DE2013510A1 - New herbicides - Google Patents

Description

United States Borax & Chemical Corporation,

3075, Wilshire Boulevard, Los Angeles , California,

9000-5, USA

New herbicides

The present invention "relates to the use of 6-halo and 6-trifluoromethyl-2,4-dinitro-1,3-phenylenediamines as Active ingredients in herbicides.

The 6-halo and used as herbicides according to the invention 6-Trifluoromethyl-2,4-dinitro-1,3-phenylenediamines correspond the general formula '

wherein X is a halogen atom such as chlorine, bromine, iodine and
3? Luoratom or the trifluoromethyl group and H ^, Rp, R ^ and E ^, which can be the same or different, hydrogen atoms. Can be alkyl, alkenyl or alkynyl groups,

0098A1 / 1974

where at least one of the groups E ^ ,, E ^, E-, and E ^. one der 'defined hydrocarbon groups, or IL · and Eg together and / or E ^ and E ^ together are an alkylene radical having about 2 "to 6 carbon atoms and optionally one Can represent nitrogen or an oxygen atom in the chain.

For easier naming of those used according to the invention Compounds of the above general formula the amino nitrogen atom adjacent to the halogen atoms or the trifluoromethyl group as N and the amino nitrogen atom between the two nitro groups at the entrance referred to as N ^. Thus the nitro groups are in the 2- and 4-positions and the halogen atom or the trifluoromethyl group in the 6-position of the aromatic element. From the beginning given definition of the general formula results

i "-3

that either the N or the N amino nitrogen atom is at least must have one of the hydrocarbon radicals mentioned, whereby the compounds with two unsubstituted Amino groups are excluded.

_{E 1} , R 0, E and E _A preferably represent hydrogen atoms and lower alkyl, lower alkenyl and / or lower alkynyl groups of 6 carbon atoms including the corresponding cyclic compounds and the halogen, hydroxy or lower alkoxy-substituted in the context of the above definition Derivatives thereof. Examples are the methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, n-pentyl · ·, sec-pentyl, n-hexyl, allyl , 2-butenyl, 2-butynyl, 3-butynyl, methallyl, 2-pentynyl, 2-hydroxyethyl, 4-hydroxy-2-butynyl, 2-methoxyethyl, 2,2-DLmethoxyethyl, 3-ethoxypropyl-, 2-chloroallyl-, 2-bromoallyl-, 2-bromoethyl-, ^ -Ühlorpropyl-, 1-methyl-2-methoxyethyl-, propynyl-, 4-chloro-2-butenyl-, 4-bromo-'l-butenyl-, 3-iodo-2-pentenyl-, 4-gtaor-2-butynyl-, gyclo-

00 9 8 A1 / 1 97A

BATH ORIGINAL

"201351Q-

hexyl -? Cyelopropyl, cyelobutyl, gyelohexenyl and the like.

As mentioned, E / and Ep together and / or S ^ and E ^, together, can be the molecular fragment of a structure of which the amino nitrogen is a part. Such an input structure is given by the formula -Έ 2yfworin Z is an alkylene ginippe with 2 "to 6 carbon atoms and optionally other atoms such as oxygen and nitrogen in the chain. , Diethylenä-imino- and the hexamethylene group. * Reproduced

A preferred class of the compounds used according to the invention are those in which X is a bromine or a chlorine atom or the trifluoromethyl group, E ^, hydrogen and Eoi ^ "W ²¹ ^ - ^ i hydrogen and / or alkyl groups 1 to ζ> carbon atoms, where at least one of the groups B, E ₇ and E ^. Is a so defined alkyl group.

Among these preferred compounds in which X is a bromine or chlorine atom, particularly preferred are those in which E 1 is hydrogen, E _{2 is} hydrogen or an alkyl group having 1 to 3 carbon atoms and E 1 and E 1 are hydrogen and / or Represent alkyl groups with 1 to 5> carbon atoms. These compounds are preferably unsymmetrically substituted, ie the groups

and

E,

are different from one another and the total number of carbon atoms in the groups E _y and E ^ together are about 2 to. ■ "■

OO9 8A1 / 197 U

2Q13510

Examples of compounds in this preferred group are:

N ¹ -ethyl-N ⁵ , N ^ -diethyl-2, ^ - dinitro-ö-bromo-i, 3-phenylene-

diamine,
N ¹ -Methyl-N ^ -sec-butyl-2, ^ - dinitro-ö-chloro-i, 3-phenylene-

diamine,
N -Ethyl-N -sec-butyl ^^ - dinitro-e-bromo-i, 3-phenylene-

diamine,
N ¹ -Methyl-N ⁵ , N ⁵ -di-n-propyl-2, ^ - dinitro-o-chloro-i, 3-

phenylenediamine,
■ χ -x
N ^, N ^ -Di-n-propyl-2,4-dinitro-6-chloro-1,3-phenylene-

diamine,

^^ - i, 3-phenylenediamine ,

W , li ^ -Dietliyl-2,4-dinitro-6-bromo-1,3-phenylendiamine ¹

N ¹ -Methyl-N ^, IT ^ -diethyl-2, ^ - dini

-sec-pentyl-N ^, N ^ -dimethyl-2, ^ - dinitro-e-chloro-i, J-phenylenedi amine.

As a very particularly preferred group of these compounds corresponding to the formula

-KTt,

^l 2

NO,

C.

in which X is a bromine or chlorine atom and R is hydrogen and / or alkyl groups having 1 to 5 carbon atoms, the The total number of the two Rs is 3 to 8.

Among those preferred compounds in which X is the Trifluoromethyl group, those are particularly preferred in which R ^ is hydrogen, R2 and R- is hydrogen and / or

009841/1974 - 5 -

2 η 1

Alkyl groups of 1 to 5 carbon atoms and R ^ is an alkyl group of 1 to 5 carbon atoms. The total number of carbon atoms in the groups Ro, R * and E ^ is preferably about 4 to 8, compounds in which both E ^ and E _{2 are} hydrogen are very particularly preferred.

Examples of this group of preferred compounds are

N -sec-Butyl-N ³ , N ^ -dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine, ·.

N ¹ -ethyl-N ³ , N ⁵ -diethyl-2 ₅ 4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,

W -Methyl-N ³ -sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,

N ¹ -ethyl-N ⁵ -sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,

N ¹ -Methyl-N ³ , N ³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,

H ^, N -Di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenedimain,

N ¹ -Methyl-N ⁵ , N ³ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylendiamine,

N -n-propyl-N ³ , H ³ -diethyl-2 ^ -dinitro-e-trifluoromethyl-1,3-phenylenediamine,

N ¹ -sec-pentyl-N ³ , N ³ -dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-pkenylendiamine,

N ³ , N ³ -diethyl-2,4-dinitro-e-tr if luoromethyl-1,3-phenylenediamine,. '".

N ³ - (3-pentyl) -2,4-dinitro-6-trifluoromethyl-1,3-pnenylendiamin. -

N -sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine, . ·

N ⁵ - (1-methyl-2-methoxyethyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,,.

009841/1974

The compounds used according to the invention are either crystalline solids or high-boiling liquids In general, they are only very slightly soluble in water and moderately soluble in common organic compounds Solvents such as ethanol, acetone, ether and benzene. the Compounds can be easily made by reacting one or two amines or ammonia with a 2,4-dihalo-3,5-dinitrobenzene manufacture according to the following equation:

2HX,

where the two Xj halogen atoms and X, ^ have the same meaning as given above.

