DE2013510C3 - Use of 6-trifluoromethyl-2,4-dinitro-1,3-phenylenediamines as herbicides - Google Patents

Description

It is known to use N-alkyl derivatives of 4-trifluoromethyl-2,6-dinitroaniline as selective herbicides in crops of To use dicots. The N, N-Dipropy! Derivative (called trifluralin) is used, for example, as a pre-emergence

Soil herbicide in tomatoes, cabbage, carrots, cotton, sugar beets, soybeans, crucifers, umbellifers, Peas and peanuts are used. On the other hand, 4-fviethyi-N, N-dipropyi-2,6-dinitroaniiin (is also mentioned Dipropalin) used as a selective herbicide. However, the effect of these herbicides is not satisfactory in all cases. In particular, watergrass and millet are often incompletely combated if they are used selectively It has now been found that certain 3-amino derivatives of 4-trifluoromethyl-2,6-dinitroaniline, which one also

as ö-trifluoromethyl ^^ - dinitro - ^ - plienylenediamine can have a superior effect. The invention thus relates to the use of these phenylenediamine derivatives as herbicides which correspond to the following general formula

"4.. I

wherein Ri, R ₂ , R3 and R4, which may be the same or different, are hydrogen atoms or alkyl groups which are £ j

can be substituted by halogen, hydroxy and / or alkoxy, and where at least one of the groups Ri, ψ

R ₂ , R3 and R4 are not hydrogen or Ri and R ₂ together and / or R3 and R4 together are an alkylene group

are pe with 2 to 6 carbon atoms. |

For easier naming of the compounds used according to the invention, the amino r-j is used below

nitrogen atom adjacent to the trifluoromethyl group as N ¹ and the amino nitrogen atom between the:,. '(

both nitro groups on the ring are designated as N ³ . Thus the nitro groups are in the 2- and 4-position and ψ \

the trifluoromethyl group in the 6-position of the aromatic ring. From the definition i mentioned at the beginning; 1

h ·) of the general formula it follows that either the N ¹ - or the N ³ -amino nitrogen atom at least one vi

of the aliphatic radicals mentioned, whereby the compound with two unsubstituted amino j

Groups is excluded. . "'j Preference is given to R |. R :. Ri and R4 in the context of the above definition are hydrogen atoms and lower Al Si

kyl groups with up to 6 carbon atoms including the halogen, hydroxy or lower alkoxy substituted Derivatives thereof. Examples are the methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, n-Pentyl, n-hexyl, 2-hydroxyethyl, 2-methoxyethyl. 2,2-DimethoxyäthyI-, 3-Äthoxypropyl-, 2-bromoethyl, 3-chloropropyl and 1-methyl-2-methoxyethyl groups.

As mentioned, Ri and R2 together and / or R3 and R ₄ together can be the 1-im.r ring structure of which the amino nitrogen is a part. Such a ring structure is given by the formula

reproduced, in which Z is an alkylene group having 2 to 6 carbon atoms. Examples of these are the Dimethylene, trimethylene, tetramethylene and the hexamethylene group.

A preferred class of the compounds used according to the invention are those in which R | Hydrogen and R ₂ , R3 and R _{4 are} hydrogen and / or alkyl groups having 1 to 5 carbon atoms, at least one of the groups R ₂ , R3 and R4 being an alkyl group as defined

Among the active ingredients used according to the invention, particularly preferred are those in which Ri is hydrogen, R ₂ and R3 are hydrogen and / or alkyl groups with 1 to 5 carbon atoms and R * is an alkyl group with 1 to 5 carbon atoms. The total number of carbon atoms in groups S ₂ , R ₃ and R 4 is preferably about 4 to 8. Compounds in which both R 1 and R _{2 are} hydrogen are included

Examples of this group of preferred compounds are

N'-sea-ButyI-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifluonnethyl-l 3-phenylenediamine,

N'-Ethyl-N ³ , N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine, N ^I -methyl-N ³ -sec-butyl-2,4-dinitro-6-trifluoromethyl-13 -phenylenediamine,

