CS237333B2 - Herbicide agent - Google Patents

Description

The present invention provides herbicidal compositions containing N-phenylpyrazole derivatives as active ingredients.

J. Heier. Chem. 12 (1975J, 1199-1205, PL SouthWick and B. Dhawan described the preparation of 4,4'-thiimidopyrazole [3,4-d] pyrimidines) in the expectation that these pyrimidine derivatives would have useful pharmacological properties . As starting materials, these authors used 1-phenyl-5-amino-4-cyanopyrazoles of the general formula I

Southwick and Dhawan, 5-amino-4-cyano-1- (2,4-dichlorophenyl) pyrazole and 5-amino-4-yl-1- [1,4-quinol-2-yl] -2- iucthylphenyljpyrazole. The above-mentioned work does not contain any mention that the compounds of the formula I exhibit herbicidal activity - or that it would be expected that they could show such activity.

These pyrazole derivatives apparently did not (according to the authors of the article) lead to a useful therapeutic agent (specifically antimalarial), which is 4,6-diaminopyrazolo [3,4-d] pyrimidine and its derivatives.

Japanese Patent Application No. 25,598 / 63 (published under No. 19,958/65) discloses pyrazole derivatives of the general formula II (I) in which:

R is, inter alia, hydrogen and

R‘ represents a hydrogen atom, a methyl group, a hydroxyethyl group - or a phenyl group substituted with one or more chlorine atoms and / or methyl groups.

Among the numerous pyrazole-derivatives which at 2333333 L.

(Π) in which

R1 represents a hydrogen atom or an unsubstituted phenyl group,

R ₂ is hydrogen or <lower alkyl,

R ₃ is hydrogen, halogen, nitro or cyano and ·

R @ 1 represents a lower alkyl group, an amino group or a lower alkoxy group which are useful as herbicides.

In our British Patent Publication No. 2,070,604 A it is stated that when R 1 on the pyrazole ring of compounds of formula II is a phenyl radical bearing certain substituents, R 2 is hydrogen, R 1 is cyano or substituted carbamoyl and R 4 is amino , such compounds also have useful herbicidal activity and exhibit unexpectedly advantageous herbicidal properties over the compounds disclosed in Japanese Patent Publication No. 19,958/65 - Derwent Basic No ·. G 3904, for example with closely related 1-phenyl-4-cyano-5-aminopyrazole.

Thus, the aforementioned British patent publication discloses herbicidally active N-phenylpyrazole derivatives of formula III

(III) wherein each of R @ ⁶ and R @ ⁶ , which may be the same or different, each represents an alkyl, C1 -C4 alkoxy, trifluoromethyl or trifluoromethoxy group, nitro, · cyano, · primary amino, fluorine, chlorine or bromine, each of R 7, R 8 and R 9, which may be the same or different, · represents in each case hydrogen, C 1 -C 4 alkyl or alkoxy, trifluoromethyl trifluoromethoxy, nitro, cyano, primary amino or fluorine, chlorine or bromine, or

R @ 1, R @ 7, R @ 8 and R @ 9 are each hydrogen and R @ 6 is trifluoromethoxy or preferably trifluoromethyl, and

R10 represents a cyano radical or substituted carbamoyl group of formula -CONHR ¹ · ^1, wherein ^{R If} represents methyl or ethyl and an agriculturally acceptable acid addition salts of those compounds of Formula III, wherein at least one of the symbols · R-, R6, R7, R8 _and r 9 is a primary amino group with acids.

In the above-mentioned British patent publication, the following compounds of formula III are mentioned as particularly interesting herbicides:

And 5-amino-4-cyano-1- (2,3,4-trifluorophenyl) pyrazole

B 5-Amino-4-cyano-1- (2-nitro-4-trifluoromethylphenyl) pyrazole

C 5-amino-4-cyano-1- (2,4-dichlorophenyl) pyrazole

D 5-Amino-1- (2-bromo-3,4-dichlorophenyl) -4-cyanopyrazole

E 5-Amino-4-cyano-1- [3,4-dichloro-2-methylphenyl] pyrazole

F 5-Amino-1- (tert-dichlorophenyl) -4-cyanopyrazole

G 5-Amino-4-cyano-1- (2,4-dichloro-3-methylphenylpyrazole)

5-Amino-4-fluoro-1- (2,4-dichloro-3-methoxyphenyl) pyrazole

5-Amino-4-cyano-1- (4-cyano) -4-dichlorophenylpyrazole

5-Amino-1- (4-bromo-2,3-dichlorophenyl) -4-cyanopyrazole

5-Amino-4-cyano-1- (2,3-dichloro-4-methylphenyl) pyrazole

5-Amino-4-cyano-1- (4-bromo-2-chloro-3-methylphenyl) pyrazole

N 5-amino-4-cyano-1- (2-ch-or-3,4-dimethylphenyl) pyrazole

P 5-Amino-4-cyano-1- (4-chloro-4-cyano) -methylfuranol pyrazole

Q 5-amino --- (3-chloro-2,4-dibisophenyl) -4-cyanopyrazole

R 5-Amino-1- (3-chloro-2,4-dimethlenyl) -4-cyanopyrazole

With 5-amino-10- (3-bromo-4-chloro-4-methylphenyl) -4-cyanopyrazole

5-Amino-1- (4-chloro-2,3-dimethylphenyl) -4-4-cyanopyrazole

5-Amino-1- (4-c, 4'-r-3-cyano-2-methylphenyl) -4-cyanopyrazole

5-Amino-4-cyano-1- (2,4,5-benzoic acid) pyrazole

N 5-Amino-4-cyano-1- (2,4,6-richlorophenyl) pyrazole bicyclically. the active N-phenylpyrazole derivatives of the general formula IV

X 5-Amino-4-cyano-1- (2,3,4,5-tetrachlorophenyl) pyrazole

Y 5-amino-4-cyano-1- (2,3,4,6-trifluorophenyl) -pyrazole

From 5-amino-4-cyano-1-pentachlorophenylpyrazole

AA 5-amino-4-cyano-11-pentafluoro-phenyl-pyrazole

BB 5-amino-4-cyano-1- (4-trifluoromethylphenyl) pyrazole

CC 5-Amino-4-cyano-1- (3-chloro-2,4-difluorophenyl) pyrazole

DD 5-Amino-4-N-methylcarbamoxamido-1- (2,3,4-trimethyl) pyrazole

EE 5-Amino-4-N-ethylcarbonyl-aalido-1- (2,3,4-trichloro-phenyl) -pyrazole.

The designation of the above compounds by letters A to H, J to N and P to EE serves to ease the identification of these compounds in the following.

Particularly preferred compounds of the aforementioned British Patent Publication are Compound C and in particular. then compounds D to H, J to N and P to U, and in particular compound A.

European Patent Application No. 0 026 034 also discloses that compound W [5-amino-4-cyano-1- (2,4,6-trichlorophenyl) pyrazole] has valuable herbicidal properties.

As a result of further extensive research and experimental work, it has now been found that, when the sixtstitution of Rt on the pyrazole ring of the compounds of formula II is a phenyl group substituted at the 4-position with a trifluoromethyl group, And, optionally, at the 3, 5 and 6 positions, fluorine or chlorine atoms, as further described below, such compounds exhibit unexpectedly extremely advantageous herbicidal activity over the herbicidally active N-phenylpyrazole derivatives described above. cited British patent publication and other closely related compounds known in the art.

Accordingly, the invention describes a new

(IV) wherein

R12 represents a chlorine atom,

R13 represents a hydrogen, fluorine or chlorine atom;

R-14 is hydrogen or fluorine; and

R15 represents a hydrogen, fluorine or chlorine ·, that means - if R14 is fluorine, R15 imagine fluorine or chlorine, or R 12, R · and R 15 each represents a fluorine atom and R ¹⁴ represents a hydrogen atom or · fluorine.

When R ¹³ represents a hydrogen atom, R 14 is preferably a hydrogen atom.

Representative compounds of formula (IV) according to the invention include α-amino-1- (2-chlorobenzyl) phenyl-4-cyanopyrazole (hereinafter referred to as Compound No. 1), amalmo-4-kynn-1-one. - (2,6-Dichloro-4-difluoromethyl-phenyl) -pyrazole (hereinafter referred to as Compound No. 2); or-4- (4-fluoro-4-methyl-phenyl) -pyrazole (hereinafter referred to as Compound (3)) and ammmo-4-canon-1 (2,3,5,6). As compound 4).

Herbicidal activity tests are described below. In these tests carried out with representative compounds of the general formula III described in British Patent Publication No. 2,070,604 A, with a narrow application of 2333333.

