CS195736B2 - Herbicide and process for preparing effective compound thereof - Google Patents

Abstract

1519906 Herbicidal compositions E I DU PONT DE NEMOURS & CO 14 Oct 1976 [15 Oct 1975 12 Dec 1975 26 Aug 1976] 42776/76 Heading A5E [Also in Division C2] Herbicidal compositions comprise novel compounds of formula wherein n=3, 4 or 5; R 1 is H or CH 3 ; Q is F, Cl, Br or I; X is F, Cl, Br, I, CN, OCH 3 or NO 2 ; Y is H, F or Cl; Z is H or F and V is H, F, Cl or OCH 3 , with the provisos (a) that when n=5, R 1 =H, Q=Cl or Br, Z=V=H and Y=H or F; (b) when n=3 or 4 and Q=F or I, R 1 =Z=V=H and Y= H or F; (c) when n=3 and R 1 =CH 3 , Q=Cl or Br, Y=H or F and Z=V=H and (d) when V#H, X=F, Cl or Br and Z=H, together with one or more known herbicides as listed (see Example 22) and at least one of (a) a surface active agent and (b) a solid or liquid diluent.

Description

The invention relates to a herbicidal composition and to a process for the manufacture of an active ingredient thereof.

DE-A-2 165 651 describes a group of herbicidally active isoindl-1,3-diones of the general formula:

in a cleric

R is aryl, aralkyl or benzyl. an alkyl group optionally substituted by 1 to 5 halogen atoms or a hydroxyl group, a nitro group, a cyano group, a thiocyanate group, a carboxyl group, an alkyl or halogenated alkyl group, an alkoxy group, lower. alkylthio or phenyl. The substituent R may also be optionally. substituted with a group of the formula -O-CH 2, wherein

A denotes a phenyl or naphthyl group. The phenyl group may be further 'substituted by one or more halogen atoms, nitro, lower alkyl or lower. alkoxy groups.

A typical representative of the compounds described above. patent. file is a compound of formula 1:

O

II

However, the compounds described in the above. In the patent specification, the effects of dy still exist. even betterEpjW- means. Different types. weeds are very harmful to important Kituřhi. plants, such as rice and wheat, and reduce crop yields. V. The current world situation, * Wý * is an acute food shortage, is of utmost importance. harvest the maximum yield possible. culture plants such as rice and wheat. Thus, there remains a need for a particularly effective herbicide to control various weed species, preferably without significantly damaging the treated crop plants, such as rice or wheat.

We have now discovered compounds that are highly potent herbicides, causing minimal damage to some desired crop plants, such as rice and wheat, and especially rice, the most widespread crop plant in the world.

Preparation and fungicidal effect of 2- (4-chlorophenyl) -1,2,4,5,6,7-hexahydroindazol-3 (3H) -one of formula

O

II

is described in Takeda Chem. Indian. Tapper [see Chem. Abstr. 67, 11542h (1967)].

2-Aryll4,5,6,7-tetrahydro-1-alkyl-1H-indazol-3 (2H) -ones of formula

as antlpyretics, they are the subject of DE Patent No. 668,628 [P. Beierdorf & CO. AG,. see Chem. Abstr. 33, 51312 (1939)] and US Patent 2,104,348 [ER Squibb Co., see Chem. Abstr. 32, 1869 ¹ (1933)].

DE 2 409 753 describes herbicides of the general formula

R — CON \

R ⁸

R 6 represents a hydrogen atom, an alkyl group which may be optionally substituted,. alkoxy,. phenoxy or phenyl,

R- and R8, which. they may be the same or different, each representing a hydrogen atom, an alkyl group, a phenyl group which may be optionally substituted, or an alkenyl group. group

R2 denotes an alkyl group which:. it may be optionally substituted, a cycloalkyl group or a phenyl group which may be optionally substituted, or a heterocyclic radical having an oxygen, nitrogen or sulfur atom in the ring,

R3 represents a hydrogen, chlorine or bromine atom or a low molecular weight alkyl group,

R4 represents a group of formula --S - R 5, -SO-R ⁵ or -SO 2 R ^5, and

R ⁵ denotes an alkyl group, a cycloalkyl group, an aralkyl group, a phenyl group which may. be optionally substituted, or a heterocyclic radical having an oxygen, nitrogen or sulfur atom in the ring.

The herbicides are prepared by reacting the mercaptans of the formula R5SH with an intermediate of the formula

in which

R 1, R ² , R 3 and R 5 are as defined above and

Hal represents a chlorine, bromine or iodine atom.

1-Phenyl-3,4-trimethylthiopyrazolone of the formula wherein:

R1 is hydrogen, alkyl, cycloalkyl. or an aralkyl group, a phenyl group which may be optionally substituted, or an acyl group of the general formula

O

or —COR ⁶ is disclosed in U.S. Patent No. 1,685,407 (1928) as an intermediate for the manufacture of dyes and medicaments; the preparation of 1-phenyl-3,4-trimethylenepyrazolones by C. Mannich in · Arch. Pharm. 267, 699 (1929) and Brit. No. 260,577.

R. P. Williams et al. . collaborators. ' · Describe in J. Med. Chem. 13, 773 (1970) for the preparation and anti-inflammatory activity of the compounds of formula

in which

X represents a hydrogen, chlorine or fluorine atom.

The present invention relates to novel games of a pesticidal composition for controlling unwanted vegetation and to a process for the preparation of an active compound of the formula I

wherein n is 3, 4 or 5,

R1 is hydrogen or methyl,

Q atom of fluorine, chlorine, bromine or iodine,

X is fluorine, chlorine, bromine or iodine, alkynyl, methoxy or nitro,

Y is hydrogen, fluorine or chlorine,

Z is hydrogen or fluorine; and

In a hydrogen, fluorine or chlorine atom, or a methoxy group, with the proviso that. (A) when n is 5, R1 must be hydrogen, Q must be chlorine or bromine, Z and V must be hydrogen, and Y must be hydrogen or fluorine,. (b) when n is 3 or 4 and Q is fluorine or iodine, R1, Z and V must be hydrogen and Y must be hydrogen or fluorine, (c) when n is 3 and R1 is methyl, Q is a chlorine or bromine atom, Y must be a hydrogen or fluorine atom, and Z and V must be a hydrogen atom, and (d) when V is other than hydrogen, X must be a fluorine, chlorine or bromine atom. and Z must be hydrogen.

The herbicidal compositions of the present invention can be used as both selective and universal herbicides with both pre-emergence and post-agent activity.

For a high herbicidal activity or at a favorable price, or both, preference is given to those compounds of the formula I in which, independently of one another,

1) or 3 or 4,

2) Q atom of chlorine or bromine,

3) R 1 is hydrogen · or · methyl,

4) Z and V · each hydrogen atom,

5) Y is hydrogen or fluorine, or

6) X is fluorine, chlorine or bromine, cyano or methoxy.

Among the compounds of formula I in which n is 4, those in which Q is chlorine or bromine are preferred.

Even more preferred are those compounds of formula I wherein n is 4, Q is chlorine or bromine and R 1 is hydrogen.

Of the following compounds of formula I wherein n is 4, Q is chlorine or bromine, and R 1 is hydrogen, those in which, independently of one another, are preferred,

1) Z and V are each hydrogen, x

2) X is fluorine, chlorine or bro-

3) X represents a fluorine, chlorine or bromine atom, a cyano group or a methoxy group.

Even more preferred are those compounds of formula (I) wherein n is 4, Q is chlorine or bromine, R 1 is a hydrogen atom, and Z and V are each hydrogen.

Among the compounds of formula I in which n is 4, Q is chlorine or bromine, R1 is hydrogen and Z and V are each hydrogen, because of their higher herbicidal activity or lower cost, or for both of these reasons, preferred are those compounds in which, independently of each other,

1] Y represents a hydrogen or fluorine atom, or

2) X represents a fluorine, chlorine or bromine atom, or a cyano or methoxy group.

More preferred are those compounds of formula I wherein n is 4, Q is chlorine or bromine, R1 is hydrogen, Z and V are each hydrogen, Y is hydrogen or fluorine and X is fluorine, chlorine or bromo, cyano or methoxy.

For their excellent herbicidal activity or at a very favorable price, or both, the most preferred are those compounds of formula I wherein n is 4, Q is chlorine or bromine, R 1 is hydrogen, Z and V are each individually a hydrogen atom, Y represents a hydrogen or fluorine atom and X represents a chlorine or bromine atom.

Among the compounds of formula I in which n is 3, those in which Q is a chlorine atom or a bromine atom are preferred.

More preferred are those compounds of formula I wherein n is 3, Q is chlorine or bromine, and R 1 is hydrogen.

Of the following compounds of formula I wherein n is 3, Q is chlorine or bromine and R1 is hydrogen, those compounds in which independently of one another are preferred,

1] Z and V each represent a hydrogen atom,

2] Y represents a hydrogen atom or a fluorine atom, or

3] X represents an atom, fluorine, chlorine, bromine, cyano or methoxy.

Even more preferred are those compounds of formula (I) wherein n is 3, Q is chlorine or bromine, R1 is hydrogen and Z and V are each hydrogen.

Of the compounds of formula I, in which n is 3, Q is chlorine or bromine, R1 is hydrogen, and Z and V are each hydrogen, they are, for their higher herbicidal activity, or Lower cost, or for both of these reasons, preferred compounds in which, independently of each other,

1) Y represents a hydrogen or fluorine atom; or

2) X represents a fluorine, chlorine or bromine atom, a cyano group or a methoxy group.

More preferred are those compounds of formula I wherein n is 3, Q is chlorine or bromine, R1 is hydrogen, Z and V are each hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine or bromine, or cyano or methoxy.

Because of their excellent herbicidal activity, or for a highly advantageous price, or both, the most preferred compounds of formula I are those in which n is 3 Q is chlorine or bromine, R1 is hydrogen, Z and V are each of which is hydrogen, Y is hydrogen or fluorine and X is chlorine or bromine.

Because of the high herbicidal activity or the favorable price, or both, the compounds of formula I are preferred in which Y is hydrogen or fluorine and Z and V are each hydrogen.

Even more preferred are those compounds of formula (I) wherein Y is hydrogen. or fluorine, Z and V each represent an atom of hydrogen, and in which, independently of one another,

1) Q represents a chlorine atom, or

2] X represents a chlorine or bromine atom.

For their higher herbicidal activity, or for a lower cost, or both, those compounds of formula I in which Y is hydrogen or fluorine are preferred, Z and V are each hydrogen. and Q represents a chlorine atom.

For their excellent herbicidal activity or at a very favorable price, or for both of these reasons, the most preferred compounds are those in which Y is hydrogen or fluorine, and Z and V are each individually. a hydrogen atom, Q represents a chlorine atom and X represents a chlorine atom or bromine atom.

Because of their extraordinary herbicidal activity or the favorable price, or for both of these reasons, the following specific compounds are particularly preferred: (melting point always means):

1) 1 ', 6' 6-chloro-2- [4-chloro-2-fluorophenyl] -4,67-tetrahydro-2H-indazole, mp 88-89.5 ' ^and C;

2) c- (10 -102-2- [4-chlorophenyl) -4,5,6,7-tetrahydro-1H-indazole, mp 81-84 ° C;

3-bromo-2- ^[4-C! chloro-2-fluorophenyl) -4,5A74-tetrahydro-2H-indazole, mp 95-98 ° C;

'4)

3-chloro-2- [4-quinolin-2-fluorophenyl] -4,5,6,7-ettrahydro-2H-indazole,

86-88 ° C;

c-chloro-2- [4-chloro-2-fluorophenyl] - N, N -tetrahydrotylpentaprazole,

mp 101.5. to 104 ° C; and

6)

C-chloro-2- [4-chlorophenyl] -2,4,5,6-tetrahydrocyclopentapyrazole,

mp 114.5-117 ° C.

The novel cycloalkanoylpyrazoles ^{: of the} general formula I, wherein X represents Q - chlorine or bromine, can be produced by the two-step method shown in the following by the following equations of rotation A and B:

in which

R1, η, X, Y, V and Z are as defined above,

Q is bromine, chlorine ntbo ^1,

R 'represents an alkyl group having 1 to 3 carbon atoms, f is zero or 1, and

And, the anion of the respective HA system, which has an ionization constant of at least 1X10--, for example, sulfur trusses or hydrochloric trusses.

The preparation of the pyrazolones of the general formula 3 is known from the literature; for example, 1-aryl-1,2,4,5,6,7 ' -hexahydro-3H-indazol-3-one synthesized (represented by formula 3, in which n = 4) is described by W. Dieckmann in Ann. 317, 102 [1901]. The α-keto ester of Formula 2 is mixed with a salt of the corresponding arylhydrazine of Formula 1 in a suitable solvent such as - for example - a lower alcohol - or an aromatic hydrocarbon, optionally in the presence of a cystine acceptor such as a tertiary - organic amine. alkali metal hydroxide or alkoxide, and the reaction mixture is heated under reflux for 0.5 to 24 hours. The resulting pyrazolone of formula (3) is isolated by conventional means, such as by pouring - the reaction mixture - into water and filtering off the product. The crude product is usually sufficiently pure so that it can be used directly in the subsequent reaction stage. If it is friction, the crude product can be purified by recrystallization, cross-sublimation - or other conventional working techniques well known to those skilled in the art; In the same manner, those compounds of the formula 3 can be prepared in which n is 5.

