CH636840A5 - N-Alkoxy-2,6-dinitro-4-substituted anilines, processes for their preparation, and herbicides containing these compounds - Google Patents

Description

The invention has now set itself the task of creating new herbicidally active 2,6-dinitroanilines. Slight modifications of the compounds already result in a change in their activity spectrum compared to various plant species and plant varieties. The various compounds also differ in terms of their stability and degradation behavior under different climatic, weather and soil conditions. By providing further such compounds, i5 thus increases the agrochemical's ability to select a herbicide that is specifically tailored to solving a particular problem in harmful plants.

The invention now relates to N-alkoxy-2,6-di-nitro-N-substituted-4-substituted-anilines of the formula (I)

20th

R1Q

>

0 N.?

>

fl

/

0 N '

2nd

where io R1 is methyl or ethyl,

R2 is hydrogen, Cj-Q-alkyl or C3-C4-alkenyl and

R3 represents methyl, ethyl, isopropyl or trifluoromethyl.

35 New compounds of the formula I in which R2 is hydrogen, namely compounds of the formula (II)

The invention relates to substituted N-alkoxy-2,6-dinitro-N-substituted-4-substituted-anilines, which have a herbicidal activity.

The invention also relates to a herbicidal composition which contains a new N-alkoxy-2,6-dinitro-4-substituted-aniline as at least one active ingredient.

The invention further relates to processes for the preparation of the new compounds.

A wide variety of 2,6-dinitroanilines have already been described in the chemical literature. From German Chemical Society reports 43, 1662-1685 (1910) are N, N-dipropyl-4-methyl-2,6-dinitroaniline and N, N-dimethyl-4-methyl-2,6-dinitro- known aniline. In C.A. 28,469 (1934) N, N-dimethyl-4-iodo-2,6-dinitroaniline, N, N-dimethyl-4-bromo-2,6-dinitroaniline, 4-iodo-2,6-dinitrophenyl-piperidine and 4 -Brom-2,6-dinitrophenylpiperidine described. From C.A. 5,2079 (1911) 2,6-dinitrophenyl-piperidine is known. US Pat. No. 2,212,825 describes a series of 2,6-dinitroanilines which have a trifluoromethyl group in position 4.

The suitability of 2,6-dinitroanilines in agrochemicals is first described in U.S. Patents 3,111,403, 3,257,190, 3,322,769 and 3,367,949. According to this, these compounds are said to have herbicidal activity and are particularly suitable as pre-emergence herbicides. Later a large number became related

° A

R'V / / \

\

i

/

• —Frai)

o t /

2nd

wherein R1 and R3 are defined above, are produced according to the invention by using a 2,6-dinitro-l-halo-gene-4-substituted-benzene of the formula (III)

55

60

° A

\ /

-R-

(III)

0 NT

2nd

/

where R3 has the above meaning and

X represents F, Cl, Br or J, with an alkoxyamine hydrohalide, the alkyl group of which corresponds to the radical R1 given above, in the presence of a base in a solvent.

New compounds of the formula I in which R 2 is C 1 -C 4 -alkyl or C 3 -C 4 -alkenyl, namely compounds of the formula (IV)

636840

0 fi

RV <'"V = ^ \ = /

in which R1 and R3 are defined above, are obtained according to the invention by first, as described above, preparing a compound of the formula II and this with a compound of the formula

R4Y,

wherein

R4 has the above meaning and

Y represents Cl, Br, J or (S04) 1/2, in an aprotic solvent in the presence of a strong base.

To combat harmful vegetation, the sites affected by harmful plants or corresponding seeds can be treated with a compound of the formula I.

In the general formulas given above, Ci-C3-alkyl means methyl, ethyl, n-propyl or isopropyl. C3-C4-alkenyl means allyl, crotyl and methallyl.

The new compounds according to the invention are herbicidal and regulate plant growth. Their herbicidal effectiveness can be seen in the greenhouse with application quantities of approximately 1.12 to 8.96 kg of active ingredient / ha. Certain of the present new compounds, namely compounds of the formula II, are also suitable as intermediates for the preparation of other new compounds of the formula IV according to the invention.

The new compounds according to the invention are produced by a stepwise process. This step-by-step process consists in firstly preparing a corresponding 2,6-dinitro-4-substituted-halogenobenzene with an alkoxyamine hydrohalide, such as an alkoxyamine hydrochloride, in the presence of a base in a suitable solvent to give an N-alkoxy-2,6- Dinitro-4-substituted-ten-aniline. The reaction can be carried out in a solvent containing hydroxyl groups, such as methanol or ethanol, it being possible to use a tertiary amine, such as triethylamine, as the base. The halogen substituent on the 2,6-dinitro-4-substituted-benzene is bromine, chlorine, fluorine or iodine.

An N-alkoxy-2,6-dinitro-4-substituted-aniline can be prepared as follows: 2,6-dinitro-4-methylchlorobenzene in methanol is allowed to react with ethoxyamine hydrochloride in the presence of triethylamine until the desired reaction is practically complete. The reaction is started at room temperature, the progress of the reaction being monitored either by thin layer chromatography (TLC) or by nuclear magnetic resonance spectroscopy (NMR) at intervals of about 30 minutes after the start of the reaction. The required reaction times fluctuate and are obviously influenced by the identity of the substituent in position 4 in the 2,6-dinitrobenzenes used, the 4-trifluoromethyl-2,6-dinitro-halogenobenzenes, for example, being very reactive. The reaction times can therefore vary from about 1 hour at room temperature to about 18 hours at the reflux temperature in the case of less reactive reactants. After the reaction has ended in practice, the reaction mixture is worked up to the desired product, which in the case mentioned above is 2,6-dinitro-N-ethoxy-p-toluidine and melts at about 64 to 66 ° C.

The new N-alkoxy compounds obtained by the above process are suitable as intermediates for the preparation of other new compounds of the formula IV which come under the above-mentioned formula I and are herbicidally active. Some of the new intermediates are also already herbicidally active.

When used as intermediates, one of these compounds is preferably allowed to react with a suitable alkenylating or alkylating agent in the presence of sodium hydride as the base using dimethylformamide as the solvent of choice. Examples of suitable alkylating agents for this purpose are C 1 -C 3 -alkyl halides, such as methyl iodide, methyl bromide, methyl chloride, ethyl iodide, ethyl bromide, ethyl chloride, n-propyl bromide, n-propyl chloride, n-propyl iodide, isopropyl bromide, isopropyl chloride or isopropyl iodide; C1-C3-alkyl sulfates, such as methyl sulfate, ethyl sulfate, n-propyl sulfate or isopropyl sulfate or C3-C4-alkenyl halides, such as allyl bromide, allyl chloride, crotyl chloride, crotyl bromide, methallyl chloride or methallyl bromide. The reaction temperatures can range from room temperature to about 110 ° C. The reaction temperature can range from 30 minutes at room temperature for the most reactive N-alkoxy-2,6-dinitroanilines to several hours at about 90 to 110 ° C for the less reactive N-alk-oxy-2,6-dinitroanilines. The reaction is carried out in an aprotic solvent, such as dimethylformamide, 1-methyl-2-pyrrolidinone or dimethyl sulfoxide, with dimethylformamide being preferred. The reaction proceeds in the presence of a strong base, such as sodium hydride, potassium t-butoxide or potassium hydride, with sodium hydride being preferred.