N ^l -ethyl-N ³ -sec-butyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine,

N ^l -Methyl-N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine,

N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine,

N'-methyl-N ³ , N ³ -diethyl-2,4-dinitro-6-trifluomethyl-13-phenylenediamine, N ^l -n-Prof / v | -N ³ , N ³ -diethyl-2,4-dinitro -6-trifluoromethyl-13-phenylenediamine,

N'-sea-pentyl-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamene,

N ³ , N ³ - diethy 1-2,4-dmi t ro-6- (rifluoromethyl-13-phenylenediamine, N ³ - (3-pentyl) -2,4-dinhro • 6-trifluoromethyl-13-phenylenediamine,

N ³ -sec-butyl-2,4-dinitro-6-tnjuormethyl-13-phenylenediamine,

N ³ - (1-methyl-2-methoxyethyl) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine. \

The compounds used according to the invention are either crystalline solids or high-boiling solids Liquids are generally only very slightly soluble in water and moderately soluble in usual organic solvents such as ethanol, acetone, ether and benzene. The connections go through easily Implementation of one or two amines or ammonia with a 2,4-dihalo-3,5-dinitrobenzene according to produce the following equation:

^NO > ₊ ^X NH + ^N NH - ^CF '

45 N.

Ri R ₃

<JH -> ~ * ^s [(Jl " ^JJ _ + 2HX ₁

R «

where the two Xi halogen atoms and Ri, R2, R3 and R4 have the same meaning as given in the preceding to have.

If Ri and R ₂ , R3 and R4 are the same, ie the substituted N'-amino group and the substituted N ³ -amino group are the same in the end products, the reaction takes place in one step using at least two moles of amine for each mole of the 2nd , 4-dihalo-3,5-dinitrobenzene instead.

The hydrogen halides formed can be neutralized by excess amine or a tertiary amine. If Ri and R _{2 are} different from R ₃ and R ₄ , two reaction stages are necessary in which different amines (or ammonia) are used in each stage. In the first stage, about 2 moles of the amine forming the NP group are reacted with about 1 mole of 2,4-dihdogen-3,5-dinitrobenzene. The first halogen atom that is converted is the halogen atom located between the nitro groups on the aromatic ring. This step is preferably carried out in a non-polar solvent, such as a hydrocarbon, in which the amine halide is insoluble and thus can easily be separated by filtration.

In the second stage, about 2 moles of the amine forming the N 'group are combined with the monoamine »compound implemented to form the asymmetrically substituted 13-phenylenediamine. The second stage of the reaction takes place in a closed reaction vessel, such as a sealed glass tube or an autoclave, instead, in order to avoid losses of amine and to allow easier control of the reaction. on the other hand can also be operated at atmospheric pressure in the presence of a solvent such as an alcohol in which the amine is easily soluble. If higher-boiling amines are used, it is not necessary to use a use closed reaction vessel for the reaction; rather, it suffices for the reaction to be in presence a suitable solvent.

The reaction temperature used to prepare the products used according to the invention is

ίο preferably in the range from about 20 to 120 ⁰ C and is used to achieve good yields of the desired

To achieve reaction products and a satisfactory reaction rate, both when using

a closed reaction vessel as well as when the reaction components are reacted at normal pressure in

Presence of a solvent. Hydrohalic acid is formed as a by-product, which "in presence excess amine is converted into the corresponding amine halide, which is easily washed by washing in water or filtration after dissolving the reaction product in the same solvent can be removed. The desired products can by known methods (such as recrystallization) getting cleaned.

The l-trifluoromethyl-2,4-dihalo-33-dinitrobenzenes used as starting materials can be easily removed by nitration of the l-trifluoromethyl-2,4-dihalogen-benzenes with a mixture of fuming nitric acid and fuming sulfuric acid at a temperature below 80 ° C.