By fusing 1-phenyl-4-cyano-5-nitro-pyrazole specifically disclosed in Japanese Patent Application No. 29,598/63 (published under No. 19,958/65 - Derwent Basic No. G 3904) (test substance CC1), with a narrow related 5-amino-4-cyano-1- (2,3,4-trichlorophenyl) -3-methylpyrazole (test substance CC2) and representative compounds of formula IV (compounds 1, 2, 3 and 4) were results found below.

Experiment 1 (1) Weed control efficacy test (a) General procedure

Test substances A to H, J to N and P to E, CC1, CC2, Nos. 1, 2, 3 and 4 (as defined above) are dissolved in acetone. Application is carried out using a standard laboratory herbicide spraying apparatus, using a flat fan nozzle at a speed of 2.6 km / h, at a rate of 530 liters of spray liquid per hectare (spraying is carried out at a pressure of 0.28 MPa). Solutions of test compounds A to H, J, К, M, N and Q to ЕЕ, CC1 and CC2 are prepared by dissolving 0,513 g of the test compound in acetone and bringing the volume of the solution to 34 ml [1,5%] with additional acetone. (weight / volume)), which corresponds to an active substance consumption of 8 kg / ha.

From these stock solutions, further dilutions with acetone are prepared to give consumption of test compounds 4, 2, 1, 0.5, 0.25 and 0.125 kg / ha, except for test substances C, W, AA, BB, DD , ЕЕ а CC1, in which solutions are prepared whose application results in consumption of 8, 4, 2, 1 and 0,5 kg / ha. Solutions of test substances L and P were prepared similarly, but using 0.128 grams of test substance, to give solutions whose application yielded 2, 1, 0.5, 0.25 and 0.125 kg / ha. Similarly, using 0.128 g of test substances Nos. 1, 2 and 4, solutions are prepared to give consumption of 2, 1, 0.5, 0.25, 0.125, 0.0625, 0.0312 and 0.0156 kg. / ha. Similarly, solutions of Test Compound (3) were prepared using 0.064 g of the compound to give solutions that yielded consumptions of 1, 0.5, 0.25, 0.125, 0.0625, 0.0312, and 0.06 g. 0156 kg / ha.

(b) Weed control - pre-emergence application

The weed seeds are sewn onto John Innes No. 1 compost leather (7 parts by volume of sterilized clay, 3 parts by volume of peat and 2 parts by volume of finely crushed gravel), presented in 9 cm-diameter paper mugs impregnated with bitumen. The seed doses per mug are given in the following overview:

a kind of weed the approximate number of seeds per mug (i) broadleaf weeds Sinapis arvensis 30—40 Polygonům lapathifolium 30—40 Stellaria media 30-40 (ii) Grassy weeds Avena fatua 15—20 Alopecurus myosuroides 30—40 Echinochloa crus-galli 20—30

Test compounds are applied to uncovered seeds (see paragraph (1) (a) above) at doses from 0.125 to 8 kg / ha, except for test substances L and P, which are applied at doses of 0.125 to 2 kg / ha, with with the exception of test substances C, W, AA, BB, DD, E and CC1, which are applied at doses from 0.5 to 8 kg / ha, with the exception of test compounds Nos. 1, 2 and 4, which are applied at doses of 0.0156 to 2 kg / ha and with the exception of Test substance No. 3, which is applied at doses from 0.0156 to 1 kg / ha. The seeds are sprayed with 25 ml of sharp sand. One mug is used for each treatment and for each weed species, and control trials with untreated mugs and control trials with mugs treated with acetone only are carried out. After treatment, the cups were placed in a greenhouse and irrigated from above. The weed control effects were visually evaluated 19 to 28 days after spraying. The results are expressed as minimum effective doses (MED) in kg / h0 at which we control 90% growth suppression or weed control compared to control experiments. The results are summarized in Table I below.

(c) Weed control - post-emergence application

Individual weed species are propagated and then transplanted into John Innes No. 1 composting plant, presented in 9 cm diameter paper pots impregnated with bitumen, except for deaf oats (Avena fatua), which is not transplanted but is directly sown in mugs, in the test is performed. The plants are then grown in a greenhouse until they can be sprayed with test compounds. The number of plants per mug and plant growth stages at the time of spraying are shown in the following overview:

growth stage at spraying time weed species number of plants per mug (i) broadleaf weeds

Polygonům lapathifolium5

Stellaria media5

Abutilon theophrasti3

1—1 1/2 pair of sheets

4–6 leaves pairs of leaves (ii) grassy weeds

Avena fatua10

Alopecurus myosuroides5

Echinochloa crus-galli5 leaf

1/2 sheet

1-2 leaves

Test compounds are applied to plants as described in (1) (a) above at doses from 0.125 to 8 kg / ha, except for test substances L and P, which are applied at doses of 0.125 to 2 kg / ha, except for test compounds. substances C, W, AA, BB, DD, EE, and CC1, which are applied at doses from 0.5 to 8 kg / ha, with the exception of test substances Nos. 1, 2 and 4, which are applied in doses from 0.0156 to 2 kg / ha, and with the exception of Test substance No. 3, which is applied at doses from 0.0156 to 1 kg / ha.

One cup is used for each treatment and for each weed species, and control experiments with untreated cups and controls with cups treated with acetone alone are also carried out. After spraying, the mugs were irrigated (starting 24 hours after spraying).

Evaluation of the effect on weed growth is carried out 19 to 28 days after spraying by recording the number of plants destroyed and the suppression of growth. The results are expressed as minimum effective doses (MED) in kg / ha at which weed control is suppressed 90% or weeds are destroyed compared to the plants in the control pot. The results are summarized in Table II below.

In the following tables, weed species are abbreviated with the following meanings:

(a) grassy weeds:

Am = Alopecurus myosuroides

Af = 'Avena fatua

Ec = Echinochloa crus-galli (b) broadleaf weeds:

Roe = Stellaria media

PI = Polygons lapathifolium Sa = Sinapis arvensis

At - Abutilon theophrasti

Table I tested MED (kg / ha) for pre-emergence application

substance PI Sa Sm Am Af Ec AND 0.25 0.125 0,5—1 0.5 0,5—1 0.125-0.25 (B) 0,5—1 0.5 > 8 2 2—4 1—2 C 0,5—1 0,5—1 8 4 4 1 D 0,5—1 0,25—0,5 4—8 2 4 1 E 1 1—2 2—4 2—4 2—4 0,5—1 F 0,5—1 0,5—1 2 2—4 1—2 0,5—1 G 0,25—0,5 0,25—0,5 0.5 1—2 1—2 0,25—0,5 H 0,5—1 2 1 2 1—2 2 J 0.5 0,5—1 4—8 2 1—2 1 TO 1 0.5 1—2 2—4 2—4 1 L 0.5 1 > 2 > 2 > 2 1—2 M 1 0,5—1 > 8 4 4 0,5—1 N 0.125—0.25 0.25 8 4 2—4 0,25—0,5 P 1 > 2 NR NR NR 2 Q 4 4 4 4—8 4—8 4—8 R 1—2 4—8 > 8 2—4 2—4 1—2 WITH 1—2 0,5—1 2—4 4 4 4 T 0,5—1 2—4 4—8 0,5—1 2—4 2—4 at 2 4—8 4—8 2—4 > 8 2 in 1 2 8 8 4—8 1 w 0,5—1 <0.5 2 2—4 0,5—1 . 0,5—1 X 2 1—2 0.5 2—4 2—4 2 Y 0.5 1.0 4—8 2-4 2 0,5—1

MED (kg / ha) tested for pre-emergence application

substance PI Sa Sm Am Af Ec OF 2—4 1—2 > 8 2—4 4—8 1 AA 1—2 1.0 8 2—4 1—2 1 BB 1—2 4 4—8 2—4 4 1—2 cc 1 4 > 8 4 4 1 DD 4 1 8 > 8 NR > 8 EE NR 2—4 NR NR NR > 8 CC1 8 > 8 8 NR NR > 8 CC2 NR NR NR NR NR NR no. 1 0,0312— 0,0312— 0.5-1 0,25—0,5 0.25 0.25 —0.0625 —0.0625 No 2 0,0156— <0.0156 0,0625— 0,25—0,5 0,25-0,5 0.125 —0.0312 —0.125 No 3 0.125—0.25 0,0156— —0.0312 0,0625 1.0 0,25-0,5 0.5 No. 4 0,0156— 0.0156 0.25 0.5 0,0312— 0.125 —0.0312 —0.0625 Table I I tested MED (kg / ha) for post-emergence application substance At PI Sm Am Af Ec

