DE2013509C3 - - Google Patents

Description

if halogen, hydroxy or lower alkoxy are substituted.

Tuted lower alkyl groups with 1-6 carbon atoms, examples of hydrocarbon radicals so defined

where at least one of the groups R ₁ , R _t , R ₃ and »o are methyl, ethyl, n-propyl, isopropyl,

R _{4 is} a hydrocarbon radical as defined, or η-butyl, sec-butyl, n-pentyl, sec-pentyl, n-hexyl,

R ₁ and R ₂ together form an alkylene group with 2-hydroxyethyl, 2-methoxyethyl, 2,2-dimethoxy

2 to 6 carbon atoms and / or R _{3 means} ethyl, 3-ethoxypropylene, 2-bromoethyl, 3-chloropropyl

and R ₄ together is an alkylene group with 2 to pyl, l-methyl-2-methoxyethyl, chlorhexyl, cyclo

6 carbon atoms denotes the optionally »5 propyl and cyclobutyl group.

by an oxygen atom in the chain under- As mentioned, R ₁ and R _{2 can} together and /

can be broke. or R ₃ and R ₄ together represent the molecular fragment

2. N ³ , N ³ - diethyl - 2,4 - dinitro - 6 - trifluorine - be a ring structure of which the amino nitrogen is tllvyl-1,3-phenylenediamine. is a part. Such a ring structure is made possible by the

3. N ³ - (1 - methyl - 2 - methoxyethyl) - 2,4 - di- 30 Formula η ilro-6-trifluoromethyl-1,3-phenylenediamine.

- N Z

reproduced, wherein Z is an alkylene group with

The present invention relates to new 6-Trifiuor- 35 means 2 to 6 carbon atoms, which in the case of R ₃ methyl ^^ dinitro-l ^ -phenylenediamines. and R ₄ optionally by an oxygen atom in the

The inventive o-trifluoromethyl ^^ - dinitro chain can be interrupted.

1,3-phenylenediamines correspond to the general examples are the dimethylene, trimethylene,

Formula tetramethylene, diethylenoxy, diethylenimino and

R, R ₂ 40 the hexamethylene group.

\ / Preferred compounds are those in which

JsI R ₁ hydrogen, R ₂ and R ₃ hydrogen and / or alkyl

i groups with 1 to 5 carbon atoms and R ₄ one

y is NU ₂ alkyl group of 1 to 5 carbon atoms. In front-

Q '45 is preferably the total number of carbon

'X / ³ atoms in groups R ₂ , R ₃ and R _{4 are} about 4 to 8.

N Compounds in which both R and R _{2 are} water

\ β is substance are particularly preferred.

* The compounds according to the invention represent

wherein R ₁ , R ₂ , R ₃ and R ₄ , which are identical or different, can neither be crystalline solids nor high-boiling liquids, hydrogen atoms or, if appropriate, keiten. In general, they are only very slightly halogen, hydroxy or lower alkoxy-substituted and readily soluble in water moderately soluble in customary lower alkyl groups with 1 to 6 carbon atoms, organic solvents such as ethanol, acetone, at least one of the groups R ₁ , R ₂ , R ₃ and R _{4 being} an ether and benzene. The compounds can be defined as a hydrocarbon radical, or R, and 55 easily by reacting one or two amines or R, 2: together an alkylene group with 2 to 6 carbon ammonia with a 2,4-dihalogen-3,5-dinitrobenzo) Means stofl'atomen and / or R ₃ and R ₄ together according to the following equation:

X ₁ ^{Rl R =}

Y 'N + 2HX ₁

NC ₂ ^X R ₄

"J

3 4

_where bcidiebeidenXjhalogenatome andR ₁ , R ₂ , R ₃ UiIdR ₄ I. ^ dichloro-SS-dinitrobenzotrifluoride, 30 ml of ethanol have the same meaning as given above. and added 20 ml of diethylamine. The reaction tube If Ri ^{and R} * ^R s ^{and R} 4 are the same, ie they were melted shut and the substituted N ^ amino group and the substi heated to 94 to 99 ° C in a bath for 46.5 hours. The cooled N ³ -amino group in the end products was then immediately opened, 5 reaction tube was opened and the content was evaporated to dryness, the reaction in one step was used. The residue obtained was extracted from at least two moles of amine for each mole of boiling diethyl ether with 200 ml and the 7 4-dihalo-3,5-dinitrobenzene instead. The insoluble amine formed is filtered off. The ether extract, the hydrogen halide compounds can be evaporated to dryness and the residue dissolved in 40 ml of excess amine or a tertiary amine neutral io boiling 95% ethanol and 10 ml of water. If R, and R _{2 are} different from R ₃ and R _4, the product crystallized and became the On cooling, two reaction stages are necessary in which the product is filtered off. The desired product was used as a crystalline solid with a different amine (or ammonia) in each stage yield of 30%. In the first stage, a melting point of approximately 72.5 to 74.5 ° C. is obtained. After environmental i mole of the N ³ group-forming amine having about 15 crystallization, the product melted at 74 ° to 75 ° C. ΪΜ0Ι of the 2,4-dihalo-3,5-dinitrobenzene in the opposite direction.