The pyrazolones of the formula 3, in which п jt 3, can be prepared by:

the corresponding arylhydrazine is mixed with the alkyl-2-oxocyclopentyl carboxylate in a suitable solvent, such as in tolute or chlorobenzene, and the reaction mixture is heated to boiling while water is distilled off. The obtained hydrazone is then cyclized to the pyrazole of formula 3 in which n is 3 by adding to the hydrazone solution

The methods described in A-rch can also be used to prepare the pyrazolones of formula 3 wherein n is 3. Pharm. 267, 699-702 (1929) and J. Med. Chem. 13, 773 (1970).

Alternatively, the hydrazone can be desalted and then cyclized by treatment with two equivalents of n-butyllithium in a suitable solvent such as tetrahydrofuran at a temperature in the range of 0 to 60 ° C for 2 to 18 hours.

The pyrazalones of formula 3 wherein n is 3 are isolated by pouring the reaction mixture into water, separating the organic layer and acidifying the aqueous portion with a mineral acid such as hydrochloric acid or sulfuric acid. The desired product is obtained from the acidified aqueous fraction by filtration, centrifugation, extraction or other similar processes.

According to the invention, the novel cycloalkanopyrazoles of the formula I in which Q represents a chlorine atom are obtained by heating the annealed pyrazolones. of formula '3 with phosphorus oxychloride' (formula 4, Q stands for chlorine). To prepare compounds of formula I wherein Q is; or a bromine atom, it is used to react phosphorus oxybromide (formula 4, Q denotes a bromine atom), in the presence of N, N-dialkylaniline and dimethylformamide (reaction equation B). 1 to 3 equivalents of an alkali metal alkoxide, such as sodium methoxide, and the mixture is heated at 80 to 130 degrees Celsius for 1 to 5 hours;

The reaction may optionally be carried out in an inert solvent such as methylene chloride or toluene; however, preferably no solvent other than phosphorus oxychloride or phosphorus oxybromide is used. The reaction mixture is heated to 100 to 180 ° C, preferably 140 to 150 ° C, for 1 to 10 hours. The crude reaction mixture is dissolved in an inert organic solvent, for example chloroform, methylene chloride or toluene, and the solution is washed with a dilute aqueous base solution, for example sodium or potassium hydroxide, and then with water. The organic portion is dried, the solvent is removed by rotary evaporation or distilled off, and the crude pyrazole of formula (I ') obtained is purified by distillation, sublimation or crystallization from an aqueous solvent.

Compounds of formula I wherein Q is iodine are prepared from the corresponding aminopyrazoles by diazotizing with nitrous acid and reacting the resulting diazonium salt with potassium iodide as described in Spanish Patent No. 394,208 [Chem. Abstr. 83, 972834 (1975)]. . The desired aminopyrazoles are obtained by reacting the appropriate α-cyancyclohexanone or α-cyancyclopentanone with the appropriate arylhydrazine in a suitable solvent such as toluene. the total reaction sequence of the preparation of compounds of formula I in which Q is iodine is represented by the following reaction equations' Az and B.2:

195738

The necessary α-cyanoketones can be produced by a number of methods well known to those skilled in the art. For example, α-cyancyclohexane can be obtained from α-chlorocyclohexanone and sodium cyanide by the method of R. Meyer, Helv. Chim. Acta 16, 1291 (1933). α-Cyancyclopentanone can be prepared from adiponitrile by treatment with a strong base such as lithium dialkylamide and acid hydrolysis of the resulting intermediate, according to the process of DE 591 269, published January 1934 [Chem. Abstr. 28, 117 (1934)]. α-Cyancycloaliphatic ketones can also be obtained from the enamines of the respective cycloalkanones by treatment with cyanogen chloride, according to the method of Μ. E. Kuehne, J. Am. Chem. Soc. 81, 5400 (1959).

The cycloalkanopyrazoles of formula I, in which Q is a fluorine atom, can be prepared, as shown in reaction equations Аз and Вз, by photolysis of the corresponding 3-diazonium fluoroborates (Equation Вз), obtained by diazotation of 3-aminoprazrazoles with nitrous acid in fluoroboric acid medium Аз), by the method described by ED Bergmann, J. Am. Chem. Soc. 78, 6037 (1956).

Equations Аз а Вз:

uv ----- _¥ sKF

The starting β-ketoesters of formula (I) are either commercially available compounds or can be prepared by methods which are extensively described in the literature (see G. Stork et al. J.

Am. Chem. Soc. 85, 207 (1963)]. The general process of their preparation is illustrated in the following equations C, D and E:

(6) (7)

Italy (9)

Ehamines of formula 7 are prepared by heating the ketones of formula 5 with morpholine of formula 6 (pyrrolidoin may also be used) in a suitable solvent, such as benzene, toluene or chlorobenzene, while removing the water formed by azeotropic distillation (equation С). To the obtained enamine (7), ethyl chloroformate (8) is added and the mixture is heated to a temperature of 70 ° C until the solvent is boiled for 1 to 10 hours. The reaction of the resulting enamine hydrochloride of formula (8) and the mixture is heated to the temperature of formula (9) contained in the filtrate is converted to the β-ketoester of formula (2) by hydrolysis with aqueous mineral acid (e.g. hydrochloric acid). 75 ° C (E equation). The product obtained is isolated by conventional methods such as extraction into a suitable organic solvent followed by evaporation of the solvent. The crude product can be further purified, for example, by distillation under reduced pressure, sublimation or crystallization.

When 3-methylcyclohexanone 5a is used as the starting material, a mixture of methyl substituted β-ketoesters (2a and 2b) is obtained as described above. When this methylsubstituted / S-ketoester mixture is reacted with an arylhydrazine, a mixture of 4- and 6-methylsubstituted 2-aryl-1,2,4,5,6,7-hexahydro-3H-indazol-3-ones is formed ( За a 3 (b); NA- ^r pursuing action of phosphorus oxyhalide of the formula 4 yields a mixture of 4-methyl- and 6-methyl-3-halo-2-aryl-tetrahydroindazoles of formula I. When a mixture of isomeric methyl cyclohexanone л partitioned, then the reaction with the aryl hydrazine gives isomer 2a the substance За, and the isomer 2b the substance 3b.

In the case of 2- or 4-methylcyclohexanone, said β-ketoester synthesis is more specific and predominantly a single isomer is formed as shown schematically in reaction equations F and G.

2-Methylcyclliolhexanone provides 7-methyl-3-halo-24aryl-4,5,6,7-tetrahydroindazole, and 4-methylcyclohexanone provides 5-methyl-3-halo-4,5,6,7-tetrahydromdazole.

Equation F:

evhCcc G:

5 7 3 7

The necessary alkyl-2-oxocyclopentanecarboxylates can be prepared by the methods described above, or by the methods described in Organic Chemistry Monorgaph 15, 1-203 (1967).

The preparation of arylhydrazines of formula (1) from the corresponding anilines is well described in the literature, see, for example, GH Coleman, Organic Synthesis collective volume I, page 442 (published by J. Wiley & Sons, New York) and H. Kindler et al. 419 092. The general procedure for their preparation is illustrated by Equation H.

Equation H:

Y Y 1) NaNO 2 / HA 2 HA T iT x ^ y 'Z 2) NA ^ O _b x' I II TZ in 3) HA in Italy (11) (1)

Aniline of formula 11 is diazotized at about -5 ° C to 4-5 ° C with sodium nitrite in an aqueous acid medium (acid of formula HA in which A is as defined above), such as in an aqueous hydrochloric acid medium obtained a solution of the diazonium salt is mixed at 0 to 20 ° C with an aqueous solution of sodium bisulfite, heated at 50 to 80 ° C for 0.5 to 2 hours, and then acidified with a mineral acid. An arylhydrazine salt with an acid of formula 1 is obtained, which often crystallizes directly from the reaction mixture and can be isolated by filtration or other conventional methods. The hydrazine obtained can in most cases be used for the next reaction without further purification.

Certain hydrazines used to prepare compounds of Formula I are novel. For example, 4-chloro-2-fluorophenylhydrazine hydrochloride is a novel compound which can be prepared as described above. The following new hydrazines can also be produced as follows:

hydrochloride

4-bromo-2-fluorophenylhydrazine hydrochloride 2-fluoro-4-methylphenylhydrazine hydrochloride

2,4,6-Trifluorophenylhydrazine 2-fluoro-4-nitrophenylhydrazine hydrochloride 4-Cyano-2-fluorophenylhydrazine hydrochloride

The method described by M. S. Gibson et al., J. Chem. Soc. (C) 1970, 2106, and M. SrGibson et al., J. Chem. Soc. (C), 1974, 215.

Typical substituted anilynes used as starting materials for the preparation of the above hydrazines can be prepared by the methods described below. For example, 4-chloro-2-fluoroaniline can be prepared from 2‘-fluoroacetanilide (see G. Schiemann and H. G. Baumaarten, Chem. Berichte 70, 1416 (1937)) by the following sequence of reactions:

Grade A

Step A-O

НН-С-СН * о II

сн.соон —э -4

CL

Grade В;

О

II

p atha-nol ·

HCt

VOÓ8.

5'736

Stupán C

N »OH

Stage A:

Chlorination of acetanilides in acetic acid is well known to those skilled in the art and can be carried out under the conditions described by W. W. W. Reed and K. J. P. Orion, J. Chem. Soc. 91, 1543 (1907) for chlorination of acetanilides. The chlorination of 2'-fluoroacetanilide is carried out at a temperature of 25-30 ° C for several hours (e.g. 5 hours) and at atmospheric pressure. 2‘-Fluoroacetanilide is obtained.

Stage B:

The chlorofluoroacetanilide is heated in a mixture of a lower alcohol (50%) (e.g. ethanol) and concentrated hydrochloric acid (50%) for several hours (e.g. 5 hours or more) to 70-90 ° C at atmospheric pressure. The solvent mixture was distilled off under reduced pressure at 20-50 ° C to give 4-chloro-2-fluoroaniline hydrochloride as a residue.

Stage C:

The aqueous 4-chloro-2-fluoroaniline hydrochloride solution is basified at room temperature with an aqueous alkali metal hydroxide solution, such as 50% aqueous sodium hydroxide, and the liberated 4-chloro-2-fluoroaniline is extracted into a suitable water-immiscible organic solvent. for example, into ethyl ether or methylene chloride. Evaporation of the solvent under reduced pressure at 20-50 ° C gave crude 4-chloro-2-fluoroaniline.

2-Fluoro-4-bromoaniline can be prepared by bromination of 2-fluoroaniline [described in Chem. Ber. 70, 1416 (1937)] with N-bromosuccinimide as shown in the following reaction equation:

O

II v

II O

The method of brominating anilines using N-bromosuccinimide in an inert organic solvent such as methylene chloride is well known to those skilled in the art; see, for example, J. B. Wommack et al., J. Het. Chem. 6, 243 (1969). Bromination of 2-fluoroaniline is an exothermic reaction that is carried out at 0 ° C for several hours, for example 5 hours or more. The reaction mixture obtained is washed several times with water and the organic portion is dried with a suitable drying agent, for example anhydrous sodium sulfate. Distillation of the organic solvent under reduced pressure at 20 to 50 ° C gave 4-bromo-2-fluoroaniline.

2,4,6-Trifosulfate can be prepared by the reduction of 1,3,5-trifluoro-2-nitrobenzene (described by VI Siel and NJ Matsugama. US Department of Commerce, Office Serv., PB Rept. 1, 5, 510, p. 1). 1 (1960); Chem Abstract 56, 15394c (1962)], as described by G.

Schiemann and M. Seyhan, Chem. Ber. 70, 2396 (1937).

F F

NHb

F Λ

2,4-Difluoroaniline is a known compound which can be prepared as described by G. Schiemunn, M. Seyhun, Chem. Ber. 70, 2396 (1937).

4-Amino-3-fluorobenzonitrile, which is used to prepare 4-cyun-2-3-fluorophenylhydruzine hydrochloride, can be prepared by known methods, for example, by treating copper 4-bromo-2-fluorouniline in the environment with known methods. N-methylpyrrolidone, see L. Friedmun et al., J. Org. Chem. 26, 2522 (1961). The reaction mixture was refluxed for several hours and the puck was poured into ice / sodium cyanide. The solution obtained is heated for 1 to 3 hours at 50 ° C for 80 ° C, the puck is cooled, shaken with toluene, the toluene extract is washed with water and dried with a suitable drying agent. After distillation of the solvent, amino-3'-3'-fluorobenzonitrile is obtained.

The 2-fluoro-4-methoxyetiline required for the preparation of 2-fluoro-4-methoxyphenylhydrazine hydrochloride is a known compound and can be prepared as described by H. Hodgson et al., J. Chem. Soc. 1268 (1940). .

2-Fluoro-4-nitroaniline, which is used as a starting material in the preparation of 2-31-urur-4-nitro-phenylhydrazine hydrochloride, is also a known compound and can be synthesized as described by J. B. Dickey, U.S. Patent 2,434,600.

The herbicidal activity of the compounds of the invention was examined in the following test.