AND 0.125 0.125 1—2 4—8 4—8 2—4 В 0.125 0.5 > 8 > 8 > 8 8 C <0.5 <0.5 > 8 > 8 > 8 4 D 0.125—0.25 0.125—0.25 2-4 > 8 > 8 > 8 E <0.125 <0.125 2 > 8 > 8 8 F 0.125—0.25 0,25—0,5 0,5—1 NR > 8 > 8 G <0.125 0,25—0,5 4—8 > 8 > 8 4 H 0.25 0.125—0.25 0.25 > 8 8 1—2 J <0.125 <0.125 NR > 8 > 8 1—2 К 0,25—0,5 0.125—0.25 2 NR > 8 > 8 L <0.125 0,25-0,5 > 2 > 2 > 2 2 M 0.125—0.25 0,25—0,5 > 8 NR > 8 > 8 N 0.125—0.25 0,25—0,5 NR > 8 > 8 8 P 0.125—0.25 0,5—1 > 2 > 2 > 2 NR Q 0.125—0.25 0.25 4—8 > 8 > 8 > 8 R 0.125—0.25 0,25—0,5 NR > 8 > 8 > 8 WITH 0.125—0.25 0,25—0,5 1—2 NR > 8 > 8 T 0,5—1 0,5—1 NR > 8 > 8 > 8 AT 1—2 0,5—1 > 8 > 8 > 8 > 8 IN 0,25—0,5 0.5 > 8 > 8 > 8 > 8 W <0.5 <0.5 > 8 > 8 8 2—4 X 0,5—1 0.5-1 2 NR NR > 8 Y 0.125—0.25 0,25—0,5 > 8 8 4—8 2 of 0,5—1 1—2 NR > 8 NR > 8 AA <0.5 <0.5 NR 8 4 2—4 BB 1 0,5—1 NR > 8 > 8 4—8 CC 2—4 2 NR > 8 > 8 4 DD 1-2 > 8 NR NR NR > 8 EE 4—8 8 NR NR NR > 8 CC1 > 8 > 8 NR > 8 > 8 NR CC2 NR NR NR NR > 8 NR no. 1 <0.0156 0,0156— -0.0312 0.25 > 2 > 2 0.5-1 6.-2 <0.0156 <0.0156 0,0156— -0.0312 > 2.0 2,0 0.2 No 3 0156- .0.0312— ': _Г О, 0525 0,0625 > 1.0 > 1.0 1.0 No. 4 ¢ - ^ 0.0312 <6,01’5’6 0,0625 2,0 0.5-1 0, 125

The individual symbols appearing in the above tables have the following meanings:

> = much greater than> - greater than <- less than

NR = no growth suppression at any of the administered doses

Experiment 2

Comparison of the efficacy of compounds 1, 2 and 4 with compound A against Galium aparine, Veronica persica and Viola arvensis in post-emergence application

Galium aparine, Veronica persica and Viola arvensis are resistant to phenylurea herbicides such as isoproturon and chlortoluron at application rates at which the two games of bicides are normally used to suppress the growth of broadleaf weeds in cereals. The widespread use of isoproturon and chlorotoluron, especially in Western Europe, has led to the ternary fact that these three weed species are a particularly important and difficult problem in the field of weed control in winter cereals.

Test performance

All weed species are grown in John Innes compost box (7 volumes of sterilized clay, 7 volumes of peat clay and 2 volumes of finely crushed gravel. At the cotyledon stage, plants are pierced into 9 cm diameter resin impregnated mugs. In the following overview, the number of plants in the mug and the growth of the dwarf plants are kept at the time of application of the test plants:

a kind of weed height (cm) number of pages number of plants per mug Galium, aparine 4 to 9 3 to 5 (whorls) 2 Veronica persica 2 to 4 5 to 6 0 3 Viola arvensis 2 to 3 3 to 4 3

Application of test compounds is done using standard laboratory equipment for ¹ · herbicide sprayer using flat fan jet traveling at 2.6 kg / hr at a dose corresponding to 260 • liters of spray fluid per hectare (spray pressure being 0.21 MPa). Solutions of Compounds Nos. 1, 2 and 4 and Compound A are prepared by dissolving 0.154 g of the test compound in acetone and bringing the volume of the solution up to 40 ml with additional acetone, corresponding to the consumption of the active substance of 1 kg / ha. Solutions are prepared from these stock solutions by further dilution with acetone to give consumption of test compounds of 0.5, 0.25, 0.125, 0.0625 and 0.0312 kg / ha.

Each treatment was repeated on 3 cups for each chaff type, and control trials with untreated cups and controls with cups treated with acetone only were carried out. After treatment, the mugs were kept in a greenhouse and irrigated from the top, starting 24 hours after spraying. At 28 days after spraying, weed control was observed by recording the number of plants destroyed. The results obtained in each of the repeated experiments are averaged and the averaged DCs results are expressed as the doses of the individual test compounds for which 90% of the plants are destroyed (ED g ₀ kg / ha). The results are shown in the following table

III.

Table III test substance ED90 kg / ha (average of three replicates)

Galium aparine - Veronica persica - Viola arvensis

Compound No. 1 0.29 0.11 0.09 Compound No. 2 0.23 0.10 0.09 Compound No. 4 0.09 0.09 0.08 Compound A 0.75 0.29 0.31

Experiment 3

Test performance

Control of Galium aparine in winter wheat using compounds 1 and 2 and compound A

The following ingredients are prepared as wettable powders:

% (w / w) component (A) Compound A50

Arylan S90 (sodium dodecylbenzenesulfonate) 3

Sopropo-n T.36 (sodium polycarbonyl) 1

Belloid TD (condensation product of sodium naltalensullonate and formaldehyde) 5 micronized silica filler up to 100 (B) Compound No. 120

Nekal BX (sodium alkylnalthaleneullonate) 10 sodium liposullate3

Sopropon T.360,5 micronised silica. to 100 (C) Compound No. 220

Nekal BX10 sodium lignosullate3

Sopropon T.360,5 Micronised Silica to. 100 ALIGN!

These wettable powders are diluted with water and applied to the test fields of 2.5 &quot; x 2.5 m with emerging winter wheat (variety Avalon, growth stage: height about 15 centimeters) in 217.2 liters of spray liquid per hectare. 5 unfolded leaves, main shoots and 4 offshoots, false stem · erect), and Galium aparine (growth stage: approx. 7.5 cm high with 2 branches and 3 rosettes, up to approx. 20 cm with 7 to 8 branched) the treatment is repeated twice.

The individual test compounds are administered at the following doses:

Compound A:

0,5, 1 and 2 kg / ha of compound 1:

0.125, 0.25, 0.5 and 1 kg / ha · Compound 2:

0.125, 0.25, 0.5 and 1 kg / ha.

After 6 days of spraying, the percentage of Galium aparine eradication and the percentage of wheat damage was visually observed in each treated field in comparison. with unsprayed control boxes. For. each pair of repetition boxes,. the percentage of Galium aparine extermination and the percentage of wheat damage are calculated. The results obtained are shown in Table IV below.

At the time of evaluation, wheat is in the following growth stage: about 20 cm high, 6 main leaves, main shoots and 4 offshoots, the first nodium noticeable.

Table IV

test substance application rate kg / ha extermination of Galium aparine v. percent percentage of winter wheat damage Compound A 0.5 90 5 . .. · of 1. 93 13 . :.: - 2 .--- ··. 98 18 v compound no. 1 0.125 ; 70 -. 0 . · ../. 0.25 83  : 0.5  93. . ·. '·. ·. ·. '/ 3 .- · ·· .. - ·:.: -./·. . 1. 100 ALIGN! ·· 5 C ...- V.: .. compound. No 2 : 0,125 90 0 0.25 95 0 0.5 98 8 1 98  χ 5.

From the above experimental. The results clearly show the valuable herbicidal properties of the compounds of general interest. and a surprising and unexpected higher herbicidal effect, especially in the post-emergence application, which the compounds of the formula IV exhibit in comparison with the compounds. of formula III, for example with compounds A, B, C, V, W, X, Y, Z, AA and BB, with the closely related 1-phenyl-4-yl-5-aminopyrazole described in Japanese Patent Application No. 29 598/63 and closely related to 5-amino-4-cyano-1- (2,3,4-trichlorophenyl) -3-methylpyrazole, wherein the substitution of the 3-position of the pyrazole ring with alkyl. (methyl) as described in Japanese patent application no.

598/63, is combined with the substitution of the 1-position of the pyrazole ring with a substituted phenyl group (2,3,4-trichlorophenyl group), which combination has been found to contribute to high herbicidal activity for compounds of the general formula

III.

