KR800000545B1 - Process for the preparation of 2,6-dinitro anilines - Google Patents

Abstract

Title compds. (I, R = ethyl, propyl, alkyl; R1 = C1-4 alkyl, CF3, difluoromethyl, methylsulfonyl, sulfamoyl), useful as herbicides, were prepd. by reacting dinitrobezenes(II, x = Cl, halogen) with amines(III) at 0-100≰C for 1-24 hr in organic solvent. Thus, 4-difluouomethyl-N-methalyl-N-propyl-2, 6-dinitroaniline was manufd. by the reaction of 4-chloro-3, 5-dinitro- , -benzofluoride with N-propylmethalylamine and triethylamine in benzene with stirring and refluxing overnight.

Description

2.6-Dinitroniline Aniline Production Method

The present invention relates to a new class of herbicides, 4-substituted-2,6-dinitroaniline, a process for preparing the compound and a method for inhibiting weeds using the compound of the present invention.

It can be seen that the compounds of the present invention have excellent herbicidal action, that is, they have phytotoxicity against many kinds of weeds but do no harm to many major crops such as cotton and soybeans. It is good to use to control weeds.

The compound of the present invention is 2,6-dinitroaniline represented by the following general structural formula (I).

(Wherein R represents an ethyl, propyl or allyl group and R ¹ represents a C ₁ -C ₄ alkyl, trifluoromethyl, difluoromethyl, methylsulfonyl or sulfamoyl group).

The new compounds of the present invention are 2,6-dinitroanilines with metalyl amino substituents and the other amino substituents are ethyl, propyl, allyl and these compounds have a 4-substituted group selected from these groups, and these compounds are substituted with 3 of the phenyl ring. Hydrogen at-and 5-position.

과 같은기를 뜻한다.In the above formula, the term C ₁ -C ₄ alkyl is methyl, ethyl, propyl, isopropyl,

It means the same as.

Moreover, some compounds may be named differently according to the selective law of organic chemical method, but all compounds named here are named 2,6-dinitroaniline.

The invention also relates to the following.

A) a herbicidal composition having a compound represented by formula (I) together with at least one inert carrier

B) a method for preparing the herbicidal composition as mentioned in (a), wherein the compound represented by the general formula (I) is mixed with at least one inert carrier.

C) A method of inhibiting the growth of weed seeds and inhibiting the growth of weeds in agricultural lands by using the compound represented by Formula (I) in agricultural lands before weeds germinate in an effective amount for weeding.

D) A method for producing a compound represented by the general structural formula (I) prepared by reacting dinitrobenzene represented by the following general formula (II) with an amine of the following general formula (III).

(Wherein X is a halogen atom, preferably a chlorine atom and R and R ¹ have the same meaning as above)

The synthesis is preferably carried out in an organic solvent or an aqueous basic medium solution at a temperature of about 0 ° to 100 ° C. or higher and the reaction time is usually about 1-24 hours depending on the temperature. All compounds used as starting materials for synthesizing the compounds of the present invention are commercially available and can be prepared by known methods in the chemical literature.

Useful organic solvents are aromatic hydrocarbons such as benzene, toluene, alcohols such as ethanol, isopropanol, and other inert reaction solvents are tetrahydrofuran, dimethylsulfoxide.

An acid scavenger, such as triethylamine, is added to the organic solvent to absorb the hydrogen halide (eg, hydrogen chloride) liberated by the reaction.

The reaction also works well in basic medium solutions.

Sodium carbonate is preferred as the base and other bases such as sodium hydroxide or potassium carbonate are also useful.

When using a high pressure apparatus, the reaction temperature varies from about 0 ° to 100 ° C. or higher, and it is usually best to react at the reflux temperature of the reaction mixture, and no side reaction or pyrolysis occurs even if the reaction is induced at an elevated temperature.

In general, the reaction is completed at a rate with temperature. Therefore, the reaction rate can be increased by using a high boiling point reaction solvent and operating at reflux temperature.

One hour is sufficient to produce any compound in sufficient yield, and a maximum yield of compound is sufficiently obtained in 24 hours at low temperature.