puts. The first halogen atom to react is Calculated ... C 47.61, H 5.60, N 14.81%;

that found between the nitrogen groups on the aromatic ... C 47.34, H 5.58, N 14.64%.

Ring seated halogen atom. This stage will be advantageous.

possibly in a non-polar solvent like ao ^Be ! ^sp ' ^e ..'. ,. .

a m hydrocarbon carried out in which the N »N'-B, s- (d.methyl ^, 4-d.nKro.

Shalogenide is insoluble and thus by FiI- 6-fluoromethyl-U-phenylenediamine

tration can be easily separated. In the second this connection was made in a corresponding manner

Stage, about 2 moles of the group N'-forming by reacting 2,4-dichloro-3,5-dinitrobenzo- ^ mjns with the monoamine compound to form 25 trifluoride obtained with dimethylamine. The crystalline of the unsymmetrically substituted melts unoccupied at 125.5 to 126.5 ^C. C. 1,3-phenylenediamine product. The second reaction stage takes place in an elemental analysis:

closed reaction vessel as if it were closed. .. C41.00, H 4.07, N 17.39%;

zenen glass tube or an autoclave instead of found ... C 40.91, H 4.01, N 17.54%.

to avoid loss of amine and a lighter con-30. .

Trolls to allow the reaction. On the other hand, »" ,,, "·,? ' ^S ^ ' ^e ,, - ,,,, ■ ■

Even at atmospheric pressure in the presence of N ', N ^: ' -B _I s- (d.-n- _P ro _P yl) -2 4-d; n, tro-

a solution ^ miUels worked like an alcohol 6-tnnuormethyl-1,3-phenylend, am, n

in which the amine is easily soluble. When deployed this connection was made in an appropriate manner

It is not necessary for high-boiling amines to avoid an enzo-closed compound by reacting 2, - dichloro-3,5-diniiro Received reaction vessel for the reaction of cinzu trifluoride with di-n-propylamine. The product set; on the contrary, it suffices that the reaction in the poor is a high-boiling oil. using a suitable solvent. Example IV

For the preparation of the ^{Pro- N 3} -Di-sec -butvl-2 4-dinitro-

The reaction temperature used is preferred - 40 6-trifluoromethyl-1,3-phenylenediamine

wise in the range of about 20 to 120 C, namely '' ^}

both when using a closed reaction To a solution of 5.00 g (0.0164 mol) of 2,4-di-

eefäßes as well as in the implementation of the reaction compo-chloro-3,5-dinitrobenzotrifluoride in 25 ml of absolute nents at normal pressure in the presence of a Lo-ethanol and 10 ml of dioxane were 5.04 g (0.069 mol) solvent. Halogen-45 sec-butylamine is formed as a by-product, given with stirring. The resulting hydrochloric acid in the presence of over-mixture was stirred and under reflux for 24 hours The amine is heated to the boil in the corresponding amine halide flux. Then became the genius of solving which was easily converted by washing medium by evaporation under reduced pressure in water or by filtration after dissolution of the reac- separated and the residue in 75 ml of chloroform tion product is dissolved in an identical solvent. The chloroform solution was used three times can be removed. The desired products can be extracted 75 ml of water and then via sodium after known methods, e.g. B. dried by recrystalline sulfate. After removal of the mitigation solution getting cleaned. The residue is dissolved in ethanol by means of distillation

The dissolved l-trifluorine used as starting materials and the ethanolic solution can be removed by means of activated charcoal, methyl-2 4-dihalo-3,5-dinitrobenzenes. The ethanol is easily distilled off under reduced pressure by nitration of the l-trifluoromethyl-2,4-di · - and the residue is extracted with boiling halogen-benzenes with a mixture of fuming η-hexane. The hexane solution was: cooled nil nitric acid and fuming sulfuric acid at a 0 C, \ <n temperature was deposited thereby forming a Ol, produced below 8O ⁰ C. from which the hexane was decanted. Have a go

The following examples describe the production of 60 product was al with a yield of 60.7%: representative members of the clear amber oil of the invention were obtained. Connection group. "Elemental analysis:

Calculated ... N == 14.80 _{/ o}

Example 1 found ... N = 15.37%

N \ N ³ -Bis- (diethyl) -2,4-dinitro- ₆

6-trifluoromethyl-1,3-phcny] enediamine Examples V to XIV

In a thick-walled reaction glass tube with a The following examples were in corresponding

Ohalt of about 50 ml were 5 g (0.0163 mol) of manner by reaction of 2,4-dichloro-3,5-dinitro

Obtain benzotrifluoride with the corresponding amines:

VK ¹ , N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Fp .: 169 to 170'C:

VI N ³ -diisopropyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; M.p .: 66.5 to 67.5 C;

VII N ¹ , N ³ -di (2-chlorally!) -2,4-diniTO-6-trifluoromethyl-1,3-phenyl-diamine; M.p .: 82.5 to 83.5'C;

VIII N ^l , N ³ -di (2-methoxyethyl) -2,4-dinitro-fi-fluoromethanol-1,3-phenylenediamine; M.p .: 98 to 99 C;

IX N ^! , N ³ -diallyi-2,4-dinitro-6-trifluoromethyl-
!, 3-phenylenediamine; M.p .: 79 to 80 ^: C;

XN \ N ³ -di (3-methoxypropyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Oil; ¹ p

XI N \ N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Fp .: 96 to 97 C:

XII N ', N ^ dicydohexyl ^' t-iJinitro-o-irifluoromelh \ l-l, 3-pheny! Endiamsn; M.p .: 107.5 to

108 C; * °

XIII N '^' ^^^^ Di-itetramcthylenJ - ^^ - dinitro-6-triiluomethyl-1,3-phenylenediamine; M.p .: 164 to 164.5 ⁰ C;

XIV N ¹ , N ', N ³ , N ³ -di (pentamethylene) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Fp .: 139 to 140 C.

At spie! XV

N, N-di-n-propyl-3-chloro-2,6-dinitiro-4-trifluoro-

methylaniline

7.0 g (0.023 mol) of 2,4-dichloro-3,5-dinitrobenzotrifluoride, 4.64 g (0.0458 mol) of di-n-propyb.min and 40 ml of absolute ethanol are given. The pipe was melted shut and heated in an oil bath to 94 ^ to 99 ° C for 98 hours. After cooling the reaction mixture, the tube was opened and the reaction mixture was opened evaporated to dryness to give an oily residue which coalesced with boiling Diethyl ether was extracted. The insoluble din-propylamine hydrochloride was separated by filtration and washed with additional ether. The combined ether filtrals were evaporated, whereby an oily orange residue was obtained, which was dissolved in 100 ml of absolute ethanol and coated with activated charcoal was removed. The ethanol and volatiles were reduced by evaporation The pressure was separated so that 6.77 g of a viscous reddish oil were obtained.

50 N \ N ³ -di-n-propyl-2,4-dinitro-

6-trifluoromethyl-1,3-phenylenediamine

In a glass reaction tube 4.0 g (0.OIOS mol) of NN-di-n-propylO-chloro ^ / vdinitro-4-trifluoromethylaniline, 5.82 g (0.0237 mol) of 6.9% ethanolic ammonia and 35 ml of ethanol were placed . The tube was sealed shut and heated to K) OC in an oven for 68 hours. The tube was cooled and separated from the contents of the ethanol by evaporation. Water was then added to the solid orange residue in order to dissolve the ammonium chloride formed. The insoluble product was separated by filtration. Is was then dissolved in boiling 95 ", igcm ethanol. After cooling, orange-colored needles and a tribes PuKc crystallized out. The yellow powder was found to be 2A - diitroilliiormethyl - 1,3 - phenylenediamine and was obtained from the desired product through filtration

separated off after extraction with boiling hexane. The desired product dissolved in the hexane was isolated from the filtrate by evaporation of the hexane. The residue was recrystallized from 95% ethanol, whereby orange-colored needles with a melting point of 124 to 125 ^° C. were obtained.
Elemental analysis:

Calculated ... N = 15.99%

found ... N = 16.00%

Example XVI

N'.N'-Dimeihylen-N ^ NMi-n-propyl ^ -dinitro-6-trifluoromethyl-1,3-phenylenediamine

A solution of 4 g (0.0108 mol) Ν, Ν-di-n-propyI. S-chlorO.o-dinitro ^ -trifluoromethyianiline and £ 0.93 Ethylenimine (0.0216 mol) in 50 ml of absolute ethene were stirred at 35 ° C. overnight. The solvent was separated by evaporation under reduced pressure to give a residue which was extracted with boiling hexane. The hexane extract was evaporated to dryness and the residue dissolved in absolute ethanol. After decolorization with activated charcoal, the ethanol and the volatile constituents separated by evaporation under reduced pressure, whereby the desired Product was obtained as a viscous amber oil. This product was made possible by its proton nuclear magnetic properties Resonance spectrum (PNMR spectrum) identified.