Further examples of active ingredients produced in this way and used according to the invention are:

(I) N ', N ³ -bis- (diethyl) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 74 to 75 ° C.),

(II) ^ N ³ -bis- (dimethyl) -2,4-dinitro-6-trifluoromethyl-l, 3-phenylene diamine (mp. 125.5 to 126.5 ⁰ C), (IH) N _^I> N ³ -Bis- (di-n-propyl) -2,4-dinitro-6-trifluoΓmethyl13-phenylenediamine (high-boiling oil),

(IV) N ^l , N ³ -Di-sec.-butyl-2,4-dinitro-6-trifluoromethyH _r 3-phenylenediamine (clear amber-colored oil),

(V) N ^1, N ³ -DimethyI-2,4-dinitro-6-trifIuormethyl-13-phenylenediamine (mp. 169- 170 ⁰ C),

(VI) N ^l , N ³ -diisopropyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (m.p. 66.5-67.5 "C),

(VII) N ', N ³ -Di- (2-methoxyethyl) -23-dinitro-6-trifluonnethyl-13-phenylenediamine (melting point 98-99 ° C.), (VIII) N', N ³ -di { 3-methoxypropyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine (oil),

(IX) N ', N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 96-97 ° C),

(X) N ¹ , N ', N ³ , N ³ -di (tetramethylene) -2,4-diniu-o-6-trifluoromethyl-13-phenylenediamine (melting point 164-164.5 "C),

(XI) N ^1, N ^1, N ^3, N ³ -di- (pentamethyIen) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (mp. 139- 140 ⁰ C),

(XII) N ³ , N ³ -Di-n-propyl-2,4-dinitto-6-trifluoromethyl-13-phenylendfemine (melting point 124-125 ° C), (XIII) N ¹ , N ¹ -dimethylene-N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl! -13-phenylenediamine (viscous

amber oil),

yX. IV) N '-Äthyl- N ^s, N ³ -dimethyi-2,4-dini tro-6-trifluoromethyl-13-phenylenediamine (melting point 51.5 to 52.5 C ^0),
N ^l -Ethyl-N ³ -sec-butyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediaiflin (mp 923-94 ° C),

N ^l -sec.-ButyI-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifliormethyl-13-phenylenediamine (oil),

N ^l -sec.-butyl-N ³ N ³ -diethyl-2,4-dinitro-6-trifIuo'-methyl-13-phenylenediamine (oil), N ^l -methyl-N ³ , N ³ -diethyl-2.4- dinitro-6-trifloromethyl-13-phenylenediamine (m.p. 71.5-73.5 ° C), ^{N'-M ethyl-N 3} -N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl -13-phenylenedia min (m.p. 48.5-50.5 ° C), N ¹ , N ¹ -di-n-propyl-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-13 -phenylenediamine (m.p. 35.5-40.5 ° C),

N'-Ä thyI-N ³ , N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 54-55.5 ° C),

N'.N'-diethyl-N ^ N'-dimethyl ^ -dinitro-e-trifluoromethyl-U-phenylenediamine (p ^ S-46 ° C), N'-methyl-N ^ sec-butyl ^^ - dinitro-e- trifluoromethyl- ^ - phenylenediamine (mp. SI - 83 ° C), N ^I , N ^l -dimethylene-N ³ -sec.-butyI-2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (mp 92-93 ° C), N ^l , N ^l -DiäthyI-N ³ -äthyl-2,4-dinitro-6-trifluoromethyl-13-phen'ylenediamine (mp 64i-653 ⁰ C),

N ^l, N ^l-D> 'methyl-N ^3, N ³ -di-n-propyl-2,4-dinitro-6-trifluormethyI-13 phenylcndiamin (Fp.58 ^ -59.5 ⁰ C),