This manufacturing process works, for example, as follows:

A mixture of 2,6-dinitro-N-ethoxy-p-toluidine and sodium hydride in dimethylformamide is advantageously briefly stirred at about room temperature. The reaction mixture is then mixed with the alkylating agent, for example with allyl bromide, and the mixture is stirred until the reaction is practically complete. The progress of the reaction is monitored at intervals of about 30 minutes by thin layer chromatography (TLC). The reaction is complete, for example, in about 0.5 to 12 hours.

For reaction, the reaction product mixture obtained in the above manner is mixed with water and with dilute aqueous acid, advantageously dilute aqueous hydrochloric acid. In some cases, the desired product is precipitated or crystallized out of the acidified mixture, so that it can easily be filtered off. If this is not the case, the reaction mixture is mixed with a water-immiscible solvent, such as ethyl acetate, ether, benzene or toluene, in order to extract the desired product from the aqueous acidified mixture in this way. The organic solution obtained is separated off and dried with a suitable drying agent, for example anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is evaporated in vacuo to remove the solvent. The resulting residue is dissolved in a suitable solvent, for example toluene, whereupon the solution is chromatographed on a column filled with a magnesium silicate gel (Florisil) using toluene as the eluent. The eluate coming from the column becomes

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concentrated and the residue thus obtained identified by NMR spectroscopy and elemental analysis. In the present case, it is N-allyl-2,6-dinitro-N-ethoxy-p-toluidine.

With the present N-alkoxy-2,6-dinitro-4-substituted-aniline, the agrochemist is given further interesting compounds. Changes in the structure of the compounds lead to changes in their herbicidal spectrum and their stability under different conditions of soil, climate and weather. The present new connections thus offer more options for the selection of a specific connection which can satisfactorily solve a given problem. At the same time, the present new synthesis provides a superior process for the preparation of the corresponding 2,6-dinitroanilines.

The invention is further illustrated by the following examples.

Example 1 2,6-Dinitro-N-ethoxy-p-toluidine A suspension of 10.0 g (0.046 M) of 2,6-di-nitro-4-methylchlorobenzene in 100 ml of methanol is prepared and 7 are added. 6 g (0.092 M) ethoxyamine hydrochloride and 13.9 g (0.138 M) triethylamine. The reaction mixture is stirred at room temperature for 30 minutes, then heated to about 50 ° C. for 30 minutes with further stirring, then treated with a further 16.7 g (0.20 M) of ethoxyamine hydrochloride and finally heated to reflux temperature for a further 24 hours with stirring. A subsequent NMR spectroscopic investigation shows that the desired product is present in the reaction mixture in a yield of about 70%. The reaction product mixture is therefore poured onto ice-water and then filtered. The solid obtained is recrystallized from petroleum ether (boiling point 60 to 71 ° C.), giving 5.5 g of product, which melts at 64 to 66 ° C. Based on an NMR spectrum, the product is 2,6-dinitro-N-ethoxy-p-toluidine.

Example 2 2,6-Dinitro-4-ethyl-N-methoxyaniline A suspension of 10.0 g (0.043 M) of 2,6-di-nitro-4-ethylchlorobenzene in 100 ml of methanol is prepared. 7 g (0.176 M) methoxyamine hydrochloride and 22.2 g (0.22 M) triethylamine and the reaction mixture is heated to reflux temperature overnight. Then another 14.7 g (0.176 M) of methoxyamine hydrochloride are added to keep the solution colored orange. The reaction product mixture is poured onto ice and the aqueous mixture is filtered. The solid obtained is collected and dried. After recrystallization from petroleum ether (boiling point 60 to 71 ° C), 7.0 g of a material are obtained which melts at about 90 ° C. Based on an NMR spectrum and an elemental analysis, this product is 2,6-dinitro-4-ethyl-N-methoxyaniline.

Analysis for CgHuNjO 5:

calculated found

C 44.80% 45.11%

H 4.60% 4.53%

N 17.42% 17.34%

Example 3 2,6-Dinitro-N-methoxy-p-toluidine The general procedure described in Example 2 is carried out using 21.6 g (0.1 M) 2,5-dinitro-4-methyl-

chlorobenzene, 12.5 g (0.15 M) methoxyamine hydrochloride and 25.25 g (0.25 M) triethylamine are repeated to give 2,6-dinitro-N-methoxy-p-toluidine, which is about 141 to 143 ° C melts. The compound is identified by elemental analysis 5 and by its NMR spectrum. The yield is 12.5 g.

Analysis for C8HgN305:

calculated found

C 42.30% 42.50%

H 3.99% 3.87%

N 18.50% 18.42%

15

Example 4

2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toluidine

A solution of 10.0 g (0.037 M) of 4-chloro-3.5-20 dinitrobenzotrifluoride in 100 ml of ethanol is prepared and this solution is mixed with 11.21 g (0.111 M) of triethylamine and then at an interval of 30 seconds with 4.46 g (0.046 M) ethoxyamine hydrochloride. The reaction mixture is stirred for 1.25 hours at room temperature and a further 25 4.46 g (0.046 M) of ethoxyamine hydrochloride are added, as a result of which the color of the reaction mixture changes and warms. The reaction product mixture is then diluted with water for working up, whereupon the solution is acidified with dilute aqueous hydrochloric acid and extracted 30 times with ether. The combined ether extracts are washed several times with dilute aqueous hydrochloric acid and water, after which the whole is dried over anhydrous magnesium sulfate. A residue is obtained by filtering off the drying agent and concentrating the filtrate under vacuum. The residue is recrystallized from petroleum ether (boiling point 60 to 71 ° C), whereby a product melting at about 96 to 98 ° C is obtained in an amount of 9.0 g. Based on the NMR spectrum and an Elemen-40 tar analysis, this is 2,6-dinitro-N-ethoxy-alpha, alpha, alpha-tri-fluoro-p-toluidine.

Analysis for C9H8F3N305:

calculated found

C 36.62% 36.66%

H 2.73% 2.47%

N 14.24% 14.09%

50

Example 5

2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine

A solution is prepared from 27.0 g (0.1 M) 4-chloro-3,5-di-55 nitro-benzotrifluoride in 200 ml ethanol and with 25.25 g (0.25 M) triethylamine and 12, 5 g (0.15 M) methoxyamine hydrochloride were added. After adding the methoxyamine hydrochloride, the temperature of the reaction mixture rises to 50 ° C. The reaction mixture is stirred for 1.5 hours, whereupon the reaction product mixture is worked up by diluting it with ethyl acetate, washing it several times with dilute hydrochloric acid and water and drying the organic layer over anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is concentrated to a residue on a water bath. The residue is placed in the refrigerator over the weekend, which creates crystals. The crystalline product is filtered off. It melts at 135 to 137 ° C and

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weighs 21.0 g. Based on the NMR spectrum and an elemental analysis, this is 2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine.