In particular, Experiment 1 shows that, in post-emergence application, Compounds No. 1, 2, 3 and 4 are at least two to more than eight times more potent than Compound A in controlling the important weed growth of Polygons lapathifclium, Compounds No. 1, 2, 3 and 4 are at least four to more. more than 16 times more potent than Compound A and at least 32 to more than 60 times more potent

Compound No. 1, 2, 3, and 4 are at least four to more than eight times more potent than Compound A and Compound No. 1, 3, and 4 are at least eight times to Compound W than Compound W Abutilon theophrasti and Compounds Nos. 1, 2, 3 and 4 are at least two to more than eight times more potent than Compounds A and W in inhibiting the growth of Echinochloa crus-galli. Experiment 2 further demonstrates that Compound No. 1 is more than two times more potent, Compound No. 2 is more than three times more potent, and Compound No. 4 is more than eight times more potent than Compound A in terms of inhibiting Galium · aparine growth. 1, 2 and 4 are two to three times more potent than Compound A in terms of inhibiting the growth of Veronica persica and that compounds No. 1, 2 and 4 are at least three times more potent than Compound A in controlling growth of Viola arvensis, mostly in post-emergence application .

Experiment 3 demonstrates the high potency and selectivity of Compound # 1, and in particular Compound # 2, of very important growth inhibition. weeds, which are Galium aparine, in a winter wheat culture.

Thus, Compound No. 1 is twice as potent and Compound No. 2 is at least four times as potent as Compound A in inhibiting the growth of Galium aparine, with Compounds No. 1 and 2 substantially less damaging winter wheat than Compound A.

Accordingly, the invention also provides a method for controlling weed growth (i.e., undesirable vegetation) at a particular site, comprising administering to said site a herbicidally effective amount of at least one N-phenylpyrazole derivative of the general formula IV. For this purpose, N-phenylpyrazole derivatives are normally used in the form of herbicidal compositions [i. in combination with compatible diluents or carriers suitable for use in herbicidal compositions) as described, for example, below.

The compounds of formula (IV) show herbicidal activity against dicotyledonous (i.e. broadleaf) and monocotyledonous (e.g. grassy) weeds in pre-emergence and / or post-emergence application.

By "pre-emergence application" is meant application to the soil in which weed seeds or seedlings are present before the weeds have emerged above the soil surface. By the term "post-emergence application" is meant application to the above-ground or weed-exposed parts of the weeds above the soil surface.

For example, ¹ compounds of formula (IV) may be used to control broadleaf weed growth, such as:

Abutilon theophrasti (abutilon),

Amaranthus retroflexus,

Amsinckia intermedia,

Anagallis arvensis (Scarlet Pimpernel),

Atriplex patula,

Brassica nigra (mustard mustard), Capsella bursa-pastoris,

Chenopodium album (Chrysanthemum segetum), Cirsium arvense (Field Thistle),

Datura stramonium (virgin durman · cucumber),

Desmodium tortuosum,

Emex australis,

Euphorbia helloscopia (Spurge Spurge), Fumaria officinalis (Common Fumitory),. Galeopsis · tetrahit (swollen hemp), Galium aparine (bedstraw),

Geranium • dissectum, Ipomoea purpurea,

Lamium purpureum,

Lap-sana communis (Common Kale), Matricaria inodora (Scentless Chamomile), Monoohoria vaginalis,

Papaver rhoeas (Poppy),

Physalis longifolia,

Plantago lanceolata (lantern plantain),

Polygons spec, for example. Polygonum lapathifolium, Polygonum aviculare, Polygonum convolvulus and Polygonum persicaria,

Portulaca oleracea,

Raphanus · raphanistrum (radish), Rotala indica,

Rumex obtusifolius (sorrel),

Saponaria vaccaria,

Scandix pecten-veneris, Senecia vulgaris, Sesbania florlda,

Sida spinosa,

Silene alba

Sinapis arvensis (Field Mustard),

So-lanum nigrum (black eggplant),

Souclius arvensis (Field Milk),

Spergula arvensis (Field Girdle), Stellaria media (Chickweed),

Thlaspi arvense (Field Pennycress), Tribulus terrestris,

Urtica urens,

Veronica hederifolia (Ivy-leaved Speedwell),

Veronica persica (Persian Speedwell),

Viola, arvensis and Xanthium strumarium, and grassy weeds such as: Alopecurus myosurddes, Apera spica-venti, Agrostis stolonifera, Avena fat.ua (deaf oats),

And the ludovlciana

Brachiaria spnc.,

Bromus sterilis,

Bromus tectorum,

Cenchrus spec.,

Cynodon dactylou,

Digitaria sanguinalis,

Echinochloa crus-galli,

Eleusine indica (eleusin),

3 7.3 3'3

18

Setaria viridis (Green Beech) and So-rghum halepense · (Sorghum halepense), Sorghum halepense (broad-lime), as well as flatheads such as Cyperus esculentus,

Cyperus iris and Cyperus rotundus and Eleocharis acicularis.

The application rates of the compounds of formula (IV) vary depending on the nature of the weeds, the compositions used, the time of application, the climatic and soil conditions, and the nature of the crop when the growth of weeds in the crops is controlled. crop. When applied to areas where crops are or will be grown, the compounds of the invention should be applied at a dose sufficient to control weed growth without causing significant permanent damage to the crops. Taking these factors into account, • good results are generally achieved. with application rates of between 0.01 kg and 10 kg of active ingredient per hectare. It will be appreciated, however, that the compounds of the invention may be administered. . even at higher or lower doses, depending on the particular circumstances associated with the weed control problem.

The compounds of formula (IV) may be used to selectively control the growth of weeds, for example to control the growth of the aforementioned weed species by their preemergence or postemergence, directed or unmounted application, for example by directed or unmounted spraying at a weed infestation site. the area in use or will be. use .. to grow useful plants, for example. cereals such as wheat, barley, oats, corn and rice, soybeans, beans. General · a. field, peas, alfalfa, cotton, peanuts, flax, onion,. carrots, cabbage, oilseed rape, sunflowers, beet · sugar and perennial or sown meadows before or after sowing the crop or before or after emergence of the crop.

To selectively control weeds in areas infested with weeds, which are areas that are used or will be used for growing crops,. for example, the aforementioned useful plants are particularly suitable application rates of between 0.05 kg and 4.0 kg, preferably between 0.1 kg and 2.0 kg of active ingredient per hectare.

In particular, the compounds of formula (IV) may be used to selectively suppress the growth of broadleaf weeds. for example, to suppress the growth of the abovementioned broadleaf weed species by pre- or post-agent application, in particular by post-emergence application in a non-directional manner, for example by non-directional spraying,. . to the area used to grow cereals, such as wheat, barley, oats, maize and rice, before or after emergence of both the crop and the weeds.

Compounds of general interest. Formula IV are particularly useful for selectively controlling growth. Galium aparine, Veronica persica, Veronica hederifolia and Viola arvensis by post-emergence application in a non-directional manner, e.g. - the area used to grow cereals, such as wheat, barley and oats, after emergence of both the crop and the weeds.

To this. for selective control of broadleaf weeds by pre-emergence or post-emergence application to the area. used to grow cereals,. particularly suitable application rates ranging between 0.05 and 4.0 kg, preferably between. 0,1 · and 2,0 · kg of active substance per hectare.

Due to the high herbicidal activity of the compounds corresponding to the general. of formula IV, in particular compounds Nos. 1, 2 and 4 on Galium aparine, Veronica persica and Viola arvensis, are particularly suitable for post-emergence application in combination with phenylurea-type herbicides such as isoproturon and chlortoluron, for the eradication of broad. . a spectrum of weeds comprising, in addition to the three species mentioned above, Matricaria inodora, Stellaria media, Galeopsis tetrahit, Avena fatua and Alopecurus myosuroides, particularly in the emerging winter wheat and barley culture. In general, application rates of 0.125 to 0.5 kg / ha of N-phenylpyrazole derivative or 1.25 to 2.5 are suitable for this purpose. kg / ha of isoproturon or chlortoluron.

The compounds of formula (IV) can also be used to control the growth of weeds, in particular the weeds mentioned above, by pre-emergence or post-emergence application in orchards and in areas where trees are grown, for example in forests, groves and parks. plantations, such as sugar cane, palm, oil and rubber plantations. For this purpose it is possible. · mentioned. . apply the substances in a directed or non-directed manner (for example by a directed or non-directed spray). for weeds, or. the soil on which it is expected to occur, either before or after planting the trees, or. plantations, in doses between 0.25 kg and 10.0 kg, preferably between 0.1 kg and 4.0 ·. active substance per hectare.