Rp, R * and

If R ^ and Rg ^ R * and R ^ are the same, ie the substituted isf-amino group and the substituted N -amino group in the end products are the same, the reaction takes place in one step using at least two moles of amine for each mole of the 2nd _i 4-dihalo-3,5-dinitrobenzene instead of gjREgy. The hydrogen halide bonds formed can be neutralized by excess amine or a tertiary amine. If R ^ and Rg are different from R * and R ^, 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 N group are reacted with about 1 mole of the 2,4-dihalo-3,5-dinitrobenzole. The first halogen atom that is reacted is that between the nitrogen groups on

009841/1974

¹ - 7 -

aromatic sing seated halogen atom. This stage will advantageously in a non-polar solvent carried out as a hydrocarbon in which the amine halide is insoluble and can therefore be easily separated by filtration. The second stage will be about

■ '- 1
2 mol of the Έ group-forming amine reacted with the monoamino compound to form the unsymmetrically substituted Λ , J-plienylenedi amine. The second. The reaction stage takes place in a closed reaction vessel such as a sealed glass tube or an autoclave in order to avoid loss of amine and to enable easier control of the reaction. On the other hand, it is also possible to work at atmospheric pressure in the presence of a solvent such as an alcohol in which the amine is readily soluble. When using higher-boiling amines, it is not necessary to use a sealed reaction vessel for the reaction; rather, it is sufficient to carry out the reaction in the presence of a suitable solvent.

The products used for the manufacture of the invention applied reaction temperature is preferably in the range of about 20 to 120 ° 0 and is used to good To achieve yields of the desired reaction products and a satisfactory reaction rate, namely both when using a closed reaction vessel and when reacting the reaction components at normal pressure in the presence of a solvent. Forms as a by-product hydrohalic acid, which in the presence of excess Amine is converted to the corresponding amine halide, which can easily be washed in water or filtered after dissolution of the reaction product in a glei-Ghen Solvent can be removed. The desired products can be obtained by known methods such as recrystallization getting cleaned.

0Ό9841 / Ί974

- 8th

The 1,2,4-trihalogeno- or 1-trifluoromethyl-2,4-din al ο gen-3,5-dinitrobenzenes used as starting products can easily be obtained by nitrating the 1,2,4-trihalogenobenzenes or 1-trifluoromethyl-2,4 ~ dihalo - benzenes produced with a mixture of fuming nitric acid and fuming sulfuric acid at a temperature below about 80 ⁰ C.

The following examples describe the preparation of more representative ones Members of the compound group used according to the invention. It should be understood, however, that the invention not limited to the specific embodiments is·

Example I.

N ¹ , N ⁵ -Bis- (diethyl) -2,4 ~ dinitro-6-trifluoromethyl-1,5-

phenylenediamine

5 g (0.0163 mol) of 2,4-dichloro-3,5-dinitrobenzotrifluoride, 30 ml of ethanol and 20 ml of diethylamine were placed in a thick-walled reaction glass tube containing about 50 ml. The reaction tube was sealed and heated in a bath 4-6.5 hours at 94- to 99 ⁰ C. The cooled reaction tube was then opened and the content was evaporated to dryness. The residue obtained was extracted with 200 ml of boiling diethyl ether and the insoluble amine was filtered off. The ether extract was evaporated to dryness and the residue was dissolved in 4-0 ml of boiling 95% ethanol and 10 ml of water. The product crystallized on cooling and was filtered off. The desired product was obtained in a yield of 30 % as a crystalline solid with a melting point of 72.5 to 7.5 ° G. After recrystallization, the product melted at .74 to 75 ^° C. Elemental analysis ;

00984 1/1 9 7

9 -

Element ar analysis:

Calculated: Found:

C, 47.61%; H, 5.60 % \ N, 14.81% C, 47.54 ⁰ M H, 5.58%} H, 14.64%

Example II

N ¹ , N ^ -Bis- (dimethyl) -2,4-dinitro-6-trifluoromethyl-1,3- phenylenediamine -

This compound has been implemented in a similar manner of 2,4-dichloro-3,5-dinitrobenzotrifluoride with Obtained dimethylamine. The crystalline product melts

at 125.5 to 126.5 ° C. . ' '

El ement araanaly se:

Calculated: Found:

G, 41.00 ⁰ C, 40.91 %

H, 4.07% in N, 17.39% H, 4.01%; N, 17.54%

Example III

N ¹ , N ⁵ -Bis- (di-n-propyl) -2,4-dinitro-6-trifluoromethyl-1, .3- phenylendiamine _i -

This compound has been implemented in a similar manner obtained from 2,4-dichloro-3,5-dinitrobenzotrifluoride with di-n-propylamine. The product is a high boiling one oil.

009841/1974

- 10 -

Example IV

N ¹ , N ⁵ -di-sec-butyl-2,4-dinitro-6-trifloromethyl-1,3- phenylenediamine

To a solution of 5.00 g (0.0164 mol) of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 25 ml of absolute ethanol and 10 ml of dioxane were added 5 * 04-S (0-069 mol) sec-butylamine Stir given. The resulting mixture was stirred and refluxed for 24 hours. The solvent was then removed by evaporation under reduced pressure, and the residue was dissolved in 75 ml of chloroform. The chloroform solution was extracted three times with 75 ml of water and then dried over sodium sulfate. After the solvent has been removed by distillation, the residue is dissolved in ethanol and the ethanolic solution is removed using activated charcoal. The ethanol is distilled off under reduced pressure and the residue is extracted with boiling η-hexane. The hexane solution was cooled to 0 °, whereby an oil was deposited, from which the hexane was decerbed. The desired product was obtained in a yield of 60.7 % as a clear amber-colored oil.

Element ar analysis;

Calculated: N »14.80 %

Found: N - 15.37%

Examples V until XIY

The following examples were dichloro-2,4-3,5-dinitrobenzotrifluoride obtained in a corresponding manner by reacting with the corresponding amines:

009841/1974

- 11 -

7 Π13510

phenylenediamine; M.p .: 169 - 170 ° Cj

VI N ¹ , H ^ -diisopropyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Mp 66.5 to 67.5 ⁰ Cj

VII Έ * , N ^ -Di- (2-CM or allyl) -2, ^ - dinitro-ö-trifluorfflethyl-1,3-phenylenediamine; M.p .: 82.5-83.5 ° C>

VIII Έ ^Λ , N ⁵ -Di- (2-methoxyätiiyl) -2,4-dinitro-6-trifluoromethyl-1,3-phenylenediaminej mp: 98-99 ^{0 Cj}

IX N ^1, LJ ^{5-diallyl-2,4-dini1;} ro-6-trifluormetliyl-1,3 · phenylendiaminä Ϊ.p .: 79-80 ⁰ C;

X ir ¹ , li ^ -di (3-methoxypropyl) -2,4-dini-tro-6-trifluoromethyl-1 ^ -piieriylendiamiiij oil j

XI 'U ¹ , H ⁵ -Dietliyl-2, ^ - dinitro-ö-trifluoromethyl-i, 3-

, pkenylenediamine J ¹ .p .: 96 - 97 ° 0 »

XII. N ¹ , IT ⁵ -Dicyclolie3q5rl-2,4-dinitro-6-triforomethyl-1,3-plienylenediamine; Mp: 107.5 to 108 ⁰ C j

XIII 'N ¹ , N ¹ , N ⁵ , N ⁵ -di (tetramethylene) -2,4-diiiitro-6-trifluorme-

tliyl-1,3-plienylenedi8attini Mp: 164-164.5 ° 0 \

XIV U ¹ , 1T ¹ , N ⁵ , H ^ -Bi- (pent amethylene) -2 ^ -dinitro-ö

-i, 3-phenylenediamiiii mp: 139-140 ⁰ G.