Analysis for C8H6F3N305:

calculated found

C 34.18% 34.17%

H 2.15% 2.12%

N 14.95% 14.82%

Example 6

N-Allyl-2,6-dinitro-N-ethoxy-p-toluidine A mixture of 2.5 g (0.01 M) of 2,6-dinitro-N-ethoxy-p-toluidine (see Example 1) and 0.015 M sodium hydride (made from 0.72 g of a 50 percent dispersion of sodium hydride in mineral oil by repeated washing with hexane) in 75 ml of dimethylformamide and stirred for about 10 minutes at room temperature. The reaction mixture is then mixed with 2.42 g (0.02 M) allyl bromide. The mixture is stirred at room temperature for 1 hour. The reaction product mixture is worked up by adding ether and washing with aqueous hydrochloric acid. The organic solution is dried over anhydrous magnesium sulfate and filtered, and the filtrate is concentrated in vacuo to remove the solvent. The residue obtained is dissolved in toluene and chromatographed on a column filled with magnesium silicate gel (Florisil) using toluene as the eluent. The solution coming from the column is concentrated to give 1.25 g of an oil which is N-allyl-2,6-dinitro-N-ethoxy-p-toluene based on an NMR spectrum and an elemental analysis. din acts.

Analysis for C12Hi 5N305:

calculated found

C 51.24% 51.37%

H 5.38% 5.10%

N 14.94% 14.70%

Example 7

2,6-Dinitro-N-ethoxy-N-propyl-p-toluidine The procedure described in Example 6 is carried out using 5.0 g (0.021 M) of 2,6-dinitro-N-ethoxy-p-tolui-din (Example 1), 3.39 g (0.0203 M) n-propyl iodide and 0.012 M sodium hydride made from 0.59 g of a 50 percent dispersion of sodium hydride in mineral oil are repeated to give 1.2 g2,6-dinitro- N-ethoxy-N-propyl-p-tolui-din in the form of an oil.

Analysis for C12H17N305:

calculated found

C 50.88% 50.60%

H 6.05% 5.80%

N 14.83% 14.57%

Example 8

N, 4-Diethyl-2,6-dinitro-N-methoxyaniline The procedure described in Example 6 is carried out using 5.0 g (0.021 M) of 2,6-dinitro-4-ethyl-N-methoxyaniline (Example 2) , 0.02 M sodium hydride, made from 0.96 g of a 50 percent dispersion of

Sodium hydride in mineral oil, and 6.24 g (0.04 M) ethyl iodide, to give 1.0 g of N, 4-diethyI-2,6-di-nitro-N-methoxyaniline, which is at 80 to 82 ° C melts. Analysis for CnHlsN305:

calculated found

C 49.07% 49.19%

10 H 5.62% 5.37%

N 15.61% 15.42%

Example 9

15 2,6-dinitro-4-ethyl-N-methoxy-N-propylaniline

The procedure described in Example 6 is carried out using 3.0 g (0.0124 M) of 2,6-dinitro-4-ethyl-N-methoxyaniline (Example 2), 4.0 g (0.024 M) of n-propyl iodide and 0.012 M sodium hydride made from 0.58 g one

20 50 percent dispersion of sodium hydride in mineral oil, repeated, whereby 1.5 g of 2,6-dinitro-4-ethyl-N-meth-oxy-N-propylaniline is obtained, which melts at 72 to 74 ° C. Analysis for Ci2H17N3Os:

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calculated found

C 50.88% 51.01%

H 6.05% 5.80%

30 N 14.83% 14.82%

Example 10

2,6-dinitro-N-ethyl-N-methoxy-alpha, alpha, alpha-35 trifluoro-p-toluidine

0.017 M sodium hydride, prepared from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil, is mixed with 50 ml of dimethylformamide. The mixture is then mixed with 5.0 g (0.018 M) of 2,6-dinitro-N-methoxy-alpha, al-40 pha, alpha-trifluoro-p-toluidine (Example 5) and for 45 minutes at a temperature of to heated to about 65 ° C. The reaction mixture is cooled to room temperature and 5.3 g (0.034 M) of ethyl iodide are added dropwise. The reaction mixture is then stirred at 45 room temperature for 30 minutes and then at 80 ° C. for about 1 hour, after which it is examined by thin layer chromatography. There is no longer any starting material in the thin-layer chromatogram. The reaction product mixture is therefore cooled and left to stand overnight at ambient temperature. For working up, the mixture obtained is then diluted with ether and washed several times with dilute aqueous hydrochloric acid and once with water. The organic phase is then dried over anhydrous magnesium sulfate, the drying agent is filtered off and the solvent is removed under vacuum. The residue is chromatographed on a column filled with magnesium silicate gel (Florisil) using benzene as solvent and as eluent. The fractions coming first contain the desired product. These fractions are combined and evaporated in vacuo to remove the solvent. The residue obtained is recrystallized from petroleum ether (boiling point 60 to 71 ° C). The resulting product melts at 95 to 97 ° C and weighs 1.0 g. Based on an NMR spectrum and an elementary analysis, this is 2,6-dinitro-N-ethyl-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine.

Analysis for C10H10F3N3O5:

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calculated found

C 38.85% 39.86%

H 3.26% 3.23%

N 13.59% 13.88%

Example 11

2,6-dinitro-N-methoxy-N-propyl-alpha, alpha, alpha-trifluoro-p-toluidine

Petroleum ether (boiling point 60 to 71 ° C.) is stirred with 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil and the petroleum ether solution is then removed by decanting mineral oil. The remaining sodium hydride (0.017 M) is suspended in 75 ml of dimethylformamide, whereupon the whole is treated with 5.0 g (0.018 M) of 2,6-di-nitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine (Example 5) added. The reaction mixture is heated to 65 ° C. for 30 minutes, then cooled to room temperature and mixed with 5.78 g (0.034 M) n-propyl iodide. The reaction mixture is heated to 40 ° C for 30 minutes, whereupon the temperature is gradually increased to 100 to 110 ° C. The heating time is 2 hours. The reaction product mixture is then cooled and worked up. For this purpose, the reaction mixture is diluted with ether and washed in succession with dilute aqueous hydrochloric acid and water. The organic layer is dried over anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is concentrated under vacuum. The residue obtained is chromatographed on a column filled with magnesium silicate gel (Florisil) using benzene as solvent and eluent. The fractions coming from the column are concentrated and the residue obtained is recrystallized from petroleum ether (70 to 71 ° C). In this way, 1.9 g of product are obtained, which melts at about 59 to 60 ° C. The product is identified by the NMR spectrum and by elemental analysis as 2,6-dinitro-N-methoxy-N-propyl-alpha, alpha, alpha-trifluoro-p-toluidine.