Seeds of 'bloody dew (Digituria spp.), Hedgehogs' corn feet _; (Echinochloa crusgalli), Deaf Oat (Avena latua), Cassia Torah, Ichthyol spp. chemicals dissolved in an ethytotoxic solvent. At the same time, the following plants were sprayed: cotton having five leaves (including the uterine) shrubby bean 'with a third billowing leaf, a bloody dew with two leaves; cassia with three leaves (including cotyledons), four-leaf clove (including uterine) 'beet' with four leaves (including uterine), sorghum with three leaves, maize with three leaves, soya with 2 uterine leaves, 'rice' with two leaves , wheat with one leaf and sedge with three to five leaves. Treated plants and control plants were kept in the greenhouse for sixteen days, then all species were compared to control plants and evaluated visually for response to the spray. Quantitative evaluation was performed on a scale of 0 to 10; 'level 10' means complete 'destruction, level 0 means no damage. A quantitative evaluation of the type of damage was also performed:

B - incineration

C - 'chorosis, necrosis

G - 'delayed growth

H - shape effect

The results are summarized in Table 1 below, compared to the three most well-known commercial formulations, Ordram, Suturn 'and Stam F-34. The table shows that the compound according to the invention is more effective at 0.5 kg of nu-hectare in preemergence spraying on hedgehog than in the comparative preparations of 2 kg / hectare.

19'5 7'3 6 qojjo ufos

Nq

CD o

CD CD

X CD

CD Щ CM p

НОЛЗ э? 4л

Bígs' aojjnqnq

X

X 1Л.

0) W ΰ φ oo φ

B φ φ aojuasd

4qonqq · soao

Bqou · janq · Bqijazai

BABAjq · BXJQSOJ botijso

BJSSBO q-adaj oTufiAOcI

30112

O

CD cd o

Ж σ>

CD CM cd o 'PQ CD

-Φ CJ t Φ 00 • Φ s Φ Φ ř-4 P-i aojuasd • Ч'ЭГЭ. ' 8ΘΛΟ

BABA— ·: BqQjSOJ o-mso • BJSSBO qadaj aoiUijAOd №13

X

LO

X

CD o

O)

X co

Compound

ezÁa

Bfos aojjnqnq aojuasd

4qonjq saAO aqou unq

BABA J BXPISOJ aojjjso

BJSSBO qadaj aojufjAod qjujABq

Iozbj Moqpjjaq

PQ CO.

PQ o>

PQ 1П

PQ About me X

PQ CM

PQ

Me

PQ r>

PQ O

3Z4j (9S

PQ

Me

£ jl Тб X. aounqnq o »ó 1 O aotuagd

Φ co P Φ 00 ÍH Φ s Φ -M.

CO o

fi í> G>

O

X co

ČM

Áqanqq. saAO в-qou janq ΒΗΙΒΖθί

PABAJq BqQJSOJ aajjs-o

BJSSBO uodaj aojufjAod qjuiABq

IOZBJ 4Aoq5j, jaq

X

Ml

About what

CQ CM

Target

Cq co CM cd

JO £

вц / Sq

Ю o *

Bq / Ssi

CM

BÍ9S

c JL * co

Compound

CD

CD

Й

CD W)

Jh

CD s

CD ω

• Sh

Рч

CD CDs

CD ад ·. &

SФaojuasd

4tprť ($ 4 θλο uqiou wnq

HAVAJE D ^ gtsoj

33LJ} Š0

BJSS83 g3fu [iAod qojjQ э? 4л

BÍQS οομιηηηχ aoxu9§d

4ЦЭПЩ S&AO

ВЦОи ЦПЦ Й ^ 1.в? 9 (рлвлдц B> i9jsoj

Θ3Ν) 8Ο

B1SSB3 pada.i aáiufiAod

XjtiIABq

IOZbj 4Λ049ΜΘΧ

B4 / 84

5fOiH3

^ЗЦП ^ ПЯ

QOJUQSd

9 S9A0 uqou jjn: {pAPAJq BHOTSOJ

33TJjSO

BISSU3 ugdai

93lU (tA0d

ЯОЛЗ

3ZÁJ

BÍpS

ЭЭЦПЯП ^ ooiuasd

Ацэпщ seAo tH [C) U Jinjf ΒΗ1Β? Θί pABAJ> (BHQISOJ · eisoiso & 1SSB3 υθώθίΐ aaiuÍTA from эдщлвц вц / §ч

About what

OB OB OB 3B OB OB OB 5B 2B 9B 2B 9B ОС 6C ОС 0 6C 7C

CQ O ffl o

СЧ

The following examples illustrate the preparation of the compounds of the present invention. All weights are in parts by weight, percentages are by weight and all temperatures are in degrees Celsius; always means the melting point.

Example 1

Preparation of 3-chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole

(and)

Preparation of 4-chloro-2-fluoroaniline

71 parts of liquid chlorine are added to a solution of 140 parts of 2'-fluoroacetanilide in 500 parts of glacial acetic acid, while cooling the ice-water mixtures at 25 to 27 ° C over one hour, and the reaction mixture is stirred for 4 hours at 25 to 27 ° C. C. The precipitated 4‘-Ghloro-2‘-fluoroacetanilide was filtered off and the filtrate was poured into 2000 parts ice. A second crop of product precipitated, which was filtered off, combined with the first crop, and the combined material was recrystallized from 700 parts of methanol. After cooling to -45 ° C, 119 parts of 4‘-chloro-2‘-fluoroacetanilide are obtained in the form of colorless crystals of m.p. 152-155 ° C.

A mixture of 119 parts of 4-chloro-2'-fluoroacetanilide, 475 parts of ethanol and 200 parts of 37% hydrochloric acid was heated at reflux for 17 hours and then the solvent was distilled off under reduced pressure (39.99 kPa); wet, solid 4-chloro-2-fluoroaniline hydrochloride is obtained.

The still wet, solid 4-chloro-2-fluoroaniline hydrochloride was cooled in an acetone-ice bath to 10 ° C and 50% aqueous sodium hydroxide solution was added dropwise with stirring until pH 11 was reached; two layers are created. The mixture is shaken four times with 500 parts of methylene chloride, the organic extracts are combined, dried over anhydrous sodium sulfate and the solvent is distilled off under reduced pressure (39,99 kPa). 89 parts of 4-chloro-2-fluoroaniline are obtained in the form of a light brown colored oil, no ²⁵ = 1.5541.

(b)

Preparation of 4-chloro-2-fluorophenylhydrazine hydrochloride

Dissolve 20.0 parts of 4-chloro-2-fluoroaniline in a mixture of 80 parts of water with 34 parts of concentrated hydrochloric acid. The solution is cooled to 0 to 1 ° C and 32.2 parts of a 30% sodium nitrite solution are added dropwise while cooling to 0 to 10 ° C. After the nitrite was added dropwise, the reaction mixture was stirred at 0-10 ° C for 30 minutes and then the excess nitrite was quenched by the addition of a small amount of amidosulfonic acid. When the reaction mixture does not give a positive reaction in the sulfone assay, the diazonium salt is prepared for reduction. The sulfone test is described in monophropy Η. E. Fierz-David et al., Fundamental Processes of Dye Chemistry, translation by P. W. Wittam from the 5th Austrian edition, interscience Publishers, Inc., New York, 1949, p. 243.

In a separate flask, 35.4 parts of sodium bisulfite and 32.2 parts of 30% sodium hydroxide solution were dissolved in 140 parts of water. The solution was heated to 40 ° C and a diazonium salt solution was added dropwise over about 1 hour. The reaction mixture is heated to 70 ° C, 0.3 parts of sodium bisulfite is added, the solution is adjusted to pH 1.2 with 30 parts of concentrated acid and then a further 90 parts of concentrated hydrochloric acid are added. The mixture was heated at 70 ° C for 1.5 h, then cooled slowly and stirred at room temperature overnight.

The product is purified by heating the reaction mixture to 70 ° C and filtering? The filtrate is cooled to 10 ° C, the precipitated 4-chloro-2-fluorophenylhydrazine hydrochloride is filtered off and dried. 10.7 parts of a yellow-colored crystalline substance, m.p. 223 DEG C., are obtained.

(C)

Preparation of 2- (4-chloro-2-fluorophenyl) -1,2,4,5,6,7-hexahydro-3H-indazol-3-one

15.8 parts of 2-fluoro-4-chlorophenylhydrazine hydrochloride, 13 parts of 2-ethoxycarbonylcyclohexanone (supplied by the Aldrich Chemical Company) and 8.1 parts of triethylamine are dissolved in 100 parts of ethanol and the mixture is refluxed for 24 hours. ~

After cooling, the reaction mixture is poured into 1000 parts of water, the precipitated gum which solidifies on standing, is filtered off and dried;

16.1 parts of crude product having a melting point of 163 DEG-170 DEG C. are obtained, which can be used in the next step without further purification.

Using the same procedure, but using 4-chlorophenylhydrazine hydrochloride instead of 4-chloro-2-fluorophenylhydrazine hydrochloride, 2- (4-chlorophenyl) -1,2,4,5,6,7-hexahydro-3H-indazole-3- on, mp 183.5-185 ° C (literature, Chem. Abstr. 67, 11452h, reports mp 186-197 ° C).

(d)

Preparation of 3-chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole

A mixture of 10.0 parts of 2- (4-chloro-2-fluorophenyl) -1,2-a-5-hexahydro-1H-indazol-S-one and

7.3 parts of phosphorus oxychloride were heated at 130-150 ° C for 6 hours. The reaction mixture was dissolved in 100 parts of chloroform and the organic solution containing the product was washed successively with three portions of 25 parts of 10% sodium hydroxide solution and then 50 parts of water. The chloroform fraction was dried with 2-10 parts of anhydrous sodium sulfate, the desiccant was filtered off and the solvent was distilled off under reduced pressure on a rotary evaporator. The dense oily product obtained is purified by sublimation at 100 to 120 ° C at a pressure of 0.07 to 0.2 kPa to give 7.8 parts of a colorless crystalline substance, m.p. 88-89.5 ° C.

Other novel substituted anilines used in the present invention are prepared as follows.

4-Bromo-2-fluoroaniline

To a solution of 100 parts of 2-fluoroaniline in 400 parts of methylene chloride cooled to 0 ° C was added portionwise over 2 hours 160 parts of solid N-bromosuccinimide. The reaction mixture was stirred for 20 min. and then the dark red solution was washed four times with 200 parts cold water. The red colored organics were dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure (39,99 kPa). To give 164 parts of 4-bromo-2-fluoroaniline as a tan oil, n _D ²⁵ 1.5885.

4-Amino-3-fluorobenzonitrile

To a solution of 6.8 parts of 4-bromo-2-fluoroaniline in 75 parts of N-methylpyrrolidone was added 4.2 parts of copper cyanide and the mixture was heated to 190 ° C for 2 hours. The reaction solution was poured into a mixture of 200 parts of ice with 15 parts of sodium cyanide and heated in a water bath at 60-70 ° C for 2 hours. The aqueous solution is shaken 4 times with 100 ml of toluene each time, the toluene extracts are combined and washed with four 300 ml portions of water and then with 100 ml of saturated aqueous sodium chloride solution. The toluene solution of the product was dried over sodium sulfate and the solvent was evaporated; 2.6 parts of the desired product are obtained, m.p. 71-73 ° C.

The following compounds of formula (I) were prepared according to the method of Example 1, using 2-ethoxycarbonylcyclicohexanone, the salt of the corresponding hyrazine and phosphorus oxychloride:

Q Y X in of 1.1. ° c Cl H Cl H H Mp 81-84 ° C Cl H Br H. H . 86-88 ° C Cl H N02 H H 103-105 ° C Cl. H СНзО H H oil, IR bands 760 cm ¹ , 835 ¹ Cl Cl Cl H H oil, IR bands 735 cm ^-1 , 820 cm ^-1 Cl H Cl Cl H Mp 69-71 ° C Cl H F Cl H Mp 70-72 ° C Cl F Br H H 86-88 ° C Cl F СНзО H H Cl F N02 H H 108-109.5 ° C Cl F CN H H Mp 113-116 ° C Cl R F H H n _D 25 = 1.5587 Cl Cl Cl Cl - H 101-105 ° C Cl H Br Cl H Cl H CN H H 104-106.5 ° C Cl H F Cl H Mp 70-72 ° C Cl H F H H 35-37 ° C Cl Cl Br H H 78-79 ° C Cl. F F F H Cl F AND H H 83.5 - 87 ° C Cl Cl Cl H F 93.5-101 ° C Cl F F H  F 57.5 - 62 ° C Cl Cl F H H 75-78.5 ° C Cl H 1 H -H 91-103 ° C Cl Cl Cl ОСНз H 107-110 ° C Cl F Cl Cl H

195738

Using the method of Example 1, starting from the ethyl substituted 2-ethoxycarbonyl cyclohexanones, the corresponding arylhydrazines and phosphorus oxychloride, the following compounds of formula I can be prepared:

R ¹ Q Y • X IN of m.p. ° с 7-СНз— С1 'F F F н 7-СНз— С1 F F Н F 7-СНз— С1 F С1 Н Н 58—61.5 ° С 7-СНз— С1 F Вг н Н 7-СНз— С1 F F н Н 7-СНз— С1 Н С1 н Н 1 belts 1570, 835 cm- ¹ 7-СНз— С1 Н ОСНз н Н. n _n ^{2 S} = 1.5839 7-СНз— С1 F F н F 5-СНз— С1 F С1 н Н 85—88 ° С 5-СНз— С1 Н С1 н Н 96.5—99 ° С 6-СНз— С1 F С1 н Н 43.5—44.5 ° С 6-СНз— С1 F AND н Н IR bands 1600, 870, 825 cm 6-СНз— С1 Н Cl С1 Н 6-СНз— С1 Н С1 н Н 75—76 ° С 6-СНз— С1 Н CN н Н 103—105 ° С 6-СНз— С1 н ОСНз · н н n _D 25 = 1.5839 6-СНз— С1 н N02 н Н 89—91.5 ° С (4-СНз— 6-СНз— С1 н С1 н Н 47.5—52 ° С (m.p. mixtures) 4-СНз— 6-СНз— С1 F С1 н Н 41—45 ° С (m.p. mixtures) 6-СНз— С1 F AND н н 6-СНз— С1 С1 01 ОСНз Н

Example 2

Preparation of 3-chloro-2- (4-chlorophenyl) -2,4,5,6,7,8-hexahydrocycloheptapyrazole

By the method of Example 1c but using 2-ethoxycarbonylcycloheptanone (prepared according to the method of G. Stork et al., J. Am. Ohem. Soc. 85, 207 (1963)) and p-chlorophenylhydrazine hydrochloride (supplied by Aldrich Chemical Company) as starting materials. 2- (4-chlorophenyl) -1,4,5,6,7,8-hexahydrocycloheptapyrazol-3 (2H) -one (mp 224-225 [deg.] C.). of Example 1d: 3-chloro-2- (4-chlorophenyl) -2,4,5,6,7,8-hexahydrocycloheptapyrazole (mp 59-61 degrees C) was prepared.