Compounds of general formula. IV can also be used to suppress. growth. weeds, in particular weeds. above. on . in places where the crops are not grown, but where it is desirable to control weeds. . . Examples of such areas include airports, undeveloped areas of industrial enterprises, railways, roadside, river banks, irrigation canals and others. waterways, shrubs, eels or uncultivated soil.

This is particularly the case in areas where it is desirable to control the growth of weeds in order to reduce the risk of fire. When used for this purpose, where a total herbicidal effect is often desired, the active compounds are normally applied in higher doses than is normally used. used. for the treatment of crops on crops as described. above. The exact dosage depends on the nature of the vegetation to be treated and the desired effect. Pre-emergence or post-emergence application, particularly application, is particularly suitable for this purpose. in a pre-emergence, directed or non-directed manner (e.g., by a directed or non-directed spray), using dosages ranging between. 2.0 kg and 10.0 kg, preferably between 4.0 and 10.0 kg of active ingredient per hectare.

When used to control weed growth by pre-emergence ’application is possible. the compounds of formula (IV) to be incorporated into the soil on which weeds are expected to emerge. It is understood that when compounds of formula IV are used to control weed growth by post-emergence application, i.e. by application to above-ground or unprotected parts of emerging weeds, the compounds of formula IV normally also come into contact with soil where they can exert their premergenic effect on - later germinated weeds found in the soil.

In cases where particularly long-term weed control is required, application of compounds of general interest may be required. of formula IV repeat.

The present invention provides a herbicidal composition comprising 1 or more N-phenylpyrazole derivatives of formula (IV) in combination with (preferably homogeneously dispersed) one or more compatible diluents; carriers useful in the preparation of herbicidal compositions [i. diluents or carriers generally used in the art are suitable for use in herbicidal compositions and are compatible with the compound of formula (IV).

The term "homogeneously dispersed" is used to describe compositions in which the compounds of formula IV are dissolved in other components. In the broad sense, the term "herbicidal compositions" refers not only to preparations suitable for immediate use as. herbicides, but also concentrates, which must be diluted before use. The compositions of the invention preferably contain from 0.05 to 90% by weight of one or more compounds of formula (IV).

Herbicidal agents. they may contain a diluent or / and a carrier and a surfactant (for example a wetting, dispersing or emulsifying agent). The surfactants which may be present in the herbicidal compositions of the invention may be ionic surfactants or surfactants. of the nonionic type, for example sulforicinoleate, quaternary ammonium derivatives, condensate products of ethylene oxide with nonylphenols or octylphenols, or carboxylic acid esters with anliydrosorbitols, the solubility of which has been determined by etherification of free hydroxyl groups by condensation with ethylene oxide, salts of sulfuric and alkali alkaline earth metals such as dinonyl and dioctyl sodium sulfonosuccinates, and salts of high molecular weight sulfonic acid derivatives with alkali metals and alkaline earth metals such as sodium and calcium lignosulfonates.

The herbicidal compositions of the present invention may conveniently comprise from about 0.05% to about 10% of a surfactant, but may, if desired, contain the herbicidal compositions of the present invention. And a higher surfactant content, for example up to 15% in the liquid emulsifiable suspension concentrate. and up to · 25% in liquid concentrate. water soluble.

As examples of suitable. solid diluents or carriers. aluminum silicate, talc, magnesium oxide, diatomaceous earth,. tertiary calcium phosphate, powdered cork, adsorbing carbon black and clays such as kaolin and bentonite. Solid compositions which may take the form of dusts, granules or granules. wettable powders, are preferably prepared by grinding the compounds of formula IV with solid diluents or impregnating the solid diluents or carriers with solutions of the compounds of the general formula. Formula IV in volatile solvents, solvent evaporation; if necessary grinding the obtained products into powders. Granular compositions can be prepared by adsorbing the compounds of formula IV dissolved in volatile solvents to form solids. diluents or carriers in granular form. and the solvents are then evaporated, or the powdered formulations obtained are granulated as described above. Solid herbicidal compositions, in particular wettable powders, may contain wetting or dispersing agents [e.g. dispersants of the types described above),. which . may also,. if they are solid, serve as. diluents or carriers.

The liquid compositions of the invention may be in the form of aqueous, organic or aqueous solutions, suspensions and emulsions which may contain a surfactant. Suitable liquid diluents for the preparation of liquid compositions include water, ecetophenone, cyclohexanone, isophorone, toluene, xylene and mineral, animal and vegetable oils, as well as mixtures of these diluents. Surfactants which may be present in liquid compositions include ionic or nonionic surfactants (e.g., surfactants of the types described above), which, when liquid, can also serve as diluents or carriers.

Wettable powders and liquid compositions in the form of concentrates may be diluted. water or other suitable diluents, for example mineral or vegetable oils, in particular in the case of liquid concentrates in which the diluent or carrier is an oil, to form preparations suitable for immediate use. If desired, compositions containing a compound of formula (IV) may be used in the form of self-emulsifiable concentrates containing the active ingredient dissolved in emulsifiers or in solvents containing emulsifiers compatible with the active ingredients. By simply adding water to such concentrates, ready-to-use preparations are then obtained.

Liquid concentrates in which the diluent or carrier is an oil can be used without further dilution using electrostatic spray techniques.

The herbicidal compositions of the invention may optionally also contain conventional excipients such as adhesives, protective colloids, thickeners, penetration agents, stabilizers, complexing agents, anti-caking agents, colorants and corrosion inhibitors. These excipients may also serve as carriers or diluents.

Preferred herbicidal compositions of the invention are aqueous suspension concentrates containing 10 to 70% (w / v) of one or more compounds of formula (IV), 2 to 10% (w / v) of surfactant, 0.1 to 5% (w / v). thickening agents and 15 to 87.9% by volume water, wettable powders containing 10 to 90% (w / w) of one or more compounds of formula (IV), 2 to 10% (w / w) surfactant, and 10 to 10% (w / w); 88% (w / w) solid diluent or carrier, water-soluble liquid concentrates containing 10 to 30% (w / v) of one or more compounds of formula (IV), 5 to 25% (w / v) surfactant and 45 to 85% by volume of a water miscible solvent such as dimethylformamide. liquid emulsifiable suspension concentrates containing 10 to 70% (w / v) of one or more compounds of general formula (I); IV, 5 to 15% (w / v) surfactant, 0.1 to 5% (w / v) thickener and 10 to 84.9% by volume organic solvent, granules containing 2 to 10% (w / v) 0.5 to 2% (w / w) of a surfactant and 88 to 97.5% (w / w) of a granular carrier, and emulsifiable concentrates containing 0.05 to 2% (w / w) of one or more compounds of formula (IV); 90% (w / v), preferably 1 to 60% (w / v) of one or more compounds of formula IV, 0.01 to 10% (w / v), preferably 1 to 10% (w / v) by volume) of surfactant and from 9.99 to 99.94%, preferably from 39 to 98.99% by volume of organic solvent,

The herbicidal compositions according to the invention may also contain the compounds of formula IV in combination (preferably homogeneously dispersed) with one or more other pesticidally active compounds and optionally one or more compatible diluents or carriers useful in the manufacture of pesticidal compositions, surfactants and conventional surfactants. excipients as described above. Examples of other pesticidally active compounds that may be included in the herbicidal compositions of the present invention or which may be used in combination with the herbicidal compositions of the present invention include, for example, herbicides to broaden the spectrum of activity, such as alachlor [α-chloro-2]. , 6-diethyl-N- (methoixymethyl) acetanilide], asulam [methyl- (4-aminobenzenesulfonyl) carbamate], alloxydin Na [sodium 2- (1-allyloixyaminobutylidene) -5,5-dimethyl-4-methoxycarbonylcyclohexane-1, 3-dione], atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine], barban [4-chloro-2-butynyl N- (3-chlorophenyl) carbamate], benzoylprop- ethyl [ethyl 1-N-benzoyl -N- (3,4-dichlorophenyl) -2-aminopropionate], bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), butachlor [N - (butoxymethyl) -a-chloro -2,6-diethylacetanilide], butylate [S-ethyl-N, N-diisobutyl (thiocarbamate)], carbetamide [DN-ethyl-2- (phenylcarbamoyloxy) propionamide], chloropheneprop-methyl [meth yl-2-chloro-3- (4-chlorophenyl) propionate], chloropropham [isopropyl-N- (3-chlorophenyl) carbamate], chlortoluron [N '- (3-chloro-4-methylphenyl) -Ν, Ν] -dimethylurea], cyanazine [2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine], cycloate [N'-cyclohexyl-N-ethyl-S-ethyl (thiocarbamate)] ],