The herbicidal method, the herbicidal composition and the compound which improves the preparation method thereof are N-ethyl-N-metall-4-trifluoromethyl-2,6-dinitroaniline,

N-metallin-N-propyl-4-trifluoromethyl-2,6-dinitroaniline,

N-ethyl-N-metallin-4-sulfamoyl-2,6-dinitroaniline,

N-ethyl-N-metallin-4-sulfamoyl-2,6-dinitroaniline,

N-ethyl-4-isopropyl-N-metallin-2,6-dinitroaniline,

4-isopropyl-N-metallin-N-propyl-2,6-dinitroatilin,

4- (t-butyl) -N-metallin-N-propyl-2,6-dinitroaniline,

N-allyl-N-metallin-4-trifluoromethyl-2,6-dinitroaniline is preferred.

Particularly a better compound of the invention is N-ethyl-N-meryl-4-trifluoromethyl-2,6-dinitroaniline.

The following examples illustrate, by way of example, simple reactions that can produce the compounds.

Example 1

[4-Difluoromethyl-N-metall-N-propyl-2,6-dinitroaniline]

A reaction mixture containing 5.05 g of 4-chloro-3,5-dinitro-α, α, -benzofluoride, 4.5 g of N-propylmetallamine and 4 g of triethylamine in 100 ml of benzene After refluxing with stirring overnight, the reaction mixture was first washed with dilute hydrochloric acid, washed with water, and the organic phase was dried over magnesium sulfate.

The solvent is removed in vacuo and then the oily residue is dissolved in hexane and chromatographed with a column of 100 g of purified magnesium silicate.

The purified product was eluted with hexane containing an increased amount of benzene by 20%, and the product components were collected and evaporated in vacuo to 4.8 g of 4-difluoromethyl on oil as evidenced by nuclear magnetic resonance (NMR) analysis. Obtain -N-metall-N-propyl-2,6-dinitroaniline.

Elemental microanalysis gives the following results:

Maximum NMR is found to be 0.83, 1.56, 1.7, 2.93, 3.52, 4.94, 6.61, 7.89 ppm.

Example 2

[N-ethyl-N-metallin-4-sulfamoyl-2,6-dinitroaniline]

To 2.82 g of 4-chloro-3,5-dinitrobenzene sulfonamide solution in 100 ml of modified alcohol, 2.0 g of N-ethylmetallamine and 2.0 g of triethylamine were added and the mixture was stirred for two hours. After heating together under reflux, the solution is cooled and the mixture is diluted with water and stored in a cold place for several days to determine the crude product, and yellow crystals are collected and air dried.

Recrystallization of the crude product with an aqueous alcohol solution yields 1.62 g of N-ethyl-N-metallin-4-sulfamoyl-2,6-dinitroaniline having a melting point of 123-125 ° C. Analysis confirmed the identity. Elemental microanalysis gave the following results.

Example 3

[4-Isopropyl-N-metall-N-propyl-2,6-dinitroaniline]

To 2.45 g of 4-chloro-3,5-dinitrocumene suspended in 75 ml of modified alcohol, 2.3 g of N-propylmetallamine and 2.0 g of triethylamine were added, and the mixture was refluxed for 16 hours. Heat and cool.

The reaction mixture is diluted with 300 ml of water, extracted with 500 ml of ether, the ether extract is washed once with water, twice with dilute hydrochloric acid, once more with water and dried over anhydrous magnesium sulfate.

The organic phase is concentrated to dryness in vacuo and the residue is dissolved in hexane.

Eluting with more hexane, the solution is chromatographed with purified magnesium silicate, the product components are collected and the solvent is evaporated to yield 1.4 g of 4-isopropyl-N-metall-N-propyl-2,6-dinitro as yellow oil. Get aniline

The identity was confirmed by NMR analysis and the results of elemental trace analysis are as follows.

Maximum NMR was found to be 0.78, 1.28, 1.47, 1.68, 2.88, 2.98, 3.52, 4.89, 7.63 ppm.

The above examples are examples of typical syntheses for preparing compounds and all compounds can be readily prepared organically chemically with slight modifications in the above-described synthesis.

The general procedure described in the above examples can be used to prepare the compounds listed in the following examples and the characteristic data for each compound is shown below.