N ¹ , N ¹ -dimethyl-N ³ , N ³ -diethyl-2 _> 4-dinitro-6-trifluoromethyl-13-phenylenediiimine (melting point 114-116 ° C.). N ', N' -Diethyl-N ³ -sec.-butyl ^ -dinitro-e-trifluoromethyl-13-phenylenediamine (oil), N '-ethyl-N ³ , N ³ -di-n-propyl-2,4 -dinitro-6-trifluoromethyl-13-phenylei.diamiη (oil), N ^l , N ^I -dimethylene-N ³ , N ³ -diäthyI-2,4-dinitro-etriiiuormethyi-13-phenylenediamine (oil),

N ¹ - (2-hydroxyethyl) -N ³ -sec.-butyl-2,4-dinitro-6-trifluoro-methyl-13-phenylcndiamine (melting point 573-5WC),

N ³ - (1-methyl-2-methoxyethyl) -2,4-diriitro-6-trifluoromethyl-13-pnenylenediamine (melting point 120.5-121.5 ° C.), N ³ - (2,2-dimethoxyethyl) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 137-139 ° C.), h4 ³ - (3-chloropropyl) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 94 -943 ° C), N ³ (2-bromoethyl) ^{-2,4-dinitro-6-trifluoromethyl-13-phenylendiar-;} n (m.p. 149-15O ° C),

bo N ³ , N ³ -bis- (2-methoxyethyl) -2,4-dinitro-6-trifluoromethyl-13-phenylenediamine (melting point 93-94 ° C) /

Ν'11ΗΙΝ ³ (3Ί) 24ϋϊ6ΪίΙΗ113ΗΊαΪϊ

N ³ -sec.-Amyl-2,4-dinitro-6-trifluoromethyl-l 3-phenylenediamine (melting point 1053-1063 ° C), N ³ -Methyl-N ³ -äthyI-2,4-dinitro-6- trifluoromethyl-13-phenylenediamine (m.p. 89-89.5 ° C) N'-methyl-N ³ , N ³ -pentamethylene-2,4-dinitro-6-trifluoromethylene-13-phenylenediamine b5 (footnote 112.5- 113.5 ° C),

N ³ - (J-pentyl-2,4-dinitro-6-trifluormethy "il, 3-phenylendi8min (mp 1193 to 120.5 ⁰ C), ^N.) -Scc.bulyl-2.4-dinitro-6-trifluormcthyl- 1,3-phenylene diamine (mp. 126.5 to 127.5 ° C). N ^{l, N)} -Diätnyl-2,4-diniiro-6-lrifluormc (hyl-13-phenylenediamine (Fp.98-99 C) ,

N ', N' - diethyl-2,4 dinitro-6-trifluoromethyl-13-phenylenediamine (m.p. 85-86 ° C). N ^l , N ^l -di-n-propyl-2,4-dinitro-6-trifluoromethyl-U-phenylenediamine (melting point 75.5-76.5``C), N ^l -see.-butyl-2,4- dinitro-6-trifluoromethyl-l, 3-phenylenediamine (mp 58-6O ⁰ C.).

The compounds described above are excellent herbicides and are particularly useful as selective herbicides for controlling weeds in crops, especially grassy weeds such as: foxtail grass, water grass and crayfish. Many of the compounds according to the invention can be used to control weeds in crops of the grass family such as maize and rice and also small-grain crops and in broad-leaved crops such as cotton and soybeans. Furthermore, many of the preferred compounds are effective in controlling wild oats, which are a major problem in small grain crops such as wheat and barley. This discovery is surprising and unexpected in view of the phytotoxicity of many other aromatic amines with respect to grassy crops such as rice. It has further been found that the particular phenylenediamines according to the present invention are much less volatile than many other substituted aromatic amines and have better soil penetration and also better stability to UV light.