Using the method of Example 2, using the hydrochloride of the corresponding arylhydrazones (e.g., p-chlorophenylhydrazine hydrochloride) and phosphorus oxychloride, the following compounds of formula I can be prepared:

Q. Y X IN OF m.p. · ° C Cl F Br H H 82.5—83.0 ° C Cl F F H H Cl F OCH3 H H Cl F CN H H Cl F NOž H H Cl F Cl H . H 68-69.5 ° C Cl H CN H H 95-102 ° C Cl H Br H 'H Mp 53-55 ° C Cl F. AND H H Br. F Cl H H Br F Br H H

K k k 1 a d 3 (a)

Preparation of 2 (d-chloro-4-fluorophenyl) -1,4,5,6-tetrahydrocyclopentapyrazol-3 (2H) -one

A solution of 7.5 parts of 2-chloro-4-fluorophenylhydrazine and 6.6 parts of methyl 2-oxocyclopentacarboicyllite (supplied by Aldrich Chemical Company) in 200 parts of toluene is heated under reflux for 1-2 hours. simultaneous distillation of the water produced. The reaction mixture was cooled to 100 ° C and added dropwise. a solution of 5.0 parts of sodium methylate in 25 parts of methanol, the methanol being removed by distillation in the form of an azeotropic mixture with toluene. The azeotrope was distilled off until the internal temperature of the reaction mixture reached 110 ° C. The solution was cooled, poured into 200 parts of ice water, the organic layer was separated and the aqueous portion was shaken twice with diethyl ether. The aqueous layer is acidified with cold dilute hydrochloric acid to pH 2 with stirring. an oily product precipitates, which solidifies with age. The product is filtered off, dried and recrystallized from acetonitrile; 3.3 parts of a yellow-brown crystalline solid are obtained, m.p. 157-160 ° C.

Alternatively, the above pyrazole may be prepared as follows: 16.0 parts of 4-chloro-2-fluorophenylhydrazine and 14.2 parts of methyl 4-oxocyclopentanecarboxylate are dissolved in 100 parts of benzene and the mixture is heated at reflux for 1-2 hours. under reflux while distilling off the water produced in the form of an azeotropic mixture with benzene. The reaction mixture is cooled, solvent ₄ is distilled off under reduced pressure on a rotary evaporator, and the brown-colored oily product obtained is dissolved in 150 parts of anhydrous tetrahydrofuran. The solution was cooled to 0 ° C under a nitrogen atmosphere, a solution of 2 equivalents of n-butyllithium in hexane supplied by Foote Mineral Comipany) was added to the cold solution at such a rate that it was internal. the temperature of the mixture was maintained between 0 and 5 ° C. The reaction mixture was allowed to warm to room temperature and then stirred. The mixture was heated at reflux for 18 hours. The solution was cooled, poured into 200 parts of ice water, the organic layer was separated and the aqueous portion was shaken twice with ether · The aqueous was acidified with cold dilute hydrochloric acid to pH 2 and the resulting oily product solidified on standing, filtered, dried and recrystallized from acetonitrile. 17.5 parts of a tan-brown crystalline substance are obtained, mp 165-167 ° C. Using the same procedure, but using 4-chlorophenylhydrazine instead of 4-chloro-2-fluorophenylhydrazine, 2- (4-chlorophenyl) -1,4,5,6-tetrahydro-cyclopentapyrazol-3 (2H) -one was prepared. mp 193.5-195 ° C.

(b)

Preparation of 3-chloro-2- (4-chloro-2-fluorophenyl) -2,4,5,6-tetrahydrocyclopentapyrazole.

Following the procedure of Example 1d, treatment of 2- (4-chloro ^: 2-fluorophenyl) -1,4,5,6-tetrahydrocyclopentapyrazol-3 (2H) -one with phosphorus oxychloride afforded O-chloro-4-chloro-chloro. (4-fluorophenyl) -2,4,5,6-tetrahydrocyclopentapyrazole, mp 102-104 ° C.

By the method of Example 3, using the appropriate methyl substituted. The following compounds of formula I can be prepared from 2-oxocyclopentanecarboxylate, the corresponding hydrazine and phosphorus oxychloride:

and Y H 4 5 < ОУ-x 6 of in R1 Y X v Z mp ° C

H H Cl H H 114.5-117 ° C H Cl Cl H H Mp 119-1123 ° C H H Br H H Mp 120-112 ° C H Cl Br H H Mp 113-119 ° C H F Br H H 105-106.5 ° C H F F H H Mp 110-119 ° C H H F H H Mp 57-80 ° C H F F H F H Cl Cl Cl H H H Br Cl H H F CHsO H H H F NO2 H H H F CN H H H H CH3O H. H H H NOz H H H H CN H H 126.5-128 ° C H H Cl Cl H 95-98 ° C H H F Cl H 4-CH3— F Cl H H 4-CH3— H Cl. H H 5-CH3— F Cl H H 1 IC strips 1580, 4-CH3— F Cl H H J 905, 990 ^cm-1 5-CH3— H Cl H H 6-CH3— H Cl H H 6-CH3— F Cl H H Mp 88-93 ° C H F AND H H H Cl Cl OCH3 H 7-CH3— F Cl H H

Example 4

Preparation of 3-bromo-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-indazole

To a solution of 5.0 parts of 2- (4-chlorophenyl) -1,2,5,5,6,7-hexahydro-3H-indazol-3-one [prepared according to the method of Example 1c]] and 3.0 parts of Ν, Ν-diethylaniline 6.3 parts of phosphorus oxybromide are added in 5.0 parts of dimethylformamide under a nitrogen atmosphere. The mixture was heated at 130-170 ° C for two hours, then cooled to room temperature and shaken

100 parts diethyl ether. The ether extract was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off on a rotary evaporator. The residue was recrystallized from methanol / water to give 2.7 parts of the product, m.p. 101-102 ° C.

The following compounds of formula I can be prepared by the method of Example 4, using the corresponding fused pyrazolones of formula 3 as starting materials which can be prepared as described in Example 1 or Example 3:

R ¹ Br γ h

Г N- n R ¹ Y X 3 H F Cl ^: 3 H H Cl 3 H H Cl 3 H Cl Cl 3 H F F 3 H F . F 3 H F Br 3 4-CH3 F Cl 3 6-CH3 • F Cl 3 H F CH3O 3 H F NOž 3 H F CN 4 H F Cl 4 H F Br 4 H F F 4 H Cl Cl 4 H F F 4 H F CH3O  4 H F NOž 4 H F CN 4 H H NOž 4 H H Br 4 H H F 4 H H CH 2 O 4 H H CN 4 H H Cl '4 5-CH3 F Cl 4 H F AND 4 H Cl Cl 4 H F F 4 7-CH3 F Cl 4 H H NOž 5 H F Cl 5 H H Cl '5 H H CH3O

Example 5

Preparation of 3-iodo-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-in (dazole)

(a) Preparation of 3-amino-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-indazol-3-one

A mixture of 3.6 parts of 4-chlorophenylhydrazine, 2.0 parts of triethylamine and 20.0 parts of toluene is stirred for 15 minutes at room temperature, and then 2.5 parts of 2-cyancyclohexanone prepared from commercial 2-chlorocyclohexanone are added. and potassium cyanide [see RE Meyer, Helv. Chim. Acta 16, 1291 (1933)] and a few drops of acetic acid. The mixture was heated at reflux for 2 hours, stirred overnight at room temperature, and the solvent was distilled off. The residue is stirred with water and the solution is shaken with diethyl 2 ^A

IN

in of mp · mp ° C H H 106—110 ^o c Cl H H H 109-112 ° C H H H H H F H H H H H H H H H H H H H H 95-98 ° C H H H H H H 101—102 ⁰ C H F H H H H H H H H H H Mp 84-87 ° C H H Mp 70-73 ° C H H H H Cl H H H H H OCH3 H F H ' H H - H H H H 59—60 ^o C H H H H

ether, the ether extract was dried over anhydrous magnesium sulfate and the solvent was distilled off. The residue is recrystallized from ethanol / water to give 2.6 parts of the product, m.p. 140-142 ° C.

b] Preparation of 3-from-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-indazole

2.5 parts of 3-amino-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-indazole are dissolved in a mixture of 2.5 parts of concentrated sulfuric acid with 15 parts of water and cooled to 0 with cooling. A solution of 0.8 parts of sodium nitrite in 5.0 parts of water is added dropwise. The reaction mixture was stirred at this temperature for one and a half hours, and then the excess nitrous acid was decomposed to give amidosulfonic acid. To a solution of the diazonium salt is slowly added a solution of 1.7 parts of potassium iodide in 5.0 parts of water,

The mixture was stirred at 0-25 ° C for 2 hours, and the precipitate formed was filtered off and dried. Recrystallization from ethanol-water gave 1.7 parts of the product, mp 83 ^° C (dec.).

By the method of Example 5, using the appropriate α-cyanoketones, which are conveniently prepared by reacting the corresponding α-chlorocyclohexanone or α-chlorocyclopentanone with sodium cyanide (according to the method of RE Meyer, Helv. Chim. Acta 16, 1291 (1933)), to produce the following compounds of formula I:

YH ^ / ~ ^X Vol

Ri

Y X V

From T. mp

3 H F Cl H H 106 3 H H Cl H H 3 H F Br H H 3 H F F H H 3 H F CH5O H H 3 H F NO2 H H 3 H F CN H H 4 H F Cl H H 133—135 4 H F Br H H 4 H F F H H 4 H H CHsO H H 4 H H NO2 H H 4 H H CN H H 4 H F AND H H

Example 6

Preparation of 3-fluoro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole

a) Preparation of 2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole-3-diazonium fluoroborate

A solution of 2.5 parts of sodium nitrite in 10 parts of water and a suspension of 8.7 parts of 3-amino-2- (4-chloro-2-fluorophenyl) are added in small portions to 50 parts of 48% fluoroboric acid at 0 to 5 ° C. ) -4,5,6,7-tetrahydro-2H-indazole in 30 parts of acetic acid such that the mixture always contains an excess of nitrite (ED Bergmann, S. Berkovic and R. Ikan, J. Am. Chem. Soc. 78, 6037 (1956)] After stirring the reagents, the mixture is stirred at 0-10 ° C for 1 hour and then at 10-25 ° C for half an hour. Excess nitrous acid is quenched by addition of amidosulfonic acid, the precipitate formed is filtered off, washed with water, ethyl ether. and dried to obtain 9.0 parts of the product. In the IR spectrum of the substance was found, and the presence amlnosloučeniny substance showed absorptions at 2200 cm ^"1 corresponding N ⁺ 2. a compound of this quality can be used in the next step without Recrystallization.

b) Preparation of 3-fluoro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole

A mixture of 9.0 parts of 2- (4-chloro-3-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole-3-diazonium fluoroborate and 10 parts of potassium fluoride in 100 parts of fluoroboric acid is photolysed by irradiation with 200 W high pressure Hanovia mercury lamp for 1 hour at 0 ° C and 15 hours at room temperature. The reaction mixture was shaken with ether, the ether extract was washed with water, dried over anhydrous magnesium sulfate and the solvent was distilled off. The crude product was purified by column chromatography (on silica gel, eluting with methylene chloride), preparative thin layer chromatography (thin layer silica gel, using a diethyl ether-hexane solvent system 5: 100) and preparative gas chromatography (on Chromosorb W HP 80 / crosslinking) 100 mesh with anchored phase (15% OV-17, at 250 ° C). The product obtained was pure by gas chromatography and showed M ⁺ = 268 am / e - -240 (due to loss of C2H4) by mass spectroscopy; NMR Spectrum: σ 1.5 (m, 4H), 2.0-2.2 (2t, 4H) and 7.0 (m, 3H).