Analysis for C11H12F3N305:

calculated found

C 40.88% 40.68%

H 3.74% 3.84%

N 13.00% 13.20%

Example 12

2,6-dinitro-N-methallyl-N-methoxy-alpha, alpha, alpha-alpha

trifluor-p-toluidine 0.017 M sodium hydride, obtained from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil (method described in Example 11), are mixed with 50 ml of dimethylformamide. The mixture of sodium hydride and dimethylformamide obtained is then mixed with 5.0 g (0.018 M) of 2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine (Example 5) and the whole is heated for 20 minutes to 60 ° C. The reaction mixture is then cooled to about room temperature and 6.14 g (0.068 M) of methallyl chloride are added. The reaction mixture is then heated to 65 ° C. for 30 minutes, whereupon the temperature of the reaction mixture is raised to 90 ° C., maintained for 2 hours and the reaction mixture is finally heated to about 110 ° C. for a further 2 hours. The reaction mixture is then cooled, diluted with ether and washed with dilute hydrochloric acid and water. The

The ether layer is dried over anhydrous magnesium sulfate.

The drying agent is filtered off and the filtrate is concentrated under vacuum to remove the solvent. The residue is dissolved in benzene and the solution is chromatographed on a column filled with aluminum silicate gel (Florisil) using benzene as the eluent. The first part coming from the column is concentrated under vacuum to a residue, which is recrystallized from petroleum ether (boiling point 60 to 71 ° C). In this way, 0.5 g of a material is obtained which melts at 55 to 56 ° C. This material is identified by the NMR spectrum and by elemental analysis as 2,6-dinitro-N-methallyl-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine.

Analysis for C ^ H ^ FaNsOs:

calculated found

C 42.99% 42.75%

H 3.61% 3.39%

N 12.53% 12.31%

Example 13

N-Allyl-2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine The procedure described in Example 12 is carried out using 5.0 g (0.018 M) of 2,6-dinitro-N -methoxy-alpha, alpha, alpha-trifluoro-p-toluidine (Example 5), 4.11 g (0.034 M) allyl bromide and 0.42 g (0.017 M) sodium hydride obtained from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil, repeated to give 2.4 g of N-allyl-2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine, which melts at 77 to 79 ° C.

Analysis for ChHjqFjNsOj:

calculated found

C 41.13% 41.15%

H 3.14% 3.09%

N 13.08% 12.83%

Example 14

2,6-Dinitro-N-ethoxy-N-ethyl-alpha, alpha, alpha-trifluoro-p-toluidine 0.017 M sodium hydride, obtained from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil (according to the procedure described in Example 11) ), 50 ml of dimethylformamide and 5.0 g (0.017 M) of 2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toluidine (Example 4) are added and the mixture is then stirred for 20 minutes Room temperature. Then 5.3 g (0.034 M) of ethyl iodide are added and the reaction mixture is heated to 85 ° C. for about 2.5 hours. The progress of the reaction is followed by the NMR spectrum, which shows a content of 66% product and 33% starting material. The reaction mixture is therefore mixed with a further 5.3 g (0.034 M) of ethyl iodide and heated for a further 0.5 hours. The reaction product mixture is then allowed to cool and is diluted with ether. The ether mixture is washed several times with dilute aqueous hydrochloric acid and once with water, after which it is dried over anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is concentrated under vacuum to remove the solvent. The residue obtained in this way is dissolved in benzene, and the solution is chromatographed on a column filled with magnesium silicate gel (Florisil) using benzene as the eluent.

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The resulting fractions are examined by NMR analysis. The pure fractions are combined and evaporated to dryness to remove the solvent. In this way, 0.65 g of a product is obtained which melts at 72 to 75 ° C. The product is identified by the NMR spectrum and by elemental analysis as 2,6-di-nitro-N-ethoxy-N-ethyl-alpha, alpha, alpha-trifluoro-p-tolui-din.

Analysis for C11H12F3 N3Os:

calculated found

C 40.88% 41.09%

H 3.74% 3.44%

N 13.00% 12.88%

Example 15

N-Allyl-2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toluidine The procedure described in Example 14 is carried out using 5.0 g (0.017 M) of 2,6-dinitro-N -ethoxy-al-pha, alpha, alpha-trifluoro-p-toluidine (Example 4), 4.11 g (0.034 M) allyl bromide and 0.017 M sodium hydride, prepared from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil in the already described, repeated, which leads to 1.15 g of N-allyl-2,6-dinitro-N-ethoxy-al-pha, alpha, alpha-trifluoro-p-toluidine, which melts at 52 to 54 ° C. .

Analysis for C12H12F3N305:

calculated found

C 42.99% 42.77%

H 3.61% 3.72%

N 12.53% 12.80%

Example 16

2,6-dinitro-N-ethoxy-N-propyl-alpha, alpha, alpha

trifluoro-Np-toluidine The procedure described in Example 14 is carried out using 5.0 g (0.017 M) of 2,6-dinitro-N-ethoxy-al-pha, alpha, alpha-trifluor-p-toluidine (Example 4) , 5.78 g (0.034 M) n-propyl iodide and 0.017 M sodium hydride, made from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil, repeated to give 1.0 g of 2,6-dinitro-N-ethoxy- N-propyl-alpha, alpha, alpha-trifluoro-Np-toluidine reaches, which melts at 34 to 35 ° C.

Analysis for Ci2H14F3N305:

calculated found

C 42.74% 42.99%

H 4.18% 4.36%

N 12.46% 12.59%

Example 17

2,6-Dinitro-N-ethyl-N-methoxy-p-toluidine 0.017 M sodium hydride, obtained from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil (by the process described in Example 11), is added with constant stirring 50 ml of dimethylformamide, whereupon the whole is mixed with 4.54 g (0.02 M) of 2,6-dinitro-N-methoxy-p-toluidine (Example 3). The temperature of the mixture rises to 40 ° C. The mixture is then stirred for a further 10 minutes and 12.48 g are added to the reaction mixture

(0.08 M) ethyl iodide. The temperature of the reaction mixture increases to 90 ° C and stirring is continued for 30 minutes. The progress of the reaction is monitored by making an NMR spectrum of a small sample of the reaction mixture, which shows that the desired product is predominantly present in the reaction mixture. The reaction mixture is heated to about 90 ° C for 30 minutes with further stirring. The reaction mixture is then allowed to cool and diluted with ether, after which the whole is washed with dilute aqueous hydrochloric acid and then with water. The organic layer is dried over anhydrous magnesium sulfate, after which the drying agent is filtered off and the solvent is removed under vacuum. The residue is recrystallized from a mixture of petroleum ether (60 to 71 ° C) and ethyl acetate, giving 1.7 g of a product which melts at 47 to 50 ° C. The product is identified by the NMR spectrum and by elemental analysis as 2,6-dinitro-N-ethyl-N-methoxy-p-toluidine. 20 Analysis for C10H13N3Os:

calculated found

C 47.06% 47.06%

25 H 5.13% 5.02%

N 16.46% 16.46%

Example 18

30 2,6-dinitro-N-methoxy-N-propyl-p-toluidine

The procedure described in Example 17 is carried out using 2.0 g (0.009 M) 2,6-dinitro-N-methoxy-p-toluidine (Example 3), 3.4 g (0.02 M) n-propyl iodide and Repeat 0.5 g (0.01 M) of a 50 percent dispersion of sodium hydride 35 in mineral oil to give 0.8 g of 2,6-dinitro-N-methoxy-N-propyl-p-toluidine in the form of an oil. Analysis for CnHj 5N305:

calculated found

C 49.07% 49.30%

H 5.62% 5.36%

N 15.61% 15.62%

45

Example 19 N-Allyl-2,6-dinitro-N-methoxy-p-toluidine The procedure described in Example 17 is carried out using 4.5 g (0.02 M) of 2,6-dinitro-N-methoxy-p -