Example XV N, H - di-n-propyl-3-chloro-2,6-dinitro-4-trifluorometlaylaniline

7.0 s (0.023 mol) of 2,4-chloro-3,5-dinitrobenzotrifluoride, 4.64 g (0.0458 mol) of di-n-propylamine and 40 ml of absolute ethanol were placed in a thick-walled glass tube with a content of about 50 ml given. The tube was melted shut and heated ^{to 94 to 99 °} C. in an oil bath for 98 hours. After cooling the reaction mixture, the boring was opened and the reaction mixture was evaporated to dryness, whereby an oily residue was obtained, which was extracted with boiling diethyl ether. The insoluble di-n-propylamine hydrochloride was separated by filtration and added with additional ether

009841/1974 - 12 -

7 1351Π

washed. The combined ether filtrates were evaporated, whereby an oily orange residue was obtained which was dissolved in 100 ml of absolute ethanol and removed with activated charcoal became. The ethanol and volatiles were separated by evaporation under reduced pressure, so that 6.77 S of a viscous reddish oil was obtained.

N ^, N -di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3- • phenylenediamine

In a glass reaction tube, 4.0 g (0.0108 mol) of N, N-di-n-propyl-I-chloro- ^, 6-dinitro-4-trifluoromethylaniline, 5.82 g (0.0257 mol ) 6.95% ethanolic ammonia and 35 nil ethanol. The tube was melted shut and heated ^{to 100 ° C. in an oven for 68 hours.} The tube was cooled and the ethanol was separated from the contents 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. It was then dissolved in boiling 95% ethanol. After cooling, orange-colored needles and a yellow powder crystallized out. The yellow powder was found to be 2,4-dinitrotrifluoromethyl-1,5-phenylenediamine and was separated from the desired product by filtration 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 to give orange-colored needles melting at 124-125 ⁰ C were obtained.
Elemental analysis:
Calculated: N - 15.99 %
Found: N - 16.00%

00 984 1 / 197Ä

Example ZVI .

N ¹ , Ε " ¹ -Dimethylen-N ⁵ , N ^ -di-n-propyl-2,4-dinitro-6-trifluoro methyl-1,3-phenylenediamine - -

A solution of 4 g (0.0108 mol) of N, IT-di-n-propyl-3-c] iloro-2,6-dinitro-4-trifluoromethylaniline and 0.93 g (0.0216 mol) of ethyleneimine in 50 ml of absolute ether were stirred "over seam at 35 ⁰ G. the solvent was removed 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 components were separated by evaporation under reduced pressure, whereby the desired product was obtained as a viscous amber oil. This product was identified by its proton nuclear magnetic resonance spectrum (PNMR spectrum).

Example XVII

N ¹ -ethyl-N ⁵ , N ³ -dimethyl-2 ^ -dinitro-e-trifluonethyl-1,3- phenylenediamine

N, N-Dimethyl-3-chloro-2,6-dinitro-4-trifluoromethylaniline was with ethylamine in a fused tube as in Example XV described, implemented, whereby the desired Product obtained with a melting point of 51 »5 to 52.5 ° C became.

The following products are also, as described above, obtain-:

009841/1974

201351Ω

N ¹ -ethyl-N ^ -sec-butyl-2, A-dinitro-ö-trifluoromethyl-i, 3-

phenylenediamine} mp: 92.5-94 ⁰ C; N ¹ -sec-butyl-N ⁵ , N ⁵ -dimethyl-2, 4-dinitro-6-trifluoromethyl-

1,3-phenylenediamine oil;
N ¹ -sec-butyl-N ⁵ , N ⁵ -diethyl-2,4-dinitro-6-trifluoromethyl-

1,3-phenylenediamine} 01}
N ¹ -Methyl-N ⁵ , N ⁵ -diethyl-2,4 ~ dinitro-6-trifluoromethyl-1,3-

phenylenediamine} mp: 71.5 to 73.5 ⁰ C; n ' ¹ -Methyl-N ^, N ^ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-

1,3-phenylenedimain} Pp: 48.5 - 50.5 ⁰ Ci N ¹ , N ¹ -Di-n-propyl-N ⁵ , N ⁵ -dimethyl-2,4-dinitro-6-trifluoro-

methyl-1,3-phenylenediamine} m.p .: 39.5 - 40.5 ° 0}

-N ⁵ , N ⁵ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-

phenylenediamine m.p .: 54- - 55.5 ° 0} N ¹ , N ¹ -dietbyl-N ⁵ , N ⁵ -dimethyl-2 ^ -dinitro-ö-trifluoromethyl-

1,3-phenylenediamine m.p .: 45-46 ° 0; N ¹ -Methyl-N ^ -sec-butyl-2,4-dinitro-6-trif Iuo3? Methyl-1,3-

phenylenediamine} m.p .: 81 - 83 ° C} N, N -dimethylene-N ^ -sec-butyl-2,4- (UnXtPo-O-trifluoromethyl-

1,3-phenylenediamine} mp: 92-93 ° C | N ¹ -propargyl-N ^, H ^ -di-n-propyl-2,4-dinitro-6-trifluoromethyl

1,3-pb.enylenediamine} 01}
N ¹ -propargyl-N ⁵ , N ⁵ -diethyl-2,4-dinitro-e-trifluoromethyl-

1,3-phenylenediajnin; oil}
N ¹ , N ¹ -diethyl-N ⁵ -ethyl-2,4-dinitro-6-trifluoromethyl-1,3-

phenylendimain} mp: 64.5 to 65.5 ^{0 1} Oj N -propargyl - "^ - sec-butyl-2,4-dinitro-6-trifluoroethyl

1,3-phenylenediamine} mp 55-54 ⁰ O;

N ¹ , N ¹ -Dimethyl-N ⁵ , N ⁵ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine} mp: 58.5-59> 5 ° Q | N ¹ , N ¹ -dimethyl-N ⁵ , H ⁵ -diethyl-2 ^ -dinitro-e-trifluoromethyl-

1.3-phenylenediaain} mp: ^{114-116 ° 0} N 1} , H -diethyl-H ⁵ -sec-butyl-2,4-dinitro-6-trifluoromethyl-

1,3-phenylenediamine oil j N ¹ -ithyl-N ⁵ , N ⁵ -di-n-propyl-2

1,3-phtnylenediamine 01}

009841/1974

1351G

1 ^ -phenylenediamine oil;
N ¹ -propargyl -! ^, ^ - dimethyl-2 ^ -di

} Fp: 66-67 ° 0j N ¹ - (2-Hydroxyät: hyl) -N ^ - sec-butyl-2,4-dinitro-6-trifluoro-

metlayl-i, J-phenylenediaminej P.p .: 57.5-58.5 ° C; N -Gyclopentyl-IT ~ metallayl-2, A-dinitro-6-trifluoromethyl-

1,3-piie] 3ylenediamiii5 m.p .: 87-88.5 ⁰ Gj N ^ - (1-methyl-2-met: hoxyethyl) -2,4-dinitro-6-trifluoromethyl-