Example XVII

N'-ethyl-N ³ .N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine

N, N - dimethyl - 3 - chloro - 2,6 - dinitro - 4 - trifluoromethylaniline was with ethylamine in a fused tube as described in Example XV, reacted, whereby the desired product with a melting point of 51.5 to 52.5'C obtained would.

The following products are also obtained as described above:

N'-Ethyl-N ³ -sec.-butyl-2,4-dini (ro-6-trifluoromethyl-1,3-phenylenediamine: Mp .: 92.5 to 94'C; N ¹ -scc.-butyl-N ³ , N ³ -dir; iethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenedinine; oil;

N ¹ -scc.-BUtyl-N ³ , N ³ -diethyl-2,4-dinitro-6-trinuomethyl-1,3-phenylenediamine; Oil;

N'-methyl-N ³ .N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediarnine: Mp .: 71.5 to 73.5 ^C C; N ¹ -meth \ iN ^: '.N ³ -di-n-piOpyl-2., 4-dinitro-6-trifluoromethyl-1,3-phenyl-diamine; Fp .: 48.5 to
50.5 X:

N'.N'-di-n-propyl-N ^: ', N ^:) -dimel: hyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; M.p .: 39.5 to 40.5 ^: C;

N ¹ -ethyl-N ³ .N ³ -diethyl-2,4-dinitro-6-tri1uoromethyl-1,3-phenylenediamine: Mp .: 54 to 55.5 ³ C ^- N ¹ .N ' ^I -diethyl-N ³ . \ ^{: i-} dimethyl-2,4-dinitro-6-tri- 'fluoromethyl-1,3-phen \! enediamine; Mp .: 45 to 46'C N ¹ -Metiyl-N ^{: l} -scc.-buiyl-. '^> , 4-dinitro-6-trifluoromethyl-1.3-phenvlenediamine: Γρ .: 81 to 83'C:
N '.N' -Dinieth \ ^l len- \ ³ -sec.-butyl-2,4-dinitro- (i-trifluoromethyl-1,3-phenylenediamine; Mp .: 9 " ¹ to 93 C;

N'-propargyl-N ³ .N ^{: i} -di-n-propyl-2,4-dinitro-6-trifliormethy! -1.3-ph <? Ny! Enediamine; Oil:
N "-Propargyl-V ^t .N ^{: i} -diethyl-2.4-dinitro-6-trifluoromeihvl-1.3-phenvlcndianiiii: Oil:

N'-N'-diethyl-N ^ ethyl - ^ - dinitro-o-trifluorometh \ ll, 3-phcnylcndiamine: Ι ^Γ ρ .: 64.5 to 65.5 ^! C: N'-l'ropargyl-N ^ -sec.-hulyl ^ .A-dinitro ^ i-trifluoromethyl-1,3-phenylenediamine; Γρ .: 53 to 54 C: N'.N'-Dimcthyf-N ^ .N ^ di-n-propylO ^ -dinitro-6-tri (luormclliyl-1,3-phenylenediamine; l ^; p .: 58.5 up to 59.5'C:

NVN'-dimethyl-N ^ N ^ diethyl ^ -dinilro-ö-trifluoromethyl-1,3-phenylenediamine; Γρ .: 114 to 116 C:

N'.N'-diethyl-N'-sec.-bulylO ^ -dinitro-ö-trifluoromethyl-1,3-phenylcndiamine; Oil; N ^I -A * ethyl-N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoroniethyl-1,3-phenylenediamine: oil;

6-trifluoromethyl-1,3-phenylcndiamine; oil; N'-propargyl-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: mp: 66 to 67 C; N ¹ - (2-hydroxyethyl) -N ³ -sec.-huiyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Fp .: 57.5 to 58.5'C:

N ³ -cyclopentyl-N ³ -methyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Mp .: 87 to 88.5 "C; N ³ - (1-methyl-2-methoxyethyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Mp .: 120.5 to 121.5" C: '

N ³ - (2,2-dimethoxyethyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: M.p .: 137 to 139 "C; N ³ - (3-chloropropyl) -2,4-dinilro-6-trifluoromethyl -1,3-phenylenediamine; mp .: 94 to 94.5 ° C; N ³ - (2-bromoethyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: mp .: 149 to 150 ° C; N \ N ³ -Bis- (2-methoxyethyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; m.p .: 93 bis