50 toluidine (Example 3), 4.8 g (0.04 M) allyl bromide and 0.96 g (0.02 M) of a 50 percent dispersion of sodium hydride in mineral oil were repeated to give 0.67 g of N-allyl-2 , 6-dinitro-N-methoxy-p-toluidine, which melts at 80 to 82 ° C.

55 Analysis for C ^ H ^ N ^ s:

calculated found

C 49.44% 49.29%

60 H 4.90% 4.78%

N 15.72% 15.59%

Example 20

65 N-allyl-2,6-dinitro-4-ethyl-N-methoxyaniline

0.017 M sodium hydride, obtained from 0.82 g of a 50 percent dispersion of sodium hydride in mineral oil (according to the procedure described in Example 11), is added.

9

636 840

ren), with 50 ml of dimethylformamide. The suspension obtained is then mixed with 3.0 g (0.012 M) of 2,6-dinitro-4-ethyl-N-methoxyaniline (Example 2) and the mixture is stirred for about 5 to 10 minutes. Then 2.9 g (0.024 M) of allyl bromide are added and the reaction mixture is stirred for 30 minutes at room temperature. A sample of the reaction mixture is examined by NMR analysis, which shows that 70 to 80% of the desired product and 20 to 30% of the starting material are present. The reaction mixture is then heated to 90 ° C. with stirring for 1 hour. A subsequent NMR analysis shows that the reaction has ended. The reaction product mixture is therefore worked up accordingly. To this end, the mixture is mixed with dilute hydrochloric acid and alcohol. The organic layer is separated and dried over anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is chromatographed on a column filled with magnesium silicate gel (Florisil). The fractions coming from the column are examined by means of an NMR spectrum, the product-containing fractions being combined and evaporated to dryness in vacuo. The residue is recrystallized from petroleum ether (boiling point 60 to 71 ° C.), giving 1.7 g of product which melts at about 83 to 85 ° C. The product is identified by the NMR spectrum and by elemental analysis as N-allyl-2,6-dinitro-4-ethyl-N-methoxyaniline.

Analysis for C12H15N305:

calculated found

C 51.24% 51.46%

H 5.38% 5.32%

N 14.94% 14.69%

Example 21

2,6-Dinitro-4-ethyl-N-methoxy-N-methylaniline From 5.8 g (0.024 M) 2,6-Dinitro-4-ethyl-N-methoxyaniline (Example 2) and 1.15 g (0.024 M) a 50 percent dispersion of sodium hydride in mineral oil, a suspension in 50 ml of dimethylformamide is prepared. The reaction mixture is stirred for 10 minutes at room temperature, during which time the reaction temperature rises to 50 ° C. Then 6.76 g (0.048 M) of methyl iodide are added with continuous stirring over a period of 30 minutes, the temperature of the reaction mixture rising to about 90 ° C. without external heating. The reaction mixture is then examined by thin layer chromatography, which shows that there is no longer any starting material. The reaction product mixture is therefore allowed to cool, diluted with aqueous hydrochloric acid and toluene, the organic layer is separated off and dried over anhydrous magnesium sulfate. The drying agent is filtered off and the filtrate is chromatographed on a column filled with magnesium silicate gel (Florisil) using toluene as the eluent. Two products come out of the column at the same time. The mixture of two compounds thus obtained is dissolved in a mixture of 75% benzene and 25% petroleum ether (boiling point 60 to 71 ° C.) and again chromatographed on a column filled with magnesium silicate gel (Florisil). The fractions coming from the column are collected and monitored by the NMR spectra. The desired product is then eluted from the column as the second product. Those fractions which contain the desired product are combined and concentrated in vacuo, whereupon the residue obtained is recrystallized from petroleum ether (boiling point 60 to 71: C). In this way, 0.7 g is obtained

Product that melts at around 85 to 87 ° C. Based on an NMR spectrum and an elemental analysis, this is 2,6-dinitro-4-ethyl-N-methoxy-N-methyl-aniline.

Analysis for C10H13N3O5:

calculated found

C 47.06% 47.05%

H 5.13% 4.98%

N 16.46% 16.70%

The new compounds according to the invention can be used as herbicides by methods customary in agrochemistry. For this purpose, the present compounds are formulated into the corresponding agents which, in addition to the substituted 2,6-dinitroaniline, appropriately contain one or more auxiliaries such as water, polyhydroxy compounds, petroleum distillates or other dispersion media, surface-active dispersants, emulsifiers and finely divided inert solids. The concentration of the substituted 2,6-dinitroaniline in these agents can be different, depending on whether one wants to have an emulsifiable concentrate or a wettable powder, followed by dilution with another inert carrier, such as water, to form the finished product Treatment agent takes place, or whether the agent should be applied directly to the plants as dust.

To formulate appropriate treatment agents, it is therefore expedient to first form a liquid or solid concentrate, which is then diluted to the desired use concentration. Emulsifiable liquid concentrates can be prepared, for example, by adding 1 to 30 percent by weight of the respective active ingredient and an emulsifier to a suitable water-immiscible organic liquid. The concentrates obtained after this can then be further diluted with water to form spray mixtures which have the form of oil-in-water emulsions. Such spray mixtures contain the respective herbicidal active ingredient, a water-immiscible solvent, an emulsifier and water. Suitable emulsifiers for this purpose are nonionic emulsifiers, ionic emulsifiers or mixtures thereof, and examples include condensation products of alkylene oxides with phenols and organic acids, polyoxyethylene derivatives of sorbitan esters, such as polyoxyethylene sorbitan monooleate or polyoxyethylene sorbitan monolaurate, complex ether alcohols, such as polyglycol glycols, or ionic aralkyl sulfonate compounds such as alkylamine dodecylbenzenesulfonate.

Examples of suitable water-immiscible organic liquids are aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons and mixtures thereof, for example petroleum distillates.

Solid concentrated mixtures can be prepared by incorporating 1 to 90 percent by weight of the substituted 2,6-dinitroaniline into a finely divided inert solid as a carrier, such as bentonite, fuller earth, diatomaceous earth, silicon dioxide, expanded mica, talc or lime. Together with the substituted 2,6-dinitroaniline, dispersants and / or wetting agents can also be incorporated into the solid carrier in order to form wettable powder concentrates in this way, in concentrations of 1 to 75 percent by weight, which are then in water or another Allow hydroxyl-containing carriers to disperse to form spray solutions.