1,3-phenylenediamine; M.p .: 120.5-121.5 ° 0; U ⁵ - (2,2-Dimetlioxyätliyl) -2, ^ - dinitro-ö-trifluoromethyl-i, 3-

pheiiylendiamiii; Mp: 137-139 ° N ^ ~ (3-Clilorprop5rl) -2 _s 4-dinitro-6-trifluoromethyl-1,3-

ph.enylendlaminj mp: 94 to 94.5 ⁰ G; N ^ - (2-bromoethyl) -2,4-dinitro-6 ~ trifluoromethyl-1,3-plienylene-

diamine; Mp: ^149-1 50 ⁰ C; "

1,3-piieDylendiamIn} Fpj 93 - 94 ⁰ Gj] lf-Cyclopropyl-2,4-dinitro-6-trif! Normethyl-1,3-pkenyl en-

diaminf Fp; 180 - 181.5 ⁰ G ^
N ¹ -Heti3yl-lT ³ - (3-peiityl) ^ 2 _s 4-diiiit3? O ~ 6-tPifluoromethyl-1,3-

phenylenediamines mp: ^{73.5-74.5 0} Gj li ^ -sec-amyl-2,4-diii ± tro-6-trifluoi! ittetli5rl ~ 1,5-plienylene- '

diamirtj mp: 105.5 to 106.5 ⁰ Gj
N ¹ -Methyl-U ^, ^ ⁵ - diethyl eno3qy-2,4-dinitro-6-trifluoromethyl-

1,3-pkeüylendiamiiii Fp: 201-203 ⁰ Gi N? -Ket3ayl-N ⁵ -ätliyl ~ .2 ^ -dinitro-ö-trifluoromethyl-i, 3-

in} F.p .: 89 - 89.5 ° G}

-2,4-dinitro-6-trifluormetbyl-1,3-phenylene, mp 72-73 ⁰ Gj

-K ^, 2i ⁵ -peiitametliyleii ™ 2, ^ - dinitro-ö-trif luoromethyl- _? 3-ph.eBylenediamine m.p .: 142.5 - ^ 3.5 ⁰ Gj

i, 3-plienylene

diaiain} mp: 119.5 to 120.5 ⁰ Gj

09841 / Ί974 ·.

L-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Pp: 127.5 to 128.5 ⁰ C; - (2-chloroallyl) -2, 4 ~ dinitro-6-trifluoromethyl-1,3-pheny-

lenediamine; Pp: 102 - 103 ° G}
-sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylene-

diamine; Pp: 126.5 to 127.5 ⁰ O;
⁵ , iT ^ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine} Pp: 98-99 ⁰ C;

I 1
, N-diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediaminej Pp: 85-86 ⁰ G;
, N -Di-n-propyl ^ j ^ -dinitro-ö-tr if luormethyl-1,3-

phenylenediamine; Pp 75.5 - 76.5 degrees C "sec- butyl-2 ^ - dinitro-ö-trifluoromethyl-1,3-phenylendiaminj pp: 58-60 ⁰ O.

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

Example XVIII

2,4-I) chloro-3,5-diuitro'benzotrif luoride

Fuming sulfuric acid (600 ml) containing 30 to 33 % free S (K) was stirred in a 2-1 three-necked flask immersed in an ice bath, to which was added fuming 90% nitric acid (585 ml) g (0.692 mol) of 2,4-dichlorobenzotrifluoride added. This slurry was then heated to 76 ⁰ C under Hühren, and held for 96 hours at 76 ^ 1 ⁰ C. the mixture was then cooled and taken off the acid from the crust of the crystalline product 1000 ml of water were then added to the broken up pests and the slurry was extracted with 50½ ml of toluene with stirring

009841/1974

- 17 ~

Toluene solution was mixed 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. 166.6 g (79 % d-th.) Of the desired 2,4-dichloro-1,5-dinitro "benzotrifluoride were obtained with a melting point of 6-72 ° 0. After recrystallization from ethanol, the product melted at 74Ms 75 ° G··

Example XIX

N- (3-pentyl) -3 ^ -di

^, 6-dinitroaniline

3-Pentylamine (6.00 g; 0.0688 mol) was added to a stirred solution of 1 ^^ - trichloro ^^ - dinitrobenzene (9 * 338 g; 0.0344 mol) in 200 ml of cyclohexane, divided over 15 minutes . After stirring for one hour at room temperature, the reaction mixture was 1? Heated to boiling under reflux for hours and then evaporated to dryness under reduced pressure. The residue was extracted with 250 ml of boiling cyclohexane, which was then decanted off and evaporated. The residue obtained was then taken up in chloroform, extracted with 3N hydrochloric acid and then with water, the chloroform solution was dried over sodium sulfate and filtered and the chloroform was separated off by distillation. The remaining oil was taken up in 25 ml of η-hexane, cooled and filtered, whereby 0.5 g of unreacted starting material was obtained. The piltrate was evaporated to give 9.24 g (83.3 %) of N- (3-pentyl) -3,4-dichloro-2,6-dinitroaniline as an oil identified by its NJEiR spectrum.

009841/1974

-18 -

N- (3-pentyl) -6-chloro-1, 4-dinitro-1, 3-phenylenediamine

A mixture of 5.00 g (0.0155 mol) of N- (3-pentyl) -3,4-dichloro-2,6-dinitroaniline and 6.89 S (0.0310 mol) of a 7.66% solution of ammonia: in absolute ethanol was melted in a glass tube with about 30 ml of absolute ethanol. After heating at 94 ° C for 72 hours, the reaction mixture was freed from volatile constituents and the residue was suspended in 500 ml of water. It was filtered off and the residue is crystallized from ethanol, whereby 1.89 g (40.3%) of the crude product of melting point 118.5 to 121.5 ⁰ C were obtained. This product was taken up in 60 ml of hot cyclohexane, the solution was filtered, evaporated and the residue was recrystallized from 95% strength ethanol. It was the desired product in the form of shiny orange rectangles of melting point 119 "3 - received 120.6 ⁰ O.

example N ^, N ^ -diethyl-a-chloro · ^ Λ-dinitro-i, 3-phenylenediamine

This product was obtained in a similar manner by reacting N, N-diethyl-3, ^/ t-dichloro-2,6-dinitroaniline with ammonia. The crystalline product melts at 110-111 ⁰ C.

Example XXI N ^ »N ^ -di-n-propyl-6-bromo-2 Λ-dinitro- ₁ 3-phenylenediamine

This product was obtained in a similar manner by reacting N, N-di-n-propyl-3, A-dibromo-2,6-dinitroaniline with ammonia. The crystalline product melts at 119 to 120 ⁰ C.

00984 1/1974

3Ω1351Ω

Example ΣΣΙΙ

Έ ,! N "~ I) i-i- ^ propyl- $ ~ ciilor-2,6 ~ dinitro-4-fluoroaniline

A mixture of 8.0 g (0.0314 mol) of 2,4-diehlor-3,5-dinitrofluorobenzene, 6.35 g (0.0628 mol) of di-n-propylamine and 75 ml of cyclohexane was absorbed for 15.5 hours 58 - 72 ⁰ G heated. The di-n-propylamine hydrochloride was filtered off and the solvent was evaporated from the filtrate, leaving an oil. The oil was taken up in cold pentane, the solution filtered and evaporated under reduced pressure. 100 g (96.5%) of l, lT-di-n-prop7l-3-chloro-2,6-dinitro-4-fluoraniline, which was identified by its MGR spectrum, were obtained.