By the method of Example 6, using the appropriate 3-amino compounds (see Example

5a) the following compounds of formula I can be prepared:

3B

R ^{1 F} YH

Z v

η R ¹ γ x in 3 H F Cl H 3 H H Cl H 3 H F Br H 3 H F CN H 3 H F CH3O H 3 H H Br H 3 H H CN H 4 H H Cl H 4 H . F Br H 4 H F CN H 4 H F CH3O H 4 II H .Br H 4 H F NOž. H 4 H F AND H

H H H

H

H

H

H

H

H

H H H

H

H

Suitable formulations of the herbicidal compositions containing the active compound of the formula I are dusts, granules, pellets, solutions, suspensions, emulsions, wettable dusts, emulsifiable concentrates and the like. Many of them can be applied directly. The spray preparations can be diluted in a suitable environment and the diluted spray can be used in quantities ranging from a few liters per hectare to several hundred liters per hectare. hectare. High-percentage concentrates are intended as intermediates for the production of other formulations. Herbicidní. compositions according to the invention contain about 0.03%. up to 99% of the active ingredient; and active ingredients, and at least one of the following excipients: a) a surfactant (s) in an amount of from 0.1% to 20%, and b) a solid or liquid diluent (s) in an amount of about 1%. to 99.95. . %. Specifically, they can. the herbicidal compositions to be used contain the components in the following approximate amounts:

Ingredients (weight percent)

Preparation Active Substance Diluent (s) Surfactant (s)

wettable dusts, 5—90 1—94 ' 1—10 oil suspensions, emulsions, solutions 5—50 40—95 0—15 (including emulsifiable concentrates) aqueous suspensions 5—50 40—94 1-20 dusts 0,05—25 70—99,95 0—5 granules and pellets 0,05—95 1—99.95 0—15 high-percentage concentrates 90—99 0—10 0—2

Of course, the active ingredients may be present in the formulations in lower or higher amounts, depending on the intended use and the physical properties of the compound used. Sometimes it is desirable to have a higher surfactant content relative to the active agent; this can be achieved either by mixing the surfactant directly into the formulation or by adding it to the tank before spraying.

Typical solid diluents suitable for the above herbicidal compositions are described in the handbook; Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, NJ Suitable solid diluents are finely divided or granulated solids from the group consisting of attapulgites, organic materials, calcites, diatomaceous earth , dolomites,. gypsum, kaolinity, limestone, mica, montmorilionoids, phosphates, pyrophyllites, sulfur, sand, talcum,. tripolites, vermiculite and synthetic substances. In the group then listed. synthetics include, for example, precipitated, hydrated silica, precipitated, hydrated calcium silicate, precipitated calcium carbonate, and synthetic organic materials. Solid solvents with higher absorbency are more suitable for wettable dusts and denser solvents are more suitable for dusts.

Typical liquid diluents and solvents are described in: Marsden, "Solvents Guide", 2nd Edition, Interscience, New York, 1950. Solubility below 0.1% is suitable for suspension concentrates; concentrated (high-percentage) solutions should not be separated into phases at 0 ° C. In "McCutcheon's Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood, New Jersey, 1975, as well as the Sisely Encyclopedia, and Wood &quot; Encyclopedia of Surface Active Agents &quot;, Chemical Publ. Co., New York, 1964, discloses suitable surfactants and the recommended uses of which All herbicidal compositions may further contain minor amounts of other ingredients such as suds suppressors, caking agents. , corrosion, microbial growth and the like, or which visibly indicate the area that has been treated with the herbicidal composition.

Sometimes, it is desirable to add components which reduce the volatility of some of the compounds of formula I. Thin film-forming materials such as the like may be used as such additives. polyvinylpyrrolidones having a molecular weight of from about 20,000 to about 100,000, polyvinyl alcohols having a molecular weight of from about 20,000 to about 150,000, and polyoxyethylenes having a molecular weight of from about 100,000 to about 6 X10 ⁶ . These are just a few. examples of thin film additives. Any material capable of forming a thin film on the solid active ingredient in the herbicidal composition or on the active ingredient after application as a liquid spray and upon drying of the diluent may be used. Another way to reduce the volatility of substances lies. wherein the compounds of formula (I) are incorporated into resins, waxes, gums, rubbers, and the like, and thereafter from these combinations. processes herbicidal compositions.

Processes for producing said herbicidal compositions are o. well known. Solutions are prepared by simply mixing the individual components. The finely powdered solid preparations are. produced by mixing the ingredients and usually comminuting the mixture, for example in a hammer mill or microniser. Suspensions are prepared by wet grinding (see, for example, Littler, U.S. Patent 3,060,084).

The granules can be produced in various ways. For example, a preformed granular carrier may be sprayed with a solution of the active ingredient. Suitable preformed granular carriers may be the abovementioned solid diluents having a size. particles in the range of USS sieve number 200 (74 microns) to USS sieve number 10 (2000 micro meters). Advantageous size. The carrier particles within the crosslinking range of the USS screen are number 140 (105 microns to USS screen No. 20 (840 microns)).

Depending on the nature of the carrier, the active ingredient either remains on the surface of the carrier or is absorbed into the carrier. If it remains effective. usually on the carrier surface, a binder is usually used to keep the active substance on the surface. The binder is to bind the active ingredient to the surface of the carrier. strong enough to prevent loss during normal handling and shipping. more than 10% of the active substance. Suitable binders include substances which are at least partially soluble in any liquid used in the manufacture of the granules and which adhere to the surface of the granules. Water-soluble binders are preferred. Suitable binding agents include, but are not limited to. these examples, for example water-soluble polymers such as. polyvinyl alcohols having a molecular weight of from about 20,000 to 20,000. about 150,000, polyvinylpyrrolidones having a molecular weight of about 20,000 to about 100,000, and polyoxyethylenes. having a molecular weight of from about 100,000 to about 6 X10®. Other suitable binders include lignin sulphonates, starches, sugars and some surfactants listed in "McCutcheon's Detergents and Emulsifiers 1975 Annual", M C Publ. Corp., Ridgewood, NJ.

The active ingredient may be sprayed onto the preformed granules in the form of a solution in a suitable solvent which may or may not be present. does not have to be removed from the product. If the active ingredient is a liquid, it can be sprayed onto the carrier or mixed with the carrier directly. If the active substance is solid, it can melt and apply the melt directly in the same manner as the liquid. If it is necessary to produce granules with a very low active substance content,. the active ingredient can be vaporised onto the carrier. Granules can also be produced by agglomeration processes. For example, the active ingredient and the finely divided solid diluent are mixed, and the mixture is agglomerated by methods well known to those skilled in the art, such as by spraying the mixed mass with a suitable amount of liquid in a fluid or rotary granulator. The active ingredient and solid diluent may also be mixed with other suitable ingredients and pelletized. . The pellets can then be 'crushed' into granules of the desired size. Pellets can be manufactured by known agglomeration processes, see, for example, Browning JE: "Aglomeration", Chemical Engineering, December 4, 1967, pp. 147 et seq., And the "Perry's Chemical Engineer's Handbook, 4th edition" ,. McGraw-Hill, N.Y., 1963, p. 8—59 et seq.

For more information on the method of making herbicidal compositions, see, for example:

Η. M. Loux, U.S. Pat. No. 3,235,361;

February 15, 1966, column 6, line 16, through column 7, line 19, and examples 10-41.

R.W. Luckenbaugh,. U.S. Patent 3,309,192 of March 14, 1967, Col. 5, line 43, through Col. 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162 —164, 166, 167, 169—182.

H. Gysin and E. Knusli, U.S. Patent 2,891,855, issued June 23, 1959, Col. 3, line 66, to Col. 5, line 17, and Examples 1-4.

G.. C. Klingman: “Weed Control as a. Science ', John Wiley &amp; Sons, Inc.,' New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans: "Weed Control Handbook", 5th edition, Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

Example 7

Granules c-chloro-2- (4-chlorophenyl) -4,5,6,7-tetrahydro-2H-indazole 10% granulated attapulgite (low volatile material, particle diameter 0.71-0.30 mm, ie cross-linking) 25—50 mesh sieves according to

USS) 90%

The active ingredient is heated to about 90 ° C and sprayed onto the preheated dust-free attapulgite granules with stirring in a mixer. The granules are allowed to cool and then packaged.

Example 8

C-CoI 4 - (2,4-difluorophenyl) -4,5,6,7-etrahydro-1 H -indazole solution 20% dimethylformamide 80%

Both components. are mixed and. stir until dissolved. The solution can be used for small volume applications.

Example 9,

Extruded pellets 2- (4-chlorofluorophenyl) -4,5,6,7-etrahydro-1 H -indazole 1% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate sodium 1% polyoxyethylene (o. average molecular weight 4X10 ⁶ ) 1% calcium-magnesium bentonite 82%

The components are mixed, ground in a hammer mill and moistened with 12% water. The moistened mixture is extruded in the form of cylindrical bars of 3 mm diameter, which are cut into pellets about 3 mm long. The obtained pellets are dried and can then be used directly or crushed so that the obtained grains pass through a USS No. 20 screen (0.84 mm aperture). The material obtained - is screened again, and the granules retained on the 'USS No. 40 sieve (0.42 mm holes) are packaged for use and the finer granules that have passed have been recycled. All the compounds of formula I can be formulated in this manner.

Example 10

Emulsifiable concentrate

З-оЫот-γ- (4-chlorophenyl) -4,5,6,7-tetrahydro-1H-indazhl 2'5 ·% mixture of oil-soluble sulfonates and polyethylene glycol ethers 4% xylene 71%

The individual components are mixed and mixed until complete dissolution of the ingredients. When filling the solution into commercial packs, a fine sieve is included as a filter to ensure that no ci-, rusty undissolved substance is present in the product.

Example 11 '^;

Aqueous suspension

3-chloro-4- (4-chlorophenyl) -4,5,6,7-

-tetrahydro-1 H -indazole 50.0% polyacrylic acid (as thickening agent) 0.3% polyethylene glycol ether dodecylphenol - 0.5% sodium hydrogen phosphate 1.0% sodium - 0.5% polyvinyl alcohol 1.0% pentachlorophenol 0.4 ° / o water 46.4 '%

The components are mixed and the mixture is ground into a sand mixer so that the size of all solid particles is substantially below. five microns.

Example 12

The wettable powder сЫ-c-2? -2 - (0 RF-chloro-fluorophenyl) @ - -0,5,6,7-tetrahydro-rH-0-indazhl hhlo ^ί RR- (4-chloro-RF-fluorophenyl) - 0,0,6,7-tetrahydro-1H-indazole sodium alkylnaphthalenesulfonate sodium ligninsulfonate sodium synthetic amorphous silica kaolinite%

2%

2%%

%%

The components are mixed thoroughly and the mixture is micronized on a jet mill to an average particle size of about 15 microns. The micronized product is mixed again, sieved through USS No. 50 (0.3 mm holes) and packaged.

Example 13

Highly concentrated concentrate

O-chloro-r- (O-chloro ^, -fluorophenyl) 195736

-4,5,6,7-tetrah-ydro-2H'indazole 99% trimethylnonyl-polyethylene glycol ether 1%

In the mixer, the active ingredient is sprayed with a surfactant, after thorough mixing, the mixture is sieved through a USS No. 40 sieve (0.42 mm diameter holes) and then packaged.The concentrate must be further formulated for practical use.

Example 14

Low percentage granules

3-chloro-2- (4-chloro-2-fluorophenyl) -

-4,5 ₎ 6,7-tetrahydro-1 H -indazole 0.5% polyvinylpyrrolidone 1% granulated attapulgite (low volatile material, particle diameter 0.59-0.25 mm, ie USS 30-60 mesh screening) 98.5 ° / o

Forty grams of a solution containing 2.5 percent 3-chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydroth 2 H -indazole and 5% polyvinylpyrrolidone dissolved in methanol was slowly sprayed onto the granulated attapulgite (197 g) in a fluid bed. After the entire solution has been sprayed, the granules are fluidized until all methanol has evaporated. The granules are then packaged for use.

Example 15

Extruded pellets of c-eOH-Z- [4-chlorophenyl) -2,4,5,6-.

-tetrahydrocyclopentapyrazole 25% anhydrous sodium sulphate 10% crude calcium ligninsulphonate 5% sodium alkylnaphthalenesulphonate 1% calcium-magnesium · bentonite 59%

The components are mixed, ground in a hammer mill and wetted with 12% water. The moistened mixture is extruded in the form of cylindrical bars of 3 mm diameter which are cut into pellets of about 3 mm long. The obtained pellets are dried and can either be used directly or crushed so that the obtained grains pass through the USS No. 20 screen (0.84 mm aperture). The material obtained is screened again, and the granules retained on the USS No. 40 screen (0.42 mm apertures) are packaged for use, and the finer granules that have passed through the screen are recycled.

Example 16

Granule

3-Chloro-2- (4-fluoro-2- (4-fluoro-1,2,3,6-tetrahydro-cyclopentapyrazole) 2% granulated attapulgite (low volatile material, average of 0.71-0.30 mm particles, i.e. 25-50 mesh screening according to USS) 98%

The active substance is heated to about 110 ° C and the melt is sprayed onto the preheated, granulated, dust-free granulated attapulgite with stirring. The granules are allowed to cool and then packaged.