5

10th

15

20th

25th

30th

3 p

40

45

50

55

60

65

636 840

Examples of suitable surface-active agents for this are condensed arylsulfonic acids and sodium salts thereof, sodium lignone sulfonate, alkylaryl polyether alcohols, sulfonated nonionic mixtures or anionic wetting agents.

Scatter granules can be made using cal-cinched attapulgite clay as a solid diluent. Dry dispersions can be prepared on herbicidally inert carriers, such as vermiculite or peat moss.

The new compounds according to the invention can be used for the treatment of a soil surface or site infected with weed seeds in the form of a dust preparation, granule formulation or spray solution which each contain one or more of the present new compounds as herbicidal active ingredient. Typical soil areas that can be treated in this way are arable areas on which useful plants grow, as well as various other places, such as gravel or gravel roads, clay tennis courts, walkways or road embankments, where weeds are to be removed. When used in the open field, the order quantities for the respective compounds are of course larger than the quantities required for the greenhouse given above. If the compounds according to the invention are used in practice in this way, then this is done by known spraying, dusting or distributing appropriate active substance-containing agents onto the surface to be treated in each case in amounts of active substance from 1.12 to 36 kg / ha or, if necessary, even slightly more, for example an amount of 56 kg of active ingredient per ha.

As already mentioned above, the novel compounds according to the invention are active as herbicides. The herbicidal activity of these compounds has been demonstrated on the basis of the tests specified below.

Investigation 1

For these investigations, a mixture of a part of wall sand and a part of crushed topsoil is used as soil. For the respective plantings, the soil is placed in appropriate picking boxes made of sheet metal (length 31.5 cm, width 21.5 cm, depth 8 cm), which have holes and channels on the bottom for drainage. Each pricking box is filled two-thirds with earth, after which the earth is leveled and contained. All seeds are placed in rows perpendicular to the longitudinal axis of the pricking boxes, one type of seed per row. The large seeds of purple winds and maize are planted in rows about 1 cm deep, which you pull with a hand press. The remaining seeds, namely all small seeds, are sown by sprinkling the seeds in rows on the surface of the soil in the seed boxes, after which all seeds are covered with sieved soil at a height of about 0.5 to 1.0 cpi . The amount of seeds used per plant type and the respective plant types are shown in the following table:

A - maize (Zea mays) 4 B - millet (Digitaris sanguinalis) 350 C - foxtail (Amaranthus retroflexus) 350 D - millet (Setaria italica) 200 E - Indian mallow (Abutilon theophrasti) 100 F - purple bindweed (Ipomoea purpurea) 25 - Zinnia (Zinnia elegans) 20

During the first irrigation after sowing the seeds, each picking box is treated with 2.5 g of a fertilizer solution. The pricking boxes used for the post-emergence examinations are planted 10 to 13 days before the actual treatment and then placed in a wax room until the day of the treatment. Depending on the light intensity, 12 are left on the pricking boxes every day

10th

exposure to light for up to 18 hours, and keeping it at a temperature of 23 to 27: C. The pricking boxes used for the pre-emergence tests are planted on the same day that they are treated accordingly. S After the treatment, all pricking boxes are brought into a greenhouse.

The compounds used for these investigations are applied in amounts of 8.96 kg / ha. Such an agent (8.96 kg / ha) is formulated by dissolving 120 mg of the respective active ingredient in 2.5 ml of a solvent mixture of acetone and ethyl alcohol in a ratio of 1: 1 together with a small amount of Toximul R and Toximul S. The solution thus obtained is then diluted with deionized water to a total volume of i5 25 ml. Toximul R and Toximul S are surface active mixtures based on sulfonates and nonionic compounds and these products are available from Stepan Chemical Company, Northfield, Illinois.

20 The herbicidal compositions thus formed are applied to each pricking box using a modified DeVilbiss atomizer to which an air source is connected. In the pre-emergence tests, the respective herbicidal compositions are sprayed onto the surface of the soil in the seed box after the seeds have been sown. In the post-emergence studies, the respective herbicidal compositions are sprayed onto the foliage of the plants 10 to 13 days after sowing the seeds from which the plants grow. Each pricking box is treated with 30 12.5 ml of the agent to be examined. This results in an application rate of 8.96 kg / ha.

After the treatment, all containers are placed in the greenhouse and, depending on the season, watered if necessary 12 to 13 days after the treatment. Subsequently, each type of plant is subjected to an assessment of the herbicidal activity. The following rating scale, from 1 to 5, is used for this assessment:

• 1 = no damage 40 2 = slight damage

3 = moderate damage

4 = severe damage

5 = kill

The following table summarizes the results obtained when investigating some of the compounds according to the invention. Column 1 of this table identifies the compound used in each case by specifying the respective example number, column 2 of the table shows the application amount in kg / ha, in which the respective containers are treated with the respective active ingredient, and columns 3 to 9 are the assessment values for the respective damage to the individual plant seedlings.

The plants used for the investigations are identified by the letters from the Al-55 alphabet explained later.

Investigation 2

Further investigations of certain compounds which fall under the general formula given above regarding their suitability as pre-emergence herbicides are carried out against a broader spectrum of plants. The plant species used for these investigations are planted in the same pricking boxes made of galvanized sheet metal as were already used in the previous examination 1, the same soil also being used. Each pricking box is 2/3 filled with earth, whereupon the earth is also leveled and contained. With these pre-emergence

11

Table I

636840

Compound application quantity Assessment of plant damage in kg / ha pre-emergence post-emergence

A

B

C.

D

E

F G

A

B

C.