The use according to the invention can take place both before the crop plants sprout and also afterwards. by applying the active ingredients to the soil in which the weeds will grow. Already Accrued weeds can be killed or prevented from growing or the seeds germinating undesirably riiän / cn be vefnihdei'i. In this way, the connections can be used in the meantime are to control the growth of weeds by adding a phytotoxic amount of one or several active ingredients according to the present invention in the place to be protected, d. H. the soil in which the Grasses grow, or will grow, or applied to the foliage of growing plants. The term "weeds" as used above and below denotes the growth of all Including unwanted plants. ~

In general, the amount used is about 0.1 to about 28 kg / ha of one or more of the active ingredients, to achieve effective control of unwanted plant growth. Preferably the Products used in amounts of from about 0.28 to about 5.6 kg per hectare. With these amounts, the unwanted weeds with little or no damage to the desired crop plants killed or stunted in growth

The following examples illustrate the herbicidal effectiveness of some typical representatives of the invention Links.

Example I.

The compounds under investigation became more representative of a large class by the preemergence method Weeds and crops evaluated. Greenhouse boxes were filled with goosefoot, grass, wild oats, foxtail grass. Winch. Water grass. Rice. Beet, cotton, corn. Planted barley and soybeans. At the The same day the flat coasts were planted, they were treated with an ethanolic solution of the test Compound sprayed in an amount equivalent to 2.24 kg / ha. The boxes were kept in the greenhouse and watered if necessary. 21 days after the treatment, the plants were tested for herbicidal activity evaluated and classified on a scale from 0 to 9, where 0 = no effectiveness, 5 = Significant damage with little killing and 9 = means complete killing. The following results were crhal'en.

Table I.

Test substance D. activity CH WHERE F. M. R. V. 'R rice SB CO CR OR B. SO (DTP - 2,4-L) initro-6-trifluoromethyl- P. SB B. ₅ 1,3-phenylenediamine) 0 5 9 0 CO 9 0 4th 3 SO I. 0 0 N'-ethyl-N ³ -sec-butyl-DTP 9 1 8th 9 1 9 0 4th 1 4th 0 I. '■ methyl- N ³ -sec-butyl- DTP 9 1 2 7th 0 2 9 0 3 0 0 0 0 N'.N'-dimethyl-NM ^ -diethyl-DTP 9 3 8th 9 1 9 0 I. 0 I. 1 I. ο N'-sec-butyl-N ^ -dimethyl-DTP 9 0 3 9 0 7th 0 0 0 0 I. 0 N '-sec-butyl-N ³ , N ³ -diethyl- DTP 2 1 5 6th 0 4th 0 I. 1 0 0 0 N '.N' - dimethylene-N ³ , N ³ -di-n-
propyl-DTP
N, N-di (n-propyl) -2,6-dinitro-4- 8th 8th 9 8th 7th 6th 8th 8th 6th 8th 9 9 5 trifluoromethylaniline ("trifluoroaline") *) 9 N.N-D- (n-propyl) -2,6-dinitro- 8th 9 9 8th 8th 7th 9 5 9 8th 9 p-toluidine ("Dipropalin") *) 8th N-Allyl-N - (/? - chloroethyl) -4- 7th 9 8th 8th 9 8th 7th 6th 9 9 8th trinuormeinyi ^ .o-diniiroaniiin ") 8th o N-propyl-N - (/? - chloroethyl) -4- 9 9 8th 8th ■ / 8th 9 6th 9 9 9 trifluoromethyl-2,6-dinitroaniline ^# ) 9 N-sec.-ButyM-trifluoromethyl ^ .e- 7th 9 9 9 8th 7th 8th 8th 9 8th 8th dinitroaniline *) 9 5P = goosefoot F Foxtail grass Corn CH - grass M - Wind" Sugar beet barley WHERE - wild oats W - cotton Soybeans *) Comparison means. Water grass example

The compounds to be tested were both pre-germinated and post-germinated evaluated herbicide to be used on a large class of weeds and crops. Greenhouse flat boxes were planted with the plant species tested in Example 1 and the boxes on the same day Planting with an ethanol solution of the substances to be tested in an amount corresponding to 2.24 kg / ha sprayed