Example 4

N-allyl-N-metall-4-trifluoromethyl-2,6-dinitroaniline, melting point 53-54 ° C

Example 5

N-metall-N-propyl-4-sulfamoyl-2,6-dinitroaniline, melting point 93-95 ° C

Example 6

N-ethyl-N-metallin-4-trifluoromethyl-2,6-dinitroaniline, melting point 54-57 ° C

Example 7

N-metall-N-propyl-4-trifluoromethyl-2,6-dinitroaniline, melting point 41-43 ° C

Example 8

4- (t-butyl) -N-metall-N-propyl-2,6-dinitroaniline, melting point 59-61 ° C.

Example 9

4- (t-butyl) -N-ethyl-N-metallin-2,6-dinitroaniline, melting point 68-70 ° C

Example 10

4- (s-butyl) -N-ethyl-N-metallin-2,6-dinitroaniline, oil phase: Maximum NMR is 0.89, 1.04, 1.28, 1.63, 1.68, 2.71, 3.02, 3.48, 4.87, 7.53.

Example 11

N-ethyl-4-isopropyl-N-metall-2,6-dinitroaniline, melting point 52-54 ° C

Example 12

N-ethyl-N-metall-4-methyl-2,6-dinitroaniline, melting point 48-50 ° C.

Example 13

N-ethyl-4-fluoromethyl-N-metall-2,6-dinitroaniline, melting point 68-70 ° C

Example 14

N, 4dimethyl-N-metallin-2,6-dinitroaniline, oily phase: max. NMR 1.04, 1.28, 1.68, 2.73, 3.03, 3.50, 4.88, 7.61 ppm.

Example 15

N-allyl-N-metall-4-methyl-2,6-dinitroaniline, oil phase: Maximum NMR is 1.63, 2.43, 3.50, 3.60, 4.84, 4.92-5.28, 5.85, 7.64 ppm.

Example 16

4-ethyl-N-methylene-N-propyl-2,6-dinitroaniline, oil phase: maximum NMR is 0.79, 1.28, 1.47, 1.68, 2.70, 2.89, 3.52, 4.88, 7.59 ppm.

Example 17

4- (s-butyl) -N-metall-N-propyl-2,6-dinitroaniline, oil phase: Maximum NMR is 0.82, 0.88, 1.30, 1.13-1.9, 1.68, 2.73, 2.87, 3.50, 4.88 , 7.54 ppm.

Example 18

N-allyl-4- (s-butyl) -N-methylyl-2,6-dinitroaniline, oil phase: maximum NMR is 1.68, 3.54, 3.67, 4.93, 4.97-5.35, 5.85, 6.69, 8.00 ppm .

Example 19

N-allyl-4-difluoromethyl-N-metall-2,6-dinitroaniline, oil phase: Maximum NMR is 1.68, 3.54, 3.67, 4.93, 4.97-5.35, 5.85, 6.69, 8.00 ppm.

Example 20

N-allyl-4-ethyl-N-metall-2,6-dinitroaniline, melting point 37.38 ° C.

Example 21

N-metall-4-methyl-N-propyl-2,6-dinitroaniline, melting point 48-50 ° C.

Example 22

N-allyl-N-metallin-4-sulfamoyl-2,6-dinitroaniline, melting point 128-129 ° C

Example 23

N-Metalline-4-methylsulfonyl-N-propyl-2,6-dinitroaniline, melting point 110.5-112.5 ° C

Example 24

N-allyl-4-isopropyl-N-metall-2,6-dinitroaniline, oil phase: Maximum NMR is 1.32, 1.63, 3.03, 3.47, 3.58, 4.83, 4.9-5.3, 5.83, 7.64 ppm.

Example 25

N-allyl-4- (t-butyl) -N-metall-2,6-dinitroaniline, oil phase: maximum NMR is 1.37, 1.63, 3.46, 3.57, 4.83, 4.9-5.28, 5.83, 7.78 ppm .

The compounds of the present invention are evaluated using the following preparation test methods.

The test plants filled the soil surface with sand and medium, mixed the same mixture and allowed the plants to grow on galvanized steel plates 35 cm long, 25 cm wide and 8 cm deep. The bottom of the plate was dug and drilled to make a drain. 120 ml of the compound was dissolved in a 2.5 ml solution containing 10 g of an emulsifier in a mixture of 1 liter of acetone and 1 liter of ethanol to form a test compound, and 2.5 ml of 22.5 ml of water containing 0.045% of an emulsifier. After dispersing the solution, the aqueous solution was diluted appropriately to prepare a method for supplying an appropriate amount of test compound when 12.5 ml of the dispersion was used for each plate.