Example 17 ........... ......

Low percentage granules

3-chloro-2- (4-chlorophenyl) -2,4,5,6-tetrahydrocyclopentapyrazole 0.2% anhydrous sodium sulphate 10% crude calcium lignin sulphonate 5% sodium alkylnaphthalenesulphonate 1% finely ground attapulgite clay 83.8 ° / o

The components are mixed, ground in a hammer mill and transferred to a fluidized bed granulator. Water is added to the pulverulent material in a fluid manner, until small granules are formed. The water supply is then stopped, but the fluidization of the mixture is continued until the resulting granules have dried. The granular material is removed from the granulator and sieved through USS No. 20 sieve (0.84 mm diameter holes). The passed granules are re-screened on the USS No. 40 screen (0.42 mm diameter holes). The retained granules are packaged for use, less than 0.42 mm · are recycled. Granules larger than 0.84 are crushed and also recycled.

Example 18

Extruded pellets

3-chloro-r- (4-chlorophenyl) -4,5,6,7-tetrahydro-1 H -indazole 0.1% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% polyoxyethylene [o · average molecular weight weight 4X10 ⁶ ) 1 ° / o calcium-magnesium bentonite 82.9%

The components are mixed, ground in a hammer mill and moistened with about 12% water. The wet mixture is extruded and cut into rolls of about 1 mm diameter and about 2 mm length. The obtained small pellets are dried and packaged. They can be applied directly as such.

Example 1 9

Low percentage granules

3-chloro-r- (4-chloro-r-fluorophenyl) -

-4,5,6,7-tetrahydro-1 H -indazole 0.05% dimethylformamide 5% granulated attapulgite (low volatile material, particle diameter 0.59-0.25 mm, ie USS 30-60 mesh) 94, 95%

Dissolve 0,1 g of 3-chloro-r- (4-chloro-r-fluorophenyl) -4,5,6,7'-tetrahydro-1 H -indazole in

9.9 g of dimethylformamide are sprayed very slowly with 190.1 g of granulated attapulgite, rapidly mixed in a drum granulator. After addition of the active ingredient solution, the material was stirred for a few more minutes, but dimethylformamide was not removed. The granules are packaged directly for use.

Example 20

Emulsifiable concentrate

3-chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-etrahydro-2H-indazole 20% oil-soluble sulfonates with polyethylene glycol ethers 6% aromatic hydrocarbon solvents, flash point 38 —46 ° C

The components are mixed together until completely dissolved. Prior to filling into a commercial package, the solution is filtered through a fine sieve to remove any foreign insoluble material.

Example 21

Low percentage granules

3-chloro-2- (4-chloro-2-fluorophenyl) -.

-4,5,6,7-etrahydro-2-indazole 0.1% sodium lignin sulphonate 5% preformed sand granules with particle sizes ranging from USS screen No. 140 (105 microns) to USS screen No. 50 (297 microns) 94.9%

0.5 g of 3-chloro-2- (4-c (chloro-2-fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole and 25 g of sodium lignin sulphonate are dissolved in 50 g of water and the solution is sprayed slowly, with stirring, onto preformed sand granules (474.5 grams) After spraying the active ingredient solution, the granules are heated with stirring until the water is removed.

The herbicidal compositions according to the invention may contain, in addition to the active compound of the formula (I), other chemical agents commonly used in agriculture, such as, for example, fertilizers, plant growth regulators or herbicides.

For example, the compounds of formula I may be combined with the following herbicides:.

(1)

5-tert-butyl-3- (2,4-di-chloro-5-isopropoxylthyl) -1,3,4-oxadiazol-2-one;

(2)

3-Isopropyl- (1H) -benzo-2,1,3-thiodiazin-4-one 2,2-dioxide;

(4)

2,4-di-chloropenoxyacetic acid and its esters and salts thereof.

Combinations with grass herbicides:

(1)

2.4- <1ΐεΜθιΌ ^ ε ^ οεΐονύ acid and its esters and salts thereof;

(2)

S- (2,2,2-trichlorallyl-4-methyl-thiocarbamate);

(3) 2- [4- (2,4-2,6-Phenoxy (phenoxy)] -piperidine (4) 1,2-dimethyl-3,5-diphenyl-1H-pyrazolium m-methyl sulfate;

(5)

4-Chloro-2-butynyl-1-chlorobacacanilate.

The compounds of formula I can also be combined with other herbicides; in particular, because of their effectiveness against a wide variety of weeds, combinations thereof with bromacil [3- (selective-butyl) -S-bromo-4-methyluracil], with diuron, [3- (enyl) -1,1 - ^ (l ^ ^] ^ (^ 'thylmočovina] 3-cyclohexyl-L-mtthyl -6-dimethylamino) - i ¹ _{i-tt-i phthalazin-2)} 4- (1H, 3H) -dione, with paraquat (l, l ^{<-dimethyl-4,4'-bipyridiniový} ion], a m- (^ ^ -άπηθϋ ΙιΐΓθίάο) Ι ^ ^ ιΙ γο acid

2-methyl-4-chlorophenoxyacetate, its salts or esters,

6-methylthio-2,4-bls (ethylamino) -s-triazine;

46 with 4-amino-O-tert-butyl-3-methyl-4-thio-as-triazin-5 (4H) -one or with n-nitrephenelethyry such as

2,4,6-trichlyphenyl-4-nitrophenyl ether and 21'-dichlorophenyl-4-nitrophenyl ether. *

Above specific chemical. the compositions used in agriculture are given merely as examples of compounds which can be mixed with the active compounds of the general formula I and do not limit the scope of the invention in any way.

Example 2 4

For industrial use can be. produce granules of the following composition:

3-chloro-2- (n-chlorophenyl) -4,5,6,7-chloro-dydro-2H-indazo] 5%

3-Cyclohexyl-1-methyl-6-dimethyl-aminotriazine-2,4 (0H, 3H) -dione 5% granulated attapulgite (low volatile material, particle diameter 0.71-0.30 mm, i.e. mesh with 25-50 holes mesh according to

USS) 90%

The active ingredients are mixed, mixed. heated to about 90 ° C and the melt sprayed preheated, dust-free granules of attapulgite, with stirring in a mixer. The treated granules are allowed to cool and then packaged.

The compounds of formula (I) may be used to selectively control undesirable vegetation, for example, to control hedgehog corns in crops of useful plants such as rice, in particular rice, wheat and peanuts. The compounds can also be used for post-emergence weed control in certain crops of useful plants, such as rice. The compounds of formula (I) may further be used for the controlled treatment of various crops of useful plants, for example soy, peanuts, cotton, garden beans and row crops of rice, for the purpose of pre-emergence or permissive weed control.

The compounds of the formula I can be used for controlling weeds in transplanted crops such as rice, tobacco, tomatoes, cabbage, sweet potatoes (batat), lettuce, celery, pepper and eggplant. The treatment can be carried out by applying the herbicidal composition to the soil surface before planting the plants and planting the crop plants in the treated soil, or by incorporating the herbicidal composition into the soil prior to planting and replanting the crop plants in the treated soil. The herbicidal composition can also be applied after planting of the useful plants, provided that the chemical composition does not get on the leaves of the plants (see Table IV).

The exact amount of the compound of formula I to be used in a given situation depends on many factors, for example the desired end result, the expected use of the treated plants, the crop and weed species, the soil type, the formulation used, the method its application, on prevailing weather conditions, on leaf density and the like. Since so many variable factors play a role in the application of the herbicidal composition, it is not possible to accurately determine the application rate appropriate for all situations. Generally speaking, the compounds of formula I may be applied at a rate of from about 0.015 kg / ha to about 15 kg / ha, preferably from about 0.03 kg / ha to about 10 kg / ha. Lower dosages within these ranges are generally selected for application to lighter soils, to low soils. organic materials, for selective weed control in crop plants or in situations where long-term persistence of the preparation is not desired.

The herbicidal activity of the compounds of the formula I was determined by means of tests carried out in greenhouses, as described in detail below.

Test 1

Seeds of the cudweed (Digitaria spp.), Hedgehogs (EchinccУlca crusgalli), wild oat (Avena iatua), cassia (Cassia torah), oat - grass (Ipomoea sp.), · Beet (Xanthium sp.),. Sorghum, maize, soybean, rice, wheat and sedge were grown in nutrient media and treated with a chemical agent dissolved in a non-toxic agent. . At the same time, they were a herbicidal agent. Sprayed cotton plant in five leaf stage (including uterine), bean in the stage of three developing triple leaves, rosette in the stage of two leaves, hedgehogs legs in the stage of two leaves, oat in the stage of one leaf, cassia in the stage of three leaves ( (including inheritance), bean in stage. four leaves (including uterine), sorghum in three-leaf stage, maize in three-leaf stage, soybean in stage two. uterine leaves, two - leaf rice, wheat. one leaf stage and sedge in the 3-5 leaf stage. Treated plants and control plants were grown in a greenhouse for 16 days, then all plant species were compared to controls and visually evaluated for how they reacted to the treatments.

The results of the evaluation of the substances tested in this manner are shown in Table 1.

The reaction of the plants is expressed on a scale beginning with 0 = no damage to the plant and ending with 10 = complete killing. plants. The letter symbols used have the following meanings:

SJ9

B = burns,

G = growth slowdown,

C = necrosis / chlorosis,

E = suppression of emergence,

H = effect on plant shape,

X = axilla stimulation.

The plants on which testing was carried out are indicated in the table i with the following letters:

a - bob, b - cotton c - sorghum d - maize e - soybean f · - wheat g - oat wild h - rice i - hedgehog corns j - dew k - winder i · - beet m - cassia n - sedge.

2/5 10B 9B 5B 6B 5B 2B 2B 2B 10B CB 7B 7B 3B 2C 1C 2C 1C 2C 9C 1C ЮС 6H

5H 6H

Application of postemergence preemergence

2/5 8В 8В 2В 7В 4В 2В 2В 2В 6В 8В 10В 6В ЗВ 2В 0 0 0 000 ЗН 3G ω

CM c

tO ω o

O O 'o <=> I

Application of postemergence preemergence

X o yH ω o o

ϋ in o

o CD

O

ω CD CM

Д

O.

o o o o ω CD o

O

CD

CJ O ω

Ю ω

O

Axis ω ω Tf <CM and ω rH ω ω гЧ

Postemergence preemergence application c

Μ «Μ φ

О tí s

q- <

Φ

Β (Β

Sat About CM CM Ο Ο u o 00 CN Ο ο o o στ oo y ο У ω o 3S ο e στ cm ο o ^{ο C.} ω ο ο τ-Η rH o o. o o rH rH on _ω 00 ^ω  ' o o 0 oo ° ^ο ° ⁰⁵ 0 o CD o ο ο στ ο 0 0 O go S 0 ” 03 ot ⁰³ OT ^ο ω 3 ⁰³ By ot cq cd Ο ο στ στ Ι ϋΟ 0) H S pa pq 00 rH PQ PQ ld ld PQ PQ CO f Й Q S S

pq t>. pa op pq O) PQ o t — 1 PQ PQ CO O CQ o rH o rH rH LD « PQ PQ O PQ K O S CD rH LD OO PQ PQ PQ PQ O O O O rH rH rH rH PQ PQ pq PQ στ nu στ στ PQ PQ pq PQ CD what στ στ

PQ PQ oo στ

PQ PQ oo στ

PQ PQ στ

PQ PQ co

PQ PQ στ oo

PQ στ

Q O O O O O

ω ο Ч

PQ στ pq oq o rH rH

LD

M

O CM O ω CM O 0 00 . CD O O CM CM O 0 > 4 O O LQ oo O TO CM 0 CM O CM u rH 0 rH CQ 0 l rH PQ CQ rH CM PQ PQ CM PQ CQ CD CD PQ PQ WHAT CM PQ PQ oo LD PQ CQ LD oo CQ CQ WHAT CM CQ CQ CM CQ CQ WHAT WHAT PQ CQ LD oo CQ PQ LD CM PQ PQ oo CQ PQ CD CD LD CM CM