3 3 '

M, H? - ^ - Di-n-propyl-2,4-dinitro-6- fluoro-1,3-phenylenediamine

A solution of 7.34 g (0.0224 mol) of Ii, 3Si-di-n-propyl-3-chloro-2 ^ -dinitro - ^ - fluoroaniline, 12.87 S (0.0458 mol) of a 6, 06% solution tob. Jjfflmoniak in absolute ethanol and 2,317g (0.0229 mol) ■ Iriäthyiamin in about 35 ml of absolute Ithanol were heated in a zügeschmolsenen.i ^ rrex-EOHR 72 hours 98 ⁰ G. The contents were then evaporated under reduced pressure and zvr Srockne and extracted twice with the stoopest ge 100 ml of boiling cyclohexane. The pooled filtered cyclohexane effluent was evaporated to dryness and the remaining oil was taken up in hot n-hexane, the solution filtered and evaporated to give an oil. This EohOil was efeesiatographed over 250 g of activated aluminum oxide using penthan, 2; 1-paxltan-benzene and 1t2-pentane-benzene as eluents. After an initial fraction of 1 ', H, H? _? H ⁵ -iCetra-n-prop3rl- «2,4-dinitrO'-6 ~ fluoro-1 _? 3- "phenylenediamine was obtained li ^ _i H ^ -di-n .-. Propyl ~ 2,4-dinitro'-6-fluoro-1,3-phenylenediamine. Recrystallization twice from

- 20 -

I QO 9 841/1974. . . ■ ■

BATH

aqueous ethanol gave the desired product as orange needles melting at 90.5 to 91 ₅ 5 ^C

Example XXIII

1 -5
N, N -Piäth _l yl-6 - chloro-2,4-dinitro-1,5-phenylenediamine

With stirring, a solution of 6.79 g (0.025 mol) of 1,2,4-TrIChIOr-J, 5-dinitrobenzene in 200 ml of ethanol was dissolved in a solution of 20 ml of 70% strength aqueous ethylamine in 50 ml of ethanol at room temperature admitted. An additional 20 ml of the 70% aqueous ethylamine solution was then added to the stirred mixture. The resulting solution was refluxed for one hour and then stirred at room temperature overnight. The mixture was cooled in an ice-water bath and then filtered, whereby 5.70 g of the desired product in the form of an orange solid with a melting point of 96.5-98 ⁰ O was obtained. After recrystallization from ethanol, the product melted at 97.5 to 98.5 ⁰ C

The following products were obtained as described above:

N-sec-butyl-2,4- dinitro-6-chloro-1,3-phenylenediamine;

_ Fp: 124.5 - 125.5 ° 0 \
N-sec-butyl-2,4-dinitro-6-bromo-1,3-phenylenediaminej

Mp: 140.5 to 141.5 ⁰ C;
N - ^, N- ^> -diethyl-2,4-dinitro-6-bromo-1,3-phenylenediamine}

M.p .: 107-109 ⁰ Qi
N ^ -Isopropyl-2,4-dinitro-6-bromo-1,3 -phenylenediamines

Fg: 148-150 ⁰ O;
N ^ -sec-amyl-2,4 ~ dinitro ~ 6-bromo-1,3-phenylenediaminej ϊ.ρ .; 115 - 116.5 ⁰ Cj

009841/1974

- 21 -

9Q1351Q

³ - (methyl-2-methoxyethyl) ^^ - dinitro-e-chloro-i, 3-phenylenediamine; Pp: 138.5-141 ⁰ C;

N, N -Bis- (2-ehlorallyl) -2,4-dinitro-6-chloro-1,3-phenylene-

diamine; Pp: 99.5 to 100.5 ⁰ G;
N, N ^ -dicyclopropyl-2,4-dinitro-6-chloro-1,3-phenylenediamine;

Pp: 112-113 ⁰ C;

"5
H, Ii -diallyl-2,4-dinitro-6-bromo-1,3-phenylenediamine;

P.p .: 82.5-83.5 ° 0; '. -

Egg ¹ , K ¹ -dirne thyl-N ⁵ , N ³ -diethyl-2,4-dinitro-6-chloro-1,3-phenylenediamine; Pp: 67-68 ⁰ G;

Έ -ethyl-N ^ -sec-butyl-2,4-dinitro-6-chloro-1,3-phenylenediamine; Pp: 72.5 to 74 ⁰ G;

Ή ^ , N ^ -pentamethylene-2,4-dinitro-6-chloro-1,3-phenylenediamine;

P.p .: 123.5-124.5 ° 0;

1 -5 ^)

N, N, II ^, n ^ -Tetra-n-propyl-2,4-dinitro-6-fluorine-1 j 3-phenylendiamine; Oil;

N -Methyl-N ' ³ -sec-' butyl-2,4-dinitro-6-chloro-1,3-phenylenediamine

Pp; 105-108 ⁰ C;

N ^, U "^ - Di-n-propyl-2,4-dinitro-6-chloro-1,3-phenylenediamine; Pp: 122.5-123.5 ⁰ O;.

N ^1, H ¹ -Dirnethyl-K ^, N ^ -dimethyl-2,4-dinitro-6-chloro-i, 3-phenylendiaminj Pp: 77-78 ⁰ G;

H ¹ , N ⁵ -diethyl-2,4-dinitro-6-fluoro-1,3-phenylenediamine; Pp: 146 to 147.5 ⁰ O;

N ¹ -methyl-K ⁵ , N ⁵ -di-n-propyl-2,4-dinitro-6-chloro-1,3-phenylenediamine; oil;

XX

L-N-, N ^ -diethyl-2 ^ -dinitro-ö-chloro-i, 3-phenylene-

diamine; Pp: 82.5-83.5 ^P G;
N ^, N ^ -dimethyl-2,4-dinitro-6-bromo-1,3-phenylenediamine}

Pp: 143-143.5 ° G; ■
N, N -dicyclohexyl ^, 4-dinitro-6-bromo-1,3-phenylenediamine;

Pp: 113 - 114 ⁰ G.

- 22 -00 98A1 / 1 97 4

The joints described introducing are excellent Herbicides and particularly valuable as selective herbicides for controlling weeds in crops, especially grass-like weeds such as Foxtail grass, water grass and crayfish grass. Many of the compounds of the invention can be used to control weeds in desired crops of the grass family such as maize and rice and also small-grain plants as well as in broad-leaved crops such as cotton and soybeans are used. Furthermore, many are preferred Compounds effective in controlling wild oats, which is a major problem in small grain crops such as Representing wheat and barley.

Aquatic grass and similar weeds are a serious problem in rice crops and the discovery of a potent one selective = egg-acting herbicide to combat this Weed is a significant advance. 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 Substituted aromatic amines are and penetrate better into the soil and also have better stability against UV light to have.

The inventions can be applied both before the crop plants sprout or afterwards, i.e. H. you can click on the Soil can be applied in which the weeds will grow, or they can be used to control the weeds kill or prevent their growth or the germination of the seeds of unwanted plants. So can the compounds according to the invention are used to

009841/1974

■ ■ - 25 - -

control the growth of weeds by adding a phytotoxic amount of one or more of these 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 be applied to the foliage of the growing plants. Under the term "weeds" like #r above and below "is used, growth all unwanted plants included.

In general, the application level is from about 0.1 to about 25 pounds of one or more of the active ingredients per acre to to achieve effective control of undesired plant growth. Preferably the products are in quantities from about 0.25 "to about 5 pounds per acre. At these amounts are the unwanted weeds without or killed or growth inhibited only with very little damage to the desired crop plants.

The following examples illustrate the herbicidal effectiveness some typical representatives of the compounds according to the invention.