N ³ -cyclopropyl-2,4-dinitro-6-irifluoromethyl-

1,3-phenylenediamine: m.p .: 180 to 1.5 C; N'-methyl-N ³ - (3-pentyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: m.p .: 73.5 to 74.5 ^° C; N ³ -sec.-amyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: Mp .: 105.5 to 106.5.degree. C;

N ¹ -meth'yl-N ³ .N ³ -diäthyienoxy-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: Mp .: 201 bis

N ³ -Methyl-N ³ -äthy '.- 2,4-dinitro-6-trifluorometh \ i-1,3-phenylenediamine: Mp .: 89 to 89.5 "C; N ³ , N ³ -diallyl-2,4-dinitro -6-trifluoromethyl-1,3-phenylenediamine; m.p .: 72 to 73 ^: C:

N'-methyl-Na ^^ pentamethylene ^^ - dinitro-6-trifluoromethyl-1,3-phenylenediamine; M.p .: 112.5 to 113.5 ° C;

N ³ - (3-pentyl) -2,4-dinitro-6-trifluonethyl-1,3-phenylenediamine: Mp .: 119.5 to 120.5X; N ¹ -Methyl-N ³ -cyclohexyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; M.p .: 127.5 to 128.5 ^; C:

■ N ³ - (2-chloroallyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; M.p .: 102 to 103'X; N ³ -sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: M.p .: 126.5 to 127.5 "C; N ³ .N ³ -diethyl-2,4-dinitro-6 -trif! uorrnethyI-1,3-phenylenediamine; mp .: 98 to 99 C:

N'.N'-diethyl ^^ - dinitro ^ -trifluoromethyl-1,3-phenylenediamine; M.p .: 85 to 86 ⁼ C; N ¹ .N ¹ -Di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine: Mp .: 75.5 to 76.5 C; N'-sec-ButylO ^ -dinutro ^ -trifluoromethyl-1,3-phenylenediamine; M.p .: 58 to 60C.

The following example illustrates a typical manufacture for the 2,4-dihalo-3,5-dinitrobenzotrifluoride intermediatesc.

Example XVIIl

2,4-dichloro-3,5-dinitroben7-trifluoride

Fuming sulfuric acid (600 ml) containing 30 to 33% free SO 2 was immersed in an ice bath 2-1 three-necked flask stirred. This was done

ίο fuming 90% nitric acid (585 ml) added. Then 148.8 g (0.692 mol) of 2,4-dichlorobenzotrifluoride were added. This slurry was then heated to 76 ° C with stirring and for 96 hours at 76 \ - held for 1 ° C. The mixture was then cooled and the acid removed from the crust of the crystalline product. 1000 ml of water was then added to the broken solids and the slurry extracted with 500 ml of toluene with stirring. The toluene solution was replaced with a further 500 ml of toluene% 'and then washed successively with 500 ml of water, twice with 500 ml of 5% sodium bicarbonate solution and finally with 500 ml of water. The toluene was removed by evaporation under reduced pressure and the residue was dried overnight. There were 166.6 g (79 "O d. Th.) Of the desired 2,4-dichloro-3,5-dinitrobenzotrifiuorid of melting point 67 to 72 ⁰ C obtained. After Umkrisiallisation from ethanol, the product melted at 74-75" C .

The compounds described above are excellent herbicides and are particularly useful as selective herbicides to control weeds in crops, especially grassy ones Weeds such as foxtail grass, water grass and crab grass. Many of the invention Compounds can be used to control weeds in desired crop plants Grass family such as maize and rice and also small-grain plants and in broad-leaved crops how cotton and soybeans are used. Furthermore, many of the preferred compounds are effective for controlling wild oats, which is a major problem in small grain crops such as Representing wheat and barley.

Water grass and similar weeds are a serious problem in rice crops, and the Discovery of an effective selectively acting herbicide to control these weeds is one significant progress. This discovery is surprising and unexpected in terms of phytotoxicity many other aromatic amines in relation to grassy crops such as rice. It was further found that the particular phenylenediamines according to the present invention are much less volatile than many others are substituted aromatic amines and penetrate better into the boron and also have better stability to UV light.