D

E

F

G

2nd

8.96

1

4th

4th

4th

1

1 1

2nd

5

5

5

4th

3rd

3rd

3rd

8.96

1

5

5

4th

1

1 1

2nd

5

4th

5

3rd

3rd

5

8.96

1

2nd

2nd

3rd

1

1 1

1

3rd

2nd

2nd

2nd

2nd

2nd

6

8.96

1

4th

4th

3rd

3rd

2 1

3rd

4th

4th

4th

3rd

3rd

3rd

7

8.96

4th

4th

3rd

4th

3rd

3 2

3rd

4th

4th

3rd

4th

3rd

3rd

8th

8.96

4th

5

4th

5

3rd

3 2

2nd

4th

4th

4th

3rd

3rd

2nd

10th

8.96

1

2nd

2nd

2nd

1

1 1

1

2nd

2nd

1

2nd

1

1

11

8.96

2nd

3rd

2nd

3rd

2nd

1 1

1

1

1

1

1

1

1

13

8.96

1

2nd

3rd

3rd

1

1 -

1

3rd

2nd

2nd

1

2nd

1

14

8.96

1

2nd

1

2nd

1

1 1

2nd

2nd

1

1

1

1

1

15

8.96

1

2nd

2nd

2nd

1

1 1

2nd

3rd

2nd

1

1

2nd

16

8.96

3rd

3rd

2nd

4th

2nd

2 -

2nd

3rd

2nd

2nd

2nd

2nd

2nd

17th

8.96

2nd

4th

3rd

3rd

3rd

1 1

3rd

5

4th

5

3rd

3rd

-

18th

8.96

1

4th

3rd

3rd

3rd

2 1

3rd

5

4th

4th

4th

4th

3rd

19th

8.96

1

4th

2nd

3rd

3rd

1 1

2nd

5

5

5

3rd

2nd

3rd

21st

8.96

1

4th

3rd

4th

2nd

1 1

2nd

4th

5

3rd

3rd

3rd

2nd

For each order quantity, one works with two tick boxes, each containing 10 indicator types. The seeds of the individual plant species are sown in rows parallel to the longitudinal axis of the pricking boxes, one type of plant in each case on half a row, the rest of the procedure being the same as in the previous investigation 1. The plant types used for this and the approximate amounts of seeds used in each case The following table shows: A - Maize (Zea mays) 4 B - Cotton (Gossypium hirsutum) 6 C - Soybean (Glycine max) 6 D - Wheat (Triticum aesitivum) 40 E - Alfalfa (Medicago sativa) 100 F - Sugar beet ( Beta vulgaris) 25 G - Rice (Oryza sativa) 46 H - Cucumber (Cucumis sativus) 8 J - Tomato (Lycopersicon esculentum) 30 K - Chicken millet (Echinochloa crus-galli) 50 L - White goose foot (Chenopodium album) 100 M - Blood finger millet (Digitaria sanguinalis) 100 N - Mustard (Brassica juncea) 50

O - field foxtail (Amanrathus retroflexus) 150 P - millet (Setaria italica) 100 Q - wind oat (Avena fatua) 25 R - Indian mallow (Abutilon theophrasti) 25 S - common thorn apple (Datura stramonium) 25 T - purple vine (Ipomoea purpurea) U - Zinnia (Zinnia elegans) 20

25 For the pre-emergence investigations at hand, the seed boxes are planted on the same day that the treatment with active ingredient is carried out, covering the seeds at a height of 0.5 to 1.0 cm with soil. The chemicals are formulated as described in test 1, the desired concentrations of the test solutions then being formed by serial dilution, which give the desired application amount. The active ingredient is applied using a modified DeVilbiss atomizer 35 to which an air source is connected. Each pricking box receives 12.5 ml of spray solution. After treatment, the pricking boxes are placed in the greenhouse.

The herbicidal activity caused by the individual chemicals is assessed approximately 18 to 21 40 days after the pre-emergence treatment. The extent of the plant damage occurring is again determined on an assessment scale ranging from 1 to 5, and thus, as in the case of study 1.

45 The following table II shows the results obtained during the pre-emergence investigation of the compounds mentioned against crop plants, grasses and broad-leaved weeds. In this table, the compounds used in each case are identified in column 1, the application quantities in kg / ha with which each picking box has been treated with active ingredient are indicated in column 2, and the damage values for the respective plant seedlings are listed in the remaining columns.

Table II

Assessment of pre-emergence plant damage

connection

Application quantity in kg / ha

ABCDEFGH

J

K

L

M

N

O

P

Q

R

S

T U

2nd

2.24

11111111

1

1

2nd

3rd

1

2nd

2nd

1

1

1

1 1

4.48

11111111

1

4th

3rd

4th

2nd

4th

3rd

1

1

1

1 1

3rd

2.24

11111111

1

3rd

2nd

3rd

1

3rd

2nd

1

2nd

1

1 1

4.48

11111112

2nd

4th

3rd

4th

1

4th

3rd

1

2nd

2nd

1 1

6

1.12

11111111

1

4th

1

2nd

1

2nd

2nd

1

1

1

1 1

2.24

11111111

1

4th

2nd

4th

1

3rd

3rd

1

1

1

1 1

4.48

12 1112 11

3rd

4th

3rd

5

2nd

4th

4th

1

2nd

1

1 1

636 840 12

Tables (continued)

Assessment of pre-emergence plant damage

connection

Application quantity in kg / ha

A B

C D E

F

G

H

J

K

L

M

N

0

P

Q

R

S T U

7

1.12

1 1

1 1 1

1

1

1

1

3rd

3rd

4th

1

3rd

3rd

1

1

1 1 1

2.24

1 1

1 1 1

2nd

1

2nd

1

4th

4th

5

1

3rd

3rd

3rd

2nd

1 1 1

4.48

1 1

1 2 2

3rd

2nd

2nd

3rd

4th

4th

5

2nd

4th

4th

4th

2nd

2 2 2

8th

1.12

1 1

1 1 1

1

1

1

1

2nd

3rd

4th

1

1

2nd

2nd

1

1 1 1

2.24

1 1

1 1 1

1

1

1

1

4th

4th

5

1

2nd

3rd

3rd

2nd

1 1 1

4.48

2 1

1 2 1

3rd

1

2nd

2nd

5

5

5

2nd

4th

4th

4th

3rd

2 1 1

21st

2.24

1 1

1 1 1

1

1

1

1

1

2nd

2nd

1

2nd

2nd

2nd

1

1 1 1

4.48

1 1

1 1 2

2nd

1

1

1

4th

2nd

4th

1

3rd

3rd

2nd

2nd

1 1 1

Investigation 3

The same compounds as were investigated after test 2 and some additional compounds are also tested for their behavior as post-emergence herbicides against the seven plant species specified in test 1, using the post-emergence test already described in test 1.

The herbicidal activity of the individual compounds is assessed 12 to 14 days after the post-emergence application.

2oThe extent of the plant damage achieved is again determined, as in the previous investigations, on a rating scale from 1 to 5.

The results obtained in these tests are shown in Table III below.

Table III

Assessment of plant damage after emergence

connection

Application quantity in kg / ha

B

D

G

2nd

1.12

2nd

3rd

3rd

3rd

1

2nd

2nd

2.24

2nd

4th

4th

3rd

2nd

3rd

2nd

4.48

2nd

4th

4th

3rd

2nd

3rd

3rd

3rd

1.12

1

3rd

2nd

4th

2nd

2nd

2nd

2.24

2nd

3rd

3rd

3rd

1

1

2nd

4.48

1

4th

4th

4th

2nd

2nd

2nd

6

1.12

1

2nd

1

1

1

1

1

2.24

1

2nd

2nd

2nd

1

1

1

4.48

2nd

2nd

3rd

3rd

2nd

7

1.12

1

2nd

1

1

1

1

1

2.24

1

2nd

1

2nd

1

1

1

4.48

2nd

3rd

2nd

2nd

3rd

2nd

8th

1.12

1

2nd

1

1

1

1

1

2.24

2nd

2nd

1

2nd

1

1

1

4.48

1

3rd

3rd

2nd

1

2nd

1

17th

1.12

1

2nd

1

1

1

1

2nd

2.24

2nd

2nd

2nd

3rd

2nd

2nd

2nd

4.48

2nd

2nd

3rd

3rd

3rd

2nd

2nd

18th

1.12

2nd

2nd

2nd

2nd

2nd

1

1

2.24

2nd

3rd

3rd

3rd

3rd

2nd

2nd

4.48

2nd

4th

3rd

4th

4th

3rd

3rd

19th

1.12

1

2nd

2nd

2nd

2nd

1

2nd

2.24

2nd

3rd

2nd

3rd

3rd

2nd

2nd

4.48

2nd

3rd

3rd

3rd

3rd

2nd

2nd

21st

2.24

1

2nd

2nd

1

1

1

1

4.48

2nd

3rd

4th

3rd

2nd

2nd

2nd

The results from the tables above show that the present compounds are herbicidally active.