Example ZZIV

The compounds under investigation became more representative of a large class of herbicides to be applied as priming Weeds and crops evaluated. Greenhouse boxes were filled with pigweed, cheat, wild oats, foxtail grass, Morning glory, water grass, rice, sugar beet, cotton, corn, barley and soybeans planted »on the same 3? Ag the They were planted in the 3? Salmon boxes with an ethanol Dissolve the compound to be tested in an amount appropriate sprayed two pounds per acre. The boxes were kept in the third house and watered when necessary. 21 days after

009841/1974

_ 24- -

201351Q

The plants were treated with respect to the herbicidal Effectiveness evaluated and on a range from 0 to 9 On a scale where O = no effectivenessj 5 = Significant damage with little killing and 9 = means complete killing. The following results were obtain:

Q09841 / 1974

Tabel I. CH WHERE i ¹ M. 00 W E SB GO CR I. B. • so I.
ro *
< Π Test substance Activity * 0 LfN 9 0 OR 9 ρ 4 3 O 0 I. 1
< D. (DTP «2.4-Einitro-6-tri £ luor-
methyl-i, 3-phenylendi amine) P. 1 8th 9 1 B. 9 0 4 1 4th 0 1 < »U ^ l - ^ - sec-butyl-W 9 1 2 7th 0 SO 9 0 3 Q O 0 Q N ¹ -Metbyl-N ^ -sec-butyl-DTP 9 3 8th 9 1 9 ο 1 0 1 1 1 SN ¹ ^ ¹ -Dimethyl-Er ⁵ , li ³ -diethyl-DTP 9 0 3 9 0 7 ο ο 0 O. 1 0 S 1 -sec-butyl-N ⁵ , N ³ -dimetnyl-DTP 9 Λ 5 6th 0 4 Ö Λ 1- 0 0 0 ^ N ^ -sec-butyl-IT ³ , N ³ -diethyl-DTP 2 Morning glory = Cotton ΓίΕΓ, N —dimethylene — N, N ~ di — n— 8th Water grass = Corn * P = Pigweed M = rice = Barley CH =, Cheat W = Sugar beet = Soda beans WO = wild oats R = 3? = Black swiss grass SB = ι ■ σ »
■ ι ■. ■

Example XXV

The compounds under investigation were both as before Herbicide to be used both after germination and after germination on a large class of weeds and crops evaluated. Greenhouse flat boxes were planted with the plant species tested in Example XXIV and the Boxes on the same day of planting with an ethanol Solution of the substances to be tested sprayed at an amount equivalent to 2 US pounds per acre.

Another set of plach boxes was made with the same plants planted and treated after the plants have germinated and grown to about 2.5 cm tall. These boxes were also treated with an ethanol solution of the substances to be tested in an amount equivalent to 2 US pounds Treated per acre to determine post-germination activity. The hatch boxes were kept in the drift water and watered if necessary. 22 days after the treatment, the boxes were evaluated and, as described in Example XXIV, classified. The following results were obtained:

Table II Test sub- ' To Test sub To punch A 4th punch B 4th before 2 before O Plant species 8th 3 9 3 Pigweed 2 3 Cheat 9 8th 9 8th Wild oats 3 4th Foxtail 9 8th 9 9 grass O ü 4th υ Morning glory 9 9 Water grass O υ rice

Test sub ; To punch C 3 before
· ■■■■■ ** ■■ 2 8th 3 3 5 9 3 9 7th O υ 9 O

009841/1374

ORIGINAL INSPECTED

Test sub " To Eestsub - punch A 1 punch B Plant enar t before 6th Before after Sugar beet 6th Q 9 4 cotton O 0 4 4 Corn 0 3 4 2 barley 0 1 0. Soybeans 0 3 4

Test sub To punch 0 1 before 3 2 0 0 1 O 3 O 0

Test substance A =

-Methyl-N ⁵ , N ⁵ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine;

■ χ τ.

Test substance B = N, ir-di-n-propyl ^^ - dinitro-G-trifluoromethyl-i , 3-phenylenediamine;

N ¹ -methyl-N ⁵ , N ⁵ -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenedi amine.

Test substance C =

Example XKVI

Greenhouse flat boxes were planted mit'Pigweed, Erebsgras, wild oats, Eiesenfuchsschwanzgras, sorghum, Vassergras, rice, Johnson grass, cotton, corn ", barley and soybeans" On-the same day the Bepflanung the Έ1 were achkästen with a äthanolisehen solution to be tested the substance sprayed in an amount corresponding to 1 US-pounds per acre. the e ¹ I achkäst s were held in the greenhouse and watered as needed. 16 days after the treatment, the JFlachkästen were evaluated and with respect to the herbicidal activity as described in example XXIV The following results were obtained:

00 9841 / 197.4

- 28 -

ORIGINAL INSPECTED

Table III

Test substance

Activity*

(DTP = 2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine)

Έ ^Λ , N ⁵ diethyl DTP

C. C. U

N ', N ^ -di-n-propyl-DTP, N ¹ -ethyl-N ⁵ , N ⁵ -diethyl-DTP

propyl DTP

* Pigweed = P
OB = crab grass WO = wild oats Έ = foxtail grass

ro

CB WO 1 SG WE JG 00 OR B SO

4th 2 1 3 3 2 0 4th 1 0 0 = Cotton 0 0 5 2 2 0 1 0 2 0 0 0 = Corn 0 0 6 4 7th 1 3 0 5 ■ 1 0 0 = Barley 1 5 5 5 8th 0 8th 0 VJl 0 0 0 0 3 = Sorghum 7th 0 6th 0 VJi 0 0 0 0 SG 00 = Soybeans W. = Water grass OR R. = Rice B. JG SO = Johnson grass

■ "■ - 29 - Example XXVII Soybeans, ί & U I kj U the to testing White XXIV on the herbi- Table IV Test substance UUSoA! / La / Activity* A. VL O MI Greenhouse flat boxes were with US pounds per acre the described, entered (DTP = 2 ^ -Dinitro-e-trifluor- zen and millet planted. During the day Sub- obtain: methyl-1,3-pkenylenediamine) SO 1 3 9 3amtblatt, 5 loading 11 3
N, IT -dimethylene-N -sec-butyl- O 1 9 here were planted sprays. The boxes were kept in the greenhouse and kept at Be DTP O 2 3 8th Boxes with an ethanol solution may be watered. 19 to 21 days after treatment were up DTP. O 3 VJl 9 punch in an amount corresponding to 5 checked the boxes and related the plants N-Propargyl-E ^ -sec-butyl-DTP O Λ Q cidal effectiveness as in example N ¹ propargyl N ⁵ , N ⁵ diethyl DTP 2 I.
4th VJi C 9 levels. The following eesuitates were N -propargyl-N, N -di-n-propyl-
DTP Λ 4th 4th 9 N ^ -Oyclopentyl-N ^ -methyl-DTP I.
O '4 3 9 N ⁵ allyl DTP 2 3 2- 9 ] j3_ (3-chloropropyl) -DTP O 5 • 6 9 N ⁵ - (2 ~ chloroallyl) -DTP O VJl 9 9 N ⁵ , N ⁵ -Bi s- (2-methoxyethy]> - DTP 4th 2 O 8th N ^ _- (1-methyl-2-methoxyethy3) -DTP 4th 8th VJl 9 N ⁵ - (2-bromoethyl) -DTP O 8th 9 9 " ⁵ -isobutyl DTP 2 7th 8th 9 Vr- * sec-imyl-lXIIP 4th 7th 8th 9 N ⁵ - (3-pentyl) -D0? P ^ 4th

ORiGiNAL INSPECTED

! Ie st substance

(DTP = 2,4-dinitro-6 ~ trifluoromethyl-1,3-phenylenediamine)