2,4-D (2,4-dichlorophenoxyacetic acid), dalapone (2,2-dichloropropionic acid),

2,4-DB. [4- (2,4-Diclilorpheno = xy) butyric acid], desmedipham [3- (ethoxycarbonylamino) phenyl-N-enylcarbamate], diallate [S-2,3-dichlorallyl-N, N-dilsopropyl (thiocarbamate). ], dicamba [3,6 (Dichloro-2-methoxybenzoic acid), dichlorprop [(+) -2 (2-, 4-dichloro-phenoxy) propicic acid], difenzoquate [1,2-dimethyl-3,5-diphenylpyrazolium salt) dimefuron {4- [2-chloro-4- (3,5-dimethylureido) phenyl] -2-tert-butyl-1,3,4-oxadiazolin-5-one, dinitramine (N1, N ¹ -diethyl- 2,6-dlnltl ⁱⁿ C ^ -4-fluoromethyl-tl'l mf-phenylenediamine), diuron [N {3,4-dichlorophenyl) - N, N-dimethylurea],

EPTC [S-ethyl-N, N-isopropyl ((hiocarbamate)], ethofumesate [2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-ylmethylsulfate), flampropylpropyl [. isopropyl (+) -2- (N-benzoyl-3-chloro-4-fluoroanilino) propionate], methylpropyl [methyl- (+) -2- (N-benzoyl-3-chloro-4-fluoroanilino)] propionate], finoirmeturon - [N '- (3-trifluoromethylphenyl) - N -dimethyl-4-oxo], ioxynil (4-hydroxy-3,5-diiodobenzonitrile), isoproturon. [N' - (4-isopropylphenyl) -, N-dlf methylurea], linuron [N- (3,4-dichlorophenyl) -N-methoxy-N-methylurea],

MCPA (4-chloro-2-methylphenoxyacetic acid),

MCPB [4- (4- (2-chloro-2-methylphenoxy) butyric acid], mecoprop [(+) -2- (4-chloro-2-methylphenoxy) propanoic acid], metamitron [4-amino-3-methyl-6] -phenyl-1,2,4-triazin-5 (4H) -one], methabenzylthiazuron [N- (benzothiazol-2-yl) -NX-dimethylurea], metribuzin [4-amino-6-methyl] -cyclohexanediamine; Butyl 3 - ((mephthylthio) -1,2,4-triazin-5 (4H) -one), molinate [S-ethyl-N, N -hexamethylene (thiocarbamate)], oxadiazole [3f (2,4) -dlchlcr 5 - lscpropoxyfenyl) f5-t-butyl-3,4-cxadla.zσllnf2fcn], paraquat [l, l ^s -dlmethylf4,4 ^C fblpyrldylcvé salts], pebulate [s-propyl N-butyl N-ethyl (thiocarbamate)], phenmedipham [3- (methoxycarbonylamino) phenyl-N- (3-methylphenyl) carbamate], prometryn (4,6-bisisopropylamino-2-methylthfo-1,3,5-trizaine), propachlor (.alpha.-chloro-N-isopropylacetamide), propanil [N- (2-chlorophenyl) propionamide], propham (isopropyl-N - [(R) -butyl] -benzamide), pyrazone [5-amino] -4'-chloro-2-phenylpyrrolidin-3 (2H) -one], simazine (2-chloro (cr-4,6-lisethylamine), 3,5-triazine). .

TCA (trichloroacetic acid), thiobencarb [S- (4-chlorobenzyl) -N, N-diethylthiolcarbamate], triallate [Sf 2,3], - [(4] chlorallyl-N, NfdllsOf propyl (thiocarbamate)] .] and trifluoroaline - (2,6-ЬпШго-Н ^^ 1ргору -. 4-trifluoromethylaniline), .... ...

insecticides such as carbaryl (1-naphthyl N-methylcarbamate), synthetic pyrehtroids, such as permethrin and cypermethrin, and fungicides, such as

2,6-Methyl-N- (1-butylcarbainoyl-benzimidazol-2-yl) -carbamate, 1,2-bis (3-methyl-bicyclo-2-fluoro) -o) benzene, isopropyl -carbamoyl-3- (N-dichlorophenyl) hydantoin and 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butane-2-C) n.

Other biologically active substances which may be present in the herbicidal compositions of the present invention or which may be used in combination with such compositions are plant growth regulators, for example succinamic acid, (2-chloroethyltrimethylammonium chloride and 2-chloro (crethanephosphonic acid), or industrial fertilizers, such as nitrogen, potassium and phosphorus containing fertilizers, and trace elements known to be necessary for the successful development of plants, such as iron, magnesium, zinc, manganese, cobalt and copper.

The herbicidal compositions according to the invention which comprise - compounds of formula IV, in particular compounds Nos. 1, 2 and 4 in combination (preferably homogeneously - dispersed) with isoproturon and chlortoluron, and optionally - one or more compatible carriers, diluents, surfactants agents and conventional excipients useful in the preparation of pesticidal compositions, in particular N-phenylpyrazole derivative (s), isoproturon or chlortoluron in a weight ratio of 1: 2.5 to 1:20, are particularly suitable for post-emergence application to inhibit the growth of Galium aparine, Veronica persica, Viola arvensis, Matricaria inodora, Stellaria media, Galeopsis tetrahit. Avena fatua and Alopecurus myosuroides, especially in the emerging winter wheat and barley culture.

The pesticidal active substances and other biologically active materials which can be added to the herbicidal compositions according to the invention or used in combination with the herbicidal compositions according to the invention, such as the aforementioned substances, can optionally be used in the form of an acidic character. conventional derivatives such as alkali metal salts, amine salts and esters.

The invention also includes products based on at least one of the N-phenylpyrazole derivatives of the general formula IV, or preferably the herbicidal composition described above, in particular the herbicidal concentrate which is

5-Amino-4-yyan-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole

Ethylan KEO (a condensation product of nonylphenol and ethylene oxide containing 9 to 10 moles of ethylene oxide per mole of phenol) dimethylformamide must be diluted prior to use containing at least one N-phenylpyrazole derivative of the general formula IV or the aforementioned herbicidal composition. or a herbicidal composition containing them, for use in controlling weed growth. The aforementioned containers may be containers normally used for storing - ambient temperature chemicals and herbicides, in particular in the form of concentrates, for example cans and metal drums, which may optionally be internally coated, and plastic containers, glass bottles and plastic bottles and, if the contents are solid, such as granular herbicidal compositions, boxes, for example cardboard boxes, plastic boxes and metal boxes or bags. These packages should normally be large enough to accommodate an amount of N-phenylpyrazole derivative or herbicidal composition sufficient to treat at least about 40 ares of land in terms of weed control, but should not exceed a size suitable for normal handling .

The instructions provided with these packages may be printed directly on the packages, or the packages may be labeled or labeled with the instructions. Said guides usually state that the content of the package, if necessary after dilution, is applied to control weed growth at application rates of between 0.01 kg and 10 kg of active ingredient per hectare, in the manner and for the purposes described above.

The herbicidal compositions of the present invention have the following examples.

Example 1

5-Amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole is made into a water-soluble concentrate of the following composition:

(w / v) up to 100 -% vol

The above formulation is prepared by dissolving Ethylan KEO in a portion of dimethylformamide, adding the active ingredient and heating with stirring until the solids are dissolved. The resulting solution was adjusted to a volume of 100% by adding the remaining portion of dimethylformamide.

liters of the aforementioned composition can be dissolved in 200 liters of water and sprayed postemergently per hectare of emerging spring wheat cultures to eradicate Amaranthus retroflexus, Setaria viridis, Polygonum lapathifolium, Abutilon theophrasti, and Solanum nigrum.

In the above water-soluble concentrate, 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole can optionally be substituted with any other compound of formula IV.

5-Amino-4-cyano-1- (2,6-difluoro-4-trifluoromethylphenyl) pyrazole

Ethylan BCP (condensation product of nonylphenol and ethylene oxide containing 9 moles of ethylene oxide per mole of phenol)

Aerosil (silica with fine particles)

Celite PF (carrier based on sintetic magnesium silicate)

The above formulation is prepared by adsorbing Ethylan BCP onto Aerosil, mixing with the other ingredients, and grinding in a hammer mill to form a wettable powder which can be diluted with water and applied at a dosage of 1.0 kg wettable. powder in 300 liters of spray liquid. per hectare postemergence to the emerging winter wheat culture to suppress the growth of Galium aparine, Veronica persica, Viola arvensis, Galeopsis tetrahit and Stellaria media.