The inventions can be applied both before the cultivated plants sprout or afterwards, d. that is, they can be applied to the soil in which the weeds will grow, or they can used to kill the weeds or prevent their growth or germination of the Prevent seeds from unwanted plants. The compounds according to the invention can thus be used for this purpose control the growth of weeds by adding a phytotoxic amount one or more of these active ingredients according to the

709S19 / 110

9 10

lying turn at the place to be protected, d. Ii. N ² -Athyl-N ² -n-prop \ l-3-nitro-5-irifluoromethyl-

the soil in which the grasses grow or grow 1,2-phenylcndiamine (4670),

or on the foliage of the growing plant N ² , NM) in-propyl-3-nitro-5-trifiuormethyl-

zen are applied. Under the expression »Un- 1,2-phenylcndiamine (4486),

herbs ", as used above and below 5 N ^s -Athyi-N '- n-butyl-3-nitro-5-trifluoromethyl-

the growth of all unwanted plants will 1,2-phenylenediamine (4671).

locked in.

In general, the application amount is ,, agendas ^The previously known compounds according to

about 1.13 to about 283 g of one or more of US Patent 34 42 639 were also in 11.3,

Active ingredients per m ³ , in order to effectively control the io ²² > ^{6 45} < ^{2 or} 90.4 g / m ³ :

to achieve unwanted plant growth. Pre-N, N-diethyl-2,4-dinitro-6-trifluoromethylaniline

preferably the products are used in quantities of about (4483),

2.83 to about 56.5 g per m ^{3 were} applied. With these N-ethyl-Nn-propyl-2,4-dinitrü-6-trifluormcthyI-

Quantities are the unwanted weeds without aniline (4467),

or only with very little damage to the gene 15 N- (3-pentyl) -2,4-dinitro-6-trifluoromethylaniline

desired crops killed or in wax (4669),

inhibited. N.N-Di-n-propyl ^ -dinitro-o-trifiuormetbyl-

., ..., u ·. ^{an) lin} ( ⁴⁴⁸⁴ J-

Comparison test benchmark N-Ethyl-N-n-butyl-2,4-dinitro-6-trifluoromethyl-

The following experiments were carried out in greenhouses 20 aniline (4668).

carried out using three plant boxes with each of the compounds examined. The plant boxes were kept in the greenhouse. That irrigates with and as needed. 28 days after the box marked Be-A was treated with the useful plants, the boxes were evaluated and the maize, cotton, rice and soybeans, the box marked with B in terms of herbicidal activity in the box was compared with the weeds Unchandeled control plants - crab grass, foxtail, goosefoot, purslane and classes. The four crops showed no damage. Lambsquarter and the box marked with a C The weeds were both on complete removal rr.it the weeds. Johnson grass, sand burdock, killing as well as deterioration of the vegetable wax velvet leaf and water grass planted. The seeds of the turns of the remaining plants according to the following weeds were classified at a depth of 6 mm and the 30 step scale: Seeds of the useful plants planted at a depth of 3 cm. The connections to be tested were listed in “. ■, ~ - ~ -

-,, · 1 τ- r j η j -j i ^ · obstruction of the plant kill

Athenaic solution to the bottom of each box in growth

the specified amount sprayed on the same day, "-

where the seeds are inserted. 35 0 = ineffective 5 = <25% kill

The following compounds according to the invention 1 = <10% damage 6 = 25-50% destruction

were in an amount or 2 = 10-40% damage 7 = 50-75 ° ^o killing accordance 2.83

5.65 g / m ³ applied: 3 = 40-70% damage 8 = 75-99% destruction

N ³ , N ³ -diethyl-2,4-dinitro-6-trifluoromethyl- 4 => 70% damage 9 = 100% destruction 1,3-phenylenediamine (3584), 40

N ³ - (3-PentyI _r 2,4-dinitro-6-trifluoromethyl- Each plant species was tested both in terms of the pro-

1,3-phenylenediamine (3830), percentage destruction as well as in relation to the percentage

N ³ , N ³ -Di-n-propyl-2,4-dinitro-6-trifluoromethyl- tual damage to the remaining plants.

1,3-phenylenediamine (3153). grades, where the first number is the percentage kill

The following previously known compounds according to ⁴⁵ ££. "* T'vft / *, ΓΕΚί- ^Sc ^ ^d ! ^GUnS £

US Patent 34 66 329 have been in used in amounts corresponds FCO v '° ^edeute j ⁵ ^ ^15% Abtotung

N ² , N-diethyl-3-nitro-5-tnfluonnethyl- the following results are observed with the weeds-

1,2-phenylenediamine (4485), 50 pays attention:

3584 4485 4 ^ ₃ ¹ Z ^{4 1} Z ' ² 12 4 8 12 4 8

Crab grass 9 9 0/2 7/0 7/4 8/4 0/1 6 3 6/3 9

Foxtail S / 4 8/4 0 0/1 0/1 6/2 0/1 OP 63 8/4

Goose foot 8/4 8/4 0/1 7/3 8/3 9 0 0 / Ϊ 0/2 8/3

Purslane 8/4 9 0/1 5/2 7/2 8/4 0 0 03 74

Lambsquarter 8/4 9 0 0/1 5/2 8/4 0 0 Vn 8/4

Johnson grass 7/4 8/4 0 0/1 0/2 5/3 0 5P * Z 83

Sand burdock 6/3 7/4 0 0 O ₀ / l 0 ο / ί 02 03

Velvet sheet 0/3 5/3 0 0/2 5/2 6/3 0/1 01 0 OP

Water grass 8/4 9 0 0/2 0/2 7/3 01 0 6/4 9

Average: 7/4 8/4 0/0 2/1 4/2 6/3 0/0 1/1 3/3 6/4

3584 = N ^J , N ³ -diethyl - ?. 4-dir _: i: ro-6-trifluoromethj ^: -1,3-phenylenediamine (according to the invention) 4485 = N *, N ^s -diethyi-3-nitro-5- trifluonneth> il, 2-phenylenediamine (according to US-PS 34 66 329) 4483 = N, N-diethyl-2,4-dinitro-6-trifluoromethylaniin (according to US-PS 34 42 639)

4670 2 4th G 4667 2 4th 8th 1 6/3 8/4 9 1 7/4 8/4 9 Crab grass 0/1 0/2 7/3 8/4 5/3 8.4 S / 4 8/4 Foxtail 0 8/3 7/3 8/4 5/3 0/2 7/3 7/4 Goosefoot 6/2 0/2 6/3 8/4 0/2 0/1 0/3 8/4 Purslane 0/2 0/2 0/3 6/4 0 0/1 0/2 8/4 Lambsquarter 0/2 o / i 6/3 8/4 0 S 4 8/4 9 Johnson grass 0 0 0/1 0/2 5/2 0/3 0/2 7/4 Sand burdock 0 0 0 5/2 0/1 0/1 5/1 5/2 Velvet leaf 0 5/3 7/4 8/4 o / i s / i 7/4 8/4 Water grass o / i 2/2 5/3 7/4 6/3 3/2 5/3 8/4 average 1/1 4670 --- N'-Äihyl-N ^ n-propyl-S-nitro-S-trifluoromethyl- 1,2-phenylenedi amine 2/2 34 66 329). (according to US-PS

yppyyp g

4667 = N-ethyl-Nn-propyl-2,4-dinitro-6-trilluomethylaniline (according to US Pat. No. I ¹ S 34 42 639).

3830 1/2 4669 2 4th 8th 1/4 9 1 5/2 8/4 9 Crab grass 9 9 0/2 5/1 7/5 s: 4 Foxtail 8/4 8/4 0/2 0 0 6/2 Goosefoot 8/4 9 0 0 0 6/2 Purslane 8/4 8/4 0 0 0/2 0/2 Lambsquarter 8/4 8/4 0 5/3 7/4 8/4 Johnson grass 9 8/4 0/1 0/2 0/1 0/3 Sand burdock 8/4 7/4 0 0/1 0/2 0/1 Velvet leaf 0/3 8/4 0 0/3 5/3 7/4 Water grass 8/4 8/4 0/2 2/1 3/2 5/3 Average: 7/4 o / i

4830 = N ³ - (3-pentyl) -2,4-dinitro-6-trifluomiethyI-1,3-phenylenediamine (according to the invention). 3669 = N- (3-pentyl) -2,4-dinitro-6-fluoromethylaniline (according to US Pat. No. 3,442,639).

3153 1/2 4486 2 4th 8th 4484 2 4th f 1/4 9 1 5/3 8/4 9 1 8/4 9 < Crab grass 9 8/4 0/3 5/3 8/4 6/4 6/3 8/4 8/4 t Foxtail 8/4 8/4 0/3 0/1 6/4 0/3 6/3 7/2 8/3 ι Goosefoot 8/4 9 0/2 0/1 7/4 7/4 0/2 5/4 8/4 j Purslane 8/4 8/4 0/2 o / i 6/3 7/4 5/3 6/4 8/4 ; Lambsquarter 8/4 8/4 0/1 5/1 5/2 6/4 0/1 6/4 8/4 ; Johnson grass 8/4 8/4 0 0/1 0/2 7/3 5/2 7/4 7/4 Sand burdock 7/3 6/3 0 0/1 0/1 0/1 0 0 0/1 < Velvet leaf 5/3 6/4 0/1 5/3 6/4 7/4 0 7/4 8/4 Water grass 6/4 8/4 0/2 2/2 5/3 5/4 0/1 6/3 7/4 Average: 7/4 0/2 2/2

3153 = N'.N'-Di-n-propyW ^ -dinitro-fi-trifluormcthyi-l ^ -phenylcndiamine (according to the invention). 4486 = N ^ N'-di-n-propyW-nitro-S-trifluoromethyl-1-4 -phynylenediamine (according to US Pat. No. 3,466,329). 4484 = N.N-Di-n-propyl-2,4-dinitro-6-irifluoromethylapyline (according to US Pat. No. 3,442,639).