N ⁵ , N ⁵ diethyl DTP

N ¹ -methyl-N ⁵ , N ⁵ -pentamethylene DTP

N ¹ -methyl-N ⁵ - (3-pentyl) -DTP N ¹ , N ¹ -diethyl-DTP
Ή -sec-butyl-DTP

N ¹ - (2-hydroxyethyl) -N ⁵ -secbutyl-DTP

* S0 »soybeans
VL β velvet leaf

Activity* VL O MI SO 7th 8th 9 5 O 2 9 0 6th 5 9 3 4th 8th 9 3 4th 9 9 3

0 α oats
MI m millet

Example XXVIII

N ⁵ - (1-Methyl-2-methoxyätl ^ l) -2 _i 4-dinitro-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 soil at an amount equivalent to 0.25 pounds per acre and then placed in a greenhouse shallow box by mixing. On the same day, foxtail grass, wild oats, millet, water grass, crayfish grass, pigweed, velvet leaf and corn were planted in the mixed treated soil. The flat boxes were kept in the greenhouse and watered if necessary. 14 days after the treatment, the Ilach boxes were checked and the plants were classified for herbicidal activity as described in Example XXIV. The following results were obtained:

I / I3 / H

ORIGINAL INSPECTED

Table V Activity s level e Plant species 8th Foxtail grass 8th Wild oats 9 millet 9 Water grass 9 Crab grass 9 Pigweed ■ 5 ■ ■ ■ Velvet leaf O Corn O cotton * Example XXIX

Greenhouse flat boxes were planted with soybeans, velvet leaf, oats and millet. On the day of the planting were the boxes of an ethanolic solution of the substance to be tested in an amount equivalent to 5 US pounds per acre sprayed. The flat boxes were kept in the greenhouse and watered when necessary. 21 days after treatment were made the boxes checked and the plants with regard to the herbicidal effectiveness, as described in Example XKIV, classified. The following results were obtained:

Table TI

Test substance

(DPD = 2,4-dinitro-1,3-phenylenediamine)

N ⁵ , N ⁵ -diethyl-6-bromo-DPD N ^, N ^ -di-n-propyl-6-chloro-DPD

N ¹ -methyl-N ⁵ , N ⁵ -diethyl-6-chloro-DPD.

N ¹ -ethyl-N ⁵ , N ⁵ -diethyl-6-chloro-, DPD

Activity * SO VL

MI

O O

3 2

9 9

- 32

ORIGINAL INSPECTED

Test substance

(DPD = 2,4-dinitro-1,3-phenylenediamine)

N ^, N ^ -Di-n-propyl-6-bromo-DPD N ⁵ -sec-butyl-6-chloro-DPD N ¹ , N ⁵ -diethyl-6-bromo-DPD N ⁵ , N ⁵ -diethyl- 6-chloro-DPD N ¹ , N ³ -diethyl-6-chloro-DPD Π ^ _ (3_pentyl-) 6-chloro-DPD

N ⁵ , N ⁵ -pentamethylene-6-c3ilor-DPD

N ⁵ - (1-methyl- ^ - methoxyethyl-chloro-DPD

N ^, N ⁵ -di-n-propyl-6-fluoro-DPD N ^, sec-amyl-6-bromo-DPD N ^, N ^ -dimethyl-6-bromo-DPD N ⁵ -aetyl-6-bromo -DPD N-isopropyl-6-bromo-DPD

Activity* VL 0 MI SO 5 3 9 2 3 1 9 2 O 0 4th O. 3 3 9 0 0 2 6th 2 6th 9 2 0 2 7th ü 4th 2 9 2 5 8th 9 2 3 2 9 0 ü O 8th 0 0 O 9 0 4th 0 9 1

DPD

* SO = soybeans VL = velvet leaf

O = oats MI = millet

Example XXX

Λ 1 'A. ~ Λ

N, N, N) Ν -Tetramethyl ^ j ^ -dinitro-e-chloro-i, 3-phenylenediamine has been found on corn, millet, rye grass, wheat, beans, mustard, cucumber and snap beans both before and after germination applied. The substances to be tested were in an acetone-methanol solution in an amount corresponding to 25 pounds per acre applied. The plants were im Hothouse kept and watered when necessary. 30 days after After the treatment, the plants were tested and the herbicidal effectiveness was rated on a scale from 1 to 10, where 0 = no activity and 10 = complete

- 33 -

ΤΠΓ9ΤΓΓΤΤΤ9 ~ Τΐ ~

ORiGWAL INSPECTED

201351Q

Means mortification. The following results were obtained:

Table YIl

plant

Activity level

Millet rye grass oat beans Mustard Cucumber Snap Bean Corn

before If ach 4- O 9 3 7th 3 O O 9 9 5 6th O 3 • o

Example XXXI

The substances to be tested were evaluated as pre-germination herbicides with respect to a large class of representative weeds and crops. Greenhouse laugh boxes were made with an ethanol solution substance to be tested was sprayed at an amount equivalent to 0.5 pounds per acre and the chemical product was in The upper, about 2.5 cm thick layer of the soil was mixed in. The fish boxes were then covered with foxtail grass, wild Oats, millet, raccoon grass, crayfish grass, French beans, morning planted glory, tomatoes, corn, rice, soybeans, cotton, barley, flax and pigweed. The flat boxes were in Hothouse kept and watered when necessary. 21 days after the treatment were the plants in relation to the herbicidal Efficacy evaluated and, as described in Example XXIV, classified. The following results were obtained!

- ■ 34 ί-

Ο 9.8 / 4 1/1974

ORIGJWAL INSPBCTED

Test substance I. Table VIII C. WHERE MI W CB BB M. T C. E. CO B. EX P. SO I. I. 5
a)
JT (DPD = 2,4-dinitro-1,3-phenylenediamine) VYY
VJi
I. Activity* E. 2 7 6 8
5 7 8 9 O
0 2
3 1
2 O
O 1
■ 1 1
1 0
0 0
O 7th
6th 1
.2 VM I. N ^ -sec-butyl-6-chloro-DPD
N-sec-butyl-6-bromo-DPD CO 5 2 6 8 O 2 O O O O O O 4th O I. ■ K ^ - ^ ithyl-Ii ^, N ^ -diethyl-6-chlorine-DPD
y | Jt -γ η 2
3 B. 5 2 7 9 1 3 2 O O 0 O 0 6th 0 Ή , K -dimethyl, ^, N ^ -diethyl-6-
chlorine-DPD 5 JX 009 2 P. ~ Corn co * ¥ = S ¹ UChS tail grass SO - ice WHERE - Wild oats ä cotton MI - millet - barley CD W = water grass = Flax CB = erebs grass = Pigweed BB = French beans = Soybeans M = morning glory > T - tomatoes

'- 35 -

Since a relatively small amount of one or more of the invention active 2,4-dinitro ~ 1,3-phenylenediamine Should be distributed as evenly as possible over the area to be treated, the products are preferably with conventional, liquid or solid carriers for herbicides mixed. So can the products with a powdery Carrier mixed or impregnated on it and suitable carriers are e.g. B. lime, talc, clays, bentonite, Calcium chloride, vermiculite, calcium carbonate and the like, on the other hand the active ingredients can also be in a liquid carrier such as water, kerosene, alcohols, diesel oil, xylene, benzene, Glycols, ketones and the like. Be dissolved or suspended. A surface-active substance is preferably added, to aid dispersion, emulsification and coating. The surfactant can be both ionic how to be non-ionic, liquid, or solid. As used herein, the term "surfactant" is intended to include all of such Include compounds commonly referred to as humectants, dispersants and emulsifiers. Typical surfactants are alkylarylsulfonates, the fatty alcohol sulfate, the sodium salt of naphthalene sulfonic acid, Alkylaryl polyether alcohols, long-chain quaternary Ammonium compounds, sodium salts of alkyl sulfonic acids based on petroleum products, polyoxyethylene sorbitan monolaurate and the like. This dispersion and humidification Chemicals are sold under numerous trademarks and can either be in the form of the pure compounds, in In the form of mixtures of several compounds, the same general group, or in the form of mixtures of compounds different groups are used. Surfactants can also be added to herbicide products, which contain an inert solid carrier.

