ :

Calculated: C, 46.85; H, 4.23; N, 12.61.

Found: C, 46.79; H, 4.01; N, 12.58.

Further materials may be obtained by evaporation of the filtrate and recrystallization of the crude product obtained. 79 g of product are obtained with a melting point of 54-57 ° C.

The test for herbicidal activity of the preparation containing the active ingredient of formula (I) and the results of the test are set out below.

The plants to be examined are seeded in a 1: 1 mixture of sand and medium heavy humus. Plates made of galvanized steel with flat bottomed, perforated and perforated bottom 35x25x8 cm are filled with 4.54 liters of soil mixture and the soil mixture is leveled. Seeds of test plants are seeded in rows perpendicular to the longitudinal axis of the tray and covered with soil. After sowing, each tray is sprayed with 0.57 liters of solution containing 2.5 g of soluble 18-25-18 fertilizer.

1.774 g of TOXIMUL R and 0.785 g of TOXIMUL S (commercial products marketed by Stepan Chemical Company, which are mixtures of calcium dodecylbenzene sulfonate and ethoxylated alkylphenol) are dissolved in a mixture of 100 ml of ethanol and 100 ml of acetone. . The solution thus obtained, in 5 ml portions (containing 0.029 g of TOXIMUL R, 0.020 g of TOXIMUL S, 1.98 g of acetone and

HU 208 221 Β

(1.97 g of ethanol) is dissolved in 120 mg of the compound of the formula I to be tested and the resulting solution / dispersion is diluted to 50 ml with 45 ml of demineralized water.

Half of the resulting aqueous dispersion (25 mL) was sprayed onto two trays (12.5 mL per tray; 30 mg test compound and 0.1 wt% surfactant) corresponding to 4.0 kg / ha.

The other half of the resulting aqueous dispersion (25 mL) was diluted to 100 mL with an appropriate amount of TOXIMUL R and S surfactant and demineralized water, and 25 mL of the resulting solution was sprayed onto two trays [12.5 mL per tray; 7.5 mg of test compound and 0.1% by weight of TOXIMUL R and S (60: 40)], corresponding to 1 kg / ha. The drug-containing composition is applied to the area to be treated on the day of sowing with a spray gun.

After treatment, the trays are placed in a greenhouse of optimum temperature and humidity for the growth of the particular plant. Twelve days after treatment, the plants are examined and the condition of the plants is characterized by numbers ranging from 1 to 5. A value of 1 indicates normal growth of the plant, and a value of 5 indicates that the plant has not hatched at all or has died shortly after hatching. THE

Values of 2, 3 and 4 indicate mild, moderate and severe damage. The results of the experiment are shown in Table I below.

The letters in the table refer to the following plants: A: corn, B: cotton, C: soybean, D: wheat, E: alfalfa, F: sugar beet, G: rice, H: cucumber, I: tomato, J: cocksfoot (Echinochloa) crus galli), K: Chenopodium album, L: Digitaria sanguinalis, L: Mustard (Brassica sp.), N: Porpoise (Amaranthus retroflexus), O: Brassica (Setaria sp.), P: Wild oat (Avena sp.), R : Abutilon theophrasti, S: duckweed (Ipomoea sp.), T: cinnia (Zinnia sp.).

Table I

Quantity (Kg / ha) crops ABCDEFGHI weeds JKLMNOPRST 1 111322312 4352343212 4 413332412 4452444321

To prevent the growth of weeds or the germination of weed seeds, a composition comprising a compound of formula (I) is applied to the area to be treated prior to emergence of the weeds.

As can be seen from the data in Table I, the composition containing the compound of formula (I) can be used very advantageously for the selective control of parasitic weeds among many crop plants. It is of particular importance from an agricultural point of view that the composition containing the compound of formula (I) does not damage the cotton, soybeans and sugar beet. Of course, the composition containing the compound of formula (I) can also be used very advantageously to control parasitic weeds between other crop plants such as potatoes, tomatoes, tobacco, onions, melons and cucumbers.

As can be seen from the data in Table I, the composition containing the compound of formula I is suitable for controlling a wide variety of weeds. In addition to the weeds listed in Table I, this composition is generally effective against the following weeds: Solanum nigrum, Chenopodium album, Folaronum convolvulus, Datura stramonium, Portulaca oleracea, Convolvulus arvensis, Fumaria officinalis, Echinochloa crus-galli, Set. Phalaris minor.

Preferably, the herbicidal composition is applied prior to sowing the seeds of the crop plants, but after the soil preparation is applied to the area to be treated. In general, it is very advantageous to loosen the soil layer after application with a roller plow or similar agricultural tool and at the same time to distribute the herbicidal composition to a depth of 5 to 15 cm in the topsoil.