One gallon of soil mixture is placed in each plate and leveled, the test plants are planted in the soil in a line perpendicular to the longitudinal axis of the plate, covered with soil and seeded with 1 pint of fertilizer solution containing 2.5 g of soluble fertilizer. Were planted in the subsoil, then covered with soil and seeded with 1 pint of fertilizer solution containing 2.5 g of soluble fertilizer and added to each plate.

Seeds were planted using the test compound on the plate and uniformly disperse the compound dispersion on the soil on the same day. After treatment, the plates were transferred to a greenhouse with a temperature and humidity suitable for plant growth, the plants were observed for 12 hours after treatment, and each seed was rated at 1-5 scale.

Evaluation 1 indicates that the plants germinate and grow normally, and Evaluation 5 indicates that the plants do not germinate or die after germination, and evaluations 2, 3, and 4 indicate mild, moderate or severe damage, respectively. The compounds of the invention were tested at 1 and 4 lbs./acre to observe the results and the evaluation is as follows.

Compound numbers are the same as those in the above examples.

The novel compounds of the present invention are best for use in the novel weeding methods shown herein, which use the effective amount of the compounds of the present invention to moisturize the crops prior to germination of the weeds and prevent the weed seeds from germinating in the crops. It is a way to suppress weed growth. A more specific method is to use the above named compounds.

As can be seen clearly from the above data, the weeding method can be safely used for many economically important crops, especially for cotton, soybeans and beets.

Other crops that can benefit from the compounds are potatoes, tomato, tobacco, onions, melons, cucumbers. As exemplified by the above data, the present compounds inhibit many weeds that harm and erode crops. Some mixtures include other harmful weeds such as black paper, kenopodium album, gomari, daturastramonium, purslane, convolvulus albanis, humaria opusinalis, blood, tussock, poa anua, pallaris mino Suppress

In general, it is best to use the compound to reapply before seeding the crop or after it is prepared for sowing the crop. Usually, it is most effective to mix the compound on top of the soil by using the compound on farmland and then mixing the soil with an apparatus such as a hoe hoe, a rotary tiller, or a disc lathe. The mixing device should mix the compound into a soil layer about 2-6 inches deep. The herbicidal method should be carried out using a herbicidal amount of effective compound on the crop.

In general, the amount of harmful herbicide is about 0.25-10 lbs./acre and a good coverage range is about 0.5-4 lbs./acre. Those skilled in the art will appreciate that amounts below or above the above-mentioned ranges are necessary to obtain the best results in the practice of this herbicidal method.

The compounds, herbicidal methods, and herbicidal compositions of the present invention inhibit the growth of young weeds and the germination of weeds depending on the type of weed and the degree of compound used. For example, the entire population of weeds is killed as shown in the herbicide test data. As another example, only germinating weeds can damage or kill or damage parts of the weeds. Damage to young weeds growing on crops gives crops a high profit because crops that normally grow are shaded by late growing weeds. In particular, the shadowing effect of crops is good for shrub-rich crops such as cotton or legumes. The compounds of the present invention can be used in cropland in pure form, but it is more convenient to use one of the herbicidal compositions indicated here.

The herbicidal compositions of the invention are one or more compounds of the invention in combination with at least one inert carrier, wherein the inert carrier is a liquid or a solid. Inert carriers required for the preparation of the composition are commonly used in the field of agricultural chemistry and will be described slightly to form the present herbicidal composition to clarify the best method.

-6lbs./gal의 액체와 같은 사용하기에 편리한 활성화합물을 뜻하며 유기용매는 이의 용매결과 값에 따라 선택한다.The compounds are also formed into concentrated compositions and used in soil in the form of dispersions or emulsions containing about 0.1-1% of the compound. Compositions that can be dispersed or emulsified in water are elaborately divided solids, commonly known as raid powders, or liquids, commonly known as concentrates. The herbicide powder that can be raided means a well-mixed mixture of the active compound, the inert carrier and the surfactant. The concentration of the active compound is usually about 10-90%, and the inert carrier is attapulgite clay, montmorillonite clay, diatom. Excellent surfactants selected from refined silicate and contained in about 0.5-10% of the swoop powder are nonionic surfactants such as sulfonated lignin, condensed naphthalenesulfonic acid, alkyl sulfates, and ethylene oxide additives of phenol. Herbicidal concentrates of typical compounds that can be emulsified are water and insoluble organic solvents and emulsifier mixtures are soluble in inert carriers.