s

Claims (10)

636 840 1. N-alkoxy-2,6-dinitro-N-substituted-4-substituted-anilines of the formula 0 N. vrv R2 V = * 1 0 h 2nd \ / (IV) wherein R1 is methyl or ethyl, R4 is C! -C3-alkyl or C3-C4-alkenyl and R3 is methyl, ethyl, isopropyl or trifluoromethyl, characterized in that a compound of the formula II is prepared by the process according to claim 5 and this with a compound of the formula R4Y, wherein R4 has the above meaning and Y represents Cl, Br, J or (S04) ./ 2, in an aprotic solvent in the presence of a strong base. 2nd wherein R1 is methyl or ethyl and R3 represents methyl, ethyl, isopropyl or trifluoromethyl, characterized in that a 2,6-dinitro-l-halogen-4-substituted-benzene of the formula (III) wherein R3 has the above meaning and X represents F, Cl, Br or J, with an alkoxyaminohydrohalide, the alkyl group of which corresponds to the above-mentioned radical R1, in the presence of a base in a solvent. 2,6-dinitro-4-ethyl-N-methoxy-N-methylaniline. 2,6-dinitro-N-methoxy-N-propyl-p-toluidine, N-allyl-2,6-dinitro-N-methoxy-p-toluidine, N-allyl-2,6-dinitro-4-ethyl-N-methoxyaniline, 2,6-dinitro-N-ethyl-N-methoxy-p-toluidine, 2,6-dinitro-N-ethoxy-N-propyl-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-N-ethoxy-N-ethyl-alpha, alpha, alpha-trifluoro-p-toluidine, N-allyl-2,6-dinitro-N-ethoxy-alpha, aIpha, alpha-trifluoro-p-toiuidin, 2,6-dinitro-N-methoxy-N-propyl-alpha, alpha, alpha-tri- fluoro-p-toluidine, 2,6-dinitro-N-methallyl-N-methoxy-alpha, alpha, alpha-tri- fluoro-p-toluidine, N-allyl-2,6-dimtro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-4-ethyl-N-methoxy-N-methylaniline. 2,6-dinitro-N-methoxy-N-propyl-p-toluidine, N-allyl-2,6-dinitro-N-methoxy-p-toluidine, N-allyl-2,6-dinitro-4-ethyl-N-methoxyaniline, 2,6-dinitro-N-ethyl-N-methoxy-p-toluidine, 2,6-dinitro-N-ethoxy-N-propyl-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-N-ethoxy-N-ethyl-alpha, alpha, alpha-trifluoro-p-toluidine, N-allyl-2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-N-methoxy-N-propyl-alpha, alpha, alpha-tri- fluoro-p-toluidine, 2,6-dinitro-N-methallyl-N-methoxy-alpha, alpha, alpha-tri- fluoro-p-toluidine, N-allyl-2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluor-p-toIui-din, N-allyl-2,6-dinitro-N-ethoxy-p-toluidine, 2,6-dinitro-N-ethoxy-N-propyl-p-toluidine, N, 4-diethyl-2,6-dinitro-N- methoxyaniol, 2,6-dinitro-4-ethyl-N-methoxy-N-propylaniline, 2,6-dinitro-N-ethyl-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 2. N-alkoxy-2,6-dinitro-N-substituted-4-substituted-anilines according to claim 1, characterized in that these are: 2,6-dinitro-N-ethoxy-p-toluidine, 2,6-dinitro-4-ethyl-N-methoxyaniline, 2,6-dinitro-N-methoxy-p-toluidine, 2nd wherein R1 means methyl or ethyl, R2 is hydrogen, Ci-C3-alkyl or C3-C4.-alkenyl and R3 represents methyl, ethyl, isopropyl or trifluoromethyl. 2nd PATENT CLAIMS 3rd 636 840 3. Herbicidal agent, characterized in that it contains, as at least one active ingredient, a new N-alkoxy-2,6-dinitro-N-substituted-4-substituted-aniline of the formula 0 R \ V— \ 3 (I R> K => ~ R ° y * ' wherein R1 means methyl or ethyl, R2 is hydrogen, Cj-Cs-alkyl or C3-C4-alkenyl and R3 represents methyl, ethyl, isopropyl or trifluoromethyl. 4. Herbicidal composition according to claim 3, characterized in that it contains at least one of the following compounds as active ingredient: 2,6-dinitro-N-ethoxy-p-toluidine, 2,6-dinitro-4-ethyl-N-methoxyaniline, 2,6-dinitro-N-methoxy-p-toluidine, 2,6-dinitro-N-ethoxy-alpha, alpha, alpha-trifluoro-p-toIuidin, 2,6-dinitro-N-methoxy-alpha, alpha, alpha-trifluor-p-tolui- din, N-AllyI-2,6-dinitro-N-ethoxy-p-toIuidin, 2,6-Dinitro-N-ethoxy-N-propyl-p-toluidine, N, 4-DiethyI-2,6-dinitro-N- methoxyaniline, 2,6-dinitro-4-ethyl-N-methoxy-N-propylaniline, 2,6-dinitro-N-ethyl-N-methoxy-alpha, alpha, alpha-trifluoro-p-toluidine, 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 5. Process for the preparation of new N-alkoxy-2,6-dinitro-4-substituted-anilines of the formula (II) 0 NL e \ - * 'n «v y— \ / —cu K \ 0 i / 6. The method according to claim 5, characterized in that a t-amine is used as the base. 7. The method according to claim 5 or 6, characterized in that a solvent containing a hydroxyl group is used as the solvent. 8. The method according to claims 5 to 7, characterized in that one works at a temperature of 0 to 70 ° C. 9. Process for the preparation of new N-alkoxy-2,6-dinitro-N-substituted-4-substituted-anilines of the formula (IV) OK 'VC 0 N 10. The method according to claim 9, characterized in that sodium hydride is used as the strong base. Dinitroaniline found with similar herbicidal activity. In particular, reference is made to US Pat. Nos. 3,321,292, 3,617,251, 3,617,252, 3,672,864, 3,672,866.3,764,624 and 3,877,924 and BE-PS 787,939. However, none of the best-known 2,6-dinitroanilines has N-alkoxy substituents.