In order to provide a suitable herbicidal effect, the compound of formula (I) is usually applied in the form of a formulation containing 0.25 to 10 kg / ha, preferably 0.5 to 4 kg / ha. It will be apparent to those skilled in the art that the amount of active ingredient to be applied will vary depending on several factors. Thus, in some cases, we may have to deviate from the above limits.

The composition of the compound of formula (I) inhibits the emergence of weeds and the growth of emerged weeds to varying degrees depending on the type of weed and the amount of active ingredient applied. As can be seen from the experimental data presented above, in some cases the active ingredient completely kills the weeds, in other cases the weeds are only partially destroyed or this compound only damages but does not destroy the weeds. However, it is also very advantageous for the crop plants if the active ingredient only slows down the growth of the weeds, since the normally growing crop can suppress the slow growing weeds. This suppressive effect is particularly pronounced in bush-like crops (such as cotton and beans).

The compound of formula (I) is applied in the form of herbicidal compositions to the area to be treated. In addition to the active ingredient, the herbicidal compositions contain at least one inert carrier. Liquid or solid materials commonly used in the preparation of agricultural chemicals and compositions may be used as inert carriers. The herbicidal compositions can be prepared in a manner known per se.

Preferably, the herbicidal compositions are marketed in the form of concentrates to be diluted prior to use. The concentrates are formulated into aqueous dispersions or emulsions containing from about 0.1% to about 1% by weight of the active ingredient prior to use. The water dispersible or emulsifiable concentrates may be finely divided solids (wettable powders) or liquids (emulsifiable concentrates).

Wettable powder formulations have an active ingredient content of about 3

They contain an inert solid carrier and a surfactant. The wettable powder compositions generally contain from 10 to 60% by weight of the active ingredient. Suitable inert carriers are, for example, attapulgite clay, montmorillonite clay, diatomaceous earth or purified silicates, while surfactants include, for example, lignin sulfonates, naphthalene sulfonates, alkylbenzenesulfonates, alkyl sulfates and nonionic surfactants such as ethylene oxides, and the like. Wettable powder formulations generally contain from 0.5 to 10% by weight of a surfactant.

Emulsifiable concentrates generally contain 50-600 g / l of active ingredient. For the preparation of emulsifiable concentrates, water-immiscible organic solvents such as aromatic solvents such as xylenes and petroleum fractions, preferably high-boiling aromatic and olefinic petroleum fractions and terpene-type solvents such as rosin derivatives may be used as carriers. Emulsifiable concentrates generally contain from 0.5 to 10% by weight of an emulsifier; for example, the surfactants listed in wettable powder formulations may be used as emulsifiers.

The compound of formula (I) may also be converted into granular formulations. These formulations are evenly distributed throughout the crop area to be treated. Granular formulations generally contain the herbicidal active ingredient in a form applied on a coarse inert carrier (usually coarse material). Granular compositions generally have a particle size of 0.1 to 3 mm. Granular formulations are generally prepared by dissolving the active ingredient in a suitable solvent, such as kerosene or a heavy aromatic petroleum fraction, and applying the solution to the surface of the particulate carrier with stirring. A less economical method may be to disperse the active ingredient in a paste made from wet clay or other carrier material, and then dry the paste and grind it into coarse particles.

The herbicidal compositions can be applied to the crop to be treated using conventional equipment. The aqueous dispersions may be applied, for example, by means of hand-held, tractor-mounted or self-propelled sprayers. Equipment for applying granular compositions is well known in the art. When applying the herbicidal compositions, it is only necessary to ensure that a sufficient amount of the active ingredient is applied to the crop area and that the active ingredient is distributed evenly over the area to be treated.

The compositions of the invention are illustrated by the following examples.

Example 2

Emulsifiable concentrates can be prepared as follows.

The dinitroaniline of formula (I) and the emulsifier are dissolved in a suitable solvent with vigorous stirring and the resulting solution is filtered.

a) Active ingredient: N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline 10% by weight emulsifier: mixture of anionic and nonionic surfactants [dodecylbenzene sulfonate and alkylphenoxy polyoxyethylene] ) ethanol mixture (Stepan agent 555-66A)] 3 wt% solvent xylene 87 wt%

b) Active ingredient: N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline 33% emulsifier: mixture of anionic and nonionic surfactants [dodecylbenzene sulfonate and alkylphenoxy polyoxyethylene ) ethanol mixture (Stepan agent 555-66A)] 5 wt% solvent xylene 62 wt%

c) Active ingredient: N-ethyl-N-metallyl-4- (trifluoromethyl) -2,6-dinitroaniline 40% by weight emulsifier: a mixture of anionic and nonionic surfactants [dodecylbenzene sulfonate and alkylphenoxy polyoxy] ethylene) 25 ethanol mixture (Stepan agent 555-66A)] 6% solvent xylene: o-chlorotoluene 1: 1 54% w / w

d) Active ingredient: N-ethyl-N-metallyl-4- (trifluoromethyl) -2,6-dinitroaniline 60% by weight emulsifier: mixture of anionic and nonionic surfactants [dodecylbenzene sulfonate and alkylphenoxy polyoxy] ethylene) 35 ethanol (Stepan 555-66A) 9% w / w cyclohexanone 31% w / w.