An active compound that is convenient to use, such as a liquid of -6 lbs./gal. The organic solvent is chosen according to its solvent result.

Effective organic solvents refer to fragrances, ie petroleum such as xylene and petroleum components, especially heavy aromatic naphtha with high boiling naphthalene and olein components. In addition, other organic solvents, such as terpene solvents containing rosin derivatives, are used. The emulsifier, which is a 0.5-10% emulsion concentrate, is selected from the same type of surfactant used in rapid powder. Granular compositions are in a convenient form for use of the compounds to distribute the composition simply and evenly over the crop, and typical herbicides are compounds which are dispersed in a granular inert carrier of coarse ground clay.

The particle size of such granules is usually about 0.1-3 mm and the general forming method is to dissolve the compound in a solvent such as kerosene or heavy aromatic naphtha and to use the solution in a carrier in a suitable mixer, the mixture consisting of squeezed clay It is dispersed in wheat flour, dried and roughly ground to produce the desired granular product, which is slightly uneconomical. The herbicidal composition can be used on farmland using common apparatus.

For example, a composition dispersed in water can be used as a nebulizer, delivered by hand, assembled by a tow truck, having a rubbing force, or towed by a rope. Granular compositions can be used in many commonly used instruments, and the operator using the instrument must take great care in using the amount of the composition per acre to supply the compound in the desired ratio of use and for use in the farmland.

In the present invention, herbicidal composition means a compound represented by the general formula (I) as the only active ingredient, and they also mean other herbicides such as urea herbicides, for example:

3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea,

3- (4-chlorophenyl) -1-methoxy-1-methylurea,

3- (4-bromophenyl) -1-methoxy-1-methylurea,

3- (3,4-dichlorophenyl) -1,1-dimethylurea,

N′-4- (4-chlorophenoxy) phenyl-N, N-dimethylurea,

N ′-(3-chloro-4-methoxyphenyl-N, N-dimethylurea,

Triazine herbicides are as follows:

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,

4-amino-6-t-butyl-3- (methylthio) -1,2,4-triazine-5-one,

2-chloro-4,6-bis (ethylamino) -1,3,5-triazine,

-부틸아미노-1,3,5-트리아진,4-ethylamino-2-methylthio-6-

Butylamino-1,3,5-triazine,

Phenoxy herbicides include:

4- (2,4-dichlorophenoxy) -butyric acid,

4- (4-chloro-2-methylphenoxy) -butyric acid,

-톨릴))옥시]-프로피온산,2-[(4-chloro-

-Tolyl)) oxy] -propionic acid,

-프로필)-4,6-디니트로페놀, 3,5-디니트로-N,N-디크로필설파닐아미드, 5-아니노-4-클로로-2-페닐-3-피리다존,Carbamic acid herbicides are for example isopropyl-N- (3-chlorophenyl) carbamic acid, and amide herbicides are N- (4-chlorophenyl) -2,2-dimethyl-bareramide and 2- (α-naph Methoxy) -N, N-diethyl-propionamide, 2- (1-methyl-

-Propyl) -4,6-dinitrophenol, 3,5-dinitro-N, N-dichlorophyllsulfanamide, 5-anino-4-chloro-2-phenyl-3-pyridazone,

-부틸-1,3,5-티아디아졸)-1,3-디메틸우레아와 같은 제초제로 있으며, 티올카르밤산 제초제는 s-에틸-N,N-디프로필티오카르밤산이다.1- (5-

-Butyl-1,3,5-thiadiazole) -1,3-dimethylurea and thiolcarbamic acid herbicide is s-ethyl-N, N-dipropylthiocarbamic acid.

Claims (1)

Preparation of 2,6-dinitroaniline represented by the following general structural formula (I), which is prepared by reacting dinitrobenzene represented by the following general formula (II) with an amine represented by the following general formula (II). Way.

(Wherein R is ethyl, propyl, allyl group and R ¹ represents C ₁ -C ₄ alkyl, trifluoromethyl, difluoromethyl, methylsulfonyl, sulfamoyl group, X is preferably a halogen atom) Hydrochloric acid atoms).