5-Amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenylpyrazole)

Ethylan BCP Sopropon T 36 (sodium polycarboxylic acid) ethylene glycol

Rhodigel 23 (thickener · resin-based · poly sac harid-xa nthate) distilled water

The above formulation was prepared by thoroughly mixing and grinding the individual components in a ball mill for 24 hours. The concentrate thus obtained can be dispersed in water and postemergently applied to the resulting winter barley culture (at an application rate of 1.0 kg of aqueous suspension concentrate in 300 liters of spray liquid per hectare) to control Galium aparine, Veronica persica, Viola arvensis, Stellaria media and Galeopsis tetrahit.

5-amino-4-cyano-1- (2-chloro-4-trifluoromethylphenyl) pyrazole

Ethylan TU, (the condensation product of nonylphenol and ethylene oxide containing 10 moles of ethyleneoaid per mol · phenol)

Bentone 38 (organic derivative of a special magnesium-montmorillonite thickener)

Aromasol H (aromatic solvent consisting mainly of isomeric trimethylbenzenes)

The above formulation is prepared by thoroughly mixing the ingredients for 24 hours. · And ground in a ball mill. The emulsifiable suspension concentrate thus obtained can be diluted with water and in a dose of 2.0 kg of emulsifiable suspension concentrate in

T00 liters of spray liquid per hectare

Example 2

A wettable powder is prepared from the following ingredients:

% (w / w)% (w / w]% (w / w]% (w / w)

Similar wettable powders can be prepared in an analogous manner to that described above; by • 5-amincPkyarnl- [2,6-cdíchlor-- ^of L · -trifluormeithylfenyllpyrazol with other compounds of formula IV.

Example 3

An aqueous suspension concentrate is prepared from the following ingredients:

% (weight / volume)

1.09 (w / v)

0.2% (w / v)% (w / v)

0.15% (w / v) to 100% v / v

Similar aqueous suspension concentrates may be prepared as described above in which the 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole is replaced by other compounds of formula IV.

Example 4

An emulsifiable suspension concentrate is prepared from the following components:

% (w / v)% · (w / v)

0.5% (w / v) to 100% by volume postemergence applied to the emerging spring wheat culture to suppress the growth of Setaria viridis, Polygons sonvolvulus and Chenopodium album.

Similar emulsifiable suspension concentrates may be prepared as described above

Example 5 by substituting 5-amino-4-cyano-1- (2-chloro-4-trifluoromethylphenyl) pyrazole for some other compound of formula IV.

5-Amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole

Ethylan BCP oleic acid Aromasol H granular attapulgite (30/60) (sorption silica clay)

The above formulation was prepared by mixing phenylpyrazole with Ethylan BCP, oleic acid and Aromasol H and spraying the granular attapulgite. The granulate thus obtained can be applied at an application rate of 20 kg of granulate per hectare to suppress the growth of Echinochloa crus-galli, Eleocharis acicularis and Monochoria vaginalis. The application is carried out either pre-emergence or on weed-seedlings in the transplanted rice culture under irrigation conditions.

5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole

Ethylan KEO dimethylformamide

Ethylan KEO is dissolved in a portion of dimethylformamide and, after addition of the pyrazole derivative, the mixture is heated with stirring until all solids are dissolved. The volume of the solution obtained is then adjusted to 100% by adding the remainder of dimethylformamide; vol. The water-soluble concentrate thus formed can be diluted with water and applied at a rate of 10 liters of water-soluble concentrate in 200 to 2000 liters of spraying agent.

5-Amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole

Arylan S (sodium dodecylbenzenesulfonate) Darvan No. 2 (sodium lignosulfate) Celite PF

The above composition is prepared by mixing the individual components and grinding the mixture in a hammer mill. The wettable powder obtained can be diluted with water and applied postemergently at a rate of 1.0 kg of wettable powder in 300 liters of spray liquid per hectare to suppress the growth of Galium aparine, Veronica persica, Viola arvensis and Galeopsis tetrahit in the resulting winter wheat culture.

Similar wettable powders may be prepared as described above, substituting 5-amino-4-cyano-1- (2,3,4-trichlorophenyl) pyrazole with a compound of formula IV.

Example 8

A wettable powder containing 50% (w / w) of 5-amino-4-cyano-1- (2,6-diZ of the following ingredients) is prepared as a granulate:

% (w / w)% (w / w)% (w / w)% (w / w)% (w / w)

A similar granulate can be prepared as described above, substituting a compound of formula IV for 5-amino-4-cyano-1- (2,6'-dichloro-4-trifluoromethylphenyl) pyrazole.

Example 6

A water-soluble concentrate is prepared from the following ingredients:

% (w / v)% (w / v) to 100% v / v liquid per hectare to control Galium aparine, Veronica perslica, Viola arvensis and Galeopsis tetrahit. The application is carried out postemergence on the resulting crop of winter wheat in the harvesting stage.

Example 7

A wettable powder is prepared from the following ingredients:

% (w / w)% (w / w)% (w / w)% (w / w) chloro-4-trifluoromethylphenyl] pyrazole, prepared as described in Example 2 above, can be diluted with water and applied at an application rate of 0.1 kg of wettable powder in 300 liters of spray liquid per hectare to suppress the growth of Abutilon theophrasti and Polygons convolvulus.

The application is carried out postemergence in a spring wheat culture at a time when the weed plants of the above weeds are still very young.

Example 9

A wettable powder containing 50% (w / w) of 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole, prepared as described in Example 2, can be diluted with water and applied in an application a dose of 20 kg of wettable powder in 600 liters of spray liquid per hectare to achieve a total herbicidal effect on vegetation growing in a place where crops are not grown.

5-Amino-4-cyano-1- (2,3,5,6-tetrafluoro-4-trifluoromethylphenyl) pyrazole

Soprophor BSU (condensation product of tristyrylphenol and ethylene oxide, containing 18 moles of ethylene oxide)

Arylan CA (70% calcium dodecylbenzenesulfonate solution) isophorone

Aromasol H

The above formulation is prepared by dissolving Soprophor BSU and Arylan CA in a portion of isophorone, adding a phenylpyrazole derivative with heating, and stirring until all solids are dissolved, then adding the remaining isophorone and adding a volume of the resulting solution by adding Aromasol H adjusted to 100% vol. The emulsifiable concentrate thus obtained can be diluted with water and applied at a rate of 2.5 liters of emulsifiable concentrate in 500 liters of spray liquid per hectare to suppress the growth of Galium aparine, Stellaria media, Veronica persica, Veronica hederifolia and Viola arnsisis. The application is carried out post-emergence in the resulting winter wheat culture.

Example 11

1.25 liters of an aqueous suspension concentrate containing 50% (w / v) of 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole, prepared as described in Example 3, and 15 liters of a commercial 50% (w / v) aqueous suspension concentrate containing isoproturon is mixed with water in a spray tank and applied, at an application rate of 0.125 kg of N-phenylpyrazole derivative and 1.5 kg of isoproturon in 200 liters of spray liquid per hectare. winter wheat to suppress the growth of Alopecurus myosuroides, Stellaria media, Matricaria inodora, Galium aparine, Veronica persica and Viola arvensis. Thus, the application is carried out post-emergence.

Derivatives of N-phenylpyrazole derivative of general formula IV wherein R ^12, R ^13, R ^{| Z} 'and ^R15 are as hereinbefore defined, may be prepared by cyclising a compound of formula V

R ¹² R ¹³

Example 10

An emulsifiable concentrate is prepared from the following ingredients:

% (weight / volume)

3.75% (w / v)

3.75% (w / v)% i (w / v) to 100% v / v in which each of the general symbols has the above meaning.

The cyclization may be carried out in the presence of an inert organic solvent such as a C 1 -C 4 alkanol (e.g. ethanol), acetic acid or ethoxyethanol at a temperature ranging from room temperature to the reflux temperature of the reaction mixture.

Compounds of formula (V) above may be prepared by reacting a compound of formula (VI)

(VI) wherein - the individual general symbols are as defined above, or acid addition salts thereof (e.g., hydrochloride), with a compound of formula VII

NC / ° « ⁶

NCT (VII) wherein

R ¹⁶ represents a straight or branched (C 1 -C 4) alkyl group, preferably an ethyl group.