Example 3

A wettable powder composition is prepared as follows:

The active ingredient is ground, the additives are added and the blended mixture is passed through an air mill.

a) Active ingredient: N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline 60% wetting agent: Na-lauryl sulfate dispersant: lignin sulfonate silica 4% 10% 21% clay

(b) an active substance

N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline 20 wt% wetting agent: Na-lauryl sulfate 5 wt% dispersant: lignin sulfonate 4 wt% silica 10 wt% clay 61 wt%.

Example 4

(a) As regards the quantity of granules

2.6% by weight of N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-di60

A solution of about 60% by volume of 221 Β nitroaniline in xylene at 30 ° C is then sprayed onto a magnesium silicate granulate in a rotary drum.

b) A solution of 12% by weight of the granulate in N-ethyl-N-methyl-4- (trifluoromethyl) -2,6-dinitroaniline with xylene at 30 ° C is made up to 60% and the solution is rotated sprayed onto magnesium silicate granules in a drum.

Example 5

Prior to planting peanuts or cotton, the soil is treated with the following formulations in the following application rates.

(a) One month after peanut planting, weed control for Solanum nigrum.

The following results are obtained:

preparation Rate of application of active substance (kg / ha) Percent weed control THE 1.25 100 B 1.25 79

b) Seven weeks after the cotton is planted, the degree of weed control for Solanum nigrum is evaluated.

The following results are obtained:

preparation Rate of application of active substance (kg / ha) Percent weed control THE 1.0 87 C 1.0 55

The formulas marked with the letters A, B and C are as follows:

A (emulsifiable concentrate)

Component Quantity by weight

N-Ethyl-N-Methyl-4- (trifluoromethyl) 2,6-dinitroaniline 33 Blend of calcium dodecylbenzene sulfonate and alkylphenoxypolyoxyethylene ethanol 5 xylene 100% required B (emulsifiable concentrate)

Component Quantity by weight

N-Butyl-N-Ethyl-4- (trifluoromethyl) -2,6-dinitroaniline 18 Emulsifier mentioned in "A" 4 xylene 100% required "C" (emulsifiable concentrate)

Component Quantity by weight

N, N-di-n-propyl-4- (trifluoromethyl) -2,6-dinitroaniline 48 required emulsifier 4 xylene 100%

Example 6

The following describes comparative experiments in which the compound of formula (I) and two closely related analogs are disclosed in U.S. Patent No. 3,257,190. N-allyl-N-methyl-2,6-dinitro-4- (trifluoromethyl) aniline (Compound D) and N-allyl-N-ethyl-2,6-dinitro-4, known from U.S. Pat. (trifluoromethyl) aniline (Compound E) was investigated for herbicides against Solanum ptycanthum and Solanum sarrachoides.

In the trials, the test compounds were used at rates of 0.28, 0.56, 1.12 and 2.24 kg / ha (using technical grade materials). The test compounds were mixed with Toximul R and Toximul S in a 1: 1 by volume ratio of acetone to ethanol (both produced by Stepan Chemical Co., 83/93 Rue de Paris, Noisy de Sec, France) and calcium dodecyl as an anionic component. benzene sulfonate and a polymeric ethylene oxide derivative as a nonionic component) (3: 2 by weight) and the resulting solutions are diluted with tap water to the treatment concentration.

Suitable amounts of clayey-sandy soil (78.4% sand, 14.4% mud, 7.2% clay and 2.3% organic matter) for each treatment were placed in stainless steel tanks, which were then placed in a modified concrete mixing machine and while rotating, the test solutions are sprayed onto the soil samples in the tanks.

After thorough rotation and thus incorporation into the soil, the treated soil is filled into plastic pots. The plastic pots are 9.2x9.2 cm at the soil surface and 6.8x6.8 cm at the bottom, with a thickness of 7.0 cm in the dry state of 500 g and a surface of 84.6 cm ² . Spraying is carried out at a rate such that 2.5 ml of spray is applied to a tile soil. This means that the utilization rates given in the following tables correspond to the following concentrations:

Application rate (kg / ha) mg of active ingredient per pot (500 g of soil) ppm (weight of active substance relative to soil weight) 0.28 0.24 0.48 0.56 0.48 0.96 1.12 0.95 1.90 2.24 1.90 3.80

Seeds of the said weeds are then planted in pots and treated with 0.5 cm soil layer.