* δθ

Λ

'CH 2/5 7B ^7B ЗВ 2B IB 2B 2B 3B 7B 2B 8B ЗВ ЗВ 0 0 1C 1H 2C 1C 0 8C 2C О О 2C

O

'So со g' 2 O)> ω o

already

O O O O ° o O O O O 0 WHAT O O X r-1 O X г — 1 Й o 0 Ю

0 к К 0 O 0 m гЧ LJ OJ ΙΩ OJ O 0 0 Ю 0 Д К 0 t— < О r-i r4 rH CD 00 CD 0 o 0 00 0 X rH b o. o r4 0 O r-4 0 0 CM CD 0 O r4 O 0 0 0 0 0 00 what CD OJ O 00 0 0 0 0 0 0 0 Ю СО b CD CD r4 CD 0 0 0 no 0 0 0 0 Ю m 00 b гЧ 00 E 0 0 Д 0 К tb 00 00 rK 00 О CD 0 0 0 O 0 0 ^ 0 X 0 Ж CD b r-Ч b OJ PEOPLE »W O r4 0 Д 0 0 o 00 0 0 t— <b » what Т-Ч 00 r4 О 00 CQ ca ca ca ca CQ ca OJ r4 r4 r-4 00 гЧ 0J CQ ca 02 / ca ca CQ CQ CD OJ Ю 00 00 WITH 00 ca aa ca ca ca CQ CQ in Ю 0J CD ca ca ca ca ca CQ CQ O O CD CD O O O r4 r4 r4 r4 r4 ca ca ca ca CQ Kpq CQ 00 OJ rH ь rH ca ca ca CQ CQ CQ CQ O r4 o rH 00 00 b CD CD ca ca ca ca | CQ CQ what Ю 00 ’Ф CM CD ca ca ca ca CQ CQ CQ what CD Г-) 00 0J гЧ Ю ca ca ca ca CQ CQ ' CQ ь CD r4 TF OJ 0J OJ ca X ca ca CQ CQ CQ ca 00 U) 00 b r4 oo ca SC ca ca CQ CQ ca ca £ 00 LO CD 0J WHAT Ю .CD ТГ CD O ca ca CQ ca CQ CQ rH O OJ b OJ 00 ω ca ca ca CQ Q CQ Q CQ CD 00 o тЧ 00 CD CD b Ю CD ca ca ca ca CQ . CQ CQ o tH CD CD CD b 00 O r4 OJ Ю UO LIMB ID LIMB CM 0J OJ OJ CM OJ

φ о

fi а

r — I _

д Ф * гН ьо

Ен Φ а _л ф Λ ф Ен ^and bo

O ri

«Η bo ω Φ

TΦ л o.

eQ

C0

O O C O O O what O O in C rH O X rH 0 CD O 0 m O O X rH C Tfi o o rH 0 what C LO O X tH  O у o U0 C 0 0 C rH tn rH co in WHAT it CM O O u E 0 C C CD CD CO CO CM CD o tH O ω 0 0 O C C WHAT CM LO what LIMB CD O CD 0 o cm co ω CO o tH C rH C o rH X ω 0 0 0 0 C C O CM LO rH tO cm tn rH rH WHAT 0 CM 0 WHAT O O 0 0 m! X CD ω я ^y ® C £ X c 'S 0 ю X CM C0 rH o, CM OJ CM rH CD O Q ω O C CM CD CM LJ tH CM ca Bye CQ O Bye · C 00 CM rH, rH in CQ Bye CQ PQ pq CQ WHAT O rH CM rH in Bye PQ PQ . CQ pq CQ What O- CM what it PQ Bye CQ CQ PQ CQ co O O O O o. rH rH rH rH rH ' M 0 pa 0 CQ C CQ pq CQ CO rH to 05 rH ID what CD. tH CD O PQ CQ CQ CQ CQ cn CD CD WHAT CD O rH at Bye CQ CQ  CQ .0 what what WHAT 03 / CD O pq. CQ CQ CQ C CD CM CM CM CM it X ω Bye CQ CQ CQ CQ CM Ю CM CM CM CM what O PQ CQ CQ CQ PQ CM what ТГ it it CC o E Bye CQ CQ CQ X CM CO LIMB WHAT ’Φ it 0. Bye CQ CQ CQ CQ CM CD WHAT in what bx m pq CQ CQ CQ WHAT o rH CD tx CD O rH PQ o Bye CQ CQ ca CQ tH and O, CD 00 CD rH in in Ю Ю LIMB LO CM CM 04 / CM CM CM

CO .3 ri ri o ω

195738

Application of postemergence preemergence bO ω TJ o

and

WITH

Д13

4-4 ь <4-4 ω та ω

хэ tb

СЛ o

B ’Pi

o o O o O CJ rH CJ CJ LID τ — 1 O R0 rH rH WHAT o o rH CJ 0 tH ud CD 14 CJ O rH CM O Š 1 Ы o rH CD CM Ы CJ o rH rH CJ o rH 8 ° CD CD СО Ю CJ E CD CM oo UD rH CD oo o “» CJ x CD rH CD E PEOPLE E 00 ω ы by 5 rH rH CJ O rH R o cj o CJ CJ ы w CJ S ⁰⁵ CD CD 00 CD o o rH rH O rH ω o CJ CJ CJ CJ CJ CJ CJ <N t4 00 LIMB CM (D oo CD и о ж a> cm CJ CJ E 00 rH 00 CJ co CJ 14 CJ CJ o rH rH CJ o rH Ulul CJ CJ CJ O CJ o CJ - CO CD CM CO σ> co people CD CD CD O rH

O

O

CM

CJ X Ч О ωcj οcd

OQca

CMτ — I

PQ PQ

00

PQ UD

PQ O rH ca o

PQ in

PQ (X

PQ O

PQ O

PQ

O)

PQ PQ

CD 14

PQ PQ

PQ PQ

LÍDCM

PQ PQX

Í4 ЮЮ

CQPQ t400

PQ O rH

PQ O

PQ oo

PQ CD

PQ PQ About CD

Q О Ж Q ьС тЧ ™ E co rH L · * rH CJ X О Ж CJ ^ CJ E CM 5; см 05 cm co CM (4 CJ о ж CJ E CJ 0 σ? CM CD rH CD rH CO PQ PQ CQ PQ 00 rH OO rH PQ PQ CQ CQ O rH people WHAT CM PQ PQ PQ PQ what CD PQ PQ CQ CQ O rH CD O rH what PQ PQ PQ CQ CD 00 14 PQ CQ PQ CQ oo rr & CD PQ CQ. CQ CQ Tfl limb limb PQ CQ PQ CQ 00 00 00 CM PQ CQ PQ CQ CD CM what rH CQ CQ X CQ CQ O CD PQ CQ CQ E CQ 14 LÍD cd what PQ CQ CQ CQ CD what PEOPLE PEOPLE CQ CQ CQ CQ O rH CD CD oo PQ CQ CQ CQ CD 14 O rH CD LIMB LIMB PEOPLE CM CM CM CM

PQ PQ cq oo co cd

PQ PQ X PQ

CD 00 Ш CD

PQ PQ CD)

CQ CD CD CD

PQ CQ O

PQ O

CQ O

CQ O

CM

PEOPLE

CM

Application of postemergence preemergence

O о О ω 00 о ω 1 о F CM о 1 гЧ 1 O 1 1 о о about what о о о е см O o rH О ω о гЧ О) ω д гН 00 ω o О ω о о о о о rH гЧ гН гЧ гН AT' о О no no Ю гЧ СТ) еч ω ω к о Ř ω о ω σι гН гН гЧ СТ) ω О О СО ω r-H гН гН СТ) ю О X ж О CD О со СТ) ю О о rH О ω Е гН СО о о гН О К СМ СТ) ω о о no и о со СТ) СТ) гЧ СО СО со со со СО со гН см см со СО СО со СО СМ см о гН см СО СО СО со СО О см со о гЧ СО О t-H СО 00 СО О гН со СТ) СО СТ) СО СО СО со со со о. СТ) СТ) ΙΌ СО О гН га СО со СТ) со о гН со СТ) СО СО со со со со со г-> СТ) 00 СО СО со со со 00 см см о гЧ Ьх СО СО со со со СО см см см СО СО со со со СТ) со со СТ) 00 со о СО со со со тН Me со ь- <£> СО со со со со; тН ΙΌ 1ч СТ) со m со со со о гН о rH СТ) СТ) СТ)> со о гН со со со о т — 1 со О) со.: ·! о г. *; см Ю ΙΌ см см, СМ см

195738

Application of postemergence preemergence

O ιη

X co

O what ω o in

X CD

X

CD

0) tn ω CD Ό U o rH oo WHAT O O O Д CM O and < ΰ O and ca tn <—4 CQ > r>

г

Φ tt> φ t-1

* And * o ω

CU CD

4D

I * W)

CQ O

CQ CD

CQ Ο

CQ

PQ

Cq тГ pa co oo

CQ CD

CQ

CD m

CM

ο O rH O O O O O O ο O O rH 1 1 o rH O o o rH O ο o 0 rH 00 what O O 1 PD PD O X WHAT cd CM O o rH O 'o. rH O w o rH o o rH O what O CM o O rH X od E rH O u E AT O rH U E o E O O E O O rH CO CO od rH in rH oo PD AFTER O O O O Jh co O O ω O CD rH AFTER rH rM O Q O o O rH o X O O X O O PD w co CM ° o rH rH τφ PM PD O O ω of"" O E o K O O O O rH ТГ rH CM CO rH cm m WHAT tm O O o  E / “4 £ O O O rH oo CM in PM O O o rH O X 0 O E O O o 0 O rH. b> t— ( rH in rH AFTER rH PO O O O o E O O O O O rH CD rH m AFTER WHAT PD O CQ CQ Q oq CQ ? CQ PQ TM rH rH rH rH rH CQ OQ CQ CQ PQ PQ -and· CQ PQ CM O rH rH rH Ьч tn rH rH CQ CQ Bye PQ oo CQ CQ PQ CM CD what CM what PM PM rH CQ · CQ Bye CQ PQ CQ PQ PQ 00 O rH what ΤΦ O rH PD in PM CQ CQ O rH oq oq PQ X PQ QQ CQ WHAT what PM AFTER WHAT E + PM Bye CQ O rH oq PQ CQ CQ PQ oq ιη - what PD oo PM X Bye CQ oq oq CQ PQ PQ PQ in O ΤΦ what in what O. AFTER CQ PQ CQ CQ PQ PQ CQ PQ CM from CM rH AFTER rH PD what CQ CQ CQ PQ PQ PQ PQ PQ rH oo rH rH rH PM in PM Bye PQ CQ PQ PQ CQ CQ AND tn CD CD in TM what oo 1 CQ PQ O rH CQ PQ PQ CQ CQ PQ CD in tM AFTER WHAT PD AFTER PQ PQ CQ PQ PQ PQ PQ CQ in CD bs PM in TM bs TM PQ OQ pq CQ PQ CQ PQ PQ in co rH o rH CD PD PD oo in CQ CQ O, rH Bye CQ PQ PQ CQ CQ oo CD WHAT PD in oo rm in tn tn tn CM CM CM PM PM PM PM CM

о о о

ООО

ООО

о

о о гЧ о

PQ

СО со см

Xi ьо ю

СО

о о о 0 0 0 00 ю 00 0 0 Q Д оо ОТ оо 0 0 0 см 00 ю 0 0 0 ь 00 от 0 0 д со ю TJ1 д гЧ о о д о о д LIMB rH Щ о гЧ 0 гЧ 0 ю О 02 / 02 / со см т-Ч гЧ СО 02 / СО гЧ гН 00 СО 03 / СО ш LD хН со СО СО СП СО ОТ СО СО СО U0 Xt < ю 02 / со 02 / от от ОТ 02 / со 02 / 00 см см СО со 02 / ю 00 гЧ

о

1Л т-Ч о

гЧ о

о гЧ о

гЧ см см оо см <=> о см

0 гЧ Щ о

СО см оо гЧ

СО о см о оо см д

со о см со д

см ш

ь

СО О

СО ь

со

The biological activity of the compounds of formula (I) is further elucidated in Table 2. The data given in this table show that the compounds of formula (I) do not have a phytotoxic effect on two important crop plants, rice and wheat, and thus have selective herbicidal activity.

The test compounds were applied as a solution in a non-phytotoxic solvent to the following plant seeds sown in clay pots: hybrid rice, Japanese rice, hedgehog (Echinochloa crusgalli), lamb (Ipomoea sp.), Wheat, oat (Avena fatua), roof brome (Bromus tectorum) and corn brome (Bromus secalinus); In some cases, the seeds of Brassica arvensis, Broomica (Kochia scoparia) and Field fox (Alopecrus myosuroides) were also included in the testing. The plant material required to test the post-emergence activity of the compounds was obtained by planting some or all of the above-mentioned plant species (after germination). After treatment, the plants were grown in a greenhouse and three weeks after application, they were visually evaluated for how they reacted to the test chemical (as described in Table 1).