Another set of flat boxes were planted with the same plants and treated after the plants germinated and grown about 1 inch (2.5 cm) tall. These boxes were also made with an ethanol Solution of the substances to be tested in an amount corresponding to 2.24 kg / ha treated according to the activity determine germination. The flat boxes were kept in the greenhouse and watered if necessary. 22 days After the treatment, the boxes were evaluated and, as described in Example 1, classified. the the following results were obtained:

Table Il

Plant species Test substance A Test substance B Tesl substance C

before after before after after

Goosefoot 8 4 9 4 8 3

Grass 2 2 3 0 3 2

Wild oats 9 3 9 3 9 3

Foxtail grass 9 8 9 8 9 5

Winch 0 3 4 4 0 3

Water grass 9 8 9 9 9 7

Rice 0 0 0 0 0 0

Sugar beet 6 19 4 2 1

Cotton 0 6 4 4 0 3

Corn 0 0 4 2 0 0

Barley 0 0 10 0 1

Soybeans 0 3 3 4 0 3

Test substance A - N'-methyl-N ³ , N ³ -di-n-propyl-Z4-dinitro-6-trifluoroniethyl-1,3-phenylenediarnine. Test substance B = N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-1J-phenylenediamine. Test substance C = N ^I -methyl-N ³ , N ³ -diethyl-Z4-dinilro-6-trifluoromethyl-U-phenylenediamine.

Example 3

Greenhouse flat boxes were filled with goosefoot, crab grass, wild oats, giant foxtail grass, sorghum, Water grass, rice, Johnson grass. Cotton, corn, barley and soybeans planted on the same day of the

The flat boxes were planted with an ethanolic solution of the substance to be tested in an amount sprayed accordingly 1.12 kg per hectare. The flat boxes were kept in your greenhouse and when needed watered. Sixteen days after the treatment, the flat boxes were evaluated and for herbicidal Effectiveness as described in Example 1, classified. The following results were obtained:

Table III

Acid substance activity

(DTP = 2.4-Diniiro-6-trifluoroniethyl-P CB

1,3-phenylenediaminej

WHERE F

SG W JG CO CR B

SO

N ', N ³ -diethyl-DTP N'.N'-di-n-propyl-DTP N'-ethyl-N ³ , N ³ -diethyl-DTP N'-ethyl-N ³ , N ³ -di-n -propyl-DTP N, N-di- (n-propyl) -2,6-dinitro-4-trifluoromethylanil ("trifluralin") *) N, ND- (n-propyl) -2,6-dinitrop-toluidine ( "Dipropalin") *) N-Aliyi-N - (/ y-chloroethyl) -4-trifluoromethyl-2,6-dinitroaniline *) N-propyl-N - (/? - chloroethy!) - 4-trifluoromethyl-2, 6-dinitroaniline *) N-sec-butyl-4-trifluoromethyl-2,6-dinitroaniline *)

4th 5 1 3 3 2 O 4th 1 0 0 0 O 5 2 7th 1 3 O Oil 1 0 0 1 5 6th 4th 8th O 8th O 5 0 0 0 0 3 5 5 7th O 6th O 5 0 0 0 0 8th 9 8th

Goosefoot crab grass wild oats

SG

Fox tail grass

Sorghum

Water grass

JG

CO

Johnson grass

cotton

CR -

SO -

Corn

barley

Soybeans

*) Comparison means.

example

Greenhouse flat boxes were planted with soybeans, velvet leaf, wheat and millet. On the day of planting the boxes were filled with an ethanolic solution of the substances to be tested in an amount corresponding to Sprayed 5.6 kg per hectare. The boxes were kept in the greenhouse and watered when necessary. 19 to 21 Days after the treatment, the boxes were checked and the plants for herbicidal effectiveness, as described in Example 1, classified. The following results were obtained:

Test substance (DTP = 2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine) activity
SO VL