HU 208 221 Β cover. One row of each of these species is planted in pots. Under controlled conditions, three replicate experiments were performed in each case. After treatment, the treated pots should be placed in a greenhouse equipped with an additional light source. Here we provide 16 hours of light per day and a temperature of 24-28 ° C. For the first series of experiments on Compound I and Compound D, the herbicidal activity is evaluated 21 days after treatment, and for the second series of experiments on Compound I and Compounds D and E 20 days after treatment. The results obtained are shown in Table II. and III. table.

II. spreadsheet

Test compound application rate kg / ha Percentage of weed control Solanum ptycanthum Duplicate experiment Average Solanum sarrachoides Duplicate experiment Average I 11th III. First 11th III. D 0.28 0 0 0 0d ²⁾ 0 0 0 0d D 0.56 0 0 0 0d 0 0 0 od D 1.12 0 0 50 17-c-d 0 0 0 od D 2.24 15 75 60 50 b 0 0 0 od Of formula (I) 0.28 75 25 30 43b-c 0 0 0 od Of formula (I) 0.56 20 90 60 57 b 0 20 45 22 c Of formula (I) 1.12 60 65 70 65a-b 40 30 80 50 b Of formula (I) 2.24 98 90 85 91 a 100 95 90 95 a control 0 0 0 0 od 0 0 0 od

III. spreadsheet

Test compound application rate kg / ha Percentage weed control ¹ * Solanum ptycanthum Parallel experiment Average Solanum sarrachoides Duplicate experiment Average I II. III. I II. III. E 0.28 0 0 0 0d ²⁾ 0 0 0 0d E 0.56 0 0 0 od 0 0 0 od E 1.12 0 0 0 od 0 0 0 od E 2.24 0 0 0 od 0 0 0 od D 0.28 0 0 0 od 0 0 0 od D 0.56 0 0 0 od 0 0 0 od D 1.12 0 0 0 od 0 0 0 od D 2.24 65 55 60 60b 50 60 25 45 b Of formula (I) 0.28 0 0 0 od 0 0 0 od Of formula (I) 0.56 50 35 50 45 c 30 25 40 32 c Of formula (I) 1.12 60 60 60 60b 30 55 55 47 b Of formula (I) 2.24 85 90 80 85 a 95 92 95 94 a control 0 0 0 0 od 0 0 0 od

Explanations to Appendix II. and III. table:

h; Percentage weed control is a value based on visual damage estimates where 0% is no effect and 100% is complete extinction or no plant emergence.

the means with the same letters are not significantly different at the 5% probability level (see "Duncan's Multiple Rank Test" by Steel, RGD and Toni, J, H. in "Principles and Procedures of Statistics", 1960, p. 481 of the book published by McGraw-Hill New York Publisher).

Claims (5)

PATENT CLAIMS CLAIMS 1. A herbicidal composition for controlling weeds of the solan species, characterized in that the active ingredient is present in an amount of 1.0 to 60% by weight as an active ingredient. Composition according to claim 1, characterized in that the composition is a wettable powder comprising 10 to 60% by weight of the active ingredient of the formula I, 0.5 to 10% by weight of one or more surfactants, preferably sodium lauryl. sulphate and lignin sulphate, and 10.5 to 89.5% by weight of an inert carrier, preferably silica and clay. Contains 2,6-dinitroaniline derivatives in an amount of from 40% to 99% by weight of an inert solid or liquid, organic or inorganic carrier, natural or artificial, preferably silica, clay, magnesium silicate or xylene and optionally anionic and / or nonionic surfactant. mixed with material. Composition according to claim 1, characterized in that the composition is an emulsifiable concentrate comprising 6 to 60% by weight of the active ingredient of the formula I, 0.5 to 10% by weight of an emulsifier, preferably calcium dodecylbenzenesulfonate and alkyl. a mixture of phenoxy polyoxyoxyethylene ethanol and 18 to 93.5% by weight of an inert solvent, preferably xylene or a mixture of xylene and ortho-chlorotoluene. Composition according to claim 3, characterized in that the composition is an emulsifiable concentrate comprising 30 to 40% by weight of the active ingredient of the formula I, 3 to 7% by weight of an emulsifying agent, preferably calcium dodecylbenzenesulfonate and alkylphenoxy. polyoxyethylene ethanol and 53-67% by weight of an organic solvent, preferably xylene. A process for the preparation of a 2,6-dinitroaniline derivative of formula (I), comprising reacting a dinitrobenzene derivative of formula (II) wherein X represents a halogen atom with an amine of formula (III).