The plants on which this testing was carried out are indicated in Table 2 with the following letter symbols:

aa - hybrid rice ‘bb - japanese rice cc - hedgehog corns dd - ealbread ее - wheat ff - oat deaf gg - rooftop hh - cereal brome ii - mustard jj —- bee broom kk - foxtail

Application preemergence postemergence ьо

Ч-Ч ω φ

TJ TJ

CJ ω cú c and bO bo

TJ TJ о

CJ

what

PQ о ю o-cn

O O CM

O 0 i 0 0 O O o o o 00 O o CO i O CO 00 O .0 0 f 0 0 O 0 o o o what o ow .1 ABOUT WHAT o uo o os

ООО о о о о

o o o O CD o o o O o o o o o o o o m m what what o О Т-Ч (4

O O o o o o O O O O i bo ω 0 0 0 O O O 1 co About CM CO O 00 00

| ё оооо

О со о о о о

см со СО гЧ TJ1 см

см со СО гЧ 00

со

Q0CM гНОО ^ СМ

Η Η 'Η Н тЧ Н

1С 1C 4G 4G

Application kg preemergence postemergence

Compound (per ha) aa bb cc dd ее ff gg hh ii jj kk aa bb cc dd ее ff gg íhh

O o Οχ ООО о о о q Q rH Ю ГМ е> О Q О н ООО 0 0 0 0 U о O 00 ООО о о н ю н о о -н -г ООО

0 0 0 0 0 0 о о о о см тН со со со ООО со о о о о о о о о см о о о о 00 ООО о о о о / о о о о О о ООО О О О о о о о 0 0 0 0 0 0 0 0 0 о ME о о см со Оχ О О гЧ ООН со о о о о о о о о о ООО ООО о о о о

O I oooo oooo oooo oooo

10G 0 1G 4G 7G 5G

CD CO <D CM CO

M <rH 00 CM rdOOMCM 00 rH M <CM rH ζπ г-1 rH rH rH rH rH rH rH rH ”rH r-ϊ rH

195738

Application kg preemergence postemergence

Compound (per ha) aa bb cc dd ее ff gg hh ii jj kk aa bb cc dd ее ff gg hh

CQ CQ CQ CQ CM CD CO

CQ CQ CQ CQ ji CO CO CD CD

CQ CQ 'Q Q H Ш

CQ CQ

O RH rH

Cq cq cq pq

LO ю CD 'CQ CQ o rH b

CQ

ОС Q ^H

CQ

O O O rH

O 0 0 1 O O O 00 O O O o o rH what O о 1 O O O O O O CD CD 0 O 0 0 O O O what O O Ю o o rH O O o o Ю O O O O O O O O 0 0 0 O O O O O O Ю o o O O O rH 00 what O O O O O O O 0 0 0 | O O O O O O rH o a rH LO O o 1 O O CD CD O O O O

O O O CD O O O O O O CD CD O O O O O O O O O 0 0 0 what 0 0 0 O 0 Q 0 0 · * · 0 0 O O CD 0 CM O CD b what CD O O CD O O CM b what 0 0 what tH rH O O O CD O O O O O O CD 0 O CD 0 O O O O O 0 0 CD 0 0 0 0 O CD O O O O O xT xf what O CD O CM 0 O O 0 O O 0 CM CD CD Me CM CM CD CM CD CD 00 rH Xt < CM rH 00 CM rH CM 00 rH CM 00 tH Me CM rH 00 CM rH tH rH rH rH rH rH r-l rH rH rH rH rH rH rH rH rH tH rH rH

ла _on ш mmmmm ω what cq

ГЧm r-/ / Ts i — t

Application kg preemergence postemergence

Compound (per ha) aa bb cc dd ее ff gg hh ii jj kk aa bb cc dd ее ff gg ihh

u-> oo oo cd o rH O CD CD O rH rH t — 1 rH | 1 AND AND AND PQ ca ca PQ | 1 1 .1 1 1 O O O O 1 rH rH rH rH CQ CQ PQ PQ PQ PQ 03 / F O O CD CD O LD in O O 1 rH rH rH 0 O PQ PQ PQ PQ PQ PQ PQ what b-x CD O O O bx CD O O rH rH г-1 rH U O CC PQ PQ CQ PQ PQ PQ PQ what t> x O O O c0 oo O O rH rH rH rH rH

0 0 PQ PQ Q CO CO o O H Ю Ю)

AND PQ PQ CQ CD CD PQ PQ PQ PQ CQ PQ PQ 1 1 (D O O rH t> O D O CD O O 1 rH rH rH rH rH rH rH CQ Bye CQ CD CD PQ PQ PQ PQ CQ PQ PQ CQ CD CD O CD 1_O CO CD O O CD O O CD O rH rH rH rH rH r-i rH rH CQ 0 0 PP PQ O O O CD Q Q Я C "( CD O O CM CM CQ O o PQ PQ CD O CD CM O O RH rH CD O O in what AND AND 1 1 AND 1 1 1 AND AND I 1 1 ы w ы ω о ы o O 0 0 O 0 and [ Ί 1 1 1 1 1 1 1 1 AND l 1 1 1 Ю CD ID CD O) CD CD 0Q what o rH 1 1 .1 1 O O O CD | 1 AND AND AND I I 1 o Q.O O | | | 1 F 0 0 0 ID CD CD rH O rH 1 1 1 1 1 1 1 1 1 O 1 1 1 1 1 CD 00 CD 0 CD | 1 | and | AND I 1 | 0 0 O 1 1 AND AND AND 0 0 0 0 O O m O 1 1 1 1 l 1 1 1 1 O ABOUT CO CO CD 1 1 1 1 1 O O o o rH rH rH rH rH 0 CD CD CD CD CD CD CD CD CD ω 0 CD 0 0 CD 4—> O) CD rH O CD O O CD CM CD (D O rH O 00 00 чф CD CD WHAT CD rH o rH O CD O 0 CD CD CD CD CD O o o o o 0 0 0 0 O CM CD and O O CD O CD Ю Ю CD <D O what is it about? CD O CD O O O O O rH rH rH rH i — 1 O CD CD CD CD ω cd CD 0 0 0 Ц 0 0 CD 0 0 0 0 CD rH WHAT O CD O CM O CM CM co CD O H Ю CD O 00 CM CD CD rH O O 00 rH CM CD 0 cd no CD 0 0 CD O O O O O O O O rH rH co тН O O O O CM O O O rH CM O O o o CD CD CD CM CD 0 AND O O O CM CD and O O O O O rH CD CD O CM O O O 1 CD CD O o o o CM CD CD CD CD CD CD CD CD CD no CD 0 CD CD CD  CD 0 0 0 0 0 0 0 LJ CD O O what uo CD CD CD O O LQ CD CD O O 00 O O CD O 00 CD rH rH rH rH rH rH rH rH rH CD O O O 1 CD O CD CD O o o CD rH O Q OO G O O O and O O O o o

CM

195738

Application kg preemergence postemergence

Compound (per ha) aa bb cc dd ee ff gg hh ii jj kk aa bb cc dd ee ff gg hh ii jj co

CQ co

C3 CO o o

CQ CC qQ o.

o in

CD C7D

0 0 O O O O O O O O CM WHAT C 0 0 O O O O O 00 O O WHAT WHAT 0 0 0 O CM O O what O O O O T-1 O O O O O O O O O O

0 0 0 O O O Ю O O 00 xfl 0 0 0 O 0 CD tH Ю CD O O oo xr 0 0 0 O O O CM Φ O O CM CC O 0 O O O O O O rd

0 _ C o CD o o about what o o o o. CD O CO o rH CD oo ^O C O 0 C 0 0 0 0 0 O  0 about what what what CD CD o o CO CD CD in CD O O o CM tH

O O O O

CM Ή rH

o o o o

O O O rH

CM what he rH

what

CM co rH 00

195738

Application kg preemergence postemergence

Compound (per ha) aa bb cc dd ее ff gg hh ii jj kk aa bb cc dd ее ff gg ihh

o Q o what o ° o u o o ω 0 o what O) o o о со σ>

From the above data it is clear that the compounds of formula (I) at a low concentration effectively control unwanted vegetation, for example hedgehog, but have a relatively weak effect on crop plants, such as rice. In wheat cultures, the compounds at low concentrations limit the growth of deaf oat, corn bean, roof brome and, if tested, mustard, flat grass and foxtail, with only a slight effect on wheat.

The following Table 3 is presented to further elucidate the biological effect of the compounds of Formula I. The data show a selective herbicidal effect of the test compounds on various weed species in field irrigated rice crops.

Field irrigated rice culture was imitated by planting Japanese rice plant seedlings in a two-leaf stage in a vat of ground containing Echinochloa crusgalli seeds, flooded with water and maintaining the water level a few centimeters above the soil surface. The test compounds were applied directly to the water flooding plants and after three weeks the response of the plants to the treatment was evaluated.

Table 3

Compound

Rate, kg / ha

Japanese rice hedgehog corns leg

1/32 0 9G 1/16 0 9C 1/8 3B 10C 1/4 0 10C 1/16 0 7G 1/8 0 9G 1/4 0 10C 1/2 2B 9C 1/32 0 9C 1/8 0 10C 1/64 0 9C 1/32 0 9C 1/16 0 9C 1/8 1B 10C 1/16 0 7G 1/8 0 9G 1/4 0 90 1/2 1B 10C 1/32 0 0 1/8 0 5G 1/64 1G 8G

These data show that the test compounds of formula I, when applied at low doses, effectively kill unwanted vegetation, such as hedgehog, but have a relatively weak effect on rice.

To prove the utility of the compounds of formula I in planted crops, 30X30X15 cm metal containers were filled to a depth of 13 cm by gassing with Fallsington sand-clay soil and admixed to the top of the soil in each pot to a depth of 2.5 cm over the area seeds of the following weeds: hedgehogs corn (Echinochloa crusgalli), bloody dew (Digitaria sanguinalis), rind (Setaria faberii), durman (Datura stramonium), opium (Abutilon theophrasti) and moth (Ipomoea purpurea).

The weed-sown soil was pre-emergence treated with the test herbicidal compound by spraying on the soil surface and incorporating the active ingredient into the soil to a depth of 2.5 cm. The following doses were administered:

Compound dose

0.016 kg / ha

0.12 kg / ha

1,0 kg / ha in acetone a

Control 0

Compound A (3-Chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-terahydro-2H-indazole)

Compound A Compound A

Compound A was dissolved by spraying at a rate of 560 liters / ha. Immediately after this treatment, the following crop plants were planted in the soil: pepper (Delaware Belle, 12.5 cm high), tomato (Bonny Best, 10 cm high), cabbage (Wisconsin Golden Acre, 12.5 plant) cm), and tobacco (Coker 319 species, 10 cm high plants) Four pots were planted in each pot, the pots were placed in a greenhouse and manually irrigated as needed 18 days after treatment, visually evaluated by the plant reaction; Table 4.

ιη О о о О 00 О © '8 > ω «α о о "

19573В

Claims (8)

the object of the invention CLAIMS 1. A herbicidal composition comprising at least one surfactant, at least one solid or liquid carrier and, as active ingredient, a cycloa-ananopyrazole of the formula I in which n is 3, 4 or 5, R ¹ is hydrogen or methyl, Q is fluorine, chlorine, bromine or iodine, X is fluorine, chlorine, bromine or iodine, cyano, methoxy or nitro, Y is hydrogen, fluorine or chlorine, Z is hydrogen or fluorine, and V is hydrogen, fluorine or chlorine or methoxy, with the proviso that (a) when n is 5, the R ¹ be hydrogen, Q must be chlorine or bromine, Z а V must both be hydrogen and Y must be hydrogen (b) when n is 3 or 4 and Q represents a fluorine or iodine atom, R ¹ , Z and V must denote hydrogen atoms and Y must denote a hydrogen or fluorine atom, (c) when n is 3 and R ¹ represents methyl, must. Q denotes a chlorine or bromine atom, Y denotes a hydrogen or fluorine atom and Z and V denotes a hydrogen atom, and (d) when V has a meaning other than hydrogen, X denotes a fluorine, chlorine or bromine atom and Z denotes an atom hydrogen. 2. The herbicidal composition according to claim 1, characterized in that it contains at least one surfactant, at least one solid or liquid carrier and, as active ingredient, 1,3-chloro-2- (4-chloro-2-fluorophenyl) -4,5. , 6,7, -tetrahydro-2H-indazole. 3. A herbicidal composition as claimed in claim 1, comprising at least one surfactant, at least one solid or liquid carrier, and 1,3-chloro-2- (4-chlorophenyl) -4,5 as the active ingredient. 6,7-tetrahydro-2-H-indazole. 4. The herbicidal composition of claim 1 comprising at least one surfactant, at least one solid or liquid carrier, and 1,3-bromo-2- (4-chloro-2-fluorophenyl) -4,5 as the active ingredient. , 6,7-tetrahydro-2H-indazole. 5. A herbicidal composition according to claim 1, characterized in that it contains at least one surfactant, at least one solid or liquid carrier and, as active ingredient, 1,3-chloro-2- (4-bromo-2-fluorophenyl) -4,5. , 6,7-tetrahydro-2H-indazole. 6. The herbicidal composition according to claim 1, characterized in that it contains at least one surfactant, at least one solid or liquid carrier and, as active ingredient, 1,3-chloro-2- (4-chloro-2-fluorophenyl) -2,4. 5,6-tetrahydrocyclopentapyrazole. 7. The herbicidal composition of claim 1 comprising at least one surfactant, at least one solid or liquid carrier, and 1,3-chloro-3- (4-thiophenyl) -2,4,5,6 as the active ingredient. -tetrahydrocyclopentapyrazole. 8. A process for the preparation of cycloalkanpyrazoles active according to item 1 of general formula I wherein n is 3, 4 or 5, R ¹ is hydrogen or methyl, Q is a chlorine or bromine atom, X is fluorine, chlorine, bromine or iodine, cyano, methoxy or nitro, Y is hydrogen, fluorine or chlorine, Z is hydrogen or fluorine; and V is hydrogen, fluorine or chlorine or methoxy, with the proviso that (a) when n is 5, the R ¹ denote hydrogen, Z а V must each be hydrogen and Y must be hydrogen or fluorine, (b) when n is 3 and R ¹ is methyl, it must No. Y is hydrogen or fluorine, and а V must be hydrogen, and (c) when V has a meaning other than hydrogen, X must be fluorine, chlorine or bromine, and Z must be hydrogen, of the formula wherein n, R ¹ , X, Y, Z and V are as defined above, reacted with at least one equivalent of a phosphorus oxyhalide of the formula POQs in which Q is chlorine or bromine.