Ml

N'.N'-dimethylene-NP-sec.-butyl-DTP N ', N'-dimethylene-N ³ , N ³ -diethyl-DTP N ³ - (3-chloropropyl) -DTP N ³ , N ³ -bis - (2-methoxyethyl) -DTP N ^J - (1-methyl-2-methoxyethyl) -DTP N ³ - (2-bromoethyl) -DTP N ³ -isobutyl-DTP N ³ -sec.-amyl-DTP N ³ - (3-Pentyl) -DTP N ³ -sec.-Butyl-DTP N \ N ³ -Diethy] -DTP N'-methyl-N ³ , N ³ -pentamethylene-DTP N '- methyl-N ^J - (3- pentyl) -DTP N'.N'-diethyl-DTP N'-sec-butyl-DTP N '- (2-hydroxyethyl) -N ³ -sec.-butyl-DTP

N, N-Di ^ n-propylV2,6-dinitro-4-trifluoromethyl-aniline ("Trifluralin") *) N.N-D- (n-propyl) -2,6-dinitro-p-toIuidine ("Dipropalin") ·) N-AHyl-N-f / f-chloroethyl ^ -trifluoromethyl-Ze-dinitroaniline *) N-propyl-N - (/? - chloräthyi) -4-trifluoromethyl-2,6-dinitroaniline) N-sec-butyl-4-trifluoromethyl-2,6-dinitroaniline *)

0 1 3 9 0 0 1 9 0 4th 3 9 4th 5 6th 9 4th 5 9 9 0 2 0 8th 2 8th 5 9 4th 8th 9 9 4th 7th 8th 9 4th 7th 8th 9 5 7th 8th 9 0 0 2 9 3 6th 5 9 3 4th 8th 9 3 4th 9 9 0 0 4th 9 9 8th 8th 9 9 9 8th 9 7th 7th 8th 8th 8th 7th 8th

SO
Vl.
O
MI

Soybeans Samtblatl oat millet

*) Calibrants.

Table V Activity level Plant species 8th Foxtail grass 8th Wild oats 9 millet 9 Water grass 9 Crab grass 9 Goosefoot 5 Velvet leaf 0 Corn 0 cotton

Example 5

N ^? - (l-Methyl-2-methoxyethyl) -2,4-diniiro-6-trifluoromethyl-1,3-phenylenediamine is particularly valuable for the selective control of weeds in maize and cotton crops. For example, an ethanolic solution of the compound was applied to buoys in an amount equivalent to 0.28 kg per hectare and then placed in a greenhouse flat box by mixing. On the same day, foxtail grass, wild oats, millet, water grass, crab grass, goosefoot, velvet leaf and corn were planted in the mixed treated beds. The flat boxes were kept in the greenhouse and watered if necessary. 14 days after the treatment, the flat boxes were tested and the plants with regard to the herbicidal activity, as described in Example 1,

ίο classified. The following results were obtained:

Since a relatively small amount of one or more of the active 2,4-dinitro-13-phenylenediamines according to the invention should be distributed as evenly as possible over the area to be treated, the products preferably mixed with customary liquid or solid carriers for herbicides. So can the products mixed with a powdery carrier or impregnated onto it. Suitable carriers are e.g. B.

Lime, talc, clays, bentonite, calcium chloride, vermiculite, calcium carbonate. On the other hand, the active ingredients also in a liquid carrier such as water, kerosene, alcohols, diesel oil, xylene, benzene, glycols or ketones be dissolved or suspended. A surfactant is preferably added to the dispersion, Support emulsification and coating. The surfactant can be both ionic and non-ionic, be liquid or solid. The term "surfactant" used here is intended to include all such compounds include, commonly referred to as humectants, dispersants, and emulsifiers. Typical surface-active substances are alkyl aryl sulfonates, the fatty alcohol sulfates, the sodium salt of naphtha sulfonic acid, A.! Ky! Ary! Poiyäthera! Kohc! E,! Angkettige qusrterr.äre AmrttoniunvVerbindijngen, Natriurrisslzc of alkyl sulfonic acids based on petroleum products, polyoxyethylene sorbitan monolaurate and the like. and humectants are sold under numerous trademarks and can be found in either Form of pure compounds, in the form of τ mixtures of several compounds, the same general Group or in the form of a mixture of compounds from different groups. Surfactants can also be added to herbicide products that have an inert solid Contain carrier.