The reaction of a compound of formula VI with a compound of formula VII can be carried out in the presence of an inert organic solvent such as a C 1 -C 4 alkanol (e.g. ethanol), acetic acid or ethoxyethanol at a temperature ranging from room temperature to boiling point. a reflux condenser, and optionally in the presence of (V) an alkali metal (e.g. sodium or potassium) acetate, carbonate or bicarbonate. An acid addition salt of a compound of formula (VI) is used, and is reacted with a compound of formula (VII) in the presence of an alkali metal (e.g., sodium or potassium) acetate, carbonate or bicarbonate.

Alternatively, derivatives of N-phenylpyrazole derivative of general formula IV wherein R ^12, R ^13, R ^{1 '1} and R ¹⁵ are as defined above, by reacting the compound vzorct VI with a compound of formula VII as hereinbefore described without isolation intermediate compounds of formula V from the reaction mixture. When the reaction of a compound of formula VI with a compound of formula VII is carried out in acetic acid, optionally in the presence of an alkali metal acetate (e.g. sodium or potassium), depending on the solubility of the intermediate compound of formula V in the reaction medium It may be precipitated and optionally isolated prior to its cyclization to the compound of formula IV, which is carried out as described above, preferably by heating in an inert organic solvent, for example in ethoxyethanol, to reflux the reaction mixture.

The isolated compounds of formula (V) exhibit similar herbicidal activity to the corresponding cyclic N-phenylpyrazole derivatives of formula (IV) and are believed to exhibit this herbicidal activity of compounds of formula (V) as a result of their cyclization to compounds of formula (IV).

Compounds of formulas VI and VII can be prepared by methods known per se. The term "methods known per se" as used herein refers to the methods hitherto used or described in the chemical literature.

The following Examples and Reference Examples illustrate the preparation of compounds of Formula IV.

Example 12

To a solution of 0.6 g of sodium acetate in 15 ml of glacial acetic acid, 1.84 g of ethoxymethylenemalononitrile was added under magnetic stirring at room temperature [see Huber, J. Amer. Chem. Soc., 65, 2224 (1943)] and 3.7 g of 2,6-dichloro-4-trifluoromethylphenylhydrazine. After stirring for 15 minutes, a colorless solid precipitated out of the clear brown solution, stirring was continued for a further 15 minutes, then filtered. The resulting solid was washed successively with acetic acid, water, aqueous sodium bicarbonate solution and water to give 3.4 g of 2,6-dichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile as colorless crystals, m.p. 153-154 ° C.

The 2,6-dichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile thus obtained was heated to reflux in 15 ml of ethoxyethanol for 45 minutes. The upper solution is filtered, the filtrate is cooled, diluted with 5 ml of water and filtered. 2.5 g of 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole are obtained in the form of off-white crystals, m.p. 165-167 ° C.

By analogy to the replacement of 2,6-dichloro-4-trifluoromethylphenylhydrazine with the following appropriately substituted phenylhydrazines, the following compounds are obtained:

from 2-chloro-4-trifluoromethylphenylhydrazine via 2-chloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile (brown powder, m.p. 138-143 ° C) 5-amino-1- (2-chloro-4-trifluoromethylphenyl) -4-cyanopyrazole crystallization from toluene resulted in light brown crystals, m.p. 185-187 ° C;

from 2,3,5,6-tetrafluoro-4-trifluoromethylphenylhydrazine (prepared as described by Alsop et al. in J. Chem. Soc. 1962, 1801) through 2,3,5,6-tetrafluorophenyl-4-trifluoromethylphenylhydrazinomethylenemalononitrile ( pale yellow solid, m.p. 90-93 ° C) 5-amino-4-cyano-1- (2,3,5,6-tetrafluoro-4-trifluoromethylphenyl) pyrazole resulting from crystallization from toluene as off-white crystals, m.p. melting 122 to

122.5 ° C.

Example 13

To a solution of 4.40 g of ethoxymethylenemalononitrile and 1.47 g of anhydrous sodium acetate in 34 ml of glacial acetic acid was added 10.1 g of 2,3,6-trichloro-4-trifluoromethylphenylhydrazine while stirring at room temperature in a single portion. After stirring at room temperature for 1 minute, fine precipitation precipitated. The reaction mixture was stirred at room temperature for 2 hours, then left overnight. stand at room temperature and filter. The solid precipitate was washed sequentially with a small amount of glacial acetic acid, saturated aqueous sodium bicarbonate, and water to give 9.6 g of 2,3,6-trichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile as a light brown powder, m.p. 169-170 degrees. Celsius.

The 2,3,6-trichloro-4-trifluoromethylphenylhydrazinmethylenemalononitrile thus obtained was refluxed in 50 ml of ethoxyethanol for 1 hour, the hot solution was filtered, the filtrate was cooled, diluted with 70 ml of water and the solid precipitate was filtered off. 6.36 g of 5-amino-4-cyano-1- (2,3,6-trichloro-4-trifluoromethylphenyl) pyrazole are obtained which, after crystallization from 25 ml of toluene, is obtained in the form of a dark yellow crystalline solid, m.p. 187 ° C.

Reference Example 1

The phenylhydrazines used as starting materials in Examples 12 and 13 were prepared as follows.

4.3 g of 2,6-dichloro-4-trifluoromethylphenylaniline (described in U.S. Pat. No. 3,850,955) are dissolved with stirring in 23 ml of glacial acetic acid and a solution is added at 55 to 60 ° C.

1.5 g of sodium nitrite in 11 ml of concentrated sulfuric acid. The resulting solution was cooled to 0-5 ° C and a solution of 6.4 g of stannous chloride in 14 ml of concentrated hydrochloric acid was added with vigorous stirring, whereupon a cream colored solid precipitated. The mixture was filtered and the solid product was added to a mixture of aqueous ammonium hydroxide and ice. The resulting mixture was extracted six times with 500 ml of diethyl ether each time, the combined ether extracts were dried over sodium sulfate, filtered and evaporated to dryness. 3.7 g of 2,6-dichloro-4-trifluoromethylphenylhydrazine are obtained in the form of colorless crystals of melting point 54 to 56 ° C.

By analogy to the substitution of 2,6-dichloro-4-trifluoromethylaniline with 2-chloro-4-trifluoromethylaniline (described in U.S. Pat. No. 3,850,955), 2-chloro-4-trifluoromethylphenylhydrazine is obtained as a colorless solid, m.p. Deň: 32 ° C.

In an analogous manner, 2.6

Dichloro-4-trifluoromethylaniline 2,3,6-trichloro-4-trifluoromethylaniline affords 2,3,6-trichloro-4-trifluoromethylphenylhydrazine as a white solid, m.p. 72-74 ° C.

Reference Example 2

The 2,3,6-trichloro-4-trifluoromethylaniline used as the starting material in Reference Example 1 was prepared as follows.

A mixture of 20 g of 3-chloro-4-trifluoromethylaniline (described in British Patent No. 459,890) and 12 ml of hydrochloric acid (density 1.18) is suspended in 600 ml of water and refluxed under stirring and heating. Chlorine gas (from 13 ml of liquid chlorine) was introduced through the condenser. Stirring is continued for 15 minutes after the chlorine gas has ceased. After cooling, the reaction solution is extracted three times with 250 ml of dichloromethane each time, the combined organic extracts are washed with water, saturated aqueous sodium hydrogen carbonate solution and again with water, dried over anhydrous sodium sulphate and evaporated. The red colored oily residue yielded an orange oil by distillation, b.p. 143-147 DEG C./20 mbar, which crystallized on standing.

12.26 g of 2,3,6-trichloro-4-trifluoromethylaniline are obtained in the form of an orange-colored solid, m.p. 37-39 ° C.

Claims (3)

OBJECT OF INVENTION Herbicidal composition, characterized in that it contains at least one N-phenylpyrazole derivative of the general formula IV as active ingredient R ¹³ represents a hydrogen, fluorine or chlorine atom, R ¹⁴ represents a hydrogen or fluorine atom; R ¹⁵ represents a hydrogen, fluorine or chlorine atom, provided that when R ¹⁴ represents a fluorine atom, R ¹³ represents a fluorine or chlorine atom, or R ¹² , R ¹³ and R ¹⁵ are each fluorine and R ¹⁴ represents a hydrogen or fluorine atom. 2. A composition according to claim 1, wherein the active ingredient of the formula IV is 5-amino-1- (2-chloro-4-trifluoromethylphenyl) -4-cyanopyrazole; 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole, 5-amino-4-cyano-1- (2,3,6-trichloro-4-trifluoromethylphenyl) pyrazole; or 5-amino-4-cyano-1- (2,3,5,6-tetrafluoro-4-trifluoromethylphenyl) pyrazole. in which R ¹² represents a chlorine atom,