00 9 84 1 IA 97 4

The present invention also includes concentrated preparations containing the active ingredient, which are described below e.g. B. can be used with water to the desired concentration for application to plants and soil. The advantage of such concentrates is that they can be manufactured by the manufacturer in a form that the consumer only needs to mix them with locally available carriers, preferably water, thereby minimizing shipping costs while a product is being delivered, that can be deployed with a minimum of equipment and effort. Such concentrates may contain from about 5 to about 99 wt.% Of one or more of the active 2,4-dinitro-1,3-phenylenediamines, along with a liquid or solid carrier or diluent. Liquid carriers that are miscible with the active ingredients or other liquids in which the active ingredients can be suspended or dispersed can also be used. Here, too, a surface-active substance is generally added in order to facilitate the solution or dispersion in water. In such concentrates, however, the carrier material itself can also comprise the surfactant.

The herbicidal preparations can also have other advantageous ones Contain additives such as humectants, oils and substances that increase contact. There can also be other herbicides such as sodium borates, sodium chlorate, chlorophenoxy-acetic acid, substituted uracils and ureas, triazines, benzimidazoles, carbamates, anilides, amides and halogenated fatty acids admixed with the herbicide preparations according to the invention will.

The following examples illustrate the preparation of suitable herbicide preparations according to the present invention.

0 0 9 8 4 1/1 974

ORIGINAL

Example XXXII

5 % H ¹ -propargyl-N ^, N ^ -dimethyl - ^, 4-dinitro-6-trifluoromethyl-1,3-phenylenediamine (powder)

95% granulated clay

A granulated preparation can be produced in that the aforementioned ingredients in dry Be mixed uniformly in a rotary mixer. A fine spray of water is applied to the mixture during of the mixing process sprayed on to the active ingredient on the clay to adhere. The material is then exposed to air during Continuing the mixing process dried, whereby a granular preparation is obtained, which on the ground or plantings can be applied by hand or by means of a mechanical spreader.

example

85 % N ^ jH ^ -Di-n-propyl-a ^ -dinitro-e-trifluoromethyl-i, 3-

phenylenediamine

14 % bentonite-i-clay

1 % sodium lauryl sulfate as a surfactant

The preparation, which is a wettable powder, is produced in that 2,4-dinitro-1,3-phenylenediamine is finely divided and uniform with the powdery Bentonite clay and powdered sodium lauryl sulfate is mixed. The wettable powder can be added to water or added to a hydrocarbon oil and mechanically stirred to ensure uniform dispersion will. This dispersion can be done with conventional equipment Soil or planting can be sprayed.

- 38 -

0-9 841/1974

2Q13510

Example 3OQQV .

25 % N ¹ -ethyl-N ⁵ , N ⁵ -diethyl-2 ₎ 4 ~ dinitro-6-trifluoromet] 3yl-

1,3-phenylenediamine

5 % aromatic sulphonic acid-oxide condensate as surface-active substance

70 % xylon

The 2,4-dinitro-1,3-phenylenediamine is dissolved in xylene and forms a concentrated solution. The emulsifier is then dissolved and a liquid preparation of an emulsifiable one Get concentrate. The emulsifiable concentrate can be added to water to give the product the desired one Dilute concentration. It can then be sprayed onto the ground or vegetation using conventional equipment.

Example XXXV

5% N ^, N ^ -Di-n-propyl-2,4-dinitro-6-chloro-1,3-pb.enylene-

diamine (powder) 95% granular clay

A granular formulation can be prepared as described in B _e ispiel XXXII. It can be applied to soil or planting by hand or using a mechanical spreader.

Example XXXYI

85 % N ^, N ^ -diethyl-2,4-dinitro-6-bromo-1,3-plienylenedi «min 14 % bentonite clay
1 % sodium lauryl sulfate as surfactant

009841/1974

ORIGINAL INSPECTED

The ingredients are, as described in Example XXXIII ", processed into a wettable powder product. This wettable powder product can, as described in Example XXXIII, can be converted into a sprayed dispersion " and with übliclieii equipments on the ground or planting be sprayed on.

Example XXXVII '■,.

25% N ¹ -ethyl-N ⁵ , F ³ -diethyl-2,4-dinitro-6-bromo-1,3-phenylenediamine

5% aromatic sulfonate oxide condensate as surface-active substance.
70 % xylene

The components can be used in the same way as in example XXXIV described, to an emulsifiable concentrate or a spray liquid that is applied to the soil or planting using conventional equipment can.

Claims;

~ -7

009841/1974

Claims (1)

Claims;
1. Use of compounds of the general formula wherein X is a halogen atom or the trifluoromethyl group and R ^, Έ-2 * Rz and R ^, which can be the same or different, are hydrogen atoms, alkyl, alkenyl or alkynyl groups, where at least one of the groups R ^, Rp, R ^ and R ^ a so defined hydrocarbon radical iat> or R / j and ^ together and / or R, and R ^, together an alkylene group with 2 to 6 carbon atoms and optionally a nitrogen or an oxygen atom in the chain are all herbicides. · Use according to claim 1, characterized that X is a bromine or chlorine atom, Rxj is hydrogen, Rg is hydrogen or an alkyl group with 1 to 5 carbon atoms and R, and R ^ ,, the can be the same or different, hydrogen or Represent alkyl groups of 1 to 5 carbon atoms. 3 · Use according to claim 2, characterized in that that the groups -N and 009841/1374 ORIGINAL INSPECTED ■ - 41 - ' are different from one another and IU and R ₂ ,, 'contain a total of 2 to 8 carbon atoms. 4. Use according to claim 2, characterized in that X is a bromine or a chlorine atom, Ütj and Hg are hydrogen and R ^ and R ^, which can be the same or different, represent hydrogen or alkyl groups with Λ to 5 carbon atoms, the total number of carbon atoms being 3 to 8. 5. Use according to claims 2 to 4, characterized in that the active ingredient is N ⁵ , N ⁵ -methyl-2,4-dinitro-6-chloro-1,3-phenylenediamine- 6. Use according to claims 2 to 4, characterized in that the active ingredient is N ⁵ - (3j-bentyl} -2,4-dinitro-6-chloro-1,3-phenylenediamine. 7. Use according to claim 1, characterized in that X is the xrifluoromethyl group, R _{1 is} hydrogen, R ₂ and Η ,, which can be identical or different. Are hydrogen atoms or alkyl groups having Λ to 5 carbon atoms and R ^ is an alkyl group having 1 to 5 carbon atoms. 8. Use according to claim 7, because the total number of carbon atoms in the groups R ^, _Λ H ₂ , Ηχ and H ^ is about 4 to 8. , 9. Use according to Aüspruoh 7 or θ only control of undesired plant growth in the cultivation of cotton, So ^ abohnan, quay or rice, 'BH / pi iNSPE <$ TED