13 14

4Γ.71 -> • 4 s 46 <iX 2 •1 8th 1 0 (. 2 7 3 1 0 4 6.4 6/4 krabbcngias 0 0/1 0 1 5 2 ο, ι s 3 7.4 6-4 Foxtail. 0 5/2 6; 2 8/7 0 0/1 0/2 0/2 Goosefoot 5/2 0 5/2 5/1 0 0/1 0/3 0/3 Purslane 0 0 0/2 0 2 0 0/1 0 3 0/3 Lambsquartcr 0 0 0'2 5/2 0 0/3 0.3 0/4 Johnson grass 0 0 O ¹ I 0 0/1 0 0/2 0/2 Sand quills 0 0/1 0 0/1 0 0 0 0 Velvet leaf 0 0/1 0 0/1 0 0/3 0/3 7 4 Water glass 0 1/1 2 1 3/2 0 1/2 1/3 2/3 Average: 1/0 0/0

4671 N ⁵ -ethyl-N ^s -n-bulyl-3-nitrc-5-trinuornicth \ ll, 2-phcnylcndiamine (according to IS-I ¹ S 34 66 329). - N-Ethyl-N-ni-butyl-2,4-dinilro-6-trine ('methylaniline (according to S. PS 34 42 639).

In addition, the following compounds according to the invention were applied in an amount corresponding to 5.65 cm ³ :

V-N1ethyl-N ^ N ³ ^ iethyl-2,4-dinitro-6-trifluoroniethyl-1,3-phenylenediamine (Λ), N ^I- methyl-N ³ -sec.-butyl-2,4-dinitro-6 -trifluoroethyl-1,3-phenylenediamine (B), N ¹ .N ¹ -dimethyl-N ³ .N ³ -dipropyl-2,4-dinitro-2,6-trinuomethyl-1,3-phenylenediamine (C), N '- (2-hydroxyethyl ) -N ³ -scc.-butyl-2,4-dinitro-6-trif! I! Ormethy! - !, 3-phenylenij '! Amine (D).

N ³ - (3-chloropropyl) -2,4-diniitro-6-trifluorometh \ l-1,3-phenyldiamine iE),

N ³ - (l-methyl-2-methoxyethyl) -2,4-dinitro- The others falling under the general formula

6-trifluoromethyl-1,3-phenylenediamine (F). Compounds show a comparable effect.

Crab grass A. 3 B. C. η [■: '4 F ^; Fox swan / 8th, τ 8/4 7/2 1 8th .3 9 (iänsefuß 6th ■> 5/2 0 0 S. 9 30th Larnb Quarter 6; T 7/3 8/3 1 3 6.4 Johnson grass 5 / 3 8/3 6/3 5., '2 7th .4 9 Sand Velcro c 5 5/2 6th 9 Samthlalt 0 1 1 3 8 4 35 Water crashes 3 4th 1 2 ~> Ί / 4 3 8th' 5 3 6/2 1 1 9

Claims (1)

1 2 denotes an alkylene group with 2 to 6 carbon atoms, which is optionally replaced by an oxygen atom 1. 6 - trifluoromethyl -., 4 - dinitro - 1,3 - phe- can be interrupted in the chain,
nylenediamines of the general formula For easier naming of the inventively described 5 applied compounds of the above general R ₁ R ₁ formula will be adjacent to the amino nitrogen atom \ / the halogen atoms or the trifluoromethyl group N as N ¹ and the amino nitrogen atom between the both nitro groups on the ring designated as N ³ , ic Thus the nitro groups are in the 2- and 4-digit P iung and the trifluoromethyl group in the 6-position y ^{s of} the aromatic ring. From the aforementioned 'N> definition of the general formula it follows that Yp ^ either the N ¹ or the N ³ amino nitrogen atom »5 at least one of the named hydrocarbon wherein R ₁ , R ₂ , R ₃ and R ₄ , which must have the same or different radicals, whereby the compounds with can be, hydrogen atoms or given two unsubstituted amino groups excluded