Concentrated preparations containing the active ingredients are subsequently applied (e.g. with water) to the desired concentration for application on plants and soil brought the advantage of such concentrates lies in the fact that they can be made by the manufacturer in a form that the consumer can only use on Place accessible carriers, preferably water, must mix, thus minimizing shipping costs be lowered. Such concentrates can contain from about 5 to about 99 percent by weight of one or more of the active 2,4-Dinitro-13-phenylenediamines together with a liquid or solid carrier or diluent

contain. Liquid carriers that are miscible with the active ingredients or other liquids in which the Active ingredients that can be suspended or dispersed can also be used. Here too will generally a surfactant is admixed to facilitate dissolution or dispersion in water. In however, for such concentrates the carrier material itself can also comprise the surfactant.

The herbicide preparations can also contain other beneficial additives such as humectants, oils and

Contain contact-increasing substances. Other herbicides such as sodium borates, sodium chlorate, Chlorophenoxy acetic acids, substituted uracils and ureas, triazines, benzimidazoles, carbamates, anilides, Amides and halogenated fatty acids are added to the herbicide preparations according to the invention and used with them will.

The following examples illustrate the production of suitable herbicidal preparations according to the present invention

Invention.

Example 6

5% powdered active ingredient
95% granulated clay

A granulated preparation can be produced in that the above-mentioned ingredients in be mixed uniformly in a rotary mixer when dry. A fine spray of water is on

the mixture is sprayed on during the mixing process in order to allow the active ingredient to adhere to the clay. That Material is then air-dried while continuing the mixing process, thereby obtaining a granular preparation which can be applied to soil or plantings by hand or by means of a mechanical spreader.

Example 7

85% N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-l 3-phenylenediamine 14% bentonite clay 1% sodium lauryl sulfate as surface-active substance io

The preparation which is a wettable powder is produced in that the 2,4-dinitro-13phenylenediamine is finely divided and uniformly mixed with the powdered bentonite clay and the powdered sodium lauryl sulfate. The wettable powder can be added to water or a hydrocarbon oil and mechanically agitated to ensure uniform dispersion. This is:; Dispersion can be sprayed onto the ground or planting using conventional equipment. - T

Example 8 i

25% Ν ^! -ΑΛνί-Ν ³ , Ν ³ -αΐ3Λν1-2,4-όίηίΐΓθ-6-ΐπΠυοΓπιβΐην1-13-phenylenediamine 20 a

5% aromatic sulfonic acid oxide condensate as a surface-active substance Ά

70% xylene r.

The 2,4-dinitro-13-phenylenediamine is dissolved in xylene and forms a concentrated solution. The emulsifier

is then dissolved and a liquid preparation of an emulsified concentrate is obtained. The emulsifiable 25: ■;

Concentrate can be added to water to dilute the product to the desired concentration. \ li E? can then be sprayed '..' on the ground or vegetation using conventional equipment. %

Claims (1)

Patent claims: 1. Use of compounds of the general formula Ri R ₂ NO ₂ N R4 wherein Ri, R ₂ , R3 and R4, which can be the same or different, are hydrogen atoms or alkyl groups, which can be substituted by halogen, hydroxy and / or alkoxy, and where at least one of the groups Ri, R2, R3 and R4 is not hydrogen or Rj and R ₂ together and / or R ₃ and R4 together are one Are alkylene groups with 2 to 6 carbon atoms, as herbicides. Z Use according to claim 1, characterized in that Ri is hydrogen, R ₂ and R ₃ , which are the same or can be different, are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms and R4 is an alkyl group having 1 to 5 carbon atoms 3. Use according to claim 2, characterized in that the total number of carbon atoms in the groups Ri, R ₂ , R3 and R * is about 4 to 8 4. Use according to claim 2 or 3 for controlling undesired plant growth in crops of cotton, soybeans, corn or rice.